JP2010059039A - Thin-pieced substance and coating composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass composition for a thin-pieced substance, which improves melt moldability of glass for forming the thin-pieced substance and has good chemical resistance. <P>SOLUTION: The glass for forming the thin-pieced substance substantially contains no alkali, while containing a composition composed of 36-50% by mass of SiO<SB>2</SB>, 5-7% by mass of B<SB>2</SB>O<SB>3</SB>, 6-25% by mass of ZnO, 8-14% by mass of Al<SB>2</SB>O<SB>3</SB>, 21-24% by mass of CaO and 0-7% by mass of MnO<SB>2</SB>, with the total of the composition being 95-100% by mass. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a flaky substance contained as particles in paints, inks, cosmetics, plastics, films and the like.

The flaky material controlled to an appropriate size is contained as particles in paints, inks, cosmetics, plastics, films and the like. Since the surface of the flaky material has flatness, in an article in which particles made of flaky material are dispersed, light is incident on or reflected by the flat portion of the flaky material, Gives unique sensitivity such as glitter. In addition, there is also one in which the surface of a flaky material is coated with metal in order to give further glitter. The flaky material is obtained from one having a composition of E glass as described in Patent Document 1. In Patent Document 2, a glass composition for improving the alkali resistance of a flaky material is used. In Patent Document 3, a glass composition for a flaky material is used to increase the lifetime of a kiln during melt molding. Possible glass compositions are disclosed.
JP 63-201041 A JP-A-9-110453 JP 2001-21395 A

Since the flaky substance is used as a filler for paints and resin moldings, it is preferable that the chemical durability is high. In addition, when a metal coating is applied to the surface of a flaky material, it may be treated in an acidic and alkaline solution (aqueous solution), and therefore, it is preferable to have excellent acid resistance, alkali resistance, and water resistance. From the viewpoint of durability as described above, the glass forming the flaky material preferably has a high SiO ₂ content. However, a high SiO ₂ content makes glass melting difficult, leading to increased costs for the flaky material. An object of the present invention is to provide a glass composition for a flaky material that improves the melt moldability of the glass forming the flaky material and has good chemical durability.

The flaky material of the present invention is
SiO _2: 36~50 mass%
B ₂ O _3: 5~7 wt%
ZnO: 6 to 25% by mass
Al ₂ O _3: 8~14 wt%
CaO: 21 to 24% by mass
MnO ₂ : 0 to 7% by mass
And a total of the composition is 95 to 100% by mass, preferably 98 to 100% by mass, and more preferably 100% by mass.

The phrase “substantially not containing alkali, that is, Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ , Cs ^+” means that they are not intentionally introduced into the glass composition even though they are contained as impurities. .

  The flaky material of the present invention is effective in reducing the cost of the flaky material because the glass composition forming the material has a low melting temperature and is excellent in melt moldability. Moreover, since chemical durability, such as water resistance, acid resistance, and alkali resistance, is also favorable, it is effective for use as a filler for paints and resin moldings.

The flaky material of the present invention is
SiO _2: 36~50 mass%
B ₂ O _3: 5~7 wt%
ZnO: 6 to 25% by mass
Al ₂ O _3: 8~14 wt%
CaO: 21 to 24% by mass
MnO ₂ : 0 to 7% by mass
And a total of 95 to 100% by mass of the composition is substantially free of alkali.

SiO ₂ in the composition contained in the glass forming the flaky material is a basic component of the glass. If it is less than 36% by mass, the chemical durability such as acid resistance of the glass tends to be lowered, and if it exceeds 50% by mass, the glass has a high melting temperature, leading to an increase in the cost of the flaky material. Therefore, the content of SiO ₂ in the composition is more is preferably set to 36 to 45 mass%.

B ₂ O ₃ in the composition lowers the melting temperature of the glass. If it is less than 5% by mass, the effect of lowering the melting temperature of the glass is low, and if it exceeds 7% by mass, chemical durability such as alkali resistance tends to be low. The _B 2 _{O 3} in the composition for further 5.5-6.5 mass%, also more preferably be 6 to 6.5 mass%.

Al ₂ O ₃ in the composition improves chemical durability such as water resistance of the glass. If it is less than 8% by mass, the effect of improving water resistance is small, and if it exceeds 14% by mass, devitrification of the glass tends to occur. _Al 2 _{O 3} of the order composition, more preferably set to 8.5 to 14 mass%.

  CaO in the composition lowers the melting temperature of the glass. If it is less than 21% by mass, this effect is small. On the other hand, if it exceeds 24% by mass, the glass tends to be devitrified, and the homogeneity of the melt is lowered when the glass is formed, making it difficult to obtain a flaky material. For this reason, it is preferable to make CaO in a composition into 21.5-23.5 mass% further.

  ZnO in the composition improves chemical durability such as alkali resistance of the glass. From this point of view, this effect is small at less than 6% by mass. On the other hand, if it exceeds 25 mass%, the glass tends to be devitrified. Therefore, ZnO in the composition is further preferably 6.3 to 24.5% by mass, and more preferably 11 to 24.5% by mass.

MnO ₂ in the composition may be introduced in order to improve the water resistance of the glass. However, if it exceeds 7% by mass, the glass tends to be devitrified, and the homogeneity of the melt is lowered when the glass is formed, making it difficult to obtain a flaky material.

  The said composition is contained in 95-100 mass% in glass. In addition to the composition described above, other components such as iron oxide, sulfur trioxide, antimony oxide, zirconium oxide, and titanium oxide may be introduced into the glass in a range that does not substantially change the gist of the present invention.

  The thickness of the flaky material obtained in the present invention is preferably 0.1 to 10 μm, more preferably 0.2 to 7 μm. If it is thicker than 10 μm, cracks are likely to occur in the cross section of the thin piece, and if it is thinner than 0.1 μm, the thin piece tends to be brittle. In addition, it is preferable that both main surfaces (part which is not an end surface) of a thin piece are substantially parallel.

  For the purpose of further improving the dispersibility in the article, the aspect ratio of the flaky material (ratio of the major axis to the thickness) may be set to 3 to 300, preferably 10 to 200.

  The coating composition dispersed using the flaky material of the present invention as a filler has a resin component, preferably a curing agent. As the resin component, various resins having a crosslinkable functional group can be used. Preferred examples include curable resins having a crosslinkable functional group such as a polyester resin having a crosslinkable functional group, an acrylic resin having a crosslinkable functional group, an epoxy resin having a crosslinkable functional group, and a fluorine-containing resin having a crosslinkable functional group. Examples thereof include resins. Examples of the crosslinkable functional group include a hydroxyl group.

  The number of crosslinkable functional groups contained in the resin may be 1 or more per molecule, but is preferably 2 or more. In particular, the hydroxyl value of the resin is preferably 1 to 300 mgKOH / g, more preferably 5 to 250 mgKOH / g, and particularly preferably 10 to 150 mgKOH / g. The number average molecular weight of these resins is preferably 300 to 15000, more preferably 500 to 5000, and still more preferably 500 to 3000.

  The resin component is preferably used together with a curing agent. Examples of the curing agent include, for example, a polyisocyanate compound containing two or more isocyanate groups and / or blocked isocyanate groups in the molecule, a melamine resin, a urea resin, and the like. Examples of the polyisocyanate compound include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, dicyclohexylmethane-4,4′-diisocyanate and the like.

  Examples of the blocked isocyanate compound include those prepared by blocking a part or all of the isocyanate groups of the isocyanate compound with a blocking agent. Examples of this blocking agent include ketoxime blocking agents such as ε-caprolactam, methyl ethyl ketoxime, methyl isoamyl ketoxime, methyl isobutyl ketoxime, and azoles such as 3,5-dimethylpyrazole and 1,2,4-triazole. Blocking agents, phenolic blocking agents such as phenol, cresol, catechol and nitrophenol, alcoholic blocking agents such as isopropanol and trimethylolpropane, active methylene blocking agents such as malonic acid esters and acetoacetic acid esters Is mentioned.

  The coating composition may contain various additives such as a curing catalyst, a solvent, an ultraviolet absorber, an antioxidant, and a flow modifier as necessary. The coating composition is prepared by heating the coating composition, adjusting the viscosity to a desired level by adding an organic solvent or a reactive diluent, etc., and then air spraying, electrostatic air spraying, roll coater, flow coater, dipping type. Apply using a general-purpose coating machine, brush, bar coater, applicator, etc., so that the film thickness after drying is usually 0.3 to 300 μm, and at a temperature of 50 to 300 ° C. for 5 seconds to 48 hours. The coating is applied to the support by, for example, curing. Examples of the support include plastic and metal. Further, these supports may be subjected to primer treatment.

Silica sand as the SiO ₂ source, boric acid as the B ₂ O ₃ source, zinc white as the ZnO source, aluminum oxide as the Al ₂ O ₃ source, calcium carbonate as the CaO source, lithium carbonate as the Li ₂ O source, Sodium carbonate as Na ₂ O source, potassium carbonate as K ₂ O source, zirconium silicate as ZrO ₂ source, manganese dioxide as MnO ₂ source, magnesium carbonate as MgO source, barium carbonate as BaO source, SrO source It took strontium carbonate as These were prepared to have a desired composition and then put into a platinum crucible and heated and melted at 1200 to 1500 ° C. for about 6 hours in an electric heating furnace.

  Next, the glass melt was stirred with a platinum rod in the middle of heating and melting to homogenize the glass. Next, the molten glass was poured into a mold to form a glass block, which was transferred to an electric furnace maintained at 600 to 700 ° C. and gradually cooled in the furnace. The obtained glass sample was homogeneous without bubbles or striae.

  Table 1 shows the compositions contained in the glass of each example and the evaluation results of each example.

<Evaluation of Glass of Each Example>
1. Devitrification temperature The devitrification temperature was obtained by cutting a glass rod of about 3 mmφ collected from a molten glass by a pulling method into a length of about 2 to 3 mm. In a temperature gradient furnace (manufactured by Ozawa Science Co., Ltd.), the temperature was measured at a set temperature for 2 hours and then measured by a rapid cooling method. For measuring the devitrification temperature, a polarizing microscope ECLIPSE E600 POL manufactured by Nikon was used. The temperature between the temperature at which devitrification was confirmed and the temperature at which it could not be confirmed was defined as the devitrification temperature.

2. Working temperature and melting temperature Working temperature and melting temperature were measured by a platinum ball pulling method, and liquid phase temperature was measured by a rapid cooling method using a platinum holder and a temperature gradient furnace.

3. Thermal expansion coefficient The thermal expansion coefficient was calculated | required from the elongation amount in 30-300 degreeC when it heated up at 5 degree-C / min using the thermomechanical analyzer TMA8310 (Rigaku Denki Co., Ltd. product).

4). Chemical durability Acid resistance, alkali resistance and water resistance were measured as chemical durability. In each measurement, a part of the glass sample was pulverized with a ball mill until the particle size became 250 to 425 μm, and the granular or flaky glass was precisely weighed in specific gravity. Next, after immersing the granular or flaky glass in a 0.01N nitric acid aqueous solution, a 10% by weight sodium hydroxide aqueous solution or ion-exchanged water maintained at 80 ° C. for 24 hours, the weight reduction rate (%) is calculated. Calculated. The lower the weight loss rate, the higher the acid resistance, alkali resistance or water resistance. The chemical durability of the granular glass was equivalent to that of E glass. Moreover, the acid resistance of flake shaped glass was equivalent to E glass, and it has confirmed that alkali resistance and water resistance were superior to E glass. Among them, the content of SiO ₂ is _36-45% by weight in the _composition, B 2 _{O 3} content of 6-6.5 wt%, ZnO content of 11 to 24.5 wt%, _Al 2 _{O 3} containing The flake glass whose amount is 8.5 to 14% by mass, the CaO content is 21.5 to 23.5% by mass, and the MnO ₂ content is 0 to 7% by mass is the flakes made of acid-resistant E glass. It was the same as the glass-like glass, and the alkali resistance and water resistance were better than the flaky glass made of E-glass, and it was confirmed that the glass had extremely excellent chemical durability.

<Preparation of flaky material>
About the glass of each Example, when flaky glass was produced with a well-known technique, it has confirmed that it could produce stably. The tip of a platinum pipe having an inner diameter of 4 to 6 mmφ was immersed in glass melted in an electric furnace at 1200 to 1500 ° C., and air was immediately blown in using an air gun. The air pressure was set so that the flake thickness was 5 μm.

  The glass of each implementation had an operating temperature of 1040 ° C. or less, and the glass forming operation was easy, contributing to a reduction in production costs.

<Metal coating of flaky material>
As described below, when the flaky glass of each Example was subjected to silver plating treatment, it was confirmed that the flaky glass could be uniformly coated with silver without being deteriorated during the treatment. Diluted hydrochloric acid was added to a 0.5 wt% tin (II) chloride aqueous solution to adjust the pH to 2 to 2.5, and then flaky glass was added and stirred for 15 minutes, followed by filtration and washing with water. Next, the filtered flaky glass was charged and uniformly dispersed in a solution in which a 0.5 mol / l sodium hydroxide aqueous solution and ammonia water were added to a 1.25 wt% silver nitrate aqueous solution. Further, the flaky glass was added, and potassium potassium tartrate tetrahydrate and glucose were dissolved in ion-exchanged water. Then, a solution uniformly added with methanol was added and stirred for 30 minutes. Thereafter, the flaky glass with the film formed thereon was filtered, washed with water, and dried with a dryer at 100 ° C. for 30 minutes to obtain a glittering flaky material.

Claims (2)

SiO _2: 36~50 mass%
B ₂ O _3: 5~7 wt%
ZnO: 6 to 25% by mass
Al ₂ O _3: 8~14 wt%
CaO: 21 to 24% by mass
MnO ₂ : 0 to 7% by mass
A flaky material comprising a glass containing substantially no alkali and comprising 95 to 100% by mass of the total composition. A coating composition comprising the flaky material according to claim 1 and a resin component.