The following is a condensed translation of the Japanese patent. Go to for the complete patent (original Japanese or English machine translation), go to https://www.j-platpat.inpit.go.jp/ and search for patent number: 6567788
(19) [Publication country] Japan Patent Office (JP)
(12) [Kind of official gazette] Published examined patent application (B1)
(11) [Patent number] Japanese Patent No. 6567788 (P6567788)
(24) [Registration date] August 9 (2019.8.9)
(45) [Publication date] 2019/8/28
(54) [Title of the invention] Glass coating layers formed by coating application
(51) [International Patent Classification]
C03B 8/02 (2006.01)
B05D 7/24 (2006.01)
B05D 1/36 (2006.01)
B32B 17/00 (2006.01)
[Problem] To provide a method for forming a glass coating layer capable of creating desirable characteristics such as high impact resistance to a surface of various products including those made of plastic, metal, rubber, wood, paper but especially for glass.
[Method] (1) thorough mixing a polysilazane, silicate and an organic solvent causes a reaction of the water in the organic solvent with the polysilazane and the silicate to obtain a pretreatment liquid containing colloidal silica fine particles (2) further mixing the polysilazane with the pretreatment liquid (3) When applied to object, coating forms layers with a stone wall structure that can be repeated with more applications.
Scope of Claims
(1) mixing and stirring a polysilazane, a silicate, and an organic solvent with water in the organic solvent reacting with the polysilazane and the silicate to obtain a pretreatment liquid containing colloidal silica fine particles
(2) further mixing the polysilazane with the pretreatment liquid to obtain a coating composition ;
(3) applying a coating composition to an object to be coated a number of times to form a glass coating layer that has a stone wall structure
The present invention relates to a method of forming a glass coating layer which is useful for surface modification of various goods and the glass coating layer obtained by the method.
[Background of the Invention]
Many goods with resin, metal, glass, rubber, leather, wood and paper surfaces are in use.
While these have good physical properties such as ease of molding, coloration, electrical insulation and the like, they are softer than a metal and glass surfaces and vulnerable to scratching.
In addition, while metal objects may have excellent surface scratch resistance, they may dent when dropped or hit, and glass glass will crack.
In Patent Document 1, for example, Patent Document 2 discloses a method of producing a silica film coated article in which a silane coupling agent is applied on a substrate to form a solid film, a layer of a polysilazane containing liquid is formed on the solid film, and a silica conversion reaction occures. It is proposed to provide a method of manufacturing a hydrophilic silica film resin molded article in which a mixed solution of polysilazane and polystyrene is applied to a surface of a resin molded article, or a resin molded article is immersed in a mixed solution of polysilazane and polystyrene to be air dried.
In addition, in the method using a polysilazane coating, a high temperature is required to form a film, and it is difficult to apply to a plastic product having a low heat resistance, so that Patent document 3 is used. It is proposed that “poly (alkyl) – silazane compound” and perhydropolysilazane be dissolved in an inert organic solvent at a concentration of from 1 to 40% by weight of these 2.
[Patent document 1]JP 2003-183016A
[Patent document 2]JP 2006-89674A
[Patent document 3]The description of Japanese Patent No. 4767317
[Problem to be solved by the invention]
However, when a coating layer is formed on the surface of an iron plate or an acrylic plate by using the coating agent of Patent Document 3, the coating layer has a sufficient hardness and is excellent in bending peelability, impact resistance, and film formability, but when dropped, the coating layer may be lost.
In addition, particularly with portable devices to include smart phones in recent years, glass displays often causes a crack or break when dropped or hit. Even if a coating layer is formed on the surface of a glass plate using the coating agent of Patent Document 3, this cannot be sufficiently suppressed.
This goal of the present invention is to provide high surface protection to plastic, metal, wood and particularly glass objects by provide a method for forming a glass coating layer capable of imparting characteristics such as an excellent impact deformation resistance.
[Means for solving the problem]
(1) Mixing and stirring polysilazane, a silicate, an organic solvent, and water in the organic solvent reacting with the polysilazane and the silicate to obtain a pretreatment liquid containing colloidal silica fine particles.
(2) mixing the polysilazane with the pretreatment liquid to obtain a coating composition
(3) applying a coating composition to an object to be coated a number of times to form a glass coating layer having a stone wall structure.
A method for forming a glass coating layer is provided.
In the method for forming a glass coating layer of the present invention, it is preferable that the polysilazane contains an organic polysilazane and an inorganic polysilazane.
In the glass coating layer forming method of the present invention, it is preferable that the catalyst be a Pd catalyst.
In the method of forming a glass coating layer of the present invention, it is preferable that the surface to be coated be made of plastic, metal, glass, rubber, resin, leather, wood or paper.
The present invention also provides a glass coating layer formed by the glass coating layer forming method of the present invention, wherein the glass coating layer has a stone wall structure.
[Effect of the Invention]
According to the method of forming a glass coating layer of the present invention and the glass coating layer obtained by the method, excellent characteristics such as impact resistance can be imparted to the surface of articles such as plastic molded articles, metal molded articles, glass molded articles, rubber molded articles, leather molded articles, woody articles and paper products, among others.
The vitreous coating layer formation method and the glass coat obtained by this of the present invention
When applying the coating, it is not necessary to mix other additives and chemical liquids and the glass coating layer can be formed on the surface of various products at room temperature in a short time. Further, in the glass coating layer forming method and the glass coating layer obtained by the method of the present invention, multiple coating can be performed multiple times. Excellent peel and protective properties remain even when a glass coating layer having a thickness of 1 to 10 μ m or more is formed on the surface of various molded articles and bent. In addition, a glass coating layer having a pencil hardness of 6 to 9 H or more is obtained with excellent film formability, flexibility, impact resistance and adhesion.
[Brief Description of the Drawings]
[Fig. 1]FIG. 4 is a transmission electron microscope (TEM) image of a cross-section of a glass coating layer
[Best mode for carrying out the invention]
Hereinafter, a method of forming a glass coating layer according to an embodiment of the present invention and a glass coating layer obtained by the method will be described, but the present invention is not limited thereto.
1. Vitreous Coating Layer Formation Method
In the method for forming a glass coating layer of the present embodiment, (1) a polysilazane, a silicate, and an organic solvent are mixed and stirred, and moisture in the organic solvent is used. The aforementioned polysilazane and the aforementioned silicate are made to react, and the aforementioned polysilazane is further mixed to the first process and the (2) aforementioned pretreatment liquid which obtains the pretreatment liquid containing a colloid silica particle, A 2 step of obtaining a coating composition and a 3 step of forming a glass coating layer having a stone wall structure by applying the coating composition to an object to be coated are included in the step (3).
(1) First step
In a first step, polysilazane, a silicate, and an organic solvent are mixed and stirred, and water in the organic solvent is reacted with the polysilazane and the silicate, and stirring is continued until generation of gas is stopped, thereby obtaining a pretreatment liquid containing fine colloidal silica particles. Mixing may be performed by a conventionally known method, and may be mixed at room temperature (e.g., 15 to 30 ° C., preferably 20 to 25 ° C.) and atmospheric pressure.
The inventors have found that if polysilazane, a silicate, and an organic solvent are mixed and stirred, the water contained in the organic solvent reacts with the polysilazane and the silicate to form colloidal silica fine particles. The inventors have found that a glass coating layer having unprecedented structure and characteristics can be formed through the second and the third steps described below.
As the polysilazane, the following organic polysilazane and / or inorganic polysilazane can be used.
The organic polysilazane in the present invention is represented by, for example, the following formula (1)
(SiR 1 R 2 NR 3) -. (1)
(In the formula, R 1, R 2 and R 3 each independently represents a hydrogen atom, an alkyl group or a vinyl group, and R 1, R 2 and R 3 each represents a hydrogen atom.
The compound which comes out and has a main framework consisting of the unit shown.
As an example of an organic polysilazane having a main framework consisting of units represented by formula (1), R 1 is represented by the following formula :
Examples thereof include a compound having a main framework of the formula (1) wherein R 2 is independently a hydrogen atom or a methyl group, and R 3 is a hydrogen atom or a tri (C 1-6 alkoxy) silyl C 2-6 alkyl group such as a 3 – (tri C 1-6 alkoxysilyl) propyl group.
As an example of a specific combination of (R 1, R 2, R 3) in Formula (1), (R 1, R 2, R 3) is (methyl group, hydrogen atom, hydrogen atom), (methyl group). The combination which is a methyl group, a hydrogen atom, (a methyl group, a methyl group and a methyl group), (a methyl group, a methyl group, a 3-(triethoxysilyl)propylgroup (a hydrogen atom, methyl, 3-(triethoxysilyl)propylgroup)), etc. is mentioned.
Further, the organic ******* may be composed of the same repeating unit or may contain different repeating units.
The organic polysilazane may be soluble in a solvent or may be uniformly dispersed in a solvent. Further, the number average molecular weight of the organic polysilazane (A) to be used is preferably 100 to 50000, more preferably 300 to 10000.
Further, the organic polysilazane may be one having a chain, a cyclic or a crosslinked structure, or one having a plurality of these structures in the molecule at the same time. In the present invention, any of these may be used, and each of these may be used alone or in any combination.
Examples of the organic polysilazane include at least 1 selected from hexamethyldisilazane, **********, cyclotetrasilazane, and tetra methyldisilazane. These can be obtained from the market and used. Particularly preferred is hexamethyldisilazane available under the trade name HMDS 3 from Shin-Etsu Chemical Co., Ltd.
Further, under the trade name of “******”, it is commercially available from Sanwa Chemical Co., Ltd. under the trade name of “HTa 1500” or the like, and this product can be obtained and used as an organic solvent.
– Inorganic polysilazane
In the present invention, in addition to the organic polysilazane, the following formula (2) is used.
(SiH 2 NH) -. (2).
It is preferred to use an inorganic polysilazane, I. e., perhydropolysilazane, which is a compound having a structure consisting of units shown.
Inorganic polysilazane is a compound composed solely of silicon, nitrogen and hydrogen, and is an inorganic polymer that does not contain an organic component such as carbon, and the like. For example, under the trade name of “Aquamica”, a product of AZ Electronic Materials Co., Ltd. is available from AZ Electronic Materials Co., Ltd., and these products can be obtained and used as an organic solvent solution having various solid concentrations. NN110,NN310,NL110A,NL120A,NL150A,NL160A,NP110,NP140,SP140,UP140. Particularly preferred is the product No. NL 120 a which is a solution of dibutyl Ether.
Further, under the trade name of “******”, the product is commercially available from Sun Chemical Co., Ltd. under the trade name of an item number ANN 100, a ANAX system, an ANP 140 system, an ANP 300 system and the like. These products can be obtained and used as organic solvents of various solid concentrations.
(B) silicate ;
A silicate (silicate) performs the role which reacts also to a polysiloxane and promotes formation of a colloid silica particle while itself hydrolyzes with moisture. As such a silicate, so-called alkoxysilane (so-called inorganic binder) can be used.
For example, the alkoxysilane may be a compound in which 3 to 4 alkoxy groups are bonded to silicon, and when dissolved in water, the alkoxysilane is polymerized to form a high molecular weight SiO. sub. 2 body that is linked to – OSiO. sup. -.
As the alkoxysilane, one containing at least 1 kinds of polyfunctional alkoxysilanes selected from the group consisting of tetraalkoxysilane, trialkoxysilane, dialkoxysilane and alkoxysilane oligomer can be used. The alkoxysilane oligomer is an alkoxysilane having a high molecular weight formed by condensation of monomers of an alkoxysilane, and is an oligomer having 1 or more siloxane bonds (- OSiO -) in 2 or more molecules.
Examples of the tetraalkoxysilane include silane tetrasubstituted with an alkoxy group having 1 to 4 carbon atoms such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraiso-propoxysilane, and tetrat-butoxysilane. Specific examples thereof include “ethyl silicate 28 (molecular weight 208)” manufactured by Corcoat Co., Ltd.
Examples of the trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, triiso-propoxysilane, and triiso-propoxysilane. Examples thereof include silanes substituted with an alkoxy group having 1 to 4 carbon atoms, such as tri-butoxysilane, and silanes substituted with an alkyl group, such as “KBM – 13 (methyltrimethoxysilane)” and “KBE-2 (methyltriethoxysilane)”, and the like. 13.
Silang by which disubstituted was carried out as an example of the above-mentioned dialkoxy silane by the alkoxy group of the carbon numbers 1-4, such as dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyl diethoxysilane, and diphenyl diethoxysilane, Examples thereof include silanes in which a part of “KBM – 22 (dimethyldimethylsilane)” and “KBE- 22 (dimethyl diethoxysilane)” are substituted with an. dimethoxy.
Further, examples of the alkoxysilane small molecule oligomer include an alkoxysilyl group alone or a relatively low molecular weight alkoxysilane oligomer having an organic group and an alkoxysilyl group. Specific examples thereof include “Methylsilicate 51 (molecular weight 470)” manufactured by Corcoat Co., “ethyl silicate 40 (molecular weight 745)”, “X – 40 2308 (molecular weight 683)” manufactured by Shin-Etsu Chemical Co., Ltd.
In order to form a glass coating layer having a higher hardness, the present invention provides a method for producing an alkoxysilane. Preferred is a combination of tetraalkoxyoxysilane, tetraalkoxysilane and trialkoxysilane, a trialkoxysilane or dialkoxysilane in which a part is substituted with an alkyl group, and an alkoxysilane oligomer in which a functional group is an alkoxysilyl group. By using these, it is possible to further eliminate the risk that the hardness of the glass coating layer is increased by 3 dimensional crosslinking of siloxane bonds between the binder molecules, and to further enhance the adhesion of the surface to be coated.
(C) Organic solvent
The pretreatment liquid in the present invention contains an organic solvent together with the polysilazane (A) and the silicate (B). It polysilazane [ above-mentioned / organic ] (A) Reaches and describes above as this organic solvent.
There is no particular limitation on the organic solvent which is inert to the inorganic polysilazane (B).
Methanol, ethanol, n-propanol, isopropyl alcohol and the like can be mentioned from the viewpoint of appropriate swelling property, volatility and environmental hygiene on the surface of a plastic molded article or the like. Further, it is preferable to use an ether organic solvent, for example, at least one selected from dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether and limonene. The inventors have experimentally found that isopropyl alcohol is suitable in the first step.
Furthermore, the pretreatment liquid may include a catalyst for accelerating curing at a low temperature or at a normal temperature. Curing can be performed at a low temperature depending on the type and amount of the catalyst, and in some cases, curing can be performed at room temperature (for example, 15 to 30 ° C, preferably 20 to 25 ° C). It includes a catalyst, which is preferably in the form of a solution and includes a base catalyst, a metal catalyst, and the like.
Examples of the base catalyst include amines (e.g., monoalkyl amine, dialkylamine, trialkylamine, diethylpropylamine, monoarylamine, diarylamine, and cyclic amine) and nitrogen-containing heterocycles (e.g., 2,6 – lutidine, 4-methylmorpholine, and the like).
Examples of the metal catalyst compounds include nickel, tin, titanium, platinum, rhodium, cobalt, iron, ruthenium, osmium, palladium, iridium, and aluminum. In particular, the present inventors have found experimentally that an aqueous palladium chloride solution containing palladium is suitable.
The concentration (mixing ratio) of each component in the pretreatment liquid may be appropriately determined as long as the effect of the present invention is not impaired. For example, 20 to 40 cc of organic polysilazane, 40 to 60 cc of inorganic polysilazane, and isopropyl alcohol. It is sufficient that the silicate 28 containing 300 to 500 cc is used. .
2 Step (2)
Next, the polysilazane is further mixed with the pretreatment liquid containing the colloidal silica fine particles to obtain a coating composition. Mixing may be performed by a conventionally known method, and may be mixed at room temperature (e.g., 15 to 30 ° C., preferably 20 to 25 ° C.) and atmospheric pressure.
The polysilazane mixed at this time, when forming a glass coating layer, the colloidal silica fine particles in the pretreatment liquid form large glass particles, but play a role of filling and bonding between the glass particles, The inventor has speculated.
It has been found experimentally that the coating composition preferably comprises an organic solvent as described above and a catalyst as described above. In particular, we have found experimentally that in the 2 step, a t- butyl ether and a palladium catalyst are suitable.
The concentration of each component in the coating composition (blending ratio) may be appropriately determined as long as the effect of the present invention is not impaired. It is sufficient that 3 to 4 liters of dibutyl Ether, 200 to 300 cc of organic polysilazane, 20 to 40 cc of inorganic polysilazane, and 3 to 6 cc of a 20% dibutyl Ether solution of palladium chloride catalyst are used.
When the viscosity of the obtained coating composition is high, the strength of the obtained glass coating layer increases, and when the viscosity is low, the strength of the obtained glass coating layer tends to decrease.
3 Step (3)
Then, the coating composition is applied to an object to be coated to form a glass coating layer having a stone wall structure. It may be applied one or more times. However, in order to form a glass coating layer having high hardness and strength, as well as buffering properties and flexibility, it is preferable to apply as many times as possible as uniformly as possible.
The inventor uses the speed and hardness at which the colloidal silica fine particles in the pretreatment liquid prepared in the first step cure and the speed and hardness at which the polysilazane added in the second step cures, using the colloidal silica. A coating layer having a stone wall structure in which relatively hard and soft parts coexist is formed as a reaction product by the stone part made of fine particles and the joint part made of polysilazane that fills and bonds between multiple stone parts.
In this stone wall structure, different forms of glass silica are composited. Basically, a composite coating layer is formed. The relatively hard part and the soft part exist alongside and buffer each other. If the object coated having the obtained glass coating layer on the surface is, for example, a glass plate, it may not crack or break even when hit.
Note that there is no particular limitation on what the coating can be applied to. The surfaces to be coated (surfaces to be treated) may be made of plastic, metal, glass, rubber, resin, leather, wood or paper. Also, there is no particular limitation on the shape of the article or surface. In particular, the inventor has found experimentally that a surfaces of a smart phones, tablets and display units made of a glass are particularly suitable for treatment.
There is no particular limitation on the method of applying the coating and examples include the following methods most suitable for the shape of an article to be coated or a surfaces to be processed such as by hand, spray, dipping, brush and roll coating, flexographic, ink jet and the like.
Unlike conventional methods, a hand coat method can be used from the viewpoint of curing speed as described above. For example, by hand coating, even if an article to be coated or a surface to be treated has a complicated shape, a uniform coating layer can be easily be formed.
Although there is no particular limitation on the amount of coating, the amount of coating may be determined according to the surface performance required for the article to be coated. In general, it is a 0.1~100g/m2 in terms of solid content, and preferably 1 to 20 g / m 2. If the coating amount is 0.1 g / m 2 or more, a coating layer having sufficient characteristics can be formed. If the coating amount is 100 g / m 2 or less, the transparency of the coating layer can be reliably maintained and the design of the article to be coated and the surface to be processed can be protected from damage.
A notable feature of the method of forming a glass coating layer of the present invention is that after application of the coating composition as described above, no special heating is required for curing. Although the formation of the coating layer is promoted by heating the coating layer, it is not advisible because it may affect the article to be coated and the surface protected.
Regular curing accomplished by evaporation of the organic solvent in the coating composition and the moisture into the air.
After a reaction with water, an example curing rate is dry to the touch in 2 hours, and a film having a pencil hardness of 6 to 9H or more in about 2 to 3 days.
(1) 50 cc of dibutyl Ether 10% of hexamethyldisilazane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name : HMDS 3) as an organic polysilazane; 30 cc of a 10% solution of perhydropolysilazane as an inorganic polysilazane (trade name : Aquamica NL 120 a, manufactured by Clariant Japan Co., Ltd.) and 400 cc of ethyl silicate 28 containing isopropyl alcohol manufactured by Corcoat Co., Ltd. were mixed and stirred for 10 minutes, and then stirred for several minutes. Thus, a pretreatment liquid containing colloidal silica fine particles is prepared. It was confirmed by an electron microscope that colloidal silica fine particles were formed.
(2) Next, 4 liters of dibutyl Ether, 200 cc of the same organic polysilazane, 30 cc of inorganic polysilazane, and 5 cc of a 20% dibutyl Ether solution of palladium chloride were mixed with each other to prepare a dispersion liquid coating composition.
(3) 17 used iPhones 4 (registered trademark) manufactured by Apple Corporation were prepared, and the coating composition prepared as described above was applied on the display by a hand coating method using a nonwoven fabric. Specifically, a nonwoven fabric soaked with a coating composition under an environment of room temperature (20 ° C.) and pressure was applied by rubbing the whole display in a circular shape. The process was then repeated a few times and coating composition was allowed to dry and cure for 2 days. Next, the following evaluation tests were conducted.
(1) Surface hardness (H) ;
The surface hardness of the obtained glass coating layer was measured as pencil hardness according to JIS standards with a surface hardness of 9H.
2) Drop test
An iPhone 4 (registered trademark) having a glass coating layer formed thereon was dropped from a a height of 1 m onto concrete. After inspection, no crack or cracks were found.
(3) Impact resistance
A DuPont impact deformation test was performed on a display having a glass coating layer formed thereon, and it was visually observed whether or not cracks or cracks occurred in the display. No cracks were found.
(4) A film-forming sex
Surface was checked as to whether or not a clear, smooth coating layer was formed. A good film (glass coating layer) was formed.
(5) Structural observation
The cross-sectional structure of the glass coating layer formed as described above was observed using a transmission electron microscope (TEM) under the conditions of FEI Technai G2, F30 (300 kV), use of Gatan Enfina, and a beam focusing diameter of 0.7 nm. . The result is shown in FIG. 1. The size of the scale bar is 200 nm.
From the above results, it was found that according to the method for forming a glass coating layer of the present invention, a glass coating layer having a sufficient hardness and excellent drop resistance, impact resistance, and film formability was obtained. It is particularly effective for smartphones and the like in the drop resistance and impact resistance test of the glass display.
As shown in FIG. 1, a portion (stone portion) made of colloidal silica fine particles, a portion (joint portion) made of glass silica filling the space therebetween, and a complex stone wall-like structure were formed. It was recognized that a glass coating layer, which could be called a so-called composite coating layer, was formed. As a result, it is presumed that the drop resistance and impact resistance of the glass display were improved.
The glass coating layer forming method and the glass coating layer obtained by the method of the present invention can impart excellent characteristics such as an excellent impact resistance to the surfaces of plastic molded articles, metal molded articles, glass molded articles, rubber molded articles, leather molded articles, wooden articles and a paper products (particularly glass molded articles).