JP2696829B2 - High refractive index coating film and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial applications]   The present invention relates to plastic, metal, ceramic, and glass.
Optical thin film for improving abrasion of a substrate such as an optical fiber and the production thereof
About the method.   For more information, see Plastics, Metals, Ceramics, Gas
By applying it on the surface of a substrate such as a lath, scratch resistance,
Abrasion resistance, water resistance, chemical resistance, stain resistance, heat resistance, possible
Improves dyeability and weather resistance, and has a different refractive index from the substrate
High refractive index effective to generate light interference guided by
The present invention relates to a coating film and a method for producing the same. [Conventional technology]   Conventionally, silicon-based coating films have abrasion resistance,
Excellent heat, weather resistance, plastic, wood, metal table
By applying to the surface, it has been used to improve the characteristics of the base material
And industrial applications in the metal and plastic fields
It is broad. The disclosed technology includes, for example, rice
Colloidal silica described in National Patent No. 3986997 and the like
Hard coat derived from methyltrimethoxysilane or
Colloidal silica and epoxy resin such as Japanese Patent Publication No. 57-2735
Hard coat derived from Si-based material
Alkyl trialkoxy sila described in -29102 and the like
, A hard coat derived from ortho-organosilicate
And others.   In addition, the dyeability and flexibility of these hard coats are increased.
As a method, JP-A-56-161475 and JP-A-59-102964, and JP-A-59-102964 are used.
Nos. 193969 and 58-222160 include bis (alkoxysilicon
B) Compound and colloidal silica and, if necessary,
Coating compositions comprising coupling agents are disclosed
Have been.   On the other hand, the sol-gel method is used to
The formation of a wearable thin film is also noted. That is, as a typical example
Metal alcoholate in the presence of a solvent
Pre-condensation polymerization if necessary, and after application, by heating, etc.
Completes thermal decomposition and polycondensation to form an amorphous film.
is there. Examples of disclosure of these technologies include, for example, surface, V
ol.19, No.8, 430-437 (1981), and the Japanese Society of Rheology
Magazine, Vol. 14, 9 (1986) or Physic of Thin Films,
Vol.5,87-141 (1969) and Thin Solid Films, Vol.77,129
−139 (1981). The advantage of this method is that
Arbitrarily mix degradable or hydrolysable metal materials
Ability to select the refractive index as a result
In particular, to obtain a thin film with a higher refractive index than glass
Can be done.   On the other hand, it cures at a relatively low temperature and is suitable for plastic materials.
In the compositions for high refractive index thin films that can be used, there are few disclosed technologies.
However, antimony is expected to have a relatively high refractive index.
JP-A-57-168922 discloses a coating composition using
Examples of using tetraalkyl zirconium
It is described in JP-A-57-37301. [Problems to be solved by the invention]   However, among the aforementioned examples, U.S. Pat.
JP-B-57-2735, JP-B-55-29102, JP-A-56-161475
Nos. 59-102964, 59-193969, 58-222160
In the example, the refractive indices of the coatings are all about 1.5,
Having the same refractive index as a typical resin substrate
There is a problem as a functional film.   Japanese Patent Application Laid-Open Nos. 57-168922 and 57-37301 are
The problem of poor water resistance and the refractive index is not high enough
Have.   Also disclosed in Surface, Vol. 19, No. 8, 430-437 (1981), etc.
In the method called the sol-gel method, high temperature
Required for thermal deformation of plastic materials and metal substrates.
In this case, there is a problem that oxidation is caused.   Therefore, the present invention has been developed to solve these problems.
It has been studied diligently and its purpose is to
Low, so that it can be formed on plastic or metal
It can be cured by heat and has abrasion resistance, water resistance and chemical resistance
Excellent refractive index from 1.5 to 1.95
The purpose is to obtain a coating film that can be set arbitrarily.   Furthermore, by setting the refractive index arbitrarily,
Obtain a coating film that can be applied to the formation of anti-reflection films and reflection-enhancing films
Things.   Furthermore, high refractive index coatings that express these functions
To obtain a manufacturing method of a thin film. [Means for solving the problem]   The high refractive index coating film of the present invention, (1) 5 to 90% by weight of the following A, 95 to 10% by weight of the following B,
And the following C is contained in an amount of 0 to 60% by weight. A: Cerium oxide fine particles having a particle size of 1 to 50 millimicrons. B: General formula     O_{(3-a) / 2}R_aSiXSiR_aO_{(3-a) / 2}   (Wherein, R is a hydrocarbon group having 1 to 6 carbon atoms)
X represents an organic group containing 2 to 40 carbon atoms.
And a represents an integer of 0 to 2. )
An organosilicon compound having a unit. C: Silica fine particles having a particle size of 1 to 50 millimicrons.   Also, a method for producing a high refractive index coating film of the present invention
Is (2) Coating containing the following A, D and C
At least the composition, flow control agent and catalyst
Is dissolved or dispersed in a solvent containing 1% by weight of water
Coating agent manufacturing process to manufacture a coating agent,   Coating agent for applying the coating agent to a substrate
Coating process, and   80-200 ° C the coating agent applied on the substrate
A coating agent curing step of curing at a temperature of   5 to 90% by weight of the following A, 95 to 10% by weight of the following B, and
High refractive index coating film containing 0 to 60% by weight of the following C
Is manufactured. A: Cerium oxide fine particles having a particle size of 1 to 50 millimicrons. B: General formula     O_{(3-a) / 2}R_aSiXSiR_aO_{(3-a) / 2}   (Wherein, R is a hydrocarbon group having 1 to 6 carbon atoms)
X represents an organic group containing 2 to 40 carbon atoms.
And a represents an integer of 0 to 2. )
An organosilicon compound having a unit. C: Silica fine particles having a particle size of 1 to 50 millimicrons. D: General formula     Y_(3-a)R_aSiXSiR_aY_(3-a)   (Wherein, Y is an alkoxyl group, an alkoxyl
Lucoxyl, acyl, alkenoxy, acyloxy
Group selected from the group consisting of
R represents a hydrocarbon group having 1 to 6 carbon atoms.
X represents an organic group containing 2 to 40 carbon atoms.
In addition, a represents an integer of 0 to 2. Yes represented by
Silane compounds.   Next, focusing on the composition of the coating composition,
Further details on the refractive index coating film and its manufacturing method
State it.   Regarding the refractive index adjustment, the bulk bending of cerium oxide
The folding ratio is about 2.2, and silica fine particles or general formula Since the bissilane compound is approximately 1.5,
Mainly by changing the composition ratio of
The coating film has a refractive index of 1.50 to 1.95,
In addition, it can be set arbitrarily in the range from 1.55 to 1.85. Refractive index
However, at 1.85 or more, the film hardness slightly changed, and 1.
It is impossible to extract a refractive index of 95 or more.   Here, the cerium oxide as A can be 5 to 90% by weight.
When the content is 5% by weight or less, there is no effect of adjusting the refractive index.
If it is 90% by weight or more, the film becomes brittle. Next, B
Although the bissilane compound is suitably 95 to 10% by weight,
In particular, it is better to reduce this usage. B is 95% by weight or less
Above, the hardness of the film decreases, and when it becomes less than 10% by weight, the film elasticity
The strength is insufficient and it falls off. Next, silica which is C
The amount of the fine particles is suitably from 0 to 60% by weight. That is, there is no C
However, if the amount of cerium oxide fine particles in A is small,
If the refractive index is not so high, lower the refractive index
To be added as a selective agent. Therefore, the use of the present invention
Set the composition ratio of A, B, and C within the above range for the target refractive index.
Is to change.   The cerium oxide of the present invention has a particle size of 1 to 50 millimicrons.
Is used. Particle size is 50mm or more
Of interface between cerium oxide particles and silane-based binder
Reflection is in the visible range, impairing the transparency of the coating film
You. In the case of less than 1 millimicron,
They tend to be poorly aqueous and require more severe curing conditions.
It becomes important.   Cerium oxide is generally in the form of cerium dioxide,
Colloidal liquid dispersed in water or solvent is readily available,
Operation is easy. However, the invention is not limited to this. For example,
Recently, the pulverization method or the vapor phase synthesis method, etc., with remarkable technological progress,
Is obtained by dispersing uniformly in a dispersion medium
It seems possible.   The silica fine particles have the same principle as the cerium oxide fine particles.
For this reason, a similar form can be used.   Next, the bissilane compound described in B is coated
As a raw material for use in liquids, General formula Wherein X is -CH_Two−, −CH_TwoCH_Two−, −CH_TwoCH_TwoCH_Two−, Selected from. Here, b is 1 to 4. Also,
Y is an alkoxy such as methoxy, ethoxy, propoxy, etc.
Alkoxy groups such as
Halogen groups such as chloro and bromo, hydrogen and isopropenoki
These are selected from the group
Essence due to hydrolysis or partial dehydration condensation when combined
The condition is satisfied if desorbed in the presence of water or a catalyst.
It is considered.   Further, a methyl or ethyl group represented by R is directly attached to silicon.
Are added to obtain flexibility and elasticity.
It is possible.   These are solution-type coating liquids,
And heat-cured to form a coating film
General and advantageous. For this, A and C are water or
A sol dispersed in alcohol, organic solvent, etc. is desirable,
Addition of appropriate stabilizers, dispersants and the like is also permitted. Also, B
Raw materials are also available in water or acidic water in a solution or without solvent.
Perform hydrolysis to convert the leaving group to a hydroxyl group in advance.
Can do things. Mix these, dilute with an appropriate solvent and use
Can be. Solvents include alcohols, ketones,
Tell is useful.   In addition to these, surfactants for improving coatability,
A catalyst may be added to promote ranol condensation polymerization.
It is for. Examples of these include, for example, JP-A-56-99
Acids, organic acid salts, coordination compounds described in
Persalts such as ammonium perchlorate and magnesium perchlorate
Examples include salts, titanium alcoholates, and various salts.
It is.   The thickness of the high refractive index coating film of the present invention is 0.1 to 30.
Preferably it is microns. Also, anti-reflection or
When used as a reflection enhancement film,
It goes without saying that the film thickness is designed. As the application method
As is well known, spray method, dip method, spinner
-Method, flow coating method, roll coating method, brush coating method, etc.
To apply.   In addition, although dyeability can be obtained only with A, B and C,
Epoxy compounds and polyethylene
Add glycol, polyhydric alcohol, polyhydric fatty acid, etc.
You can also.   The coating composition thus obtained is applied to a substrate.
After drying, air drying, heat curing or irradiation with active energy rays
Hardening by hot air at 80 ° C to 200 ° C.
It is preferable to conduct a condensation reaction in the inside. Base material with particularly poor heat resistance
In this case, the temperature is preferably between 80C and 150C. Or live
Within a few seconds with far infrared laser etc.
It is also conceivable that the heat damage can be reduced by the treatment.   Coating set obtained by mixing as described above
The product is made of various optical inorganic glass or polycarbonate
First, polystyrene, polymethacrylate, poly
Vinyl chloride, polyethylene terephthalate, CR-39 ,
Other styrene and nuclear substituted halogenated bisphenol
Transparent plastic such as copolymer with nomer or allyl resin
Exhibit the effect by applying to stick material
You. [Action]   The present invention relates to inorganic fine particles A and C and B
A, B and C
Is insufficient in hardness, abrasion resistance, water resistance and adhesion by itself
is there. However, with A or A and C as nuclei,
The reactive group of B condenses on the surface or the periphery to form bonds or fill
The characteristics are improved by the effect of the indentation.   Furthermore, all the condensation reactive groups are made of silicon-based material.
, Si-O-Si bond, light resistance of the resulting film,
Durable, harder, more chemical resistant membrane
Was obtained.   Furthermore, cerium oxide having a refractive index of 2.2 and a refractive index of about 1.5
~ 1.46 bisicilan compound and silica fine particles are mixed
By doing so, it is possible to obtain any high refractive index film
Was. Here, the target refractive index is, for example,Indicated by Where W_AIs the weight percent of A, (W_B+ W_C)
The weight percent of the sum of B and C indicates the porosity. According to this formula
The target refractive index is calculated and used. 〔Example〕   Hereinafter, the present invention will be described in more detail by examples,
The present invention is not limited to these. Examples
The middle part indicates parts by weight. Example 1. (1) Preparation of coating liquid   Into a glass flask equipped with a magnetic stirrer,
Water-dispersed cerium dioxide sol (solid content 30%, average particle size 5mm
(Micron) and add 150 parts.
After slowly adding 200 parts of isopropyl alcohol,
60 parts of tris (trimethoxysilyl) ethane were slowly added.
Next, 40 parts of 0.1 N hydrochloric acid solution was added dropwise over 30 minutes. One
Therefore, a small amount of flow control agent and a small amount of antioxidant
After the addition, filtration was performed to obtain a coating solution. (2) Coating and curing   A plasma treatment is applied to the coating liquid thus obtained.
Based on the theory, polycarbonate lens with activated surface
Was dipped and applied by the Dippig method. this
The pulling speed at that time was 200 mm / min. Next, 5 minutes
After air drying, heat and cure in a heating furnace at 100 ° C for 3 hours.
Was. The lens thus obtained has no interference fringes and is transparent.
It was very clear. (3) Evaluation method and results (4) Evaluation test and results   The obtained lens is tested and evaluated by the following method.
did. Table 1 shows the results. a) Scratch resistance:^#0000 steel wool (trade name "bon
200g load using Star “Nihon Bonstar Co., Ltd. product”
Then, the surface of the test piece of 1 cm × 3 cm square is rubbed 10 times,
The degree of scratching was visually evaluated in the following stages. Rank A: The above range is not damaged at all. Rank B: 1 to 10 scratches are made within the above range. Rank C: 10 to about 50 scratches are made in the above range. Rank D: Countless scratches, but a smooth surface remains
I have. Lang E: Due to scratches on the surface, the surface smoothness is impaired
You. b) Chemical resistance; immersed in water, alcohol, kerosene for 48 hours
Then, the surface condition was examined. Acid resistance and detergent resistance are 0.
1N hydrochloric acid and 5% kitchen height (Kao Soap Co., Ltd.)
Manufactured) aqueous solution for 12 hours, and the surface condition was examined. c) Weather resistance; Phedometer with xenon lamp
(Suga Test Machine Co., Ltd.) Surface after exposure for 200 hours
I checked the condition. d) Adhesion: The adhesion of the film shall be in accordance with JISD-0202.
It was performed by a scut tape test.   In other words, using a knife, cut at 1 mm intervals
To form 100 squares of 1 mm. Then on it
Heterophane adhesive tape (product name "Cellotape" Nichiba
90 ° direction from the surface after strongly pressing
After peeling off all at once, the square where the film remains
Was used as an adhesion index. e) Dyeability: Dyeing at 80 ° C for 5 minutes using disperse dye
Was performed, and the extinction ratio of the test lens was measured. The staining solution is 1
In pure water with a dye (trade name “Seiko Black Sgle
-D "Seiko Epson Corporation) and dyeing aids (products)
Name "Seiko Plux Dyeing Aid" Seiko Epson
2 g each).
The dimming rate is measured by a BPI photometer (BPI Co. Ltd.)
And a case where a dimming rate of 20% or more was shown as good. f) Refractive index; coating liquid applied to silicon wafer
After coating and curing, use an ellipsometer to measure the refractive index of the coating film.
And the film thickness were measured. Examples 2 to 4, Comparative Example 1   In Example 1, 150 parts of water-dispersed cerium dioxide sol
Instead of cerium dioxide sol (solid content 30%, average particle size
5mm micron, aqueous sol) and silica sol (solid type)
30%, average particle size 10 millimicron, aqueous sol)
The procedure was the same as in Example 1, except that
High refractive index coating films having various refractive indexes were prepared.   Table 1 summarizes the characteristic evaluations. Example 5   In Example 1, bis (trimethoxysilyl) eta
Bis (methyldimethoxylyl) ethane instead of 60 parts
60 parts and ethylene glycol diglycidyl ether 10 parts,
Except adding 0.05 parts of magnesium perchlorate
A coating liquid was prepared in the same manner as in Example 1.   This coating solution is applied to the polished plasma
It was applied to a panel made of styrene and cured at 90 ° C. for 3 hours. this
The panel had a good appearance without interference fringes. Example 6 Formation of antireflection film (1) Preparation of high refractive index coating liquid   Methyl cellosolve 75 was added to 25 parts of the coating film obtained in Example 1.
To obtain a high refractive index coating solution. (2) Preparation of low refractive index coating liquid   25 parts of the coating film obtained in Comparative Example 1, polyethylene glycol
Rudiglycidyl ether 2 parts, methyl cellosolve 75
Parts, 0.1 part of ammonium perchlorate
Ting solution. (3) Formation of anti-reflection lens   Polydiethylene surface activated by alkali treatment
First, use a high-quality glycol diallyl carbonate lens.
The refractive index coating liquid was applied by a spinner method. Ko
The working conditions are as follows. 15 seconds at 500 rpm 40 seconds at 3000 rpm   After heating at 1000 ℃ for 30 minutes and curing,
Next, apply the low refractive index coating solution to the high refractive index coating
The coating was carried out in the same manner as the coating solution.   Thereafter, heating is performed at 100 ° C for 30 minutes and further at 130 ° C for 2 hours.
Thus, a cured film consisting of two layers was obtained.   This lens shows a strong green reflection and, as a result of spectroscopy,
The average reflectance in the visible region is 4%, indicating anti-reflective properties.
Was. The reflectance of the cloth was 8%. Examples 7 and 8   In Example 1, bis (trimethoxysilyl) eta
Use the binder components shown in Table 3 instead of 60 parts
The procedure was the same as in the example except that
Was obtained. These reviews
As a result, good results were obtained in all cases. 〔The invention's effect〕   As described in detail above, the present invention has a high refractive index,
Also need cerium oxide fine particles with excellent chemical resistance
The silica particles added according to the formula have excellent crosslinkability and physical properties.
In combination with chemically stable bissilane compounds
It is. And change the refractive index to a normal plastic material
Set it to a suitable range and / or use a high
It is possible to obtain a refractive index. That is, high refractive index material
Cerium oxide as a material and silicon as a low refractive index material.
Calcium or bissilane compound is calculated by the formula described in the present invention.
The desired refraction by mixing
Get the rate.   In particular, in the vapor deposition method, the refractive index is limited depending on the material.
On the other hand, in the present invention, it is possible to obtain the calculated target refractive index.
Therefore, it is effective for optical multilayer film applications.   Furthermore, the coating film of the present invention can be made of plastic or gold.
Plastic lens and film
Anti-reflection film, reflection enhancement film,
Useful as a protective coat.

   ────────────────────────────────────────────────── ─── Continuation of front page    (56) References JP-A-62-31802 (JP, A)                 JP-A-60-262834 (JP, A)                 JP-A-60-262833 (JP, A)

Claims (1)

(57) [Claims] A high-refractive-index coating film comprising the following A in an amount of 5 to 90% by weight, the following B in an amount of 95 to 10% by weight, and the following C in an amount of 0 to 60% by weight. A: Cerium oxide fine particles having a particle size of 1 to 50 millimicrons. B: Formula _{O (3-a) / 2} R a SiXSiR a O (3-a) / 2 ( In the formula, R represents 1 -C represents a hydrocarbon group of 6, X is 2 to no Represents an organic group containing 40 carbon atoms, and a represents an integer of 0 to 2.) C: Silica fine particles having a particle size of 1 to 50 millimicrons. 2. A coating composition manufacturing step for preparing a coating agent by dissolving or dispersing a coating composition, a flow control agent, and a catalyst in a solvent containing at least 1% by weight of water, containing the following A, D, and C; A coating agent applying step of applying to the substrate, and a coating agent curing step of curing the coating agent applied to the substrate at a temperature of 80 to 200 ° C .; A method for producing a high refractive index coating film, comprising producing a high refractive index coating film containing 95 to 10% by weight of B and 0 to 60% by weight of the following C. A: Cerium oxide fine particles having a particle size of 1 to 50 millimicrons. B: Formula _{O (3-a) / 2} R a SiXSiR a O (3-a) / 2 ( In the formula, R represents 1 -C represents a hydrocarbon group of 6, X is 2 to no Represents an organic group containing 40 carbon atoms, and a represents an integer of 0 to 2.) C: Silica fine particles having a particle size of 1 to 50 millimicrons. D: General formula Y _(3-a) R _a SiXSiR _a Y _(3-a) (wherein, Y is an alkoxyl group, an alkoxyalkoxyl group, an acyl group, an alkenoxy group, an acyloxy group, a halogen group and a hydroxyl group. Represents a leaving group selected from the group consisting of: R represents a hydrocarbon group having 1 to 6 carbon atoms; X represents an organic group containing 2 to 40 carbon atoms; An organic silane compound represented by the following formula: