JP2006343378A - Spectacle frame and its production method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problems with an ordinary spectacle frame made by using a petroleum-based resin as a frame of spectacles that, even if such frame is molded in compliance with the face due to the soft nature of the resin, the frame is deformed during use and the points coming into contact with a human body are roughened in surface or whitened by friction and moisture absorption. <P>SOLUTION: The spectacle frame is constituted by providing the whole or prescribed portion of the spectacle frame with a molding made of a casein-based resin as a base, and providing the surface of the molding with a coated hardening layer of a coating material hardening layer essentially composed of prepolymer obtained by bringing mono- or poly- hydric alcohol selected from (A) polyoxyalkylene polyol, (B) hydrooxyalkyl poly(meth)acrylate, (C) polyhydrooxyalkylene glycidyl polyether or (D) perfluoropolyoxyalkylene polyol having 1 to 3 hydroxyl groups in average one molecule and organic diisocyanates into reaction and having average 2 to 5wt% free NCO groups. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an improvement in a frame of eyeglasses and a manufacturing method thereof.

The frame of spectacles is generally composed of a lens insertion frame and a pad, front, temple, modern, etc., and has a structure that is supported by the ear and nose. However, if the lens is made of plastic, the entire frame is made of resin, or the front part is made of metal such as gold or titanium, and the modern earring is made of resin and integrated with the gold or titanium with screw grooves. Some are rimless or do not have an edge to hold the lens part.
The present invention relates to an improvement of a spectacle frame using a special resin molding for all or a predetermined part of the spectacle frame. In the present invention, the term “spectacle frame” refers to the entire frame portion other than the spectacle lens.

As for the frame of eyeglasses, it is known that some of the high-end products are made using the upper shell or the modern one, etc., but the upper shell is used for rare animals. For this reason, import is prohibited and it is not possible to make new glasses.
Even if it is a luxury item that uses gold as a frame for eyeglasses, the modern part cannot be replaced with an ordinary plastic molding because it can not be used. For example, in a luxury item in which diamonds are scattered on the frame. If the modern resin is not improved, the high-quality feeling is significantly hindered.

The glasses frame that is currently widely used does not come out with a resin that changes to the upper shell, so attempts have been made to create something visually similar to the upper shell using a general-purpose resin such as celluloid or acrylic resin. The material is heated in a humidified state and is processed by bending, pasting, etc. using the unique thermoplasticity of the shell, and it is transparent, hard and does not deform at room temperature or body temperature, and does not deform at all. It has excellent characteristics such as no scratches caused by friction on the surface and no whitening due to moisture absorption, and it causes insect damage in the long term. On the other hand, general-purpose resins such as celluloid and acrylic resin that are widely used at present are highly flexible even at room temperature, and even those having a pencil hardness of about H have not been obtained.
For this reason, when processing according to the face, it is unavoidable that deformation due to processing distortion, body temperature in the wearing state, natural moisture absorption, etc., causing deviations from the face when wearing, will naturally occur. In other words, it has a problem that it becomes opaque due to fine scratches.

Various resins have been studied as alternatives to the shark shell, but because the shark shell is a kind of protein, there are casein resins made from milk protein and soy protein, which are artificial protein resins, resinated with formalin. Compared to physical properties, it has high hygroscopicity, less thermoplasticity in humidified state, insufficient friction resistance, easily scratches the surface, and weak bending strength. However, this is about traditional craft products.There is no problem with the thermoplasticity in the humidified state in the spectacle frame, and extreme bending is not necessary, so there is no problem in bending strength and resistance. It was found that there was a problem in that the friction was insufficient and the surface was easily scratched. The causes of these problems are the same protein system in both shellfish and casein resin, but are thought to be based on the molecular structure, that is, the number of molecular chains, the state of branching, and the difference in molecular weight. If the surface condition such as abrasion resistance can be improved without losing at least the processability of the casein resin in a humidified state and bending strength due to transparency and surface polishing, etc., an eyeglass frame similar to Shako will be obtained. In view of the above, the present inventors have obtained knowledge that certain types of urethane resins meet this requirement, and have reached the present invention.
A protein resin using fibroin as a raw material was also developed for the purpose of traditional crafts. However, since fibroin is made from silkworm thread, it is expensive, not marketed, and at least not applied to spectacle frames.

That is, to date, all or part of the spectacle frame is made of a general-purpose resin, and even if it is bent in a humidified state, the product will be naturally deformed due to the influence of air temperature and body temperature, and will be easily cracked and broken. There is a problem that the side that comes into contact with the ears is frictionally scratched finely or moisture penetrates into the resin and the surface becomes rough, cloudy and opaque due to short-term use. However, there is no change in the situation at present. .
Incidentally, the superlative of the upper shell is called white shell and is colorless or light yellow transparent, and the one called upper trout is red or yellow transparent, and there is a variegated thing called average armor. The production of such an armor-like object has never been successful.

  In order to improve such a spectacle frame made of a general-purpose resin, the surface of the resin is coated with another wear-resistant resin, or an inorganic or organic additive is blended in the resin and molded. Attempts were also made to improve the characteristics, but satisfactory results have not been obtained, and even if the resin is different even if a wear-resistant resin is applied or applied to the surface of a general-purpose resin, Due to the difference in thermal expansion, the bonding between layers is insufficient, and there is a problem of delamination, so that no satisfactory product has been obtained to date.

Japanese Patent Publication No. 7-49555 Japanese Patent Publication No. 7-71824 JP-A-2005-121686

The inventor of the present invention is also a kind of protein resin, transparent brownish or yellowish transparent, and to some extent preferred shellfish is also a protein, by subjecting the surface to special urethane processing, We have succeeded in providing eyeglass frames that solve various problems.
That is, the invention of claim 1 is provided with a molded body based on casein resin on the whole or a predetermined portion of the spectacle frame, and (A) a polyoxyalkylene polyol, (B) on the surface of the molded body. Mono having an average of 1 to 3 marine groups in at least one molecule selected from hydroxyalkyl poly (meth) acrylate, (C) polyhydroxyalkylene glycidyl polyether or (D) perfluoropolyoxyalkylene polyol Alternatively, it is characterized in that it is provided with a coating / curing layer of a paint containing a prepolymer whose essential component is 2 to 5% by weight of a free NCO group obtained by reacting a polyhydric alcohol and an organic diisocyanate. Eyeglass frame to
In the invention of claim 2, the coating and curing layer of the coating applied to the surface of the molded body based on casein resin has a pencil hardness of H or more and a coating thickness of 5 to 30 μm. It is the spectacles frame of description.

  According to a third aspect of the present invention, in manufacturing the spectacle frame according to the first aspect, after the spectacle frame material is completely cleaned, the casein-based resin molded body is provided on all or a predetermined portion of the spectacle frame. A step of cleaning the surface of the casein-based resin molded body of the spectacle frame and then roughening; and (A) a polyoxyalkylene polyol on the surface of the roughened casein-based resin molded body, (B) Hydroxyalkyl poly (meth) acrylate, (C) polyhydroxyalkylene glycidyl polyether, or (D) perfluoropolyoxyalkylene polyol, average 1 to 3 marine groups per molecule The content of free NCO groups obtained by reacting mono- or polyhydric alcohols having organic groups with organic diisocyanates is 2 to 5% by weight A step of applying a paint containing a certain prepolymer as an essential component, and a volatile component so that the coating layer of the paint is treated at about 30 to 40 ° C. under reduced pressure or by flowing dry air so as not to cause foaming in the coating film. It is a method for manufacturing a spectacle frame, comprising a step of curing while removing and a step of performing necessary grinding and puffing after curing.

In other words, the spectacle frame using general-purpose resin is deformed in a short period of time when worn by humans, no matter how improved it is, and it becomes opaque when it comes into contact with the human body. Deterioration phenomenon such as whitening in about 3 months is unavoidable and the aesthetic appearance is unavoidable, and when modern is screwed to the temple, moisture penetrates from that place and there is a tendency to promote whitening of the material, scratches on the surface Although there are many problems that are easy to stick, attempts have been made to use casein, which is a protein. However, problems similar to those of conventional general-purpose resins have not been solved, and improvements have been demanded.
Further, it has been found that even when casein resin is conventionally used instead of a general-purpose resin, there are problems similar to those of the general-purpose resin. For this reason, various attempts have been made, such as double coating with other polyamide resins, epoxy resins, silicone resins, etc., or addition of other additives to casein resin to improve the properties, but the hygroscopicity has not been improved. In the double coating, delamination is unavoidable, and it is generally easy to break.
In addition, the shell and casein resin are both susceptible to insect damage over a long period of time.

As a result of intensive studies to solve this problem, the present inventor has focused on the fact that casein resin and shellfish are both proteins, and have reached a novel spectacle frame and a method for producing the same.
The eyeglass frame obtained by surface-treating casein resin with a special urethane resin according to the present invention is hard, and the one molded and adjusted according to the face in a humidified state is loose even if humans repeatedly wear and remove it. The casein resin is water resistant and wear resistant, and the parts that come into contact with the human body or pinch with fingers are less prone to whitening due to scratches or moisture absorption. Even when applied as such, there is no water absorption phenomenon at the threaded portion, and an amazing result is that the appearance and molding dimensions do not change at all even after long-term continuous use for one year or more.

On the other hand, general-purpose resin is generally flexible, and when it is used for a spectacle frame, even if the angle is adjusted according to the face, it can be deformed according to the processing strain after it is removed and left unused when not in use. Even glasses frames used in modern times may be deformed even when left in their natural state, and by wearing glasses according to the human face, they are affected by body temperature and moisture, especially on human skin. On the contact side, as a result of the action of moisture absorption or evaporation and the action of friction applied and removed, the luster was lost and deformation and cracks were observed after about three months. Even if various inorganic and organic fillers are added to the resin to improve it, there are problems such as becoming harder than necessary, becoming brittle, increasing hygroscopicity, and losing transparency. In addition, attempts to coat other resins in a double layer have been inevitably caused by delamination in addition to the same problems as described above, and no effective countermeasure has been found until now.
Note that even if the above-mentioned general-purpose resin is coated with the same resin paint as that of the present invention, delamination occurs and a satisfactory product cannot be obtained.

In other words, casein resin is a resin made from milk or soy protein, and its molecular structure is not as complex as that of the shell, and it has a transparency and appearance similar to the shell, but contains approximately 80% protein. It is characterized by the fact that it contains about 1 to 3% of oil and fat components, and the properties by heat are slightly different from the shell, and the properties with respect to moisture are also slightly different from the shell, and the water resistance is somewhat bad, but the hardness is quite good. Have.
However, with eyeglass frames made of casein resin alone, the resin has water absorption, and transparent processed products will gradually whiten, and it will be avoided that the parts that come into contact with the human body are scratched by friction and become rough. Although there is a problem that it is not possible, the surface treatment with a special urethane-based paint according to the present invention has a transparency, strength, and wearability that is almost similar to the shell.

In other words, as a result of intensive studies, the present inventors have found that the special protein structure of the shark shell is complex between the shell and casein proteins, and the molecular structure is different even at the age and place of origin of the shell turtle. The casein resin has a molecular weight of about 70 to 300,000 even if the surface of the casein resin molded body is painted with a resin paint, and the network structure is also different from the shell, so the heat processability in a humidified state is poor, Although it was thought that the bending strength was insufficient, the resin-coated product of the present invention surprisingly succeeded in completely solving this problem.
That is, the surface of the casein-based resin layer can be applied, for example, by surface treatment for cleaning, for example, by washing with a neutral detergent, regardless of the content of oil components contained therein, or by roughening the surface. By enlarging the surface area with the layer, the following coatings can be easily obtained: (A) polyoxyalkylene polyol, (B) hydroxyalkylene glycidyl poly (meth) acrylate, (C) polyhydroxyalkylene glycidyl polyether or (D ) The content of free NCO groups obtained by reacting mono- or polyhydric alcohols selected from perfluoropolyoxyalkylene polyols having an average of 1 to 3 hydroxyl groups in one molecule with organic diisocyanates is 2 Apply paint with 5% by weight prepolymer as an essential component, It found to be able to form a coating film cured at 30 to 40 ° C..
At that time, the surface of the coating is dried by reducing the pressure or flowing dry air, and volatile components such as solvent and moisture are completely removed, and a cured coating can be obtained without foaming the molded product. did.
In addition, this paint film is firmly bonded to the internal casein resin, and this resin-coated film provides a hard-coated processed product having high hardness and excellent stain resistance, and has a spectacle frame as a product. It is easy to mold in a humidified state, does not cause delamination due to bending or the like, and even when worn by a human, the contact surface with the skin is not scratched, dirty or opaque. In addition, the same level of upper Toro and Nami-Kou that can be placed on the upper shell product can be mistaken for natural armor by adding a colorant (dye or pigment). The product can be realized by adding a white pigment such as zinc oxide or titanium oxide, and if a green pigment is added, a green product can be easily obtained.

  In the present invention, the casein resin is a polymer having a peptide bond represented by the following chemical formula 1, and the casein resin molding is applied to all or a part of a spectacle frame, for example, modern, for a special case according to the present invention. By providing a coating film with a paint film, it is possible to maintain a good appearance of the processed product for a long period of time by coating with a strong coating film. Since it has a polypeptide bond, it can chemically react with the active hydrogen and the free NCO group in the paint to obtain a coated film product having excellent adhesion.

According to the present invention, selected from (A) polyoxyalkylene polyol, (B) hydroxyalkyl poly (meth) acrylate, (C) polyhydroxyalkylene glycidyl polyether or (D) perfluoropolyoxyalkylene polyol. A prepolymer having a free NCO group content of 2 to 5% by weight obtained by reacting a mono- or polyhydric alcohol having an average of 1 to 3 marine groups in at least one molecule with an organic diisocyanate is essential. An eyeglass frame (Claim 1) comprising a coating and hardening layer of a paint as a component.
A casein resin is coated with a coating material of polyurethane, acrylic, epoxy, or fluororesin alone or mixed, and can be cured in air at room temperature to obtain a product having high hardness and excellent stain resistance.

  In the reaction of the mono- or polyol of the present invention with the organic diisocyanate, the equivalent ratio of NCO / OH is preferably 1.5 to 2.0, and when this is reacted at a value smaller than 1.5, the resulting paint Becomes high in viscosity and deteriorates workability. On the other hand, if the NCO / OH equivalent ratio is reacted at a value larger than 2.0, unreacted free isocyanate is not preferable in terms of hygiene during work. Furthermore, when the content of free NCO groups in the paint is less than 2.0% by weight under the above conditions, curing is slow and stickiness remains on the coating film. On the other hand, when the content of the terminal NCO group is more than 5.0% by weight, foaming occurs when it is cured by reacting with moisture.

The polyol used in the present invention is (A-1) a polyhydric alcohol having 2 to 3 hydroxyl groups in one molecule, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol. 1,4-butylene glycol, 1,6-hexanediol, neopentyl glycol, bisphenol A, trimethylol ethane, trimethylol propane, glycerin, etc. are added with ethylene oxide and other alkylene oxides such as propylene oxide, styrene oxide, etc. Polyoxyalkylene polyol, or (A-2) polyoxyethylene polyol obtained by addition polymerization of only the above polyhydric alcohols with ethylene oxide and other alkylene not containing an ethylene oxide unit A polyether polyol containing oxide units, or
(A-3) A polyol having no alkylene oxide unit, or a polyol such as a polybutadiene styrene copolymer polyol or a polyacryl polyol is used.

  In addition, (B) hydroxyalkyl di or tri (meth) acrylate has an alkyl group of about 2 to 28 carbon atoms, and the alkyl moiety is linear, cyclic or branched, saturated or unsaturated. Di or tri (meth) acrylate is used. The alkyl group of the compound preferably has 2 to 12 carbon atoms. Some desirable hydroxyalkyl di- or tri (meth) acrylates are from hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxy (meth) acrylate, hydroxybutyl (meth) acrylate and compounds having the following formula 2 You can choose.

（式中ＲおよびＲ′は水素原子またはメチル基を示す）で表わされる化合物の１種または２種以上を１〜１０重量部とアクリル酸エステルおよびメタクリル酸エステルからなる不飽和化合物の１種または２種以上を９０〜９９重量部を共重合して得られた共重合物を使用することもできる。）

(Wherein R and R ′ represent a hydrogen atom or a methyl group) 1 type or 2 or more types of a compound represented by 1 to 10 parts by weight and one type of an unsaturated compound comprising an acrylic ester and a methacrylic ester A copolymer obtained by copolymerizing 90 to 99 parts by weight of two or more kinds can also be used. )

Examples of the compound (monomer) represented by the above general formula include hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, and the like.
Further, polyhydroxyalkylene diglycidyl polyether, (D) perfluoropolyoxyalkylene polyol, polyalkylene glycol, particularly polyethylene glycol, alkylfluoropropene and alkylfluoropropene dimer (for example, hexafluoropropene and its dimer) 1: 1 ( Fluorine-containing compounds such as (molar ratio) adducts are also used.
The average molecular weight of the polyols used in the present invention is preferably 1000 to 8000, particularly preferably 2000 to 4000.

  As the organic diisocyanates used in the present invention, diisocyanates used for usual urethane resins can be used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4 / 2,6 isomer ratio 65/35 (weight ratio) tolylene diisocyanate, 2,4 / 2,6 isomer ratio 80 / 20 (weight ratio) tolylene diisocyanate 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, metaxylylene diisocyanate, phenyl diisocyanate, 1,5-naphthalene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4-diphenylmethane diisocyanate, A single or mixture of isophorone diisocyanate, terminal diisocyanate prepolymer and the like, preferably those which are easy to handle in a liquid state at room temperature, are suitable.

  In order to accelerate the curing reaction of the paint of the present invention with moisture, known organometallic salts as catalysts for urethanization reaction, for example, organic lead compounds such as lead naphthenate, lead octylate, lead stearate, tin naphthenate, octyl An organic tin compound such as tin oxide, tin laurate, tetra-nbutyltin, n-butyltin trichloride, trimethyltin hydroxide, dimethyltin dichloride, dibutyltin dilaurate or the like may be added.

In practicing the present invention, the method of first coating the casein resin can be used without any particular limitation. For example, a modern molded product or a modern molded product inserted in a temple is cleaned with a neutral detergent, then roughened by a conventional method such as file sanding or spraying with moist powder, and the surface is removed by puffing. The step of adjusting, and then the step of dip-coating in the coating solution of the composite paint described above (in addition to immersing in the solution, a method of applying with spray, brush, roller, etc. can also be selected and implemented), It consists of a step of forming a coating film by causing a curing reaction of the resin while removing volatile components such as solvent, moisture and other generated or contained vaporized components by flowing dry air or degassing under reduced pressure.
In addition, the heating temperature for drying is 30 ° C. to 40 ° C., more preferably at room temperature or even 30 ° C. even when heated, and is preferable because it does not cause heat change or foaming in the molded product. The curing time varies depending on the amount and time when the coating film is formed and the standing time after the coating film is formed. In addition, the coating term is almost completely cured if left at room temperature for about 1 day, and it is easy to obtain a coating film without foaming if left at room temperature for 1 to 5 days.
The thickness of a preferable coating film is about 5 μ to 30 μ, more preferably about 0.1 μ to 5 μ.

Further, the spectacle frame (all or a part) obtained by coating the surface of casein resin with a special resin according to the present invention is hard, and if it is molded in accordance with one face, it will loosen even after repeated loading and unloading. Even if the entire frame of the glasses is treated with casein according to the present invention, or a part thereof, for example, at least a modern part obtained by surface treating casein with the present invention, A remarkable result is that it is abradable and does not cause a whitening phenomenon caused by scratches or moisture absorption in a portion that touches the human body or is pinched with a finger after a long period of time of one year or more.
If the modern type using conventional general-purpose resin or the like is worn on the human body as spectacles, the contact surface to the human body will lose luster as a result of wearing as early as 2 to 3 months, and the surface becomes rough and rough. It was estimated in the accelerated aging test of 80% humidity, 50 ° C., and ultraviolet irradiation that the coated film applied by the above method would hardly lose its gloss even when worn as glasses for more than one year. The surface was rough and could be used without any change in roughness. Conventionally, in the modernity of modified and aged celluloid and acrylic resin, the surface was cleaned by dismantling and re-bonding by heating and humidification and re-joining, but according to the present invention, the regeneration treatment is performed. It can be used while maintaining a good appearance for a long time. Also, the product according to the invention is not susceptible to insect damage.

Thus, the spectacles coating film formed from the paint of the present invention is excellent in surface properties such as wear resistance, hot water resistance, and heat resistance. Examples are provided to specifically describe the present invention.
In addition, the performance evaluation of the coating film was implemented by the following method.
(1) Adhesion test The number of squares remaining when a cellophane tape (registered trademark) was applied and quickly peeled off after attaching 100 squares of 1 mm x 1 mm to the sample surface with a cutter knife having a sharp tip. Displayed.
(2) Scratch resistance test Steel wool was attached to a scratch resistance tester manufactured by Fukuda Machine Industry Co., Ltd., and the degree of scratching on the surface was visually observed after reciprocating the test piece surface 10 times with a 1 kg load. The evaluation was made in 5 grades from A to E, where A was a state where no scratch was found and E was a state where the casein resin fabric was very easily damaged.
(3) Heat resistance test Leave in an air oven set at 130 ° C. for 3 hours, and visually observe the appearance of the coating film. The case where the coating film was free from cracks, blistering, whitening and the like and having a good appearance was marked with ◯, and the case where it was poor was marked with ×.
(4) Warm water resistance test Leave in boiling water for 2 hours and visually observe the appearance of the coating film. The case where the coating film was not peeled off, blistered, cracked, whitened or the like and the appearance was good was evaluated as ◯, and the case where it was poor was evaluated as ×.
(5) Pencil hardness test In accordance with the test method of JIS K-5400 (1979.6.14), display with the highest hardness that does not damage the film when a load of 1 kg is applied using a pencil hardness tester. However, the pencil used was “Mitsubishi High Uni” [Mitsubishi Pencil Co., Ltd. product].

Example 1.
1000 g of polyoxypropylene ether polyol having an average molecular weight of 3000, a hydroxyl number of 3, and a hydroxyl value of 56.1 (mgKOH / g) and 2,4 / 2,6 isomer ratio of 80/20 (weight ratio) tolylene diisocyanate (hereinafter referred to as T- Prepolymer I having a free NCO group content of 3.5% by weight and a viscosity of 21000 cps (25 ° C.) was reacted in a 2 L four-necked flask in a nitrogen stream at 90 ° C. for 4 hours. . Got.
The prepolymer I.V. Is diluted with the solvent toluene, xylene and 3 methoxybutyl acetate so that it becomes 15 to 18 seconds with a Ford cup viscometer, and then the glasses frame provided with the casein-based resin layer previously washed with a neutral detergent and degreased is painted. It was dipped in and pulled up at a speed of 50 to 100 cm per minute to obtain a smooth, hard and glossy coating film.

Comparative Example 1
Reaction of 1000 g of polyoxypropylene ether polyol having an average molecular weight of 3000, a hydroxyl number of 3 and a hydroxyl value of 56.1 (mgKOH / g) and T-80D 1200 g in a 2 L 4-neck flask at 90 ° C. in a nitrogen stream for 4 hours. A prepolymer having a free NCO group content of 5.5% by weight and a viscosity of 15000 cps (25 ° C.) II. Got. The prepolymer II. As for Example 1. In the same manner as above, it was applied to a casein-based resin modern processed product.

Example 2
600 g of 2-hydroxyethyl acrylate and 900 g of T-80DI were reacted with a catalyst of dimethyl tin dineodecanoate in a solvent of 400 g of M-pyrrole N methylpyrrolidone, and the content of free NCO group was 3.0% by weight. And a prepolymer III having a viscosity of 20400 cps (250 ° C.) was obtained. This prepolymer III was diluted with solvent toluene so that it would be 25-40 seconds with a viscometer of Fort Cup # 4, washed with neutral detergent and degreased, and applied to a modern soft brush. It was dried and cured for 24 hours.

Comparative Example 2
600 g of 2-hydroxyethyl acrylate and 1500 g of T-80DI were reacted with a catalyst of dimethyl tin dineodecanoate in a solvent of 400 g of M-pyrrole N methylpyrrolidone, and the content of free NCO group was 6.0% by weight. A prepolymer IV with a viscosity of 22400 cps (25 ° C.) was obtained. For the prepolymer IV. In the same manner as above, it was applied to a casein-based resin modern processed product.

Example 3
Fluorine-containing polyurethane having a free NCO group content of 3.5% by weight by reacting 800 gr of a 1: 1 (molar ratio) radical adduct (both ends OH) of polyethylene glycol having an average molecular weight of 400 and hexafluoropropene dimer (both ends OH) and 170 DI Got V. This polymer V. was converted to Example 2. In the same manner as above, casein resin was applied to Modern.
Table 1 shows the scratch resistance test, heat resistance test, hot water resistance test and pencil hardness evaluation test results of Examples 1 to 3 and Comparative Examples 1 and 2.

  According to this comparative test, it can be seen that the present invention has very superior mechanical properties, water resistance, and moisture resistance compared to modern using only a casein resin that is not painted. It can be seen that it is very superior compared to modern products that use In addition, the coating process is relatively simple, but completely forms a cured coating film without foaming. Therefore, it is easy to bend in water vapor or warm water, and has improved strength. The effect cannot be imagined from the casein resin itself.

Further, a comparison between the frame material according to the present invention and a normal acrylic resin material is as shown in Table 2 below, and it can be seen that the present invention is far superior. The

The perspective view of an example of the frame of spectacles of the present invention The perspective view of an example of the modern part of the spectacles of this invention

Explanation of symbols

1 Frame 2 Temple 3 Modern

Claims (3)

  A molded body based on a casein resin is provided on the whole or a predetermined portion of the spectacle frame, and (A) a polyoxyalkylene polyol, (B) a hydroxyalkyl poly (meth) acrylate, Mono- or polyhydric alcohols having an average of 1 to 3 marine groups in at least one molecule selected from (C) polyhydroxyalkylene glycidyl polyether or (D) perfluoropolyoxyalkylene polyol, and organic diisocyanates A spectacle frame comprising a coating and hardening layer of a paint containing a prepolymer having a free NCO group content of 2 to 5% by weight as an essential component.   The spectacle frame according to claim 1, wherein the coating and curing layer of the coating applied to the surface of the molded body based on casein resin has a pencil hardness of H or more and a coating thickness of 5 to 30 μm.   A process of providing a casein-based resin molded body in the whole or a predetermined portion of the spectacle frame after the spectacle frame material is completely cleaned in manufacturing the spectacle frame according to claim 1, and the casein system of the spectacle frame. The surface of the resin molded body is cleaned and then roughened, and the surface of the roughened casein-based resin molded body is subjected to (A) polyoxyalkylene polyol, (B) hydroxyalkyl poly (meta Mono- or polyhydric alcohols having an average of 1 to 3 marine groups in at least one molecule selected from) acrylate, (C) polyhydroxyalkylene glycidyl polyether or (D) perfluoropolyoxyalkylene polyol and organic A prepolymer having a free NCO group content of 2 to 5% by weight obtained by reacting with diisocyanates is essential. The process of applying the coating material and the coating layer of the coating material is cured at about 30 to 40 ° C. under reduced pressure or by the flow of dry air to remove volatile components so as not to cause foaming in the coating film. And a step of performing necessary grinding and puffing after curing.

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