JPH01503072A - Wettable, hydrophilic, flexible and oxygen permeable copolymer composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] l　Name of invention Wettability, hydrophilicity, flexibility and oxygen permeability copolymer composition 2 Technical field The present invention relates to novel copolymer compositions and further provides increased oxygen permeability, softness, Hydrophilic, highly miscible, dehydration resistant, adhesion resistant and stable contact lenses and eye patches Or to copolymers for artificial skin for burn or injury dressings.

For polymeric substances in some fields of medicine, a basic requirement is that It is hydrophilic, soft, wettable with body fluids, adhesion resistant, and stable. Conventional methods of many different polymeric materials, e.g. contact lenses, eye patches, artificial membranes e.g. surgical and uses in the field of medicine, such as in burn dressings, membranes of artificial lung organs. is taught. Such polymers have certain desirable properties for their special medical uses. , but it also has other undesirable properties that reduce its ephemeral nature. .

In the field of contact lenses, contact lenses are especially the most desirable Extended; many required features for successful wearable use. There is. We will look at the advantages and disadvantages of materials developed during each period in the history of contact lenses. To summarize, we have listed each of the most needed characteristics of a desirable contact lens. Selected numbers are listed below; 1. Oxygen permeability: 2. Softness; 3. Tree parentage: 4. Stability; 5. Long-term functional (body fluid or tear) wettability; 6. Dehydration resistance; and 7. Adhesion resistance.

The development of plastic materials for contact lenses has been a long journey. the first During the period, a hard plastic material, polymethyl methacrylate (PMMA), was used. It was done. In general, this node lens provides good features 4 and 6 listed above. However, features L2.3.5 and 7 have major drawbacks. later hide Rogel lenses, namely poly 2-hydroxyethyl methacrylate (polyHEMA), are , although popular because it generally offers good features of 2.3.4.5.6 and 7. However, it still had the drawback of the above-mentioned feature 1 in terms of oxygen permeability. Insufficient oxygen to the cornea Negative feeding can lead to severe damage to the cornea, including corneal ulcers, infections and thickening. Ras. Thus, patients these days basically have two main types of HGP lens materials: i.e. hard molds made from acrylic silicone and acrylic fluorosilicone I started looking at gas permeable lenses (HGP). Generally, HGP lenses are 1.4 or higher. and 6, but still have the poor characteristics of 2.3.5 and 7. are doing. This drawback results in corneal abrasion, corneal distortion and discomfort. Many cases occur. Lens users can therefore now enjoy all of the desirable features mentioned above. We are looking forward to having a soft gas permeable (SGP) lens that we can provide. .

Some inventions of SGP lenses include, for example, Chang U.S. Pat. ．． 182.822 and 4,343.927; Japanese-Chinese U.S. Patent No. 4.139 ．． No. 513, and U.S. Pat. No. 4.246.38 to LeBoeuf. No. 9 teaches. Lenses made from these patented materials have high oxygen permeability , offer good characteristics of softness and hydrophilicity, but they are has not been able to overcome the relatively poor quality of the 6 features.

The materials described in the Chang patent are highly oxygen permeable, flexible and hydrophilic. but Surprisingly, the inventors have discovered that this highly hydrophilic material has long-term durability. I found that the lenses were not good enough for wearing. The lens I will be using from now on is Very soft and hydrophilic, but surprisingly long-term functional (tear) wettability Poor quality. This lens is excellent for certain everyday wear, but it is Not suitable for wearing.

The materials described in the National or Lepoeuf patents would have similar drawbacks.

Obviously, it has all the desirable features mentioned above and also has the state of the art. In a new era, having a breakthrough in providing copolymers that enhance visual It is highly desirable and useful for humans in need of correction. As a result, will enjoy the benefits of contact lenses and be less bothered by their drawbacks. Tremendous efforts have been made over the past 12 years in the search for such copolymers. The inventors have now discovered a new copolymer system.

Table 1 summarizes each period of development of the above-mentioned lenses. U.S. Patent No. 4. No. 182.822 and No. 4.343.927 are hereby incorporated by reference. shall be cited as such.

Although the invention primarily relates to contact lenses, the unique properties of the materials of the invention are , in the medical field, such as eye patches for sustained release of drugs or protection against corneal damage or disease. protective equipment, bandages for the treatment of injuries or artificial skin for the treatment of burns, for lung organs; It is also highly desirable in the field of artificial lung membranes.

Table 1 Lenses, materials or patent claims at different times in contact lens development Summary of General Characteristics of Advantages and Disadvantages of Compositions Lenses, Materials or Patents Teachings The claimed composition has not been taught for a long time. Item I Hard type PMMA 4,6 1.2.3.5.7■ Soft type hydrogel , Poly HEMA 2.3.4.5.6.7 1 ■ Hard type gas permeability' 1, Acrylic silicone 1.4.6 2, 3, 5.72, Acrylic fluor ■ Soft type gas permeability 4 Chang, country or Repoyouf patent 1.2.3,4 5,6.7V Invention 1.2.3.4.5 ．． 6.7a) The numbers shown in the table indicate the desired following for a successful contact lens: Corresponds to the characteristics: 1. a-element permeability; 2. Softness; 3. Tree parentage; 4. Stability; 5. long Wave source wetness of the period: 6. Dehydration resistance: and 7. Anti-fouling.

b) PMMA is polymethyl methacrylate; polyHEMA is polymethacrylate 2-hydroxyethyl acid.

C) Acrylic silicone e.g. U.S. Patent No. 4.152.508; No. 3°808 ．． Those described in No. 178; acrylic fluorosilicone, for example, No. 1-126,052 (Chemical Abstracts, No. 05.191777c) what is described in.

d) Chan's patents are U.S. Pat. No. 4,182.822 and 4.343.927. No. 4.139.513; National Patent No. 4.139.513; Robert's patent is related to U.S. Pat. No. 4,246,389.

detailed description of the invention The present invention relates to novel copolymers particularly suitable for manufacturing certain medical devices. Main departure The purpose of light is substantially increased oxygen permeability, softness and hydrophilicity, and long-term body fluid retention. (Tears) Contact lenses, eye patches, and artificial materials with wettability, dehydration resistance, and adhesion resistance To provide a new and useful copolymer for producing artificial membranes for skin or lung organs. That is.

The novel copolymer disclosed herein is (A) at least one amide acrylic 1-85, preferably 15-65, most preferably preferably 25 to 65% by weight; (B) at least one vinylcarvone ml to 35%; Preferably 1-20, most preferably 1-15% by weight: (C) At least one copolymerizable vinyl organic siloxane preferably from 1 to 90° from 5 to 75, most preferably from 10 to 65% by weight: and optionally (D) At least one copolymerizable vinylic fluorinated monomer, preferably 1 to 901 preferably 1 to 65%, most preferably 10 to 65% by weight; and optionally (E) At least one acrylic alkanol 1-80, preferably 1-65, most preferably and preferably 20 to 50% by weight. Manufactured by.

To avoid confusion, "acrylic" is used throughout this specification and claims. ``methacrylic'' is also included when referring to It should be noted that when referring to acrylic acid, methacrylic acid is also included.

Amidoacrylics suitable for the practice of this invention have the general formula % [wherein PvG is a compound known in the art, preferably essentially vinyl (CH, -CRI -), Acrylad (CH! = CRI COO-R, -), Acrylamide ( Copolymerization selected from the group consisting of CH*-CRICON Rs-Rs-) RX is H, -CH, Co.

R7 and C1-C, selected from the group of alkyl; R1, R1, R2, R6 and and R2 may be the same or different and may be substituted or unsubstituted, and from the group consisting essentially of H, C, ~C, alkyl, phenyl and cyclohexyl selected]. Preferably, the amidoacrylic is N,N-dialkylmeth Acrylamide, most preferably N,N-dimethylmethacrylamide.

PVG may be styrenyl (CH!-CHCaH1). selected The amidoacrylic is preferably in liquid form under atmospheric conditions.

Vinyl carboxylic acid (hereinafter referred to as VCA) that can be used in the practice of the present invention is general formula PVG'-(A)n [In the formula, pvc' may be the same as or different from the above-mentioned PVG, and has the same definition as above. 1 range, where PVG' is acryloxy (CH, -CR, C00-) Atte is also good; A is an acidic hydrogen group selected from the group of -H and -CO○H; n is an integer of at least l] has. VCA therefore has more than one A group. In this way, VCA is less also one carboxylic acid group (-COOH) and preferably acryloxy and styrene a polymerizable vinyl selected from the group of

Preferably the VCA is essentially methacrylic acid, acrylic acid, itafonic acid, methacryloxybenzoic acid, methacryloxyethanoic acid, and vinyl benzoic acid selected from the group consisting of. The selected VCA is preferably liquid at atmospheric conditions. It's the body shape. VCAs can be used alone or in mixtures. methacrylic acid When using a VCA such as More preferably it is kept below 15% and most preferably below 10%.

Copolymerizable vinyl organosiloxane (hereinafter referred to as C O5) is a liquid and contains polysiloxanyl, one polymerizable atom. It comprises cryl and one group linking these two groups. such a meta The structure of the essential component units of Kryloquine-X-polysiloxane is shown below: [Wherein, X is a group consisting of alkyl, alkenyl, phenyl and cyclohexyl] and may be substituted or unsubstituted: Preferably X is alkylene- (CHz)n (where n is an integer of at least 1, preferably 1 to 1O): a is an integer from 0 to 2, and b is an integer from 0 to 3: each CoS is at least contains one M and the molar ratio of N to M is at least 11, preferably in the range of 1 to 25. ]

Obviously, the desired CO5 may include, without departing from the essence of the invention, e.g. heavy metal groups and bonds. The radicals can be easily converted into other forms. Thus, an essential component of useful CO5 The general formula of the compound can be written as follows: [wherein P is a polymerizable vinyl group, e.g. Vinyl, acrylamide, styrenyl, methacryloxy; chain is A chemically bonded chain that may be straight or branched, but whose length is at least one chemical and each CO8 contains at least one M' and a model of N' and M'. The value of the ratio is at least 1; N' and R# are H1-substituted and unsubstituted alkaline Kyl, alkenyl, cyclohexyl and phenyl, such as -CH,, CF x CF s, CHx COOR-CHs CHx C0N-(ci’1x)z, -CM, OH, etc.; more preferably, the chain is 1 to 12 chemical bonds].

For purposes of this specification, the term molar ratio is based on the exact molecular weight of the copolymer itself. rather than being used as such as in the case of conventional polymers. the molecular weight of the units present in the copolymer or the average molecular weight of the units. It should be noted here that it is used.

The structure of CO5 as defined above can be illustrated as follows: H*C-C(CHs　)Cot-(CHx)s-5i　[-0-5i　(CHs )! -0-S 1(CHs)sl s [wherein, COS is one M group, but a =O5 and six N groups, including three b-2 and three b-3, -N and The molar ratio of M is 6:1].

Methods for producing the desired CO5 are well known in the art, e.g. U.S. Pat. No. 4.12 No. 0,570, No. 4,153.641, No. 3.808.178, No. 4.34 This is the method described in No. 3,927.

A typical example of CoS is 1. Pentamethyldisiloxanyl methyl methacrylate, 2. γ-Methacrylox cypropyltris(pentafluorophenyl)silane, 3.1-methacryloxypropyltris(trimethylsiloxanyl)silane, 4. methacryloxymethyl hebutamethylcyclotetrasiloxane, 5. trimethy Lucilyl methyl methacrylate, 6.1-methacryloxypropyltrimethoxy Silane, acid catalyzed trimethylacetoxysilane, pentamethylacetoxy Reaction products with disiloxane and/or hexamethylacetoxytoxytoxysiloxane (Based on GC analysis, the product contains at least one CO5 with one M group and containing one CoS with two M groups).

Copolymerizable vinylic fluorinated monomers that can be used in the practice of this invention The mass (hereinafter referred to as CMFM) has the general formula % formula % [Wherein, PvG# is vinyl, methacryloxy, methacrylamide, and styrenyl selected from the group consisting essentially of, preferably methacryloxy; is substituted or unsubstituted fluorinated alkyl, cyclohexyl and phenyl selected from the group consisting of ]. Fluorization is carried out by methods known in the art. be able to. The preferred ft CV FM is described in U.S. Patent No. 3,950.315 and No. 3.808.179; Special Publication No. 61-109.756 (Chemical Abst Rakutsu, 105.232482y) and Special Publication No. 59-214.822 (Chemica such as those described in Le Abstracts, 102.226074 p. It is something. A typical example of CVFM is 1.1.1-dihydrofluoropropyl methacrylate, 2.1,1.18-) Lihydrofluorooctadecanyl methacrylate, 3.1.1-bis(pentaf) fluorophenyl) methyl methacrylate, 4, fluorostyrene, 5, trifluoroethyl methacrylate, 6.2,2,3,3,4,4.5.5 , 6.6.7.7-dodecafluoropentyl methacrylate, 7.2-hydroxy-4,4,5,5,6,6,7,7,8,8,9,9,l 0゜11.11.11-hexadecafluoro-10-trifluoromethylunde sil methacrylate, 8.2.2.3.3,4,4.5.5-octafluoropentyl methacrylate , It is. Preferably alkyl is selected from 01-C2°. used in the present invention. Acrylic alkanols that can be used include acryloxyalkanol and acrylamide. selected from the group consisting of doorcanol. In addition, alkanol here is C1-C 4 alcohol. Preferably the acrylic alkanol is 2-acryloxy Tanol, 3-acryloxypropanol and 3-acryloxy-1,2-propanol selected from the group of pandiols.

The novel body fluid or densely mixed system of the present invention has high oxygen permeability, softness and hydrophilicity. The copolymer is modified for stability, long-term body fluid wettability, dehydration resistance, and adhesion resistance. It is about changing. VCA to previous technology U.S. Patent No. 4.343.927 Incorporation into the described copolymer can be used to improve the quality of the material or lenses made from it. Substantially improves body fluid or tear wettability. Such copolymers may be coated with the fluorocarbons of the present invention. If acrylic acrylate and acrylic alkanol are further introduced, protein adhesion resistance can be improved. sex is substantially increased. The introduction of acrylic alkanol into the copolymer is Very I: Substantially improves desired coloration. CF). C.

~C1° alkyl methacrylate, styrene, acrylonitrile and methacrylic At least one copolymerizable property modifier selected from the group consisting of amides 1- Other physical properties of the copolymer of the present invention can be improved by copolymerizing with 30% by weight. Some improvements may be made, such as strength, optical properties, hardness, and surface properties.

The convenience of the copolymers of the present invention is due to the fact that in the material I; 0.1 to 30% by weight, preferably 0.1 to 10% by weight of at least one of Therefore, it can be improved. The crosslinking agent contains at least two polymerizable vinyl or acrylic Contains a ru group. Representative examples of crosslinking monomers that are suitable for the practice of this invention are polyols. dimethacrylates or higher functional polyol methacrylic esters, e.g. , di, tri or tetraethylene glycol dimethacrylate, butylene glycol ludimethacrylate, neopentyl diacrylate, and pentaerythritol Such as triacrylate or tetraacrylate. At least two of the above CO5 containing M groups can also be used as a crosslinker as described herein.

Methods for producing the desired comonomers and the copolymers of the present invention are well known in the art. and are described in particular in the specifications and examples of the references cited above. of the present invention Techniques for manufacturing contact lenses from compositions are also well known in the art. Ru. For example, the copolymers of the comonomer mixtures of the present invention are described in U.S. Pat. No. 4,182.822 or the Examples of No. 4,182.822. can.

The novel copolymer system of the present invention has been successfully developed; provides the desired characteristics of contact lenses. can be provided. This lens has increased oxygen permeability, softness and hydrophilic properties. It also has stability, long-term body fluid or tear wettability, dehydration resistance and adhesion resistance. This The wearing comfort is thus substantially improved.

This lens can be worn continuously for long periods of time. Copolymer is soft type gas permeable It can be processed into a (SGP) lens. Preferably, the water content of this SGP lens is It can be adjusted to 30-75% by weight after watering. That is, the water content is the same as that of the above copolymer. It can be adjusted by adjusting the amounts of (A) and (B). as desired Riko's new copolymer can also be used to make hard-base gas permeable (HGP) lenses. I can do it. Preferably, the water content of the HGP lens of the present invention is the same as that of the above-mentioned comonomer (A). By adjusting the amount of and (B), also adding a certain amount of crosslinking monomer It is thereby adjusted between 1 and 8% by weight. The hydrophilicity and Due to wettability, the softness of the lens surface is increased substantially, so that long-term tear moisture remains properties, water availability and sedimentation resistance. Therefore, the comfort of wearing the lenses and the period of wearing them is substantially improved.

The unique properties of the materials of the invention make them suitable for certain medical applications, such as eye patches for sustained drug release or corneal applications. protection against injury or disease; as a dressing for the treatment of injuries or as a dressing for burns; It is also highly desirable for artificial skin, artificial lung membranes, etc. In these application fields Most of the copolymers of the present invention can be cast into thin films from liquid comonomers. It can be processed into thin films or membranes by known techniques such as. This way Such uses of the copolymers of the invention are also included in preferred embodiments of the invention. It is. A transparent comonomer is required for use in contact lenses: If there isn't, that's not the case.

Best method embodiment 1 for carrying out the method of the present invention This example illustrates a general method for making the copolymers of the present invention.

NNDMA (N,N-dimethylacrylamide) 14 (weight)%, MA (meth) Acrylic acid) 6%, TMPT (1,1,1-trimethylolpropane trimethac lylate) 14% and MPTS [conc. γ-Metal prepared according to Example 15 of U.S. Pat. No. 3,808,178 except that Copolymerization of 66% tacryloxypropyltris(trimethylsiloxane)silane manufactured a body. First, each component was added to 0.2% t-butylperoxyvinyl alcohol according to the composition. Placed in an inert plastic tube with barreto. The composition is then purged with nitrogen. Deoxidized for 10 minutes.

The plastic tube was then placed in a 45°C water bath for 4 hours and then placed in a 95°C oven for 4 hours. There was a time device. The transparent rod was then cut into button shapes and heated at 120°C for 6 hours under high vacuum. Post-processed and hardened. The button was gradually cooled. Lenses made from this copolymer is transparent and I;. The oxygen permeability (in DK units) of this lens is D at a water content of 38%. Compared to polyHEMA with about 8 K units and PMMA hard type lenses with less than 1 K unit, about 60 (cm'/sec/Ozmj!/mj!X+nmHg). This Len The lenses were able to absorb about 4% water compared to about 0.5% for PMMA lenses.

Desirable hydrophilicity and high oxygen permeability of the lens contribute to extended wear of contact lenses. Increased softness and comfort for use.

Example 2 This example demonstrates the functional (body fluid or tear) wettability of the copolymer or lens of the present invention. Illustrating a substantial increase. Furthermore, tear wettability must not only depend on the hydrophilicity of the material. I will also give an example.

The tear wettability of contact lenses in the human eye is defined as the thin film of tears on the lens surface. tear breakup time (BUT) It can be projected. BUT is in tears here! or lens until the film is dispersed Dry I on the surface; flesh from opening individual eyes with lenses until spots appear This is the time monitored visually.

Lenses made from the above copolymer after thorough hydration in physiological saline BUT was approximately 2 minutes in human eye testing. However, the technology of the recent past, i.e. NNDMA20 (1 quantity) as described in National Patent No. 4,343.927 %, the BUT of a lens made from a copolymer of 15% TMPT and 65% MPTS is It took about 0.5 minutes after complete hydration. BUT of the present invention is superior to past technologies The substantial increase, approximately 400% in this example, is the increase in contact lens extension. Lengthened! Highly desirable for two wears. Both lenses have similar water content or hydrophilicity However, the thick miscibility or BUT was dramatically different. Thus, in this embodiment, the lens or that the fluid or thick miscibility of the copolymer depends not only on the hydrophilicity of the material. Also exemplified.

Example 3 This example shows that this lens has functional (body fluid or tear) wettability, dehydration resistance, and adhesion resistance. Figure 3 illustrates the novelty of the present invention, which is shown to be substantially increased.

The lens was made of NNDMA 50% (by weight), MA 5%, MAA (methacrylate) of the present invention. 4% MPT, 41% MPT, and 1% TMPTO. Living After equilibration in physical saline, the lenses were subjected to human eye testing. Part B UT was 2 minutes. This lens was very comfortable on the same tested eye for several weeks. I was able to wear it well. During or at the end of wear, there are no problems with wicking, dehydration. I did not experience any problems, adhesion issues, stability issues. However, the recent technology mentioned above NNDMA55%, MMA (methyl methacrylate) 5% and MPT54 Lenses made from similar compositions with 0% hydrate completely in saline. It was not suitable to be worn all night after use. This problem is solved by the latest technology. Due to the synergistic effect of the relatively poor properties of wettability, dehydration resistance and adhesion resistance of lenses. It was the underlying cause.

Example 4 This example substantially improves the stability, long-term temperature and humidity, dehydration resistance, and adhesion resistance of this lens. 2 illustrates the novelty of the present invention, which increases the novelty of the invention.

The lens was made of NNDMA 24% (by weight), MA 6%, and EGDM (ethylene film) of the present invention. made from a composition of 10% glycol dimethacrylate) and 360% MPT. ;. After saturation in physiological saline, the lenses were subjected to human eye testing. So BUT was approximately 2 minutes. This lens wears very comfortably for about 20 days in a row. I was able to use it. During wear, problems with wettability, dehydration resistance and adhesion resistance are avoided. I didn't experience it. This lens has substantially increased oxygen permeability, approximately 53 DK units, It had softness and hydrophilicity.

! l! Travel example 5 The lens was made of NNDMA of the present invention 39% (by weight), MA 2.2%, MPT546. % and HEMAl I made from a composition of 2.8%; Completely in physiological saline After hydration, the lenses were subjected to human eye testing. It has an excellent UT and And the lens reflects the excellent mixability, dehydration resistance and adhesion resistance of the present invention. I was able to wear it very comfortably for about 30 consecutive days.

Example 6 γ-methacryloxypropyltris(trimethylsiloxy)silane 50 (weight) %, methacrylic*10%, NNDMA40% and TMPTO.

Thin films (approximately 20-50 microns) cast from 1% comonomer compositions are very It is permeable to oxygen, flexible, hydrophilic, and wettable to body fluids, and therefore water-resistant in physiological saline. After the sum, there was compatibility. This film was excellent as a dressing for burns or injuries. Ma The callus membrane not only provides the necessary physiological response, but also provides emotional support to the patient. It also offered comfort and the transparency of the bandage, allowing doctors to see the progression of the disease. Furthermore, this membrane It could also be used as a protective membrane against membrane damage, disease or drug release.

Examples 7 to 26 Some representative compositions of the present invention are shown in Tables 1 and 2.

Table 2 Representative compositions of the present invention*) MN-N,N-dimethyl Methacrylamide, NN-N, N-dimethylacrylamide iMA-Methacryl acid, IA-itaconic acid, HM-HEMA.

sl-γ-methacryloxypropyltris(pentamethyldisiloxanyl)sila N: S2! Trimethylsilylmethyl methacrylate: S3-γ-methacryloxy Reaction product of propyltrimethoxysilane with trimethylacetoxysilane: 5 4-methacryloxymethylhebutamethylcyclotetrasiloxane; S5-penta Methyl dicycloxanyl methyl methacrylate; FPM-1,1-dihydrofur Orglovir methacrylate): MMA-methyl methacrylate; St-styrene , EGDM-ethylene glycol dimethacrylate, TGM-tetraethylene Recall Dimethacrylate: TMPT - As defined herein.

Table ■ Representative compositions containing different fluorinated monomers and acryloxyalkanols , MN%MA, Sl, MMA and TMPT have the same meanings as in Table 2.

Fl ■ Fluorostyrene; F2- Trifluoroethyl methylate; F3-1 ゜1-bis(pentafluorophenyl)methyl methacrylate); F4-1.1゜ 18-trihydrofluorooctadecanyl methacrylate); HP-3-methacrylate Ryloxypropertool; and HG-3-methacryloxy1,2-propanediol Le.

Although the invention has been described above in connection with preferred embodiments, the specific forms mentioned It is not intended that the invention be limited to this embodiment. As defined in the claims below. Covers all such changes, modifications and equivalents as fall within the spirit and scope of the invention. It is intended that

, industrial applicability - The copolymers of the invention are suitable for producing long-wear contact lenses for the correction of vision. It is useful for The copolymer can be used in eye patches, artificial skin for burn or injury dressings, or It should also be very useful for developing artificial membranes for lung organs.

international search report 1mm□ A″”””-PCT10S8B100006

Claims (29)

[Claims] 1. (A) At least one amide acrylic; (B) At least one vinyl carbo (C) Structural formula of essential component unit M, CH2=C(CH3)-CO2-X-(CH3)aSiO3-a/2 and N , (CH3)bSiO4-b/2 [Wherein, X is alkylene-(CH2)n-, where n is an integer from 1 to 10] a is an integer of 0 to 2; and b is an integer of 0 to 3; all molecules contains at least one M group and the molar ratio of N to M is at least 1] (D) at least one methacryloxy-X-polysiloxane having one fluorinated alkyl methacrylate; and (E) at least one acrylic alkanol, provided that the amount of (A) is 1-85% by weight, the amount of (B) is 1-35% by weight, the amount of (C) is 1-90% by weight; The amount of (D) is selected from the range of 1 to 90% by weight, and the amount of (E) is 1 to 80% by weight. selected, and the remainder consists of comonomer (F) and/or (G), where (F) is at least is a copolymerizable vinyl monomer which is a property modifier, and (G) is a crosslinking monomer. A copolymer of comonomers. 2. Claimed to have substantially improved functional wettability, fouling resistance and oxygen permeability. A contact lens made from a copolymer according to scope 1. 3. (A) is N,N-dialkyl methacrylamide and N,N-dialkyl acrylate; selected from lylamide, with the alkyl selected from C1-C2; Tacrylic acid, acrylic acid, itaconic acid, methacryloxybenzoic acid, methacryloxybenzoic acid selected from sietanic acid and vinylbenzoic acid; (C) is a. pentamethyldisiloxanyl methyl methacrylate; b. γ-Methacryloki Cypropyltris(pentamethyldisiloxanyl)silane; c. γ-methacryloxypropyltris(trimethylsiloxanyl)silane; d. methacryloxymethylheptamethylcyclotetrasiloxane; and e. Trimethylacetoxy of γ-methacryloxypropyltrimethoxysilane silane, pentamethylacetoxydisiloxane and/or heptamethylacetoxydisiloxane selected from the group consisting of reaction products with citrisiloxane; is selected from C1 to C20; and (E) is 2-acryloxyethanol, 3 -acryloxypropanol and 3-acryloxy1,2-propanediol selected from the group provided that the amount of (A) is 15 to 65% by weight and the amount of (B) is 1 to 20% by weight amount%, the amount of (C) is 5 to 75% by weight; the amount of (D) is 1 to 65% by weight, and (E) A copolymer according to claim 2, wherein the amount of is selected from 1 to 65% by weight. 4. (B) is selected from methacrylic acid and itaconic acid, and (E) is 2-alcolic acid. Chryloxyethanol; the amount of (A) is 25 to 65% by weight, and the amount of (B) is 1 ~15% by weight, the amount of (C) is 10-65% by weight; the amount of (D) is 10-65% by weight , and the amount of (E) is 20 to 50% by weight, the copolymerization according to claim 3 body. 5. The water content of the lens after complete neutralization in physiological saline is 30-75% by weight A contact lens made from the copolymer of claim 2. 6. In (C), X is substituted or unsubstituted alkyl, cyclohexyl and phenyl. 7. Claim 1, wherein the comonomer comprises (A), (B), (C) and (D). Copolymer according to items 1 to 6. 8. Claims 1 to 6, wherein the comonomer comprises (A), (B) and (C). Copolymers as described. 9. (C) is the next essential component unit M', P-chain-R'aSiO3-a/2 and N', R''bSiO4- b/2; [wherein P is a polymerizable vinyl group; chain is at least one chemical bond] is a linking group for conjugation; every molecule contains at least one M' group; The molar ratio is at least 1; R' and R'' are H, substituted and unsubstituted alkyl selected from the group consisting of kyl, alkenyl, cyclohexyl and phenyl; a is is an integer of 0 to 2, and b is an integer of 0 to 3] at least one copolymerizable vinyl organosiloxane having D) is the general formula PVG'-Y [In the formula, PVG' is vinyl, methacryloxy, methacrylamide, and styrenyl. a copolymerizable vinylic group selected from; and Y is a substituted or unsubstituted fluorinated alkyl, cyclohexyl and phenyl. ]. at least one copolymerizable fluorinated vinyl monomer having Copolymers according to items 1 to 6. 10. Claim 1, wherein the comonomer comprises (A), (B), (C) and (D) Copolymer according to item 9. 11. Claim 9, wherein the comonomer comprises (A), (B) and (C) Copolymer of. 12. Copolymerization according to claim 9, wherein the chains are selected from 1 to 12 chemical bonds. body. 13. In (C), the number of M' groups in each molecule is 1, and the moles of N' and M' are 10. A copolymer according to claim 9, wherein the ratio is at least 1. 14. A burn or injury dressing made from the copolymer according to claim 11. Artificial membrane against. 15. Corneal damage, disease or Protective membrane for the eyes from drug release. 16. Eye patches, artificial skin, burn and injury bandages, and soft contact lenses. can be hydrated to a soft, pliable state suitable for use in the manufacture of gas permeability, hydrophilicity, human tear wettability, dehydration resistance, adhesion resistance and stability. (A) is liquid under atmospheric conditions and has the formula PVG-CONR 2R3 [In the formula, PVG is vinyl (CH2=CR1-), acrylate (CH2=CR1C OO-R2-), acrylamide (CH2=CR1CONR2-R3-), and A copolymer selected from the group consisting of styrenyl (CH2=CH-C6R5-) is a vinyl group with the proviso that R1 is -H, -CH2COOR2 and C1-C6 alkyl group. and R2 and R3 are -H, C1-C6 alkyl, are the same or different members selected from the group consisting of phenyl and cyclohexyl; at least one N,N-disubstituted (meth)acrylamide having 1 to 85 amount%; (B) 1 to 35% by weight of at least one vinyl carboxylic acid; and (C) the following M and and N component unit; M=P-chain-R'aSiO3-a/2 and N=R''SiO4-b/2 [wherein P is a polymerizable vinyl group; chain is at least one chemical bond is a linking group containing R' and R'' are H, alkyl, alkenyl, cyclohexyl selected from the group consisting of sil and phenyl; a is an integer from 0 to 2; b is from 0 to is an integer of 3; and all molecules contain at least one M unit and N and The molecular ratio of M is at least 1] 1 to 90% by weight of at least one polymerizable vinyl polysiloxane containing; and any remaining fluorinated alkyl methacrylate, acrylic 1 selected from the group consisting of lyalkanol, unsaturation modifier and crosslinking monomer A copolymer set is a reaction product of monomers comprising one or more comonomers. A product. 17. Monomer (A) is N,N-dialkyl acrylamide and N,N-dialkyl methacrylamide, where alkyl is methyl or ethyl and monomer (B) is acrylic acid, methacrylic acid, itaconic acid, methacrylic acid Selected from the group consisting of cybenzoic acid, methacryloxyethanoic acid, and vinylbenzoic acid and monomer (C) is a. Pentamethyldisiloxanyl methyl methacrylate b. γ-methacryloxypropyltris (pentamethyldisiloxanyl) Silane; c. γ-methacryloxypropyltris(trimethylsiloxanyl)silane; d. methacryloxymethylheptamethylcyclotetrasiloxane; and e. Trimethylacetoxy of γ-methacryloxypropyltrimethoxysilane silane, pentamethylacetoxydisiloxane and/or heptamethylacetoxydisiloxane selected from the group consisting of reaction products with citrisiloxane; However, monomer (A) is 15 to 65% by weight, monomer (B) is 1 to 20% by weight, and The soft copolymer set according to claim 16, containing 5 to 75% by weight of monomer (C). A product. 18. Monomer (C) has M and N units M=CH2=C(CH3)-CO2-X-(CH3)aSiO3-a/2 and N =(CH3)bSiO4-b/2 [wherein X is a C1-C10 alkylene group] The soft copolymer composition according to claim 16 or 17, which is X-polysiloxane. thing. 19. formula PVG′′-Y [In the formula, PVG'' is vinyl, methacryloxy, methacrylamide, and styrene. Y is selected from the group consisting of alkyl, cyclohexyl and phenyl. is a fluorinated group selected from the group consisting of further comprising 1 to 90% by weight of at least one fluorinated vinyl monomer having The flexible copolymer composition according to claim 16 or 17, comprising: 20. Monomer (D) is a fluorinated alkyl methacrylate, provided that The alkyl has 1 to 20 carbon atoms, and the monomer (D) is in an amount of 10 to 65% by weight. 20. The flexible copolymer composition according to claim 19, which comprises: 21. Contains 1 to 80% by weight of at least one acrylic alkanol monomer (E) The soft copolymer composition according to claim 16 or 17. 22. Monomer (E) is 2-acryloxyethanol, 3-acryloxypropano 3-acryloxy-1,2-propanediol; and the flexible copolymer of claim 21 present in an amount of 20 to 50% by weight. Composition. 23. C1-C20 alkyl methacrylate, styrene, acrylonitrile and a polymerizable surface property modifier selected from the group consisting of methacrylonitrile (F ) 1 to 30% by weight of the soft copolymer according to claim 16 or 17. Coalescing composition. 24. Claim 16 further comprising 0.1 to 30% by weight of crosslinking monomer (G) Or the soft copolymer composition according to item 17. 25. 2-acryloxyethanol as acrylic alkanol monomer (E) 20-50% by weight and at least one C1-C20 fluorinated alkyl methacrylate further comprising 10 to 65% by weight of rate monomer (D), provided that monomer (A) is 2% by weight. 5 to 65% by weight, monomer (B) is present in 1 to 20% by weight, and monomer (B) is present in 1 to 20% by weight; The flexible copolymer according to claim 17, wherein the polymer (C) is present in an amount of 10 to 65% by weight. Composition. 26. made from the composition of claim 16 or 17 and having high gas permeability and affinity. Soft contacts that are water-based, have high tear dispersion time, dehydration resistance, adhesion resistance, and stability. To lens. 27. Contains 30-75% water by weight after complete hydration in physiological saline solution A soft contact lens according to claim 26. 28. A burn and injury treatment prepared from the composition according to claim 16 or 17. Artificial skin membrane for bandages. 29. Corneal damage, eye disease produced from the composition according to claim 16 or 17 Eye protection for disease or drug release.