JP3369882B2 - Paint with improved printability and glass substrate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint having improved printability and a glass substrate using the same. More specifically, it eliminates the cissing of the paint that tends to occur when the paint is printed on the glass substrate, The present invention relates to a glass base material which is excellent in leveling and which prevents the increase in viscosity during continuous printing to further improve printability and enables secondary workability such as cutting.

[0002]

2. Description of the Related Art Today, door glass of shops and offices, partition glass, shelf glass, etc. are cut into various shapes according to various designs at the construction site, so secondary workability is only important. In addition, designability including colors is also emphasized.

Conventionally, as a method for coloring glass, a glass frit method in which a colorant comprising a glass frit, a pigment, and a binder is printed on the glass surface and baked at a temperature of 500 ° C. or higher, or a colored polyester film is a polybutyral film is used. A laminated glass method is used in which a laminated glass having a five-layer structure is sandwiched and further sandwiched with glass plates, and a pigment is added to an organic resin for paint, and the glass plate surface is coated with a method such as spraying or brushing.
An organic resin method is known in which heat treatment is performed at a temperature of 00 ° C. or lower to cure and color the resin.

[0004]

However, in the glass frit method, since the glass is baked at a temperature of 500 ° C. or higher, the glass is in a semi-strengthened state during cooling, so that the secondary workability (cutting) cannot be performed. It was Further, the laminated glass method also has a complicated structure and manufacturing process, resulting in a high cost. Further, in the organic resin method, since a low boiling point solvent is used, it is difficult to screen print, and there is a problem that chemical resistance such as acid resistance and base resistance is poor due to weak adhesion between the colored film and glass. Was.

The present invention solves the above problems, allows secondary workability such as cutting, eliminates the cissing of the paint that is likely to occur during printing, and is excellent in leveling after printing. Another object of the present invention is to provide a coating material and a glass base material that prevent further increase in viscosity during continuous printing and further improve printability.

[0006]

[Means for Solving the Problems] That is, according to the invention of claim 1 of the present application, at least one trifunctional silicon alkoxide containing an ureido group is contained in an organic resin in an amount of 1 to 25% by weight and a primary particle diameter of 15 nm. The following is a coating composition having improved printability, which contains 2 to 4% by weight of silica fine powder and 30 to 70% by weight of a high boiling solvent having a boiling point of 150 to 250 ° C., and at a temperature of 150 to 300 ° C. Since baking is possible and the addition of silica fine powder with a primary particle size of 15 nm or less, the repelling of the paint on the glass substrate after printing such as screen printing is eliminated and it remains after printing such as screen printing. It has excellent leveling that the traces of the screen mesh that disappears over time disappears, and the increase in viscosity during continuous printing is reduced, making it possible to print even when the number of printings increases. It

The invention according to claim 2 of the present application is characterized in that the organic resin contains 1 to 25% by weight of at least one trifunctional silicon alkoxide containing a ureido group and a primary particle diameter of 1
2 to 4% by weight of silica fine powder of 5 nm or less, and 15
The high boiling point solvent having a boiling point of 0 to 250 ° C. is 30 to 70
It is a glass base material obtained by heat-treating the coating material for printing containing 100% by weight on the surface of glass at 150 to 300 ° C, and the coating material provided on the base material is capable of polycondensation reaction.
Since it is baked at a temperature of up to 300 ° C and a coating film is attached, secondary workability such as cutting is possible, and a glass substrate having excellent chemical resistance is obtained.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The organic resin used in the present invention is a resin generally used in paints, such as acrylic resin, alkyd resin, polyester resin, epoxy resin,
One or a mixture of two or more of melamine resin, urea resin and the like is dissolved in a low boiling point solvent having a boiling point of 20 to 150 ° C. such as toluene, xylene, acetone, butanol and butyl acetate. Nonvolatile resin content is 30 ~ 8
It is 0% by weight. Among the organic resins used in the present invention, a mixture of an acrylic resin and a melamine resin is particularly excellent in the hardness, transparency, chemical resistance, weather resistance and heat resistance of the glassy film.

3 containing an ureido group used in the present invention
The functional silicon alkoxide is selected from, for example, γ-ureidopropyltriethoxysilane and γ-ureidopropyltrimethoxysilane. The amount added is 1 to 25% by weight, preferably 5 to 15
%, And if less than 1% by weight, the adhesiveness of the membrane,
Chemical resistance decreases. On the other hand, if it exceeds 25% by weight, the film after heat treatment will turn yellow and the heat resistance will decrease.

The high boiling point solvent used in the present invention is 150 to
It has a boiling point of 250 ° C., and examples thereof include carbitol, dimethylformamide, dimethylimidazolidinone, terpinol, diacetone alcohol and the like. The reason for limiting the boiling point to a high boiling point is that when the boiling point is less than 150 ° C, the composition of the present invention tends to be clogged with the mesh of the screen during printing, and when it exceeds 250 ° C, the solvent does not volatilize during heat treatment. is there. The content of the high boiling point solvent is 30 to 70% by weight and is adjusted according to the screen printing conditions.

The fine silica powder used in the present invention is
Amorphous synthetic silica, which is a silicic acid anhydride type obtained by a dry method, has a primary particle size of 15 nm or less, and a typical example thereof is Aerosil. The primary particles are in a state in which the fine powder is not aggregated, the secondary particles are large particles in which the primary particles are aggregated, but the silica fine powder used in the present invention is the primary particles, and the secondary particles are unsuitable. is there. When this silica fine powder is dispersed as primary particles in an amount of 2 to 4% by weight, repellency of the coating material is eliminated, leveling after printing is excellent, and viscosity increase during continuous printing is prevented to further improve printability. If the primary particle size is outside this range, the light transmittance of the coating film after printing will be poor. The addition amount is 2 to 4% by weight as described above. If it is less than 2% by weight, there is a problem that the viscosity increase of the paint during continuous screen printing becomes too large. If it exceeds, the light transmittance will be poor and the leveling after printing will be poor.

In the method for producing a coating material having improved printability according to the present invention, a trifunctional silicon alkoxide containing a predetermined amount of an ureido group is added to an organic resin dissolved in a low boiling point solvent, and a boiling point of 150 to 250 ° C. 20 to 120 ° with a rotary evaporator, etc.
Distillation is carried out at C to evaporate the low boiling point solvent in the organic resin to produce a matrix agent. Then, silica fine powder having a primary particle diameter of 15 nm or less is added to the matrix agent and mixed with a strong shear stirrer such as a homogenizer or an ink roll to prepare a coating material. By using a strong shear stirrer, the silica fine powder can be dispersed mainly as primary particles.

The above paint can be applied directly to the surface of a glass substrate by a screen printing method to adjust the film thickness up to about 500 μm. If the film thickness is made larger than that, bubbles tend to enter during the heat treatment stage. The glass base material used is not particularly limited in terms of material as long as the surface is flat, and therefore alkali glass, quartz glass, float glass, tempered glass, etc. are used. The heat treatment may be carried out under the condition that the mixture of the organic resin and the trifunctional silicon alkoxide undergoes the polycondensation reaction.
It is 10 to 60 minutes under an ambient temperature of 300 ° C. 1
If the temperature is lower than 50 ° C, the polycondensation reaction of the mixture of the organic resin and the trifunctional silicon alkoxide will not occur, and
Above 00 ° C, the coating turns yellow.

This screen-printing procedure is based on a horizontally placed screen (eg polyester plain weave, 255
Underneath the (mesh), a printed circuit board (glass) is placed with a space of several millimeters. After the composition is placed on this screen, a squeegee is used to spread the composition over the entire screen. At this time, there is a gap between the screen and the printed board. Then, the squeegee is pressed against the screen so that the screen comes into contact with the printed board, and the screen is moved to perform printing. After that, this is repeated.

In the present invention, in addition to the above four components, various additives such as silica powder having a secondary particle diameter of 1 to 30 μm, ceramic powder, organic and inorganic pigments, metal powder, fluorescent dye, and ultraviolet absorber are used. , Antibacterial agents can be used.

[0016]

Next, the present invention will be described in more detail with reference to specific examples. Examples 1-2, Comparative Examples 1-5 As shown in Table 1, as an organic resin, an acrylic resin dissolved in toluene, a butylated melamine resin dissolved in butyl acetate, and a trifunctional silicone containing a ureido group. Γ-Ureidopropyltriethoxysilane was used as the alkoxide, and carbitol was used as the high boiling point solvent.

These raw materials are mixed according to the formulation shown in each table, and the mixture is distilled at 90 ° C. by a rotary evaporator to volatilize butyl acetate and toluene in the organic resin, and then have a predetermined particle size. A fine silica powder, silica powder, was added and stirred with a homogenizer to obtain a coating material.
The obtained coating material was screen-printed (polyester # 355 mesh) on a glass substrate and heat-treated for 30 minutes in an oven set at 200 ° C. to complete the polymerization, and a 20 μm-thick coating film was prepared on a glass plate. .

Leveling property after screen printing, cissing, haze ratio of coating film, increase in viscosity during continuous printing,
The results of acid resistance and base resistance of the coating film were obtained. The results are also shown in Table 1. The evaluation method is as follows.

1. After the screen printing of the leveling paint on the glass substrate, the time until there is no mesh behind was measured. In this case, ◯ indicates that almost no time is required, Δ indicates that leveling is performed within about 1 minute, and x indicates that leveling is not performed.

2. Haze ratio of coating film The light transmittance and haze ratio of a coating film prepared on a glass substrate were measured with a turbidimeter. In this case, as the evaluation of the transparency of the coating film after printing, ◯ indicates transparent, Δ indicates a slightly white and turbid state, and X indicates a considerably turbid state.

3. Viscosity increase during continuous printing After screen-printing continuously on 20 glass substrates, the increase in viscosity of the paint was measured with a viscometer. The screen printing was carried out for 30 minutes. When the viscosity of the paint is too great to use after printing 20 sheets, x,
When it could be used, it was marked as ○.

4. Apply the coating film prepared on the acid-resistant glass substrate to 1N hydrochloric acid aqueous solution.
Immersion was carried out for 4 hours, and changes in light transmittance (ΔT) and changes in appearance (discoloration, peeling of coating film) after immersion were examined.

5. The coating film prepared on a base-resistant glass substrate is immersed in a 1N aqueous sodium hydroxide solution for 24 hours, and the change in light transmittance (ΔT) and the change in appearance (discoloration, peeling of the coating film) after immersion. ) Was investigated.

[0024]

[Table 1]

According to these results, the coating material of this example disappears in a short time even after the mesh after printing, has a good leveling property, has a good light transmittance of the coating film, has no cissing, and does not have cissing during continuous printing. It can be seen that the increase in viscosity is small and the printability is excellent. On the other hand, Comparative Example 1 in which silica fine powder is not added, or when the amount of silica fine powder added is small (Comparative Example 2)
In the case of a large amount (Comparative Example 3) or the particle size of silica fine powder (Comparative Examples 4 and 5), the leveling property, the light transmittance of the coating film, the cissing, and the increase in viscosity during continuous printing were observed. It can be seen that there is a problem in the printability judgment because either of them is missing. The acid resistance and base resistance of the coating films formed on the glass substrates of this example and comparative example are excellent.

[0026]

As described above, according to the invention of claim 1 of the present application, by adding a predetermined amount of fine silica powder having a particle diameter of 15 nm or less, the paint repels on the glass substrate after printing such as screen printing. Eliminates the repelling that occurs, and is excellent in leveling where the traces of the screen mesh left after printing such as screen printing disappears over time,
Further, the increase in viscosity during continuous printing is reduced, and there is an effect that printing can be performed even if the number of printings is increased.

Further, in the invention of claim 2 of the present application, after printing the coating material for printing on the surface of the glass, 150 to 300 °
It is a glass base material heat-treated at C, and the coating material provided on the base material is baked at a temperature of 150 to 300 ° C. at which a polycondensation reaction is possible and a coating film is attached, so that secondary workability such as cutting is achieved. It has the effect of becoming a glass base material that is made possible and has excellent chemical resistance.

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C09D 201/02 B32B 17/10 C03C 17/30 C09D 7/12

Claims (2)

(57) [Claims] 1. At least one trifunctional silicon alkoxide containing an ureido group is added to an organic resin in an amount of 1 to 2.
2% silica fine powder having a primary particle diameter of 15 nm or less at 5% by weight
A paint having improved printability, characterized in that it contains 30 to 70% by weight of a high boiling point solvent having a boiling point of ˜4% by weight and a boiling point of 150 to 250 ° C. 2. At least one trifunctional silicon alkoxide containing an ureido group is added to the organic resin in an amount of 1 to 2.
2% silica fine powder having a primary particle diameter of 15 nm or less at 5% by weight
-4% by weight and 30-70% by weight of a high-boiling solvent having a boiling point of 150-250 ° C is printed on the surface of glass and then heat-treated at 150-300 ° C. And a glass substrate.