JPS59115840A - Low reflectivity coating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a low reflectance coating film having a multilayer structure that is applied to the surface of a transparent substrate such as glass or transparent plastic to reduce the surface reflection of the substrate. be.

Transparent materials such as glass or transparent plastic are preferably used for windows, doors, show windows, showcases, optical lenses, etc. of buildings, vehicles, etc. However, the surface of such materials has the disadvantage that it causes glare and dazzle due to reflection of sunlight and illumination light, and furthermore, the transparency and see-through characteristic of the material are impaired due to reflection of the surrounding scenery. easy.

In addition, in recent years, the use of sunlight has been promoted due to energy conservation policies, and solar collectors have been developed, but in order to improve heat collection efficiency, it is necessary to The goal is to eliminate or reduce reflection loss from the source and allow a large amount of energy to pass through.

Conventionally, anti-reflection methods for the surface of transparent substrates such as glass or transparent plastic have been developed for all optical components. Vacuum deposition or sputtering methods for forming thin films have been put to practical use in optical lenses, eyeglass lenses, filters, and the like. In addition, it is possible to form a low-reflectivity coating film by coating, spraying, or immersing a low-reflection treatment agent made of a polymeric substance on the surface of a transparent substrate such as glass or transparent plastic. Treatment methods or low-reflection treatment agents have been proposed.

However, in the above methods, the vacuum evaporation method or the sputtering method is limited to small precision optical parts due to the size of the equipment and the cost, and is not suitable for continuous production.

When a coating film of a low-reflection treatment agent is formed by coating, spraying, or dipping, the formed low-reflection coating film may be damaged by cleaning operations to prevent contamination, etc.
- It has shortcomings in hardness and durability, such as peeling.

Based on the recognition of the above-mentioned problems, the inventors of the present invention have proposed a method of coating, spraying, dipping, etc. on the surface of a transparent substrate such as glass or transparent plastic without impairing the transparency and see-through of the substrate. Various studies and studies have been carried out in order to provide a low-reflectance coating film that makes the surface of the substrate low-reflectivity using the above method or a new method, and has good durability and maintains its performance over a long period of time.

As a result, polyfluorinated group-containing compounds have a low polarizability of fluorine atoms and therefore a low refractive index, such as 08F,
Refractive index of 8 (25°C, same below) fil, 271, (C
4F, )3N id 1,290, (CF2=CF2/
The polymer of cF'30CF=CF,) is 1.330, and it is possible to reduce the reflectance by forming a coating film on the surface of a transparent substrate such as glass or transparent plastic. The chemical group-containing compound has a strong cohesive force to the substrate, but the hardness of the coating film depends on the film thickness, and a certain amount of total film thickness is required, but a thin film is preferable from the viewpoint of low reflection performance. In order to improve the hardness of a thin film of a fluorinated group-containing compound, a transparent coating film made of another material with high adhesive strength and hardness is formed on the surface of a transparent substrate, and a polyfluorinated group-containing compound is applied on the coating film. It has been found that by forming a thin film consisting of the following, a coating film with excellent low reflection performance and film hardness can be obtained.

Based on this knowledge, the present inventors have found that a coating film formed on the surface of a transparent substrate such as glass or transparent plastic (hereinafter referred to as the "lower coating film") firmly adheres to the transparent substrate, has high hardness,
A silane compound or a transparent compound that is transparent, has good adhesion to the polyfluorinated group-containing compound formed on the coating film, and has a refractive index comparable to or higher than that of the transparent substrate. The thin film formed on the coating film (hereinafter referred to as the upper layer thin film) is preferably made of a compound containing a polyfluorinated group and forms a thin film of a polymer. The present invention was completed based on the discovery that by creating a coating film with such a multilayer structure, a coating film with high hardness and excellent low reflection performance can be obtained even if it is a thin film.

That is, the present invention provides a low reflectance coating film to be applied to the surface of a transparent substrate such as glass or transparent plastic, which comprises a coating film of a silane compound or transparent resin having a refractive index comparable to or higher than that of the transparent substrate, and the coating film. The present invention provides a low reflectance coating film with a multilayer structure, which is characterized by forming a thin film of a polyfluorinated group-containing compound with a thickness of 0.2 μm or less on the film.

In the present invention, the silane compound having a refractive index comparable to or higher than that of the transparent substrate in the lower coating film has the general formula (x(A)
c) A silane coupling agent represented by aSi(Z)bY4-ab is preferred. The general formula % Formula % NGO-1 is an alkylene group, 2 is a lower alkyl group having 1 to 4 carbon atoms, Y is a norogen, an alkoxy group is excursion, a is an integer of 1 to 3, and b is O or 1 to 3. 2 integer, C is O
or an integer of 1. As such a silane coupling agent (for example, C:H2-CHCH,,0(CH2,)
3Si(OCH3)3, Numa(CH, NH(鵠%)
5i (OCH3) 3゜\doW horse (CH,), 5i (OCR,, ), C%20H
81(0(1'H3)3. C4=CH8iC13°CH3 0I(2=CC00(CH2)3S1(OCH3)3.
H8(CII2)3S1(OcH9)3゜NC0(CH
2) 3Si (QC:2H5)3. C1(CH2)3
Si(OCI(3)3゜0H2=C4CH2NH(CH
2) 2NH(C:H2)3Si(OCH3).

0te)ca, c4sBocH,)3. The refractive index of such a silane coupling agent condensate is 1.47 to 1.60, which is comparable to or thicker than that of transparent plastics such as glass or polycarbonate. Preferable results can be obtained even when two or more types of sila/compounds are used in combination.

A transparent resin having a refractive index comparable to or higher than that of the transparent substrate is
Examples include epoxy resin, melamine resin, and urethane resin.

The lower coating film is appropriately selected depending on the refractive index of the transparent substrate, but if a coating with a refractive index lower than that of the transparent substrate by 0.1 or more is selected, a low reflectance coating film with excellent performance cannot be obtained. do not have.

The polyfluorinated group-containing compound of the upper thin film is, for example, “f(CH2)2Sic131 Rf(CH2)z=(
CH3)C12, (RfcH,,CH2)2sic12
゜Rf(CH2)zsl(QCl(s)3+ RfCO
NH(CH2)3Si(QC2H,)31RfCONH
CCH2)2NH(CHz)s 51(OCzHs
)s +RfBO2N(CH3) (CH,)2 C0
NHriCH,)3s1(oc2a5)s.

Rf(CHz)z 0Co(”'z)2sCcH2)3
S'(QCl3)3 +Rf(CH2)20CON
H(CHl)3si, (oc2a, )s.

RfCCH2)2NH(CH2)281(OCH3)3
+RfCCH2)2NH(CH2)2si(OCR
2cH20CH3)3゜(However, Rf has 4 to 16 carbon atoms.
polyfluoroalkyl group, m is an integer of 1 or more); silane compounds in which the polyfluoroalkyl group has an ether bond; mixtures of such silane compounds and other sila/compounds; c13Si( CH2)2 (C:F2)n(CH2)2
SiC13゜CH3C0)351(CJ(2)2 (”
2)n(CH2)2Sl(QCl9)1hHowever, n
is an integer of 4 to 16, the same applies hereinafter] and polyfluoroalkylene group-containing silanized metal compounds, and polyfluoroalkylene group-containing jepoxy compounds such as.

Also included are copolymers of polyfluoroalkyl group-containing methacrylates and methacrylic acid derivatives, for example, reaction products of polyfluoroalkyl group-containing alcohols and melamine derivatives.

Furthermore, C8F, 7CH:CH, CF3CEC-CF3.
Any plastic polymerizable compound such as C3FL87i can be used.

The low reflectance coating film of the present invention has a multilayer structure in which a lower layer coating film is formed on the surface of a transparent substrate, and an upper layer thin film is formed on the coating film, and the thickness of the lower layer coating film is at least 0.1μ, Especially 0.
It is preferable that it is 5-5μ. If the thickness of the coating film is less than 0.1 μm, the entanglement of the molecules of the coating material becomes insufficient, the strength of the coating film cannot be maintained, and the hardness of the upper thin film formed on the coating film cannot be improved. The thicker the lower coating film is, the higher the hardness of the upper thin film formed on the coating film, but it is preferable to make it thicker than necessary from the viewpoint of the influence on light transmittance, workability of coating, and economic efficiency. The upper limit is 10μ.

The method of forming the lower coating film on the surface of the transparent substrate is not particularly limited. When using a silane compound, for example, dissolve the silane compound in an organic solvent such as acetone, tetrahydrofuran, or lower alcohol, and add 5 to 50% by weight, preferably 1% by weight.
It can be applied as a 5 to 40 weight percent solution by known methods such as coating, spraying, and dipping. After coating, dry at room temperature or, if necessary, at a temperature of about 100°C for 30 minutes to 1 hour to form a coating film in which crosslinking of the silane compound has partially progressed, and then apply the upper layer thin film material on top of it to form a thin film. form. Two or more types of silane compounds may be combined. In such a case, two or more silane compounds are mixed and stirred to react, and then an organic solvent is added to adjust the viscous dust, and then applied and treated in the same manner as above. Complete coating is formed. Transparent resin? When used, for example, as an epoxy resin "Epicor) -1001,"
(Product name: Dioilka Shell Chemical Co., Ltd. product), melamine resin "Cymeru 325" (Product name: Mitsui Toatsu Chemical Co. product), urethane resin "Orestar M75-50F"
i# (black market name: Mitsui Toatsu Chemical Co., Ltd. product) is preferably used. After adding a crosslinking agent or a polymerization initiator to the epoxy resin and melamine resin and applying them to the surface of the transparent substrate to proceed with partial crosslinking, an upper layer thin film material is applied to form a thin film.

After the urethane resin is applied to the surface of the transparent substrate, it is partially polymerized and cured by moisture in the air, and then an upper layer thin film material is applied to form a thin film. Is there an antistatic agent or high refractive index in the bottom N coating material? Other components may also be included.

The method for forming the upper layer thin film made of the polyfluorinated group compound on the lower layer coating film can be carried out by any known coating method, but the preparation method suitable for coating the compound differs depending on the compound used.

i.e., the polyfluoroalkyl group-containing silane compound;
In the case of a silane compound in which the polyfluoroalkyl group has an ether bond, a mixture of such a silane compound and another silane compound, or a silane compound containing a polyfluoroalkylene group, the compound or mixture may be mixed with acetone, tetrahydrofuran, chlorine-based or Dilute with one or more mixed organic solvents such as fluorine-based solvents to form a 1 to 15 weight solvent solution, preferably a 3 to 10 weight solvent solution, and apply and spray onto the lower coating film. , by dipping or other known methods.

After coating, a thin film can be formed by curing at a temperature of 100° C. or higher for 20 minutes or more.

In the case of a polyfluoroalkylene group-containing jepoxy compound, one type of curing agent selected from polyfluoroalkylene group-containing amine compounds, other amines, BF3 salts of amines, and carboxylic acid anhydrides is added to the compound in a curing reaction. It is preferable to use a curing agent that has a low refractive index and is reacted at room temperature to 150°C for 5 minutes to 3 hours to form a partially polymerized product. In this case, even if the total amount used increases, the low reflection performance will not be affected. For example, “2N(CH2)2 (”2)6 (CH2)2NH2
can be added by 10 to 50 weight.

For copolymerization of a polyfluoroalkyl group-containing methacrylate and a methacrylic acid derivative, a polymerization initiator is added to a mixture of the compounds and heated to form a copolymer. To the reaction product of the polyfluoroalkyl group-containing alcohol and the melamine derivative, 1 part by weight of P-)luenesulfonic acid is added as a catalyst component based on the solid component, and the mixture is heated to obtain a reaction product.

Such a copolymer or reaction product can be diluted in a solvent in the same manner as the above-mentioned compounds, applied onto the lower coating film, and then cured to form a thin film.

A thin film of the plasma polymerizable compound can be formed on the lower coating film by polymerizing it in a plasma polymerization device.

The thickness of the upper thin film formed by this method is 0.2
It is preferably less than μ, particularly 0.08 to 0.2 μ. 0
．． If it is thicker than 2 μm, the performance as a low reflectance coating will be significantly inferior. The thickness of the C thin film varies depending on the coating conditions. The upper layer thin film material made of a polyfluorinated group-containing compound contains an inorganic filler, such as silica gel.

Li□SiF6. MgF2. Na2SiF6.
The hardness of the thin film can be further improved by adding MgSi'F, etc. In addition, the upper layer thin film material can be used in the usual manner, such as a solvent solution, a solvent dispersion, or an emulsion.

It can be prepared in any form such as an aerosol, or additives such as an antistatic agent and a crosslinking agent can be added as appropriate.

The visible light reflectance of the transparent substrate on which the low reflectance coating film of the present invention is formed is 0.6 to 1.4, the reflectance of ordinary soda lime glass is 42, and the reflectance of methacrylic resin is 3.
．． 9%, and an excellent effect compared to that of polycarbonate, which has a reflectance of 4.8%. Furthermore, the hardness of the coating film is pencil hardness B~〉
5H, which is a significant improvement over the pencil hardness >2B of the coating film containing only the polyfluorinated group-containing compound.

Further, transparency or visibility is not impaired.

The application of the low-reflection, low-reflection coating film of the present invention is not particularly limited, and includes, for example, windows of buildings! It can be used for glass or transparent plastic materials such as vehicle windows, doors, show windows, showcases, optical instruments, eyeglasses, and sunlight condensing members.

The evaluation method for the low reflectance coating film of the present invention is as follows. That is, a self-recording spectrophotometer reflection light measurement area.

Wavelength 540 using a device (type 323: newly manufactured by Hitachi)
This is done by measuring the reflectance of mμ at an incident angle of 5°.
The hardness of the coating film was determined by measuring the stylus pressure using an ank (manufactured by Taylor Hobson), and the hardness of the paint film was measured by measuring the hardness of lead algae using a lead umbrella scratch tester (JXB-K 5401). Ta.

EXAMPLES The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

Synthesis Example I RfCH=CH2 (However, Rf: Cn'2n4-
t, n: 6.8.10゜12 mixture with average value 9.0) 49.6 F (0.1 mol), H81C
1315,9j (0.12 mol), H2PtCl6.
A 50% isopropanol solution 01M' of 6H200 was placed in a pressure-resistant glass ampoule with an internal volume of 100 vtl, and reacted at 85° C. for 200 hours with shaking. After the reaction was completed, a reaction product was obtained by distillation under reduced pressure.

When the reaction product is analyzed by gas chromatography, Rf
(C)I2)2SiC:13(b,P, 85℃~1o
o℃/3~5wnHy), and the conversion rate Fi9 to that is
It was 5%.

Synthesis row 2 Reaction product Rf(CH2)2EiiC1 of synthesis I+01
350.3t (008 mol) and 15f of methanol were mixed, and the mixture was reacted with dry nitrogen to remove the generated HCl1.The end point of this reaction was to remove the generated HCl-
<Confirmed by quantitative determination. After the reaction was completed, excess methanol was distilled off to obtain a reaction product. When the reaction product was analyzed by gas chromatography, it was found to be Rf(CH2)2Si(OCH
3) The conversion rate to 3-dashi was 100 yen.

Synthesis Example 3 RfCOOCH(CH3)2 (However, Rf: Cn
l'2n4-t, n: 6°8, IQ, average value 9.0 in a mixture of 12) 111.2f (0.2 mol), H2N(CH2)3Si(QC, H5) 344.2
? (0.2 mol), dry tetrahydrofuran 150
9 is equipped with a thermometer, stirrer, and cooling pipe with an internal volume of 300 m.
The mixture was placed in a four-bottle flask and reacted for 5 hours at reflux temperature [approximately 80° C.] while stirring under a stream of dry nitrogen. Tetrahydrofuran was distilled off to obtain a reaction product. The reaction product was analyzed by gas chromatography and was found to be RfCO
The conversion rate to NH(CH2)3(OC2H5)3 was 100%.

Synthesis νS4 Via, CF3 CF3CF2CF2O+CFCF20% CFCOO
C2H569,017' (0.1 mol), H2N (cI
(2) 3Bi, (OC2H5)322.1F (0.1 mo/l), 150 f'i of dry tetrahydrofuran was reacted in the same manner as in Synthesis Example 3. The gas content of the reaction product was 100%.

Synthesis example 5 CH2: CHC,F1□CH-CH222,6F (
0.22 of a 50% isopropanol solution of H81C1325,9 (0.19 mol), H2Pj, C16.6H20 was placed in a glass pressure-resistant ampoule with an internal volume of 100 - 200 °C at 85 °C with shaking. Time reacted.

After the reaction, add 30 fluorocarbons (R-113: Asahi Glass Co., Ltd. product)
2 was added, filtered, and low boiling point substances were distilled off from liquid f to obtain a reaction product. When the reaction product was analyzed by gas chromatography, it was found to be 13Si(C-bleached C6) (1 quotient 5iC13), and the conversion rate to it was 97%.

Synthesis Example 6 Reaction product C13S1(CH2)2C6F1 of synthesis sequence 5
□(CH2)2SIC1335? (o, o 56 mol) and methanol 157 were mixed and reacted in the same manner as in Synthesis Example 2 to obtain a reaction product. When analyzed by gas chromatography, the 7'Co reaction product was (HaCO)aSi
(CH2)2CaF+2(CH2)2Si(OCH3)
3, and the conversion rate to it was 100.

Synthesis Example 7 EC6F12 Engineering 22. , 2 f (0.4 mol),
CH2 = CHCH20H92,8r (1.6 mol) was placed in a four-lobe flask with an internal volume of 500 mJ equipped with a thermometer, a stirrer, and a cooling tube, and the internal temperature was raised to 80°C while stirring under a stream of dry nitrogen. . To this, add α,α'-azobisisobutyronitrile for a total of 10.5 liters every 30 minutes to 1 hour.
f was added, and the reaction was carried out at a reaction temperature of 80°C to 95°C for 12 hours. When analyzed by gas chromatography, the reaction products were HOCH2CM-CH2C6F', 6CH2CH-CH
20H, and the conversion rate thereto was 90H. Next, this reaction product 61 f (0.1 mol), 25% Na
OH aqueous solution 35 f (0.22 mol) f Place in a flask similar to that described in 4iJ, react at 50°C to 60°C for 300 hours, extract the reaction mixture with ether, and after distilling off the ether, distill under reduced pressure. The results were as follows: H7).

Synthesis Example 8 τH3 CH2= C-Coo C2H4Rf (However, Rf:
cn'2n41 +n: 6.8.10.12 mixture with average value 9.0) 10F, Swissobutyronitrile o
37, Fon (R-113: Asahi Glass Company product) 501i”
Place in iloomJ glass pressure-resistant ampoule and heat at 65°C.
A copolymer was obtained by reacting for 5 hours.

Synthesis Example 9 CH3 CH2=C-Coo(CH2)2Rf (However, Rf:
cn'2n-1-t +n: 6.8.10.12
Average value for a mixture of 9.0) 10r, ronitrile 0.37
, Freon (R-113, product of Asahi Glass Co., Ltd.) 30f, and tetrahydrofuran 20S'1100m/glass pressure-resistant ampoule were charged and reacted at 65° C. for 15 hours to obtain a copolymer.

Synthesis example 10 CH30CH20H20CH3 \/ " RfC,, H40H (s Rf: cnFZn+1
, n: 6.8.10°12 mixture with average value 9.0) 34.3 f (0.67 mol)'11
The mixture was placed in a 00ml three-necked flask, heated to 12°C, and reacted for 22 hours after distilling off the methanol produced, to obtain a mixture in which the reaction product with RfC2H40H and melamine were partially condensed.

Synthesis Example 11 CH,, pHcH20(CH2)3Si(QC2H5)
383.4 f, H2N(CH2)2NH(CH2)3
Si(OCH3) 366.6 rS: Pour into a 500 ml four-bottle flask equipped with a thermometer, stirrer, and cooling tube, react at 80°C for 2 hours, cool to room temperature, and add tetrahydrofuran. 1701 was added and the viscosity was 6.
A 7 cp silane compound solution was prepared.

Synthesis Example 12 CH2-C1(CH20(CH2)3Si(QC2H5
8 139 F, 0. 1N-HCl. ' Place the mixture in a four-bottle flask with an internal volume of 5 o'me equipped with a 27 ft stirrer and react at room temperature for 48 hours, then add a 30% methanol solution of silica sol W 1501 and 51 g of methanol to prepare a silane compound solution with a viscosity of 3.5 cp. was prepared.

Examples Reaction product of Synthesis Example 2 Rf(OH2)2Si(OCH3
)325? Freon (R-113: Asahi Glass Company product):
Acetone = 5007 diluted with a mixed solvent with a heavy needle ratio of 3:1
A solution of a polyfluorinated group-containing material was prepared. Separately, a glass plate (soda lime glass 5 x 5
cm) was prepared, immersed in the silane compound solution of Synthesis Example 11, pulled up at a pulling rate of 9 and Oct. 7 minutes, and then dried at room temperature for 30 minutes. Next, it was immersed in the polyfluorinated group-containing compound solution prepared earlier, pulled up at a pulling rate of 4.5 crn/min, and then cured at 160°C. The thickness of the coating film formed on the glass surface after treatment was 2.1μ, the pencil hardness of the coating film was B1, and the reflectance was 06%.

Examples 2 to 4 Synthesis Example 1 of the polyfluorinated group-containing compound of Shoshihi 111
A glass plate was treated in the same manner as in Example 1, except that the reaction product Rf(CH2)2S i C13 was changed to Synthesis Example 3CONH(CH2)3Si(QC2H5)3, and the coating film thickness and pencil hardness were and reflectance was measured.

The measurement results are shown in Table 1.

Example 5 Reaction product of Synthesis Example 6 (HaCO)3si(CH2)z
CsF, 2(CH2)2Si(○CHs)s 21.2
y, Aceto 7150f, Freon (R-113: Asahi Glass Co., Ltd. product) 128f, 1% acetic acid aqueous solution 0.6 r't-
A polyfluorinated group-containing compound solution was prepared by stirring at room temperature for 12 hours. Separately, a glass plate treated with a silane compound in the same manner as in Example 1 was prepared, immersed in the solution prepared in advance, and treated in the same manner as in Example 1. The coating film formed on the glass surface after treatment had a thickness of 1.6 μm, a pencil hardness of 5111, and a reflectance of 1.3%.

Example 6 Reaction product of Synthesis Example 5 C13Si(CH, 汲C6F',
□(Q(2) After processing in the same manner as in Example 5 except that 2Si C13 was used, the thickness, pencil hardness, and reflectance of the coating film were measured.

The measurement results are shown in Table 2.

Example 7 Synthesis 1] Reaction product of 6 (H3co)s 51(CH
2) 2-p, F)2 (CH2)2Si(,0CH3
)317. Of? , Rf(CH,)2S,t(O
CH3) 3a, 4? (However, Rf is CnF2n+
1, n (RF:, 6.8.10.12 +7) Mixed ell Te average value 9.0), Aceto 7150 f, 7
A polyfluorinated group-containing compound solution i was prepared by stirring at room temperature for 12 hours. After treating this solution in the same manner as in Example 5, the thickness, pencil hardness, and reflectance of the coating film were measured.

The measurement results are shown in Table 2.

Example 8 Reaction product O13'')(sl(''2)2O2 of Synthesis Example 6
% (”z)2si(OcHa)al 9, l?,
Cm2CH-CH20(CH2), 5i(QC2H5)
32.5 F, Ace\1 ton 150F, Freon (Fj-113: Asahi Glass product)
12.8r and 0.75f of a 1% acetic acid aqueous solution were stirred in the same manner as in Example 7 to prepare a polyfluorinated group-containing compound. After treating this solution in the same manner as in Example 5, the thickness, pencil hardness, and reflectance of the coating film were measured.

The measurement results are shown in Table 2.

Example 9 1'1L06r, H2N(CH2)2C4Il'1ll
After reacting (CH2)2NH242f at 120°C for 3 hours,
Acetone: Freon (R-113: Asahi Glass Company product), =2
06f: A solution of a polyfluorinated group-containing compound was prepared by diluting with a mixed solvent of 103r. Separately, a glass plate treated with a silane compound in the same manner as in Example 1 was prepared, immersed in the solution prepared in advance, and pulled up at a pulling rate of 8.8ff.
After pulling up at a rate of i/min, curing was performed at 160°C. The thickness of the coating film formed on the glass surface after treatment was 21 μm, and the pencil hardness and 3H1 reflectance of the coating film was 1.4%.

Examples 10 to 12 To each of the copolymer of Synthesis Example 8□9 and the mixture of Synthesis Example 10, 1% P-)luenesulfonic acid was added, and total fluorocarbon (R-113: product of Asahi Glass Co., Ltd.): acetone was added, respectively. A 5-candy solution was prepared by diluting with a mixed solvent at a weight ratio of 3:1. A glass plate treated with a silane compound in the same manner as in Example 111 was prepared separately and immersed in the solution prepared in advance.Examples 13-15 A glass plate treated with a silane compound in the same manner as in Example 1 was prepared. , CF3-CmiC-CF3, C8F, 7CI
l=CH.

A plasma-polymerized thin film was created on the surface of each C5F1s''r using a gas diluted with argon, and the thickness, hardness and reflectance of the coating were measured.

The measurement results are shown in Table 4.

Table 4 Examples 16 to 25 The silane compound treated on the glass plates in Examples 1 to 6 and 9 to 12 was changed to the silane compound of Synthesis Example 12, and after being immersed and pulled up, it was dried at 100°C for 1°. is Example 1~
After processing in the same manner as in Examples 6 and 9 to 12, the thickness, pencil hardness, and reflectance of the coating film were measured.

The measurement results are shown in Table 5.

Examples 26-30 After processing in the same manner as in Example 5 except that a solution diluted to 5002 was used, the thickness, lead chain hardness, and reflectance of the coating film were measured.

Measurement results are shown in Table 6. Ethylenetetramine-90:10
(Weight ratio) Melamine camphor resin “Cymeru 325” (product name: Nimitsui Toatsu Chemical Co., Ltd. product): “Catalys” 600
0''' (Product name: Mitsui Toatsu Chemical Products) = 99:l (weight ratio) tlo.

The partial polymer heated at ℃ for 10 minutes was treated in the same manner as in Example 5, except that the solution was changed to 5001 by diluting it with 75ff tetrahydrofuran. It was measured.

The measurement results are shown in Table 7.

Example 33 The silane compound treated on the glass plate in Example 5 was diluted with urethane resin "Olestar M75-50Fi" (trade name: Mitsui Toatsu Chemicals) 75fi detrahydrofuran to create a solution of 5002. After processing in the same manner as in Example 5, the thickness of the coating film, lead hoe hardness, and reflectance were measured.

All measurement results are shown in Table 7.

Table 7 Examples 34 to 46 The glass plate of the transparent substrate in the example was replaced with a polycarbonate plate (product of Asahi Glass Co., Ltd.), and the curing temperature was set to 100.
Examples 1 to 6.9 to 10.13.21.2 except that the temperature was ℃
After processing in the same manner as in 6.27 and 31, the coating film thickness, pencil hardness and reflectance were measured.

The measurement results are shown in Table 8.

Examples 47 to 60 The glass plate of the transparent substrate in the example was changed to a polymethyl methacrylate plate (manufactured by Mitsubishi Rayon Co., Ltd.) or a polystyrene plate (Pellet Y plate made by Dow Chemical Company), and the curing temperature was changed to 100 ° C. is Example 1, 5.9.1
After processing in the same manner as 0.13.21 and 31, the coating film thickness, lead-silver hardness and reflectance were measured.

The measurement results are shown in Table 9.

Comparative Examples 1-12 Table 1O shows the measurement results of the reflectance of the same glass plates, polycarbonate plates, polymethyl methacrylate plates, and polystyrene plates used in the examples.

Example 1. Thickness, pencil hardness, and reflectance of the coating film after treatment in the same manner as in 10.13 and 34 (only a thin film of the polyfluorinated group compound), except that the treatment with the Nran compound was not performed. The measurement results are shown in Table 10.

Example 1. Thickness, pencil hardness, and reflectance of the coating film after processing in the same manner as in 26 and 31 except that the thin film formation treatment of the polyfluorinated group compound was not performed (lower coating film only) The measurement results are shown in Table 10.

Comparative Examples 13 to 16 In Example 1, a silane compound was applied to a glass plate with a brush to a coating thickness of 10μ or more to form a coating film, and a polyfluorinated group-containing compound was applied on the coating film. After the prepared solution was cast and cured at 160° C., the thickness, pencil hardness and reflectance of the formed coating film were measured.

In addition, in Examples 1.5 and 34, the glass plate or polycarbonate plate was not treated with the silane compound, but the prepared solution of the polyfluorinated group compound was directly cast to a thickness of 0.5 mm or more, and the glass plate was After curing the polycarbonate plate at 160° C. and 100° C., the thickness of the formed coating film, the pencil hardness and reflectance of the coating film were measured.

All measurement results are shown in Table 11.

Procedural Amendment (Ki) July 3, 1981 Mr. Kazuo Wakasugi, Commissioner of the Patent Office■, Minor Case Indication 1987 ``'Samurai Permit Application No. 225787 2, Name of Invention Low Resistance!) 1 Rate Coating 3, Amendment Relationship with one case Patent applicant address 2-1s2 Marunouchi, Chiyoda-ku, Tokyo Name (
004) Asahi Glass Co., Ltd. 4, Agent 5, Detailed explanation of the invention column 6 in the subject specification of hIi, Contents of amendment (1) Page 7, line 2 of the specification “CH2= CH+OH2NB(OH2)z NH(O
H2)3Si(O0)la ), J is [CH2-CH+
CH2NH(CH2)zNH(CH2)3si(OCH
3)3. ” is corrected.

(2) Page 7, line 3 of the specification “0 Lee-0H2(:!H2S1(OCH2)3J)”
Corrected to XD-aH2aH2s1(OCH3)3j.

(3) Bottom line r (H300)35i(OH2)2(OFz)n(C
H2) 25i (OCH3), j to r (Ha C0
)35i(OH2)2(OFz)n(OHz)zsi(
Correct it to 00) (3) 3 + j.

(4) Specification page 10, line 1 1 - Rf(CI()20H and) is replaced with Rf(OH,
) 20H”.

(5) On page 12, line 12 of the specification, "polyfluorinated group compound" is corrected to "polyfluorinated group-containing compound."

(6) In the 7th line of page 20 of the specification, “equipped” is corrected to “equipped”.

Claims (2)

[Claims] (1) In a low reflectance coating film treated on the surface of a transparent substrate, a coating film of a silane compound or transparent resin having a refractive index comparable to or higher than that of the transparent substrate, and a polyfluorinated group-containing compound on the coating film. A multilayer structure low reflectance coating film characterized by forming a thin film consisting of. (2) The low reflectance coating film according to claim 1, wherein the thin film of the polyfluorinated group-containing compound has a thickness of 0.2 μm or less.