JP2000073012A - Coating agent - Google Patents

Abstract

(57) [Problem] To form a ceramic film having UV cut properties or water repellency, etc., which can be coated on an object to be coated without placing the object at a high temperature or heating. A coating agent is provided. SOLUTION: The number average molecular weight containing a silazane structure represented by the following general formula (1) in a molecular chain is 100, for example.
~ 100,000 amine residue-containing polysilazane;
nO mixed, sprayed, rubber products, painted surface,
Or used to protect wood products. General formula (1):

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a coating agent,
In particular, it relates to a coating agent used for protection of rubber products, painted surfaces or wooden products.

[0002]

2. Description of the Related Art In various products, UV (ultraviolet)
In many cases, protection by an inorganic substance is required for performing a cutting treatment or a water-repellent treatment. For example, various automobiles,
Tires for aircraft and the like are generally made of rubber and are easily deteriorated when exposed to ultraviolet rays, and are also easily deteriorated when water is used. Therefore, it is preferable to coat with a material having UV cut or water repellency.

[0003] In addition, since protection of a wheel portion of a wheel by resin alone is insufficient, it is necessary to further protect the resin by coating the resin with an inorganic substance. That is, the wheel portion of the wheel is made of a metal such as an aluminum alloy, for example, but its surface is made of resin to prevent the iron powder from being damaged during maintenance or repair, or from being hit by a stone or the like during traveling. Although it protects, however, iron powder stuck in the protective film on the wheel surface,
The tip of the iron powder passes through the protective film and hits the surface of the wheel itself made of an aluminum alloy, causing damage. Such a thing is not preferable because it causes rust of the wheel, and therefore, is higher in hardness than resin,
There is a demand for protection by inorganic substances having a strong protective effect.

[0004] Those requiring protection by inorganic substances include wood products as well as rubber products such as tires and metal products protected by resin such as wheels. Wood products have the problem of degradation by rot fungi. That is, the tree has originally have rot fungi, if the rot fungus is activated, but the deterioration becomes severe, the rot fungi is high becomes so that the humidity is, for example, 90% or more, and supply of oxygen molecules 0 ₂ The presence activates the tree as a nutrient and degrades the tree. Although many wood products are protected by various resins, etc., they cannot effectively block oxygen molecules O ₂ and steam (moisture), which may reach the surface of the wood products themselves and activate rot fungi. There is. Therefore, the oxygen molecule 0 ₂
It is effective to cut wood and steam, and also to have water repellency and UV cut properties to prevent deterioration of wooden products.

[0005]

However, there have been almost no suitable coating agents made of inorganic substances for protecting rubber products such as tires, resins protected by resin such as wheels, and wood products. This is because ceramics are very suitable as inorganic coating agents, but sintering is generally indispensable for ceramics, and high temperature treatment such as several hundred degrees Celsius to several thousand degrees Celsius is required for sintering. is necessary. However, when the sintering process is performed at such a high temperature, there is a problem that a product to be coated cannot withstand the high temperature.

However, development of a coating agent for forming a ceramic film, which does not require sintering, is simply coated at room temperature, is transparent, and sufficiently obtains protection such as water repellency or UV cut properties. As a result, the present inventor came up with the idea of utilizing it for rubber products, painted products, metal products or wood products, and came to the present invention.

The present invention has been made in order to solve such a problem, and it is possible to coat an object to be coated without placing the object at a high temperature or heating it. An object of the present invention is to provide a coating agent capable of forming a coating film having cut properties or water repellency.

[0008]

According to a first aspect of the present invention, there is provided a coating agent containing a silazane structure represented by the above general formula (1) in a molecular chain and having a number average molecular weight of 100 to 100,000.
(Hereinafter referred to as “first polysilazane” for convenience), polysilazane having a silazane structure represented by the general formula (2) (hereinafter referred to as “second polysilazane” for convenience) and / or Or a polysilazane having a silazane structure represented by the general formula (3) (hereinafter, referred to as “third polysilazane” for convenience);
It is characterized by being mixed with ZnO and used to protect rubber products, painted surfaces, or wood products.

Therefore, according to the first aspect of the present invention, the first polysilazane, the second polysilazane, and the third
Is a material that can be applied at room temperature to form an inorganic ceramic film (room temperature hardening type ceramic agent), and can protect the coated object physically and chemically by itself. In addition, since the ZnO contained therein has a UV-cutting property, the object to be coated can be protected from UV light (ultraviolet light). Therefore, it is very effective for protecting rubber products such as tires. This is because, for example, a tire or the like has a property of being easily degraded by UV light, but the UV light can be cut off by the coating agent of claim 1.

[0010] The coating agent of claim 1 is extremely effective in protecting a painted surface. That is, for example, the wheel part is coated with resin, but iron powder stabs it, damaging the wheel surface, rusting from that part,
The phenomenon of spreading occurs. Therefore, the resin surface can be covered with an inorganic ceramic film by coating with a coating agent, and the resin surface can be physically covered.Therefore, there is less danger that the wheel surface will be scratched and rusted by iron powder. Because you can.

Further, the coating agent of the first aspect is extremely effective for protecting wooden products. This is because this coating agent can form a ceramic film on the surface of wood products at room temperature and protect it physically and chemically, causing activation of decay fungi present in wood products. moisture made, thwart the arrival of the oxygen molecule O ₂ of wood surface with a ceramic film, because it is possible to prevent wood degradation by activation of rot fungi Te than the (decay).
Moreover, the wooden products can be protected from UV light by the UV cut property of ZnO, and can be prevented from being deteriorated by UV light.

[0012] The coating agent of the second aspect is the first,
An aliphatic fluorinated compound is reactively added to or mixed with at least one of the second and third polysilazanes (this mixture is hereinafter referred to as a "fourth polysilazane" for convenience), and is used as a rubber product, a painted surface, or the like. It is used to protect wood products. As the aliphatic fluorinated compound to be mixed with the first to third polysilazanes, first, an alcohol having an alkyl fluoride group can be mentioned, and then, a silane compound having an alkyl fluoride group can be mentioned.

Therefore, according to the coating agent of the second aspect, the fourth polysilazane is obtained by reacting or mixing the first, second or third polysilazane with the aliphatic fluorinated compound as described above. It has been confirmed that the first or third polysilazane has a water repellency that is not present in the first to third polysilazanes due to the reaction or mixing, and is applied to an object to be coated at room temperature similarly to the first to third polysilazanes to form a ceramic film. It can be formed (cold-setting ceramic agent), and can physically and chemically protect an object to be coated. Therefore, as with the first to third polysilazane ceramic films, not only can the coating target be physically and chemically protected, but also the water repellency can be further increased. It can be protected very effectively.

Therefore, first, it is very effective for protecting rubber products such as tires. This is because, for example, tires and the like have a property that they are easily degraded when kept wet with water, but the fourth polysilazane itself has various properties (such as properties that can be stably protected physically and chemically) possessed by a general ceramic film. ), Because it has excellent water repellency and can be effectively protected from water such as tires.

Further, the coating agent of the second aspect is very effective in protecting the painted surface. This is because, for example, the wheel portion is coated with resin, but iron powder stabs into it, damaging the wheel surface, causing rust and spreading from that portion, but by coating this coating agent, This is because the resin surface can be covered with the ceramic film described above, and the resin surface can be physically covered, so that the possibility that the wheel surface is damaged by iron powder and damaged and rusted can be reduced.

The coating agent according to the second aspect is also very effective for protecting wooden products. Because, the present coating agent can form a ceramic film at room temperature on the wood surface, physically, it is possible to chemically protected, moisture (steam) and oxygen molecules 0 ₂ wooden surface This is because it is possible to prevent the decay fungi existing in the tree itself from being activated by preventing the decay fungus from being reached by the ceramic membrane.

Wood products are liable to be deteriorated when they are kept in contact with water. However, due to the water repellency of the coating agent, the wood products can be effectively protected from moisture by ceramics formed by applying the coating agent.

[0018] The coating agent according to claim 3 is a coating agent according to claim 2, wherein Zn0 is added.

Therefore, according to the coating agent of the third aspect, the coating agent of the second aspect is mixed with ZnO having a UV-cutting property. Can be. Therefore, in addition to the properties of a normal ceramic film, the coated object can be protected by a ceramic film having water repellency and UV-cutting properties.

The coating agent according to a fourth aspect is the coating agent according to the first, second or third aspect, wherein a fluorescent agent is added.

Therefore, according to the coating agent of claim 4, since the fluorescent agent is added, it is determined whether or not the object to be coated is coated with the coating agent depending on whether or not it shines by irradiating black light, for example. Can be easily identified. In other words, the coating agent has an effective protective effect on the object to be coated even if it is formed thin, and when it is thin, the transparency is high and the undercoat looks clear, which is very preferable in many cases. There is a face that it is difficult to distinguish whether or not there is. This is not preferable from a work viewpoint. However, according to the present coating agent, since a fluorescent agent is contained, by applying a black light, those coated with the coating agent shine, and those not applied do not shine. Whether or not a coating agent is applied can be easily identified. Accordingly, it is possible to eliminate a kind of mistake in which an uncoated product is mistakenly shipped as a coated product.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION The first embodiment of the coating agent of the present invention is characterized in that a first polysilazane, a second polysilazane and / or a third polysilazane are mixed with ZnO. The first polysilazane and the second polysilazane were applied for patents in Japanese Patent Application No. 09-227420 filed by Tonen Co., Ltd., one of the present applicants, and their molecular formulas and manufacturing methods are described in the application form of the same application. The details are described in the specification and drawings attached to the above. Also, the third
Is a polysilazane that has been widely known before the same application. In the present embodiment, the polysilazane is added with ZnO effectively by adding ZnO, and it is used for protecting rubber products such as tires, painted surfaces with resin and the like, and wood products. Is proposed.

In this case, the first, second and / or third polysilazane is dissolved in a solvent such as butyl ether (butyl ether is for example about 97% by weight, polysilazane is for example about 3% by weight), and this is mixed with UV-cutting polysilazane. ZnO
(Zinc oxide). The mixing ratio between the solvent in which the polysilazane is dissolved and ZnO is, for example, about 1: 1 by weight. It is preferable to use ZnO having, for example, the following ultrafine particle characteristics.

Average particle size (BET method): 31 nm (0.
031 μm), particle shape: polyhedron, specific surface area (BET)
Method): 35 m ² / g, crystal system (X-ray diffraction): hexagonal system (Zinclts), angle of repose: 44 degrees, true density: 5.6 g / cm
³ , apparent specific gravity: 0.24 g / cm ³ , purity: 88.95
%, PH (pH of boiling water, JIS K5101A)
Method): 7.0, adsorbed moisture (JIS K0068 drying loss method):
A solution in which 0.4% polysilazane is dissolved and ZnO is mixed is coated by spraying the solution onto a material to be coated using a spray gun. Then, a ceramic film is formed by natural drying. It should be noted that the above items are merely specific examples of the embodiment to the extent of getting tired.

A second embodiment of the coating agent of the present invention is a coating agent comprising a fourth polysilazane and used for protecting rubber products, painted surfaces, or wood products.

The fourth polysilazane is produced by reacting or mixing the above-mentioned first to third polysilazanes with the above-mentioned aliphatic fluorine compound. As the aliphatic fluorinated compound to be mixed with the first to third polysilazanes, first, an alcohol having a fluorinated alkyl group can be used. More specifically, F (CF ₂ ) _n CH ₂ OH, F
(CF ₂ ) _n CH ₂ CH ₂ OH, F (CF ₂ ) _n (CH
_{2) m OH, (CF 2} ) 2 CF (CF 2) n (CH 2)
_{m OH, H (CF 2)} n (CH 2) m OH, (CF 3)
₂ CHOH, CF ₃ CHFCF ₂ CH ₂ OH, (CH
₃ ) ₂ C (CH ₃ ) CH ₂ OH [wherein n = about 1
-10, m = about 1-10] is an example.

Fat mixed with the first to third polysilazanes
Next, as a fatty acid fluorine compound, an alkyl fluoride group-containing
A silane compound is exemplified. More specifically, CF_Three C
H_TwoCH_Two Si (OCH_Three )_Three , CH_Three (CF_Two )_Five C
H_Two CH_Two Si (OCH_Three ) _Three , CF_Three (CF_Two )₇ C
H_Two CH_Two Si (OCH_Three )_Three , CF_Three (CF_Two )₇C
H_Two CH_Two CH_Three Si (OCH_Two ), Etc., and CF_Three 
(CF_Two )₇ CH_Two CH_Two SiCl_Three Etc. or these
Partial hydrolysis is an example.

To obtain the fourth polysilazane, a method for reacting or mixing a fatty acid fluorine compound with the first to third polysilazanes is disclosed in Japanese Patent Application No. Hei 6-167962 by Tonen Co., Ltd., one of the present applicants. The method may be the same as the method in which an aliphatic fluorine compound is reacted with polysilazane of the polysilazane-based coating composition in the technique disclosed in Japanese Patent Application Laid-Open No. Hei 8-27425. The method is described in, for example, JP-A-8-27425, line 14 from the bottom right column (column 10) on page 6 to line 29 on the left column (column 11) of page 7 (paragraphs 0049 to 005).
There is a description of 2), and the method as described may be used.

The fourth ceramic can form a ceramic film by coating at normal temperature, and the ceramic film has not only the same protective properties as a normal ceramic film but also has particularly excellent properties in water repellency. From that
It is newly proposed to use this in particular for protecting rubber products, painted surfaces or wood products. This fourth
Is also dissolved in, for example, a solvent, for example, butyl ether (butyl ether is, for example, about 97% by weight, polysilazane is, for example, about 3% by weight), and is coated by spraying it onto the object to be coated using a spray gun. Then, a ceramic film is formed by natural drying.

In the third embodiment of the coating agent of the present invention, ZnO is mixed with the fourth polysilazane so that the coating agent of the second embodiment has the same level of UV cut properties. According to this, in addition to the protective properties of a normal ceramic film, it is possible to obtain properties in which the water repellency of the fourth polysilazane itself and the UV cut properties of ZnO are added. The method of mixing ZnO may be the same as that described in the first embodiment, for example, but this is merely an example.

The fourth embodiment of the coating agent of the present invention proposes to add a fluorescent agent to each of the above-mentioned coating agents. According to this, light is generated when a black light is applied to the ceramic film, and it can be confirmed that the coating (coating of the ceramic film) is performed by the light. As an example of the fluorescent agent, first, germanium oxide,
Examples include those containing magnesium, iron, and the like, which emit green light when exposed to black light. The amount of the fluorescent agent added to the coating agent is preferably, for example, about 2%. Also, a drug called anthracene can be used as a fluorescent agent.

The thickness of the ceramic film formed by coating each of the above coating agents is 0.01 μm to several tens μm.
It is preferable to use, in particular, 0.1 μm to 1 μm.
m is more preferred.

[0033]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the illustrated embodiments. 1 (A) to 1 (C) show different examples of the coating agent of the present invention. In the drawing, 1a,
1b and 1c are objects to be coated, 1a is a rubber product, for example, a tire, 1b is an aluminum wheel, and the surface thereof is coated with a resin 2. The reason why the wheel 2 is coated with the resin 2 is to prevent the wheel surface from being damaged.
There is a problem that the surface of the wheel 1b is damaged and deteriorates due to rust and the like, and it gradually spreads. Therefore, it is necessary to protect the wheel 1b with an inorganic substance. 1c is a wood products, In some cases the surface is coated, there is a case where unpainted, in any case, through an oxygen molecule O ₂ and steam, the wood itself When this reaches the surface of the wood itself There is a need to protect the wood products themselves with inorganic substances since they may activate the decay fungi originally present therein, and as a result, the wood products themselves may be gradually deteriorated.

Reference numeral 3 denotes a ceramic film formed by spraying the coating agent according to any one of claims 1 to 4 at room temperature, from 0.01 μm to several tens μm (particularly 0.1 to 1 μm).
Is more preferable). Specifically, a polysilazane serving as a base (first to fourth polysilazanes; details thereof are described in the embodiment of the present invention or Japanese Patent Application No. 9-22742).
No. 0 or JP-A-8-27425), dissolved in a solvent such as butyl ether (butyl ether is, for example, about 97% by weight, polysilazane is, for example, about 3% by weight), and mixed with, for example, ZnO (the fourth polysilazane is particularly strong). This is not necessary when it is not necessary to obtain a UV cut effect.) For example, the object to be coated 1a to 1c is sprayed using a spray gun. It goes without saying that a fluorescent agent is mixed in order to emit light when irradiated with black light.

Originally, the above-mentioned coating agent obtained by using the first to third polysilazanes and adding ZnO thereto can be applied at ordinary temperature to form an inorganic ceramic film. Can be protected both physically and chemically, and when ZnO is added to it, it has a UV-cutting property, so that the object to be coated can be protected from UV light (ultraviolet light). . Therefore, first, for example, the rubber product 1a such as a tire
It is extremely effective for protection of This is because, for example, a tire or the like has a property of being easily deteriorated by UV light, but can cut UV light by a UV cut effect of ZnO.

It is also very effective in protecting the painted surface. This is because the coating of the coating agent allows the resin surface to be covered with an inorganic ceramic film, which can be physically covered.Therefore, there is a risk that iron powder will stick and the wheel surface will be damaged and rusted. This is because it is possible to reduce

It is also very effective in protecting wood products. The reason is that this coating agent can form a ceramic film on the surface of wooden products at room temperature and protect it physically and chemically, so that water and oxygen molecules that cause decay fungi are activated. reaching the 0 ₂ of wood surface is because it is possible to prevent a ceramic membrane. Moreover, the wooden products can be protected from UV light by the UV cut property of ZnO, and can be prevented from being deteriorated by UV light.

The coating agent using the fourth polysilazane also has the same effect as the above-mentioned coating agent, and is most suitable for protecting rubber products, painted surfaces, and wood products. This fourth
The coating agent using polysilazane does not have good UV-cutting properties when ZnO is not added. However, in other respects, it has almost the same protective properties and excellent water repellency. This is because the polysilazane itself has water repellency. When ZnO is added to the fourth polysilazane, UV
The cut effect can be enjoyed and the protection effect can be more perfect.

When a fluorescent agent (for example, germanium oxide, magnesium, iron or the like or anthracene) is added to each of the above-mentioned coating agents (addition amount: for example, 2%), light (for example, green light) is applied when a black light is applied. ). Therefore, when the coating agent is coated, the coating agent coated with the black light shines, and the non-coated one does not shine. Therefore, it is easy to determine whether the coating agent is coated or not based on whether the coating material is shining or not shining.
Therefore, it is possible to eliminate a mistake that an uncoated product is mistakenly shipped as a coated product.

Each of the above-mentioned coating agents can be supplied in a state in which it is directly detachably connected to a spray gun and put in a sprayable cartridge. Regarding this, a technical proposal has already been made by Techno System Co., Ltd., one of the applicants of the present application, in Japanese Patent Application No. 10-160159 (title of invention: paint cartridge and spray gun).

[0041]

According to the first aspect of the present invention, the first polysilazane, the second polysilazane, and the third polysilazane can be applied at room temperature to form an inorganic ceramic film. , Which itself can physically and chemically protect the object to be coated, and since the ZnO contained therein has a UV-cutting property, the object to be coated is protected from UV light (ultraviolet light). can do. Therefore, it is very effective for protecting rubber products such as tires. This is because, for example, tires and the like have the property of being easily degraded by UV light.
This is because V light can be cut.

The present coating agent is also extremely effective in protecting the painted surface. For example, although the wheel part is coated with resin, iron powder stabs it and damages the wheel surface, rust occurs from that part, and the phenomenon of spreading occurs, but by coating with a coating agent, The surface of the resin can be covered with a ceramic membrane, which can be physically covered, so that iron powder will stick and damage the wheel surface,
This is because the possibility of rusting can be reduced.

The present coating agent is also very effective for protecting wood products. This is because this coating agent can form a ceramic film on the wooden product surface at room temperature and protect it physically and chemically, so that moisture (steam) and oxygen that activate rot fungi are activated. The reason is that the ceramic film can prevent the molecule 0 _{2 from} reaching the wooden product surface. Moreover, the wooden products can be protected from UV light by the UV cut property of ZnO, and can be prevented from being deteriorated by UV light.

According to the coating agent of the second aspect, the fourth
The polysilazane can be applied to an object to be coated at room temperature similarly to the first, second, and third polysilazanes to form a ceramic film, and can physically and chemically protect the object to be coated. It is possible to protect the object to be coated very effectively because it is water-repellent. Therefore, it is very effective for protecting rubber products such as tires. This is because, for example, tires and the like have a property that they are easily degraded when kept wet with water, but the fourth polysilazane itself has various properties (such as properties that can be stably protected physically and chemically) possessed by a general ceramic film. ), Because it has excellent water repellency and can be effectively protected from water such as tires.

The coating agent of claim 2 is extremely effective also for protecting a painted surface. That is, for example, the wheel part is coated with resin, but iron powder stabs it, damaging the wheel surface, rusting from that part,
Although the phenomenon of spreading occurs, by coating this coating agent, the resin surface can be covered with an inorganic ceramic film and it can be physically covered, so that iron powder is stuck and the wheel surface is damaged This is because the risk of rusting can be reduced.

The present coating agent is also very effective for protecting wood products. This is because the coating agent can form a ceramic film on the surface of a wooden product at room temperature and protect it physically and chemically, so that moisture (steam) and oxygen molecules O ₂ are deposited on the surface of the wooden product. This is because the ceramic membrane can prevent the decay fungi originally existing in the wooden product itself from being activated. Also,
Wood products are easily deteriorated because they keep in contact with water, but the water repellency of the coating agent allows the wood products to be effectively protected from moisture by the coating agent.

According to the third aspect of the present invention, the coating agent of the second aspect is mixed with ZnO having a UV-cutting property, so that the coating agent of the second aspect can have a UV-cutting property. Therefore, in addition to the properties of a normal ceramic film, the coated object can be protected by a ceramic film having water repellency and UV-cutting properties.

According to the fourth aspect of the present invention, since the coating agent contains a fluorescent agent, it is illuminated by irradiating black light with the coating agent illuminated by the coating agent, and uncoated by the black light. Whether or not the coating agent has been coated can be easily discriminated from whether or not it is lit. Therefore, it is possible to eliminate a mistake that an uncoated product is mistakenly shipped as a coated product.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A to 1C are explanatory views of another embodiment of the coating agent of the present invention.

[Explanation of symbols]

1a: rubber product (for example, tire), 1b: object to be coated (aluminum wheel), 1c: wooden product, 2
... Resin, 3 ... Coating agent (ceramic film)

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yasuo Shimizu 1-3-1 Nishitsurugaoka, Oi-machi, Iruma-gun, Saitama F-term in Tonen Research Laboratory (reference) 4J038 DL171 GA09 HA186 MA14 NA19 PA07 PC06 PC07

Claims (4)

[Claims] 1. A compound having a silazane structure represented by the following general formula (1) in a molecular chain and having a number average molecular weight of 100 to 10.
A polysilazane containing 0000 amine residues, a polysilazane having a silazane structure represented by the following general formula (2) and / or a polysilazane having a silazane structure represented by the following general formula (3) are mixed with ZnO. A coating agent characterized by being used to protect rubber products, painted surfaces, or wood products. General formula (1): General formula (2): General formula (3): (Wherein R ¹ , R ² and R ³ represent hydrogen, a hydrocarbon group or a hydrocarbon-containing silyl group, and in the general formula (3),
^At least one of ¹ and R ³ represents hydrogen, and A and A ²
Represents a divalent hydrocarbon group, B represents an N-hydrocarbon-substituted amine residue or a cyclic amine residue, B ² represents a divalent chain amine residue or a divalent cyclic amine residue, p and q Represents 1 or 0, and when B represents an N-hydrocarbon group-substituted amine residue or B ² represents a divalent chain amine residue, p and q represent 1, and B represents a cyclic amine residue. Alternatively, when B ² represents a divalent cyclic amine residue, p and q represent 1 or 0. ) 2. The general formula (1) according to claim 1,
A coating characterized by reacting or adding an aliphatic fluorinated compound to at least one of the polysilazane-based coating agents of (2) and (3) to protect rubber products, painted surfaces, or wood products. Agent. 3. The coating agent according to claim 2, wherein Zn0 is added. 4. The coating agent according to claim 1, wherein a fluorescent agent is added.