JPS5831314A - Silicone composition for contact lens - Google Patents

Abstract

PURPOSE:To obtain a harmless composition for a hard contact lens with high oxygen permeability by mixing specified organopolysiloxane with specified organohydrogenpolysiloxane and reacting and hardening the mixture in the presence of platinum catalyst. CONSTITUTION:Organopolysiloxane (A) in which >=2mol% of all the org. groups bonded directly to the silicon atoms is allyl groups or beta-methylvinyl groups is mixed with organohydrogenpolysiloxane (B) having >=2 hydrogen atoms bonded directly to a silicon atom in one molecule, and the mixture is reacted and hardeed in the presence of platinum catalyst (C) for addition reaction. The preferred amount of the hydrogen atoms in the component B is 0.3-5.0mol/1mol allyl group or beta-methylvinyl group in the component A. The amount of the component C is 1-30ppm of the total amount of the components A, B. A physiologically harmless and innoxious silicone composition with high oxygen permeability suitable for use as the material of a hard contact lens is obtd.

Description

[Detailed description of the invention]

The present invention is a V silicone composition for contact lenses. 419 is suitable for 8-cord contact lenses and 9-cord
y composition. Regarding compositions for contact lenses, many are already known, such as Medelmetactul resin (MM).
A), cellulose acetate butray) (OAB), &
Contact lenses made from 9-gone modified MMA have been put into practical use. However, although items made from MMA and OAR have good cutting workability during lens processing,
Those made from MMA have extremely low oxygen permeability, and those made from OAB, which meet physiological oxygen demand, still have insufficient T11 permeability, so they cannot be used for long periods of time. There was a significant drawback that the device to the eyeball of time was not possible. In order to improve this, a substance made of modified MMA, which is a combination of V9 cone, which has the best oxygen permeability among known substances but has weak mechanical strength, and MMA, which has mechanical strength, was developed. Although it was. This is also continuous day and night! It has not yet reached the point where it can snow. Therefore, it has a high oxygen permeability and is physiologically harmless. Attempts have been made to manufacture eight-doped contact lenses using only non-toxic fern cones, for example in JP-A No. 11B! No. 4-130,948 proposes a Huntact lens consisting of a curable phenylbo-9v rokinane with sufficient vinyl groups or polyacylopentenylsiloxy groups to impart the desired hardness. However, this product is the same as the vinyl J& (E810H engineering OK) in Kukina and the hydrogen group (-81111
Because it is hardened by an addition reaction with 3, it is mechanically brittle and often breaks during cutting into lenses (2), resulting in poor yields; This invention has the disadvantage that it easily breaks, and furthermore, industrial materials with sylacyl-pesitenyl groups are difficult to supply industrially and are expensive. 41 This is related to 1) silicon atom; at least 2 moles of all directly connected organic 1 are allyl JI! and/or organopolysilochitin which is based on β-metalbinyl, 2) organohedromycin having at least two hydroxyl crystals directly bonded to a C2 silicon atom in one molecule, and 3) addition It is characterized by consisting of a platinum-based reaction catalyst. To explain this, the present inventors have conducted various studies on silicone compositions for contact lenses, and found that the main organopolysiloxane of this composition is Aral & (Mi-810H, g/
or! -methylvinyl group (3810H-dHOH,)
Silicon C; Directly connected water I
The cured product of V-rokinane obtained by addition reaction with I (Mi-81H) has strong mechanical strength. Moreover, since this is a silicone composition and has excellent oxygen permeability, they discovered that it is useful as a material for Funtact lenses. The present invention was completed by confirming that polysiloxane is industrially easily available, and therefore relatively inexpensive C-contact lenses can be manufactured. The organopolysiloxane as the first component constituting the silicone composition of the present invention contains silicon + 1 [child &:
It has at least 2 mol % of directly linked allyl groups and/or β-mesorvinyl groups. This substance has a chain-like monobranched molecular structure. Although it may be any cyclic type, this allyl group is used to increase the hardness of the addition reaction product. ! - The content of notervinyl groups should be at least 2%. However, other organic components that are directly connected to silicon atoms 42 in this V lokitin are methyl 1. Etel bottle, propyl steamer,
It may be an alkyl group such as Budel's grave, or a phenyl group, tolyl group, hydrogen group, etc., and these are <1 = There is no reason to limit this, but 1 Usually, 30% or more of this is a methyl group. be done. In addition, this yakina ν may contain hydroxyl groups, alkoxy V groups, etc. directly bonded to silicon in its molecules, but these functional groups generate water and alcohol gases through condensation reactions and harden. In the material ζ: Since there is a risk of foaming or flagging, this should be 1% by weight or less in i/Cl chitin, and 0.8% by weight or less for *. In addition, this organopolyzolocina y is used in various viscosities from liquid to solid, but for example, when it is side-grouped in a 50% toluy liquid, the viscosity at 221°C is 3o1 or less. If this is used, the mechanical strength of this cured product will be significantly reduced and the processability such as demolding and cutting will be inferior, so the viscosity of the 50% Tornizi solution should be 3 op or more. is preferable. Note that the first component is an Adel group and/or!
- Organoboriν-rokinane containing a mesorvinyl group is co-hydrated with organochlorosilane, organoalkoxyVν or acetoxysilane corresponding to each component constituting this polyνROKI1#-V in a water-containing swam bud system. After decomposition, the silanols are condensed and polymerized in the presence of an aqueous or alkaline catalyst. Although it can be produced easily by a so-called equilibration reaction, it is also possible to deplete various low-molecular-weight molecules containing various components constituting this Botushirokina ν, and then to react with an acid or alkali catalyst. It can also be produced by equilibration in the presence of The second component of this V-cone composition is the organoid CF dievol/rokina, which is known for use in addition-reactive silicone compositions. This may be polysilochitin having at least two silicon-bonded hydrogen groups in one molecule, including a silicon atom ζ;
Other groups that combine are alkyl groups such as methyl group, ethyl group, propyl group, and bf7S/ group. Alternatively, it may be a monovalent aromatic residue such as a phenyl group or a tolyl group. In addition, this organohycyyyempogV lokitin may be either chain-like, mono-branched, or cyclic, and it also has a viscosity of 10 to 100,000 mm at 2B"C.
The platinum-based catalyst for the addition reaction as the third component is also known, and includes metal platinum, chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid. Examples include complex salts of olefin and olefin ν. The silicone composition of the present invention is made into a contact lens adhesive by combining the above-mentioned first component and second component and curing this by reaction in the presence of a platinum-based catalyst as the third component. , organopolyV as this first component
The mixing ratio of rokinane and the organohedlodiene polyνloki-fy as the s22 component is determined by the allyl group in the first component and/or! - Preferably 0.3 to 5.0 mol of hydrogen groups in the second component per 1 mol of methylvinyl.
The amount is preferably in the range of 8 to 4.5 moles, which means that if the hydrogen group in the second component is 0.3 moles or less, it is allyl S. ! -The methyl V vinyl group remains unreacted, so that the cured product after the reaction is sufficient! 1! ! l! Not shown. As a result, the surface of the molded product may become damaged and become islands. This is because physiologically unfavorable disorders may occur, and on the other hand, 5 molar or more is too excessive. Further, the amount of the platinum-based catalyst as the third component in the mixture of both may be a known catalyst amount, and this is usually 1 to 571III with respect to the total amount of the first component and the second component.
It may be in the range of 30 pprm. Incidentally, fine particulate inorganic fillers may be added to this composition in order to improve the mechanical strength and surface hardness of the cured product after the reaction and to reduce the shrinkage rate of the molded product. When adding this, it is necessary to pay careful attention to the size of the particles and the method of dispersing and incorporating them so as not to lose the original transparency of the lens. It is best to completely homogeneize and disperse this composition.Also, in order to color the intended contact lens, it is possible to add an organic dye that is compatible with this composition. However, this is also because the C= reaction proceeds gradually even at room temperature in the silicone composition of the present invention to which this third component is added. 2 to 1000 moles of lli! to platinum atoms in a platinum-based catalyst containing OH etc. as a third component! May be added within the range. According to this 6; the reaction is suppressed below room temperature and proceeds above 100°C. In order to manufacture a contact lens from the silicone composition of the present invention described above, the calculated amount of the first component and the second component may be 11 at room temperature. The mixture containing each component obtained in this way is then decompressed under reduced pressure. After foaming, pour it into a mold, and at this point
It is cured by heating at 00° C. or higher, preferably 130 to 200° C., for 1 hour or more, and in order to prevent the formation of flags and warpage due to distortion of the cured product, 1: is. After heating at 130 to 150°C for 1 to S hours. It is best to heat the product at 180 to 200°C for one day and night.This cured product has a compressive strength of 5.0 KP/a+1 or more due to its mechanical strength and restoring force against deformation during use.
<-Co-A/hardness needle (GYZJ-935 type) requires a hardness of 60 or higher. For this curing condition, avoid rapid heating or rapid cooling. It is possible to change the temperature in stages. Desirable.The cured product obtained by curing the silicone composition of the present invention by the above-described method satisfactorily satisfies the above-mentioned mechanical strength and hardness, has good cutting workability, is transparent, and has low oxygen permeability. This model (7) has excellent optical properties and physiological properties, so it is suitable for use in 8-domain contact lenses, corneal pairs, and intraocular lenses.

It is said that it can be widely used as an optical device such as [Interocular]. In addition, in order to process this cured product into contact lenses, etc., it is sufficient to give it a desired shape and thickness by cutting and polishing. Soruding method (
Alternatively, the centrifugal casting method, which is commonly used in the manufacture of soft lenses, may be applied.Also, contact lenses made from this composition usually have a hydrophobic surface. If necessary, the surface may be made hydrophilic by a known method such as low-temperature plasma processing. Next C: Examples of the present invention will be given. Example t cHIstoL, unit 304 l*s C@”i 11
10 th unit S o peak h-s (Cslldm81
0 units 10% kllk. (CTo-CHCH snow) CH1810 units consist of 504 units. Solid organoborisilokinane $(sol) luene 111 as the first component with a hydroxyl group content of 115% by weight
The viscosity at 5°C is 1α2). C@HaII Otori OLl unit! 504 rubles (CHs)
@H1i to, liquid organohydride-diempolyskinan (viscosity at 25"cK 2
To this, add 100 parts by weight of the 0 mixture (LOOJ part of chloroplatinic acid (20 ppm as platinum)).
and acetylene alcohol (Cl) as a reaction inhibition phase.
-C (C12)@0H) (2 parts of L was added to make the -Km record evenly. Next, this was defoamed in a vacuum defoaming machine (1')), straight 11so = x height So■ It was poured gently into a circular O aluminum metal plate, heated at 10 Stl: for 10 hours and at 150°C for 24 hours to harden, and after cooling, the cured product was taken out from the gold layer, resulting in a colorless transparent @O A gaseous solid is obtained,
When this physical property measurement was carried out, the results shown in Table 1 were obtained according to the manufacturing conditions. *Example 2 <CH, -CHCHs>28CK# composed only of cIIIs to units Allyl methylpolysiloxane (501
1) Lez) Drops 1110 Viscous 11 & 1 sp) 100
In step 11, 1.7 parts of the organohydride diembolyzed w4I as the second component which had been previously subjected to fRteflN1 was mixed, and the same amount of platinum-based catalyst and reaction inhibitor as in the Km example were added thereto and balanced. After being dissolved, it is defoamed in a vacuum degassing machine, and then gently poured into a diameter st 1■ x height So■O Aruden Ekumu Metal 11 d, 10! ic"t'1011, 180
When heated at 481161 °C and left to cool, a colorless, glassy mlI product was obtained, which had a par excellence of 6S, FElaIIA@? ,? '? /sF
Showing 01151.夷總儒5cH@5toL、Unit: 104k 16s Cs HI
S S Ol, I unit 10M lou, (CsHs)sll
lo unit 104 rou, □(CIE@-CI[C
Hs) CMIII 10 20 rolls (C1l@CH
-CH) CHd10 unit consists of 10 baskets. Surrounded organopolysilonane (+5011) luene 11 as the first component with a hydroxyl group content of α1i weight -
1 m 10 viscosity S@ν) 100 @Ks 8 tons of am-like organohydride-diene polysilane as the second component used in Example 1! After adding the same amount of the platinum-based catalyst and reaction inhibitor as in Example 1, the same amount of platinum-based catalyst and reaction inhibitor as in Example 1 were added to uniformly dissolve the two. The viscosity of CO is 1! LroroO・νO4 became a clear liquid. Next, after defoaming this in a vacuum degassing machine. diameter! i0g 040 is Percoll hard 1j7Q, compressive strength f
il 111 klld O thing'lk k showing. Example 4 Cl1g1io1. , unit 184%, (CHI),
1110. . Unit S-% Roux and (CHI-CHCHI) CRIB
Organopolysiloxane (viscosity 1480) as the first component, consisting of 40 io units and a hydroxyl group content of α ink weight - K, l! Application Example 1 The organohide q diene polysilane used as the second ingredient was added to the second ingredient.
After blending in the amounts shown in the table to completely reduce both, add 100 parts of this mixture (LOOJ part of platinum II chloride (20 ppm in terms of platinum) and c-c-c (CIEs).
) 0.2 part of acetylene alcohol as a reaction inhibitor represented by moir was added to uniformly dissolve them. Next, this was defoamed using a vacuum defoaming machine.
Pour it gently into Aluminum gold 11 of ■×Mansa sO■ at 105℃ for 5 hours, then at 150C for 244 hours.
When heated at 80°C for 24 hours and then allowed to cool, the cured product taken out from the metal lid was a glassy solid with a deep golden color.
These physical properties were as shown in the second flK.过实例翫18 parts of organoene polysilicon p-xane as the first component used in Example 1 was blended, and both were completely converted to KfII! After this was dissolved, 2 parts of chloroplatinic acid α00 and acetylene alcohol (CHmC-C(CHs)) were added as a reaction inhibitor.
, OH) was added to uniformly dissolve them, and the viscosity of the mixture was 4SOO@p. Next, this is degassed in a vacuum deaerator, and then the diameter is
HX height IQ■O Aruden! Static Kt11 was soaked in a gold powder made by Rimu for 7S'C"el 0 hours, and after heating at 150'C for 24 hours, it was left to cool. After filtration, a colorless transparent glass-like compound was obtained. is Percoll hardness 4s% compressive strength Zf&
t,/s10 physical properties. REFERENCE EXAMPLE The cured products obtained in each of the above-mentioned Examples are used as the main body, and the known O cutting and polishing method is used! When hard contact lenses were made and their lil characteristics as contact lenses were measured, the results shown in Table 1 were obtained, and all showed excellent characteristics as bar-tone tact lenses. (Remarks) 1) For Example 1%4, 420 samples were used. iJ) The above test items show the measurement results using the following O method. ■...Whether cracks, cracks, etc. occur during cutting with a commercially available cutting machine.■...Meyermine end point bite angle 90@. A SmO scratch was made with a load of 5 t, and the width of the scratch was measured with a mirror.■ Measured with an Atsube refractor.■ Measured the light transmittance of -1so-son.■...
2!5'Immersed in CO water for 48 hours Shown as ilO weight change...Measured by 0-droplet method shown as water absorption value and dimensional change rate after water absorption■...Values after mother tree treatment with low temperature plasma l
Shin-Etsu Chemical Co., Ltd.

Claims (1)

[Claims] υ silicon atom ζ; at least 2 moles of all directly bonded organic groups are aral groups and/or! -Organopolyzolocina yυ which is a mederubi di- group Silicon atoms ζ in one molecule
; V Ricosi composition for contact lenses, which comprises organohydrogenbolycia chitin V having at least two directly bonded hydrogen groups; and a platinum-based catalyst for a top extension reaction.