CN1552654A - Irregular decorative pattern coating glass container and producing method thereof - Google Patents
Irregular decorative pattern coating glass container and producing method thereof Download PDFInfo
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- CN1552654A CN1552654A CNA031288812A CN03128881A CN1552654A CN 1552654 A CN1552654 A CN 1552654A CN A031288812 A CNA031288812 A CN A031288812A CN 03128881 A CN03128881 A CN 03128881A CN 1552654 A CN1552654 A CN 1552654A
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Abstract
A glass container with coated decorative irregular pattern on its surface and its productive technology are disclosed. Its special paint is prepared from melamine resin, polyol compound and silane chelating agent. Said irregular pattern is formed through spraying said paint on the surface of glass container, and baking for solidifying it.
Description
Technical field
The invention relates to irregular pattern application Glass Containers and production method thereof.Specifically, just be to use the glass tailor-(made) coating of strong adhesion to be sprayed at the Glass Containers surface, form irregular pattern clearly.
Background technology
For a long time, in order to improve the sight of Glass Containers, prevent that the Glass Containers content is rotten, people are at Glass Containers surface spraying thin film, and this film is even, chromatic.In addition, the use solvent as Japanese kokai publication hei 2-127100 communique is showed dissolves a part of film, makes whole coating be nature rock decorative pattern.Open the solvent that flat 2-229582 communique is showed as the spy, make a part of film be mobile sample, thereby make whole coating be marbling, and spray the layer of transparent protective membrane again at this coatingsurface.This type of working method is well-known.
This type of application coating hardness height, coating and Glass Containers surface adhesion force height.The glass tailor-(made) coating that this type of application is used, its main component are the melamine resins.About these at document 1 (" application synthetic resins cross the threshold " Bei Gang association three works, polymer association publishes, the 134th ~ 139 page), document 2 (the melamine resin of " resin material lecture 8 ", three-wheel one youth, Song Yongyingfu work, Nikkan Kogyo Shimbun publishes, the 291st ~ 316 page) all on the books.
After the glass tailor-(made) coating is sprayed at the Glass Containers surface,, form solidified coating, can improve decoration, the sight of Glass Containers, can be used as the protective membrane of Glass Containers again through being heating and curing.
But this kind glass tailor-(made) coating also has a problem, and that uses dissolution with solvents part film exactly, forming nature rock decorative pattern, or make a part of film be mobile sample, when forming marbling with solvent, coating and Glass Containers surface adhesion force can reduce, and coating is peeled off easily.
In addition, text printout also will be carried out in general application Glass Containers surface, and the material in the container is carried out brief description, but the used printing ink of comment mostly is epoxies printing ink, and the coating on Glass Containers surface again because of the difference of its characteristic, is repelled with epoxies printing ink sometimes mutually.
For addressing this problem, the spy opens on the flat 11-181334 communique and has showed, (A) stiffening agent that is formed by polyol resin (a1) and the reaction of isocyanation esterification thing is (a2) as a certain composition, with the common property of thin film resin that constitutes of other compositions.(B) part of alkoxysilane compound containing trialkylsilyl group in molecular structure adds the water decomposition condensation compound.(C) the inorganic aggregate (c1) of size 0.1 ~ 40 μ m and the organic polymer particle (c2) of particle dia 0.01 ~ 30 μ m.The coating of being showed is by (A)+(B)+(C) form.
The coating of showing on the Te Kaiping 11-80662 communique is formed by Resins, epoxy and polyol compound reaction.
The coating of showing on the Te Kaiping 8-283660 communique, its main component urethane resin is obtained by isocyanate compound and polyol compound reaction.
More than various coating, its strength of coating deficiency also has film thin inadequately, shortcomings such as film poor flatness in addition.
More than various coating, when its coatingsurface carried out text printout, epoxies printing ink did not improve with the problem that coating is repelled mutually.
Summary of the invention
For addressing the above problem, the present invention has carried out persistent research, has created the present invention finally.The melamine resin that always uses of industry can continue to use for a long time, just adds some polyol compounds and silane sequestrant in the proper ratio again.The formed coating of this coating, promptly the strong adhesion on irregular pattern coating and Glass Containers surface can not repel mutually with the printing ink of comment yet.
In other words, added polyol compound, can reduce the hardness of coating, added the silane sequestrant, coating is repelled mutually with comment printing ink.Yet by discovering, polyol compound and silane sequestrant just can be avoided the problems referred to above as long as add in the proper ratio, and coating and Glass Containers surface adhesion force are strong, and coatingsurface can carry out literal, pattern printing with various printing ink.
Generally speaking, purpose of the present invention is exactly, and provides the application Glass Containers of irregular pattern and the production method of this kind container to society.The coating of this application Glass Containers and Glass Containers surface adhesion force are strong, and coatingsurface is fit to various ink printings.
By method of the present invention, promptly with respect to melamine resin 100 weight unit, the content of polyol compound is in 50 ~ 400 weight unit scopes, and the content of silane sequestrant is in 5 ~ 100 weight unit scopes.Glass tailor-(made) coating so that this ratio blending forms is sprayed at the Glass Containers surface, both can form irregular pattern, can address the above problem again.
Method of the present invention is added polyol compound and silane sequestrant in the proper ratio, by both additive effects, can prevent that coating hardness from reducing, and keep the sticking power of coating and Glass Containers, and coatingsurface is fit to various ink printings.
In the coating of application Glass Containers of the present invention, the melamine resin is the melamine resin that methylates, or butylation melamine resin, or the melamine resin after either party the process alkylation among both is good.
Because this kind melamine resin and polyol compound can fully react, thereby the sticking power on coating and Glass Containers surface is optimized, and the curing speed of coating also is optimized.
In the coating of application Glass Containers of the present invention, polyol compound is that the mixture of propylene polyol compound and lactone polyol compound consists of good.
By the additive effect of propylene polyol compound and lactone polyol compound, can prevent that coating hardness from reducing, and the sticking power on coating and Glass Containers surface is optimized, coatingsurface is fit to various ink printings.
In the coating of application Glass Containers of the present invention, with respect to polyol compound 100 weight unit, the content of lactone polyol compound is good in 0.1 ~ 30 weight unit scope.
Polyol compound adds in the coating by this ratio combination, because the effect of lactone polyol compound, polyol compound can not influence the sticking power on hardness, coating and the Glass Containers surface of coating, thereby is optimized, thereby coatingsurface can adapt to various ink printings.
In the coating of application Glass Containers of the present invention, the hydroxyl value of polyol compound is good in 5 ~ 500mgKOH/g scope.
The reaction of the polyol compound of this hydroxyl value and melamine resin, silane sequestrant is positive, stable.Thereby coating hardness is stable, the strong adhesion on coating and Glass Containers surface.
The hydroxyl value of polyol compound can be used titration measuring.
In the coating of application Glass Containers of the present invention, the silane sequestrant is an Ammonia silane sequestrant, or epoxies silane sequestrant is good.
This one type of silane sequestrant only needs on a small quantity, can fully react with melamine resin, polyol compound, from the result, can prevent that coating hardness from descending, and the strong adhesion on coating and Glass Containers surface.
In the coating of application Glass Containers of the present invention, also contain tinting material.With respect to melamine resin 100 weight unit, the content of tinting material is good in 0.1 ~ 100 weight unit scope.
Add tinting material in the coating, can make coating present needed color, improve the ornamental and aesthetic feeling of Glass Containers, can also interdict ultraviolet ray, prevent that material in the container is subjected to illumination and goes bad.
In the coating of application Glass Containers of the present invention, the content that also contains solidifying agent is good in 0.1 ~ 30 weight unit scope.
Add solidifying agent in the coating, can improve the stability of coating in storage, transportation, can improve the curing speed of coating again.
In the coating of application Glass Containers of the present invention, also added immiscible material.With respect to melamine resin 100 weight unit, the content of immiscible material is good in 0.1 ~ 30 weight unit scope.
The immiscible material that adds in the coating, silicone oil etc. for example can utilize the immiscible property of immiscible material and coating, produces the natural separation phenomenon, makes coating manifest irregular pattern.Rather than,, make solvent manifest irregular pattern at the locally sprayed solvent of coatingsurface as traditional method.Method of the present invention can not influence the hardness of coating, and the sticking power of coating and Glass Containers, and traditional method causes that easily coating hardness descends, and sticking power weakens.
The coating of application Glass Containers of the present invention, dope viscosity is 1 * 10 ° ~ 1 * 10
6In mpa.s (25 ℃) scope is good.
The coating of this kind viscosity, easy to use, be convenient to spraying, film forming thickness is thin, and coatingsurface is smooth smooth.
The production method of application Glass Containers of the present invention comprises two operations, i.e. spraying process and curing process.
Spraying process is ratio with respect to melamine resin 100 weight unit promptly, the content of polyol compound is in 50 ~ 400 weight unit scopes, the coating of the content of silane sequestrant in 5 ~ 100 weight ranges in inhomogeneous mode, is sprayed on the Glass Containers surface.
Curing process promptly spraying the Glass Containers that finishes in inhomogeneous mode, is heating and curing, and makes vessel surface manifest irregular pattern.Production method of the present invention can solve the problem that exists in the traditional method.
By this method can produce effectively, to produce coating adhesion strong, the application Glass Containers that the coatingsurface printing adaptability is wide.
In application Glass Containers production method of the present invention, the characteristics of spraying process are: after the glass tailor-(made) coating is sprayed at the Glass Containers surface in even mode, spray one deck solvating agent again.
Can also be made in irregular pattern on the specific position by this method.
In the application Glass Containers production method of the present invention, before the spraying process, should be with the polyol compound processing that feels secure on the Glass Containers surface.
After the Glass Containers surface felt secure with the dictatorship compound, coating and Glass Containers surface friction pull just were guaranteed, and the application Glass Containers quality that is produced is good, and the coating friction pull is strong.
In application Glass Containers production method of the present invention, before spraying process, should heat the Glass Containers surface with flame.
With flame the Glass Containers surface is heated, can remove the organism that vessel surface adheres to, improve the lubricious degree of vessel surface, further improve adhesive force of coatings.
Description of drawings
Fig. 1 is in the polyol compound, the content of lactone polyol compound and the graph of a relation between the adhesive force of coatings;
Fig. 2 is the content of silane sequestrant and the graph of a relation between the adhesive force of coatings;
Fig. 3 is the spraying method (one) of irregular pattern coating;
Fig. 4 is the spraying method (its two) of irregular pattern coating;
Fig. 5 is the spraying method (its three) of irregular pattern coating;
Fig. 6 is the spraying method (its four) of irregular pattern coating;
Fig. 7 is the spraying method (its five) of irregular pattern coating;
Fig. 8 is the explanatory view of prime coat;
Fig. 9 is the flame treating synoptic diagram;
Figure 10 is the synoptic diagram of coatingsurface protective layer;
Figure 11 is the synoptic diagram of coatingsurface printing processing.
Embodiment
[the 1st embodiment]
The 1st embodiment is meant and with each component proportions is: with respect to melamine resin 100 weight unit, the content of polyol compound is in 50 ~ 400 weight unit scopes, the coating of the content of silane sequestrant in 5 ~ 100 weight unit scopes, be sprayed at the Glass Containers surface, form irregular pattern application Glass Containers.
Below with regard to each moiety of glass tailor-(made) coating, the characteristics of Glass Containers elaborate.
1. melamine resin
(1) kind 1
The kind of melamine resin also comprises the inductor of melamine resin except that the melamine resin.For example: methylol type melamine resin, imines type melamine resin, imines type alkane etherified melamine ammonia resin, methylol type alkane etherified melamine ammonia resin, alkane etherified melamine ammonia resin etc.
Wherein, in the alkane etherified melamine ammonia resin, moieties be methyl, ethyl, n-propyl group, i-propyl group, n-butyl, i-butyl better.
Wherein, the melamine resin of imines type, methylol type, water tolerance is relatively poor, for improving the water tolerance of coating, it is good should using imines type methyl alkane etherified melamine ammonia resin, imines type butyl alkane etherified melamine ammonia resin, methylol type alkane etherified melamine ammonia resin, methylol type butyl alkane etherified melamine ammonia resin.
(2) kind 2
Above-described melamine resin, for example alkane etherified melamine ammonia resin mixes comparatively ideal of back use with Synolac, acrylic resin, Resins, epoxy, vibrin, urethane resin etc.
By with these mixed with resin, can improve the sticking power between coating and the Glass Containers surface, and the smoothness of coating and film can be improved also.
Be mixed together certain resin content of use with alkane etherified melamine ammonia resin: with respect to melamine resin 100 weight unit, the content of this resin should be controlled in 10 ~ 500 weight unit scopes.
Its reason is the content such as less than 10 weight unit of this resin, can not show additive effect.And this resin content surpasses 500 weight unit, can reduce coating curing speed, and coating curing is temperature required also will to be improved.
Therefore, it is ideal that the content of this resin is controlled in 30 ~ 300 weight unit scopes, and it then is even more ideal being controlled in 50 ~ 200 weight unit scopes.
(3) kind 3
Remove above-mentioned melamine resin, the polyvalent alcohol sex change melamine resin that also has polyol compounds such as the acrylic resin of hydroxyl, the Resins, epoxy of hydroxyl, the vibrin of hydroxyl, the urethane resin of hydroxyl and the generation of alkane etherified melamine ammonia resin reaction in addition, this material also are ideal comparatively.
This polyvalent alcohol sex change melamine resin can improve the friction pull of coating, can improve the smoothness and the film of coating.
The content of the polyol compound that reacts with alkane etherified melamine ammonia resin: with respect to melamine resin 100 weight unit, the content of this polyol compound should be controlled in 10 ~ 500 weight unit scopes.
Its reason is the content such as less than 10 weight unit of this polyol compound, does not show reaction effect.And the content of this polyol compound surpasses 500 weight unit, can significantly reduce coating curing speed, reduces coating hardness.
Therefore, it is ideal that the content of this polyol compound is controlled in 50 ~ 400 weight unit scopes, is controlled in 100 ~ 300 weight unit scopes then even more ideal.
(4) solidifying agent
Melamine resin planted agent adds solidifying agent (comprising the curing catalyst, as follows).
The solidifying agent that is fit to the melamine resin has ammonium chloride, ammonium sulfate, chlorination ammonium salt, urea inductor or the like, can select for use a kind of or makes up more than two kinds and use.
The content of solidifying agent: with respect to melamine resin 100 weight unit, the content of solidifying agent should be controlled in 0.1 ~ 30 weight unit scope.
Its reason is the content such as less than 0.1 weight unit of solidifying agent, no additive effect.The content of solidifying agent is as surpassing 30 weight unit, and the reaction of solidifying agent and melamine resin is difficult to control, preserves, transportation stability is poor.
2. polyol compound
(1) kind 1
Polyol compound in general, the compound that intramolecularly contains hydroxyl all can use.For example: propylene polyol compound, polyester polyols alkylol cpd, fluorine-containing polyol compound, lactone polyol compound or the like.
In these polyol compounds, propylene polyol compound and lactone polyol compound mix the back and use comparatively ideal, because only need add the hardness that can fully improve coating on a small quantity, can not influence the curing speed of coating again.
When propylene polyol compound/lactone polyol compound mixes, mixture ratio should be controlled in 50 ~ 99.9/50 ~ 0.1 weight ratio scope, be controlled in 70 ~ 99/30 ~ 1 weight ratio scope then comparatively desirablely, be controlled in 80 ~ 98/20 ~ 2 weight ratio scopes then even more ideal.
(2) kind 2
Polyol compound, the polyol compounds that use 1 Jie ~ 3 to be situated between are comparatively desirable.
For the ease of with the reaction of melamine resin, silane sequestrant, use the such multivalence unit alkylol cpd of divalent, 3 valencys comparatively desirable, use the polyol compound of 3 valencys then even more ideal.
When using the polyol compound of 3 valencys, be to improve the surface adhesion force with Glass Containers, three hydroxyls need not total overall reaction, only need make one of them hydroxyl reaction just enough.
Its principle be residual unreacted hydroxyl value can with the hydroxyl reaction on the prime coat of Glass Containers surface, that is to say, after polyol compound and melamine resin, the reaction of silane sequestrant, again with Glass Containers surface prime coat on hydroxyl reaction, can improve the sticking power on coating and Glass Containers surface.
(3) kind 3
1. the definition of propylene polyol compound is meant, the co-polymer of the propylene monomer of hydroxyl and other ethylene unsaturated monomer.
Resemble the propylene monomer that this kind contain hydroxyl hydroxyalkyl class (Jie) acrylate such as 2-hydroxyethyl (Jie) acrylate, 2-hydroxypropyl (Jie) acrylate, 4-hydroxybutyl (Jie) acrylate are arranged.
Ethylene unsaturated monomer has methacrylic ester, ethyl propylene acid esters, propyl group acrylate, n-butylacrylic acid ester, i-butylacrylic acid ester, γ-alkyls acrylate such as butylacrylic acid ester.
Also have aromatic ethylene compounds such as vinylbenzene, vinyl toluene in addition.
Also have vinyl compounds such as vinyl acetate between to for plastic, vinylformic acid, methacrylic acid.
The propylene polyol compound can increase the flexibility of coating, makes coating and combining of Glass Containers surface become more tight.Based on this factor, the propylene polyol compound preferably uses lactone denaturing acrylamide polyol compound.
2. polyester polyols alkylol cpd
The definition of polyester polyols alkylol cpd is meant, the copolymerization condenses of many Jie carboxylic acid and alcohol component.Carboxylic acid like this has terephthalic acid, m-phthalic acid, phthalic acid, hexanodioic acid, nonane diacid or the like.
Alcohol component has ethylene glycol, divinyl ethylene glycol, tri-ethylene glycol or the like.
3. fluorine-containing polyol compound
Fluorine-containing polyol compound is to be formed by the strong polymerizability unsaturated monomer of hydroxyl and the copolymerization of fluoro alkene monomer.Or make the polymerization of fluoro alkene monomer form the not fluorine monomer of hydroxyl and the polyol compound that the propylene polyol compound mixes.
The strong polymerizability of hydroxyl is unsaturated hydroxyl alkanes Vinyl Ethers such as hydroxyethyl Vinyl Ether, hydroxypropyl Vinyl Ether, hydroxybutyl Vinyl Ether.
Also have hydroxy kind allyl ethers such as ethylene glycol allyl ether, divinyl ethylene glycol allyl ether, tri-ethylene glycol allyl ether in addition.
Fluoro alkene hydroxyl monomer has titanium dioxide alkene hydroxyl monomer, three to fluoridize alkene hydroxyl monomer, tetrafluoride alkene hydroxyl monomer.Ethylene fluoride specifically arranged, fluoridize vinylidene, chlorine trifluoride ethene, tetrafluoroethylene etc.
4. lactone polyol compound
The lactone polyol compound, for example internal ester monomer (gamma lactone, β-lactone, delta-lactone) must be used the ethanol class, perhaps uses aromaticity liquid, alkaline agent open loop, and the compound after the use open loop is comparatively desirable.
For example, caprolactone monomer, di-isopropyl internal ester monomer perhaps carry out open loop respectively with many Jie alcohol with rudimentary alcohol such as methyl alcohol, ethanol, and the compound after the use open loop is comparatively desirable.
(4) hydroxyl value
The hydroxyl value of polyol compound should be controlled in 5 ~ 500mgKOH/g scope to good.
Its reason is hydroxyl value such as not enough 5mgKOH/g, and the curing reaction base unit weight very little, and is poor with the reactivity of melamine resin, silane sequestrant, and the solidified nature of polyol compound itself is also poor.
And surpass 500mgKOH/g when hydroxyl value, and the wetting ability base is residual too much in the coating, and the water tolerance of coating, acid resistance, alkali resistance are poor.
Therefore, it is ideal that the hydroxyl value of polyol compound is controlled in 10 ~ 300mgKOH/g scope, is controlled in 30 ~ 200mgKOH/g scope then even more ideal.
(5) molecular-weight average
It is good that the molecular-weight average of polyol compound should be controlled in 200 ~ 500,000 scope.
Its reason is a mean molecule quantity not sufficient 200, and the physical strength of coating is low.Surpass 500,000 and work as molecular-weight average, the viscosity of coating is too high, the spraying difficulty.
Therefore, the molecular-weight average of polyol compound is controlled at 300 ~ 500, is ideal in 000 scope, is controlled in 500 ~ 20,000 scope then even more ideal.
(6) content
The content of polyol compound, with respect to melamine resin 100 weight unit, it is good that the content of polyol compound should be controlled at 50 ~ 400 weight unit.
Its reason be polyol compound contain quantity not sufficient 50 weight unit, can not manifest additive effect.Surpass 400 weight unit and work as content, the reactive of coating obviously reduces, and the hardness of coating is low, pencil hardness test.
Therefore, with respect to melamine resin 100 weight unit, it is ideal that the content of polyol compound is controlled in 100 ~ 300 weight unit scopes, is controlled in 150 ~ 250 weight unit scopes then even more ideal.
The front is narrated, and polyol compound should be selected several being used in combination to good.
But when being used in combination, the content of polyol compound calculates as 100 weight %, and the content of propylene polyol compound should be controlled in 50 ~ 99.9 weight % scopes.
Its reason be the content of propylene polyol compound as less than 50% of gross weight, the tack of coating and poor heat resistance, and surpass gross weight when 99.9% when the content of propylene polyol compound, the tack of coating can obviously reduce on the contrary.
Therefore, it is ideal that the content of propylene polyol compound is controlled in 70 ~ 99% scopes of gross weight, is controlled in 80 ~ 98% scopes of gross weight then even more ideal.
When selecting several polyol compounds to be used in combination, the content of polyol compound calculates as 100 weight %, and the content of lactone polyol compound should be controlled in 0.1 ~ 50 weight % scope.
Its reason be the content of lactone polyol compound as less than 0.1% of gross weight, the tack of coating obviously reduces, coatingsurface is not suitable for various printings processing.And the content of working as the lactone polyol compound surpasses 50% of gross weight, and the tack of coating can obviously reduce on the contrary.
Therefore, it is ideal that the content of lactone polyol compound is controlled in 1 ~ 30% scope of gross weight, is controlled in gross weight to 2 ~ 20% scope then even more ideal.
Referring now to Fig. 1, explain concerning between the content of the lactone polyol compound in the polyol compound (mixture of propylene polyol compound and lactone polyol compound) and the adhesive force of coatings.
Each moiety of glass tailor-(made) coating is respectively: mixture 210 weight unit of melamine resin 100 weight unit, propylene polyol compound and caprolactone polyol compound, uride propyl group three ethoxy silane sequestrants 25 weight unit, phosphoric acid class solidifying agent 5 weight unit, organic solvent 540 weight unit.
Polyol compound wherein, in the polyol compound of per 100 weight unit, the variation of caprolactone polyol compounds content is from 0.05～50 weight unit.
The evaluation criteria of coating and Glass Containers surface adhesion force is that the evaluation criteria of following example 1 is evaluated enforcement.
Among Fig. 1, transverse axis is represented caprolactone polyol compounds content in the polyol compound of per 100 weight unit.D-axis represents to adopt the number (individual/100 lattice) that comes off of per 100 lattice that the Horizontal Price Movement lattice glass gummed paper mounting method of JISK-5400 measured.
In addition, the initial stage measurement result is represented with solid line A.The measurement result with dashed lines B of (40 ℃ * 95%RH, 24 hours) represents after the humidity test.
Measure, evaluate the standard of back with example 1,160 ℃ * 10 minutes condition is carried out baking-curing, and the thickness of coating is 20 μ m.
Can be clear that from Fig. 1 in the polyol compound (100 weight unit), the caprolactone polyol compounds content is in 1～30 weight unit scope the time, the test after initial stage test, the humidity test, its number average that comes off is (individual/100 lattice) below 4.During caprolactone polyol compounds content 0.05 weight unit, its number average that comes off of test after initial stage test, the humidity test is (individual/100 lattice) more than 10.And when the caprolactone polyol compounds content is 50 weight unit, the test after initial stage test, the humidity test, its number average that comes off is more than 5, slightly increases.
Think the sticking power that improves coating and Glass Containers surface, the number that comes off after the test of reduction initial stage, the humidity test, the caprolactone polyol compounds content is effective in 0.1～30 weight unit scope in polyol compound (100 weight unit), the caprolactone polyol compounds content is more effective in 1～20 weight unit scope, and the caprolactone polyol compounds content is the most effective in 2～10 weight unit scopes.
3. silane sequestrant
(1) kind 1
The silane sequestrant has front three methoxy silane, front three Ethoxysilane, benzene front three methoxy silane, γ-uride propyl trimethoxy silicane, γ-uride propyl-triethoxysilicane, γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-(2-aminoethyl) first dimethoxy silane, first Trimethoxy silane, γ-chloropropyl trimethoxy silane, dimethyldimethoxysil,ne or the like.
In these silane sequestrants, react low with melamine resin, polyol compound, the silane sequestrant that can improve coating adhesion has: γ-uride propyl trimethoxy silicane, γ-uride propyl-triethoxysilicane, γ-An Bingjisanyiyangjiguiwan, γ-An Bingjisanjiayangjiguiwan, γ-(2-aminoethyl) aminopropyl trimethoxysilane, γ-aminosilane sequestrants such as (2-aminoethyl) first dimethoxy silane.
(2) kind 2
It also is comparatively ideal using the partial condensate of silane sequestrant.By using partial condensate can improve adhesive force of coatings.
The partial condensate of silane sequestrant can be that the part of the alkoxyl group that contains in the silane sequestrant adds water decomposition, decomposes the hydroxy thing that the back generates, and also can be hydroxy and oxyalkylation reaction, with the resultant of silanol be combined into.
(3) kind 3
Except above-mentioned silane sequestrant, can also use altogether with other silane sequestrant and above-mentioned silane sequestrant, effect is better like this.
Other silane sequestrant has γ-uride propyl trimethoxy aluminium, γ-uride propyl group three oxygen base aluminium, gamma-aminopropyl-triethoxy-aluminium, γ-aminopropyl aluminum methylate, γ-(2-aminoethyl)-aminopropyl aluminum methylate, γ-aluminum chelating agents such as (2-aminoethyl) aminopropyl first dimethoxy aluminium.
Also have γ-uride propyl triethoxy titanium, γ-uride propyl trimethoxy titanium, gamma-aminopropyl-triethoxy-phthalein, γ-aminopropyl trimethoxy titanium, γ-(2-aminoethyl) aminopropyl trimethoxy titanium, γ-titanium sequestrants such as (2-aminoethyl) aminopropyl first dimethoxy titanium.
(4) content
The content of silane sequestrant, with respect to melamine resin 100 weight unit, the content of silane sequestrant should be controlled in 5 ~ 100 weight unit scopes.
Reason is the content such as less than 5 weight unit of silane sequestrant, can not show additive effect.And the content of working as the silane sequestrant surpasses 100 weight unit, and the reaction of silane sequestrant and melamine resin is difficult to control, and the hardness of coating is low.
So with respect to melamine resin 100 weight unit, it is ideal that the content of silane sequestrant is controlled in 10 ~ 50 weight unit scopes, is controlled in 20 ~ 40 weight unit scopes then even more ideal.Referring now to Fig. 2, elaborate to concerning between the content of silane sequestrant and the adhesive force of coatings.
Among Fig. 2, transverse axis is represented the content with respect to 100 weight unit melamine resins, silane sequestrant (uride propyl-triethoxysilicane), and d-axis represents to adopt the number (individual/100 lattice) that comes off of per 100 lattice that the checker glass gummed paper mounting method of JISK-5400 measured.
In addition, the initial stage measurement result represents that with solid line A the measurement result with dashed lines B of moisture-proof experiment back (40 ℃ * 95%RH, 24 hours) represents.
After measuring, evaluating, with the standard of example 1,160 ℃ * 10 minutes condition is carried out baking-curing, and the thickness of coating is 25 μ m.
Can be clear that from Fig. 2 the content of silane sequestrant is when 5 ~ 10 weight unit scopes, the initial stage tests, the test after the humidity test, and its number average that comes off is (individual/100 lattice) below 2.When the content of silane sequestrant is 0.5 weight unit, the initial stage test, the test after the humidity test, its number average that comes off is (individual/100 lattice) more than 10.And when the content of silane sequestrant surpasses 100 weight unit, the initial stage test, the test after the humidity test, its number average that comes off is (individual/100 lattice) more than 2 or 2.
So, be raising coating and Glass Containers surface adhesion force, the number that comes off after test of reduction initial stage and the humidity test, it is ideal that the content of silane sequestrant is controlled in 10 ~ 80 weight unit scopes, is controlled in 20 ~ 50 weight unit scopes then even more ideal.
4. immiscible material
(1) kind
Add some immiscible materials in the glass tailor-(made) coating, utilize their separation phenomenon, form assorted spot decorative pattern naturally, effect is also good.Addible immiscible material has: nonpolar polymer, nonpolar neat (molecular weight) polymkeric substance, non-polar monomer, plasticizer, hydrocarbon, benzene, toluene, fluorine cpd, silicone oil, silicone particle, silicone polymer or the like, can select for use wherein a kind of, perhaps two kinds, be used in combination more than two kinds.
Wherein, silicone oil, silicone particle, silicone polymer result of use are preferable, and separation efficiency height, irregular pattern are clear.
(2) content
With respect to melamine resin 100 weight unit, the content of immiscible material should be controlled in 0.1 ~ 30 weight unit scope.
Reason is the content such as less than 0.1 weight unit of immiscible material, inferior separating effect, and irregular pattern is fuzzy.And the content of working as immiscible material surpasses 30 weight unit, and hardness, the sticking power of coating obviously reduce.
5. character and state
The glass tailor-(made) coating is better with liquid state, is convenient to spraying.The viscosity of glass tailor-(made) coating also should be controlled at 1 * 10
0~ 1 * 10
6In mpa.s (25 ℃) scope is good.
Reason is viscosity such as less than 1 * 10
0Mpa.s is easy to generate problems such as sagging, and the thickness of coating is also inhomogeneous.Surpass 1 * 10 and work as viscosity
6Mpa.s, overweight coating does not reach the filming requirement, and spraying method also is subjected to all restrictions in addition.
So, the viscosity controller 1 * 10 of glass tailor-(made) coating
0~ 1 * 10
6In mpa.s (25 ℃) scope is ideal, is controlled at 1 * 10
1~ 1 * 10
3Then even more ideal in mpa.s (25 ℃) scope.
The adjusting of glass tailor-(made) coating viscosity should be used viscosity modifier or organic solvent.
6. irregular pattern
So-called irregular pattern is inhomogeneous, the irregular decorative pattern that manifests of coatingsurface just.
Irregular pattern comprises marbling, natural parmelia saxatilis line, japanning style, Rubus corchorifolius style, Chang Pu showy flowers of herbaceous plants sample etc.The irregular pattern on Glass Containers surface is good with even, multiple.
7. Glass Containers
The kind of Glass Containers does not have any special restriction, can be bottle for cosmetics, drug bottle, beverage bottle, artistic design bottle or the like.
[the 2nd embodiment]
The 2nd embodiment comprises the production method of spraying process and curing process.
Spraying process is meant the aforesaid glass tailor-(made) coating of blending ratio, is sprayed at the Glass Containers surface in inhomogeneous mode.
Curing process is meant that the Glass Containers that spraying is finished is heating and curing, and forms irregular pattern.
Below be elaborated with regard to each operation, in the 1st embodiment, done detailed description as for the composition of glass tailor-(made) coating, no longer repeat.
1. spraying process
Spraying process is meant a glass tailor-(made) coating, is sprayed at the Glass Containers surface in inhomogeneous mode.
Spraying method has multiple, and electrostatic spraying, electrophoresis spraying method, drum process, spray method or the like are for example arranged.
In this several method, spray method is comparatively desirable.The spray equipment simple structure of spray method, easy to maintenance.The coating of spray method is thin and evenly, even if surface shape complexity, Glass Containers that curved surface is many also can reach satisfied spraying effect.And when using spray method, also can establish several fog-spray nozzles more.But a fog-spray nozzle spray material, other fog-spray nozzle can spray the solvent of dissolution of coatings.
The moulding of irregular pattern can be adopted following several method:
1. inhomogeneous mode spraying method
Shown in Fig. 3 (a), glass tailor-(made) coating 12 with the drops drippage, is blowed to Glass Containers surface 11 unevenly.Then, this is coated with bottling is heating and curing, form the irregular pattern coating 13 shown in Fig. 3 (b).
2. inhomogeneous solvent spraying method
Shown in Fig. 4 (a), glass tailor-(made) coating 25 is sprayed at Glass Containers surface 21 in even mode, form the uniform coating 22 of one deck thickness.Then, shown in Fig. 4 (b), the solvent 28 of dissolution of coatings is sprayed at coating 22 surfaces in inhomogeneous mode, reheat solidifies, and forms the irregular pattern coating 24 shown in Fig. 4 (c).
3. mechanically shape's method
Shown in Fig. 5 (a), glass tailor-(made) coating 35, be sprayed at Glass Containers surface 31 in even or inhomogeneous mode, form coating 32.Then, shown in Fig. 5 (b), with the method that sandblasts the part 39 of coating is removed, reheat solidifies, and forms the irregular pattern coating 34 shown in Fig. 5 (c).
4. immiscible partition method 1
Shown in Fig. 6 (a), in glass tailor-(made) coating 42, add immiscible material 45, as silicone oil, then the coating that contains immiscible material is sprayed at Glass Containers surface 41 equably.Then, shown in Fig. 6 (b), utilize the separation phenomenon between coating and the immiscible material, form uneven coating, reheat solidifies, and forms the irregular pattern coating 44 shown in Fig. 6 (c).
5. immiscible partition method 2
In glass tailor-(made) coating 52, add boiling point less than 100 ℃, the organic solvent 55 of solubilized coating, and water 56.This is contained solvent 55, and the coating of water 56 is sprayed at Glass Containers surface 1 equably.Then, shown in Fig. 7 (a), temperature does not surpass 100 degree, earlier organic solvent 55 evaporations is removed.Utilize the separation phenomenon between coating 52 and the water 56, form the irregular pattern coating.Follow, shown in Fig. 7 (b), Heating temperature will surpass 100 degree, and the water evaporation is removed again.Last reheat solidifies, and forms the irregular pattern coating 54 shown in Fig. 7 (c).
2. curing process
(1) baking condition
Baking condition can be set suitable storing temperature according to the temperature of reaction of employed glass tailor-(made) coating.Temperature generally is that storing time is about 10 minutes in 140 ℃ ~ 250 ℃ scopes.150 ℃ ~ 230 ℃ * 10 minutes then comparatively desirable, and 160 ℃ ~ 220 ℃ * 10 minutes then even more ideal.
(2) coat-thickness
Coat-thickness should be controlled in 0.5 ~ 300 mu m range to good.
Its reason is coat-thickness less than 0.5 μ m, and coat-thickness is inhomogeneous, and coating hardness is low.Surpass 300 μ m and work as coat-thickness, overweight coating, difficulty is heating and curing.
So it is ideal that coat-thickness (solidifying back thickness) is controlled in 1 ~ 100 mu m range, is controlled in 10 ~ 50 mu m ranges then even more ideal.
(3) pencil hardness
Coating hardness should be controlled in pencil hardness (JISK5400 standard) 2H ~ 6H scope to good.
Reason is the not enough pencil hardness 2H of coating hardness, and low, the poor heat resistance of coating hardness is described.Surpass hardness 6H and work as coating hardness, coating comes off from the Glass Containers surface easily.
So coating hardness is controlled in pencil hardness (JISK5400 standard) 3H ~ 5H scope more satisfactory, is controlled in 4H ~ 5H scope then even more ideal.
3. bottoming operation
In coating manufacturing process of the present invention, for improving the sticking power of Glass Containers 61 and coating 63, as shown in Figure 8, between should have prime coat 64.
Prime coat can be epoxy resin prime coat, polyurethane sex change epoxy resin prime coat, also can be the polyester resin prime coat.
With the above-mentioned prime coat coating that contains polyol compound, for example: polyol compound/organic solvent, polyol compound/silane sequestrant/organic solvent, polyol compound/melamine resin/silane sequestrant/organic solvent.Be sprayed at the Glass Containers surface.Uniform coating of the formed thickness of prime coat coating and color need not be handled, and can directly use.
4. Glass Containers heating process
In coating forming method of the present invention, before spraying process, should shown in Fig. 9 (a), carry out heat treated (flame treating) to Glass Containers 71.By heating, can improve the lubricious degree of vessel surface, get rid of the organism that vessel surface adheres to, improve the sticking power of Glass Containers 71 and coating 73.
Consider that from factors such as the lubricious degree in Glass Containers surface flame treating can adopt the high liquefied petroleum gas (LPG) of combustion heat value, the flame contact can be controlled in 0.5 ~ 30 second scope.
The Glass Containers surface temperature should be controlled at when flame treating in 50 ~ 200 ℃ of scopes.Be controlled at 60 ~ 180 ℃ of scope Nei Gengjia, be controlled in 70 ~ 150 ℃ of scopes best.
5. wash bottle operation
In coating forming method of the present invention, before spraying process, also should clean Glass Containers.
Used water or alcohol wash both can improve the smooth finish of vessel surface, can remove organism, dust that vessel surface adheres to again, thereby improved sticking power.
Water or alcohol can adopt spraying method or water spray means, perhaps bottle are immersed in the water and clean.
6. protective membrane forms operation
After the irregular pattern coating forms, can spray layer of transparent protective membrane 85 again on coating 83 surfaces for good as shown in figure 10.Protective membrane 85 not only can be strengthened coating 83, and can make coating 83 smooth surfaces, smooth.
And the protective membrane raw material is preferably selected the colourless transparent resin raw material for use, certainly according to container purposes needs, also can select coloured material or opaque resin raw material for use.
Protective layer thickness can be controlled in 1 ~ 100 mu m range.
Reason is protective layer thickness less than 1 μ m, does not strengthen the effect of coating.Surpass 100 μ m and work as protective layer thickness, protective layer itself comes off easily, and became uneven.
So it is good in 5 ~ 50 mu m ranges that protective layer thickness is controlled at, and is controlled at 10 ~ 30 mu m range Nei Zegengjia.
7. literal, pattern print manufacturing procedure
More than after each operation finishes, also can shown in Figure 11 (a), carry out various printings processing on coating 93 surfaces.
For example, use a pendular ring epoxy resins, a liquid urethane resin or vibrin printing ink to print.
Literal, pattern printing can improve the ornamental and ornamental of container, can the material in the container be described, but displaying contents amount or the like.
In addition, use a pendular ring epoxy resins, a liquid urethane resin, vibrin ink printing after, the condition with 120 ℃ ~ 220 ℃ * 20 minutes is heating and curing, and printing word, pattern and coating are combined closely.
In addition, tear open mutually with coating, should have in the printing ink and contain and the congener silane sequestrant of silane sequestrant for preventing printing word, pattern.
8. cycling and reutilization operation
What occur in application, printing processing is defective, can recycling.
After the bottle pulverizing, put in the glass dissolving stove, with about 600 ~ 1100 ℃ heat, in glass melting, the coating of glass surface also decomposes (distillation) is removed.
At this moment, it is preferable to come thermolysis (distillation) to remove coating with about 800 ℃ * 10 minutes heating condition.It is then even more ideal to come thermolysis (distillation) to remove coating with the heating condition about 600 ℃ * 10 minutes.
With respect to melamine resin 100 weight unit, the content of silane sequestrant should be controlled at below 100 weight unit conversely speaking.If the content of silane sequestrant surpasses 100 weight unit, even come thermal degradation with the heating condition about 800 ℃ * 10 minutes, the silane sequestrant also may be residual in addition.
So, remove coating for the ease of 800 ℃ * 10 minutes heating condition, the content of silane sequestrant should be controlled at below 100 weight unit.
[example]
Below, content of the present invention is described in detail by example.Technical scope of the present invention is not limited to the scope that example is put down in writing, and can suitably change in purpose scope of the present invention, applies in a flexible way.
[example 1]
1. the making of glass tailor-(made) coating
Use following ratio, each raw material is put in the container that has agitator,, stirred 30 minutes with room temperature condition.(stirring velocity: the viscosity of the glass tailor-(made) coating that 1000rpm) obtains is 40mpa.s (25 ℃), and solid form accounts for 39 weight %.
Propylene polyol compound 180 weight unit
(hydroxyl value 300mgKOH/g molecular-weight average 3,000)
(hydroxyl value 200mgKOH/g molecular-weight average 1,000)
Uride propyl group three ethoxy silane 25 weight unit
The phosphoric acid class is solidified catalyst 5 weight unit
Dimethylbenzene 300 weight unit
Jealous woman acid butyl 150 weight unit
In the table 1 of back, the melamine resin represents that with A1 the propylene polyol compound represents that with B1 the lactone polyol compound represents that with B2 uride propyl group three ethoxy silane represent that with C1 phosphoric acid class curing catalyst is represented with D1.As follows.
2. the evaluation of glass tailor-(made) coating
Coating after mixing is evaluated with regard to its storage-stable performance, baking sintering character, and evaluation result is as shown in table 1.
(1) storage-stable performance
The glass tailor-(made) coating under 20 ℃ constant temperature, is preserved a week, and then the visual observations throw out, observation caliber is as follows.Evaluate the storage stability of coating with this method.
Excellent: sediment-free.
Very: small throw out is arranged, and hand stirs and promptly can be changed into homogeneous solution.
In: throw out is arranged, and mechanical stirring (1000rpm) can be changed into homogeneous solution.
Difference: throw out is arranged, and mechanical stirring (1000rpm) can not become homogeneous solution.
(2) baking sintering character 1 (outward appearance)
Use spray method, the glass tailor-(made) coating is sprayed at carboy surface (the high 10cm of bottle, diameter 4cm, oral area height 3cm, mouth diameters 2cm) equably.Then, the solvent that can dissolve coating, isopropanol solvent sprays to vessel surface in the water droplet mode, and the fine rotation container, makes solvent be flow state.With different baking conditions, baking respectively in 160 ℃ * 10 minutes, 180 ℃ * 10 minutes, 200 ℃ * 10 minutes makes coating curing, forms the irregular pattern coating.After this, use visual method,, the baking sintering character (outward appearance) of coating is evaluated with following standard.10 in detected bottle, the average result of evaluation sees Table 1.
Excellent: three different baking conditions, the equal irregular pattern of the coating of formation is clear, and outward appearance is beautiful.
Very: 180 ℃ * 10 minutes, 200 ℃ * 10 minutes baking condition, formed coating irregular pattern is clear, outward appearance is beautiful.
In: 200 ℃ * 10 minutes baking condition, the coating irregular pattern of formation is clear, outward appearance is beautiful.
Difference: 200 ℃ * 10 minutes baking condition can not form clear, beautiful coating.
(3) baking sintering character 2 (with the adhesion property of glass surface)
Use spray method, the glass tailor-(made) coating is sprayed at the carboy surface equably.(the high 10cm of bottle, diameter 4cm, oral area height 3cm, mouth diameters 2cm) then, the isopropanol solvent that can dissolve coating, sprays to vessel surface in the water droplet mode.
With different baking conditions, baking respectively in 160 ℃ * 10 minutes, 180 ℃ * 10 minutes, 200 ℃ * 10 minutes makes coating curing, forms the irregular pattern coating.After this, with the checker glass gummed paper mounting method of JISK-5400, measure the number that comes off of per 100 lattice.10 in detected bottle, the average result of mensuration sees Table 1.
Excellent: three different baking conditions, coating shedding number average are 0/100 lattice.
Very: 180 ℃ * 10 minutes, 200 ℃ * 10 minutes baking conditions, coating shedding number are 0/100 lattice.
In: 200 ℃ * 10 minutes baking conditions, coating shedding number are 0/100 lattice.
Difference: 200 ℃ * 10 minutes baking conditions, coating shedding number are more than 1/100 lattice.
(4) baking sintering character 3 (pencil hardness)
Use spray method, the glass tailor-(made) coating is sprayed at the carboy surface equably.(the high 10cm of bottle, diameter 4cm, oral area height 3cm, mouth diameters 2cm) then, the isopropanol solvent that can dissolve coating, sprays to vessel surface in the water droplet mode.With 160 ℃ * 10 minutes condition, baking-curing formed the irregular pattern coating again.After this, according to the regulation of JISK-5400, JISS6006, carry out pencil hardness test with pencil.10 in detected bottle, the average result of mensuration sees Table 1.
(5) moisture resistance properties
With with the same method of baking coking property 2, the glass tailor-(made) coating is sprayed to vessel surface with spray method, then with 160 ℃ * 10 minutes condition, baking-curing formed the irregular pattern coating.Again this is coated with bottling in the humidity cabinet of 40 ℃ * 95%RH, placed 24 hours and 72 hours.Then bottle is taken out, room temperature environment (25 ℃ * place 1 hour in 50%RH) after, with the checker glass gummed paper mounting method of JISK-5400, measure the number that comes off of per 100 lattice.10 in detected bottle, the average result of mensuration sees Table 1.
(6) literal, pattern printing adaptability energy
With with the same method of baking coking property 2, paint spay-coating to vessel surface.Then with 200 ℃ * 10 minutes condition, baking-curing formed irregular pattern.With a liquid type epoxy printing ink, carry out the lines printing at coatingsurface.After this, with following standard, can judge the printing adaptability of coating with visual method.10 in detected bottle, the average result of mensuration sees Table 1.
Excellent: as to know the wide lines of printing 0.2mm.
Very: can know the wide lines of printing 1.0mm.
In: can know the wide lines of printing 2.0mm.
Difference: a liquid type epoxy printing ink is torn open mutually, can not know the wide lines of printing 2.0mm.
[example 2 ~ 5, comparative example 1 ~ 2]
The influence of polyol compound to coating is discussed below.Be in the example 1, the content of polyol compound (propylene polyvalent alcohol+interior ester polyol) is 210 weight unit, and example 2 then is 100 weight unit, example 3 is 150 weight unit, and example 4 is 250 weight unit, and example 5 is 300 weight unit, other component proportionss are all constant, and are the same with example 1.
In addition, the content of polyol compound is 40 weight unit in the comparative example 1, and the content of polyol compound is 500 weight unit in the comparative example 2, and other component proportionss are all constant, and are the same with example 1.
Can be clear that from evaluation result, the content of polyol compound few (comparative example 1), adhesive force of coatings, wet fastness are poor.The content of polyol compound is big, and coating not only sticking power, wet fastness is poor, and pencil hardness is low, and printing adaptability is also poor.
So the content range of the polyol compound of the present invention regulation is suitable, coating not only sticking power, wet fastness is strong, and the pencil hardness height, and printing adaptability is wide.
[table 1]
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | |
| ??A1 | ????100 | ??100 | ??100 | ??100 | ??100 | ?100 | ??100 |
| ??B1 | ????180 | ??80 | ??130 | ??180 | ??180 | ?20 | ??180 |
| ??B2 | ????30 | ??20 | ??20 | ??70 | ??120 | ?20 | ??320 |
| ??C1 | ????25 | ??25 | ??25 | ??25 | ??25 | ?25 | ??25 |
| ??D1 | ????5 | ??5 | ??5 | ??5 | ??5 | ?5 | ??5 |
| Dimethylbenzene | ????300 | ??300 | ??300 | ??300 | ??300 | ?300 | ??300 |
| The acetic acid butyl | ??150 | ??150 | ??150 | ??150 | ??150 | ??150 | ??150 |
| ??IPA | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 | ??90 |
| Storage stability | Excellent | Excellent | Excellent | Excellent | Excellent | Excellent | Excellent |
| Outward appearance | Excellent | Excellent | Excellent | Excellent | Excellent | In | In |
| Sticking power | Excellent | Very | Excellent | Excellent | Very | Difference | Difference |
| Pencil hardness | Excellent | Excellent | Excellent | Very | In | Very | Difference |
| Wet fastness | Excellent | Excellent | Excellent | Excellent | Very | In | Difference |
| Printing adaptability | Excellent | Very | Excellent | Excellent | Very | In | Difference |
A1: melamine resin B 1: propylene polyol compound
B2: lactone sex change polyol compound C1: uride propyl group three ethoxy silane
D1: the phosphoric acid class is solidified catalyst IPA: Virahol
[example 6 ~ 8, comparative example 3 ~ 4]
The influence of the content of silane sequestrant to coating is discussed below.Also be in the example 1, the content of silane chela agent makes 5 weight unit, and example 6 then is 10 weight unit, and example 7 is 50 weight unit, and example 8 is 100 weight unit, and other component proportionss are all constant, and are the same with example 1.
In addition, in the comparative example 3, the content of silane sequestrant is 0.5 weight unit, and the content of silane sequestrant is 300 weight unit in the comparative example 4, and other component proportionss are all constant, and are the same with example 1.
Can be clear that from evaluation result, the content of silane sequestrant very few (comparative example 3), friction pull, the wet fastness of coating are poor.And the content of silane sequestrant too much (comparative example 4), coating not only friction pull, wet fastness is poor, and pencil hardness is low, and printing adaptability is also poor.
So the content range of the silane sequestrant of the present invention regulation is suitable, coating not only friction pull, wet fastness is strong, and the pencil hardness height, and printing adaptability is wide.
[table 2]
| Example 1 | Example 6 | Example 7 | Example 8 | Comparative example 3 | Comparative example 4 | |
| ????A1 | ????100 | ????100 | ????100 | ??100 | ??100 | ??100 |
| ????B1 | ????180 | ????180 | ????180 | ??180 | ??180 | ??180 |
| ????B2 | ????30 | ????30 | ????30 | ??30 | ??30 | ??30 |
| ????C1 | ????25 | ????10 | ????50 | ??100 | ??0.5 | ??300 |
| ????D1 | ????5 | ????5 | ????5 | ??5 | ??5 | ??5 |
| Dimethylbenzene | ????300 | ????300 | ????300 | ??300 | ??300 | ??300 |
| The acetic acid butyl | ????150 | ????150 | ????150 | ??150 | ??150 | ??150 |
| ????IPA | ????90 | ????90 | ????90 | ??90 | ??90 | ??90 |
| Storage stability | Excellent | Excellent | Excellent | Excellent | Excellent | In |
| Outward appearance | Excellent | Excellent | Excellent | Excellent | Very | In |
| Sticking power | Excellent | Very | Excellent | Very | Very | Difference |
| Pencil hardness | Excellent | Very | Excellent | Very | Very | Difference |
| Wet fastness | Excellent | Excellent | Excellent | Very | Difference | In |
| Printing adaptability | Excellent | Very | Excellent | Very | In | Difference |
[example 9 ~ 11]
The influence of the content of solidifying agent to coating is discussed below.Be in the example 1, the content of solidifying agent is 5 weight unit, and example 9 then is 1 weight unit, and example 10 is 10 weight unit, and example 11 is 30 weight unit, and other component proportionss are all constant, and are the same with example 1.
Can be clear that from evaluation result the content that solidifies catalyst is (example 9) more after a little while, adhesive force of coatings, pencil hardness are lower slightly.And the content that solidifies catalyst (example 11) more for a long time, adhesive force of coatings, pencil hardness, wet fastness are all less better.
So the content range of the curing catalyst of the present invention's regulation is suitable, the storage stability of coating is good, and adhesive force of coatings, pencil hardness, wet fastness, printing adaptability are all very desirable.
[table 3]
| Example 1 | Example 9 | Example 10 | Example 11 | |
| ??A1 | ????100 | ????100 | ????100 | ????100 |
| ??B1 | ????180 | ????180 | ????180 | ????180 |
| ??B2 | ????30 | ????30 | ????30 | ????30 |
| ??C1 | ????25 | ????25 | ????25 | ????25 |
| ??D1 | ????5 | ????1 | ????10 | ????30 |
| Dimethylbenzene | ????300 | ????300 | ????300 | ????300 |
| The acetic acid butyl | ????150 | ????150 | ????150 | ????150 |
| ??IPA | ????90 | ????90 | ????90 | ????90 |
| Storage stability | Excellent | Excellent | Excellent | Very |
| Outward appearance | Excellent | Excellent | Excellent | Very |
| Sticking power | Excellent | Very | Excellent | Very |
| Pencil hardness | Excellent | Very | Excellent | Very |
| Wet fastness | Excellent | Very | Excellent | Very |
| Printing adaptability | Excellent | Very | Excellent | Very |
[example 12 ~ 14]
The influence of tinting material to coating then is discussed, and in example 1, tinting material does not add.And in example 12, with respect to melamine resin 100 weight unit, tinting material adds 5 weight unit, and 13 of examples add 10 weight unit, and example 14 adds 30 weight unit, and other component proportionss are all constant, and are the same with example 1.
Can be clear that from evaluation result the content of tinting material is (example 14) more for a long time, performances such as adhesive force of coatings slightly reduce.
So the colorant content scope of the present invention's regulation is suitable, can prevent performance decrease such as adhesive force of coatings.
[table 4]
| Example 1 | Example 9 | Example 10 | Example 11 | |
| ??A1 | ????100 | ????100 | ????100 | ????100 |
| ??B1 | ????180 | ????180 | ????180 | ????180 |
| ??B2 | ????30 | ????30 | ????30 | ????30 |
| ??C1 | ????25 | ????25 | ????25 | ????25 |
| ??D1 | ????5 | ????5 | ????5 | ????5 |
| Tinting material | ????0 | ????5 | ????10 | ????30 |
| Dimethylbenzene | ????300 | ????300 | ????300 | ????300 |
| The acetic acid butyl | ????150 | ????150 | ????150 | ????150 |
| ??IPA | ????90 | ????90 | ????90 | ????90 |
| Storage stability | Excellent | Excellent | Excellent | Very |
| Outward appearance | Excellent | Excellent | Excellent | Very |
| Sticking power | Excellent | Excellent | Very | Very |
| Pencil hardness | Excellent | Excellent | Very | Very |
| Wet fastness | Excellent | Excellent | Excellent | Very |
| Printing adaptability | Excellent | Excellent | Excellent | Very |
[example 15 ~ 17]
The different sorts of polyvalent alcohol then is discussed, to the influence of coating.In the example 1, what use is the mixture of propylene polyol compound/lactone polyol compound, and that use in the example 15 is propylene polyol compound/polyester polyols alkylol cpd (hydroxyl value 300mgKOH/g, molecular-weight average 3000) mixture, that use in the example 16 is propylene polyol compound/fluorine-containing plain polyol compound (hydroxyl value 300mgKOH/g, molecular-weight average 3000) mixture, then only use propylene polyol compound (hydroxyl value 300mgKOH/g, molecular-weight average 3000) in the example 7 separately.Other component proportionss are all constant, and are the same with example 1.
Evaluation result shows, under the identical situation of usage quantity, adopts propylene polyol compound/both blending meanss of caprolactone polyol compound, and the best performance of coating more.
[table 5]
| Example 1 | Example 9 | Example 10 | Example 11 |
| ??A1 | ????100 | ????100 | ????100 | ????100 |
| ??B1 | ????180 | ????180 | ????180 | ????180 |
| ??B2 | ????30 | |||
| ??B3 | ????30 | |||
| ??B4 | ????30 | |||
| ??C1 | ????25 | ????25 | ????25 | ????25 |
| ??D1 | ????5 | ????5 | ????5 | ????5 |
| Dimethylbenzene | ????300 | ????300 | ????300 | ????300 |
| The acetic acid butyl | ????150 | ????150 | ????150 | ????150 |
| ??IPA | ????90 | ????90 | ????90 | ????90 |
| Storage stability | Excellent | Excellent | Very | Excellent |
| Outward appearance | Excellent | Very | Very | Excellent |
| Sticking power | Excellent | Very | Very | Very |
| Pencil hardness | Excellent | Very | Very | Very |
| Wet fastness | Excellent | Very | Excellent | Very |
| Printing adaptability | Excellent | Very | Excellent | Very |
A1: melamine resin B 1: propylene polyol compound
B2: lactone sex change polyol compound B3: polyester polyols alkylol cpd
B4: fluorine-containing plain polyol compound C1: uride propyl-triethoxysilicane
D1: the phosphoric acid class is solidified catalyst IPA: Virahol
[example 18 ~ 20]
Bottle cleaning performance and flame treating effect are discussed now.
Example 2 be coated with bottling, before application, bottle was washed for 3 seconds (example 18) with ethanol, water washed for 3 seconds (example 19) to bottle, with liquefied petroleum gas (LPG) bottle was carried out flame treating (example 20), 1000 ℃ of temperature, flame 1 second of duration of contact.Evaluation result shows that bottle cleaning and flame treating not only can not reduce the various performances of coating, can improve the friction pull of coating on the contrary.
[table 6]
| Example 2 | Example 18 | Example 19 | Example 20 | |
| Vial is handled | Do not have | Ethanol cleans | Water cleans | Flame treating |
| Storage stability | Excellent | Excellent | Excellent | Excellent |
| Outward appearance | Excellent | Excellent | Excellent | Excellent |
| Sticking power | Very | Excellent | Excellent | Excellent |
| Pencil hardness | Excellent | Excellent | Excellent | Excellent |
| Wet fastness | Excellent | Excellent | Excellent | Excellent |
| Printing adaptability | Very | Very | Very | Very |
[example 21 ~ 23]
The prime coat effect is discussed now.
Example 2 be coated with bottling, before being coated with bottle, the toluene of caprolactone polyol compound (50 weight unit) (50 weight unit) solution spraying (example 21) on vessel surface, injecting time is 1 second.Caprolactone polyol (50 weight unit) solution spraying (example 22) on bottle surface, injecting time 1 second, toluene (50 weight unit) solution spraying (example 23) on bottle surface of caprolactone polyol compound (50 weight unit) and uride propyl-triethoxysilicane (10 weight unit) and melamine resin (30 weight unit), injecting time 1 second.The coating of each self-forming is compared with the coating of example 2.
[table 7]
| Example 2 | Example 21 | Example 22 | Example 23 | |
| Bottoming is handled | Do not have | ????B2 | ????B2/C1 | ????A1/B2/C1 |
| Storage stability | Excellent | Excellent | Excellent | Excellent |
| Outward appearance | Excellent | Excellent | Excellent | Excellent |
| Sticking power | Very | Excellent | Excellent | Excellent |
| Pencil hardness | Excellent | Excellent | Excellent | Excellent |
| Wet fastness | Excellent | Excellent | Excellent | Excellent |
| Printing adaptability | Very | Excellent | Excellent | Excellent |
[invention effect]
The present invention's application glass container, its coating composition comprise a certain amount of polyol compound and the agent of silane chelating. Use this kind coating, the irregular pattern coating that baking is shaped, with the strong adhesion of glass vessel surface, coating surface can adapt to various printing processing.
In addition, the mixture that contains propylene polyol compound and lactone polyol compound in the special-purpose coating of glass. Thereby, only needing the baking condition with 160 ℃ * 10 minutes, every well behaved irregular pattern coating can be shaped.
Also have, the present invention's irregular pattern is coated with bottling, recyclable cycling and reutilization. Coating is in the temperature below 600 ℃, with regard to decomposes, distil, be removed. Can guarantee the cycling and reutilization of vial.
The application method of the application of the invention, even use the special-purpose coating of the glass that contains a certain amount of polyol compound and the agent of silane chelating, it is strong also to produce coating adhesion to high efficiency, the coating surface printing adapts to wide irregular pattern application glass container.
Claims (15)
1, a kind of irregular pattern application Glass Containers, it is characterized in that, its surface is coated with the glass tailor-(made) coating, form irregular pattern on this Glass Containers surface, the prescription of this glass tailor-(made) coating is: with respect to melamine resin 100 weight unit, the content of polyol compound is in the 50-400 weight unit, and the content of silane sequestrant is in the 5-100 weight unit.
2, application Glass Containers as claimed in claim 1, it is characterized in that, wherein the feature of melamine resin is: the melamine resin that methylates, or butylation melamine resin, or the melamine resin after either party the process alkylation among both.
3, application Glass Containers as claimed in claim 1 or 2 is characterized in that, wherein the feature of polyol compound is: the mixture by third rare polyol compound and lactones polyol compound is formed.
4, as the described application Glass Containers of one of claim 1 to 3, it is characterized in that wherein the feature of polyol compound is: with respect to polyol compound 100 weight unit, the content of lactones polyol compound is in 0.1 ~ 30 weight unit scope.
5, as the described application Glass Containers of one of claim 1 to 4, it is characterized in that wherein the feature of polyol compound is: the hydroxyl value of polyol compound is in 5 ~ 500mgKOH/g scope.
6, as the described application Glass Containers of one of claim 1 to 5, it is characterized in that wherein the feature of silane sequestrant is: Ammonia silane sequestrant, or epoxies silane sequestrant, or either party sequestrant among both.
7, as the described application Glass Containers of one of claim 1 to 6, it is characterized in that, in the glass tailor-(made) coating that blending forms, also added tinting material, the content of this tinting material: with respect to melamine resin 100 weight unit, the content of tinting material is in 0.1 ~ 100 weight unit scope.
8, as the described application Glass Containers of claim 1 to 7, it is characterized in that, in the glass tailor-(made) coating that blending forms, also added solidifying agent, the content of this solidifying agent: with respect to melamine resin 100 weight unit, the content of solidifying agent is in 0.1 ~ 30 weight unit scope.
9, as the described application Glass Containers of one of claim 1 to 8, it is characterized in that, in the glass tailor-(made) coating that blending forms, also added immiscible material.The content of this immiscible material, with respect to melamine resin 100 weight unit, the content of immiscible material is in 0.1 ~ 30 weight unit scope.
10, as the described application Glass Containers of one of claim 1 to 9, it is characterized in that the viscosity of glass tailor-(made) coating is 1 * 10 ° ~ 1 * 10
6In mpa.s (25 ℃) scope.
11, a kind of manufacture method of application Glass Containers is characterized in that, comprises two operations, i.e. spraying process and curing process;
Spraying process: with respect to melamine resin 100 weight unit, the content of polyol compound is in 50 ~ 400 weight unit scopes, the content of silane sequestrant is in 5 ~ 100 weight unit scopes, and the glass tailor-(made) coating with this ratio is sprayed on the Glass Containers surface in inhomogeneous mode;
Curing process: the Glass Containers that spraying is finished is heating and curing, and makes vessel surface manifest irregular pattern.
12, application Glass Containers manufacture method as claimed in claim 11 is characterized in that, in spraying process: will be drop-shaped glass tailor-(made) coating, and spray to the Glass Containers surface in inhomogeneous mode, and be bonded in the Glass Containers surface.
13, as claim 11 or 12 described application Glass Containers production methods, it is characterized in that, in spraying process: after the glass tailor-(made) coating is sprayed on the Glass Containers surface in inhomogeneous mode, spray one deck solvating agent again.
As the described application Glass Containers of one of claim 11-13 production method, it is characterized in that 14, before spraying process, the operation that feels secure in addition is promptly with the polyol compound processing that feels secure on the Glass Containers surface.
15, as the described application Glass Containers of one of claim 11 to 14 production method, it is characterized in that before spraying process, also having the container heating process.Promptly the Glass Containers surface is heated with flame.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031288812A CN1552654A (en) | 2003-05-28 | 2003-05-28 | Irregular decorative pattern coating glass container and producing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031288812A CN1552654A (en) | 2003-05-28 | 2003-05-28 | Irregular decorative pattern coating glass container and producing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1552654A true CN1552654A (en) | 2004-12-08 |
Family
ID=34322289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031288812A Pending CN1552654A (en) | 2003-05-28 | 2003-05-28 | Irregular decorative pattern coating glass container and producing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1552654A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830698A (en) * | 2017-03-10 | 2017-06-13 | 蓝思科技（长沙）有限公司 | A kind of spraying coating process of 3D glass products |
-
2003
- 2003-05-28 CN CNA031288812A patent/CN1552654A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830698A (en) * | 2017-03-10 | 2017-06-13 | 蓝思科技（长沙）有限公司 | A kind of spraying coating process of 3D glass products |
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