JPS6042441B2 - plastic cleanse - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a plastic lens having a cured coating film that has excellent surface hardness, scratch resistance, heat resistance, etc., and that adheres extremely firmly to a plastic lens base material. A cured coating film containing mainly a reaction product of diarylidene pentaerythrite and an unsaturated alcohol having a hydroxyl group and an acryloyl group or a methacryloyl group in one molecule is formed on the surface of a plastic lens base material. Regarding plastic lenses.

In general, plastic lenses made from materials such as polycarbonate, polymethyl methacrylate, and polyallyl diglycol carbonate are lighter than conventional glass lenses, have excellent impact resistance, and can be manufactured quickly. Because of its advantages such as being flexible and inexpensive, it is widely used as lenses for eyeglasses, sunglasses, cameras, telescopes, etc. However, conventionally developed plastic lenses made from the above-mentioned plastics generally have significantly lower surface hardness than glass lenses, so they are susceptible to contact or collision with other objects, or being pulled by other objects. The surface is easily damaged by the action, and therefore not only the aesthetic appearance of the product is impaired, but also the optical properties are significantly deteriorated. Various methods have been proposed to overcome these drawbacks of plastic lenses. For example, a method is known in which a silicone-based or melamine-based polymerizable monomer or oligomer is applied to the surface of a plastic lens and then cured to form a coating film having improved surface hardness on the surface of the plastic lens. However, although the surface hardness of plastic lenses manufactured by these methods is improved, it is not completely satisfactory, and the adhesion between the coating film and the plastic lens base material is poor, so the interface between them is The coating film is prone to cracking and peeling off, and this tendency is particularly pronounced in high temperature and high humidity conditions, and the difference in refractive index at the interface between the coating film and the plastic lens surface is large, resulting in a decrease in light transmittance. It has disadvantages such as the tendency to cause optical distortion. As a result of various studies aimed at improving the drawbacks of conventional plastic lenses, the present inventors discovered that a cured coating containing mainly a specific polymerized oligomer having a spiroacetal structure in its molecular structure was applied to the surface of a plastic lens base material. The plastic lens formed by forming a film does not reduce the original transparency and impact resistance of the plastic lens itself, and has high surface hardness, abrasion resistance, scratch resistance, heat resistance, chemical resistance, and dyeing resistance. The present invention was completed based on the discovery that the plastic lens base material and the coating film have excellent adhesive properties.

That is, the present invention provides a cured coating film mainly containing a reaction product of diarylidene pentaerythritol and an unsaturated alcohol having a hydroxyl group and an acryloyl group or a methacryloyl group in one molecule, on the surface of a plastic lens substrate. The present invention relates to a plastic lens characterized by being formed. Examples of the base material of the plastic lens used in the present invention include polyallyl diglycol carbonate, polymethyl methacrylate, polycarbonate, polystyrene, polyvinyl chloride, cellulose acetate, and the like.

To manufacture the plastic lens base material used in the present invention, for example, a casting method, a molding method (injection method), a breath molding method, or the like is used.

The diarylidene pentaerythrite used in the present invention is represented by the following formula.

Examples of the unsaturated alcohol having a hydroxyl group and an acryloyl group or a methacryloyl group in one molecule that can be a reaction partner with diarylidenepentaerythrite include 2-
Hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 1,6-hexanediol monoacrylate, neopentyl glycol monoacrylate, glycerin diacrylate, trimethylolpropane diacrylate, pentaerythritol triacrylate, 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, glycerin dimethacrylate,
Examples include trimethylolpropane dimethacrylate and pentaerythritol trimethacrylate, and each molecule must contain one hydroxyl group and one or more acryloyl or methacryloyl group. For the reaction between diarylidene pentaerythritate and an unsaturated alcohol, 1 to 2.2 moles of unsaturated alcohol are used per mole of diarylidene pentaerythrite, and an acidic acid such as valatoluenesulfonic acid or diethyl sulfuric acid is used. It is carried out in the presence of a catalyst.

The reaction product thus obtained (hereinafter abbreviated as unsaturated spiroacetal oligomer) has at least one acryloyl group or methacryloyl group in one molecule, and its molecular weight ranges from 300 to 100, preferably 400.
It is preferable that it is 600-600. If the molecular weight is less than 300, the curability will not be sufficient, while if the molecular weight is more than 1000, the viscosity will be too high, resulting in poor workability and a long time required for curing, which is not preferred. Next, as a typical example, if we describe the product obtained by the reaction of diarylidene pentaerythrite and 2-hydroxyethyl acrylate, as shown in the following formula [1] or formula [■], both An unsaturated spiroacetal oligomer having the formula [1] having an acryloyl group at the end or the formula [■] having an acryloyl group at one end as a main component is obtained.

Alternatively, the unsaturated spiroacetal oligomers represented by formula [1] or formula [■] can be easily produced by changing the reaction ratio of diarylidene pentaerythrite and unsaturated alcohol. For example, when producing an unsaturated spiroacetal oligomer having formula [1] as a main component, 1.8 to 2.2 mol of unsaturated alcohol is preferably used per 1 mol of diarylidene pentaerythritol. Unsaturated spiroacetal whose main component is the formula [■]. When producing a system oligomer, 1.0 mol of unsaturated alcohol is added to 1 mol of diarylidene pentaerythritol.
~1.2 mol is preferred.

The unsaturated spiroacetal oligomer represented by formula [1] or formula [■] may be used as it is, or may be used after removing components such as unreacted unsaturated alcohol. The unsaturated spiroacetal oligomers represented by formula [1] or formula [■] may be used alone or in combination.

Further, if necessary, half or less of these unsaturated spiroacetal oligomers may be replaced with other reactive monomers or oligomers copolymerizable with these unsaturated spiroacetal oligomers.

Other copolymerizable reactive monomers or oligomers may be any monomers that can be copolymerized with the unsaturated spiroacetal oligomer and can be mixed uniformly, such as styrene, methylstyrene, ethylstyrene,
Styrenic monovinyl aromatic compounds such as chlorostyrene: vinylpyridine, 2-methyl-5-vinylpyridine,
Nitrogen heterocyclic compounds such as vinylpyrrolidone: Aromatic divinyl compounds such as divinylbenzan, divinyltoluene, and divinylnaphthalene; Aliphatic compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, pentaerythritate tetraacrylate, etc. Polyvinyl compound: Examples include reactive monomers used as materials for plastic lenses such as allyl diglycol carbonate and methyl methacrylate, and reactive oligomers such as unsaturated polyester and epoxy acrylate.

Among these, styrenic monovinyl aromatic compounds,
The use of nitrogen heterocyclic compounds, aromatic polyvinyl compounds, and aliphatic polyvinyl compounds is preferable in terms of improving the dyeability of the surface coating film, and the use of reactive monomers used as materials for plastic lenses is preferable. It is preferable in that it improves the adhesion of the coating film to the lens substrate. These copolymerizable reactive monomers or oligomers may be used alone or in combination of two or more.
Furthermore, a surfactant, an antifogging compound such as a silicone resin, and other additives can be added to the unsaturated spiroacetal oligomer used in the present invention, if necessary.

The unsaturated spiroacetal oligomer used in the present invention can be used as it is, but if necessary, an organic solvent may be added thereto for the purpose of adjusting the viscosity. Any organic solvent may be used as long as it mixes uniformly with the unsaturated spiroacetal oligomer, a reactive monomer or oligomer copolymerizable with this oligomer, and other additives, and does not soak the plastic lens base material. For example, esters, ketones, cycloaliphatic ethers, etc. are often used. The amount of organic solvent is
It is not more than 10 parts by volume per 10 parts by volume of unsaturated spiroacetal oligomer. If the amount of the organic solvent exceeds 10 parts by weight, the curability will be impaired, which is not preferable. When carrying out the present invention, an unsaturated spiroacetal oligomer is applied to the surface of a plastic lens base material.

As the coating method, any known method such as a dipping method, a spraying method, a flow coater method, etc. may be used, and the film thickness is 10 to 300 P1, preferably 30 to 120 P.
, apply it so that it becomes . When the film thickness is less than 10p, the surface hardness of the coating film is insufficient. On the other hand, if the film thickness is 300p or more, the impact resistance and optical properties will deteriorate, which is not preferable. The coating layer of the plastic lens coated with the unsaturated spiroacetal oligomer is cured by heating, light irradiation, ultraviolet ray irradiation, radiation irradiation, or the like. In this case, it is preferable to add a polymerization initiator to the unsaturated spiroacetal oligomer, and if necessary, further add a polymerization accelerator, a polymerization regulator, and other additives. Good too.
Examples of the polymerization initiator include photosensitizers such as benzoin, benzoin methyl ether, benzoin isopropyl ether, acetophenone, benzophenone, and anthraquinone; combination systems of benzophenone and aliphatic amine, benzoyl peroxide, azobisisobutyronitrile, Examples include radical generators such as methyl ethyl ketone peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, and dicumyl peroxide. The amount of polymerization initiator added is 1
It is 0.1 to 1 rut amount part with respect to 0 heel amount part. When the coating layer is cured by heating, light irradiation, ultraviolet ray irradiation, radiation irradiation, etc., it can be cured either in the air or in an inert gas atmosphere, such as in the presence of nitrogen gas, carbon dioxide gas, argon gas, helium gas, etc. You may do so. A colored plastic lens can be produced by using the unsaturated spiroacetal oligomer of the present invention to which a dye or pigment is added, or by forming a cured coating film and then dyeing it.

A feature of the use of the unsaturated spiroacetal oligomer of the present invention is that the adhesiveness between the cured coating film and the plastic lens substrate is extremely good, and even when left under high temperature and high humidity, the cured coating film remains attached to the plastic lens substrate. It does not peel off from the material and has extremely excellent surface hardness, abrasion resistance, scratch resistance, impact resistance, solvent resistance, water resistance, and transparency.

The plastic lens of the present invention is useful as, for example, lenses for eyeglasses, sunglasses, watches, cameras, etc., as well as lenses for industrial materials such as gas masks and welding protective masks.

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 A polymer with a molecular weight of about 472 and a viscosity of 3 was obtained by reacting 1 mole of diarylidene pentaerythritol and 2 moles of 2-hydroxypropyl acrylate on the surface of a polyallyl diglycol carbonate lens produced by an injection method. After applying a composition consisting of 100 parts by weight of a reaction product of .7 poise and Gardner color number 2 to 3 and 1 part by weight of benzophenone by a spray method, ultraviolet rays emitted from a 2KW high-pressure mercury lamp were applied from a distance of Md on both sides of the lens. was irradiated for 1 minute to produce a polyallyl diglycol carbonate lens having a transparent cured coating film with an average film thickness of 70 IL.

What is the surface hardness of the obtained lens in terms of pencil hardness? and big,
It was found to have extremely excellent surface hardness, and almost no scratches were observed in the scratch test with steel wool.

In addition, the cured coating film formed on the lens surface has grooves deep enough to reach the lens base material. We made 100 square grids with a knife, pasted adhesive tape on them, and then peeled off the adhesive tape.As a result, we repeated the adhesive tape peeling test several times. Even when the film was turned over, no peeling of the cured coating was observed, indicating that it had excellent adhesion. Furthermore, JIS-B-
As a result of measuring strain according to 9905, no strain was observed at all. Example 2 A lens having a molecular weight of 575.5 mm was obtained by reacting 1 mole of diarylidene pentaerythritol and 1.5 moles of trimethylolpropane diacrylate on the surface of a lens manufactured by an injection method or made of polymethyl methacrylate. Reaction product 1 with viscosity 19.4 poise and Gardner color number 2-3
After applying a composition consisting of 0 parts by weight, 1 part by weight of benzophenone and 1 part by weight of dimethylaminoethanol by a spray method, both sides of the lens were coated at 10C in a nitrogen gas atmosphere.
A lens made of polymethyl methacrylate having a transparent cured coating film with an average film thickness of 30p was manufactured by irradiating the lens with ultraviolet rays emitted from a 2KW high-pressure mercury lamp for 1 minute from a distance of 7n.

Below, as a result of measuring physical property values in the same manner as in Example 1,
The surface hardness was comparable to the pencil hardness, and in an adhesion test using a checkerboard adhesive tape, the cured coating did not peel off from the substrate even after repeating the adhesive tape peeling test 20 times.
Furthermore, in warm water at 80℃. The cured coating film did not peel off from the substrate and no cracks were observed in the cured coating film even after being left in a constant temperature room at 30° C. and 90% relative temperature for 10 days. Example 3 A transparent film with an average film thickness of 70p was produced in the same manner as in Example 1, except that a polycarbonate lens manufactured by an injection method was used instead of the polyallyl diglycol carbonate lens used in Example 1. A polycarbonate lens with a hardened coating film was manufactured.

The adhesiveness between the cured coating film of the obtained lens and the lens substrate was good, and the surface hardness was also high.

Example 4 Molecular weight 44 viscosity obtained by reacting 1 mole of diarylidene pentaerythritol and 2 moles of 2-hynodroxyethyl acrylate on the surface of a polyallyl diglycol carbonate lens manufactured by an injection method. 4.4 poise, Gardner color number 2-3 reaction product 1
After applying a liquid composition consisting of 0 parts by weight and 1 part by weight of benzoin isopropyl ether by a spray method, 10C7! UV rays emitted from a 2KW high-pressure mercury lamp were irradiated for 1 minute from a distance of , and the average film thickness was 80p.
A polyallyl diglycol carbonate lens having a transparent cured coating film was manufactured.

Below, as a result of measuring physical property values in the same manner as in Example 1,
Is the surface hardness in terms of pencil hardness? Even in a scratch test using steel wool, almost no scratches were observed.

Furthermore, as a result of an adhesion test, no peeling of the cured coating was observed, and no peeling or cracking of the cured coating occurred even under high temperature and high humidity environments. Furthermore, no optical distortion was observed in this lens. Example 5 Diarylidene pentaerythritol 1 was applied to the surface of the polyallyl diglycol carbonate lens used in Example 4.
To 100 parts by weight of a reaction product obtained by reacting 1 mole of 2-hydroxyethyl acrylate with a molecular weight of 33, a viscosity of 1.8 poise, and a Gardner color number of 2 to 3, 1 part by weight of benzophenone and 1 part by weight of dimethylaminoethanol were added. After applying the liquid composition containing the following parts by weight using a curtain flow coater method, 2K was applied from a distance of 10 cm on both sides of the lens.
A polyallyl diglycol carbonate lens having a transparent cured coating film with an average film thickness of 70 μm was produced by irradiating it with a W high-pressure mercury lamp for 1 minute.

Below, as a result of measuring physical property values in the same manner as in Example 1,
The surface hardness was a pencil hardness of ■, and no scratches were observed in the scratch test with steel wool.

Further, as a result of an adhesion test, no peeling of the cured coating was observed, and neither peeling nor cracking of the cured coating occurred even in a high temperature and high humidity environment. Furthermore, no optical distortion was observed in this lens. Example 6 Liquid composition 100 used in Example 4 was applied to the surface of the polyallyl diglycol carbonate lens used in Example 4.
A liquid composition prepared by adding 5 parts by weight of an equal weight mixture of ethyl acetate and dioxane as an organic solvent was applied by a spray method, and then heated to remove the organic solvent.

After that, both sides of the lens are 10C! A polyallyl diglycol carbonate lens having a transparent cured coating film with an average film thickness of 30 IL was produced by irradiating the lens with a 2 KW high-pressure mercury lamp for 1 minute from a distance of n. This lens had good adhesion between the cured coating film on the surface and the lens base material, high surface hardness, and excellent optical properties as a lens.

Example 7 Liquid composition 1 (4) used in Example 4 was applied to the surface of the polymethyl methacrylate lens used in Example 2.
A liquid composition containing 30 parts by weight of trimethylolpropane triacrylate as a copolymerizable reactive monomer was applied in the same manner as in Example 4, and irradiated with a high-pressure mercury lamp to form a transparent film with an average thickness of 50P. A polymethyl methacrylate lens with a cured coating film was manufactured.

Below, physical property values were measured using the same method as in Example 1, and the surface hardness was determined by pencil hardness. No scratches were observed even in a scratch test using steel wool.

Further, as a result of an adhesion test, no peeling of the cured coating was observed, and neither peeling nor cracking of the cured coating occurred even in a high temperature and high humidity environment. Furthermore, no optical distortion was observed in this lens. Example 8 Molecular weight: 8901, viscosity: 23 poise, Gardner color obtained by reacting 1 mole of diarylidene pentaerythritol and 2 moles of pentaerythritol trimethacrylate on the surface of the polymethyl methacrylate lens used in Example 2. A liquid composition prepared by adding 1 part by weight of benzoin to 10 parts by weight of the reaction product of Numbers 2 to 3 was applied by dipping, and then cured by ultraviolet irradiation in the same manner as in Example 4, resulting in an average film thickness of 60 μm. A polymethyl methacrylate lens with a transparent cured coating was produced.

The physical properties were measured in the same manner as in Example 1, and the surface hardness was on the pencil hardness scale, and no scratches were observed in the scratch test with steel wool.

Further, when an adhesion test was conducted, no peeling of the cured coating was observed, and neither peeling nor cracking of the cured coating occurred even in a high temperature and high humidity environment. Furthermore, no optical distortion was observed in this lens. Example 9 5 parts of the unsaturated spiroacetal oligomer used in Example 4 and the unsaturated spiroacetal oligomer used in Example 8 were applied to the surface of a cellulose acetate dust mask lens manufactured by a breath molding method. After applying a liquid composition consisting of 5 parts by weight and 1 part by weight of benzoin isobutyl ether by a flow coater method, it was cured by ultraviolet irradiation in the same manner as in Example 4, and acetic acid had a transparent cured coating film with an average film thickness of 120p. Manufactured cellulose dust mask lenses.

The adhesion between the cured coating film on the surface of this lens for a dustproof mask and the lens base material was good, the surface hardness was excellent, and the transmission characteristics as a lens for a dustproof mask were also excellent.

Claims (1)

[Claims] 1 Formation of a cured coating film on the surface of a plastic lens substrate that mainly contains a reaction product of diarylidene pentaerythritol and an unsaturated alcohol having a hydroxyl group and an acryloyl group or a methacryloyl group in one molecule. Features a plastic lens.