JP3447102B2 - Method for producing transparent UV-absorbing ceramic film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTIONPerhydroPolysilaza
Dense with ultrafine particles of ceramics and ceramics as essential components?
With high hardness and UV absorption, thick film construction is also possible.
Related to ceramic membrane. [0002] 2. Description of the Related Art The present applicant has previously described fillers in polysilazane.
Discloses a coating composition filled with
No. 1-203476). Filler is ceramic particles
Particle size from submicron to several tens of μm or
More than that. In addition, metal alkoxide or its condensation
Particles on coating film by sol-gel method based on multimer
UV protection thin film with UV absorber with diameter of 5-200nm
A coating liquid composition for forming a film is disclosed
JP-A-5-89798). This coating solution contains
Are soluble in alcohol and compatible with metal alkoxides.
Organic dispersant is added. On the glass surface, an organosilicon compound is
Applying a coating solution in which a metal compound is dispersed or dissolved in an organic solvent
To form a transparent protective film with a refractive index close to that of glass
Technology (sol-gel method) disclosed in JP-A-3-150237
It has been disclosed. Specifically, as an organosilicon compound
Acetyl ace
Tonatochelate compounds have been used. [0004] The above-mentioned polysilazane series
The coating composition is dense, high hardness and thick film is possible.
Although it has certain features, transparent UV absorbing films have been
Could not be obtained. Fillers disperse visible light and
This is because the filler transforms the silazane. On the other hand,
In the sol-gel method, organic components are removed during firing,
Polysilazane coating in terms of density, hardness and film thickness
Did not reach. Therefore, the present invention has been made in view of these problems.
, Dense, hard and transparent UV-absorbing ceramics
With the aim of making it possible to obtain
I do. [0006] The present invention achieves the above object.
In order to achieve, mainly the general formula (I): [0007] Embedded image [0008]soHaving a main skeleton consisting of the units represented
Number average molecular weight of 100-50,000PerhydroPolysilazane
To the coating solution mainly composed of
5-0.1 μmHigh dispersion processingTiO_Two15 ultra fine particles
Applying and baking a coating composition containing up to 85% by weight
To form a transparent UV-absorbing ceramic film with a hardness of 9H or more.
obtainA transparent UV-absorbing ceramic film
A manufacturing method is provided. The filler has an average particle size of 0.1 μm or less.
Preferably 0.05 μm or lessHigh dispersion processingUltra fine particles
This allows transmission of visible light and
LamixHigh dispersion processing TiO_TwoTo choose
ByPerhydroBecause of its excellent compatibility with polysilazane,
The desired dense, hard, and transparent ceramic film is obtained.
And the ceramic coating is easily
m, and can be made to have a thickness of about
V) Ultraviolet absorbing transparent ceramic
It can be used as a membrane. Average particle size of the ceramic ultrafine particles used
Is small, it is difficult to obtain.
Because it is difficult to obtain a transparent ceramic film,
The lower limit of the average particle size of the ceramic ultrafine particles to be used is 0.
005 μm, and preferably 0.01 μm. Up
The limit is 0.1 μm, preferably 0.05 μm. Effect of the present inventionIs the high dispersion processing TiO_TwoNo
Obtained by using Lamix ultrafine particlesWas.
Specifically, for exampleIfKokosan TiO_TwoPowder IT-U
D (particle size 0.02 μm, high dispersion treatment type) is preferred
No. In this case, add to the xylene solution of silazane
If stirring or ultrasonic dispersion, dispersion with a ball mill are performed
Good. As appropriateDispersants can also be added. [0012]UseToPerhydroPolysilazane has a chain
, Cyclic, or crosslinked
Some devices have these multiple structures at the same time.
These can be used alone or as a mixture. UsePerhydroRepresentative examples of polysilazane and
Such as, but not limited to:
In thingsAbsent. ThatThe production method is described, for example, in JP-B-63-163.
No. 25, D. Seyferth et al. Communication of Am. Ce
r. Soc., C-13, January 1983. This
What is obtained by these methods is poly-
Is a mixture of polymers, but basically contains a chain portion in the molecule.
Including an annular portion, [0014] Embedded imageCan be represented by the following chemical formula: Perhide
An example of the structure of lopolysilazane is shown below.
You. [0016] Embedded image [0017] [0018] [0019] [0020] [0021] [0022] [0023] [0024] [0025] [0026]Other, specialKaihei 1-138108, 1
-138107, 1-203429, 1-20
No. 3430, No. 4-63833, No. 3-320167
Increase the molecular weight as reported in
The former four publications), the hydrolysis resistance was improved (later 2).
Person), inorganic silazane high polymer or modifiedPerhydroPolysila
TheGoodThey can be used as well. UsePerhydroThe molecular weight of polysilazane is
If it is too small, the yield at the time of firing is low, which is not practical. one
If the molecular weight is too large, the stability of the solution is low and a sound membrane
Can not be obtained. Used for these reasonsPerhydroPo
The molecular weight of lysilazane is a number average molecular weight and the lower limit is 100.
More preferably, it is 500. The upper limit is 50,000 and is preferred
Or 10,000. If the added amount of the ceramic ultrafine particles is small,
No effect, the lower limit of the added amount of ceramic ultrafine particles is 5
Parts by weight, preferably 15 parts by weight. On the other hand, many
If too long, voids are formed in the film, so the upper limit is 95%.
Parts by weight, preferably 85 parts by weight. However, this
HerePerhydroPolysilazane and ceramic ultrafine particles
The total weight is 100 parts by weight. Ceramic ultrafine particlesPerhydropolicy
Should be evenly dispersed in the Razan coating solution.
You. As a method of uniformly dispersing, a high dispersion type (Z
S-303, IT-UD, etc.)
Sonic dispersion and dispersion with a ball mill are sufficient.
You. As the solvent, aliphatic hydrocarbon, alicyclic carbon
Hydrocarbons, hydrocarbon solvents for aromatic hydrocarbons, halogenated
Halo such as tan, halogenated ethane, halogenated benzene
Genated hydrocarbons, aliphatic ethers, alicyclic ethers, etc.
Ethers can be used. A preferred solvent is methylene chloride
, Chloroform, carbon tetrachloride, bromoform,
Tylene, ethylidene chloride, trichloroethane, tetrac
Halogenated hydrocarbons such as loroethane, ethyl ether,
Isopropyl ether, ethyl butyl ether, butyl
Ether, 1,2-dioxyethane, dioxane, dime
Tyldioxane, tetrahydrofuran, tetrahydropi
Orchid, cellosolve acetate, carbitol acetate
Ethers such as pentanehexane, isohexane,
Chilpentane, heptane, isoheptane, octane, a
Sooctane, cyclopentane, methylcyclopentane,
Cyclohexane, methylcyclohexane, benzene,
Hydrocarbons such as ruene, xylene, ethylbenzene, etc.
You. When using these solvents,Perhydro
To control the solubility of polysilazane and the evaporation rate of solvent
, Two or more solvents may be mixed. Solvent usage
(Proportion) is more workable depending on the coating method used.
Is selected according to the required film thickness.Pe
LehydroAverage molecular weight and molecular weight distribution of polysilazane
Solvent in coating composition
Can be mixed up to about 99% by weight, preferably
The solid content can be mixed in the range of 3 to 50% by weight.
Wear. In the coating composition, if necessary,
Filler dispersant, leveling agent, defoamer, antistatic
Agent, pH adjuster, surface modifier, plasticizer, drying accelerator, flow
Stoppers may be added. Composition for coating as described above
The material is applied to the substrate once or more than once and then fired
Silicon-nitrogen-oxygen system or silicon-nitrogen-oxygen-carbon system
A coating film made of Lamix is formed. The base on which the coating composition is applied is
Not limited to, glass, plastics, ceramic
Or metal or the like. Coating as a coating
As a cloth means, a usual coating method, that is, spin coating is used.
Coating, dipping, roll coating, bar coating, brush coating, spraying
Coating, flow coating and the like are used. Also, before applying
Surface treatment with sanding, degreasing, various blasting, etc.
And the adhesion performance of the coating composition is improved. [0034] Coating by such a method and drying
After drying, heat and bake. This firing allows the ceramic
Containing ultra fine particlesPerhydroPolysilazane is crosslinked and shrunk
Oxidation or hydrolysis depending on the firing atmosphere
To form a tough coating. The above firing conditions arePell
HydroIt depends on the molecular weight and structure of polysilazane.
You. Firing temperature isPerhydroPolysilazane is ceramic
Temperature is usually 400 ° C. or higher, but lower
Of ceramic typePerhydroPolysilazane
Then it can be at a reasonable low temperature, for example, 130-350 ° C.
No. The rate of temperature rise is not particularly limited, but is slow at 5 to 20 ° C./min.
A gentle heating rate is preferred. The firing atmosphere is oxygen, air
Either medium or inert gas may be used.
Aerial is more preferred. Fine metal particles by firing in air
AdditionPerhydroOxidation of polysilazane or in air
Hydrolysis by the coexisting steam proceeds, as described above.
Mainly Si-O bond or Si-N bond at low firing temperature
It becomes possible to form a tough coating as a body. Thus, the coating composition of the present invention
When fired, hardDegree 9High hardness of more than H (pencil hardness) and
A dense ceramic film is obtained, and its visible light transmittance is 8
It can be 0% or more, and even 95% or more. What
The preferred embodiments of the present invention are listed below.
You. (1) The transparent UV-absorbing ceramic film according to claim 1
Manufacturing method. (2)PerhydroPolysilazane, number average
Perhydroperhydropolysila having a molecular weight of 200 to 10,000
TheInA method of (1). (3) TiO_TwoHas an average particle size of 0.05 μm or less.
(1) The method of (2). (4) Manufacturing method of (1), (2) and (3)
Transparent UV cut inorganic with hardness of 9H or more formed by
Membrane. [0038]Reference Example 1 The following raw materials were used. (A) Tonen perhydropolysilazane PHPS-1 (M
n ≒ 800) 20 wt% xylene solution. (B) ZnO dispersion ZS-30330 manufactured by Sumitomo Cement
wt% toluene solution. (A) and (B) are mixed and mixed with a stirrer.
The mixture was stirred for an hour to obtain a uniform coating liquid. The mixing ratio is
Total solids (PerhydroPolysilazane + Zn in ZnO)
0 wt%, 43 wt%, 69 wt%, 79 wt%, 9
2 wt%. Spin coating solution obtained
And apply it on quartz glass (3000 rpm × 20
Sec), heat at 10 ° C / min, hold at 400 ° C for 1 hour and bake
Done. The thickness was about 0.5 μm. Each sample (including a ZnO-free film)
The optical characteristics are shown in FIG. According to this, any sample
Has a visible light transmittance of 95% or more, and ultrafine ZnO
The fact that they are uniformly dispersed in the film is supported. Also,
The UV absorption effect of ZnO is well exhibited, and 92 wt.
% Of ZnO (perhydropolysilazane is calcined
After that, SiO 2 of density 2_Two80 vol%
Equivalent), with a wavelength of 360
It can be seen that UV of nm is cut by about 90%. The hardness of each sample was 9H or less.
Above, that an extremely dense inorganic film is formed
Understand. This is a perhydropolysilaza that does not contain organic groups
This is due to the use of a completely inorganic UV-cut film.
And is characterized. [0042]Reference example 2 The following raw materials were used. (C) Tonen perhydropolysilazane PHPS-2 (M
n ≒ 1200) 40 wt% xylene solution. (C) andReference example
Mix the ZnO dispersion liquid (B) used in 1 and stir the mixture.
The mixture was stirred for 3 hours to obtain a uniform coating solution. mixing ratio
Is 75 wt% (5% after firing)
0 vol%). The obtained coating solution was coated with a
Coating on stainless steel plate (SUS304)
And dried at room temperature for 15 minutes. Pre-bake at 150 ° C for 5 minutes
To remove the solvent completely, and bake at 400 ° C for 1 hour.
Thus, a ZnO-containing ceramic film having a thickness of 5 μm was obtained.
The hardness of the obtained film is 9H or more, which is at the level of an optical microscope.
No defects such as cracks and pinholes were observed.
Was transparent. [0044]Example 1 The following raw materials were used. (D) Idemitsu Kosan, TiO_Two  Powder IT-UD.Reference example
20% by weight of xylene solution of PHPS-1 used in (1)
, The powder of (D) was added thereto, and ultrasonically dispersed for 20 minutes.
One coating solution was used. The mixing ratio is T
iO_Two17% by weight, 29% by weight and 44% by weight
Was. The obtained coating liquid is applied to a spin coater.
On quartz glass (3000 rpm x 20
Sec), raise the temperature at 10 ° C / min, hold at 400 ° C for 1 hour
Fired. The thickness was about 1 μm. Minutes for each sample
The optical characteristics are shown in FIG. According to this, any sample
The transmittance of visible light at 500 nm is 90% or more.
Yes, ultra fine TiO_TwoAre uniformly dispersed in the film
Is supported. Also, TiO_TwoUV absorption effect
(Especially UV-B) is well exhibited, and 44 wt% Ti
O_TwoBy addition, UV of 300nm is cut by 100%
You can see that it is. Further, as shown in Table 1, the hardness was
Is 9H or more, and an extremely dense inorganic film is formed.
You can see that Also, as shown in Table 1, a high refractive index film is available.
It turns out that it is use. [0047]   Table 1 TiO_Two/ Perhydropolysilazane-based     TiO_TwoAddition amount (wt%) Refractive index Hardness   (TiO _Two + Silazane) standard            0 1.46> 9H            17 1.60 ＞ 9H            29 1.64> 9H            44 1.68 ＞ 9H [0048] According to the present invention, a dense and high-hardness transparent
A UV absorbing ceramic film is obtained. This membrane is complete
It is inorganic and has excellent weather resistance. It is also possible to increase the thickness. Obedience
Therefore, it is suitable for automobile glass and building material glass. Sa
Furthermore, it is also useful as a high refractive index film. Also, since it can be obtained as a thick film, it can be used for various substrates.
When used as a sealing film for holes and holes,
No gas or water barrier film. Also resistant to mechanical shock
There are features.

[Brief description of the drawings] FIG. 1 shows the light transmittance of a coating film of Example 1. FIG. 2 shows the light transmittance of a coating film of Example 2.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-138107 (JP, A) JP-A-5-311120 (JP, A) JP-A-2-169673 (JP, A) JP-A-2- 265976 (JP, A) JP-A-3-134069 (JP, A) JP-A-6-329989 (JP, A) JP-A-57-67681 (JP, A) JP-B-63-16325 (JP, B1) (58) Field surveyed (Int.Cl. ⁷ , DB name) C09D 183/16 C01B 21/087 C08K 3/22 C08L 83/16 C09D 1/00

Claims (1)

(57) [Claims] [Claim 1] Mainly, general formula (I): In the coating solution a number average molecular weight is composed mainly of 100 to 50,000 of perhydro polysilazane having a main skeleton composed of units represented an average particle diameter 0.005~0.1μ
The high dispersion treatment TiO ₂ ultrafine particles m 15 to 85 wt%
The applied coating composition is applied and baked to obtain a hardness of 9
A method for producing a transparent UV-absorbing ceramic film, comprising obtaining a transparent UV-absorbing ceramic film of H or more .