JPS60103304A - Plastic lens having high-refractive index - Google Patents

Abstract

PURPOSE:To improve abrasion resistance, and to reduce surface reflection by forming successively a hard coat layer of an inorganic dielectric substance and an antireflection layer on the surface of a high-refractive index plastic lens consisting of a specified copolymerized resin. CONSTITUTION:(A) a monomer expressed by formula I [R<1> and R<2> are -OCH2CH2-, etc., X is halogen other than fluorine, (a) and (b) are 1-4, and (m) and (n) are 0-4] and (B) a monomer expressed by formulas II, III, or IV are copolymerized. And a hard coat layer consisting of an inorganic dielectric substance such as silicon oxide and silicon oxynitride is formed by vacuum deposition on the surface of a plastic lens consisting of the obtained copolymerized resin. Then an antireflection layer consisting of a single or a multiple layer of an inorganic dielectric substance (e.g., ZnO2 and Al2O3) or of a metallic layer and an inorganic dielectric substance layer is formed thereon to obtain the desired high-refractive index plastic lens.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a thermosetting synthetic resin high refractive index lens having an inorganic hard coat layer and an antireflection layer.

[Prior art]

Synthetic resin lenses, especially diethylene glycol bis(allyl carbonate) lenses, have been improved with the development of anti-reflection technology, hard coat technology, and hard anti-reflection technology in addition to their safety, ease of processing, and fashionability. , which has become rapidly popular in recent years. The use of plastic for eyeglass lenses is
There is a growing demand for cylindrical lenses, that is, thin plastic lenses made of high refractive index resin materials. The refractive index of diethylene glycol bis(allyl carbonate) polymer is 1.50, and several technical proposals have been made to overcome this drawback. For example, JP-A-54-4
In 1965, a copolymer of diethylene glycol bis(allyl carbonate) and benzifre methacrylate was developed; in JP-A-54777/i86, a copolymer of diethylene glycol bis(allyl carbonate) and thiiodostyrene was developed; and in JP-A-58-155+3 For example, a copolymer of diallyl terephthalate or diallyl isophthalate and methyl methacrylate prepolymer is disclosed as a lens material. The problem in manufacturing lenses using these copolymers is that the allyl groups have completely different reactivities (
The purpose is to react meth)acrylic groups or vinyl groups. In other words, the acrylic or vinyl group, which has a fast reaction rate, polymerizes first, and the allyl group, which has a slow reaction rate, polymerizes later. Not only do they not copolymerize, but the allyl compound is completely
1 (They are not combined and extracted as unreacted products. -Also, since the (meth)acrylic compound or vinyl compound that is polymerized first is a monofunctional monomer, it is 100% combined and completely incorporated into the polymer chain. It is impossible to get the refractive index to a certain extent, and some of it may be extracted or thermally unstable. Ezufu'7+: ?A leg.

Also, in JP-A-55-13747, for example, bisphenol
) A lens material made of a copolymer of VA dimethacrylate-1 and phenyl methacrylate or pendyl methacrylate-1 has been proposed. This technology involves a reaction between a (meth)acrylic group and a vinyl group, which have similar reactivity, but it is extremely difficult to control during lens manufacturing. However, even if it is carried out underwater, it is difficult to control the lens internally or on its surface, which tends to cause optical defects.In addition, the vinyl (meth)acrylic group is difficult to control on the reactive surface. The drawback is that it is very sensitive and easily influenced by the outside world, and that it is difficult to control anything other than polymerization cooling. Furthermore, since the second monomer is a monofunctional supermer, there are also defects such as thermal stability due to unreacted supermer and poor organic solvent resistance, as in the above example.

The inventors of the present invention have published JP-A-57-54901y JP-A-58-1
In 8602, a copolymer of a styrene monomer, a di(meth)acrylate having a halogen-substituted aromatic ring, and an allyl compound or a bifunctional di(meth)acrylate was proposed as a lens ladle material. Although excellent synthetic resin high refractive index lenses can be obtained using these techniques, they still suffer from the difficulty of controlling the polymerization reaction and the difficulty of completing the polymerization reaction. However, in terms of dyeing with disperse dyes, lenses have another disadvantage in that they are much more complicated than lenses made of diethylene glycol bis(allyl carbonate) resin.

Furthermore, in the case of plastic lenses, there is a difference between ν and l in terms of wear resistance. In order to improve this point, in general, 319 # S'02 rA1 is applied to plastic H.
203. A method has been adopted in which an inorganic hard coat film is provided by vapor depositing ZrO2 or the like. However, the adhesion may not be good or effective for all base materials. [Objective] In view of the above points, the object of the present invention is to provide a method that greatly facilitates the management of vehicle chassis processes. - Synthetic tree Hk obtained by polymerization using
(j) To obtain a synthetic resin box refractive index lens with excellent abrasion resistance and antireflection effect by providing a hard coat layer made of an inorganic substance on the surface of the product refractive index lens and further providing an antireflection layer thereon.

〔overview〕

dll 10-X each 1 [Mu-n or Shiri-go in late 41
A hard coat layer made of an inorganic dielectric substance is provided on the surface of the lens obtained by copolymerizing Nasco monomer, and a single layer or multiple layers of an inorganic dielectric substance, or a metal layer and an inorganic dielectric layer are formed on the hard coat layer. The present invention relates to a synthetic resin high refractive index lens characterized by being provided with an anti-reflection layer consisting of:

A, O whose general formula represents one or more monomers O -o-cH2-cH-cr (2---=CI) represented by (It)
X is halogen excluding fluorine, a and b are each independently 1
In and n each independently represent an integer of 4. ) C-0-CH2-CH-CH2 伶1,: -()-CH2-CH-CH2 or more monomers selected from.

Since most of the monomers whose general formula is represented by (1) are solid at room temperature, they cannot be dissolved in component B or in a mixture of component B and a trifunctional diallyl compound as a third component. used. The composition ratio of A and B is the AJI refractive index and Atsube number of the resin lens to be obtained.

It is best to decide based on the balance between coloring, impact resistance, dyeability, adhesion of inorganic vapor deposited substances and organic hard coats, fI% flammability, and durability.

Monomer A can exhibit the highest refractive index.The nuclear-substituted halogen whose general formula is Bromine is preferable in terms of balance with properties.The content of component A depends on the solubility of component B, or the solubility of 25 to 95% by weight is preferable in view of the fact that it is a resin, improved dyeability, improved adhesion to inorganic and organic coatings, and improved flame retardancy.

Typical examples of component A include Example Eva, 2
．． z-bis(4-allylcarbonyloxy-5,
5-dichlorophenylene/V) 7"lopane, 2,2-bis(4-allyloxycarbonyloxy-3,5-diglomophenylic)V) propane, 2,2-bis[4-(2
-Ali7reoxycarbonyloxyethoxy)-6,5
-dichlorophenyl]propane, 2,2-his[4-(
2-allyloxycarbonyloxyethoxy) -S,
S-dibromophenyl]propane.

2.2-bis(-(2-aryl7leoxycarbonyloxyethoxy)-2,5,5,6-titrapromopheneyl)propane, 2.2-bis(4-(2-aryloxycarbonyloxyethoxy) 2,2-Bime(4-(s-allyloxyprobogoxy)-3,5-dipro-phenyl)-3,5-diglomophenyl]propane, 2, 2-bis(4-(2-allyloxyethyl)-4s dibromophenyl)propane, 2.2-bia, (4-(2-7
/reoxycarbonyloxy(2-hydroxy)-
10boxy) -5,5-dibromophenyl]propane, bis(4-allyloxycarbonyloxy-5+5diglomophenyl)nurphyto, bis(4-(2-allyloxycarbonyloxyethoxyl)]sulfide, bis[4-(2-allyl) [oxycarbonyloxyethoxyhenyl] sulfide, bis(4-(2-allyleoxyethoxy)-3.5-dibromophenyl] sulfide
7-on, bis('4-(2-aryloxycarbonyloxyethoxy)-3.5-dibromophenyl]ether, bis(4-(2-allyloxycarbonyloxyethoxy)-S, S-diglomophenyl) Examples include methane.

1 Bh, V, min, diallyl orthophthale, diallyl infucrate, diallyl terephthalate, etc. may be used alone or in combination of two or more. A lens can be formed by polymerizing only component B, but the cause is that the polymer yellows, although it does not cause sharpening, and adhesion to inorganic and organic coatings.9 Resistance to staining with disperse dyes. It has poor impact resistance and cannot be used as a lens material. The main purpose of adding component B is to dissolve component A and make it a liquid so that it can be injected into a casting mold at room temperature without significantly lowering the refractive index of component A. In addition, since component B is a diallyl compound, the reaction control time is relatively 10 years, and since it is bifunctional, there is less unreacted polymer that does not bind to the polymer chain.The content of component B is 5 to 75%. If the percentage is too high, coloring may occur, adhesion to inorganic and organic coatings may deteriorate, and dyeability with disperse dyes and impact resistance may also deteriorate.

It is fully possible to improve the properties and functions of a lens by adding a third component, a shear compound, to the A and B components of the present invention.

For example, diethylene glycol bisallyl carbonate is added as a third component to improve impact resistance and light resistance.

It is possible to improve dyeability and adhesion to inorganic and organic hard coat films. It is also possible to increase the overall refractive index by adding a monomer such as naphthalene dicarboxylic acid diallyl ester (sialyl tartrate).
In addition to f, close contact with glass mold and inorganic/organic coating film 1
You can also increase your sex. Other diaryl esters with dicarboxylic compounds
(The characteristics of each can be obtained.

The synthetic resin lens according to the present invention has a high refractive index, can be controlled in lens manufacturing by 1111, and has good dyeability and adhesion with inorganic and organic coatings because all the seven lenses can have a crosslinked structure. In addition, it has excellent solvent resistance, heat resistance 2, durability in daily life, cutting workability 2 dimensional stability, flame retardant due to component A, and high refractive index lens with t'-torque. It is.

High refractive index lens according to the present invention A comonomer mainly composed of IdA and B is used in the presence of a Lasica/lz polymerization initiator.
)It! Let's come together! J'41+ is received. Radical/L/Polymerization initiator r1 1.1 Not specifically specified, known ones may be used, but hydroperoxides such as [--butyl hydroperoxide, sheet t-butyl peroxide, etc.] dialkyl peroxide, diacyl peroxide such as benzoyl peroxide, peroxydicarbonate such as diisopropyl peroxydicarbonate, peroxy ester dye ketone peroxide such as t-butyl peroxybiparate, peroxycarbonate/I/ There are peroxide rivers such as, and azo compounds such as azohis (isoputilonitol/L/). The amount of Radical/I/Tonai initiator to be used is within the range of 11 to 5. It is also possible to start I (coupling) with a single unit of UV light or a radiator such as ultraviolet light tγqdA.

The high refractive index lens according to the present invention can be obtained by a known casting method. In other words, it is made by a combination of two crow molds designed to give the lens power, and an elastomer gasket designed to hold the two glass molds and obtain a specific thickness. Radical) V It can be obtained by injecting the monomer of Item 11 containing a polymerization initiator and subjecting it to thermal oxidation.

Conditions such as heating and heating may vary depending on the blending ratio of monomers, the type of Hayabusa 9 initiator used, and the concentration, but in general, heating from room temperature to 60°C and heating to 160℃
It is desirable to complete the polymerization at a temperature of about 100 mL, and it is also desirable to polymerize gradually at a low temperature for a long time. It is also possible to inject the mixture after precoagulating the monomers in the presence of a coagulation initiator to thicken the mixture. This narrow η1-coupling not only reduces the monomer body collection L1, but also prevents liquid leakage from the cavity.

Forward, add the above casting to the 91st thread and add it to the lens! t
In order to impart various characteristics and improve the properties as much as ■, we use monomers 44+fk, an acidic agent of 100 g, and a fern prevention agent.

・! ! ``IV l!su1to agency)'', photochromic substances, various stabilizers, 'l:It7Isu agents, etc. can be used as needed.

The present invention improves the effects of AI prevention on the resins listed above (7I) and the metal oxides.

Gold 11 is coated with nitride, a hard coat layer made of transparent F+-free dielectric materials such as oxynitride, metal ash, etc., and a high refractive index resin with good adhesion to these dielectric materials Further, on this hard coat layer, gold I11 < oxide, gold oxide, !+ nitride 1. Metal oxynitride is formed from an inorganic dielectric layer such as a fully curved carbide or metal fluoride. single layer or multi-layer anti-reflection layer, or these inorganic layers + [1
, Body layer til! , is equipped with an anti-reflection pattern containing 10,000 yen of gold.

When a hard coat layer and an antireflection layer are provided on ml11M, if the 'M71'I properties between the resin and the hard coat layer are not satisfied, IIUJI? ;The only thing that can be done is to improve wear resistance. Also, the problem of cracking time occurs with balls 4, 11, and I.

By selecting the hard coat type according to the Mo1,1 resin of the present invention, it is possible to obtain a hard coat layer with a high density and good appearance. The film jII of the hard coat layer is tl,
4/Z m to 10/'m8AIi is long.

Refractive index of hard coat layer (dl, 1.551., et al.
6> or so is preferable. The refractive index of the synthetic 41' resin in the present invention is 1.57 to 1.60, and therefore
Ii 4 = 'Ititso' is widely used for hard coats.
'ff: Ita tD Te IrJ, , There is a large difference in the refractive index between Bartco-N So and the real fat, and the effect of interference of the hard coat layer appears, so the interference is used to prevent damage. If it is provided on a rough hard coat MJ, there will be a drawback that a sufficient antireflection effect cannot be achieved. In order to prevent this defect from appearing in iR1&, the hard coat h'9 and the composite IJIli lens should be long enough to be within the range of /Ij:(if the refractive index is 04,
I found this out as a result of the experiment. In order to obtain a hard coat layer with a refractive index of about 1.57 to 1.60, it is necessary to use silicon 91 oxide with a small degree of branching, aluminum oxide, yttrium oxide, ytterbium H chloride (tichnium nitride, zirconium oxide). 9 pieces of gold bJ' + oxide mixture
For the stop layer, silicon dioxide, magnesium fluoride, etc. are used as the refractive index material for 11, and titanium oxide, white oxide, etc. are used as the high refractive index material. Using metal oxides such as zirconium and tanfrylum pentoxide 6, and nitrides such as silicon nitride and aluminum nitride, materials with medium refractive index,
For F′, oxides or oxynitrides such as yttrium oxide, ytterichium oxide, and aluminum oxide are used as F′ (II).
However, since the anti-reflection of silicon oxide 1iil-.j is good enough, anti-reflection young fruit is applied.

The bar coat layer and the anti-reflection layer can be formed by a vacuum evaporation method, sputtering, or ion bluing.

[lol example]

Below, based on the actual Mlj examples, Honmaru Akira will be explained as 6 brothers to 4f Jilt, but this) C Akira is not limited to these examples. Furthermore, all parts in the examples are blood melon parts. represents. , Amanolf, Example 1 2, z-bis(4-(2-allylleoxyruboni/l
/oxyethoxy) -3,s dibromophenyl]propane 5 Q fil(, sialyl orthophthalate 50
rcl″I.

01 parts of 2(21-hydroxy-51-methylphenyl)benzotriazole were combined with γ1r and stirred, and then the chassis 1j
12 parts of Cisoderohir peroxydicarbonate were added as the starting material 411 and mixed well. After passing through the insoluble matter of this mixture M, a glass mold designed to give an expansion W of (l OD) and an ethylene mold designed so that Ll, 1. becomes 2. Oi. -Vinegar 1β vinyl chassis
) is injected between the holes made by the gas cut.

The chassis was heated in J1 for 4113 hours at 40℃, 41 hours at 44℃, 45 hours at 46℃, 311.1 hours at 49℃, 5
25 hours at 2℃, 2 hours at 56℃, 2.5 hours at 64℃, 111% at 80℃, 111% at 100℃. The gasket and the force of the laser molded gold plate are the same! I did i11.

65m with this method! Is the occurrence of peeling between the glass mold and lens when a -6, LJUD lens is mounted on the chassis of a Vi type car at IIφ less than 1 inch rB? It was j. Next 1
Bost keying was performed for 511Jr at 00°C to remove distortion inside the lens. The optical surfaces of the finished lens were very good, v and f, and there was no internal distortion, making it satisfactory as an optical material. The refractive index of the lens was 1.583.

A refractive index of 1 is applied to the lens surface obtained by the above 131
．． 11 parts m of silicon oxide of No. 60 were vacuum deposited, and on top of that, '
b 203HT a20 s + S' 02 was sequentially coated with a vacuum β1 shield to form an antireflection layer (It).The entire 114 composition is shown in Figure 1.The spectral reflectance of one element of this lens is Shown at 21 in Figure 2.20 in Figure 2
is the spectral reflectance when the antireflection layer f: is not provided.

Example 2 2.2-bis(4-(2-allyloxycarbonyloxyethogine)-6,S-dibromophenyl]propane 50 parts, diallylisophthalate 42 parts, diethylene glycol hisallyl carbonate 8 parts, 2-hydroxy- Mix and stir 0.2 part of 4-methoxybenzophenone,
1.5 parts of syn-n-fluoroyl peroxine carbonate was used as a polymerization initiator, the same as in Example 1 below. The refractive index of the lens was 1.579.

Like above? ↓) Refraction 11r ratio 1 on the surface of the lens
．． Vacuum evaporate 5I02 of 56 and 1 liter of A1.203 (1, compound fake of 211+n) II, and then
, , was vacuum-deposited with Q111m, and then Al2O3
was 0.005 p m, and j' was air-steamed at 1γf. The overall structure is shown in Figure 5, and the spectral fouling rate of one surface is shown in Figure 4.
Shown in 1. 40 indicates the reflectance of the resin material.

Example 5 Bis(4,-(2-allylleoxycarbonyloxyethoxy)-3,5-dibromophenyl)spone 5
0 part 1. 50 parts of diallylisophthalate, 2-hydroxy-4-octoxybenzophenone 02E1S,
As a polymerization initiator, 65 parts of C-2-ethylhexyl peroxydicarbonate, the same as in Example 1 below. The refractive index was 1.592.

The lens obtained as described above was added with U having a refractive index of 1.60.
A silicon Vide film was sputtered to a thickness of 0.4 μm, and then silicon oxynitride with a refractive index of 1.67, silicon nitride with a refractive index of 200, and silicon oxide with a refractive index of 1.46 were sputtered on the silicon nitride film to a thickness of 0.4 μm. Then, an antireflection layer was formed. The 11917 ft composition is shown in FIG. 5, and the spectral anti-f1.1 characteristic is shown in FIG. 6. The reflectance without coating is shown at 60.

Example 4 2.2-bis(4-allyloxycarbonyloxy-
6,5-bromophene/V) propane 45 parts, sialyl infucrate 50 parts, diethylene glycol bisallyl carbonate 5 parts, 2(2'-hydroxy-51-
Methylphenylso/' 0. 2 parts,,j. + (1.6 parts of diisopropylene peroxycarbonate was used as an intermediate initiator. The refractive index was 1.585.

- The lens obtained as described above was ion-blasted with aluminum oxide having a refractive index of 1.60 to a thickness of 1 μm in argon plasma, and then cr was reduced to 0. jl 0 2
/1 m J'J sky. ;kjN and MgF2 on top of it
The film was ion-blated in 0.12 μm argon plasma (j'i composition is shown in Figure 7. Spectral reflection characteristics are shown in Figure 8).
Shown in FIG. 80 indicates the reflectance of tt7J fat.
Lens measurement method The lens surface was inspected (1j) by second visual inspection.

Abrasion resistance: ≠0000 steel wool with IKg I6i
Applying weight, abrasion of 10 parts of the surface was carried out, and the degree of scratches was divided into the following stages.

A: ICn'LX! + No burns in all areas within the area.

13: 1 to 10 scratches within the above range.

C: 10 to 100 scratches are formed within the above range υ11.

IJ: There are countless hot water baths, but there are smooth surfaces.

E: No smooth surface remained due to scratches on the surface. Denseness of coated film 1: Tested by cross-cut tape test according to JISD-0202. That is, using a knife, incisions are made on the lens surface at intervals of 1 inch to form 100 squares of 1#In2. Next, after adhering cellophane adhesive JN tape on top of it, peel off Day 1 and apply 100
Out of the squares of the month, display the squares that are not peeled [11].

111m! Heat = 90°C outside (dry, hehe).

Table 1 shows the characteristics of the 11.1' value of the lens.

Table 1 [Effects] As described above, the present invention has excellent antireflection effects as shown in the examples, and n: iH'r': abrasion resistance r 1
111,1 febrile, δ? j? '? Raw PR with good quality =
This has the effect that it is possible to commercialize a lens with an excellent high/+i ratio of 1<+:.

4゜ Figure+M+ (D t'n) Simple glare 741 +*
I is ll'l Ij! of Example 1. 10 is a lens, 11 is a bar coat made of silicon oxide with a refractive index of 1.60, 12 is YIJ203, i 5 H', T
a20s, 14 is 5I02, and the wires 12 to 14 constitute an anti-R11 prevention film. FIG. 2 shows the spectral reflectance characteristic 21 of one surface of the lens of Example 1. The horizontal axis is the wavelength of light, and the axis is reflection 4:, 71 (zu.

FIG. 6 shows the 11'2 G+i composition of Example 2, 30 is a lens, 61 is a hole made of a mixture of sho□ and Al2O3,
62 is 5i02t 3 s is Al2O3.

FIG. 4 shows the spectral reflection characteristics 4 of one surface of the lens of Example 2.
FIG.

FIG. 5 shows the membrane structure of Example 3, and 50 is 51.5 mm.
2id silicon nitride layer, 53 nitrided (L layer, 54 (
is 111 of silicon oxide.

61th line 1 is a diagram showing the spectral irregularity characteristic 61 of one surface of the lens of actual 17ili example 60. , 71 is At203's Bartco-eye a
'1.72 is a Cr layer, and 76 is a F2 layer.

Figure C shows the spectral reflection characteristics 81 of one surface of the lens of Example 4.

Above εF）

referee 3 chant 11r11 style '1Kg + Yo　''.

Claims (1)

[Claims] A hard coat 1- made of an inorganic dielectric material is provided on the surface of a lens obtained by copolymerizing comonomers mainly composed of A and B below, and a single layer or a hard coat 1- is provided on the surface of the lens. A synthetic resin high refractive index lens characterized by being provided with an anti-reflection layer consisting of a multilayer inorganic dielectric material or a metal layer and an inorganic dielectric layer. A One or more monomers whose general formula is represented by [[ ]. -0-(: H2-CH-CH2... (I) represents either. represents an integer from 0 to 4.) COi: One or more monomers selected from H2-CII-(J(□T-0-CH2-C)f-CH21).