JPS61219020A - Spectacle frame - Google Patents

Abstract

PURPOSE:To obtain a spectacle frame which is highly resistant to corrosion and is remarkably improved in chemical resistance by providing a protective layer consisting essentially of a vinylidene fluoride copolymer having a functional group and/or the crosslinked matter of the vinylidene fluoride copolymer having the functional group. CONSTITUTION:The protective layer is obtd. by coating a fluororesin paint consisting usually of the polymer compsn. consisting essentially of the vinylidene fluoride copolymer having the functional group and crosslinking agent and crosslinking and curing the coating at an ordinary temp. and is formed to about 5-100mum film thickness. The fluorocopolymer forms the hard film when cured at an ordinary temp. and the coated film formed thereof retains the characteristics such as corrosion resistance and chemical resistance intrinsic to the fluorocopolymer as they are. The film has good adhesiveness to plastics and metals which are the material for the spectacle frame.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to eyeglass frames. More specifically, the present invention relates to an eyeglass frame provided with a protective layer that has excellent corrosion resistance, is hard and scratch-resistant, and has excellent chemical resistance.

[Conventional technology]

Conventional eyeglass frames are made of aluminum alloy, nickel alloy, copper alloy, stainless steel, or plated material.
-4K hRIs l-scream t buttock product-'7 j-
, , / J SR J-p M m 'BH Earmuffs and a metal frame, or a plastic frame made of cellulose plastic, etc. are available.

[Problem that the invention seeks to solve]

In conventional eyeglass frames, the metal parts rust and corrode due to sweat containing salt, and the resin parts swell due to the alcohols, glycols, esters, and ethers contained in hair products, which can cause lamp cracks. There is a problem with doing so. Therefore, the chemical resistance is not satisfactory.

An object of the present invention is to provide an eyeglass frame that has excellent corrosion resistance and greatly improved chemical resistance.

[Means for solving problems]

The present invention relates to an eyeglass frame provided with a protective layer mainly composed of a vinylidene fluoride copolymer having a functional group and/or a crosslinked product of a vinylidene fluoride copolymer having a functional group.

[Function and Examples]

The protective layer in the present invention is usually a vinylidene fluoride copolymer having a functional group (hereinafter referred to as a fluorine-containing copolymer).
It is obtained by applying a fluororesin paint consisting of a polymer composition containing as main components and a crosslinking agent, and crosslinking and curing it at room temperature, and having a film thickness of about 5 to 100 μm.

The fluorine-containing copolymer has properties that conventional fluororesins do not have, namely, it cures at room temperature to form a hard film, and the formed coating film has the corrosion resistance and chemical resistance of fluoropolymers. It retains its characteristics. It also has good adhesion to plastics or metals that are the materials of eyeglass frames. Each component of such a fluorine-containing copolymer,
The composition etc. are explained in detail in Japanese Patent Application No. 175123/1983.

In the present invention, the fluorine-containing copolymer usually contains 50 to 99 mol% vinylidene fluoride, preferably 65 to 85 mol%, and 1 to 50 mol% vinyl monomer having a functional group, preferably 1 to 10 mol%. or vinylidene fluoride 50 to 99 mol%, preferably 65 to 85 mol%, vinyl monomer having a functional group 1 to 50 mol%, preferably 10 olefin 30
Less than mol %, preferably 10 to 25 mol %.

Gel permeation chromatography (G
The molecular weight measured by PC (based on polystyrene) is usually 1
It ranges from 10,000 to 500,000.

The vinyl monomer having the above functional group usually has the formula: % formula %) (wherein, X is a hydroxyl group, carboxyl group or glycidyl group, k is 0 or 1, m is an integer of 0 to 10,
represents an integer of 0 to 4 [1 to 4 when X is a hydroxyl group]. ), a compound represented by the formula: %formula%) (wherein, an integer of ~4,
X is as defined above, or a compound represented by the formula: %Formula% (wherein, Y is as defined above).

The fluoroolefins other than vinylidene fluoride mentioned above are usually tetrafluoroethylene, chlorotrifluoroethylene, monofluoroethylene, trifluoroethylene, hexafluoropropene, lower fluoroalkyl vinyl ether, etc., and preferably tetrafluoroethylene or chlorotrifluoroethylene. be.

The method for producing the fluorine-containing copolymer used in the present invention includes, for example, combining each component in the presence of a solvent using a polymerization catalyst,
-20 to 150 °C, preferably 5 to 95 °C temperature and 0 to 30 kg/d G, preferably 10 kg/a
Methods such as emulsion polymerization, suspension polymerization, or solution polymerization in an aqueous medium under ml force conditions of JG or less may be employed.

Further, the fluorine-containing copolymer of the present invention can also be an acrylic material.

The above-mentioned acrylic resin means a single or copolymer of acrylate or methacrylate containing an alkyl group having 1 to 8 carbon atoms. For example, a single or copolymer of methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl acrylate, etc. Commercially available acrylic resins such as copolymers of the above acrylates or methacrylates with hydroxyethyl methacrylate, methacrylic acid, glycidyl methacrylate, styrene, acrylonitrile, etc. include Hytaloid 3004, Hythaloid 3018, Hythaloid 3046G (all Hitachi Chemical types), Acryzoink A31O -45, Acridic A314, and Acridic 47-540 (all manufactured by Dainippon Ink and Chemicals), but are not limited to these.

Preferably, the acrylic resin contains 50% by weight or more of methyl methacrylate and has a molecular weight (GPC) of 5,000 to 300,000 from the viewpoint of compatibility with the fluorine-containing copolymer. The blending ratio is usually 10 to 1900 parts by weight, preferably 25 to 400 parts by weight, of the acrylic resin per 100 parts by weight of the fluorine-containing copolymer. When blended within this range, the weather resistance, translucency, pigment dispersibility, etc. of the paint are good.

The protective layer in the present invention is usually prepared by blending a fluorine-containing copolymer with a crosslinking agent as described above, uniformly mixing and dissolving it in an appropriate solvent, and applying a coating composition to a plastic or metal frame. It is formed by applying it to the surface, crosslinking and curing it at room temperature. Curing progresses quickly at room temperature, usually within 1
A hard coating can be obtained in ~10 days, but the time required for curing can be shortened by raising the temperature and drying to a level that does not adversely affect the frame.

The crosslinking agent is a functional group (
hydroxyl group, carboxyl group or glycidyl group)
It is a compound having two or more groups capable of crosslinking the fluorine-containing copolymer by reacting with the fluorine-containing copolymer. When the functional group is a hydroxyl group, the crosslinking agent is usually an isocyanate, an acid anhydride, or the like. These include functional amines, amine resins, and compounds containing glycidyl groups. When the functional group is a glycidyl group, it is usually an amine. Examples of isocyanates include, but are not limited to, hexamethylene diisocyanate, tolylene diisocyanate, hydrogenated tolylene diisocyanate, and block isocyanates thereof. Examples of amines include diethylene triamine, triethylene tetramine, xylene diamine. , metaphenylenediamine, benzyldimethylamine, bisaminopropyltetraoxaspiroundecane, and the like, but are not limited to these. Examples of acid anhydrides include, but are not limited to, phthalic anhydride, pyromellitic anhydride, mellitic anhydride, etc. Examples of amino resins include alkyl etherified methylol melamine, alkyl etherified methylol urea, and alkyl etherified methylol melamine. Examples of compounds containing a glycidyl group include, but are not limited to, etherified benzoylguanamine, etc., having the formula: %Formula% (wherein Z is a glycidyl group, R1 is an alkylene group having 2 to 10 carbon atoms or a carbon An aliphatic diepoxide or an aromatic jepoxide represented by the formula: % formula % (in which R2 is a trivalent aromatic group and Z is the same as above). ) aromatic triepoxides represented by the following, but are not limited to these.

The amount of the crosslinking agent is preferably adjusted to 0.5 to 2 equivalents based on all the functional groups in the fluorine-containing copolymer and the acrylic resin.

As the solvent, unlike conventional fluorine-containing copolymers, a wide variety of ordinary solvents can be used. Specific examples include esters such as ethyl acetate, butyl acetate, isobutyl acetate, and cellosolve acetate; acetone, methyl ethyl ketone,
Ketones such as methyl isobutyl ketone; cyclic ethers such as tetrahydrofuran; amides such as N-dimethylformamide and N-dimethylacetamide; alcohols such as methyl alcohol, ethyl alcohol, and butyl alcohol; aromatic carbonization such as toluene and xylene One or more types of hydrogens may be used.

The concentration of the fluorine-containing copolymer varies depending on the coating method, coating manufacturing method, etc., but is usually 5 to 70% by weight, preferably 10 to 60% by weight.

Other polymers, curing accelerators, dyes, pigments, viscosity modifiers, leveling agents, anti-gelling agents, ultraviolet absorbers, light stabilizers, coatings may be added to the fluorine-containing co-electrolyte coating composition as necessary. Anti-foaming agents, dispersants, antifoaming agents, etc. may be added.

The eyeglass frames of the present invention are produced by coating a frame made of plastic, metal, etc. with a fluororesin paint containing a polymer whose main component is a fluorine-containing copolymer and a crosslinking agent, and then crosslinking and curing at room temperature to heating. It can be obtained by letting

When painting, it may be applied directly to the frame, but if necessary, one or more layers of undercoating such as acrylic resin or urethane resin may be applied to the frame.
A protective layer according to the present invention may be formed thereon.

Application to the frame can be carried out by a conventional method such as a spray method, a dip coating method, or a dipping method.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Example I VdF70-1-/L, %, CTFE20-1-/L,
% and M5FPIO mol% were added to 50 parts of methyl isobutyl ketone and mixed uniformly. An amount equivalent to N00 value 1.1 of Coronate EH and 0.05 g of dipropylene dilaure as a curing accelerator were added to OHHI3 of the fluorine-containing copolymer (crosslinking agent) and mixed uniformly to form a coating composition. was prepared.

On the other hand, 110 is a nickel alloy plate with chrome plating on its surface.
A board of 0BX50X1 crane was prepared.

The coating composition was applied to the substrate by dip coating to form a coating film with a thickness of 10 μm, and the coating was cured at 25° C. for 7 days to obtain a test piece.

Example 2 70 mol% vdF, 20 mol% CTFE and M5FP
Fluorine-containing copolymer consisting of IO mol% and MMA80
An acrylic resin consisting of mol%, EMAIO mol%, and HEMAIO mol% was mixed with methyl isobutyl ketone in a ratio of 70/30 (weight ratio) to prepare a 50% by weight varnish, and a varnish containing Coronate EH as a crosslinking agent was added. For OHHI3 of elementary copolymer and acrylic resin,
Coronate EHONCO value 1.1 equivalent amount and curing accelerator dibutyltin dilaurate per 1 g of solid content xx
To-3g was added and mixed uniformly to prepare a coating composition.

The above coating composition was applied to the same substrate as in Example 1 and cured in the same manner as in Example 1 to obtain a test piece.

Examples 3 to 4 Test pieces were obtained in the same manner as in Examples 1 and 2 using commercially available earmuffs (acetylated cellulose) of eyeglass frames as substrates.

Comparative example 1 The substrate of Example 1 itself was used as a test piece.

Comparative example 2 The substrates of Examples 3 and 4 were used as test pieces.

The following tests were conducted on each test piece obtained in Examples 1 to 4 and Comparative Examples 1 to 2. The results are shown in Table 1.

[Corrosion resistance]

Using a salt spray tester manufactured by Suga Test Instruments ■, 5% saline was sprayed onto the test piece with scratches marked with an X mark, and the test was conducted for 2000 hours, and the surface condition after the test was observed.

〔chemical resistance〕

The test piece was immersed in ethyl alcohol at 25°C for 1 hour,
Measure the degree of softening by visual judgment and pencil hardness test.

Table 1 Examples 5 to 21 Fluorine-containing copolymer or fluorine-containing copolymer and acrylic resin having the compositions shown in Table 2 (the proportions are shown in Table 2)
was dissolved in methyl isobutyl ketone, and the solid concentration was 3.
The content was adjusted to 0% by weight. O of the solid content of the solution
Example 3 to 4
Dipping coating was applied to the metal parts and acetylated cellulose earmuffs of a commercially available eyeglass frame similar to 2.
A test piece was obtained by curing at 5°C for 7 days.

Corrosion resistance and chemical resistance tests were conducted on each test piece in the same manner as in Examples 1 to 4. The results are shown in Table 2.

In addition, each abbreviation indicating a monomer indicates the following compound.

VdF: Vinylidene fluoride CTFE: Chlorotrifluoroethylene TFE: Tetrafluoroethylene M5 FP: CFt”CFCFzCHzOH3FH
A: CFz=CFCHzCHzOHHBVE: Hydroxybutyl vinyl ether GVE nigericidyl vinyl ether 7 FHA: CFz=CFCFzCFzCHzCH
gOHMMA: Methyl methacrylate EMA: Ethyl methacrylate HEMA: Hydroxyethyl methacrylate BMA Nibutyl methacrylate MA: Methacrylic acid GMA Nigericidyl methacrylate 5 F B A: CF z = CF CF t
COOH (The following is a blank space, continued on the next page) [Effects of the invention] As described above, the polymer composition containing the vinylidene fluoride copolymer having the functional group as a main component can be cured at room temperature, and is corrosion-resistant. Since a coating film with excellent corrosion resistance and chemical resistance can be formed on any type of frame, the eyeglass frames of the present invention provided with the coating film as a protective layer have extremely excellent corrosion resistance and chemical resistance. have.

Claims (1)

[Claims] 1. Vinylidene fluoride copolymer having a functional group and/or
Or an eyeglass frame provided with a protective layer mainly composed of a crosslinked vinylidene fluoride copolymer having a functional group.