FR2765583A1 - Polymerisable acrylic compositions for ophthalmic articles - Google Patents

Abstract

Polymerisable monomer composition comprises 30-100 wt.% of monomer(s) of formula CH2=C(R<1>)-(OCH2C(R')H)m-O-CH2-C(Ra)(Rb)-CH2O-(C(R")HCH2O)n-C(R2)=CH2 (I). in (I), R<1>, R<2>, R' and R" = H, CH3; Ra and Rb = 2-10C alkyl; 2 <= (m + n) <= 20; 0-70 wt.% of a different monomer(s) (II) which are radically polymerisable. The polymerised transparent substrate has 70 deg C <= Tg <= 110 deg C. Polymerisation initiator(s) is/ are added. Also claimed are transparent substrates obtained from the composition and an ophthalmic article which may contain the composition and a photochromic pigment.

Description

I

POLYMERISABLE DEMONOMERIC COMPOSITIONS,

TRANSPARENT POLYMERIC SUBSTRATES, AND ARTICLES

OF OPTICS AND OPHTHALMICS OBTAINED

The present invention relates generally to compositions of polymerizable monomers which, after polymerization, provide transparent polymerized substrates particularly suitable for the manufacture of optical and ophthalmic articles such as lenses or spectacle lenses. More particularly, the present invention relates to such compositions of polymerizable monomers which, after polymerization, lead to transparent substrates with a refractive index of value generally less than 1.54 and

preferably close to 1.5, and of low density.

The present invention also relates to the substrates obtained by polymerization of the compositions of polymerizable monomers according to the invention as well as to optical and optical articles.

ophthalmic products obtained from these substrates.

Optical and ophthalmic articles must have all of the following characteristics: - high transparency (transmission generally greater than 85% and preferably greater than or equal to 90%), with an absence or possibly very low light scattering ; a high Abbe number greater than or equal to 30, and preferably greater than or equal to 35, in order to avoid chromatic aberrations; - a low yellow index and an absence of yellowing over time; * good impact and abrasion resistance * good suitability for various treatments (hard coating deposition, anti-reflection, anti-impact primer, etc.), and in particular good ability to color * good suitability to the surfacing and edging treatments, without the overall geometry of the lens being deformed during

during these operations.

In addition, the polymerizable compositions for the manufacture of optical and ophthalmic articles should also be easy to process.

to implement on an industrial level.

It is also desirable that the compositions can be easily and quickly polymerized, in particular that they can be polymerized by photopolymerization techniques or mixed techniques of photopolymerization and thermal polymerization allowing to reduce the cycle times of manufacture of the products.

articles.

It is also desirable that the polymerizable compositions

can be used in overmolding processes.

Finally, it is also desirable for the polymerizable compositions and the polymerized substrates obtained to be suitable for photochromatization in order to obtain optical articles and

ophthalmics endowed with photochromic properties.

The object of the present invention is therefore to provide a composition of polymerizable monomers which, after polymerization,

leads to transparent substrates meeting the above requirements

above.

A subject of the present invention is also transparent substrates, in particular substrates having photochromic properties, obtained by thermal or photochemical polymerization or by a combination of these two routes,

compositions according to the invention.

Finally, a subject of the present invention is also optical and ophthalmic articles, in particular substrates having photochromic properties, such as lenses and glasses.

glasses obtained from the above substrates.

According to the invention, the composition of polymerizable monomers comprises, relative to the total weight of the polymerizable monomers present in the composition: at 100% of one or more monomers (I) of formula: R1 R 'Ra R "R2

I I I I I

CH2 = C - (OCH2CH - mO-CH2-C-CH2 (3 # CHCH2 3n C = CH2 (I) Rb in which R1, R2, R 'and R "represent, independently of each other, an atom d 'hydrogen or a methyl radical, Ra and Rb each represent an alkyl group having 2 to 10 carbon atoms and m and n are integers satisfying the relationship 2 <m + n <20; * 0 to 70% of at least another radically polymerizable monomer (II), different from the monomer (I), such as a transparent substrate resulting from the polymerization of the composition has a glass transition temperature satisfying the relationship 70 C <Tg <C; and

* at least one polymerization initiation system.

The first important constituent of the polymerizable compositions according to the invention is the monomer (s) (I)

responding to the above formula.

Preferably, in the formula of the monomers (I) above, R1 and R2 represent a methyl group, and Ra and Rb represent a C2-C6 alkyl group. Preferably, Ra and Rb represent an ethyl, propyl or butyl radical. More preferably, Ra and Rb are different from each other and in particular, Ra and Rb represent respectively an ethyl group and a butyl group (n-butyl of

preference).

Preferably, m and n are integers such that 2 <m + n <10,

better 2 <m + n <5.

Among the monomers (I) particularly recommended in

the compositions according to the invention, there may be mentioned 2,2-dialkyl (C2-

C1O) -1,3-propanediol 2x-propoxylé di (meth) acrylate and 2,2-

dialkyl (C2-C10) -1,3-propanediol 2x-ethoxylated di (meth) acrylate.

As indicated above, the particularly recommended monomers (I) are dimethacrylates and all

particularly the compound 2-ethyl-2-n-butyl-1,3-propanediol 2x-

propoxylated dimethacrylate (EBP 2PO DMA). (Meth) acrylic monomers (I) corresponding to the above formula, as well as their preparation process are described in document WO-95/11219. The monomers (I) of the compositions of the present invention can be prepared by the process described in

document cited.

Briefly, these (meth) acrylic monomers (I) are prepared by at least two steps of alkoxylation and acrylation. Initially, 2,2 (dialkyl) -1,3-propanediol is alkoxylated by reaction with the corresponding alkylene oxide. The product resulting from the alkoxylation is finally esterified with acrylic and / or methacrylic acid to obtain the desired (meth) acrylic monomer. It is also possible, instead of direct esterification with (meth) acrylic acids, to use a transesterification reaction using the corresponding (meth) acrylates. For more details on the process for preparing the (meth) acrylic monomers (I), reference may be made to

document WO-95/11219.

The monomer (s) (I) represent 30 to 100% by weight of the polymerizable monomers present in the compositions, of

preferably 30 to 70% by weight, more preferably 40 to 70% by weight.

The second important constituent of the polymerizable compositions according to the invention, which may optionally be present in these compositions, is a monomer or a mixture of monomers (II) comprising one or more (meth) acrylate functions, which is different from the monomer (I) . These polymerizable monomers (II) must be such that the transparent substrates resulting from the polymerization of the polymerizable compositions have a glass transition temperature satisfying the relationship 70 c <Tg <110 C, preferably

C <Tg <100 C.

Preferably, these monomers (II) comprise one, two or three (meth) acrylate functions, better still one or two (meth) acrylate functions. More preferably, the polymerizable monomers (II) comprise methacrylate functions, better still two methacrylate functions. A first preferred class of polymerizable monomers (II) comprises the monomers corresponding to formula: R3-O (R50-p R4 (IIa) in which R3 is an acryloyl or methacryloyl radical, R4 is a hydrogen atom, an acryloyl radical, a methacryloyl radical or a hydrocarbon group having 1 to 40 carbon atoms, R5 is an alkylene group having 1 to 5 carbon atoms and p

is an integer from 2 to 50.

Preferably, R3 and R4 represent methacryloyl groups and R5 is an ethylene, propylene or butylene group,

better still an ethylene or propylene group.

Among the monomers of formula (IIa), mention may be made of polymethylene glycol mono and di (meth) acrylates, polyethylene glycol mono and di (meth) acrylates, polypropylene glycol mono and di (meth) acrylates, alkoxypolymethylene glycol mono and di (meth) acrylates, alkoxypolyethylene glycol mono and di (meth) acrylates and polyethylene glycol polypropylene glycol mono and di (meth) acrylates. These monomers are described among others

in US-A-5,583,191.

A second class of monomers (II) suitable for the compositions of the present invention comprises the monomers corresponding to the formula: R6-Y-R7 (lib) o R6 and R7 represent a hydrogen atom, an acryloyl group or a methacryloyl group , at least one of R6 or R7 being a (meth) acryloyl group, and Y is an alkylene radical having at least 10 carbon atoms. Preferably, R6 and R7 are methacryloyl groups and Y is an alkylene group having 2 to 50 carbon atoms. A third class of monomers (II) suitable for the compositions according to the invention comprises the monomers corresponding to the formula: Rd R8O (R1 O) q- -C- (OR ') rOR9 (IIc) Re in which R8 and R9 represent a hydrogen atom, an acryloyl group or a methacryloyl group, with the proviso that at least one of R8 or R9 is a (meth) acryloyl group, Rd and Re represent H or CH3, R10 and R11 represent an alkylene group in

C1-C5, and q and r are such that the mean value q + r> 2.

Preferably, R8 and R9 are methacryloyl groups, Rd and Re are methyl groups, R10 and RI1 are ethylene groups or

propylene and 4 <q + r <50.

Among the particularly recommended monomers (II), mention may be made of tripropylene glycol di (meth) acrylate, polyethylene

glycol dimethacrylate (for example polyethylene glycol 600-

dimethacrylate), polypropylene glycol dimethacrylate (for example polypropylene glycol 400-dimethacrylate), alkoxylated bisphenol A dimethacrylate, in particular ethoxylated and propoxylated bisphenol A dimethacrylate (for example bisphenol-A 5-ethoxylated dimethacrylate-A, bisphenol A 4-ethoxylated dimethacrylate-A, 8-ethoxylated dimethacrylate and

bisphenol-A 30 ethoxylated dimethacrylate).

Among the monofunctional monomers (II), mention may also be made of aromatic mono (meth) acrylate oligomers, and

among the trifunctional monomers, the sort (2-

hydroxyethyl) isocyanurate triacrylate, trimethylol propane acrylate

ethoxylated and trimethylol propane acrylate propoxylated.

An important condition of the polymerizable compositions according to the invention is that they lead to transparent polymer substrates having a glass transition temperature such as

70 C <Tg <110 C, preferably 80 C <Tg <100 C.

When present, the monomer or monomers (II) should be such that the final polymerizable composition results in substrates having a glass transition temperature satisfying the above relationship. The monomer (s) (II) when they are present in the composition according to the invention generally represent from 20 to 60% by weight of the polymerizable monomers of the composition. Preferably, when the average value of m + n for the monomers of formula (I) present in the composition according to the invention is less than approximately 4 to 5, the proportion of monomers (II) is generally between 35 and 60% by weight relative to the total weight of the polymerizable monomers present in the composition and monomers (II) having relatively longer chains will be used, however when the average value of m + n of the monomers (I) is greater than about 4 or 5, the monomer (s) (II) preferably represent from 20 to 50% by weight of the polymerizable monomers present in the composition and monomers having relatively longer chain lengths will be used.

short.

For monomers of formula (I), the average value of which is of the order of 4 to 5, from 0 to 50% by weight of monomers (II) is used. In addition, when it is desired to obtain a polymerizable composition for the manufacture of optical or ophthalmic articles having photochromic properties, it is desirable that the composition comprises one or more monomers (II) chosen from group (A) of long-chain monomers, this group consisting of the following monomers: - monomers of formula (IIa), in which p can take the values from 10 to 50; monomers of formula (IIb) in which Y is an alkylene group of 10 to 50 carbon atoms; and

- the monomers of formula (IIc) for which q + r> 15.

This or these monomer (s) from group (A) preferably represent 5 to 15% by weight of the copolymerizable monomers of the composition. It is preferable that these long chain monomers are not present in too high a concentration because they

would lower the value of Tg too significantly.

Preferably, to obtain photochromic articles, a mixture of monomers (II) will be used, at least one of which will be chosen from the monomers of group (A) and at least one other will be chosen from the monomers (II). chain length less than those of the monomers of group (A). It is remarkable to note that the polymers obtained from the polymerizable compositions according to the invention are made photochromizable without the addition of specific monomers such as non-polymerizable plasticizers of the polyethylene glycoldibenzoate type, as described in document WO-95/10790. This is a particularly interesting advantage of the invention because such non-polymerizable plasticizers pose problems during subsequent treatments of optical glasses (vacuum treatment, etc.)

which are therefore avoided in the case of the invention.

The compositions according to the invention also comprise a system for initiating the polymerization. The polymerization initiator system may comprise one or more thermal or photochemical polymerization initiating agents or alternatively, preferably, a mixture of thermal and photochemical polymerization initiating agents. These initiating agents are well known in the art and any conventional initiating agent can be used. Among the thermal polymerization initiators that can be used in the present invention, mention may be made of peroxides such as benzoyl peroxide, cyclohexyl peroxydicarbonate, and

isopropyl peroxydicarbonate.

Among the photoinitiators, there may be mentioned in particular the oxide

2,4,6-trimethylbenzoyldiphenylphosphine, 1-hydroxycyclo-

hexylphenylketone, 2,2-dimethoxy 1,2-diphenylethane 1-one, and

alkyl benzoyl ethers.

In general, the initiating agents are used in a proportion of 0.01 to 5% by weight relative to the total weight of the polymerizable monomers contained in the composition. As indicated above, more preferably, the composition comprises both a thermal polymerization initiator and a thermal polymerization initiator.

photoinitiator.

The polymerizable compositions according to the invention can also comprise additives conventionally used in polymerizable compositions for the molding of optical or ophthalmic articles, in particular spectacle glasses and lenses, in conventional proportions, namely inhibitors, colorants, UV absorbers, perfumes, deodorants, antioxidants, anti-yellowing agents and photochromic compounds. The perfumes make it possible to mask the smell of the compositions,

in particular during surfacing operations.

To obtain optical or ophthalmic articles having photochromic properties, one or more photochromic compounds can be incorporated by any known means. The photochromic compound or compounds can either be directly incorporated in the form of a pigment in the polymerizable composition or else the photochromic material (s) can be incorporated into the polymer substrate obtained from the compositions polymerizable by a polymer.

well-known process of imbibation and thermal transfer.

Any conventional photochromic compound can be used such as

as spirooxazines and chromenes.

In the following examples, unless otherwise indicated, all the parts and percentages are expressed by weight, and the proportions of the additives, other than the polymerizable monomers, are expressed relative to the total weight of the polymerizable monomers of the product.

composition.

Comparative Example A and Example 1 The polymerizable compositions of Table I below were prepared and these compositions were cast between two flat molds having a gap of 2 mm, then they were prepolymerized.

for 3 seconds in an IST static light-curing oven.

The mold was placed vertically between two lamps, the illumination of which was adjusted to 70 milliwatts / cm2. These compositions were then polymerized for 10 minutes in a dynamic oven for thermally-assisted UV polymerization at 120 C. The molds were disassembled and the biplane polymer substrate obtained was annealed for two hours at 60 120 C. The physical properties of the

Polymeric substrates are also shown in Table I below.

below.

TABLE I

EXAMPLE

COMPARATIVE EXAMPLE

A 1 Polymerizable monomers Neopentylglycol dimethacrylate 100

EBP2PODMA - 100

Photoinitiator Additives

CGI 1850 (CIBA) 0.1% 0.1%

UV absorber Cyasorb UV 5411 (Cyanamid) 0.07% 0.07% Index nd, 25 C 1.4983 1.4930 Abbe number 54 55 Density, g / cm3 1.18 1.07 Shrinkage,% 11, 3 8.9 Color Pale yellow Colorless Tg, C 145 108 Water uptake,% O 1.7 0.6 The polymerized material obtained from the composition according to the invention has a lower density than the material of the Comparative Example A. The composition of Example 1 exhibits photochromic properties superior to those of Comparative Example A. 1 Comparative Examples B and C and Examples 2 to 5 The polymeric substrates were produced from polymerizable compositions according to 1 invention as before. The compositions and properties of the substrates obtained are shown in Table II below.

TABLE II

Example Comparative Comparative Example Example Example Example Example

C D 2 3 4 5

EBP2PODMA 0 13 40 49 55 67

BPA5EODMA 24 22 20 14 18 17

PPG400DMA 76 65 40 37 27 16

CGI1850 photoinitiator additives 0.11 0.12 0.13 0.15 0.15 0.16 UV5411 UV absorber 0.07 0.07 0.07 0.07 0.07 0.07 TPP antioxidant 0.2 0.2 0.2 0.2 0.2 0.2 Properties Index, nD, 25 C 1.4992 1.4993 1, 5012 1.4975 1.5015 1.5023 Abbe 58 58 58 58 57 57 Density, g / cm3 1,114 1,108 1,102 1,093 1,09 1,085 Colarability, Tv red, 22 29 32 35 40 45

PS 10/20

Yellow index YI, 160 / 103.2 3.3 3.2 3.1 3.5 3, 2 Insolation test OK OK OK OK OK OK Transmission Tv% 90.7 91 91.1 92 91.5 91 , 5 UV cutoff, nm 375 375 375 375 375 375 water uptake,% 1.6 1.6 1.5 1.2 1.1 0.8 Shock, 12/10, -2.00 Test performed on a glass of 1.2 mm thick OK OK OK OK OK OK center Tg (maximum tg 8), C 50 63 75 90 95 100 Hardness, MPa, 25 C 30 62 76 82 95 100 Resistance to abrasion (Bayer) (1 , 51) (1.45) (1.25) (1.11) (1.0) (0.9) EBP2ODMA: 2-ethyl-2-butyl-1,3-propanediol 2x-propoxylated dimethacrylate PPG400DMA: polypropylene glycol 400 dimethacrylate BPA5EODMA: Bisphenol-A 5-ethoxylated dimethacrylate TPP: Triphenylphosphine (antioxidant) Similar results were obtained with a mixed UV and thermal initiation system. The polymerization process then comprises a 3 second UV prepolymerization (or gel setting) followed by thermal polymerization in an air oven.

(lh, 120 C) and the catalyst used is TBPEH (ethyl-2-

tertiary butyl perethanoate) supplied by the company SPQ.

Compositions 2 to 4 provide an excellent compromise between the different properties. In all cases, the densities of the polymerized substrates obtained are much lower than those of the low index reference material, CR39 (1.32),

marketed by the company PPG Industries.

The polymerized materials obtained from the compositions

B and C are deformed during a surfacing operation.

Examples 6 to 12 The compositions indicated in Table III below were prepared and polymerized as above. Properties

materials are also given in Table III.

TABLE III

6 7 8 9 10 11 12

EBP2ODMA 80 60 60 6 60

PPG400DMA 30 20 20

SR344 30

DCPMA -0

CN131 2 - 5

SR368 - 10 5

CD501 20

CD502 20

Additives

% CGI1850 0.15 0.15 0.1510.15 0.15 0.15

% UV5411 0.07 0.071 0.07 0.07 0.070.07

% TPP 0 0.2 0.2 0.2 0.2 0.2.2 0.2

Properties Index, nD, 25 C 1.504 1.49 1.52 1.49 1.49 1.49 1.49 Abbe 57 5l5 7 7 Density, g / cm3 1.09 1.1 1.1 1.09 1 , 09 1.09 1.08 colorability Tv red, PS 20/10 41.3 3 3 40 3 3 Tg, C W920 9.5 I01 Monofunctional monomers - aromatic monoacrylate oligomer CN131 Cray Valley Difunctional monomers: - Bisphenol A diethoxylated dimethacrylate D101 Akzo - Polyethylene glycol 400 diacrylate SR344 Sartomer Dicyclopentadiene dimethacrylate DCPMA - Shin Nakamura Trifunctional monomers: - tris (2-hydroxyethyl) isocyanurate triacrylate SR368 Sartomer - Trimethylolpropane acrylate ethoxylate CD502 Sartomer Sartomer Trimethylpropane acrylate Domer 16 prepared examples CD501 prepared examples CD501 proppoproporto Domer 16 Examples CD501 proppopropropylpropyl Domer 13 Proportyl Domer 16 prepared examples CD501 Propoproporto C501 C501 proppopropylpropyl Domer 16 Examples prepared examples and polymerized as above, the

compositions indicated in Table IV below.

Photochromic compounds (T4-Gray formulation from Transitions Optical) were incorporated into the polymerized substrates obtained by imbibation with two imbibation conditions, namely: (a) 3 hours at 135 C, and (b) 6 hours at 140 C. For comparison, a commercially available CR-407 substrate (acrylic polymer

aromatic nD = 1.55, Tg = 88 C).

The photochromic kinetics of the substrates were determined

polymerized soaked at a temperature of 30 C.

The substrates were irradiated for 15 minutes in an air-thermostated cell, with UV radiation of 365 nm,

O10W / m2 and 53.4 klux.

The fading was done in the dark.

The results are given in Table V.

TABLE IV

Example Example Example Comparative example 13 14 15

D

NPG2PODMA 100 - - -

EBP2PODMA 100 50 50

PPG400DMA 10 10

EPS4.8EODMA - 30 30

BPA30EODMA - 9 -

PEG600DMA - 9

MBOL - 1 1

igniter CGI 1850 0.15 0.15 0.15 0.15 UV absorber UV541] 7 0.07 0.07 0.07 0.07 Refractive index nD - 1.5 1.5 Abbe - 57 58 Tg C 119 108 90 86 NPG2PODMA: 2x-propoxylated neopentylglycol dimethacrylate PPG400DMA: Polypropyleneglycol 400 dimethacrylate BPA4,8EODMA: Bisphenol A 4,8ethoxylated dimethacrylate BPA30EODMA: Bisphenol A 30-ethoxylated antibuthacrylMAOLMA (dimethacrylMA) 600Dibethacrylate polyethylene 600D-methacrylate 600Dimethacrylate-yellow 600-dimethacrylate-MEG600

TABLE V

Transmission% Discoloration time o minute 15 minutes t 1/2 (s) t 3/4 (s) Comparison D (a) 91.2 '41, 9 122 662 Comparison D (b) 90.4 35.9 151 874 Example 13 (a) 90.7 30.9 66 324 Example 13 (b) 90 30.8 65 310 Example 14 (a) 88.3 23.4 34 116

1 30

Example 14 (b) 87.6 25.7 35 13 5 Example 15 (a) 89.2 25.5 56 219 Example 15 (b) 88 24.7 59 300 CR 407 (a) 84 [26 34 0 121 La The composition of Example 14 exhibits photochromic properties which are superior or comparable to those of the substrate CR407. Another important aspect of the polymerizable compositions according to the invention is that they lend themselves well to the manufacture of optical and ophthalmic articles such as lenses by the overmolding technique. A technique for manufacturing lenses by overmolding on the front surface of a preform is described among others in the

documents US-A-5,531,940, US-5,372,755 and US-5,288,221.

The production of photochromic articles by overmolding is

more particularly disclosed in document US Pat. No. 5,531,940.

Briefly, this overmolding technique involves casting a polymerizable composition of an optical grade organic glass in the gap between a mold and the front surface of an optical grade organic glass lens preform and polymerizing the cast composition to forming an adherent polymerized coating on the lens surface. The lens preform can be solid or semi-thin and the coated surface of the preform can optionally be frosted. It is also possible to perform the overmolding on the rear surface of the lens of a preform. In order to demonstrate the aptitude for overmolding of the compositions according to the invention, the rear surface of a lens preform made of different organic glasses (including an organic glass obtained from a composition according to the invention ) and a mold of inorganic material of the photopolymerizable compositions according to the invention and according to the prior art. These cast compositions were polymerized by UV irradiation (between two 70 mw / cm 2 mercury lamps) for 60 seconds. The products obtained are then demolded and fractured with a hammer. The polymerized layer is considered to adhere to the preform if the pieces do not show an adhesive break at the interface between the layer and the preform. The compositions are given below and the

results summarized in Table VI.

COMPOSITION 1 (according to the invention)

EBP2PODMA 50

PPG 400 DMA 19

EPS 4.8 EODMA 30

MBOL 1

CGI 11850 0.1

UV 5411 0.07

COMPOSITION 2 (classic) Tripropylene glycol dimethacrylate (TPGDMA) 37, 4

PPG 400 DMA 48.5

D 121 14.1

TPP 0.2

CGI 1850 0.10

The lens preforms were obtained by casting the chosen composition in a mold and by carrying out a photochemical prepolymerization of 3 seconds under UV 70 mW / cm2 followed by thermal polymerization at 120 C for 10

minutes. After demoulding, annealing is carried out for 2 hours at 120 C.

TABLE VI

Lens preform Adhesion Composition _________________ ________lining Back side Frosted frosted composition 2 no 2 no 2 yes 2 no 2 yes CR39 (diethylene glycol _______102 _ _ _or_ i bis (allyl carbonate) no 2 yes BPA polyéhtoxylé DMA no 1 no 2 yes 1 no 1 yes 1 no BPA polyethoxylated DMA yes TPGDMA: Tripropyleneglycoldimethacrylate EBP2PODMA: 2-ethyl-2-butyl- 1,3propanediol 2x-propoxylated dimethacrylate BPA polyethoxylated DMA: Bisphenol A polyethoxylated dimethacrylate (Polymerisable compositions based on these polymers are described in FR-A-2 699 541) CR39: Composition based on diethylene glycol

bis (allylcarbonate) marketed by PPG Industries.

The physical properties of polymeric substrates have been

determined as indicated below.

The yellowness index was measured according to the ASTM D 1925-63 standard. The Bayer abrasion resistance was determined according to the

ASTM F 735-81 standard.

The impact resistance was determined according to the American FDA test (falling ball test) in which a 16g ball with a height of 1.27 m is dropped onto a test tube.

at an energy of 200 mJ.

OK means the glass is intact after the shock.

The exposure test consists of subjecting test pieces for 100 and 200 hours to exposure under the same conditions with a SUNTEST HANAU device emitting a radiation of 24.4 w / m2 in the spectral range of 300-400 nm and measuring

the yellow index (YI).

Colorability measurement The measurement given is the value of the transmission measured in the visible range of a glass 2 mm thick with a center colored by soaking in an aqueous bath at 94 C in which a

Red pigment "disperses Red 13" from the company Eastman Kodak.

The measurement of the Tg is carried out by DMA (dynamic mechanical analysis) on a specimen of 5.2 cm x 1 cm x 2 mm

(thickness) flat.

The test is carried out in 3-point bending.

Tg corresponds to the maximum of the ratio E '(loss modulus) E "(conservation modulus)

Claims (16)

1. Composition of polymerizable monomers, characterized in that it comprises, relative to the total weight of the polymerizable monomers present in the composition: at 100% of one or more monomers (I) of formula: R R R 'R "R2 II I I I CH2 = - C - (- OCH2CHt - m0-CH2-C-CH20 (- (- CHCH2O - tn C = CH2 (I) I Rb in which R1, R2, R 'and R "represent, independently the each other, a hydrogen atom or a methyl radical, Ra and Rb each represent an alkyl group having 2 to 10 carbon atoms and m and n are integers satisfying the relationship 2 <m + n <20; * 0 at least 70% of at least one other radically polymerizable monomer (II), different from the monomer (I), such as a transparent substrate resulting from the polymerization of the composition has a glass transition temperature satisfying the relation 70 C <Tg <110 C; and * at least one polymerization initiation system. 2. Composition according to claim 1, characterized in that the monomer (s) (II) comprise one or more functions (meth) acrylate, preferably two methacrylate functions. 3. Composition according to claim i or 2, characterized in that Ra and Rb represent a C2 to C6 alkyl group, preferably ethyl, propyl or butyl. 4. Composition according to any one of claims 1 to 3, characterized in that R1 and R2 are CH3 groups. 5. Composition according to claim 1, characterized in that that the monomer (I) is 2-ethyl-2-n-butyl-1,3-propanediol 2x- propoxylated dimethacrylate. 6. Composition according to any one of claims 1 to , characterized in that the monomer (s) (II) is (are) chosen from: a) monomers of formula R3-O (R50Ot- R4 (IIa) in which R3 is a radical ( meth) acryloyl, R4 is H, a (meth) acryloyl radical or a hydrocarbon radical having 1 to 40 carbon atoms, R5 is a C1-C5 alkylene group and p is an integer from 2 to 50; b) the monomers of formula: R6-Y-R7 (IIb) o R6 and R7 represent H, an acryloyl group or a (meth) acryloyl group, at least one of R6 or R7 being a (meth) acryloyl group, and Y is a radical alkylene having from 2 to 50 carbon atoms; and c) monomers of formula Rd R80 (R1 O) q llRd (OR11) rOR9 (Ilc) Re in which R8 and R9 represent a hydrogen atom, an acryloyl group or a methacryloyl group, provided that one at least of R8 or R9 is a (meth) acryloyl group, Rd and Re represent H or CH3, R10 and R11 represent an alkylene group in C1-C5, and q and r are such that q + r> 2. 7. Composition according to claim 6, characterized in that the monomers (IIa) are chosen from polymethylene glycol mono and di (meth) acrylate, polyethylene glycol mono and di (meth) acrylate, polypropylene glycol mono and di (meth) ) acrylate, alkoxy polymethylene glycol mono and di (meth) acrylate, alkoxy polyethylene glycol mono and di (meth) acrylate, alkoxy polypropylene glycol mono and di (meth) acrylate and polyethylene glycol polypropylene glycol mono and di (meth) acrylate. 8. Composition according to claim 6, characterized in that in formula (lIc), Rd and Re represent CH3 and R10 and RIl are ethylene or propylene groups. 9. Composition according to claim 6, characterized in that it comprises one or more monomers (II) chosen from the group (A) of long-chain monomers, this group (A) consisting of: - monomers of formula (IIa ), in which p can take the values from 10 to 50; - monomers of formula (IIb) in which Y is an alkylene group of 10 to 50 carbon atoms; and - monomers of formula (IIc) for which q + r> 15. 10. Composition according to claim 9, characterized in that the monomer (s) of group (A) represent 5 to 15% by weight. copolymerizable monomers of the composition. 11. Composition according to any one of claims 1 to 10, characterized in that the monomer (s) (II) are chosen from polypropylene glycol 400 dimethacrylate, polyethylene glycol 600dimethacrylate, bisphenol A diethoxy dimethacrylate, bisphenol A 5ethoxylated dimethacrylate, bisphenol-A 4,8-ethoxylate dimethacrylate, ethoxylated bisphenol-A dimethacrylate, aromatic monoacrylate oligomer, dicyclopentadiene dimethacrylate, tri (2-hydroxyethyl) isocyanurate triacrylate, ethoxylated trimethylolpropane acrylate and propoxylated trimethylolpropane acrylate. 12. Composition according to any one of claims 1 to 11, characterized in that the polymerization initiator system comprises one or more thermal initiators, one or more photoinitiators or a mixture of one or more initiators thermal and one or more photoinitiators. 13. Transparent polymer substrate obtained by polymerization of a composition according to any one of claims 1 to 12. 14. Optical or ophthalmic article comprising a substrate polymer according to claim 13. 15. Optical or ophthalmic article according to claim 13, characterized in that the polymer substrate is molded onto a surface of a transparent organic glass preform. 16. Optical or ophthalmic article according to any one of claims 14 or 15, characterized in that a pigment photochromic is incorporated into the substrate which constitutes it in whole or in part.