JP7446496B1 - Contact lenses and silicone hydrogel contact lenses - Google Patents

Abstract

A contact lens is provided that includes at least one silicone-containing monomer. A contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, and the weight percent of the extracted hydrophilic leachables relative to the weight of the contact lens is 1.0% to 8.0%. The present invention also provides silicone hydrogel contact lenses. [Selection diagram] None

Description

FIELD OF THE INVENTION The present invention relates to contact lenses, particularly silicone hydrogel contact lenses.

Soft contact lens materials began to be introduced in the 1960s and were originally used as hard contact lenses because soft materials solved the discomfort that was often present when wearing traditional hard contact lenses (RGP lenses). Users who were not adapted can now switch to using soft contact lenses. Therefore, soft contact lenses have become the main choice of current contact lens users.

However, conventional materials used in soft contact lenses (mainly composed of HEMA, commonly known as water gel products) have low oxygen permeability, and generally have a low Dk (oxygen permeability). It is 8-20. As a result, consumers (or users, contact lens wearers) often experience eye redness and corresponding discomfort due to lack of oxygen at the end of the day (wearing for more than 10 hours). Therefore, the main focus of development of materials for contact lenses is to find materials with high oxygen permeability. Around 2000, soft contact lens products containing silicone ingredients began to appear on the market. This is commonly known as a silicone hydrogel contact lens. The oxygen permeability of this lens is typically 40-50 or higher (eg, Johnson & Johnson's Acuvue Advanced product). Since 2010, with economic development and improved consumer health concepts, daily disposable soft contact lens products have begun to be accepted by the market. Compared to long-cycle monthly or yearly disposables, daily disposables have a significant advantage: There is no need to remove and clean the lenses every day, so the lenses can be removed after they have been damaged by cleaning operations. This can prevent eye injuries caused by wearing. Also, serious complications such as keratitis and conjunctivitis caused by bacterial infection caused by incomplete cleaning can be avoided.

The main technical hurdle in silicone hydrogel contact lenses is how to make the lenses sufficiently hydrophilic to avoid wearing discomfort due to the hydrophobic nature of the silicone component, and the industry generally Determine the hydrophilicity of the lens surface. The lens surface is treated using the industry's first plasma technology to reduce the lens surface contact angle. However, this technology requires complicated processing, increases the production cost of the lenses, and is difficult to sell as a daily disposable product. A more successful improvement to further overcome the hydrophilicity of the surface of silicone hydrogels is the addition of polyvinylpyrrolidone (PVP) as an internal wetting agent during the formulation, which can be used for plasma surface treatment. Although complicated processing is avoided, compatibility issues during formulation of PVP and silicone hydrogels require in practice the selection of specific silicone-containing components in combination. At the same time, it is necessary to add large amounts of certain organic solvents to maintain formulation stability and prevent PVP or silicone-containing ingredients from precipitating during formulation. In addition to the above two techniques, researchers have developed a formulation technique that does not require plasma surface treatment and does not require the addition of PVP separately as an internal wetting agent, and also addresses the drawbacks of this formulation technique. Because specific silicone-containing ingredients and specific hydrophilic monomers are required to achieve the desired lens properties, contact lenses are manufactured using stronger hydrophilic molding materials rather than polypropylene (PP). It is necessary to combine it with Therefore, there is a need to further develop a set of technologies that facilitate the mass production of contact lenses that meet consumer needs and are suitable for long-term wear.

The present invention provides contact lenses suitable for long-term wear by consumers and facilitates mass production of contact lenses.

The present invention provides silicone hydrogel contact lenses suitable for long-term wear by consumers and facilitates mass production of silicone hydrogel contact lenses.

In order to achieve the above advantages, one embodiment of the present invention provides a contact lens containing at least one silicone-containing monomer, and performs Soxhlet extraction using methanol as an extraction solvent to extract the extracted hydrophilic The weight percentage of the leachable material relative to the weight of the contact lens is between 1.0% and 8.0%.

To achieve the above advantages, another embodiment of the present invention provides a silicone hydrogel contact lens, comprising a first silicone-containing monomer, a second silicone-containing monomer, and a first hydrophilic monomer. , a second hydrophilic monomer, and a silicon-containing crosslinking agent.

The first silicone-containing monomer includes the following structure;

Among them, A has the following structure:

or has the following structure:

where R ₁ is H or CH ₃ or OSi(CH ₃ ) ₃ , R ₂ is H or CH ₃ or OSi(CH ₃ ) ₃ , and L ₁ is the following structure or a combination thereof:

Here, n1 is 1 to 5, m1 is 1 to 4, m2 is 0 to 1, m3 is 1 to 4, m4 is 0 to 1, m5 is 1 to 4, and m6 is 1 to 4.

the second silicone-containing monomer comprises a first structure or a second structure;
The first structure above:

where a is 0-20: R ₃ is H or CH ₃ or C ₂ H ₅ , R ₄ is H or CH ₃ or OSi(CH ₃ ) ₃ , R ₅ is H or CH ₃ or OSi( _CH3 ) ₃ , and _L2 is the following structure or a combination thereof:

Here, n6 is 1 to 5, n7 is 1 to 5, m7 is 1 to 4, m8 is 0 to 1, m9 is 1 to 4, m10 is 0 to 1, m11 is 1 to 4, m12 is 1 to 4. , m13 is 0 to 1, m14 is 1 to 4, m15 is 1 to 4;
The second structure above:

Here, c is 0 to 20; R ₁₀ is H or CH ₃ or C ₂ H ₅ , R ₁₁ is H or CH ₃ or OSi(CH ₃ ) ₃ , and R ₁₂ is H or _CH3 or OSi( _CH3 ) ₃ , and _L5 is the following structure or a combination thereof: O or NH; _L6 is the following structure or a combination thereof:

Here, n20 is 1 to 5, m34 is 1 to 4, m35 is 0 to 1, m36 is 1 to 4, m37 is 0 to 1, m38 is 1 to 4, and m39 is 1 to 4.

The first hydrophilic monomer contains an N-vinyl group. Further, the second hydrophilic monomer is different from the first hydrophilic monomer.

The silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, and the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is 1.0% to 8.0%. .

Since the present invention is manufactured using the above ingredients and proportions, the contact lenses and silicone hydrogel contact lenses prepared have the advantages of excellent hydrophilicity and suitability for long-term wear by consumers.

In order to make the above and other objects, features and advantages of the present invention clearer and easier to understand, they will be described in detail below with particular reference to embodiments.

One embodiment of the present invention provides a contact lens comprising at least one silicone-containing monomer, the contact lens being subjected to Soxhlet extraction using methanol as the extraction solvent, and the extracted hydrophilic leachables being extracted from the contact lens. The percentage by weight is 1.0% to 8.0%. Specifically, the above contact lens is, for example, a silicone hydrogel contact lens, and includes a first silicone-containing monomer, a second silicone-containing monomer, a first hydrophilic monomer, and a second hydrophilic monomer. It includes a monomer and a silicon-containing crosslinking agent.

The first silicone-containing monomer includes the following structure:

Among them, A has the following structure:

or has the following structure:

where R ₁ is H or CH ₃ or OSi(CH ₃ ) ₃ , R ₂ is H or CH ₃ or OSi(CH ₃ ) ₃ , and L ₁ is the following structure or a combination thereof:

Here, n1 is 1 to 5, m1 is 1 to 4, m2 is 0 to 1, m3 is 1 to 4, m4 is 0 to 1, m5 is 1 to 4, and m6 is 1 to 4.

The second silicone-containing monomer includes the following first structure or second structure:
First structure:

where a is 0 to 20, R ₃ is H or CH ₃ or C ₂ H ₅ , R ₄ is H or CH ₃ or OSi(CH ₃ ) ₃ , and R ₅ is H or CH ₃ or OSi( _CH3 ) ₃ , and _L2 is the following structure or a combination thereof:

Here, n6 is 1 to 5, n7 is 1 to 5, m7 is 1 to 4, m8 is 0 to 1, m9 is 1 to 4, m10 is 0 to 1, m11 is 1 to 4, m12 is 1 to 4. , m13 is 0 to 1, m14 is 1 to 4, m15 is 1 to 4;
Second structure:

Here, c is 0 to 20; R ₁₀ is H or CH ₃ or C ₂ H ₅ , R ₁₁ is H or CH ₃ or OSi(CH ₃ ) ₃ , and R ₁₂ is H or _CH3 or OSi( _CH3 ) ₃ , _L5 is the following structure or a combination thereof: O or NH; _L6 is the following structure or a combination thereof:

Here, n20 is 1 to 5, m34 is 1 to 4, m35 is 0 to 1, m36 is 1 to 4, m37 is 0 to 1, m38 is 1 to 4, and m39 is 1 to 4.

The first hydrophilic monomer contains an N-vinyl group. The second hydrophilic monomer is different from the first hydrophilic monomer.

The silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, and the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is 1.0% to 8.0%.

Lenses are also referred to herein as contact lenses. In addition, the term "lens formulation" (hereinafter simply referred to as a formulation) as used herein means a formulation consisting of a monomer, a crosslinking agent, and an initiator, and in addition to the formulation, other components such as fillers are also included. means added. Fillers will be explained in detail below. "Monomer" is used to refer to a lens formulation that can undergo polymerization by free radical polymerization during the curing process to further form a polymer; monomers generally have a chemical structure. It has an acceptable free radical double bond.

"Silicone monomer" belongs to the scope of monomers and means a chemical structure (-Si-O-) having at least one silicon-oxygen bond, and the silicone-containing monomer in this example is , for example, 3-[Tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS); Terminated polydimethylsiloxane, MPDMS The CAS No. of commonly used monomethacryloxypropyl-terminated polydimethylsiloxane is 146632-07-7. Other silicone-containing monomers used in this example include 2-(Trimethylsiloxy)ethyl methacrylate, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy) ) Methylsilane (3-(3-Methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, abbreviation: SiGMA), (Methacryloxymethyl)bis(trimethylsiloxy)methylsilane ((Methacryloxymethyl)bis(trimethylsiloxy)methylsilane l) bis(trimethylsiloxy)methylsilane), methacryloxymethylphenethyl Tris(trimethylsiloxy)silane (Methacryloxymethylphenethyltris(trimethylsiloxy) silane), O-(methacryloyloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propyl carbamate (O-(methacryloxyethyl)-3- [bis(trimethylsiloxy)methylsilyl] propylcarbamate), 3-[Tris(trimethylsiloxy)silyl]propyl vinyl carbamate. The silicone-containing monomer can be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Gelest, JNC, Shin-Etsu, Pharnocia, Bimax, and the like. Other examples of silicone-containing monomers used in this example include mono-(3-methacryloxy-2-hydroxypropyloxy)propyl-terminated mono-butyl-terminated polydimethylsiloxane ((mono-(3-methacryloxy-2-hydroxypropyloxy) ) propyl terminated, mono-butyl terminated polydimethylsiloxane)), which can be synthesized by referring to the method in US Patent No. 20030162862A1. Other examples of silicone-containing monomers used in this example include monocarbinol terminated polydimethylsiloxane (CAS No: 207308-30-3, MOHPMDS) and 2-isocyanatoethyl methacrylate (2- Isocyanatoethyl methacrylate (IEM) is a urethane ester; the urethane synthesis reaction involves diazabicycloundecene (1,8-Diazabicyclo[5.4.0] undec-7-ene (DBU)). Can be used as a catalyst.

In this example, the first silicone-containing monomer is, for example, 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, O Contains at least one of -(methacryloyloxyethyl)-3-[bis(trimethylsiloxy)methylsilyl]propyl carbamate and 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate.

The second silicone-containing monomer is, for example, monomethacryloxypropyl-terminated polydimethylsiloxane, monomethacryloxypropyl-terminated carbamate polydimethylsiloxane, mono-(3-methacryloxy-2-hydroxypropyloxy)propyl-terminated mono-butyl-terminated polydimethylsiloxane, Contains at least one dimethylsiloxane. Further, the molecular weight of the second silicone-containing monomer can be 350 to 2,500, preferably 500 to 1,500.

The total content of the first silicone-containing monomer and the second silicone-containing monomer is, for example, 15 to 60%, preferably 25 to 45% of the weight of the silicone hydrogel contact lens after removing the filler. occupy

"Hydrophilic monomer" refers to a range of monomers that are relatively hydrophilic in chemical structure. The hydrophilic monomers used in this example include N-vinyl pyrrolidone (NVP), N-Methyl-N-vinylacetamide (MVA), N,N -Dimethylacetamide (DMA), N,N-diethylacrylamide, N-(hydroxymethyl)acrylamide, N-hydroxyethyl acrylamide (N-Hydroxyethyl acrylamide), 2-Hydroxyethyl methacrylate (HEMA), ethylene glycol vinyl ether (EGVE), 1,4-butane Diol vinyl ether (1,4-butanediol vinyl ether, abbreviated as BVE), Di(ethylene glycol) vinyl ether, Hydroxypropyl methacrylate and/or Hydroxyisopropyl methacrylate ), Hydroxybutyl methacrylate (HOBMA), Poly( Poly(propylene ethylene glycol) methacrylate, Poly(ethpropylene glycol) acrylate, Glyceryl methacrylate methacrylate), glycidyl methacrylate, acrylic acid 2 -Hydroxyethyl acrylate, Hydroxypropyl acrylate and/or Hydroxyisopropyl acrylate, 4-Hydroxybutyl acrylate, Glyceride Glyceryl acrylate, N-[tris(hydroxy) N-[Tris(hydroxymethyl)methyl]acrylamide, Methacrylamide, 2-Hydroxypropyl methacrylamide, N-isopropylacrylamide ( N-Isopropylacrylamide), N,N - Includes, but is not limited to, N,N-Diethylacrylamide, N-Ethylacrylamide, 2-Methacryloxyethyl phosphorylcholine, etc. No. In this example, the preferred hydrophilic monomer selection is N-vinylpyrrolidone. A more preferred choice is a combination of N-vinylpyrrolidone (NVP) and 2-hydroxyethyl methacrylate (HEMA). The above-mentioned hydrophilic monomers can generally be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Tokyo Chemical Industry (TCI), Alfa Aesar, and the like.

In this example, the first hydrophilic monomer containing an N-vinyl group is, for example, N-vinylpyrrolidone. Further, the content of N-vinylpyrrolidone is, for example, 40% or more of the weight of the silicone hydrogel contact lens after removing the filler.

In this example, the second hydrophilic monomer includes, for example, at least one of 2-hydroxyethyl methacrylate, ethylene glycol vinyl ether, and 1,4-butanediol vinyl ether.

"UV Blocker" refers to a lens that has a component added to it to block UV wavelength light, and UV blockers commonly used in contact lenses also contain tolerable free radicals due to their chemical structure. It belongs to the monomer range because it has a radical double bond. The UV blocker used in this example is 2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]ethyl methacrylate (2-[3-(2H-Benzotriazol-2-yl)- 4-hydroxyphenyl]ethyl methacrylate (HMEPB), 2-(4-benzoyl-3-hydroxyphenoxy)ethyl acrylate (2-(4-Benzoyl-3-hydroxyphenoxy)ethyl acrylate) . The UV blockers can generally be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Tokyo Chemical Industry (TCI), Alfa Aesar, and the like.

In this embodiment, the contact lens may further include at least one non-silicon-containing crosslinking agent.

"Crosslinking agent" refers to something that can cause a crosslinking reaction when monomers undergo a polymerization reaction, and is used to ensure that the polymer produced by the polymerization reaction has the required crosslinking density. can be provided and the two polymer chains can be reacted to bond to the reticulated polymer. The crosslinking agents can be classified into non-silicon-containing crosslinking agents and silicon-containing crosslinking agents depending on whether they have a silicon-oxygen bond chemical structure (-Si-O-). Examples of the non-silicon crosslinking agent used in this example include ethylene glycol dimethacrylate (EGDMA), di(ethylene glycol) dimethacrylate, and triethylene glycol dimethacrylate. hylene glycol dimethacrylate), tetraethylene glycol dimethacrylate (TEGDMA), ethylene glycol diacrylate, di(ethylene glycol) diacrylate ylene glycol diacrylate), triethylene glycol diacrylate (Triethylene glycol diacrylate), Tetraethylene glycol diacrylate, N,N'-Methylenebis(acrylamide), N,N'-ethylenebis(acrylamide) -Ethylenebis (acrylamide)), N,N'-(1,2-dihydroxyethylene)bisacrylamide (N,N'-(1,2-Dihydroxyethylene)bisacrylamide), Trimethylolpropanetrimethacrylate (Trimethylolpropanetrimet) hacrylate, abbreviated as TEPTMA), N,N'-Hexamethylenebis(methacrylamide), Glycerol trimethacrylate, Polyethylene glycol dimethacrylate methacrylate), polyethylene glycol diacrylate ), mono-2-(Methacryloyloxy)ethyl maleate, Diurethanedimethacrylate, 3-Isopropenyl-α,α-dimethylbenzyl isocyanate enyl -α,α-dimethylbenzylisocyanate) and the like, but are not limited to these. The non-silicon-containing crosslinking agents can generally be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Tokyo Chemical Industry (TCI), Alfa Aesar, and the like.

In this embodiment, the at least one non-silicon-containing crosslinking agent includes, for example, at least one of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and trimethylolpropane trimethacrylate.

The term "silicon-containing crosslinking agent" refers to an agent that belongs to the scope of crosslinking agents and has at least one silicon-oxygen bond chemical structure (-Si-O-), and refers to the silicon-containing crosslinking agent used in this example. Crosslinking agents include, but are not limited to, the following examples: For example, methacryloxypropyl terminated polydimethylsiloxane (DMPDMS) is a commonly used methacryloxypropyl terminated polydimethylsiloxane, CAS No. 58130-03-3. Also by way of example, polyethylene glycol functionalized methacryloxypropyl terminated polydimethylsiloxane containing polyethylene glycol modification has the following structure:

Silicon-containing crosslinkers are used in combination with other crosslinkers to form suitable lens properties. In this example, a silicon-containing crosslinker is used to control the hydrophilic and hydrophobic leachables of the lens. The silicon-containing crosslinking agent can be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Gelest, JNC, Shin-Etsu, Pharnocia, and Bimax. Examples of the silicon-containing crosslinking agent used in this example include 1,3-bis[4-vinyloxycarbonyloxy)butyl]tetramethyldisiloxane. It can be synthesized by referring to the method in US Pat. No. 5,070,215A1. Other examples of silicon-containing crosslinkers used in this example include bis-3-Methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane, Synthesized with reference to the method in patent US20030162862A1, mono-(2,3-Epoxy)propyl ether terminated polydimethylsiloxane was synthesized into epoxypropoxypropyl terminated polydimethylsiloxane. (Epoxypropoxypropyl (terminated polydimethylsiloxane). Other examples of silicon-containing crosslinking agents used in this example include carbinol (hydroxyl) terminated polydimethylsiloxane (DOHPDMS; CAS No. 156327-07-0) and 2- It is a urethane of isocyanatoethyl methacrylate (2-Isocyanatoethyl methacrylate, abbreviated as IEM); -ene, abbreviated as DBU) can be used as a catalyst.

In one embodiment of the invention, the silicon-containing crosslinker includes, for example, the following structure:

where b is 0-20; R ₆ is H or CH ₃ or C ₂ H ₅ , R ₇ is H or CH ₃ or OSi(CH ₃ ) ₃ , and L ₃ has the structure or A combination of them is:

Here, n12 is 1 to 5, n13 is 1 to 5, m16 is 1 to 4, m17 is 0 to 1, m18 is 1 to 4, m19 is 0 to 1, m20 is 1 to 4, m21 is 1 to 4. , m22 is 0 to 1, m23 is 1 to 4, m24 is 1 to 4;
_R8 is the following structure or a combination thereof:

where R ₉ is H or CH ₃ or C ₂ H ₅ and L ₄ is the following structure or a combination thereof:

Here, n18 is 1 to 5, n19 is 1 to 5, m25 is 1 to 4, m26 is 0 to 1, m27 is 1 to 4, m28 is 0 to 1, m29 is 1 to 4, m30 is 1 to 4. , m31 is 0 to 1, m32 is 1 to 4, and m33 is 1 to 4.

In one embodiment of the invention, the silicon-containing crosslinker includes, for example, the following structure:

where d is 0-20; R ₁₃ is H or CH ₃ or C ₂ H ₅ , R ₁₄ is H or CH ₃ or C ₂ H ₅ , and L ₇ is is a combination: O or NH;
_L8 is the following structure or a combination thereof:

Here, n25 is 1 to 5, m40 is 1 to 4, m41 is 0 to 1, m42 is 1 to 4, m43 is 0 to 1, m44 is 1 to 4, and m45 is 1 to 4;
R ₁₅ is the following structure or a combination thereof:

where R ₁₆ is H or CH ₃ or C ₂ H ₅ and L ₉ is the following structure or a combination thereof:

Here, n31 is 1 to 5, m46 is 1 to 4, m47 is 0 to 1, m48 is 1 to 4, m49 is 0 to 1, m50 is 1 to 4, and m51 is 1 to 4.

In one embodiment of the present invention, the silicon-containing crosslinking agent is, for example, methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated carbamate polydimethylsiloxane, methacryloxypropyl-terminated polydimethylsiloxane containing polyethylene glycol modification, 1, Contains at least one of 3-bis[4-vinyloxycarbonyloxy)butyl]tetramethyldisiloxane and bis-3-methacryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane.

The molecular weight of the silicon-containing crosslinking agent is, for example, 3000 or less, preferably 1500 or less, for example 800 or less.

The content of the silicon-containing crosslinking agent is, for example, 0.1 to 6.0%, preferably 0.1 to 3.0% of the weight of the silicone hydrogel contact lens after removing the filler.

"Initiator" is used as a free radical necessary to produce free radical polymerization, and is generally used as a thermal initiator or It can be divided into photoinitiators. Initiators capable of generating free radicals by thermal initiation are thermal initiators, and initiators capable of generating free radicals by photoinitiation are photoinitiators. Photoinitiators used in this example include Irgacure® 1173 (2-Hydroxy-2-methylpropiophenone) and Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide -trimethylbenzoyl) phosphine oxide (abbreviation 819). Other examples include, for example, Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2,2-dimethoxy-2-phenylacetophenone (2,2 -Dimethoxy-2-phenylacetophenone) is used. The thermal initiators used in this example include azobisisobutyronitrile, 4,4'-Azobis(4-cyanovaleric acid), 1,1'-Azobis(cyclohexanecarbonitrile), 2,2'-Azobis(2-methylpropionamidine), 2,2'-Azobis(2-methylpropionamidine) dihydrochloride, 2,2'-Azobis[2-(2-imidazolin-2-yl)propane ]dihydrochloride (2,2'-Azobis[2-(2-imidazolin-2-yl)propane]dihydrochloride), 2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazoline -2-yl]propane} dihydrochloride (2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane} dihydrochloride), 2,2'-Azobis(1 -Imino-1-pyrrolidine-2-methylpropane) dihydrochloride (2,2'-Azobis(1-imino-1-pyrrolidino-2-ethylpropane) dihydrochloride), 2,2'-Azobis{2-methyl-N -[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} (2,2'-Azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide} ), 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide], 2,2'-Azobis[2-methyl-N-(2-hydroxyethyl)propionamide] '-Azobis (4-methoxy-2,4-dimethyl valeronitrile), benzoyl peroxide, etc. are included, Not limited to these. The initiators can generally be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Tokyo Chemical Industry (TCI), Alfa Aesar, and the like.

"Diluent" means a compound that is separately added to a lens formulation that does not have an acceptable free radical double bond to produce free radical polymerization. Refers to the ingredients. Thus, it is a chemical that cannot be polymerized with monomers or crosslinkers or initiators to form further polymers. Although some fillers have the function of chain transfer agents and may extend to some free radical polymerization processes, their chain transfer effects are generally limited to thiols ( In this example, the function of the filler as a chain transfer agent is not taken into consideration, since the filler's function as a chain transfer agent is much lower than that of a true chain transfer agent such as thiol. Fillers are commonly used to aid in the compatibility of the components of lens formulations, and solvent-based compounds are potential filler options. The fillers used in this example include ethanol, isopropyl alcohol (IPA), n-butanol, n-hexanol, and tert- Alcohols such as tert-Amyl alcohol; Esters such as ethyl acetate, butyl acetate, and ethyl lactate; Organic acids such as oleic acid; ethylene Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether , ethylene glycol hexyl ether, ethylene glycol phenyl ether glycol phenyl ether), propylene glycol monomethyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl ether ene glycol monomethyl ether), diethylene glycol ethyl ether (diethylene glycol ethyl ether), diethylene glycol monobutyl ether ( diethylene glycol monobutyl ether), diethylene glycol hexyl ether, dipropylene glycol monomethyl ether , dipropylene glycol propyl ether, dipropylene glycol butyl ether These include, but are not limited to, alcohol ethers such as. The fillers can generally be purchased commercially from chemical manufacturers such as Sigma-Aldrich, Tokyo Chemical Industry (TCI), Alfa Aesar, and the like.

In the implementation sample listed below, the finished lens product is manufactured using the following procedure. First, the specific proportions of monomers, crosslinkers and initiators are quantified and mixed into the lens formulation (or formulation for short) and also the filler in a specific weight % relative to the total weight of the formulation. After mixing with the formulation, it is stirred with nitrogen flow to ensure that the ingredients of the formulation are thoroughly and homogeneously mixed (hereinafter, the formulation with the filler mixed therein will be referred to as the mixed formulation). After the mixed compound is mixed uniformly, the mixed compound is injected into a female mold made from injection molding, and a male mold made from injection molding is pressed with this female mold. do. With the formulation mold composite thus formed, the liquid mixed formulation resides in the space between the male and female molds, followed by a curing process of the formulation mold composite. The technique of making female and male molds by injection molding is a known technique in the industry.

The curing process can use heat curing or light curing. The implementation samples listed below are mainly photocured. The light source used for photocuring may be any of ultraviolet rays, visible light, and far infrared rays. The formulation mold composite undergoes a curing process to become a lens formulation composite, where the lenses in the lens formulation composite are dry lenses (non-hydrated lenses). The lenses in the lens formulation complex are separated from the mold, and the separation method may be by mechanical force or by separating one mold (which may be male or female) from the dry lens first. , then the remaining parts of the lens formulation complex (including the dry lens and the mold part attached to it, which may be male or female) are immersed in a solvent (usually an aqueous solution containing a proportion of an organic solvent). The dry lens absorbs liquid and expands, turning it into a wet lens and separating it from the mold. Once the semi-finished lens (dry lens or wet lens) is separated from the mold, a hydration process can be performed on the semi-finished product.

The purpose of the hydration process is to clean unreacted monomers, crosslinkers, initiators, fillers, and less reactive oligomers in the semi-finished lens, and to avoid excess residue and toxic reactions in the lens product. It is desired to avoid causing irritation or causing irritation to the user when wearing the finished lens product. The hydration process can only be cleaned with water or deionized water, but usually such a hydration process has a relatively weak cleaning ability for silicone hydrogel products and requires a longer hydration process time. Alternatively, it is necessary to increase the hydration temperature to ensure cleaning of semi-finished lenses. A more common hydration process involves, for example, first rapidly swelling the semi-finished lens in an aqueous solution containing a certain proportion of organic solvent, thus accelerating the cleaning, and finally immersing it in water or deionized water. The purpose is to wash away the organic solvent from the semi-finished lens. The author tries to avoid methods that limit the hydration process as much as possible in the samples listed below, but the organic solvent concentration used in the hydration process, different process times, process temperatures, and number of hydrations are affect the characteristics of Optimal hydration steps include cleaning the lens formulation and curing process to ensure that the monomers, crosslinkers, initiators, fillers and low oligomers to be cleaned are washed with as little residue as possible in the finished lens product. It is necessary to adjust accordingly, and at the same time reduce the proportion of hydrophobic leachables and increase the proportion of hydrophilic leachables in the finished lens product.

The wet lens that has gone through the hydration process can be first placed in a buffer solution to equilibrate and then placed into a PP cup containing a buffer solution, or it can be placed directly into a PP cup containing a buffer solution. Equilibration is also possible. After that, the PP cup was sealed with aluminum foil by heat sealing method, thus isolating the lens and buffer solution from contact with the external environment, and preventing bacterial growth in the finished lens product due to separation of the aluminum foil and PP cup during the moist heat sterilization process. To avoid. The pH of the buffer is typically 6.0-8.0 and the osmolarity is typically 270-420 mOsm/kg. The buffer may be a phosphate buffered saline or a borate buffer, and polymers and surfactants or other additives having a wetting effect may optionally be added to the buffer.

Regarding the characterization of the finished lens, the contact angle was measured using a sessile drop method. To measure the water break-up time (WBUT) of a lens, hold the finished lens between tweezers, shake it gently three times, time the time it takes for dry spots to appear on the lens surface, and visually observe the result. Experience has shown that this data has a positive correlation with the tear break-up time (TBUT) of the eye when the lens is actually worn. The water content was measured in accordance with the method proposed in ISO18369-3. The oxygen permeability coefficient was measured according to the polarographic method proposed in ISO18369-4. The method for detecting leachables was based on the Soxhlet extraction method proposed in ISO 18369-4, but in order to more realistically evaluate leachables in lenses, The extraction time was set to 24 hours. When measuring hydrophilic leachables, a polar organic solvent was chosen as the extraction solvent and hydrophilic leachables were measured using methanol as the extraction solvent in the working samples listed below. When measuring hydrophobic leachables, a non-polar organic solvent was selected as the extraction solvent and hydrophobic leachables were measured using n-hexane as the extraction solvent in the working samples listed below. In Soxhlet extraction, 90 finished lenses are extracted using 180 ml of a fixed solvent, and when methanol is used as the extraction solvent, 90 finished lenses are extracted using 142.56 g of methanol (methanol density 0. If n-hexane is used as the extraction solvent, 117.9 g of n-hexane is used to extract 90 finished lenses (n-hexane density: 0.655 g/ml). This corresponds to extracting.

The leachables calculation formula for the working samples herein is defined as follows:

When the silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is, for example, 2.5% to 6%. .5%, preferably 3.0% to 5.0%.

When the silicone hydrogel contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of the extracted hydrophobic leachables relative to the weight of the silicone hydrogel contact lens is, for example, 3.2%. preferably less than 2.2%, more preferably less than 1.5%.

The silicone hydrogel contact lens has a contact angle of 70° or less and a water rupture time (WBUT) of 10 seconds or more.

Implementation sample 1: Lens formulations are blended in the following proportions. SiGMA 10.00%, MPDMS (molecular weight approximately 600-800) 15.01%, HEMA 10.01%, NVP 54.82%, EGVE 7.00%, TEGDMA 1.97%, 819 0.60%, HMEPB 0.59%, the total amount above is 100% including monomer, initiator, crosslinker. In the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are separately added (hereinafter, a mixture of fillers is referred to as a mixed formulation). Stir the mixed formulation for at least 4 hours under nitrogen flow to ensure that the mixed formulation is completely homogeneously mixed. The mixed formulation is injected into a female mold made from injection molding, and a male mold made from injection molding is pressed with this female mold. Thus forming a compound mold complex, the liquid mixed compound resides in the space between the male and female molds. This compound mold composite is cured with a UV lamp with a dominant wavelength of 365 nm, maintaining the ambient temperature between 33° C. and 38° C., and the irradiation time is 60 minutes. The formulation mold composite becomes a lens formulation composite after undergoing a curing process, at which time the lenses in the lens formulation composite are dry lenses (lenses that are not yet hydrated). The male mold of the lens compound complex was removed first, and then the female mold with the dry lens was immersed in a 30% ethanol aqueous solution for more than 2 hours, and after the dry lens absorbed the aqueous solution, it was naturally separated from the female mold. This wet lens is then sequentially subjected to the following hydration steps: immersed in a 50% ethanol aqueous solution for about 1 hour, further immersed in a 75% ethanol aqueous solution for about 1 hour, and then immersed in a 50% ethanol aqueous solution for about 1 hour, and Soak in ethanol aqueous solution for about 30 minutes, then soak in 30% ethanol aqueous solution for 30 minutes, and finally wash 6 times with deionized water (DI Water) for 30 minutes each time to avoid ethanol residue. (replace ionized water). All of the above ethanol concentrations represent volume percent concentrations. The wet lens cleaned with deionized water (DI Water) was placed in phosphate buffered saline to equilibrate, and finally the wet lens was placed in a PP cup of phosphate buffered saline, heat sealed with aluminum foil, and then sterilized. Sterilize with moist heat in a container, then open the aluminum foil after sterilization to obtain a finished lens. The following detections were performed on the completed lens, and the contact angle was 44.59 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 20.2 seconds (measured for 5 completed lenses). The water content was 66.53%, and the oxygen permeability coefficient (Dk) was 55. The finished lens was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated, and the weight percent of the obtained hydrophilic leachable with respect to the weight of the silicone hydrogel contact lens was 1.7%. there were. When the finished lens was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachable was 1.5% based on the weight of the silicone hydrogel contact lens.

Implementation sample 2: Lens formulations are blended in the following proportions. TRIS 15.51%, MPDMS (molecular weight approximately 1000) 17.45%, HEMA 11.63%, NVP 54.29%, EGDMA 0.51%, 819 0.61%, the above total amount is monomer, initiator , 100% including crosslinking agent. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. Stir the mixed formulation for at least 4 hours under nitrogen flow to ensure that the mixed formulation is completely homogeneously mixed. The mixed formulation is injected into a female mold made from injection molding, and a male mold made from injection molding is pressed with this female mold. Thus forming a compound mold complex, the liquid mixed compound resides in the space between the male and female molds. This compound mold composite is cured with a UV lamp with a dominant wavelength of 365 nm, maintaining the ambient temperature between 33° C. and 38° C., and the irradiation time is 60 minutes. The formulation mold composite becomes a lens formulation composite after undergoing a curing process, at which time the lenses in the lens formulation composite are dry lenses (lenses that are not yet hydrated). The male mold of the lens formulation complex was removed first, and then the female mold with the dry lens was immersed in a 25% IPA aqueous solution for more than 2 hours, and after the dry lens absorbed the aqueous solution, it was naturally separated from the female mold. This wet lens is then sequentially subjected to the following hydration steps: immersed in a 50% IPA aqueous solution for about 1 hour, then immersed in a 75% IPA aqueous solution for about 1 hour, and then immersed in a 50% IPA aqueous solution for about 1 hour. Soaked in IPA aqueous solution for about 30 min, then immersed in 25% IPA aqueous solution for 30 min, and finally washed 6 times with deionized water (DI Water) for 30 min each time to avoid IPA residue. (replace ionized water). All of the above IPA concentrations represent volume percent concentrations. The wet lens cleaned with deionized water (DI Water) was placed in phosphate buffered saline to equilibrate, and finally the wet lens was placed in a PP cup of phosphate buffered saline, heat sealed with aluminum foil, and then sterilized. Sterilize with moist heat in a container, then open the aluminum foil after sterilization to obtain a finished lens. The following detections were performed on the completed lens, and the contact angle was 23.53 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 23.4 seconds (measured for 5 completed lenses). The water content was 69.76%, and the oxygen permeability coefficient (Dk) was 64. The finished lens was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 2.4%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.3%.

Implementation sample 3: Lens formulations are blended in the following proportions. TRIS 15.39%, MPDMS (molecular weight approximately 900) 17.32%, HEMA 11.54%, NVP 53.88%, DMPDMS (molecular weight approximately 380-550) 1.26%, 819 0.61%, above The total amount is 100% including monomer, initiator, and crosslinker. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 2. The following detections were performed on the completed lens, and the contact angle was 34.2 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 30.4 seconds (measured for 5 completed lenses). The water content was 70.00%, and the oxygen permeability coefficient (Dk) was 75. The finished lens product was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated, and the weight percentage of the obtained hydrophilic leachable with respect to the weight of the silicone hydrogel contact lens was 2.7%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 0.8%.

Implementation sample 4: Lens formulations are blended in the following proportions. TRIS 15.20%, MPDMS (molecular weight approximately 1000) 17.10%, HEMA 11.40%, NVP 53.21%, DMPDMS (molecular weight approximately 900-1200) 2.49%, 819 0.60%, above The total amount is 100% including monomer, initiator, and crosslinker. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 2. The following detections were performed on the completed lens, and the contact angle was 46.33 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 23.6 seconds (measured for 5 completed lenses). The water content was 67.62%, and the oxygen permeability coefficient (Dk) was 83. The finished lens product was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated. The weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 3.3%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.1%.

Working sample 5: Using the same mixture formulation as working sample 2, the following method was used for the hydration step in the manufacturing method of the finished lens product: soaking in a 50% IPA aqueous solution for about 1 hour, and then adding a new 50% Soaked in IPA aqueous solution for about 1 hour, further immersed in 50% IPA aqueous solution for about 30 minutes, further immersed in 25% IPA aqueous solution, and finally soaked in deionized water for 30 minutes each time to avoid IPA residue. (DI Water) six times (changing deionized water each time). The manufacturing method for the remaining finished lens products is the same as that described in Example 2. The following detection was performed on the completed lens product, and the contact angle was 32.41 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 19.0 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated. The weight percentage of the obtained hydrophilic leachable with respect to the weight of the silicone hydrogel contact lens was 2.8%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.6%.

Working sample 6: Using the same mixture formulation as working sample 3, the following method was used for the hydration step in the manufacturing method of the finished lens product: soaking in a 50% IPA aqueous solution for about 1 hour, and then adding a new 50% Soaked in IPA aqueous solution for about 1 hour, further immersed in 50% IPA aqueous solution for about 30 minutes, further immersed in 25% IPA aqueous solution, and finally soaked in deionized water for 30 minutes each time to avoid IPA residue. (DI Water) six times (changing deionized water each time). The manufacturing method for the remaining finished lens products is the same as that described in Example 2. The following detections were performed on the completed lens, and the contact angle was 30.22 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 27.8 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens product was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 3.2%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.0%.

Working sample 7: Using the same mixture formulation as working sample 4, the following method was used for the hydration step in the manufacturing method of the finished lens product: soaking in a 50% IPA aqueous solution for about 1 hour, and then adding a new 50% Soaked in IPA aqueous solution for about 1 hour, further immersed in 50% IPA aqueous solution for about 30 minutes, further immersed in 25% IPA aqueous solution, and finally soaked in deionized water for 30 minutes each time to avoid IPA residue. (DI Water) six times (changing deionized water each time). The manufacturing method for the remaining finished lens products is the same as that described in Example 2. The following detections were performed on the completed lens, and the contact angle was 33.92 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 23.8 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens product was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 3.1%. there were. When the finished lens was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachable was 0.8% based on the weight of the silicone hydrogel contact lens.

Implementation sample 8: Lens formulations are blended in the following proportions. TRIS 9.98%, MPDMS (molecular weight approximately 900) 15.03%, HEMA 10.01%, NVP 54.80%, BVE 6.98%, TEGDMA 1.49%, DMPDMS (molecular weight approximately 380-550) 0 .50%, 819 0.60%, HMEPB 0.61%, the total amount above is 100%. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 5. The following detections were performed on the completed lens, and the contact angle was 39.75 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 34.8 seconds (measured for 5 completed lenses). The water content was 66.35%, and the oxygen permeability coefficient (Dk) was 69. The finished lens was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 4.7%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 0.6%.

Working sample 9: Using the same mixture formulation as working sample 2, the following method was used for the hydration step in the manufacturing method of the finished lens: soaking in deionized water for about 24 hours, followed by further soaking in deionized water. It was changed and washed repeatedly six times for 30 minutes each time (deionized water was changed each time). The manufacturing method for the remaining finished lens products is the same as that described in Example 2. The following detections were performed on the completed lens, and the contact angle was 30.89 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 24.2 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 6.7%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 3.1%.

Working sample 10: Using the same mixture formulation as working sample 3, the following method was used for the hydration step in the manufacturing method of the finished lens: soaking in deionized water for about 24 hours, followed by further soaking in deionized water. It was changed and washed repeatedly six times for 30 minutes each time (deionized water was changed each time). The manufacturing method for the remaining finished lens products is the same as that described in Example 2. The following detections were performed on the completed lens, and the contact angle was 31.43 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 25.6 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens was subjected to Soxhlet extraction with methanol, and the weight difference before and after the extraction was calculated. The weight percent of the obtained hydrophilic leachable with respect to the weight of the silicone hydrogel contact lens was 4.4%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.3%.

70 g of DOHPDMS with a molecular weight of about 2000 was dissolved in 300 ml of ethyl acetate and stirred in a round bottom flask until completely dissolved, then the round bottom flask was combined with a heating device and a reflux condenser, and the temperature was adjusted to 52 °C. Maintaining equilibrium at ˜59° C., an additional 5.43 g of IEM was added to the reaction (1:1 molar ratio with DOHPDMS) and 0.2 g of DBU was added as a catalyst. After about 20 hours of reaction, the ethyl acetate was discharged in a rotary evaporator and the polydimethylsiloxane having both methacryloxypropyl-terminated and urethane structures, i.e., methacryloxypropyl-terminated carbamate polydimethylsiloxane, abbreviated as DMUPDMS, was prepared. A product molecular weight of approximately 2300 could be obtained.

70 g of MOHPDMS with a molecular weight of about 1000 was dissolved in 300 ml of ethyl acetate and stirred in a round bottom flask until completely dissolved, then the round bottom flask was combined with a heating device and a reflux condenser, and the temperature was adjusted to 52 °C. Maintaining equilibrium at ˜60° C., an additional 10.86 g of IEM was added to the reaction (1:1 molar ratio with MOHPDMS) and 0.25 g of DBU was added as a catalyst. After about 20 hours of reaction, the ethyl acetate was discharged in a rotary evaporator and the polydimethylsiloxane having both monomethacryloxypropyl termination and urethane structure, i.e. monomethacryloxypropyl termination carbamate polydimethylsiloxane, abbreviated as MUPDMS, was prepared. , it was possible to obtain a molecular weight of the product of about 1150.

Implementation sample 11: Lens formulations are blended in the following proportions. SiGMA 21.43%, MUPDMS 21.06%, HEMA 8.67%, NVP 42.04%, DMUPDMS 5.34%, TEPTMA 0.53%, 819 0.30%, 1173 0.63%, above The total amount is 100% including monomer, initiator, and crosslinker. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 2. The following detections were performed on the completed lens, and the contact angle was 34.43 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 18.0 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens product was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 3.6%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 0.9%.

Implementation sample 12: Lens formulations are blended in the following proportions. SiGMA 20.88%, MUPDMS 17.45%, HEMA 10.22%, NVP 46.15%, DMUPDMS 3.69%, TEGDMA 0.62%, 819 0.48%, 1173 0.51%, above The total amount is 100% including monomer, initiator, and crosslinker. For the lens formulation, the above total amount is used as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 2. The following detection was performed on the completed lens product, and the contact angle was 31.88 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 20.4 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated. The weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 3.9%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 0.9%.

Implementation sample 13: Lens formulations are blended in the following proportions. SiGMA 21.09%, MUPDMS 20.45%, HEMA 7.93%, NVP 48.52%, TEGDMA 1.04%, 819 0.46%, 1173 0.51%, the above total amount is monomer, starting It is 100% containing agent and crosslinking agent. The lens formulation uses the above total amount as the denominator of weight %, and 10% hexanol and 10% ethyl acetate are added separately. The method for producing a finished lens product from this mixed formulation is the same as the method for Example 2. The following detections were performed on the completed lens, and the contact angle was 42.56 degrees (average value measured for 5 completed lenses), and the water rupture time (WBUT) was 12.2 seconds (measured for 5 completed lenses). The average value) was obtained. The finished lens product was subjected to Soxhlet extraction with methanol, and the difference in weight before and after the extraction was calculated, and it was found that the weight percent of the obtained hydrophilic leachable relative to the weight of the silicone hydrogel contact lens was 2.2%. there were. When the finished lens product was subjected to Soxhlet extraction using n-hexane, the weight percent of the obtained hydrophobic leachables based on the weight of the silicone hydrogel contact lens was 1.3%.

A total of 10 people wore and scored a total of 8 completed lens lenses from samples 1 to 8. During the manufacturing process, the eight pairs of lenses are separated into male and female types so that the difference in lens size specifications such as diameter, base curve, and sagittal height is within 0.2 mm. The specifications were adjusted in advance to reduce the impact that differences in size specifications between samples would have on judgments of fit. The experiment was conducted over a total of 8 working days, and subjects were asked to record their own scores on each working day, and scoring statistics were provided after the test was completed. Also, on each working day, the subjects participated in a slit lamp examination (belonging to objective scoring) and the tear film breakdown time was recorded by an optometrist. Regarding the self-rating of the wearing of the above 8 sets of sample lenses, the score of sample 8 was the highest, and the scores of samples 2, 3, 4, 6, and 7 were similar and higher than samples 1 and 5. It was somewhat good. To objectively evaluate the fit, tear break-up time (TBUT) was evaluated using a slit lamp. Among them, sample 8 had the best tear film breakdown time, and when the tear film breakdown time was measured within 10 minutes immediately after wearing the lens, a total of 10 people's tear film breakdown time exceeded 18 seconds. ; The tear film breakdown time of the samples 1 to 7 was between 10 and 18 seconds. When the test subjects wore it for more than 6 hours (the experiment was controlled between 6 and 8 hours after wearing it) and measured the tear film breakdown time for the second time, it was found that the tear film breakdown time of sample 8 was still 8. The tear film breakdown time for each of the samples 1-7 was between about 8 and 15 seconds.

Based on the detection results of the above samples and the subsequent try-on comparison experiment, it is possible to determine whether the hydrophilic leachables and hydrophobic leachables in the lens are within an appropriate range or not, allowing users to wear contact lenses for long periods of time. , and it can be seen that the important key is whether or not it is still comfortable.

Since the present invention is manufactured using the above-mentioned components and proportions, the contact lenses thus prepared have an advantage in that they have excellent hydrophilicity and are suitable for consumers to wear for long periods of time.

Although the above-mentioned embodiments of the present invention are disclosed, they are not intended to limit the present invention, and a person having ordinary knowledge in the technical field to which the present invention pertains will understand the spirit and scope of the present invention. Since some changes and modifications are possible without departing from the scope of the invention, the scope of protection of the invention is deemed to be limited by the scope of the claims.

Claims (47)

A contact lens,
comprising at least one silicone-containing monomer, the contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, and the weight percent of the extracted hydrophilic leachable relative to the weight of the contact lens is from 1.0% to be 8.0% ; and
When the contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of the extracted hydrophobic leachables based on the weight of the contact lens is less than 3.2%. Yes, contact lenses. The silicone-containing monomer is 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, O-(methacryloyloxyethyl)-3-[ The contact lens according to claim 1, comprising at least one of bis(trimethylsiloxy)methylsilyl]propyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate. The silicone-containing monomer is at least one of monomethacryloxypropyl-terminated polydimethylsiloxane, monomethacryloxypropyl-terminated carbamate polydimethylsiloxane, and mono-(3-methacryloxy-2-hydroxypropyloxy)propyl-terminated mono-butyl-terminated polydimethylsiloxane. The contact lens of claim 1, comprising: A contact lens according to claim 1, comprising N-vinylpyrrolidone. The contact lens according to claim 4, wherein the contact lens further includes a filler, and the content of the N-vinylpyrrolidone accounts for 40% or more of the weight of the contact lens after removing the filler. 2. The contact lens of claim 1, further comprising at least one silicon-containing crosslinker. The at least one silicon-containing crosslinking agent is methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated carbamate polydimethylsiloxane, methacryloxypropyl-terminated polydimethylsiloxane containing polyethylene glycol modification, 1,3-bis[4- 7. The contact lens according to claim 6, comprising at least one of vinyloxycarbonyloxy)butyl]tetramethyldisiloxane, bis-3-methacryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane. 8. The contact lens according to claim 7, wherein each of the at least one silicon-containing crosslinking agent has a molecular weight of 3000 or less. 8. The contact lens of claim 7, wherein each of the at least one silicon-containing crosslinking agent has a molecular weight of 1500 or less. 8. The contact lens of claim 7, wherein each of the at least one silicon-containing crosslinking agent has a molecular weight of 800 or less. The contact lens further comprises a filler, and the content of the at least one silicon-containing crosslinker accounts for 0.1% to 6.0% of the weight of the contact lens after removing the filler. The contact lens according to claim 7. Claim: The contact lens further comprises a filler, and the content of at least one silicon-containing crosslinker accounts for 0.1% to 3.0% of the weight of the contact lens after removing the filler. Contact lens according to item 7. The contact lens of claim 1, wherein the contact lens further comprises at least one non-silicon-containing crosslinker. 14. The contact lens of claim 13, wherein the at least one non-silicon-containing crosslinker comprises at least one of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate. The contact lens further includes a first hydrophilic monomer, at least one second hydrophilic monomer, and a filler, the first hydrophilic monomer being N-vinylpyrrolidone, the content of which is The contact lens of claim 1, wherein the filler accounts for 40% or more of the weight of the contact lens after removal. 16. The contact lens of claim 15, wherein the at least one second hydrophilic monomer comprises at least one of hydroxyethyl methacrylate, ethylene glycol vinyl ether, 1,4-butanediol vinyl ether. When the contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, the weight percent of the extracted hydrophilic leachables relative to the weight of the contact lens is 2.5% to 6.5%. The contact lens according to claim 1, characterized in that: When the contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, the weight percent of the extracted hydrophilic leachables relative to the weight of the contact lens is 3.0% to 5.0%. The contact lens according to claim 1, characterized in that: When the contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of the extracted hydrophobic leachables based on the weight of the contact lens is less than 2.2%. The contact lens according to claim 1. When the contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of the extracted hydrophobic leachables based on the weight of the contact lens is less than 1.5%. The contact lens according to claim 1. The contact lens according to claim 1, wherein the contact angle of the contact lens is 70 degrees or less, and the water rupture time (WBUT) is 10 seconds or more. A silicone hydrogel contact lens comprising a first silicone-containing monomer, a second silicone-containing monomer, a first hydrophilic monomer, a second hydrophilic monomer, and a silicon-containing crosslinker,
The first silicone-containing monomer has the following structure;

Among them, A has the following structure:

or has the following structure:

; where R ₁ is H or CH ₃ or OSi(CH ₃ ) ₃ ; R ₂ is H or CH ₃ or OSi(CH ₃ ) ₃ ; and L ₁ is the following structure or a combination thereof: :

Here, n1 is 1 to 5, m1 is 1 to 4, m2 is 0 to 1, m3 is 1 to 4, m4 is 0 to 1, m5 is 1 to 4, and m6 is 1 to 4;
the second silicone-containing monomer includes a first structure or a second structure;
Said first structure:


where a is 0-20; R ₃ is H or CH ₃ or C ₂ H ₅ , R ₄ is H or CH ₃ or OSi(CH ₃ ) ₃ and R ₅ is H or CH ₃ or OSi( _CH3 ) ₃ , and _L2 is the following structure or a combination thereof:

Here, n6 is 1 to 5, n7 is 1 to 5, m7 is 1 to 4, m8 is 0 to 1, m9 is 1 to 4, m10 is 0 to 1, m11 is 1 to 4, m12 is 1 to 4. , m13 is 0 to 1, m14 is 1 to 4, m15 is 1 to 4;
Said second structure:


Here, c is 0 to 20; R ₁₀ is H or CH ₃ or C ₂ H ₅ , R ₁₁ is H or CH ₃ or OSi(CH ₃ ) ₃ , and R ₁₂ is H or _CH3 or OSi( _CH3 ) ₃ , _L5 is the following structure or a combination thereof: O or NH; _L6 is the following structure or a combination thereof:

Here, n20 is 1 to 5, m34 is 1 to 4, m35 is 0 to 1, m36 is 1 to 4, m37 is 0 to 1, m38 is 1 to 4, and m39 is 1 to 4;
the first hydrophilic monomer includes an N-vinyl group;
the second hydrophilic monomer is different from the first hydrophilic monomer;
The silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, and the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is 1.0% to 8.0%. A silicone hydrogel contact lens characterized by: The first silicone-containing monomer is 3-[tris(trimethylsiloxy)silyl]propyl methacrylate, (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, O-(methacryloyloxyethyl)- 23. The silicone hydrogel contact lens of claim 22 , comprising at least one of 3-[bis(trimethylsiloxy)methylsilyl]propyl carbamate, 3-[tris(trimethylsiloxy)silyl]propyl vinyl carbamate. The second silicone-containing monomer is monomethacryloxypropyl-terminated polydimethylsiloxane, monomethacryloxypropyl-terminated carbamate polydimethylsiloxane, mono-(3-methacryloxy-2-hydroxypropyloxy)propyl-terminated mono-butyl-terminated polydimethylsiloxane. 23. The silicone hydrogel contact lens of claim 22 , comprising at least one of: 25. The silicone hydrogel contact lens of claim 24 , wherein the second silicone-containing monomer has a molecular weight of 350 to 2,500. 25. The silicone hydrogel contact lens of claim 24 , wherein the second silicone-containing monomer has a molecular weight of 500 to 1,500. The silicone hydrogel contact lens further includes a filler, and the total content of the first silicone-containing monomer and the second silicone-containing monomer is the weight of the silicone hydrogel contact lens after removing the filler. The silicone hydrogel contact lens according to claim 22 , wherein the silicone hydrogel contact lens accounts for 15-60% of the total amount of the contact lens. The silicone hydrogel contact lens further includes a filler, and the total content of the first silicone-containing monomer and the second silicone-containing monomer is the weight of the silicone hydrogel contact lens after removing the filler. 23. The silicone hydrogel contact lens according to claim 22 , comprising 25-45% of the silicone hydrogel contact lens. 23. The silicone hydrogel contact lens of claim 22 , wherein the first hydrophilic monomer containing an N-vinyl group is N-vinylpyrrolidone. 30. The silicone hydrogel contact lens further comprises a filler, and the content of N-vinylpyrrolidone accounts for 40% or more of the weight of the silicone hydrogel contact lens after removing the filler. Silicone hydrogel contact lenses as described. 23. The silicone hydrogel contact lens of claim 22 , wherein the second hydrophilic monomer comprises at least one of hydroxyethyl methacrylate, ethylene glycol vinyl ether, and 1,4-butanediol vinyl ether. 23. The silicone hydrogel contact lens of claim 22 , wherein the silicon-containing crosslinker comprises the following structure:


where b is 0-20; R ₆ is H or CH ₃ or C ₂ H ₅ , R ₇ is H or CH ₃ or OSi(CH ₃ ) ₃ , and L ₃ has the structure or A combination of them is:

Here, n12 is 1 to 5, n13 is 1 to 5, m16 is 1 to 4, m17 is 0 to 1, m18 is 1 to 4, m19 is 0 to 1, m20 is 1 to 4, m21 is 1 to 4. , m22 is 0-1, m23 is 1-4, m24 is 1-4; R ₈ is the following structure or a combination thereof:

where R ₉ is H or CH ₃ or C ₂ H ₅ and L ₄ is the following structure or a combination thereof:

Here, n18 is 1 to 5, n19 is 1 to 5, m25 is 1 to 4, m26 is 0 to 1, m27 is 1 to 4, m28 is 0 to 1, m29 is 1 to 4, m30 is 1 to 4. , m31 is 0 to 1, m32 is 1 to 4, and m33 is 1 to 4. 23. The silicone hydrogel contact lens of claim 22 , wherein the silicon-containing crosslinker comprises the following structure:

where d is 0-20; R ₁₃ is H or CH ₃ or C ₂ H ₅ , R ₁₄ is H or CH ₃ or C ₂ H ₅ , and L ₇ is is a combination: O or NH;
_L8 is the following structure or a combination thereof:

Here, n25 is 1 to 5, m40 is 1 to 4, m41 is 0 to 1, m42 is 1 to 4, m43 is 0 to 1, m44 is 1 to 4, and m45 is 1 to 4;
R ₁₅ is the following structure or a combination thereof:

where R ₁₆ is H or CH ₃ or C ₂ H ₅ and L ₉ is the following structure or a combination thereof:

Here, n31 is 1 to 5, m46 is 1 to 4, m47 is 0 to 1, m48 is 1 to 4, m49 is 0 to 1, m50 is 1 to 4, and m51 is 1 to 4. The silicon-containing crosslinking agent is methacryloxypropyl-terminated polydimethylsiloxane, methacryloxypropyl-terminated carbamate polydimethylsiloxane, methacryloxypropyl-terminated polydimethylsiloxane containing polyethylene glycol modification, 1,3-bis[4-vinyloxycarbonyloxy ) butyl]tetramethyldisiloxane, bis-3-methacryloxy-2-hydroxypropyloxypropylpolydimethylsiloxane, according to claim 22 . 34. The silicone hydrogel contact lens of claim 33 , wherein the silicon-containing crosslinker has a molecular weight of 3000 or less. 34. The silicone hydrogel contact lens of claim 33 , wherein the silicon-containing crosslinker has a molecular weight of 1500 or less. 34. The silicone hydrogel contact lens of claim 33 , wherein the silicon-containing crosslinker has a molecular weight of 800 or less. The silicone hydrogel contact lens further includes a filler, and the content of the silicon-containing crosslinker accounts for 0.1 to 6.0% of the weight of the silicone hydrogel contact lens after removing the filler. 34. The silicone hydrogel contact lens of claim 33 . The silicone hydrogel contact lens further includes a filler, and the content of the silicon-containing crosslinking agent accounts for 0.1 to 3.0% of the weight of the silicone hydrogel contact lens after removing the filler. 34. The silicone hydrogel contact lens of claim 33 . 23. The silicone hydrogel contact lens of claim 22 , wherein the silicone hydrogel contact lens further comprises at least one non-silicon-containing crosslinker. 41. The silicone hydrogel of claim 40 , wherein the at least one non-silicon-containing crosslinker comprises at least one of ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate. contact lens. When the silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is 2.5% to 6. 23. A silicone hydrogel contact lens according to claim 22 , characterized in that it is 5%. When the silicone hydrogel contact lens is subjected to Soxhlet extraction using methanol as an extraction solvent, the weight percent of the extracted hydrophilic leachables relative to the weight of the silicone hydrogel contact lens is 3.0% to 5.0%. 23. The silicone hydrogel contact lens of claim 22 , wherein the silicone hydrogel contact lens is 0%. When the silicone hydrogel contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of extracted hydrophobic leachables based on the weight of the silicone hydrogel contact lens is less than 3.2%. 23. The silicone hydrogel contact lens according to claim 22 . When the silicone hydrogel contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of extracted hydrophobic leachables based on the weight of the silicone hydrogel contact lens is less than 2.2%. 23. The silicone hydrogel contact lens according to claim 22 . When the silicone hydrogel contact lens is subjected to Soxhlet extraction using n-hexane as an extraction solvent, the weight percent of the extracted hydrophobic leachables based on the weight of the silicone hydrogel contact lens is less than 1.5%. 23. The silicone hydrogel contact lens of claim 22 . The silicone hydrogel contact lens according to claim 22 , wherein the silicone hydrogel contact lens has a contact angle of 70° or less and a water rupture time (WBUT) of 10 seconds or more.