JPS58142301A - Optical member made of synthetic resin - Google Patents

Abstract

PURPOSE:To increase the adhesive strength of an antireflection film to a synthetic resin substrate layer by interposing an org. hard film contg. inorg. fine- grained silica having silanol groups between the antireflection film and the substrate layer. CONSTITUTION:An org. hard film contg. inorg. fine-grained silica or a deriv. thereof having silanol groups and 20-500Angstrom average grain size such as inorg. fine-grained silica grafted on the bonding component of the hard film is interposed between an antireflection film and a synthetic resin substrate layer. The condensation product of polyol with alkyl-etherified methylolmelamine is used as the bonding component of the hard film. The preferred silica has about 3-8 silanol groups per 100Angstrom <2> on the average.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synthetic resin optical member such as a synthetic resin optical lens, and more particularly to a synthetic resin optical member having an antireflection film.

Optical members made of synthetic resin, such as optical lenses, are used as lenses for spectacles and lenses for optical equipment. Synthetic resin materials include diethylene glycol bisallyl carbonate and paulownia resin.

Acrylic thread resin, polycarbonate thread resin, styrene resin, cellulose thread resin, and other resins with excellent transparency are used, but diethylene glycol bisallyl carbonate (trade name @
CR3911) homopolymers and copolymers are mainly used. Synthetic resin optical members having an antireflection film on their surfaces are well known. The antireflection film is usually obtained by forming a multilayer film of an inorganic oxide, fluoride, or other inorganic substance on the surface of an optical member by a method such as vacuum deposition or sputtering. One problem that has not yet been fully resolved in synthetic resin optical components with anti-reflection coatings is:
One problem is that the adhesion strength between the antireflection film and the synthetic resin base material is insufficient, and the other problem is that the antireflection film does not have sufficient physical properties such as durability and abrasion resistance.

On the other hand, a major problem with synthetic resin optical members as materials is that their hardness is lower than Table III glass, and their durability and abrasion resistance are inferior.

In order to solve this problem, a method of forming a hard coating on the surface of the substrate is usually adopted. Organic hard coatings and inorganic hard coatings are known as hard coatings.
Organic hard coatings are considered inferior in terms of ease of film formation and economic efficiency, and many patents have been filed for coating paints (hereinafter referred to as coating compositions) that form organic hard coatings. .

2 in the synthetic resin optical member having the antireflection film
Of the two problems, the latter problem is thought to be solved by providing a hard coating between the base material and the antireflection film. The anti-reflective coating is extremely thin, and its durability and abrasion resistance are affected by the physical properties of the hard coating underneath the anti-reflective coating, making it less durable than an anti-reflective coating formed directly on the surface of the base material. Improved durability and wear resistance. However, the former of the above two problems, that is, the adhesion strength of the antireflection film is greatly influenced by the characteristics of the material to which it is adhered. Conventionally,
When forming an antireflection film directly on the surface of the base material of the optical part, studies have been conducted on the base material and the adhesion strength of the antireflection layer. However, the adhesion strength between the hard coating and the antireflection coating has not been sufficiently investigated. The present inventors formed antireflection coatings on synthetic resin optical members having various hard coatings, and measured the adhesion strength and physical properties of the antireflection coatings. Many coating compositions capable of forming organic hard coatings contain a hydrolyzate of silane as a hardening component. However, the anti-reflection coating formed on an organic hard coating containing a hydrolyzate of al; Therefore, we conducted various research studies on organic hard coatings containing other hardening components, and the results showed that organic hard coatings containing inorganic fine particulate silica or its derivatives as hardening components have excellent antireflection coatings. We have discovered that the bond exhibits adhesion strength. The organic hard coating containing this hardening component not only has high adhesion strength to the anti-reflection coating, but also has excellent properties as a hard coating, and therefore has excellent durability, abrasion resistance, etc. Although this does not pose any problems, the present invention is an optical member made of a synthetic resin having an antireflection film having an organic hard coating containing the above-mentioned specific hardening component between the antireflection film layer and the base synthetic resin layer. , i.e. #! In a synthetic resin base member with mK reflective spinning expansion, an average particle size between the antireflection film layer and the synthetic resin base layer! ! This is an optical member made of synthetic resin, characterized in that it is provided with an organic hard coating containing inorganic fine particulate silica having 0 to 100 μm of silanol groups or a silica conductor.

The reason why the adhesion strength between the organic hard coating containing the inorganic fine particulate silica as a hardening component and the antireflection coating is poor is not clear. However, when compared with organic hard coatings containing the alkoxysilane hydrolyzate as a hardening component, the following reasons can be surmised. The surface of the inorganic fine particulate silica or its derivatives having silanol groups in the present invention is considered to have the following structure.

The element may be a hydrogen atom or an organic residue, particularly a residue of a resin component of an organic hard coating.

These will be explained in detail later. On the other hand, Al;xysilane, such as Rm-81(OR/)4-.

The hydrolyzate of (m: an integer of 1 to 3, R and R' are alkyl groups) is thought to have the following structure.

This hydrolyzate contains little, if any, silanol groups or functional groups represented by 8l-0-A. by the way,
The R-Eli bond and the Eli-0-81 bond have higher bond energy compared to the O-HIIM bond of the Schifnol group and the O-me bond of the 8l-O-me. Therefore, R
High energy is required to cleave the bond between -81 or 8l-0-81, and it is relatively difficult to cleave these bonds and activate that part. Based on these assumptions, if we consider the case where an antireflection film is formed on a hard coating by a method such as vacuum evaporation or sputtering, molecules, atoms, ions, radicals, etc. of the material forming the antireflection layer will be absorbed by the hard coating. [On the surface! It is thought that in order to adhere firmly to Ii, it is necessary to activate the narrow surface of the hard coating. The rounding energy for activation of a hard surface is supplied by molecules, atoms, ions, radicals, electrons, light, etc., but as mentioned above, the adhesion strength of the material that forms the anti-reflection layer on surfaces that are easily activated is considered to be higher. Therefore, in the present invention, the inorganic fine particulate silica mineral having a 5l-0-me bond is easily activated.
A hard coating containing it is therefore expected to adhere strongly to the antireflection layer.

Original WAK>Kell average grain IK2 o-s o o it
Particulate silica having a D-silanol group is also called colloidal silica, and is commercially available as a stable aqueous dispersion or a very stable dispersion that can be dispersed in various solvents. This fine-grained silica consists of fl#t' spherical particles;
00 square! #i! It is said that R has about 3 to 8, usually about 3 to 4, Schifnol groups. The dispersion of finely divided silica is mainly obtained by adjusting water glass using an ion exchange process, and the finely divided silica does not contain any organic components. Considering the optical properties, the average particle diameter of the finely divided silica is preferably 1 o-zsou. A coating composition is produced using this dispersion of finely divided silica.

Commercially available dispersion media are usually water, but may also be organic solvents. It can be made into an organic solvent dispersion (from an aqueous dispersion) by solvent substitution, and the type of dispersion medium can be changed in the same way. When producing the coating composition, preferred dispersion media are water and organic solvents, with organic solvents being particularly preferred. Examples of organic solvents that can be used include alpur, esters, ethers, ketones, and others;
Ethanol, isopropanol.

The organic hard coating, in which butanol, 2-ethoxyethanol, and other monohydric alcohols having 1 to 4 carbon atoms are suitable, is made of a binding component such as a synthetic resin containing the above-mentioned hardening component. The coating composition includes a component that can be converted into a bonding component (by curing) in this bonding component. Since the bonding component is usually a synthetic resin, the coating composition may contain not only this synthetic resin but also a component that can be converted into a synthetic resin by polymerization such as addition polymerization or midline polymerization. As a component that can be used as a synthetic 1# resin or a synthetic resin, according to the usual name (even if it is a component composite before becoming a synthetic resin, it is customary to call it "-1 resin". Examples include various thermosetting resins) such as melamine resins and epoxy resins.

There are phenolic resins, alkyd resins, acrylic resins, polyurethane resins, butytool resins, etc.

A more preferred synthetic silica is a hydroxyl group that can coagulate with the silanol group of the granular silica.

A synthetic resin containing a component having a functional group such as an alkanol group or a carboxylic acid group, such as a methane-based resin,
There are epoxy resins, acrylic resins using human tetraxacrylate, butyral resins, etc.

A particularly preferred coating composition is one in which some to all of the methyl groups are alkyl etherified, and at least four of the following are present: In particular, a coating composition that combines components obtained by precondensing finely divided silica and a polyhydric alcohol, or finely divided silica, a polyhydric alcohol, and an alkyl etherified methyl-4-Pmine. is preferred. Through precondensation, the silanol groups of the moldy particulate silica react with the alcohol at the polyhydric level, and when alkyl etherified methane is used, this is combined with the polyhydric alcohol and the fine particulate silica. The polyhydric alcohol or the silanol groups of the finely divided silica react to form a precondensate. Of course, even if precondensation is not performed,
These reactions occur during curing of the coating composition. Said 81
The group represented by -0- is preferably a residue produced by the reaction of a polyhydric alcohol group or a polyalcohol group with alkyl-etherified methylolmethane.

The polyvalent Alpool residue may further be reacted with other 9-ranol groups, and the 9 groups are alkyl etherified methane groups.
It is thought that there may be cases where the residue is a reaction between a lumella electron and a silanol group. As described above, it is preferable for fine-grained silica to be grafted onto the synthetic resin, which is a synthetic component, by its silanol groups in order to obtain a smooth hard coating. Also in 11-1 and 046 other bonding components, it is preferable that the fine particles written therein are tightly bound to the bonding acid content.

The preferred composition for the buttocks is that it is easy to graft the bonded acid content of fine particulate silica, and it is especially appropriate to perform precondensation in advance and advance the core to the heel. It is. This meeting is a series of condensed methyl 4-lumen O
Alkyl ether compounds can also be conveniently used. Also,
Although the composition of the above-mentioned coating composition is not limited to 40%, the amount ratio of etherified methane:polyhydric alkali is 1:αb to 1:2. Polyvalent Al;
- It is preferable that the weight ratio of polyvalent alkaline to silica is Iga 1 to 1:4.

Covered! The solvent in the composition is alcohol and hydrocarbons.

Esters, ethers, ketones, formua.

Various other materials can also be used. For example, methanol, ethanol, propatool, buti・k7k:f
-Rou 2~Methoxyethanol, 2-ethoxyethanol,! ! - Buto Life Fuji Ethanol Toluene, Benzene,
M, M-, dimethylformua, etc. are suitable.

This solvent may be used as a finely divided V9 dispersion medium and may be round.

In addition, in order to improve the drying properties of the coating film, a low boiling point agent such as ethyl acetate, amine, methyl ethyl ketone, butyl cellosolve, etc. may be used in combination with these agents. The coating composition may be further supplemented with other ingredients. 9. For example, curing catalyst, repelinda agent, ultraviolet light WkIIiL
Agent 2 Coloring agent, etc. In addition, other curing ingredients such as the above-mentioned hydrolyzate of alkaline alcohol can be added. Although it has little effect on increasing adhesive strength, it is effective as a hardening component, and when used in combination with granular silica, it improves the hardness of hard coatings without reducing adhesive strength. It is thought that it is possible. There are other ingredients used in organic hard coatings, such as epoxy resin, unsaturated organic resin, and alkali.

Binding agent components such as organosiliconized metals, acrylic polymers, or polyvinyl butylene can be added to the coating composition.

The above-mentioned coating composition may be a 11° composition obtained by simply mixing the essential components, but it is preferably obtained by precondensation as described above. The precondensation is carried out at least two times as described above.
- Three components are mixed and preferably heated to 180°C or higher. Add other essential ingredients, such as alkyl etherified methylolmethane in the case of a precondensate of finely divided silica and polyvalent alcohol, KIJ solvent if no solvent is available, and add other essential ingredients as necessary. The ingredients are added to produce the coating composition. This coating composition can be used alone or in combination with other coating agents. This coating composition is applied directly to the surface of the base material of the synthetic resin optical member using a coating material such as Ai-Ki-Putsui-i, and is heated and cured to form a hard coating. It can be applied by spray coating, dip coating, four-color coating, spinner coating, etc.

A suitable curing temperature is $0 to 11i0°C, and a thickness Fi1 to 20μ of the calibration film is suitable.

Next, an antireflection film is formed on the surface of the hard coating on the substrate obtained as described above. The anti-reflective film can be formed by vacuum deposition, ion blating, CVD, etc., or sputtering.The anti-reflective film is formed on at least one of the innermost layer (hard coating side) and the outermost layer. It may have a layer that does not directly act as an anti-reflection layer, such as a protective layer, an adhesion-improving layer, or a hard layer (hereinafter, these three will be referred to as a protective layer). In particular, it is known as a protective layer #'i containing silica, a layer for improving adhesion to a resinous substrate made of metal resin, or an inorganic hard coating. In the present invention, the adhesion to the silica layer formed on the organic hard coating by vapor deposition or the like is excellent. The problem of adhesion strength between the organic hard coating and the antireflection layer is one problem, including the case where a silica layer is provided as the innermost layer of the antireflection layer. Even when a protective layer of silica was applied, the adhesion strength was insufficient. In the present invention, the innermost layer of the antireflection layer is 810
It may not be a silica layer such as x (x: 1 to 3). For example, it is not necessary to provide a protective layer on the organic hard coating.
Further, other protection layers such as aluminum may be provided. However, from the viewpoint of adhesion strength and other physical properties, the innermost layer of the antireflection layer is preferably a silica layer. Further, it is preferable that the outermost layer of the antireflection layer is provided with a layer that is harder than the layers inside the outermost layer that retains the antireflection effect. As with the innermost layer, the outermost protective layer is preferably a silica layer.

The antireflection layer usually has a multilayer structure except for the innermost layer and the outermost layer. Each of these 14-specific materials is laminated to a specific thickness. As constituent materials of the antireflection film, including the protective layer, the following inorganic substances are used, for example. Silica, aluminum oxide, zirconia, magnesium oxide, cerium oxide, titanium oxide, indium oxide, neodymium oxide, tantalum oxide, beryum oxide, yttrium oxide, hafnium oxide and other oxides.

Fluoride! Gnesium, cerium fluoride, porium fluoride, lithium fluoride, thorium fluoride.

Neodymium fluoride and other heptafluorides. Inorganic compounds other than fluoride in zinc sulfide and other oxides. Also, these materials include copper, gold, silver, and chromium.

It is also possible to add a small amount of aluminum, other metals, or metal compounds for coloring.

As described above, the synthetic*m optical part of the present invention includes a synthetic resin base layer and an organic hard coating layer.

and an antireflection layer. Another layer such as a primer layer may be interposed between the base material layer and the hard coating layer. Further, the anti-reflection layer may be provided with a protective layer that does not directly act on anti-reflection as described above, and when such a layer is provided, it is provided as the innermost layer and/or the outermost layer of the anti-reflection layer. Usually composed of silica, this layer may contain other inorganic substances in addition to silica. The antireflection layer is composed of a plurality of layers, and whether a protective layer is provided or not, it is composed of a plurality of layers. It is preferable that the optical member consisting of these constituent parts be a transparent body or a colored transparent body. In the colored body, the metal resin base material or hard coating may be colored, or the antireflection film may be colored.

As the optical member of the present invention, a spectacle lens is suitable, but the invention is not limited to this, and various optical members such as lenses, flat plates, and prisms for cameras and other optical equipment may be used. In the case of eyeglass lenses, the material is preferably a monomer of diethylene glycol/bisallyl carbonate or a copolymer with other copolymerizable monomers.

In addition, polycarbonate yarn wh and acrylic resin are also suitable materials.◇ The present invention will be specifically explained below using Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples and Comparative Examples Two kinds of organic hard coatings described later were formed on a spectacle lens made of a combination of diethylene glycol and bisallyl carbonate. On the other hand, a commercially available lens 2 for A- is made of a combination of diethylene glycol and bisallyl carbonate 1 and has a hard coating thought to be an organic hard coating containing a hydrolyzate of alkoxysilane as a hard component (does not contain fine particulate silica). Get the type. Hereinafter, these will be referred to as the present invention product, comparative product, Mu product, and BfR product. Each of these 50 silver mirror lenses with hard coatings was deposited at a temperature of 80C.
Then, an antireflection layer consisting of four layers was deposited using an electron gun.

The iIk inner layer is a silica layer. Regarding these, a strength test described later, an adhesion strength test of the antireflection layer, and a practical test were conducted on some samples. These test methods and results were as described below.

[Present invention &: Formation of hard film]

1nth 120 i, 100 sq. 217 parts (parts by weight: same below) of isopropanol dispersion of finely divided silica having about 3 to 4 silanol groups (silica content: 30 qb by weight) and 194 parts by weight of tetraethylene glycol After the isopropanol was distilled off, the mixture was heated at 180° C. for 8 hours to perform precondensation. Add 130 parts of hexakismethoxymethylmelamine to this and heat at 130°C until about 21 parts of methanol is distilled off. A coating composition was prepared by adding isopropanol in an amount to give a solid concentration of 30% by weight, and further adding a small amount of paratoluenesulfonic acid (curing catalyst) and a leveling agent. This coating composition was applied to the eyeglass lens and cured by heating at 120° C. for 1 hour to form a hard coating with a thickness of about 5 μm.

[Comparative product: @! Formation of quality film]

54 parts of 0.05N hydrochloric acid solution was added dropwise to 178 parts of Medeltriethoxycycne over 1 hour while keeping the liquid temperature below 10C, and then left overnight at room temperature. This hydrolyzate 1
194 parts of tetraethylene glycol was added to 60.5 parts and heated to 60° C. under reduced pressure to remove ethanol and water in the hydrolyzate. Further, 130 parts of hexakismethoxymethylmelamine was added to the resulting mixture, and the mixture was heated at 130°C for about 2 hours.
The mixture was heated until 1 part of methanol was distilled off, and isopropanol was added thereto until the solids concentration reached 30% by weight, and a small amount of a curing catalyst and a leveling agent were added to prepare a coating composition. This coating composition was applied to the eyeglass lens and cured by heating at 120°C for 1 hour to a hardness of about 5#.
A JL coating was formed.

〔Strength test〕

Load 2o using φoooo steel wool.

Rub the hard coating surface of a professional mirror lens back and forth SOO times under conditions I. The results are shown below.

[Adhesion strength test]

On the surface of the hard coating of the eyeglass lens, a 1-inch base pattern was cut with a razor, a commercially available cellophane tape was adhered sufficiently onto the surface, and then the tape was peeled off. The proportion of the anti-reflection film that remains without being peeled off is as follows.

After the results of the two tests on sweetfish, practical tests were conducted on the products of the present invention and the mu products. Select 10 eyeglass users and display the invention product on the right.
We made an i11 mirror with the product on the left side and asked the students to use it for 6 months. ! The extent of the wound is inspected every month. As a result, the scratch occurrence rate was as follows.

Claims (1)

[Scope of Claims] 1. In a synthetic resin optical member having an antireflection film on the surface, inorganic fine particles having a silanol group with an average particle size of 20 to 500 μm are provided between the antireflection film layer and the synthetic resin base layer. An optical member made of synthetic resin, characterized in that it is provided with an organic hard coating containing silica or a derivative thereof. 2. The optical member according to claim J11, wherein the derivative of inorganic particulate silica is inorganic particulate silica grafted to a bonding component of an organic hard coating. 31. The optical member according to claim 2, wherein the binding component of the organic hard coating is a condensate of a polyhydric alcohol and an alkyl etherified methylolmelamine. Table Inorganic 'Jt-shaped silica with silanol groups is
It is also imitated that it has an average of about 3 to 8 silanol groups per square meter! f. The optical member according to claim 1. (5) The optical member according to item 1 of the scope of the %f1f requirement, wherein the antireflection film is made of an inorganic material formed by vapor deposition or the like. & Synthesis 11 The optical member according to claim 1, wherein the greasy optical member is a synthetic resin eyeglass lens.
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