1]The invention workability with the texture of the coated high-color composite resin and a colored steel sheet excellent in chemical resistance relates to a method of manufacturing the same, and to apply for video consumer electronic panel.
[2]BACKGROUND
[3]Video appliances Case Tower, such as TV (Case Top), bottom chassis (Bottom Chassis) and rear cover (Rear Cover) parts have a luxurious texture to induce buying power to the consumer, and molding necessary for pressing castle, and the degree of corrosion is not a problem in more than 10 years of use and require chemical resistance.
[4]
[5]
Thus, the aluminum metal, plastic Extrusions or color coated steel sheet of the thick film used for the components as described above. Among them, the aluminum metal has a strong advantage in light and corrosion. However, the appearance of aluminum metal is here generally have a monotonous texture, typically are expensive and there the hairline (Hair-line) Color Coating after machining.
[6]
[7]
And the plastic mold can implement a variety of designs, but there is no limit of the molding is widely used as a material for the panels, the low productivity and environmental friendliness is pointed out as a problem.
[8]
[9]
On the other hand, color coated steel sheet is composed of conventional undercoating and intermediate and top coats, is usually not less than the film thickness of 30mm. Thus, one possible implementation luxurious appearance, a high productivity is low.
[10]
Detailed Description of the Invention
SUMMARY
[11]
The invention In one embodiment, the existing composite resin composition of the collar while thinning by omitting the intermediate coating from the coated steel sheet excellent in workability and chemical resistance of the fine texture, color, the composite resin composition coated zinc-coated steel sheet and a method of manufacturing the same It intends to provide.
[12]
[13]
This patent, as well as the thickness of the film thin while that through the surface-treated with organic materials to show the beautiful texture micron size metal and an inorganic pigment coat uniformly injury in effectively the action of an acid catalyst and an amine catalyst fine texture It is to be formed in a predetermined pattern.
[14]
[15]
Further, by using this excellent in physical properties such as appearance and texture, as well as the corrosion resistance is beautiful, chemical resistance, press formability and an object thereof is to provide a dedicated youngsangga panel.
[16]
Problem solving means
[17]
The present invention provides a composite resin composition as some aspects. The composite resin composition In one aspect, linear and cross-linked mixed urethane-modified polyester resin of 30 to 60% by weight, and aziridine curing agent or a melamine at least one curing agent of the curing agent of 3 to 15% by weight, an acid curing catalyst, 0.05 to 1.5 the weight% amine curing catalyst from 0.05 to 1.5% by weight, and the colored inorganic pigments from 0.1 to 15% by weight, provides a composite resin composition comprising the remainder solvent.
[18]
The urethane-modified polyester resin has the ratio by weight of linear and cross-linked 1: preferably from 4: 1 to 1.
[19]
The melamine curing agent in a weight ratio of melamine and imino melamine 1 preferably includes a 4: 1 to 1.
[20]
The melamine may be butoxymethyl melamine, hexamethoxymethylmelamine or mixtures thereof.
[21]
The imino melamine may be used trimethoxy methyl melamine.
[22]
The acid curing catalyst may be at least one acid selected from the p- toluene sulfonic acid, dodecylbenzene sulfonic acid die, dinonyl di-toluene sulfonic acid and dinonyl naphthalene sulfonic acid group consisting of a.
[23]
The acid curing catalyst may be an acid blocked with an amine series compound.
[24]
The sulfonic acid blocked with the amine compound may be a dodecylbenzenesulfonic acid neutralized amines.
[25]
The amine curing catalyst may be a primary amine, secondary amine, tertiary amine or a mixture of two or more thereof.
[26]
That the volatility of the amine curing catalyst is higher than the volatility of the acid curing catalyst is preferred.
[27]
Composite resin composition of the non-ferrous and further comprises a metal pigment, the metal pigment may further comprise in the range of 0.1 to 15% by weight of the total composition weight.
[28]
The solvent is discharged from there is dinkeop (DIN, 53211) of the composite resin composition may comprise an amount to make the viscosity takes 20 to 200 seconds.
[29]
[30]
Furthermore, the present invention comprises a composite resin coating film formed on the carrying plate and at least one side of the carrying plate, including a zinc coating layer, the composite resin film is linear and cross-linked mixed urethane-modified polyester resin, 50 to 80% by weight .; At least one curing agent from 3 to 20% by weight of the aziridine curing agent or a melamine curing agent; And a colored resin of the composite coating film formed from 3-20% by weight of the colored inorganic pigment, there is provided a zinc-plated steel sheet.
[31]
The urethane-modified polyester resin has the ratio by weight of linear and cross-linked 1: preferably from 4: 1 to 1.
[32]
The colored inorganic pigments include carbon black, carbon nanotube, graphite, graphene, ferric oxide (Fe 2 O 3 ) and titanium dioxide (TiO 2 may be at least one selected from the group consisting of a).
[33]
The colored inorganic pigment is a particle diameter of 0.01 to 20㎛, oil absorption is 60% or less may be used.
[34]
Composite resin coating layer of the colored further comprises a metallic pigment, said metallic pigment is preferably 0.5 to 20% by weight of the total weight of the composite coating film of the colored resin.
[35]
The metal pigment may be aluminum alone or an aluminum-containing alloy.
[36]
The metallic pigments are preferably flake trader of a thickness of 0.1 to 5㎛.
[37]
The metal pigments are cetyl sulfate, sodium cetyl sulfate, ammonium salts, stearyl sulfate, sodium stearyl sulfate, ammonium salt, a glycerol fatty acid ester, poly Glacier serine fatty acid ester, glyceryl receiver fun benzoate, glyceryl stearate, glyceryl Lodge carbonate, La Ness -5, La Ness -10, -15 La Ness, lanolin, route remote chloride, bromide remote set, set the remote chloride, sodium isostearate in one lactate, sorbitan laurate, sorbitan stearate, sorbitan oleate and may be at least one surface treated with an organic compound selected from the group consisting of organic compounds of formula 1-5.
[38]
Formula 1
[39]
[40]
(In the formula 1 R is a chain-like alkyl compound of C5 ~ C15.)
[41]
[Formula 2]
[42]
[43]
(In the formula 2, R is a chain-like alkyl compound of C1 ~ C10, n is an integer of 1 to 10.)
[44]
[Formula 3]
[45]
[46]
(In the formula 3 R is a chain-like alkyl compound of C1 ~ C10, n is an integer from 1 to 10)
[47]
[Formula 4]
[48]
[49]
(In the formula R 4 is a chain-like alkyl compound of C1 ~ C10, n is an integer from 1 to 10.
[50]
[Formula 5]
[51]
[52]
(In the formula 5 R is a chain-like alkyl compound of C1 ~ C10, n is an integer of 1 to 10.)
[53]
The composite resin film preferably has a thickness of from 3 to 30㎛.
[54]
The composite resin film may have a pattern.
[55]
A transparent resin film on the composite resin film may further include. The transparent resin film may be formed of at least one curing agent 5 to 35% by weight of linear and cross-linked is mixed with a urethane-modified polyester resin of 65 to 95% by weight, and aziridine curing agent or a melamine curing agent.
[56]
The transparent resin film may have a thickness of 0.1 to 3㎛.
[57]
Effects of the Invention
[58]
The resin-coated composite of colored galvanized steel sheet according to one embodiment of the present invention has the fine texture of good appearance with a predetermined pattern on a metallic texture and the coating film surface to the surface.
[59]
In the coated steel sheet of the colored composite resin in accordance with one embodiment of the invention it is possible to obtain a colored coating film of a beautiful texture by forming a very thin transparent coating material by roll coating or spray coating on the coating film surface.
[60]
In addition, the colored resin composite coated steel sheet according to one embodiment of the present invention improves the press formability and chemical resistance and, thereby can be suitably used in panels youngsangga only.
[61]
Brief Description of the Drawings
[62]
Figure 1 is a graph of the mole fraction of the non-ferrous metal and an inorganic pigment.
[63]
2 is a cross-sectional view schematically showing a layer structure of the composite resin coating film formed of the resin-coated composite zinc-plated steel sheet according to one embodiment of the present invention.
[64]
Figure 3 is a schematic diagram to apply the composite resin composition according to an embodiment of the invention showing a process for producing a coated galvanized steel sheet As shown in Fig.
[65]
Best Mode for Carrying Out the Invention
[66]
Hereinafter, a detailed description of the present invention.
[67]
[68]
Composite resin composition of the present invention colored linear and cross-linked with a predetermined weapon in the transparent resin composition composed of a urethane-modified polyester polymer with aziridine or melamine curing agent, an acid catalyst and an amine catalyst and a solvent mixture in a predetermined ratio of a pigment and It provides a composite resin composition comprising a colored metallic pigment. By curing speed difference between the inner film and the coating film surface during curing of the binder resin by the resin composition it can be continuously formed in a predetermined pattern on the coating film surface.
[69]
[70]
To this end, the composite resin composition of the present invention is a urethane-modified polyester resin of 30 to 60% by weight of the total resin composition weight; Yijiri Dean curing agent or a melamine curing agent 3 to 15% by weight; The acid catalyst from 0.05 to 1.5% by weight; 0.05 to 1.5% by weight amine curing catalyst comprises from 0.1 to 15% by weight of the colored inorganic pigment, and the balance a solvent, further said resin composition may further contain a metal pigment.
[71]
[72]
It will now be described in detail with the resin composition of the present invention.
[73]
[74]

[75]
The invention uses a urethane-modified polyester resin as a binder resin. Urethane-modified polyester resin used in the present invention can form a fine pattern on the surface of the coating film upon curing and is excellent in processability and chemical resistance.
[76]
[77]
The urethane-modified polyester resins can be used that is of 2000 ~ 40000 weight average molecular weight (Mw). For example, the weight-average molecular weight of 2000 ~ 30000 2000 25000 ~ 3000 40000 ~ 5000 40000 ~ 3000 30000 ~ 5000 ~ 5000 ~ 30000 or 25000 may be. If the molecular weight is less than 2,000 has a storage stability and workability of the solution may be deteriorated if insufficient chemical resistance and workability in the coating film, and the molecular weight exceeds 40,000.
[78]
[79]
The binder resin is in particular, it is more preferable to use the linear and cross-linked is mixed with a urethane-modified polyester resin. When using the linear and cross-linked mixed urethane-modified polyester resin as the binder resin, it is possible to improve the workability, and also easier than the predetermined pattern by the properties of the functional group to react with an acid catalyst and an amine catalyst it contributes to the formation. More preferably, the urethane-modified polyester resin may be selected from a glass transition temperature of 0 to 70.
[80]
[81]
The urethane-modified polyester composition comprises a linear structure and the crosslinked structure, a weight ratio of 1: can be formulated as a 3: 1 to 1: 4, preferably from 1: 1 to 1. While the cross-linked structure and the resin of a linear structure, and to be combined in the mixing ratio preferably in terms of physical properties and processability of the film hardness of the coating film, dense it is possible to form a solid cured film.
[82]
[83]
In addition, it is preferable to use those having a hydroxyl group (-OH) of the urethane-modified polyester resin is preferably 10 to 500, more preferably from 20 to 400. When the hydroxyl silga exceeds 500 the chemical resistance of the coating film is lowered, if it is less than 10, the crosslinking of the coating film is lowered.
[84]
[85]
Further, the urethane-modified polyester resin is the acid number, preferably of from 5 to 30㎎KOH / g may have an acid value of 10 to 25㎎KOH / g. When the acid value exceeds 30㎎KOH / g the chemical resistance of the coating film is lowered, if it is less than 10㎎KOH / g the cross-linking of the coating film is lowered.
[86]
[87]
The urethane-modified polyester resin may comprise from 30 to 60% by weight based on the total weight of the composite resin composition. If outside the above range may deteriorate the coating film upon curing the composition gun, the other degradation of the other properties is generated.
[88]
[89]

[90]
Composite resin composition of the present invention is a curing agent for the curing of the binder resin, as the curing agents there may be mentioned the aziridine curing agent and a melamine-based curing agent. These curing agents are as high reactivity, it is not particularly limited, and for example, there may be mentioned the following aziridine curing agent or a melamine curing agent of the same formula.
[91]
[92]
[93]
[94]
[95]
The formula (a) is a ahjiri Dean curing agent, wherein R is -H, -CH 3 , -CH 2 CH 3 , -CH 2 CH 2 CH 3 , -CH 2 OH or -CH 2 CH 2 and OH, these ahjiri Dean curing agents can be used alone by itself, of course, it may be used by mixing two or more kinds.
[96]
[97]
On the other hand, to the melamine curing agent include, but are not limited to, it may be a melamine of the formula (b) imino melamine, formula (c) of. If imino melamine curing reaction rate faster than the melamine advantageous for high-speed curing, and increasing the content and degree of curing is increased to increase the hardness of the coating film. On the other hand, the completely-substituted melamine provides a good surface smoothness of the coating film quality crush, while the curing rate is lower. Thus, while improving the surface quality of the coating film by using the melamine, the reaction rate it is possible to improve the response speed is fast and is already added to the furnace melamine. 1 to 1: preferably from formula (b) imino melamine and formula (c) 1 to melamine in a weight ratio of to 4 can be used as a mixture.
[98]
[99]
The melamine may be mentioned butoxymethyl melamine, hexamethoxymethylmelamine, the imino melamine can be mentioned trimethoxy methyl melamine. Examples of the melamine product that can be used in the present invention, and the CYTEC Corporation CYMEL-303, CYMEL-325, CYMEL-327, CYMEL-350, CYMEL-370, SOLUTIA's RESIMINE-7550, RESIMINE-717, RESIMINE-730, RESIMINE -747, 797 and RESIMINE-BIP's bE-3717, and the like bE-370, bE-3747.
[100]
[101]
The melamine curing agent may be contained in an amount of 3 to 15% by weight relative to the composite resin composition. There is a resin and a melamine-based curing agent is compounded in the mixing ratio may be preferably formed of a dense cured film in terms of physical properties of the coating film.
[102]
[103]

[104]
Composite resin composition of the present invention, comprises an acid catalyst and an amine catalyst as a curing reaction catalyst in order to improve the hardness of the coating film to promote the urethane-modified polyester binder resin and the curing agent is aziridine or melamine curing reaction of the molecule.
[105]
[106]
In this case, the amine catalyst, it is appropriate to use the volatility is higher than the acid catalyst. At a temperature higher by these catalysts to the difference in the cure rate occurs in the coating film and the internal surface during the curing reaction, the unevenness of the coating film surface by using such a curing speed difference is formed to form a predetermined pattern on the coating film. When thus the pattern is formed on the coating film surface can improve the surface texture by quenching effect.
[107]
[108]
As the acid catalyst, but are not limited to, the sulfonic acid may be used. Examples of the sulfonic acid, and the like p- toluene sulfonic acid, dodecylbenzene sulfonic acid die, dinonyl di-toluene sulfonic acid, dinonyl naphthalene sulfonic acid, can be used alone, these, of course, it can be used as a mixture of two or more .
[109]
[110]
The acid catalyst is preferably used to the block division of an organic chain that can be dissociated by heat. These blocking materials include the amine-based compound. With the acid in such an organic chain is blocked, but are not limited to, for example, it amine neutralized dodecylbenzene sulfonic acid.
[111]
[112]
The acid catalyst can be from 0.05 to 1.5 parts by weight based on 100 parts by weight of the resin composition. When the amount of the acid catalyst is too low increases the curing temperature of the coating film, it can not maintain the properties of the coating film, so much if the curing of the coating film so rapidly rising or deteriorates the storage stability of the solution.
[113]
[114]
In addition, amine-based catalyst is a primary amine (NH substituted by hydrocarbon 2 -R 1 ), 2 primary amine (NH-R 1 , -R 2 ), 3 secondary amine (NR 1 , -R 2 , -R 3 ) the can be used. In this case, the hydrocarbon group (R 1 , R 2 , R 3 roneun) there may be mentioned aliphatic or aromatic chain. Specific examples of amine-based catalyst usable in the present invention include, but are not limited to, diethylamine, diisopropylamine, di-isopropanolamine, di -n- propyl amine, di -n- butyl amine, diisobutyl amine , di-secondary-butyl amine, diallyl amine, diamyl amine, N- ethyl-1,2-dimethyl-propylamine, N- methyl-hexylamine, di -n- octylamine, piperidine, 2-yl-choline , and the like to choline, 4- blood of 3-picoline, morpholine, it is possible to use them alone may also be used in combination of two or more.
[115]
[116]
The amine catalyst may also be used from 0.05 to 1.5 wt% based on the composite resin composition. When the amount of the amine catalyst is too low increases the curing temperature of the coating film can not maintain physical properties of the coating film, so too rapidly up and curing of the coating film, or in many cases deteriorate the aging stability of the solution.
[117]
[118]

[119]
In the present invention, it is possible to give the color to the inorganic pigment is added to the composite resin composition. The inorganic pigments include long as it has the unique color of, but can be suitably used in the present invention, a unique color to use a combination of black and red and white pigment, 1, the black, red and white by using the pigments in a predetermined mixing ratio is preferable because of a variety of colors can be implemented.
[120]
[121]
The inorganic pigment is preferably contained in an amount of 0.1 to 15% by weight. The inorganic pigment content is difficult to implement a high cover rate and beautiful colors to less than 0.1% by weight of the steel sheet is in possession, and if it exceeds 15 wt%, the viscosity of the solution, the workability is degraded, it is difficult to obtain a beautiful surface appearance.
[122]
[123]
As the black pigment may include carbon black, carbon nanotube, graphite, graphene, etc., more preferably a carbon black from among those. Examples of carbon black pigments include, without limitation, may include four rocks (Nerox) ™ series, Printex (Printex) ™ series, a high black (Highblack) ™ series, the EVO nicks, Inc. (Germany). The carbon black black pigment is preferably about 10 ~ 100㎚, the average particle size is preferred in terms of dispersibility of the pigment to be used is that the 10-30㎚.
[124]
[125]
In addition to the inorganic pigments include red ferric oxide (Fe 2 O 3 may be mentioned). Iron oxide is non-toxic, chemical stability, there is an advantage that can be of various colors. Further, in the yellow inorganic pigment may include antimony, examples of the white inorganic pigment is titanium dioxide (TiO 2 can be given), and zinc oxide (ZnO).
[126]
[127]
The inorganic pigment is preferably used in the low oil absorption (吸油 量). Oil absorption of the pigment can be less than 60%, preferably from 5 to 50% range. Poor oil absorption is too high, the workability is difficult to obtain a predetermined pattern, it is preferable to have the oil absorption within the above range.
[128]
[129]
In addition, the average particle size (diameter) of the colored inorganic pigment is small, and is appropriate in accordance with the thinning of the film thickness, for example, may range from 0.1 to 20㎛. In particular, if the pigment particles in a predetermined pattern formed on the coating film surface are sequentially arranged can be reduced to improve the coating hardness and texture, it can be provided to further improve design property. Thus, the average size of the inorganic pigment particle is preferably in the range of the color coating dry film thickness of the composite resin composition ± 5㎛. It may be, for example, 5 to 15㎛ range.
[130]
[131]

[132]
The composite resin composition also may further comprise a metal pigment, it is possible to implement the metal texture by using a metal pigment. At this time, the metal pigments may further contain in an amount of 0.1 to 20.0 parts by weight based on the total weight of the composite resin composition.
[133]
[134]
A metallic pigment used in the present invention, if having a micron size can be used for all metals on the periodic table. For example, there may be mentioned a metal composed of the alloy containing Ag, Al, Co, Cu, Fe, Mg, Mn, Mo, Ni, Pd, Pt, Sn, W, Zn or the metal thereof.
[135]
[136]
The metal pigment used in the present invention but be used various shapes such as granular, plate-like, block, the flakes (Flake), when used as a coating material, coating film than flake trader is to give an excellent metallic feeling and a brightness desirable. It is on the pigment flakes are not particularly limited, it is preferable to use those having a thickness of 0.1 to 5㎛ to be superior to the appearance of the coating film.
[137]
[138]
Among these metal pigment is aluminum pigment has excellent gloss and is most preferred because the small specific gravity well portion in the coating film. At this time, the aluminum pigment may be constituted of only aluminum, and may be composed of aluminum and alloys with other metals. When using the aluminum alloy of the aluminum pigment, the purity is not particularly limited.
[139]
[140]
And, it is an aluminum pigment used in the present invention is not particularly limited and may be not more than the average particle size 30㎛. If there is more than the mean particle diameter 30㎛, the coating film surface becomes rough, the bar can not be obtained an excellent texture, if having a particle size of less than the above range may be preferably used in the present invention. In this case, the lower limit is not particularly limited, and preferably at not less than the 0.1㎛ manufacturability and economic point of view, furthermore, the average particle size given the agglomeration and the dispersibility of the metal pigment is more preferable to use the above aluminum pigment 1㎛ Do.
[141]
[142]
Further, the resin composition of the present invention may be used in a ceramic pigment, such as glass, mica, alumina or titania. These ceramic pigments can be textured to present a metallic metal by plating the surface of a metal to form a metal film.
[143]
[144]
The metal pigment is more preferably surface-treated with an organic compound. When the treated surface to the metal pigment to the organic compound, chemical stability to be improved to suppress the gas generation and, in the resin composition of the present invention in the manufacture and storing prevent agglomeration of the solid content, and the portion within the film manufacturing coated steel sheet, and it is possible to improve the dispersion.
[145]
[146]
In this case, the organic compound suitable for the surface treatment of the metal pigment may be used as follows.
[147]
[148]
Below may be used higher fatty acid alkali salt or ammonium salt, and mixtures thereof represented by the general formula (1).
[149]
Formula 1
[150]
[151]
(In which R is a chain-like alkyl compound of C5 ~ C15.)
[152]
In the corresponding compounds, it may be mentioned stearic acid, oleic acid and the sodium or ammonium salt or sodium ammonium salt.
[153]
[154]
In addition, it is possible to use an alkyl sulfate salt. In the corresponding compounds which are, for example, sodium salt or ammonium salt of a sulfate and cetyl stearyl sulfate.
[155]
[156]
It is also possible to use the following: alkyl ether sulfate salts of the general formula (2).
[157]
[Formula 2]
[158]
[159]
(Wherein, R is C 1 ~ C 10 and the chain-alkyl compound, n is an integer of 1 to 10.)
[160]
[161]
Next, it is possible to use the sodium salt or ammonium salt of alkylphenol ethoxylates in the following the general formula (3).
[162]
[Formula 3]
[163]
[164]
(In which R is C 1 ~ C 10 and the chain-alkyl compound, n is an integer of 1-10).
[165]
[166]
Further, it is possible to use the following polyoxyethylene fatty acid ester of formula (4).
[167]
[Formula 4]
[168]
[169]
(In which R is C 1 ~ C 10 and the chain-alkyl compound, n is an integer from 1 to 10.
[170]
[171]
Moreover, it is possible to use a polyoxyethylene sorbitan fatty acid ester of formula (5).
[172]
[Formula 5]
[173]
[174]
(In which R is C 1 ~ C 10 and the chain-alkyl compound, n is an integer of 1 to 10.)
[175]
[176]
In addition, glycerin fatty acid esters and poly Glacier serine fatty acid ester, glyceryl receiver fun benzoate, glyceryl stearate, glyceryl carbonate Lodge, La Ness -5, La Ness -10, -15 La Ness, lanolin, route remote chloride, set remote bromide, set remote chloride, sodium isostearate in one lactate, sorbitan laurate, sorbitan stearate, sorbitan oleate, and may be a mixture thereof.
[177]
[178]
Composite resin composition of the present invention a linear and cross-linked the composite resin composition by mixing the urethane-modified yijiri Dean curing agent to polyester resin or a melamine curing agent with an acid catalyst and an amine catalyst comprises a predetermined ratio was dispersed into a solvent as a binder resin after manufacture, it can be prepared by putting the after manufacture, or a mixture of the colored inorganic pigment dispersion by mixing a solvent by the addition of a colored inorganic pigment. You can also mix to add metal color pigments for the implementation of the metal texture.
[179]
[180]
The resin composition of the present invention as described above to further improve the physical properties of the coating film, as needed, in addition to the above component is a wax, a curing catalyst, pigment flocculation agent, additives of anti-foaming agents, leveling agents and the like may be blended in addition at least one kinds of . These optional additives are generally used so long as it can be appropriately used in the present invention it can be applied in a usual compounding ratio of.
[181]
[182]
It said cup portion other than the solvent component in the formulation of the resin composition, the solvent may include toluene, xylene, iso-propanol, solvent naphtha, cellosolve, cellosolve acetate, butyl cellosolve may be used. The solvent may be used in one kinds or a mixture of two or more thereof.
[183]
[184]
According to the content of the solvent, but the viscosity of the composite resin composition may vary, as the content of the solvent to be added to the composition that can be appropriately adjusted, as needed, therefore is not particularly limited. For example, in consideration of the amount of coating and adhesion of the resin composition, for example, there is discharged from dinkeop (DIN, 53211) can be adjusted in an amount such that the viscosity of the extent to which it takes 20 to 200 seconds.
[185]
[186]
As to provide a resin composition excellent in processability and chemical resistance, the coating film according to the present invention, the linear and the cross-linkable urethane modified poly inorganic pigment with a metal, such as by mixing to form a coating film above components are complex network structure in the polyester resin formed to provide the excellent press formability and hardness.
[187]
[188]
It provides a steel sheet including a coating layer formed by the composite resin composition of the present invention. The steel sheet may be provided by applying a first surface and a second previously-described colored resin composition on at least one side of the surface of the substrate steel sheet. That is, the composite resin composition may form a carrying plate of the first surface or the colored composite resin coating film of the applied to all 2 only applied, or a first side and a second side surface, and the color, as needed It may include a transparent resin coating film formed on the composite resin film.
[189]
[190]
A possession of the steel sheet can be used the zinc-plated steel sheet. Examples of the zinc-plated steel sheet, without limitation, for example, hot-dip galvanized steel sheet (GI), galvannealed steel sheet (GA), electro-galvanized steel sheet (EG), an aluminum-plated steel sheet or a zinc-aluminum-magnesium such as alloy-coated steel sheet may be used.
[191]
[192]
Composite resin of the color on the carrying plate film is provided above as being formed by a colored resin composition, linear and cross-linked is mixed with a urethane-modified polyester resin, at least one curing agent and the colored inorganic pigment of the aziridine curing agent or a melamine curing agent It includes. In accordance with the present invention, the coating composition of linear and cross-linked is mixed with a urethane-modified polyester resin of 50 to 80% by weight, at least one curing agent and from 3 to 20% by weight of the colored inorganic pigment 3-20 of the aziridine curing agent or a melamine curing agent and a weight%.
[193]
[194]
The solvent included in the composition will not remain in the steel sheet by drying. And, are not present Further, the volatile acid curing catalyst and an amine curing catalyst, may be a very small amount remaining.
[195]
[196]
Further, in the case further comprises a metal pigment in compositions for the coating film is formed, wherein the pigment contained in the coating film, the pigment may be present in an amount of 0.5 to 20% by weight of the total weight of the coating film.
[197]
[198]
Composite coating film of the colored resin is formed so as to be 5 to 20㎛ particularly more preferably 5 to 25㎛, the dry film thickness of 3 to 30㎛, preferred. If the dry film thickness of the colored composite resin coating layer of poor color and hiding power, workability, and the content of the composite resin film is less than 3㎛ solvent and excess of 30㎛ increase the production cost and low productivity is not preferable.
[199]
[200]
Above composite resin coating layer of the color it may be formed of a transparent resin coating film. Wherein the transparent resin coating film can be formed by using the same composition except that it does not contain an inorganic pigment and a metallic pigment to provide color to the composition for film formation of the colored composite resin. The transparent resin formed by coating can be formed of linear and cross-linked is mixed with 65 to 95% by weight of urethane-modified polyester resin and at least one curing agent 5 to 35% by weight of the aziridine curing agent or a melamine curing agent.
[201]
[202]
The transparent resin film can be formed so that the dry film thickness of 0.1 to 3㎛, preferably from 0.3 to 2㎛, 0.5 to 1.5㎛ more preferably. If the dry film thickness of the transparent resin film is less than 0.3㎛ not be achieved an improvement in the additional color and texture, and if it exceeds 3㎛ not effect a significant improvement in color and texture as compared to the increase of the thickness.
[203]
[204]
Composite resin composition of the transparent resin composition of the color may be coated on the first surface and / or the second surface of the substrate steel sheet in a conventional resin coating method, for example, bar-coater, a roll coater, a slot die (Slot -Die) it may be used a coating method or a curtain coater. Further, any of the application by the method, and the transparent resin composition of the above methods the composite resin composition of the color can be applied by application methods and other methods of the composite resin of the above methods the composition, and further, the by spray coating It may form a transparent resin coating film.
[205]
[206]
Drying of the composite resin composition of the transparent resin composition of the pigmented coating may also be carried out by any method generally known in the art. Drying, without limitation, can be carried out in a hot air heating method, infrared heating method or induction heating method.
[207]
[208]
Composite resin composition and the transparency of the colored resin composition is preferably set to 180 to 260 to dry PMT (Peak Metal Temperature). Without limitation, it may be specifically, for example, in the drying of the composition to a hot air treatment at 200 to 340 for the ambient temperature of 10 to 50 seconds for the hot air heating type. When the induction heating system has the composition be dried for 5 to 20 seconds at a frequency range of 5 to 50MHz, electric power of 3 to 15KW.
[209]
[210]
In another embodiment of the invention, the composite resin side to hold the steel sheet when being formed only one surface of the coating film possessing a composite resin plate is not formed, the coating film in consideration of the workability and corrosion resistance of the steel sheet is preferably formed of resin coating film.
[211]
[212]
According to one embodiment of the invention, and the coating film forming primer to both surfaces of the substrate steel sheet, there is provided a colored coating film formed of the composite resin processability is improved steel sheets which are provided as primer one embodiment of the invention on the surface of the coating film for example. On the other hand, in the case of steel sheet containing a composite resin coating film (top coat film) of the color, an undercoating film may be intermediate between the carrying plate and the composite resin coating film (top coat film).
[213]
[214]
Figure shows an cross-sectional side view of the colored steel sheet of the composite resin formed of a composite resin composition of the ferrous in Fig. Also it may be formed of a composite resin into a composite resin composition according to the invention to coat zinc plated steel sheet surface as can be seen from the 2 a. In this case, the composite resin composition can be formed by coating on the Cr-free undercoating film on the galvanized steel sheet can map the composite film as shown in b of FIG. On the other hand, it may also form a transparent resin coating film on the resin film composite upper as shown in the 2 c. Further, it is possible also to form, the composite map form a film, and a transparent resin coating film thereon by applying the composite resin composition on the undercoating film also as shown in 2 d.
[215]
[216]
In one embodiment of the present invention and are therefore not to be coat primer that is added to form a particularly limited to the first surface and / or the second surface of the substrate steel sheet, to increase the adhesion of the substrate steel sheet and colored composite resin film of the steel sheet in may be a coating property, corrosion resistance and other physical properties required for the steel sheet to be given to the steel sheet is any coating which is known to be applied between the composite resin coating film (top coat film) of the substrate steel and non-ferrous in the art.
[217]
[218]
The opaque effect of the primer and carry the steel sheet due to the increase of film thickness of a transparent resin by forming Cr-free undercoating a composite resin film is also formed on the film or films transparent leading to the composite resin coating the upper layer increases in this manner, and further by the irregular reflection of light is reduced more preferable to indicate the more beautiful color.
[219]
Mode for the Invention
[220]
And in more details with respect to the present invention to the following examples. However, the following examples as an example of specific embodiments of the invention, the present invention is not limited thereby.
[221]
[222]
Examples 1 to 12 and Comparative Examples 1 to 11
[223]
As shown below in Table 1, was prepared urethane-modified polyester resin, a curing agent, mixed with an acid catalyst and an amine catalyst, and by putting it in a solvent 100 parts by weight of a transparent resin composition. It sleeps solvent portion in the above transparent resin composition.
[224]
Subsequently, after mixing with further addition of a urethane-modified polyester resin, a curing agent, an acid catalyst and an amine catalyst, and an inorganic pigment and a metallic pigment in the same content as shown in Examples 1 to 12 and Comparative Examples 1 to 11 in Table 1 below, these It was charged into a solvent was dispersed using a high-speed bead mill dispersing machine. Thereby it was prepared a composite resin composition of the non-ferrous.
[225]
[226]
The urethane-modified polyester as a polyester resin, a weight average molecular weight of 16,000 in-cross-linkable resin ((Note) KCC manufacture, Tg = 10) and 000 of the linear resin ((Note) KCC manufacture, Tg = 60) 2 weight ratio of 1 It was used by mixing.
[227]
Wherein the curing agent is already a butoxymethyl melamine as hexamethoxymethylmelamine and melamine as exposure melamine 1: it was used as a mixture in a weight ratio of 3. Further, the aziridine curing agent used in Example 1 has the following structural formula (R = -CH of the formula (a) 3 was used having a).
[228]
As the acid catalyst was used as the amine neutralized dodecylbenzene sulfonic acid (pH = 6 ~ 7, activity = 25% manufactured, US King (King)).
[229]
The amine-based catalyst was used as dinonyl nalren naphthyl sulfonic acid (DNNSA).
[230]
The solvent was used as the cellosolve acetate cell.
[231]
Colored pigment was used as a black pigment (carbon black, Printex's EVO nicks (Printex) ™ series), red pigments (iron oxidizing agent) and the white pigment (titanium dioxide).
[232]
[233]
TABLE 1
[234]
[235]
The single-sided, as the prepared solution in Table 2 coating weight 20g / ㎡ the electro-galvanized steel sheet having an electrically zinc-plated layer (Examples 1, 4, 5, 6, 9, 10, and 14 to 22) or the electro-galvanized steel sheet the dry film thickness on the 1㎛ Cr-free steel sheet having an undercoating-treated layer (invention example 2, 3, 7, 8, 12 and 13) on the above-described examples 1 to 12 and Comparative composite resin composition of examples 1 to 11 the dry film roll to a thickness of 5 to 15㎛ - coating and PMT (peak metal temperature) curing at 230 and then dried, re-cooled to invention 1 to 22 and Comparative material composite resin coating having a first coating layer of the composite resin to 11 the steel sheet was prepared.
[236]
[237]
For the invention, material 3, 8 and 13, to form a transparent resin film (dry film thickness 1㎛) on the composite resin coating layer. At this time, the transparent resin composition is used, and was used the same ones as the composite resin composition of the second embodiment, it is formed by spraying a transparent resin composition on said resin coating layer, except that the composite that does not contain an inorganic pigment and a metallic pigment.
[238]
Figure 3 on a roll to form a composite coating layer a resin plate-composite resin coating and spraying of the transparent resin coating layer formation of the coating process was schematically illustrated.
[239]
[240]
The evaluation of surface properties of the resin composite coated steel sheet having a composite resin coating layer obtained and the results are shown in Table 2. The surface properties and the evaluation shown in Table 2 was carried out in the following way.
[241]
[242]
< Film Thickness >
[243]
The thickness of the coating film was measured with a non-destructive way Portable Thickness Gauge.
[244]
[245]

[246]
For evaluation of the color of the coating film chairman and texture, formation of a pattern formed on a particular surface or not, the size of the formed patterns, the uniformity and continuity, etc., are shown as follows.
[247]
[Evaluation standard]
[248]
◎: (very good), ○: (Excellent), △: (inferior), ×: (Very inferior)
[249]
[250]

[251]
The 60 ° specular reflection values ​​using a SHEEN's device was evaluated by measuring.
[252]
[253]

[254]
By Mitsubishi Pencil Co. (HB ~ 4H) has occurred or not was evaluated by a scratch after the 10cm line drawn at a 45 ° angle with 1000 ± 10g load.
[255]
[256]

[257]
Corrosion resistance evaluation was evaluated in the composite salt spray method (Cyclic Corrosion Test, CCT). Subjected to a relative humidity of 95% salt spray at for 5 hours conditions (concentration of 5%, and the spraying pressure condition of 1kg / ㎠ at 35) and a relative humidity of 30% for 2 hours drying, the relative humidity 95% at a temperature of 70, temperature 50 in one cycle of treatment for three hours it was evaluated by the occurrence of red rust area (Red Rust) occurred on the surface of the steel sheet, and then subjected to 100 repeated cycles.
[258]
[Evaluation standard]
[259]
◎: corrosion area is 0% ○: less than 5% corrosion area
[260]
△: corrosion area is 5 ~ 30% ×: corroded area is 30% or more
[261]
[262]
< Bending processability evaluation>
[263]
And then subjected to a tensile processing 10% of the colored-coated steel sheet, a steel sheet bent 180 ° to the surface of the pressure 1kgf it in a vice and tighten until the next time a plane (0T- bending (bending)). After attaching the adhesive tape to the bent coating film when the coating film was evaluated by peeling sikyeoteul cracks and film separation or absence of the peeling tape to the surface.
[264]
[Evaluation standard]
[265]
◎: No peeling of the coating and the coating cracks
[266]
○: the micro-cracks in the coating film look, is no peeling of the coating
[267]
△: severe cracks in the coating, no coating peeling
[268]
×: severe cracking in the coating film, coated film being peeled
[269]
[270]

[271]
When the gauze soaked in MEK (Methyl Ethyl Ketone) 1Kg load to rub into a reciprocating force of 1Kgf was determined by the number of times until the coating film peeled off.
[272]
[Evaluation standard]
[273]
◎: 100 times or more
[274]
○: more than 70 times less than 100 times
[275]
△: more than 40 times less than 70 times
[276]
×: less than 40 times
[277]
[278]
TABLE 2
[279]
[280]
Composite resin composition of the ferrous material in the invention if it contains an undercoating layer by the lower processing undercoating Cr-free dry film thickness of the coating when 10㎛ by itself, the appearance color with elegant appearance designability is a solid, composite resin coating layer if it contains (invention material 1, 4, 5, 6, 9, 10, 14 and 15) or composite resin transparent map by processing the additional transparent resin on top of the coating film (invention material 2, 3, 7, 8 , 12 and 13) and it can be seen to represent a more beautiful color. This effect is a primer and opaque effect of the substrate steel sheet increases with an increase in the film thickness of a transparent resin, and is believed to increase the sharpness of the color of the pigment by the irregular reflection of light loss results.
[281]
[282]
Comparative material from 1 and 2, the urethane-modified polyester resin is cross-linked structure of the comparative material 2 with the urethane-modified polyester resin having a cross-linked structure increases the degree of cure than in the linear structure is raised, the hardness of the coating film, and a chemical resistance superior on the other hand represents the effect, in terms of workability exhibited the effect for the column, such as a crack of the coating film occurred. On the other hand, in Comparative material 1 using the urethane-modified polyester resin having a linear structure it was characterized by the results of the comparative material 2 and opposite.
[283]
On the contrary, if the ratio by weight of linear urethane-modified polyester resin and a cross-linkable urethane modified polyester resin which does not satisfy the range of the invention in Comparative Example 6 and the comparative material 6, and 7 using the compositions of 7 respect to processability and chemical resistance the results are shown in the column for.
[284]
On the other hand, in the case of Example 1 invention material 1 to 3 with the compositions of containing the aziridine curing agent is a little low in comparison with the case consists of an alkyl group of chain structure surface hardness with a melamine curing agent containing an aromatic ring, and chemical resistance eoteuna relatively low results indicate, it can be seen as a whole has a good coating film properties.
[285]
In addition, it compared to the methyl imino melamine melamine When glass and increase the content is the high-speed curing the curing reaction speed increases and the degree of cure increases to increase the hardness of the coating film. Thus, if it is not already in the comparative material 4 using no melamine curing agent alone it has exhibited a poor processability of the resulting coating film. For the other hand, in Comparative material 3 with a melamine curing agent alone it has been evaluated as excellent processability, chemical resistance was evaluated as low.
[286]
Further, in Comparative Example 8, and Comparative material with a composition of 9, 8 and 9 workability and exhibited a result, the resistance decreased more, especially already content of no melamine, if the mixing ratio of the melamine curing agent outside the range of the invention in the case of an overdose include comparative material 9 was evaluated as the exterior design property deteriorated.
[287]
Further, the unevenness of the coating film surface during drying of the coating film the addition of an acid catalyst and an amine catalyst is formed in a predetermined pattern is formed, which results were obtained also with improved surface texture film by a quenching effect. However, in the case of the comparative material 5 with the composition of Comparative Example 5 does not contain the acid catalyst and an amine catalyst, it exhibited a result that the pattern is not formed, low hardness, and showed a poor corrosion resistance results. On the other hand, in the case of the catalyst amount small or large excess of Comparative material 10 and 11, it could be seen that it is poor appearance properties.
[288]
[289]
(A) a roll-coater, (b) solution pan, (c) back-up roll, (d) a spray coater, (e) Oven

Claims

[Claim 1]Linear and cross-linked mixed urethane-modified polyester resin of 30 to 60% by weight; At least one curing agent from 3 to 15% by weight of the aziridine curing agent or a melamine curing agent; Acid curing catalyst, 0.05 to 1.5% by weight; Amine curing catalyst from 0.05 to 1.5% by weight; Colored inorganic pigments 0.1-15% by weight; And a composite resin composition comprising the remainder solvent.
[Claim 2]
The method of claim 1 wherein the urethane-modified polyester resin has the ratio by weight of linear and cross-linked 1: 1 to 1: 4 or a composite resin composition.
[Claim 3]
The method of claim 1, wherein the melamine curing agent is melamine and the melamine furnace already at a weight ratio of 1: A composite resin composition comprising a 4: 1 to 1.
[Claim 4]
4. The method of claim 3 wherein the melamine is butoxymethyl melamine, hexamethoxymethylmelamine or mixtures of composite resin composition.
[Claim 5]
4. The method of claim 3 wherein the imino melamine-trimethoxy methyl melamine composite resin composition.
[Claim 6]
According to claim 1, wherein the acid cure catalyst is p- toluenesulfonic acid, dodecylbenzene sulfonic acid die, dinonyl di-toluene sulfonic acid and dinonyl naphthalene sulfonic acid at least one compound of the resin composition is selected from the group consisting of: a.
[Claim 7]
The method of claim 1 wherein the acid cure catalyst is a sulfonic acid compound in the resin composition would blocked with an amine series compound.
[Claim 8]
The method of claim 7, wherein the sulfonic acid blocked with the amine compound is an amine neutralized dodecylbenzene sulfonic acid resin in the composite composition.
[Claim 9]
The method of claim 1 wherein the amine curing catalyst is a primary amine, secondary amine, tertiary amine or a mixture of two or more of the composite resin composition.
[Claim 10]
According to claim 1, wherein the composite resin composition than high volatility of the amine curing volatile acid curing catalyst of the catalyst.
[Claim 11]
According to claim 1, wherein said composite resin composition, and further comprises, the metal pigment is a composite resin composition is 0.1 to 15% by weight of the total composition weight of a metal pigment.
[Claim 12]
The method of claim 1 wherein the solvent is toluene, xylene, iso-propanol, solvent naphtha, cellosolve, cellosolve at least one of a composite resin composition is selected from the group consisting of a sol-bromo acetate and butyl cellosolve.
[Claim 13]
The method of claim 1 wherein the solvent is a composite resin composition comprising in an amount that there is discharged from dinkeop (DIN, 53211) of the composite resin composition so that the viscosity takes 20 to 200 seconds.
[Claim 14]
Possession comprising a zinc-plated layer and the steel sheet comprises a composite resin coating film formed on at least one side of the carrying plate, the composite resin film is linear and cross-linked mixed urethane-modified polyester resin, 50 to 80% by weight; At least one curing agent from 3 to 20% by weight of the aziridine curing agent or a melamine curing agent; And colored inorganic pigment 3 or colored resin of the composite coating film formed as to 20% by weight, zinc-plated steel sheet.
[Claim 15]
15. The method of claim 14 wherein the urethane-modified polyester resin has the ratio by weight of linear and cross-linked 1: 1 to 1: 4 or galvanized steel.
[Claim 16]
15. The method of claim 14 wherein the colored inorganic pigment is carbon black, carbon nanotube, graphite, graphene, ferric oxide (Fe 2 O 3 ) and titanium dioxide (TiO 2 is zinc-plated steel sheet, at least one selected from the group consisting of a) .
[Claim 17]
15. The method of claim 14 wherein the colored inorganic pigment is a particle diameter of 0.01 to 20㎛, oil absorption is 60% or less of zinc-plated steel sheet.
[Claim 18]
The method of claim 14 wherein the composite resin coating layer of the colored further comprises a metallic pigment, said metallic pigment is a colored composite resin coating layer total weight of 0.5 to 20% by weight of the zinc-plated steel sheet.
[Claim 19]
19. The method of claim 18, wherein the metal pigment is aluminum alone or an aluminum-containing alloy, galvanized steel.
[Claim 20]
19. The method of claim 18, wherein the metal pigment flakes merchant galvanized steel sheet having a thickness of 0.1 to 5㎛.
[Claim 21]
19. The method of claim 18, wherein the metal pigment is cetyl sulfate, sodium cetyl sulfate, ammonium salts, stearyl sulfate, sodium stearyl sulfate, ammonium salt, a glycerol fatty acid ester, poly Glacier serine fatty acid ester, glyceryl receiver fun benzoate, glyceryl stearate , glyceryl carbonate Lodge, La Ness -5, La Ness -10, -15 La Ness, lanolin, route remote chloride, bromide remote set, set the remote chloride, sodium isostearate in one lactate, sorbitan monolaurate , sorbitan stearate, sorbitan oleate, and the galvanized steel sheet to a surface treatment with at least one organic compound selected from the group consisting of organic compounds of formula 1-5. [Chemical Formula 1] (In the formula 1 R is a chain-like alkyl compound of C5 ~ C15.) [Formula 2] (in the formula 2, R is a chain-like alkyl compound of C1 ~ C10, n is from 1 to 10 is an integer.) [Chemical formula 3] (and in the general formula (3) R is a chain-like alkyl compound of C1 ~ C10, n is an integer from 1 to 10) [Chemical formula 4] (in the formula 4, R is a chain of C1 ~ C10 and alkyl type compounds, n is an integer from 1 to 10. [Chemical formula 5] (in the formula and R 5 is a chain alkyl compound of C1 ~ C10, n is an integer of 1 to 10.)
[Claim 22]
15. The method of claim 14 wherein the composite resin film is a zinc-plated steel sheet having a thickness of 3 to 30㎛.
[Claim 23]
15. The method of claim 14 wherein the composite resin film is a zinc-plated steel sheet having a pattern.
[Claim 24]
Of claim 14 to claim 23 according to any one of claims, wherein the zinc-plated steel sheet further comprises a transparent resin film on the composite resin film.
[Claim 25]
The method of claim 24, wherein in that the transparent resin film is linear and cross-linked is mixed with a urethane-modified polyester resin of 65 to 95% by weight, and aziridine curing agent or a melamine curing agent of at least one curing agent 5 to formed of 35% by weight of zinc coated steel.
[Claim 26]
25. The method of claim 24, wherein the transparent resin coating is a galvanized steel sheet having a thickness of 0.1 to 3㎛.