JPH05100103A - Coating film and production thereof - Google Patents

Abstract

PURPOSE:To produce a molding which is white to the eyes, imparts a high-grade feel to the coating film and has a high merchandise value by adding a dye into a coating compsn. to blue the coating film. CONSTITUTION:The dye is added into the coating compsn. of the coating film essentially consisting of the hydrolyzate of the org. silicon compd. expressed by formula I to blue the coating film. In the formula I, n=1 to 3; R<1> is an alkyl group, alkoxyalkyl group; n pieces of R may be the same or different. R<2> is 1 to 6C alkyl group or aryl group; R<3> is 1 to 10C alkylene group or alkyleneoxide group or polyalkyleneoxide group; X is a functional group including an epoxy group, mercapto group, amino group, vinyl group, allyl group, acryl group or methacryl group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating film which is characterized by making the yellowing of the coating film when it is cured close to an achromatic color by making it blue, giving a white feeling to the eyes, and a high-grade feeling. The present invention relates to a manufacturing method.

[0002]

2. Description of the Related Art Among currently used plastic materials, acrylic, methacrylic, vinyl, and polycarbonate
Compared to glass, transparent plastic materials such as bonnet-based and allyl-based are superior in properties such as impact resistance, lightness, workability, and colorability, so that they are used as optical materials such as lenses and transparent glass. It is used in large quantities in place of inorganic glass. However, they have the drawback of being inferior in scratch resistance and chemical resistance to inorganic glass. As a resin having relatively excellent scratch resistance, there is a diethylene glycol bisallyl carbonate resin (hereinafter referred to as CR-39), but this is not practically sufficient. As a means for improving these drawbacks of plastic materials, for example, in Japanese Patent Publication No. 57-2735, a thermosetting coating composed of colloidal silica and epoxy group-containing alkoxysilane is disclosed.
In addition, Japanese Patent Publications 57-43168, 56-34033,
JP-A-55-29102 and JP-A-57-67666 disclose thermosetting paints containing an epoxy group-containing alkoxysilane and a tetraalkoxysilane as main components, respectively, and improve chemical resistance and scratch resistance. It's peeled off.

[0003]

These thermosetting paints have improved chemical resistance and scratch resistance, but need to be baked at a considerably high temperature. Therefore, there is a problem that the transparent molded body turns yellow due to thermal deterioration of the plastic substrate and itself.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies in order to solve these problems, and found that a coating composition containing a hydrolyzate of an organosilicon compound as a main component contained anthraquinone-based compounds. By adding an oil-soluble dye and curing it, bluing of the cured film can be performed without deteriorating the properties of the coating film and without a troublesome process, and the yellowing at the time of curing the coating film becomes achromatic. I found that it was close and made me feel white. That is, according to the present invention, in a coating film containing a hydrolyzate of an organosilicon compound represented by the following general formula (1) as a main component, a dye is added to the coating composition to perform blueing of the coating film. The present invention relates to a coating film characterized by:

[0005]

[Chemical 3]

(However, n = 1 to 3, R ¹ is an alkyl group or an alkoxyalkyl group, and n R ^{1 s} may be the same or different. R ² is a C ₁ -C ₆ alkyl group, or Aryl group, R ³ is a C ₁ -C ₁₀ alkylene group or alkylene oxide group or polyalkylene oxide group, X is a functional group containing an epoxy group, a mercapto group, an amino group, a vinyl group, an allyl group, an acryl group or a methacryl group. The present invention further comprises a coating film containing a hydrolyzate of an organosilicon compound represented by the following general formula (1) as a main component, wherein an anthraquinone oil-soluble dye is added to the coating composition, The present invention relates to a method for producing a bluing coating film characterized by being cured.

[0007]

[Chemical 4]

(Where n = 1 to 3, R ¹ is an alkyl group or an alkoxyalkyl group, and n R ¹ 's may be the same or different. R ² is a C _{1 to} C ₆ alkyl group, or Aryl group, R ³ is a C ₁ -C ₁₀ alkylene group or alkylene oxide group or polyalkylene oxide group, X is a functional group containing an epoxy group, a mercapto group, an amino group, a vinyl group, an allyl group, an acryl group or a methacryl group. Specific examples of the anthraquinone oil-soluble dye used in the present invention include C.I. I. (Color
Index) 60725, 61705, 61100, 6
1525, 62100, etc. Solvent violet
t or Solvent Blue.
These oil-soluble dyes may be used alone or in combination of two or more. Also, if red is insufficient for achromatic color, Solvent Red may be mixed and used. The addition amount of the oil-soluble dye is determined depending on the yellowing degree of the coating film,
The range of 15 to 1000 ppm of the coating film is preferable, and the range of 30 to 500 ppm is more preferable. (The degree of yellowing depends on the composition of the coating film, the curing temperature,
Determined by cure time. ) If the addition amount of less than 15 ppm is an appropriate amount, it is not necessary to carry out bluing, and if the addition amount is more than 1000 ppm, the transmittance is lowered and a high-class feeling cannot be provided. In addition, it may be possible to give a feeling of luxury by making it feel a little blue rather than making it appear white. The reason why the oil-soluble dye is used in the present invention is that when other dye is used, the dye is not decomposed and colored during the condensation reaction of the organosilicon compound represented by the general formula (1), or the characteristics of the coating film are This is because a phenomenon that lowers the value occurs. Then, specific examples of the organosilicon compound represented by the general formula (1) include vinyltrialkoxysilane, vinyltri (β-methoxy-ethoxy) silane, allyltrialkoxysilane, acryloxypropyltrialkoxysilane, and methacryloxypropyl. Trialkoxysilane, methacryloxypropyl dialkoxymethylsilane, γ-glycidoxypropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) -ethyltrialkoxysilane, mercaptopropyltrialkoxysilane, γ-aminopropyltrialkoxy. Silane, N-β (aminoethyl)-
γ-aminopropylmethyldialkoxysilane and the like can be mentioned. These organosilicon compounds may be used alone or in combination of two or more. Hydrolysates of these organosilicon compounds are produced by hydrolysis with pure water or an acidic aqueous solution such as hydrochloric acid or sulfuric acid. It is also possible to carry out the hydrolysis in a suitable solvent. As the solvent, alcohols, esters, ethers, ketones, halogenated hydrocarbons, aromatic solvents such as toluene and the like can be used according to the purpose, and a mixed solvent can be used if necessary. In the composition of the present invention, adhesion to various substrates,
For the purpose of further improving the dyeability and the adhesiveness with the inorganic vapor deposition film, it is possible to add an organosilicon compound, an epoxy compound, and inorganic oxide fine particles represented by the following general formula (2).

[0009]

[Chemical 5]

(However, m = 1 to 4, R ⁴ is an alkyl group or an alkoxyalkyl group, and m R ^{4 s} may be the same or different. R ⁵ is a C ₁ -C ₆ alkyl group or aryl. Specific examples of the organosilicon compound represented by the general formula (2) include methyltrimethoxysilane, ethyltriethoxysilane, tetramethoxysilane, and tetraethoxysilane. Epoxy compounds are widely used for paints, adhesives, casting, etc., for example, polyolefin-based epoxy resin synthesized by the peroxide method, cyclopentadiene oxide or cyclohexene oxide, or hexahydrophthalic acid and epichlorohydrin. The resulting alicyclic epoxy resin such as polyglycidyl ester, polyhydric phenol such as bisphenol A or catechol, resorcinol or (poly) ethylene glycol, (poly) propylene glycol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, Polyglycidyl ether obtained from polychloroalcohol such as diglycerol and sorbitol and epichlorohydrin, epoxidized vegetable oil, novolac type phenol resin and epichlorohydri Epoxy novolac obtained from, an epoxy resin obtained from phenolphthalein and epichlorohydrin, a copolymer of glycidyl methacrylate and methyl methacrylate acrylic monomer or styrene, further the above epoxy compound and a monocarboxylic acid-containing (meth) acrylic acid Examples thereof include epoxy acrylate obtained by ring-opening reaction of glycidyl group. Subsequently, the inorganic oxide fine particles preferably have a particle size of 5 to 30 millimicrons. As a specific inorganic oxide,
SiO ₂ , ZrO ₂ , TiO ₂ , SnO ₂ , Sb ₂ O ₅ , Ce
O ₂ , Al ₂ O _{3 and the} like can be mentioned. In addition, the complex oxide of the fine particles and the fine particles or the complex oxide of the fine particles are converted into silicon oxide and / or an organic silicon compound and / or
Alternatively, fine particles treated with an organometallic compound are also included. At the time of use, even if the fine particle powder is directly used,
It may be used as a colloidal inorganic oxide dispersed in water or an organic solvent. The composite oxide is a mixture of two or more kinds of inorganic oxides at the stage of producing fine particles, or a mixture of the inorganic oxides after being produced individually. For example CeO ₂
The composite oxide fine particles with TiO _2, complex oxide particles or the like of SiO ₂ and CeO ₂ and TiO ₂ and the like. Also,
The treatment with silicon oxide is to grow silicon oxide fine particles by a known method in a dispersion medium containing the fine particles. The treatment with an organosilicon compound or an organometallic compound is a method in which the compound is added in a dispersion medium containing the fine particles and the mixture is heated and stirred. Examples of the organosilicon compound here include those represented by the general formulas (1) and (2), and the organometallic compound means the silicon of the general formulas (1) and (2) to other metals such as Ti. , Zr and the like. It is also useful to add a curing catalyst for silanol or an epoxy compound. The most preferred catalyst includes magnesium perchlorate,
In addition, there are metal acetylacetonates such as aluminum acetyl acetate, amino acids such as amine and glycine, Lewis acids, organic acid metal salts, ammonium perchlorate and the like. The addition amount is preferably within the range of 0.01 to 5.0% of the solid content concentration. Further, it is also useful to add a silicone-based surfactant, a nonionic surfactant, a thixotropic agent, a silicone oil as a slip agent, an ultraviolet absorber, an antistatic agent or the like for improving defects on the coated surface. Furthermore, an ultraviolet absorber for the purpose of improving weather resistance,
It is also possible to add an antioxidant. As the object to be coated, plastic molded products such as CR-39 (diethylene glycol bisallyl carbonate polymer), polymethylmethacrylate, polycarbonate, acrylonitrile-styrene copolymer, polyvinyl chloride, epoxy resin, or inorganic glass, wood, metal Examples include articles. In particular, a transparent plastic material and an inorganic glass are preferable from the viewpoint that it is not necessary to pay attention to yellowing. The coating method includes a dipping method and a spray method.
Method, roll coating method, spin coating method, flow coating method, brush coating method and the like. Curing of the composition of the present invention is mainly carried out by heat treatment, but the heating temperature and curing time are the same as those of conventional thermosetting compositions.
Hereinafter, further details will be described with reference to examples.

[0011]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of coating liquid 197.3 g of methyl cellosolve and 364.8 g of colloidal silica dispersed in methanol (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name "OSCAL 1132", solid content concentration 30 wt%) were mixed. After that, γ-glycidoxypropyltrimethoxysilane 1
84.5 g were mixed. To this mixed solution, 51.0 g of 0.05N hydrochloric acid aqueous solution was added dropwise with stirring, and the mixture was further stirred for 4 hours and aged overnight, and then magnesium perchlorate 1.5.
g, silicon-based surfactant (manufactured by Nippon Unicar Co., Ltd., trade name “L-7001”) 0.2 g, hindered phenolic antioxidant (manufactured by Nippon Ciba-Geigy Co., Ltd., trade name “IRGANOX1010”) 9 g and anthraquinone oil-soluble dye (manufactured by Mitsubishi Kasei Co., Ltd., trade name "Dia
(resin Blue J ") 0.02 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid. (2) Coating and curing The coating liquid thus obtained was applied to a CR-39 spectacle lens which had been subjected to alkali treatment by a dipping method.
The pulling rate was 15 cm / min. 80 after application
After air-drying at 20 ° C. for 20 minutes, baking was performed at 130 ° C. for 120 minutes. The thickness of the cured film thus obtained is about 2
It was micron and the appearance was excellent.

Example-2 An antireflection coating thin film made of an inorganic material was formed on each of the lenses obtained in Example-1 by the following method. (1) Formation of antireflection thin film Plasma treatment (argon plasma 40
After performing 0 W × 60 seconds), an antireflection multilayer film composed of five layers of SiO ₂ , ZrO ₂ , SiO ₂ , ZrO ₂ and SiO ₂ is sequentially deposited from the substrate to the atmosphere by vacuum deposition (Vacuum Instrument Industry Co., Ltd. ), BMC-1000).
Film thickness, first of SiO ₂ with a thickness of, the next Zr0 ₂ and SiO ₂
Was formed so that the total film thickness of ZrO ₂ , the next film thickness of ZrO ₂ , and the uppermost SiO ₂ film were all λ / 4. Design wavelength λ
Was 520 nm. (2) Test and Evaluation Results The lens obtained in Example-1 (hereinafter referred to as a hard coat lens) and the lens obtained in Example-2 (hereinafter referred to as a hard multi-coat lens) are each described below. The test was conducted and the results are shown in Table 1. (A) Abrasion resistance: A load of 1 kg was applied to # 0000 steel wool, the surface was rubbed for 10 reciprocations, and the degree of scratching was visually evaluated in the following stages. A: No scratches in the area of 1 cm * 3 cm. B: 1 to 10 scratches are formed within the above range. C: 10 to 100 scratches are formed within the above range. D: Countless scratches are attached, but a smooth surface remains. E: No smooth surface remained due to scratches on the surface. (B) Adhesion: The adhesion between the base material and the hard coat film and between the hard coat film and the multi coat film is JIS D-020.
A cross-cut tape test was conducted according to 2.
That is, cuts are made at intervals of 1 mm on the surface of the substrate using a knife to form 100 squares of 1 mm 2. next,
After strongly pressing the cellophane adhesive tape (Nichiban Co., Ltd., product name "Cellotape") on it, 9 from the surface
The squares where the coating film remained after the film was pulled off in a direction of 0 degrees and peeled off were taken as the adhesion index. (C) Durability: Considering that durability is essentially an adhesive connection, the following tests were conducted,
The above-mentioned cross-cut tape test was conducted, and those having no peeling of the coat film were regarded as good. ． Water resistance / chemical resistance: Immersed in water, alcohol, or kerosene for 48 hours, and those having no change in surface condition were evaluated as good. ． Acid resistance / detergent resistance: Immersed in 0.1N hydrochloric acid and a 1% Mama lemon (manufactured by Lion Oil and Fat Co., Ltd.) aqueous solution for 12 hours, and those having no change in surface condition were evaluated as good. ． Weather resistance: The one having no change in the surface condition after being exposed to a sunshine weather meter by a carbon arc lamp for 400 hours was regarded as good. ． Heat resistance (cooling cycle property): The surface condition was examined after storage in hot air at 70 ° C. for 1 hour. 15 minutes at -5 ℃,
The cycle of 15 minutes at 60 ° C. was repeated 5 times, and those having no change in surface condition were regarded as good. (D) Yellowing Degree: The b ^* value of the uncoated lens and the hard-coated lens by CIELAB colorimetric method (JISZ-8730) was measured, and the case where there was no increase in b ^* of 10% or more was regarded as good. .

Example-3 (1) Preparation of coating liquid Isopropyl cellosolve 114.7 g, pure water 38.3 g
And 411.1 g of methyl cellosolve-dispersed colloidal silica (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name "OSCAL 1832", solid content concentration 30 wt%) were mixed, and then 176.4 g of γ-glycidoxypropyltrimethoxysilane was mixed. .. To this mixed solution, 48.5 g of a 0.05N hydrochloric acid aqueous solution was added dropwise with stirring. After stirring for 5 hours, the mixture was aged overnight. 201.8 g of neopentyl glycol diglycidyl ether (manufactured by Kyoeisha Yushi Kagaku Kogyo KK, trade name "Eporite 1500NP"), 5.5 g of magnesium perchlorate, and a silicone surfactant (Nippon Unicar Co., Ltd.) Made, trade name "L-7604") 0.2 g,
0.03 g of anthraquinone oil soluble dye (manufactured by Mitsubishi Kasei Co., Ltd., trade name "Diaresin Blue D") and 2.2 g of anthraquinone oil soluble dye (manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumiplast Red 3B")
Was added and the mixture was stirred for 4 hours and aged overnight to give a coating solution. (2) Coating and curing The coating liquid thus obtained was spray-coated on an injection-molded acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd .; trade name "Acrypet VH" 100 mm * 100 mm * 3 mmt). I did. The spray is Iwata Wider 61 (manufactured by Iwata Co., Ltd .; nozzle diameter 1 mm)
Spray pressure 3Kg / cm2, paint discharge 1
It was performed at 00 ml / min. After coating, it was air dried at 50 ° C. for 10 minutes and then baked at 80 ° C. for 8 hours. The cured coating thus obtained has a thickness of about 4 microns,
The appearance was excellent. (3) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Example-4 (1) Preparation of coating liquid 328.5 g of butyl cellosolve, colloidal silica dispersed in isopropyl alcohol (manufactured by Catalysts & Chemicals Industry Co., Ltd., trade name "OSCAL 1432", solid content concentration 30 wt%) 31
4.9 g and anthraquinone oil-soluble dye (manufactured by Mitsubishi Kasei Co., Ltd., trade name “Diaresin Violet”)
A ") was mixed with 0.06 g, and then 84.5 g of γ-glycidoxypropylmethyldimethoxysilane and 88.8 g of γ-methacryloxypropyltrimethoxysilane were mixed. 46.5 g of 0.05N hydrochloric acid aqueous solution in this mixed solution
Was added dropwise with stirring, and the mixture was stirred for 4 hours and aged overnight. To this liquid, 131.7 g of 1,6-hexanediol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd .; trade name "Denacol EX-212") was added, and after stirring, 5.3 g of magnesium perchlorate, a silicon-based surface active agent. Agent (manufactured by Big Chemie Co., Ltd .; trade name "BYK-300")
3 g was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid. (2) Coating and curing The coating liquid thus obtained was applied to a CR-39 spectacle lens that had been subjected to alkali treatment by a spinner method. The coating conditions are as follows. The rotation speed was 500 rpm for 10 seconds (the coating liquid was applied during this). The rotation speed was 2000 rpm for 1 second. The rotation speed was 500 rpm for 5 seconds. After coating, the coating was air-dried at 80 ° C for 20 minutes and then baked at 130 ° C for 4 hours. The cured film thus obtained had a thickness of about 2.2 μm and had an excellent appearance. (3) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Example-5 (1) Preparation of coating liquid 255.5 g of butyl cellosolve, anthraquinone oil-soluble dye (manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumipla")
st Blue G ") 0.08 g, methyl cellosolve-dispersed colloidal silica (manufactured by Catalysts & Chemicals Co., Ltd., trade name" OSCAL 1832 ", solid content concentration 30 wt%) 383.
After mixing 2 g, 158.4 g of γ-methacryloxypropyltrimethoxysilane and 79.2 g of γ-glycidoxypropylmethyldiethoxysilane were mixed. To this mixed solution, 55.2 g of a 0.05N hydrochloric acid aqueous solution was added with stirring, and the mixture was stirred for 4 hours and aged overnight. Glycerol diglycidyl ether (manufactured by Nagase Kasei Co., Ltd .; trade name "Denacol EX-313") 6
After adding 5.2 g and stirring, magnesium perchlorate 3.8
g, 0.4 g of a silicon-based surfactant (manufactured by Big Chemie Co., Ltd .; trade name “BYK-300”) was added, and the mixture was stirred for 4 hours and aged overnight to give a coating liquid. (2) Coating and curing With the coating liquid thus obtained, Seiko High Road S
A cloth lens for MX (manufactured by Seiko Epson Corporation) was applied by a spinner method. The coating conditions are
It carried out by the method similar to Example-4. 1 at 80 ℃ after coating
After air-drying for 5 minutes, baking was performed at 110 ° C. for 6 hours.
The cured film thus obtained had a thickness of about 2.3 μm and had an excellent appearance. (3) Test and Evaluation Results The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Comparative Example-1 In Example-1, an anthraquinone oil-soluble dye (manufactured by Mitsubishi Kasei Co., Ltd., trade name "Diaresin Blue") was used.
J ") was applied to the lens in the same manner except that 0.02 g was not added. The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Comparative Example-2 Anthraquinone oil-soluble dye in Example-4 (manufactured by Sumitomo Chemical Co., Ltd., trade name "Sumiplast Blu")
e G ") was coated on the lens in the same manner except that 0.06 g was not added. The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

Comparative Example-3 In Example-5, anthraquinone-based oil-soluble dye (manufactured by Mitsubishi Kasei Co., Ltd., trade name "Diaresin Violet")
The coating was performed on the lens in the same manner except that 0.08 g of "t A") was not added. The lens thus obtained was tested in the same manner as in Example-1, and the results are shown in Table 1.

[0020]

[Table 1]

[0021]

As described above, the coating film obtained according to the present invention does not deteriorate the characteristics of itself,
It is possible to produce a molded product having a very high commercial value, which can give a feeling of whiteness and a high-class feeling. In particular, it has a remarkable effect when applied to plastic spectacle lenses.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takao Mogami 3-5 Yamato, Suwa City, Nagano Seiko Epson Corporation (72) Inventor Hiroshi Fukushima 4-6 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Mitsubishi In Rayon Co., Ltd. (72) Inventor Akira Motonaga 4-6 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi Mitsubishi Rayon Co., Ltd. (72) Eriko Suda 4-6 Sunadabashi, Higashi-ku, Nagoya, Aichi Mitsubishi Rayon Within the corporation

Claims (2)

[Claims] 1. A coating film containing, as a main component, a hydrolyzate of an organosilicon compound represented by the following general formula (1), a dye is added to the coating composition, and bluing of the coating film is performed. Coating film characterized by: (However, n = 1 to 3, R ¹ is an alkyl group or an alkoxyalkyl group, and n R ¹ may be the same or different. R ² is a C _{1 to} C ₆ alkyl group or an aryl group; R ³ is a C ₁ -C ₁₀ alkylene group or alkylene oxide group or polyalkylene oxide group, and X is a functional group containing an epoxy group, a mercapto group, an amino group, a vinyl group, an allyl group, an acryl group or a methacryl group. ) 2. A coating film containing, as a main component, a hydrolyzate of an organosilicon compound represented by the following general formula (1), an anthraquinone-based oil-soluble dye is added to the coating composition and the composition is cured. Method for producing a characteristic bluing coating film (However, n = 1 to 3, R ¹ is an alkyl group or an alkoxyalkyl group, and n R ¹ may be the same or different. R ² is a C _{1 to} C ₆ alkyl group or an aryl group; R ³ is a C ₁ -C ₁₀ alkylene group or alkylene oxide group or polyalkylene oxide group, and X is a functional group containing an epoxy group, a mercapto group, an amino group, a vinyl group, an allyl group, an acryl group or a methacryl group. )