JPH04271301A - Optical member with hardened coating film - Google Patents

Abstract

PURPOSE:To provide an optical member with a hardened coating film having superior adhesion on the surface of a plastic molded article such as a plastic lens. CONSTITUTION:A coating film is formed on the surface of a substrate by applying and hardening a compsn. contg. an organosilicon compd. represented by a formula (A) (R<1>)a(R<3>)bSi(OR<2>)4-(a+b) (where R<1> is an epoxy-contg. group, each of R<2> and R<3> is alkyl, etc., and each of a and b is 0-1) and/or a hydrolyzate thereof, fine silica particles (B), an aluminum chelate compd. represented by a formula (C) Al.XmY3-m [where X is OL (L is alkyl), Y is at least one of compds. represented by formulae M<1> COCH2COM<2> and M<3>COCH2COOM<4> (where each of M<1>-M<4> is alkyl and m is 0-2) and zinc dialkyldithiocarbamate represented by a formula (D1) ((CnH2n+1)2NCS2)2Zn (where n is 1-6) and/or sodium dialkyldithiocarbamate represented by a formula (O2) (CpH2p+1)2NCS2Na (where p is 1-6).

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical member having a cured coating.

0002

2. Description of the Related Art In order to improve the scratch resistance of plastic molded products such as plastic lenses, it is well known to apply a hardened coating to the surface of the molded products. For example, JP-A-5
No. 7-2735 discloses that a compound containing both or one of an epoxy group and a silanol and/or siloxane group, silica fine particles with a particle size of 1 to 100 millimicrons, and an aluminum chelate compound are added to the surface of a plastic lens. A method for forming a cured film by applying and curing a coating composition is disclosed.

0003

[Problem to be solved by the invention] Said Japanese Patent Publication Publication No. 57-27
When the coating composition disclosed in Publication No. 35 is applied to a plastic lens and cured to form a cured film, depending on the type of plastic lens, the adhesion between the plastic lens and the cured film may be insufficient, and the cured film may It has the disadvantage of being easy to peel off. For this reason, plastic lenses are sometimes subjected to pretreatment such as plasma treatment or primer treatment, and then a coating composition is applied and cured, but such pretreatment only complicates the process. However, even with such pretreatment, the adhesion between the plastic lens and the cured film is not necessarily sufficient. SUMMARY OF THE INVENTION Therefore, an object of the present invention is to improve the drawbacks of the prior art and to provide an optical member having a hardened coating with excellent adhesiveness on the surface of a plastic molded product such as a plastic lens.

0004

[Means for Solving the Problems] The present invention has been made to achieve the above-mentioned object, and has a structure in which (
A) General formula (R1)a (R3)b Si(OR2)4-(
a+b) (Here, R1 is an organic group having 4 to 14 carbon atoms including an epoxy group, R2 is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R3 is an organic group having 1 to 6 carbon atoms.
a and b are integers of 0 or 1) and/or its hydrolyzate; (B) silica fine particles with a particle size of 1 to 100 millimicrons; (C) general Formula Al・Xm Y3-m (where X is OL (L is an alkyl group having 1 to 4 carbon atoms),
Y has the general formula M1 COCH2 COM2 (M1 , M
2 are all alkyl groups having 1 to 4 carbon atoms) and the general formula M3 COCH2
COOM4 (M3 and M4 both have 1 or more carbon atoms
4), and m is 0, 1 or 2.
) and an aluminum chelate compound represented by (
D1) Zinc dialkyldithiocarbamate represented by the general formula [(Cn H2n+1)2 NCS2 ]2 Zn (where n is an integer of 1 to 6)
or (D2) A cured film obtained by applying and curing a coating composition containing sodium dialkyldithiocarbamate represented by the general formula (Cp H2p+1)2 NCS2 Na (where p is an integer of 1 to 6). The gist of the present invention is an optical member characterized by having the following characteristics.

The present invention will be explained in detail below. The optical member of the present invention is characterized by having a cured film formed by coating and curing a coating composition on the surface of a base material,
The coating composition comprises the above-mentioned (A) component, (B) component, (C) component, (D1) component and/or (D2) component.
) components.

General formula (R1) used as component (A)
)a (R3)b Si(OR2)4-(a+b
) As the organosilicon compound, known ones can be used, examples of which include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyldimethoxyethoxy Examples include silane, γ-glycidoxypropyltriacetoxysilane, (3,4-epoxycyclohexyl)ethyltrimethoxysilane, γ-glycidoxypropyldimethylmonomethoxysilane, and methyltrimethoxysilane. As component (A), a hydrolyzate of an organosilicon compound can also be used, and such a partial hydrolyzate of an organosilicon compound is obtained by partially or completely hydrolyzing the above organosilicon compound. . This hydrolysis is preferably carried out in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid. The organosilicon compound or its hydrolyzate as component (A) may be used alone or in combination. Moreover, as component (A), the above-mentioned organosilicon compound and its hydrolyzate can also be used together.

Particle size 1 to 10 used as component (B)
0 millimicron silica particles are made by mixing silica particles with water,
It is used in the form of a colloidal solution dispersed in an organic solvent or a mixed solvent thereof. The silica fine particles are mainly used to improve the scratch resistance of the cured film. Examples of the organic solvent used to disperse the silica particles include alcohols such as methanol and ethanol. The particle size of the silica fine particles is limited to 1 to 100 millimicrons, particularly preferably 5 to 20 millimicrons. The reason for this is that if the particle size is less than 1 millimicron, the particles lack stability and the hardened film has poor durability.
This is because a particle size exceeding millimicrons is undesirable since the cured film may lack transparency.

General formula Al・used as component (C)
As the aluminum chelate compound represented by acetonate, aluminum di-iso-propoxide
Examples include monomethyl acetoacetate. It is also possible to use two or more of these components (C) in combination. Component (C) is a curing agent used to accelerate the curing reaction and cure at low temperatures.

However, the curing reaction promoting effect of the component (C) is still not sufficient. Therefore, in the present invention, in addition to component (C), component (D1) and/or (
D2) component is used. (D1) The general formula [(Cn H2
Examples of the zinc dialkyldithiocarbamate represented by n+1)2 NCS2 ]2 Zn include zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dipropyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dihexyldithiocarbamate, etc. can be mentioned. Incidentally, two or more kinds of these zinc dialkyldithiocarbamates can also be used in combination.

Examples of sodium dialkyldithiocarbamate represented by the general formula (Cp H2p+1)2 NCS2 Na used as component (D2) include:
Examples include sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium dipropyldithiocarbamate, sodium dibutyldithiocarbamate, sodium dipentyldithiocarbamate, and sodium dihexyldithiocarbamate. Note that two or more of these sodium dialkyldithiocarbamate compounds can also be used in combination.

By using the above-mentioned (D1) component and/or (D2) component together with the above-mentioned (C) component as a curing agent, the curing reaction is further enhanced compared to the case where only the (C) component is used as a curing agent. A cured film with excellent adhesion to the substrate and excellent scratch resistance can be obtained.

[0012] When using nickel dialkyldithiocarbamate, iron dialkyldithiocarbamate, copper dialkyldithiocarbamate, etc., which differ only in metal species from zinc dialkyldithiocarbamate as component (D1) and sodium dialkyldithiocarbamate as component (D2), these It has been confirmed that there are problems such as coloring the cured film and not dissolving in the coating composition. The same was true for zinc dibenzyldithiocarbamate.

Next, the blending ratio of each component will be explained. The amount of component (B) added is 0.000% per 1 part by weight of component (A).
01 to 5 parts by weight, particularly preferably 0.1 to 1.5 parts by weight. The reason for this is that if it is less than 0.01 part by weight, the scratch resistance of the cured film will be insufficient, and if it exceeds 5 parts by weight, the cured film will tend to crack, and there is a risk that the transparency of the cured film will decrease. ◎ The amount of component (C) added is preferably 0.01 to 0.2 parts by weight per 1 part by weight of component (A). The reason for this is that if it is less than 0.01 part by weight, curing will be insufficient, and if it exceeds 0.2 part by weight, there is a greater risk that the transparency of the cured film will decrease. The amount of component (D1) and/or component (D2) added is 0.0001 to 0.1 part by weight, particularly preferably 0.0001 to 0.1 part by weight, per 1 part by weight of component (A).
The amount is preferably 0.05 to 0.02 parts by weight. 0.00
This is because if the amount is less than 0.1 part by weight, the adhesion of the cured film will be insufficient, and if it exceeds 0.1 part by weight, there is a high possibility that the transparency of the cured film will decrease.

Furthermore, the coating composition used in the present invention contains aluminum in addition to the above-mentioned essential components in order to match the refractive index of various substrates (plastic molded products such as plastic lenses) and to further improve scratch resistance. , titanium, antimony, zirconium, cerium, and other metal oxides. Furthermore, various surfactants can be added for the purpose of improving flowability during coating and improving smoothness of the cured film. Further, ultraviolet absorbers, antioxidants, etc. can also be added as long as they do not affect the physical properties of the cured film. In order to improve the coating composition, the above-mentioned essential components and optional components are usually dissolved or dispersed in a solvent such as an alcohol, a ketone, a cellosolve, or a carboxylic acid. As a means for applying the coating composition to the surface of the substrate, commonly used methods such as dipping, spinning, and spraying can be used, but dipping and spinning are particularly preferred from the viewpoint of surface precision.

Substrates to which the coating composition is applied include copolymers containing methyl methacrylate and one or more other monomers as monomer components, diethylene glycol bisallyl carbonate homopolymers, and sulfur-containing copolymers. , copolymers containing diethylene glycol bisallyl carbonate and one or more other monomers as monomer components, acrylonitrile-styrene copolymers, polystyrene, halogen-containing copolymers, polyvinyl chloride, unsaturated polyester resins, polyethylene Examples include plastic lenses such as terephthalate and polyurethane, and inorganic glass lenses, but as a base material,
Particularly excellent adhesion and scratch resistance can be obtained when using an acrylic copolymer plastic lens. Examples of the acrylic copolymer plastic lens include a diethylene glycol bisallyl carbonate/benzyl methacrylate/diallyl phthalate terpolymer plastic lens. Further examples include diethylene glycol bisallyl carbonate/benzyl methacrylate/diallyl phthalate/alkyl methacrylate quaternary copolymers. These acrylic copolymers are disclosed in JP-A-51-125487, JP-A-54-41965, and JP-A-59.
-191708 and WO89/09418
It is disclosed in the publication No.

[0016] The coating composition is cured by hot air drying or active energy ray irradiation.
It is preferable to carry out the process in hot air at a temperature of -200°C, particularly preferably in a hot air at a temperature of 90 - 150°C. Active energy rays include far infrared rays, which can suppress damage caused by heat. In addition, before applying and curing the coating composition to the base material, chemical treatment with acid, alkali, various organic solvents, physical treatment with plasma, ultraviolet rays, etc., cleaning treatment with various detergents, and furthermore, treatment with various resins are performed. Primer treatment can also be performed.

[0017] The optical member of the present invention can also be coated with a functional film such as an antireflection film on its surface. The optical member of the present invention can be used not only for eyeglass lenses but also for camera lenses, optical filters attached to word processor displays, and automobile window glasses.

[0018]

[Examples] The present invention will be explained in detail below with reference to Examples, but the present invention is not limited to these Examples. In addition, various physical properties of the plastic lenses having hardened coatings obtained in the present examples and comparative examples were measured by the measurement methods shown below.

(1) Scratch Resistance Test The plastic lens surface was rubbed with #0000 steel wool, and the scratch resistance was visually judged. The judgment criteria were as follows. A... Hardly any scratches even if rubbed strongly B... Significant scratches if rubbed strongly C... Scratches equivalent to the lens substrate (2) Adhesion test A cross-cut tape test was conducted in accordance with JIS D-0202. . That is, 100 cross-cuts are made at 1 mm intervals, adhesive tape (trade name "Cello Tape" manufactured by Nichiban Co., Ltd.) is strongly applied, and then rapidly peeled off in a 90° direction from the surface to remove the remaining squares of the cured film. I looked into it.

(3) Appearance Test The plastic lens with the cured film was visually inspected in a dark room under fluorescent light to see if it was cloudy or discolored. The criteria for judgment are as follows. A: Cloudiness or coloring is hardly visible. B...It's a little visible. C...It's quite visible.

(4) Dyeability test The obtained plastic lens with the cured film was immersed in a solution for dyeing plastic lenses (Maron, a dye for HI-LUX manufactured by Hoya Co., Ltd.) at 80°C for 10 minutes, and the dyeing density was measured. did. The staining density was measured using light with a wavelength of λ=550 nm. Staining concentration (%) = 100 - Transmittance (%) [Example 1] (Preparation of coating liquid) γ-Glycidoxypropyltrimethoxysilane, which is the component (A), was placed in a glass container equipped with a magnetic stirrer. 100 parts by weight were added, and 16 parts by weight of 0.1N hydrochloric acid was added dropwise while stirring. After the dropwise addition was completed, the mixture was stirred for 24 hours to obtain a hydrolyzate. Next, component (B), water-dispersed silica fine particles (solid content 20%, average particle diameter 15
millimicron) 100 parts by weight, 80 parts by weight of isopropyl alcohol as a solvent, 80 parts by weight of ethyl cellosolve,
Further, 1 part by weight of a silicone surfactant as a lubricant, 4 parts by weight of aluminum acetylacetonate (component (C)) and 1 part by weight of zinc dimethyldithiocarbamate (component (D1) as a hardening agent) were added, and after thorough stirring, filtration was performed. A coating liquid was obtained.

(Formation of a cured film) An acrylic copolymer plastic lens (refractive index nd 1.56) consisting of diethylene glycol bisallyl carbonate, benzyl methacrylate, and diallyl isophthalate was cured at 45°C.
After thorough washing by immersing in a 0% NaOH aqueous solution for 5 minutes, coating was performed using the coating solution prepared by the above method using a dipping method (pulling speed 14 cm/min) and heating at 130°C for 2 hours. A cured film was formed and various evaluations were performed.

[0023] As shown in Table 1, the plastic lens having the cured film obtained by the above method was confirmed to have good scratch resistance, appearance, and dyeability, and was also excellent in adhesion. Ta.

[Example 2] 50 parts by weight of water-dispersed antimony particles (solid content 20%, average particle size 20 mm) were used together with 100 parts by weight of water-dispersed silica particles as component (B), and pretreatment with alkali The same procedure as in Example 1 was carried out except that . As shown in Table 1, the evaluation results showed that it had excellent physical properties similar to Example 1.

[0025]

[Table 1]

[Examples 3 to 9] As shown in Tables 2 and 3, component (A), component (B), component (C) and (D
A coating composition obtained by blending a predetermined amount of component 1) or component (D2) was applied to a substrate and cured to obtain an optical member having a cured film. Regarding the obtained optical members with cured films of Examples 3 to 9, various physical properties were evaluated in the same manner as in Example 1. The results are shown in Table-2 and Table-3 for Example 1.
Similar results were obtained.

[0027]

[Table 2]

[0028]

[Table 3]

[Comparative Example 1] Example 1 except that the component (D1), zinc dimethyldithiocarbamate, was not used.
I did the same thing. As shown in Table 4, the results showed that the adhesion and dyeability were insufficient.

[0030]

[Table 4]

[Comparative Examples 2 to 5] In place of zinc dimethyldithiocarbamate as the component (D1), (D1), (
Curing agents other than component D2), such as zinc dibenzyldithiocarbamate (Comparative Example 2), nickel dimethyldithiocarbamate (Comparative Example 3), iron dimethyldithiocarbamate (Comparative Example 4), and copper dimethyldithiocarbamate (Comparative Example 5) The same procedure as in Example 1 was carried out except for using the following. As shown in Table 5, the cured film had clouding, coloring, and spots, and could not be used as an eyeglass lens.

[0032]

[Table 5]

[Comparative Examples 6-7] (C) used in Example 1
Examples except that component aluminum acetylacetonate was not used and only zinc dimethyldithiocarbamate (Comparative Example 6), component (D1), and sodium dimethyldithiocarbamate (Comparative Example 7), component (D2), were used as curing agents. This was done in the same manner as in step 1. As a result, as shown in Table 6, the scratch resistance was low.

[0034]

[Table 6]

[0035]

Effects of the Invention As described above, the optical member having the cured film of the present invention has the remarkable advantages of excellent adhesion between the base material and the cured film, and excellent scratch resistance, appearance, and dyeability. .

Claims (3)

[Claims] Claim 1: A compound having the general formula (R1)a (R3)b Si(OR2)4-(
a+b) (Here, R1 is an organic group having 4 to 14 carbon atoms including an epoxy group, R2 is an alkyl group having 1 to 4 carbon atoms or an acyl group having 1 to 4 carbon atoms, and R3 is an organic group having 1 to 6 carbon atoms.
a and b are integers of 0 or 1) and/or its hydrolyzate; (B) silica fine particles with a particle size of 1 to 100 millimicrons; (C) general Formula Al・Xm Y3-m (where X is OL (L is an alkyl group having 1 to 4 carbon atoms),
Y has the general formula M1 COCH2 COM2 (M1 , M
2 are all alkyl groups having 1 to 4 carbon atoms) and the general formula M3 COCH2
COOM4 (M3 and M4 both have 1 or more carbon atoms
4), and m is 0, 1 or 2.
) and an aluminum chelate compound represented by (
D1) Zinc dialkyldithiocarbamate represented by the general formula [(Cn H2n+1)2 NCS2 ]2 Zn (where n is an integer of 1 to 6) and/
or (D2) A cured film obtained by applying and curing a coating composition containing sodium dialkyldithiocarbamate represented by the general formula (Cp H2p+1)2 NCS2 Na (where p is an integer of 1 to 6). An optical member comprising: [Claim 2] The base material is a plastic molded product.
The optical member according to claim 1. 3. The optical member according to claim 2, wherein the plastic molded product is a plastic lens.