JP2020029549A - Hydrophilic coating agent - Google Patents

Abstract

To provide a coating agent having a contact angle as small as 1-4 degrees, and having small hydrophilicity, an antirust effect and an antibacterial effect.SOLUTION: A coating agent having weather resistance, water resistance and antibacterial property, and having small contact angle and high hydrophilicity (wetting) can be provided by mixing a mixture obtained by adding nanosilica having pearl-like fine particles of 0.1-20 μm, silicate oligomer having SIO2 content of 30-80%, glass powder for low temperature firing containing boron and carboxymethylcellulose sodium with any one of isopropyl alcohol, ethanol, ethylene, ethylene glycol, an ether-based solvent, alcohol and water or a plurality of solutions, and a synthetic detergent as a phase solvent, and stirring the mixture.SELECTED DRAWING: Figure 2

Description

  The coating agent of the present invention provides a function of preventing water droplets and simplifying washing by hydrophilicity, and relates to a hydrophilic coating agent having weather resistance, water resistance and antibacterial properties.

  A urethane acrylic resin layer containing nanosilica having a particle size of 5 nm or more and less than 300 nm in a range of 0.1% by weight or more and less than 20% by weight is formed of a resin glass hard coat layer having a thickness of 12 μm or more and less than 30 μm. There is a proposal (see Patent Document 1).

  A siloxane to which an acryloyl group is added for the purpose of providing a hard coating agent capable of forming a hard coat layer having a weather resistance, easy to wash, and having a high surface hardness and a weather resistant hard coat film coated with the hard coating agent. A hard coating agent containing an oligomer, a photopolymerization initiator, and one or more members selected from the group consisting of colloidal silica, nanosilica, and nanozinc oxide powder has been proposed (see Patent Document 2).

  A transparent glass cloth sheet used for non-combustible building materials such as smoke-proof hanging walls.It is easy to handle and light-fast without causing whitening scratches inside the sheet due to bending or folding of the sheet and impairing the appearance. In providing an excellent transparent composite sheet, an adhesive containing a specific non-aromatic triisocyanate compound and a binder resin in a weight ratio of 1: 5 to 1:35 on a glass cloth treated with a silane coupling agent. An adhesive-impregnated coated glass cloth obtained by impregnating and curing the components is used as a base material, and a composite laminate is provided on both surfaces of which a soft vinyl chloride resin transparent layer is provided, and an aromatic phosphate compound and a polyol are used as the binder resin. A compound containing a compound and surface hydroxyl group-modified nanosilica particles has been proposed (see Patent Document 3).

  A conventional coating material using nanosilica powder has low adhesiveness unless an organic substance is mixed therein, and the organic substance has low weather resistance and cannot withstand use due to aging. It is possible to provide a nanosilica coating agent having good adhesiveness without mixing an organic substance. As a result, it was possible to provide a nanosilica coating agent having weather resistance and little aging (see Patent Document 4).

  It is known that nano-silica is mixed with a paint, a solution of ethanol, ethylene glycol, or an ether-based solvent to be used as a coating agent for a house outer wall, a car, a solar panel, or the like. It is known that hydrophilic silica is used as a component of a hydrophilic coating agent (see Patent Document 5). Furthermore, it is described that the hydrophilic coating agent contains hydrophilic silica, and contains an aprotic cationic resin and an alcohol and / or ether solvent as an organic binder.

  It is also known to use a hydrolyzed silicate as a hydrophilic coating agent. A method for producing a hydrophilic coating agent characterized by further adding a metal oxide sol solution to a silicate hydrolysis solution and further hydrolyzing and condensing the hydrophilic coating agent is described (see Patent Document 6). .

JP 2016-138208 A JP-A-2006-88954 JP 2014-76563 A JP 2012-41492 A JP 2014-224171 A JP 2009-280723 A

  According to the present invention, there is an increasing demand for a water-drop preventing agent for securing visibility in driving a car and, more recently, for preventing malfunction of a sensor for automatic braking and danger warning. Although many anti-waterdrop agents have been developed, the state of the art hydrophilic coating agents have not yet reached the level required by the market. For example, there are photocatalysts, surfactants, hydrophilic coating agents mainly composed of silica glass and nano-silica, but there is a problem that the photocatalyst has no effect and discolors white unless it is exposed to sunlight. Further, a hydrophilic coating agent containing a surfactant as a main component is excellent in hydrophilicity and low in cost, but has a problem in durability of the coating agent peeling off when wiped. Further, a hydrophilic coating agent containing silica glass as a main component is excellent in durability but high in cost, and has problems such as unevenness of the coating film and time required for construction. A hydrophilic coating agent containing nanosilica as a main component has a problem that a contact angle is as large as 5 to 10 degrees to which water droplets adhere and the hydrophilic function is poor in durability. It is the actual situation that each has a problem. In order to solve these problems, it is desired to have a high hydrophilicity (wetting), low cost, simple construction, and durability.

  In addition, housework has become a heavy burden on housewives due to the advancement of women in society, and labor shortages at workplaces have necessitated the need for labor savings in all fields. Cleaning is an extremely important and fundamental part of social life, but it is also a time-consuming task, and it is also a task that people do not want to do most. In the field of cleaning, water-based coating agents having a function of simplifying cleaning such as sashes, toilets, sinks, bathtubs, wash basins, etc. are difficult to clean, and easily remove dirt in the field of cleaning. Although many of them are water-repellent coating agents, some of them do not have a cleaning effect, and some are slightly hydrophilic. There are many problems and the fact is that it is not widely used. In order to solve these problems, what is desired is a material having high hydrophilicity, low cost, simple construction, and durability.

  Accordingly, the present invention provides a hydrophilic coating having both water resistance and weather resistance by forming a hard film by reducing the contact angle of water to enhance hydrophilicity, preventing water droplets, preventing stains, cleaning function, and antibacterial properties. Agent at low cost.

Means to solve the problem

  It is characterized by comprising pearl-like fine particles of 5 to 100 nm nanosilica and silicate oligomer having an SIO2 content of 30 to 80%. According to the coating agent of the present invention, it has pearl-like fine particles of 5 to 100 nm nanosilica. The pearl fine particles having a thickness of 5 to 100 nm are excellent in dispersibility, so that they can be uniformly coated without unevenness. Further, transparency can be increased. The silicate oligomer having an SIO2 content of 30 to 80% is strongly bonded to nano silica and equipment, and enhances abrasion resistance. Further, the prior art uses a surfactant or the like as a means for enhancing hydrophilicity, but there was a major problem that it was easily soluble in water and had poor durability, but by adding a glass powder for low-temperature firing containing boron. Glass powder, pearl-shaped fine particles of 5 to 100 nm nano-silica and a silicate oligomer having a SIO2 content of 30 to 80% are mixed and formed on the surface of the coating film surface, and the gap is filled with the dispersibility of the pearl-shaped fine particles of 5 to 100 nm nano-silica. In addition to making the surface smooth, the hydrophilic action of the glass powder for low-temperature firing makes it possible to improve the durability and the contact angle of water droplets to 1 to 4 degrees, which are not available in the prior art. This makes it possible to simplify washing, such as the use of water, which removes oil stains without using detergent.

  In addition, by adding sodium carboxymethylcellulose, the viscosity is increased, and it is possible to coat equipment which is hardly adhered with a solvent such as acrylic or stainless steel with ethanol.

The coating agent is desirably a liquid dissolved in a solution of any one or a combination of isopropyl alcohol, ethanol, ethylene, ethylene glycol, an ether solvent, alcohol, and water.
The mixing ratio of the raw materials is as follows: low baking containing boron in a mixture of pearl-shaped fine particles 5 to 100 nm nano silica 0.001 to 20 wt% and SIO 2 content of 30 to 80% silicate oligomer 0.001 to 20 wt% Glass powder 0.001 to 20% by weight Sodium carboxymethylcellulose 0.001 to 2% by weight is added to any one or more of isopropyl alcohol, ethanol, ethylene, ethylene glycol, ether solvent, alcohol, and water. It is desirable to mix and stir so that the total of 40 to 99% by weight and 0.0001 to 0.03% by weight of a synthetic detergent as a compatibilizer is 100% by weight.

  Experiments were carried out by changing the ratios of the respective raw materials. As a result, when the ratio of the glass powder for low temperature firing containing pearl-like fine particles of 5 to 100 nm nano-silica, the silicate oligomer by weight, and boron to the solution was increased, the color became white. It turned out to be colored and could not be used with many things such as glass and mirrors.

  In addition, when the ratio of the low-temperature baking glass powder containing boron and the weight percentage of the silicate oligomer is 30% to 80%, the weight percentage of the pearl fine particles 5 to 100 nm nano silica and the SIO 2 content is 30 to 80%, the transparency increases, It was confirmed that it was effective as a coating agent for many things such as mirrors.

  According to the results of these experiments, the mixing ratio of the raw materials of the hydrophilic coating agent having transparency and appropriate abrasion resistance, water resistance and weather resistance, and having a rust-preventive effect was as follows. 30% to 80% by weight SIO2 content 1% by weight of silicate oligomer, 0.5% by weight of glass powder for low-temperature firing containing boron and 0.2% by weight of sodium carboxymethylcellulose 31% by weight of isopropyl alcohol It is most preferable to add 0.01% by weight of a synthetic detergent as a compatibilizer to a mixture of water, 59,79% by weight of ethanol and 5% by weight of water, mix and stir.

The invention's effect

The glassy coating made by this basic nanocoating agent is formed by densely laminating nano- and sub-nano-sized nano-silica powder and boron-containing glass powder, and is not an aggregate of granular particles, but by forming a dense film coating It turned out that it has the following characteristics.
(1)) Advanced water droplet prevention (2) Simplification function of cleaning (3) Strong water resistance, weather resistance, waterproofness (4) Antibacterial property (5) Rust prevention effect.
By applying the composition to the surface of the object, the above-described characteristics can be provided.

FIG. 3 is a diagram in which nano-silica, silicate oligomer, and organic solvent are mixed in a container. The tip of the arrow is a diagram in which the mixed solution in the container is stirred by a stirrer. FIG. 3 is a diagram in which nano silica, silicate oligomer, glass powder, and an organic solvent are put in a container and mixed. The tip of the arrow is a diagram in which the mixed solution in the container is stirred by a stirrer. FIG. 2 is a view in which a coating agent is sprayed onto equipment by a spray gun for coating. It is the figure which expanded the surface of the thing which applied the coating agent of this invention product to an aluminum plate, and air-dried after spreading it 40,000 times. The glass-like coating is formed by densely laminating glass powder, nano-silica, and silicate oligomer, and the nano-silica fills the gaps and is flat rather than an aggregate of granular particles. FIG. 3 is a diagram in which half of a mirror is coated and half is left untreated, and water-colored ink is dropped one drop at a time to confirm hydrophilicity. Untreated water droplets are round polka dots, but the water is dispersed and flat in the construction area.

  Put the coating agent of the present invention on the surface of the equipment in a spray container, spray it onto the equipment, spread it evenly with a sponge, brush, etc., coat it, and dry it naturally for 2 to 3 hours to form a strong film, The hydrophilic property provides functions of preventing water drops and simplifying washing. In addition, it has both weather resistance and water resistance.

  The embodiment of the present invention has been described above, but the specific configuration is not limited to this. For example, zeolites, dyes, pigments, titanium oxide, and organic solvents can be added and blended.

  The right side glass and the right side mirror of the car were coated with the hydrophilic coating agent of claim 2, and the left side was left untreated and the left and right conditions were compared on a rainy day. It was confirmed that the water was dispersed horizontally without being attached, but that the left untreated portion had poor visibility due to water droplets adhering to the surface.

To confirm the hydrophilicity, a water drop was dropped on a glass plate and the contact angle of a polka dot was measured.

  The hydrophilic coating agent of claim 2 was coated on a hot spring mirror and compared with an untreated mirror. The untreated mirror became white and hard to see in one month, but the hydrophilic coating agent was applied. The mirror is clean after 3 months without hot spring ingredients. This is because the components of the hot spring did not adhere to the mirror due to the hydrophilicity imparted and the water dispersed and flowing down.

  To measure the water resistance of the hydrophilic coating agent of claim 2, apply the hydrophilic coating agent to a mirror of 15 cm × 25 cm and allow it to dry naturally for 3 hours, fill a bucket with water, immerse it in the bucket for three months, and add water. In order to see if the coating agent had melted off, the mirror after immersion was sprayed with water to check whether or not polka dots were formed. However, there was no polka dots, and there was hydrophilicity (wetness), and water resistance was confirmed.

  In order to measure the weather resistance of the hydrophilic coating agent of claim 2, the hydrophilic coating agent was applied to a mirror of 15 cm × 25 cm and allowed to dry naturally for 3 hours, and then left outdoors for 3 months in a place exposed to direct sunlight. In order to confirm the properties, it was checked whether water drops were applied to the mirror to form polka dots. However, it was possible to confirm a certain weather resistance without polka dots.

  In order to measure the abrasion resistance of the hydrophilic coating agent of claim 2, the hydrophilic coating agent was applied to a mirror of 15 cm × 25 cm and air-dried for 3 hours, and then water was used once a day to confirm the abrasion resistance. Three months after rubbing the surface of the mirror constructed with a moistened towel, water was applied to the rubbed mirror and it was checked whether or not polka dots would form.However, the water spread without any polka dots and the water drained quickly. The wear resistance was confirmed.

  The hydrophilic coating agent of claim 2 was coated on an aluminum wheel of a European car, and the effect of the silicate oligomer, which is a component of the coating, to prevent electrodeposition with iron powder by the antistatic function was verified. One month later, the uncoated aluminum wheels had iron powder on the discs that adhered to the entire surface, but the aluminum wheels coated with the hydrophilic coating agent had one-third the amount of iron powder deposited compared to the untreated aluminum wheels. It was confirmed that the adhesion was not so good. In addition, iron powder adhering to the unconstructed aluminum wheel did not fall off unless a strong sponge was attached to the sponge with a cleanser, but an aluminum wheel coated with a hydrophilic coating agent was wiped gently with a towel moistened with water due to hydrophilicity. fell.

  The cleaning effect was confirmed by coating the inside and outside of the bathtub with the hydrophilic coating agent of claim 2. Before the installation, the scales attached to the sides and the rough stains on the bottom could not be cleaned unless rubbed with a sponge using a detergent. The bottom was rough, and the rough stains on the bottom could be cleaned only by gently rubbing with a sponge while sprinkling with water, and the outside was in a beautiful state when sprinkled with a shower. In addition, the condition after 4 months was confirmed, but there was a cleaning effect, and long-term durability and water resistance were confirmed.

  The convenience store cleans the glass of the store every day, and it takes 30 to 40 minutes. When the cleaning effect was confirmed by applying the hydrophilic coating agent of claim 2 to a glass of a convenience store, the transparency was high, without discoloration, it was a beautiful finish that it was not possible to know whether it was coated, The dirt was removed simply by spraying water on the glass with a hose, and the water was drawn quickly, and the working time was greatly reduced to 8 to 10 minutes. Further, the hydrophilicity (wetting) effect was confirmed to be long-lasting without dropping even after 3 months. Also, after four months, the glass was once cleaned and dried, and then overcoated without peeling off the previous coating agent, but was finished neatly without discoloration or surface distortion.

  The hydrophilic coating agent of claim 2 was coated on the sink of the sink sink to check the antibacterial effect. Before the application, it was a situation that the slime appeared in one week and the user did not want to touch it. After the construction, no slime was generated even after one week, and no black mold was generated even after one month. This is because the dirt flows down with water due to the hydrophilicity, so that the environment becomes difficult for fungi to propagate.

  A comparison was made between the place where the hydrophilic coating agent of claim 2 was applied to the image of the bathroom tile and the place where it was not applied after 30 days. No black mold was generated in the worked part, but black mold was generated in the non-worked part. The antibacterial action was confirmed. This is because the environment in which mold bacteria easily occur due to the adhesion of soap scum, descaling, etc. to the porous media is used to close the pores of the media by coating, and the soap scum, descaling, etc. are less likely to adhere due to the hydrophilicity.

  The hydrophilic coating agent of claim 2 was coated on leather, synthetic leather shoes, and bags, and the waterproof effect was confirmed. However, even if a large amount of water was released, the inside of the shoes was not flooded, and discoloration was recognized. No changes such as hardening of the skin itself were observed. In addition, it was stored in a shoe box for three months in a state of being sprinkled with water, and the condition was confirmed. No mold was found.

  Since the present invention is a multi-purpose super hydrophilic coating agent, it can protect materials of all equipment, prevent mold, simplify cleaning, prevent rust, prevent solar panel coating, prevent water droplets, prevent fogging, use glass, mirrors, outdoor installations, etc. It is suitable for preventing oil film, scale, scale adhesion, dirt adhesion, waterproofing of cloth and leather products, and suppressing bacterial growth.

1 Container for mixing nano-silica, silicate oligomer and organic solvent.
2 A stirrer for stirring the mixed solution.
3 Container for mixing nano-silica, silicate oligomer, glass powder and organic solvent. 4 Container part for spray gun.
5 Equipment for applying the coating agent.

Claims (2)

  A hydrophilic coating agent characterized by being applied to a surface of a device using a solution containing pearl oligomers having a nanoparticle silica of 5 to 100 nm, a silicate oligomer having an SIO2 content of 30 to 80%, and an organic solvent.   The low-temperature firing glass powder containing boron is added and mixed in claim 1 and the mixture is applied to the surface of the equipment, and after natural drying, the applied surface has a pearl-like fine particle of 5 to 100 nm nanosilica nanosilica and SIO2 content of 30 to 80%. A hydrophilic coating agent, wherein a film is formed by mixing a silicate oligomer and a glass powder containing boric acid.