JPH11228177A - Ceramic color composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the reduction of strength to a minimum without deteriorating light shielding property by incorporating a powdery solid Component consisting of a black low m.p. glass powder having a specified compsn. and an inorg. pigment and a specified proportion of an org. vehicle to the solid component. SOLUTION: The ceramic color compsn. contains a powdery solid component consisting of 70-99 wt.% black low m.p. glass powder and 1-30 wt.% inorg. pigment and 35-100 pts.wt. org. vehicle based on 100 pts.wt. of the solid component. The black low m.p. glass powder is preferably obtd. by incorporating 1-20 wt.% one or more coloring components selected from CuO, CoO, MnO, Cr2 O3 , Fe2 O3 , Ni2 O3 , Co3 O4 and FeS into an ordinary low m.p. glass powder. The org. vehicle is preferably prepd. by dissolving 10-50 wt.% flammable resin such as cellulose resin in 50-90 wt.% solvent such as pine oil.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a ceramic color composition applied to, for example, an automobile window glass, and more particularly to a ceramic color composition applied to a thinned window glass.

[0002]

2. Description of the Related Art A ceramic color using a low-melting glass powder is baked from the inner side of a vehicle window glass, for example, a rear window glass, around a body side during bending and strengthening. This is intended to prevent the organic adhesive bonding the automobile body and the glass from being deteriorated by ultraviolet rays, to hide the protruding portion of the adhesive, to design the obtained window glass, and the like.

[0003] Conventionally, this ceramic color has been applied by screen printing or the like to the periphery of a flat sheet glass previously cut into a predetermined shape, temporarily dried, and baked simultaneously with bending and strengthening by heating the sheet glass. I have. Further, conventionally, for improving the yield of the baking process, and for eliminating the lead component contained in the low-melting glass, a composite printing with a silver paste and a ceramic color composition for eliminating problems at the time of firing are used. Various improvements have been proposed.

[0004] Such ceramic color compositions include:
Conventionally, regardless of the composition of the low melting point glass powder used, 55 to 70% by weight of the low melting point glass powder and 30 to 45% of the inorganic pigment are used.
Solid content powder containing as much inorganic pigments as possible
A rich solid content powder containing 20 to 30 parts by weight of an organic vehicle with respect to 100 parts by weight of the solid content powder is exclusively used. When printing the composition, a coarse screen of 100 to 200 mesh has been used. These are intended to improve the light shielding property, which is the main purpose of applying a ceramic color to an automotive window glass. That is, the conventional ceramic color increases the shielding power by increasing the inorganic pigment concentration, decreases the organic vehicle content, and increases the film thickness after firing by using a coarse screen mesh (normal film thickness:
(Approximately 12 to 20 μm) to further increase the shielding power.

However, the above-described conventional ceramic color composition and its application technology go against the demands of the industry in view of the strength of the baked sheet glass against impact from the uncoated surface. Things. That is,
The impact strength from the uncoated surface of the glass plate on which the ceramic color is baked is reduced by 50 to 60% as compared with the case where the ceramic color is not applied. It is already well known in the art that an increase in the thickness of a ceramic color or an increase in the amount of an inorganic pigment is correlated with the above-described decrease in strength.

Conventionally, the disadvantage of the impact strength deterioration due to the ceramic color coating and baking is that the thickness of the glass sheet used for the rear window glass is 3 mm or more (for example, 3.1 mm, 3.5 mm).
mm, 4.0 mm, etc.), and at present it has been covered with this sheet glass thickness.

However, in recent years, as typified by electric vehicles, movements to reduce the weight of vehicle bodies have necessitated a need to reduce the thickness of window glass. Sheet thickness is beginning to be adopted.
Under these circumstances, maintaining and improving the strength of the sheet glass has become an important issue, and for that purpose, it is necessary to improve the heating and strengthening process. It has become a very important issue. In particular, this strength deterioration is caused by, for example, destruction of the sheet glass in a pressure bonding step of bonding the sheet glass to an automobile body, destruction in an encapsulation step of forming a mold by injection molding urethane resin or vinyl chloride resin around the sheet glass in advance, This is a serious problem of automotive window glass against destruction due to various impacts encountered later.

[0008]

SUMMARY OF THE INVENTION As described above, the object of the present invention is to provide a conventional glass plate for an automobile window, which has become incapable of coping with a decrease in strength due to a decrease in the plate thickness. Even if the thickness of the above-mentioned glass sheet is reduced to 3 mm or less by solving the drawbacks of the ceramic color composition of It is an object of the present invention to provide an improved ceramic color composition which can be suppressed to a minimum, and does not reduce the light shielding property which is its original purpose.

The present inventor has set out the following in order to achieve the above object.
From the new idea of coloring the low-melting glass powder itself for light shielding, as a result of intensive research, the following specific black-based low-melting glass powder was used, and a predetermined mixture of this and an inorganic pigment was mixed with an organic pigment. It has been found that a new ceramic color composition that satisfies both the strength and light shielding properties meeting the above-mentioned purpose can be obtained when the vehicle and the vehicle are blended in a specific ratio. The present invention has been completed based on such findings.

[0010]

That is, according to the present invention,
A solid content powder comprising 70 to 99% by weight of a black low melting glass powder and 1 to 30% by weight of an inorganic pigment, and 35 to 100 parts by weight of an organic vehicle with respect to 100 parts by weight of the powder. A ceramic color composition is provided.

In particular, according to the present invention, the black low melting point glass powder contains CuO, CoO, MnO,
1 to 20% by weight of at least one coloring component selected from Cr ₂ O ₃ , Fe ₂ O ₃ , Ni ₂ O ₃ , Co ₃ O ₄ and FeS
The above-mentioned ceramic color composition and organic vehicle contain 10 to 50% by weight of a resin component in a solvent of 50 to 90%.
The present invention provides the ceramic color composition, which is dissolved in a weight%, and the ceramic color composition applied to the glass sheet for automobile windows, and the automotive window glass painted by applying the ceramic color composition.

According to the use of the ceramic color composition of the present invention, the ceramic color baking film can be inevitably thinned, and a desired light shielding property can be maintained even when the concentration of the inorganic pigment is reduced. According to the thinning of the ceramic color,
Deterioration of strength of the sheet glass due to ceramic color baking can be suppressed. This means that the thickness of the glass sheet can be reduced, which meets the needs of the art.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The black low melting point glass powder used in the ceramic color composition of the present invention is more preferably an ordinary low melting point glass powder and Cu as a glass component.
O, CoO, MnO, Cr ₂ O ₃ , Fe ₂ O ₃ , Ni ₂ O ₃ ,
It may contain at least one oxide selected from Co ₃ O ₄ and FeS as a coloring component in an amount of 1 to 20% by weight.

Here, the low melting point glass as the mother glass may be any of various kinds of glass conventionally used for this kind of ceramic color. Examples thereof include lead borosilicate glass containing PbO, Si ₂ O and B ₂ O ₃ as main components, bismuth borosilicate glass containing Bi ₂ O ₃ , SiO ₂ and B ₂ O ₃ as main components, ZnO, Examples thereof include zinc borosilicate glass containing SiO ₂ and B ₂ O ₃ as main components.

An example of a preferable composition of the mother glass is as follows.

[0016] PbO-SiO ₂ -B ₂ O ₃ based glass: PbO 40 to 65 _{wt% SiO 2 25~40 B2O 3 0~15 TiO} 2 0~20 ZrO 2 0~ 5 Al 2 O 3 0~ 5 ZnO 0 _{~10 Li 2 O 0~ 5 Na 2} O 0~ 5 K 2 O 0~ 5 F 0~ 5 Bi 2 O 3 -SiO 2 -B 2 O 3 based glass: Bi ₂ O ₃ 40~75 wt% SiO _{2 15~45 B 2 O 3 1~15 ZrO 2} 1~15 TiO 2 0~ 5 Li 2 O 0~ 5 Na 2 O 0~ 5 K 2 O 0~ 5 F 0~ 5 ZnO-SiO 2 -B 2 O ₃ series glass: 35 to 50% by weight of SiO ₂ B ₂ O ₃ 1 to 9 ZnO 20 to 40 TiO ₂ 1 to 10 Li ₂ O 1 to 10 Na ₂ O 1 to 10 K ₂ O 0 to 10 ZrO ₂ 0 to 5 _{V 2 O 5 0~ 5 F 0~} 5 above the mother glass is fused to the glass sheet in the mother glass alone What degree is in the range of 500 to 650 ° C., a coefficient of linear expansion is preferably those in the range of 50 to 85 × 10 ^-7. The mother glass has a temperature range of 550 to 700 for baking on sheet glass.
It may be either one that crystallizes at ° C. or one that is amorphous. In particular, when applied to a sheet glass that is pressed in a furnace, vacuum-suction-molded, and pressed out of the furnace, a mother glass that crystallizes is preferable in terms of mold release properties. Further, it is preferable that the mother glass is excellent in acid resistance.

The black low-melting glass powder used in the present invention is not a mixture of a colorless low-melting glass powder and the above-mentioned oxide or sulfide powder as a predetermined coloring component, but a glass batch. It is important that the colored glass obtained by adding the above-mentioned predetermined coloring component as a component and melting at 1000 ° C. or higher is powdered.

Here, the colored glass components contained in the mother glass are CuO, CoO, MnO, Cr ₂ O ₃ , Fe
_It is preferable to be selected from ₂ O ₃ , Ni ₂ O ₃ , Co ₃ O ₄ and FeS. In the case of an oxide, the coloring component becomes black by a combination of the above two or more kinds. Preferred examples of the combination include CuO—Cr ₂ O ₃ , CuO—MnO—Cr ₂ O ₃ ,
r ₂ O ₃ —Fe ₂ O ₃ , CoO—Cr ₂ O ₃ —Fe ₂ O ₃ , MnO—
_{Cr 2 O 3 -Fe 2 O 3} -Co 3 O 4, MnO-Cr 2 O 3 -Fe 2
O ₃ -Ni ₂ O ₃ -Co ₃ O ₄ , Cr ₂ O ₃ -Co ₃ O _{4 and the} like can be mentioned. When the above-mentioned Cr ₂ O ₃ is contained, the more this is, the more greenish black low melting point glass powder can be obtained. Fe ₂
When O ₃ is contained, black low melting point glass powder colored more brownish black as the content of O ₃ increases and bluish black as CoO or CuO is contained as the content of CoO or CuO is increased. The black low-melting glass powder of the present invention includes all of the colored black low-melting glass powder having a color tone such as green, brown, and blue.

FeS, which is a sulfide, can be used alone or mixed with the above-mentioned black-colored oxide component at an arbitrary ratio.

The color tone of the black low-melting glass powder used in the present invention varies depending on the type of the mother glass used and the melting conditions. It is preferable to determine the combination and ratio of the glass and the colored glass component, and it is particularly preferable that the amount of the colored glass component used is selected from the range of 1 to 20% by weight. When the content of the colored glass component is much less than 1% by weight, when printing and firing a ceramic color using the obtained black low-melting glass powder, even if a maximum of 30% by weight of a black pigment is blended as an inorganic pigment, In addition, there is a disadvantage that light shielding properties are insufficient. Conversely, if the colored glass component is used in an excessive amount exceeding 20% by weight, the resulting black low-melting glass powder has an excessively high viscosity at a high temperature, and can be baked on a sheet glass at a desired low temperature. It will be difficult. The preferred amount of the colored glass component is usually selected from the range of 5 to 15% by weight.

Hereinafter, the method of preparing the black low melting point glass powder will be described in detail.
The raw materials to be 99% by weight and the colored glass component 1 to 20% by weight are mixed to obtain a batch composition.
It is obtained by melting at a temperature of 1 ° C. or higher, usually about 1100 ° C. to 1300 ° C., rapidly cooling the melt in water, and pulverizing the obtained glass in a wet or dry system using, for example, a ball mill. The particle size of the black low melting glass powder thus obtained is usually about 0.1 to 20 μm, preferably 0.5 to 20 μm.
Suitably, it is about 10 μm.

The ceramic color composition of the present invention comprises 70 to 99% by weight of a black low melting glass powder having a color hiding ability obtained as described above, and 1 to 30% by weight of an inorganic pigment as an auxiliary color hiding material. It is important to contain 100 parts by weight of a solid content powder consisting of 35 to 100 parts by weight of an organic vehicle.

Here, the same inorganic pigments as those conventionally used can be used.
The inorganic pigments include, for example, CuO, Cr ₂ O ₃ , CoO, M
A combination of nO, Fe ₂ O _3, and the like, and preferably a combination of two or more selected from the above-mentioned oxides, which includes a black color is included.

The use of the above-mentioned inorganic pigment in the present invention, unlike the conventional ceramic color composition, is intended only to assist the light shielding property of the black low melting point glass powder. That is, in the present invention, the above-mentioned inorganic pigment is used in order to make the light-shielding property which is insufficient only with the black-based low-melting glass powder sufficient. The smaller the inorganic pigment is, the more preferable it is in view of the strength of the plate glass to which the composition of the present invention obtained by blending the inorganic pigment is baked. Usually, about 1% by weight of the weight of the solid content powder can sufficiently provide the above-mentioned light-shielding assisting effect. The preferred amount is in the range of about 5 to 20% by weight.

In the ceramic color composition of the present invention, as long as the above-mentioned black low melting point glass powder and inorganic pigment are used as the solid content powder, the following known various powders may be further appropriately used, if necessary. It can be added and blended.

That is, when it is desired to adjust the obtained ceramic color film to a color tone other than black,
Other inorganic pigments such as white, blue, brown, etc. can be added. In addition, for adjusting the fusion temperature, an inorganic filler such as alumina, silica, and zirconia, and for adjusting the coefficient of linear expansion, a low-expansion powder, for example, β-eucryptite, β-spodumene, cordierite, Fused silica or the like can be added.

As the organic vehicle constituting the composition of the present invention, 10 to 50% by weight of a highly flammable resin is mixed with a solvent of 50 to 50% by weight.
Those dissolved in 90% by weight can be used. Here, as the raw material of the organic vehicle, various resins and their solvents can be used without being particularly different from the conventional ones. Examples of the solvent include pine oil, α-terpineol, butyl carbitol, butyl carbitol acetate, propylene glycol, and the like. As the resin, for example, a resin having good thermal decomposability such as a cellulose resin, an acrylic resin, a methacrylic resin, a butyral resin, and a vinylpyrrolidone resin can be preferably used. In the present invention, instead of a heat-drying organic vehicle using a solvent, an organic vehicle in which an ultraviolet-curable acrylate or methacrylate oligomer, a polymer, and a photopolymerization initiator are dissolved in an ultraviolet-curable monomer is also used. it can.

The organic vehicle is a solid powder 100
35 to 100 parts by weight with respect to parts by weight,
As a result, it is possible to sufficiently reduce the thickness of the ceramic color after firing.

According to the present invention, it is possible to maintain good printability during printing of the obtained ceramic color composition based on utilizing a predetermined amount of the solvent solution of the resin having the predetermined concentration as an organic vehicle. . That is, in this type of conventional ceramic color composition, an organic vehicle is used in an amount as small as possible, particularly from the viewpoint of light shielding properties, and the resin concentration in the vehicle is reduced. Is disadvantageous in that the viscosity of the resulting paste is low enough to be unsuitable for screen printing. In contrast, in the present invention, it is possible to obtain a paste viscosity suitable for screen printing,
Moreover, the ceramic color can be made thinner.

The thinning of the ceramic color is generally performed by
This can be achieved by making the mesh of the screen used finer. However, if a high mesh of 300 mesh or more is used, clogging due to low melting point glass powder particles is likely to occur, and there is a disadvantage of causing pinholes. Also,
Depending on the printing conditions, there is a possibility that the film may be partially thickened, and it can not be said that thinning by selecting this screen mesh is very advantageous.

On the other hand, the most reliable method for forming a thin film is to make the ratio between the solid content powder and the organic vehicle rich in the organic vehicle. According to this, even if the coating is a thick film, the organic vehicle is decomposed and dissipated during firing, so that the thickness of the ceramic color after firing becomes thin, and a desired thinning can be achieved.

That is, in the present invention, based on the fact that the amount of the organic vehicle is 35 to 100 parts by weight based on 100 parts by weight of the solid content powder, when the film is printed using, for example, a 180 mesh tetron screen, the film thickness after firing is 4%. -10 μm
(In case of 20 to 35 parts by weight of a conventional organic vehicle, it is 12 to 2 parts by weight).
0 μm). However, when the organic vehicle is used in an amount of less than 35 parts by weight based on 100 parts by weight of the solid content powder, the above-mentioned thinning cannot be achieved, and as a result, the strength of the sheet glass is not improved. Conversely, the use of an organic vehicle in an amount of 100 parts by weight or more has a disadvantage that a required light shielding effect cannot be obtained even when a black low melting point glass powder is used.

The ceramic color composition of the present invention usually comprises
Using a predetermined amount of the mixed powder (solid content powder) of the black-based low-melting glass powder and the inorganic pigment and an organic vehicle, it is prepared into various forms applicable to a ceramic color according to various known methods. be able to. For example, preferably, each component is kneaded to prepare a paste form suitable for screen printing. More specifically, a butterfly mixer containing a predetermined amount of an organic vehicle prepared separately by preparing a solid content powder by previously mixing a black low-melting glass powder and an inorganic pigment and, if necessary, various additives. To obtain a desired paste-like substance by sufficiently mixing the resulting paste and kneading the obtained paste with a three-roll mill to sufficiently disperse the solid content powder in the organic vehicle. Can be. The viscosity of the paste thus obtained is generally from 150 to 100.
It is good to be about 0 poise. When a paste having a viscosity of 500 poise or more is obtained, the viscosity can be reduced by adding the solvent used for the organic vehicle.

[0034]

The present invention will be described in more detail with reference to the following examples.

[0035]

EXAMPLES AND COMPARATIVE EXAMPLES (1) Preparation of Black Low Melting Point Glass Powder An amount of a batch raw material mixture having a low melting point glass composition shown in Tables 1, 2 and 3 was melted in a temperature range of 1200 to 1250 ° C. The molten glass was quenched in water to obtain a popcorn-like glass. The glass was pulverized in water and wet using a ceramic ball in a ball mill, and the obtained slurry was dried and pulverized to prepare each black-based low-melting glass powder used in the present invention. Each of the obtained powders has an average particle size (D ₅₀ ) of 3.
It was adjusted to a range of 0 to 5.0 μm.

(2) Preparation of Ceramic Color Composition As the inorganic pigment (black), # 3700 (CuO, Cr ₂ O ₃ and MnO) manufactured by Asahi Kasei Kogyo Co., Ltd. was used.

As the organic vehicle, (A) Ethyl cellulose STD manufactured by Dow Chemical Company as a high viscosity type
A solution prepared by dissolving 12% by weight of -20 in 88% by weight of pine oil was used. The viscosity of this oil (BL viscometer 3 copy rotor, 12 rotations, 25 ° C.) is 10,000
cps (centipoise). In addition, (B) a low viscosity type prepared by dissolving 4% by weight of ethyl cellulose STD-20 in 96% by weight of pine oil was used. Its viscosity (under the same conditions) is 2000 cp
s (centipoise).

The black low melting point glass powder, the inorganic pigment and the organic vehicle prepared in the above (1) were used in Tables 1, 2 and 3
After mixing in advance in an automatic mortar and dispersing with a three-roll mill, a ceramic color paste composition sample was prepared. The viscosity is shown in each table.

(3) Preparation of fired ceramic color glass sheet Each ceramic color composition sample prepared in the above (2) was placed on a 180 mm mesh tetron on a glass sheet (soda lime glass) having a glass size of 100 mm x 100 mm and a thickness of 2.5 mm. Screen printing was performed using a screen in a pattern of 90 mm × 90 mm. Next, after temporary drying at 150 ° C. for 10 minutes, the resultant was put into a box furnace preliminarily heated to 640 to 660 ° C. for 5 minutes, taken out, and allowed to cool naturally to prepare a ceramic color fired plate glass sample.

(4) Performance test of fired ceramic color plate glass The film thickness of the fired ceramic color was measured using Surfcom 300B manufactured by Tokyo Seimitsu Co., Ltd. As for the light shielding property, TC-8600 manufactured by Tokyo Denshoku Co., Ltd.
Using A, it was determined by the transmittance of visible light. In addition, the permissible transmittance which is actually applied to an automobile window glass is 0.3% or less. These were all measured using the above-mentioned ceramic color fired flat glass sample before being subjected to the strength test.

The impact strength was measured by the following method.
That is, the plate glass was placed on a table receiving the peripheral portion of the plate glass with the ceramic color baked surface down, and the plate glass was fixed from above with the same shape as the receiving plate.
A 200 g steel ball was allowed to fall naturally from a predetermined distance to the center of the plate glass, and the maximum distance at which the plate glass did not break was measured. The test was performed on five samples prepared under the same conditions, and the average value was defined as the impact strength (falling ball strength, cm). The higher the value,
It can be said that the strength is high.

Tables 1, 2 and 3 show the mother glass (PbO-Si ₂ O-B ₂ O ₃ system, Bi ₂ O ₃ -Si
O ₂ —B ₂ O ₃ system and SiO ₂ —B ₂ O ₃ —ZnO system)
The composition of each black-based low-melting glass powder, the amount of the inorganic pigment and the organic vehicle blended therein, the viscosity of the obtained paste, the obtained ceramic color baked film thickness, transmittance and impact strength are shown. In addition, Examples show the composition of the used glass powder within the range of the present invention, and Comparative Examples show the glass powder used for the conventional ceramic color composition of this kind,
That is, the composition of the glass powder is out of the range of the present invention.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

The following is clear from the above tables.

That is, although the absolute strength itself differs depending on the type of the mother glass used, the ceramic color fired plate glass (Example) obtained by applying the ceramic color composition of the present invention employs the conventional ceramic color. The fired film thickness is 4 to 4 in comparison with the same glass sheet obtained by the above (Comparative Example).
Based on the fact that the thickness is as thin as 7 μm, it has almost twice as high strength, and it is clear that the transmittance (light shielding property) is satisfactory for practical use.

Claims (5)

[Claims] 1. Black low melting point glass powder 70 to 99% by weight
A ceramic color composition comprising: a solid powder comprising 1 to 30% by weight of an inorganic pigment; and 35 to 100 parts by weight of an organic vehicle with respect to 100 parts by weight of the powder. 2. The black low melting point glass powder contains CuO, CoO, MnO, Cr ₂ O ₃ , Fe ₂ O ₃ , N
at least one selected from i ₂ O ₃ , Co ₃ O ₄ and FeS
2. The composition according to claim 1, which comprises 1 to 20% by weight of various coloring components.
3. The ceramic color composition according to item 1. 3. The ceramic color composition according to claim 1, wherein the organic vehicle is obtained by dissolving 10 to 50% by weight of a resin component in 50 to 90% by weight of a solvent. 4. The method according to claim 1, which is applied to a glass sheet for an automobile window.
4. The ceramic color composition according to any one of items 1 to 3, 5. An automotive window glass colored by applying the ceramic color composition according to claim 1. Description: