Silicone-containing composition, silicone hydrogel obtained therefrom, and contact lens containing the silicone hydrogel

Abstract

This application relates to a silicone-containing composition, a silicone hydrogel obtained from the silicone-containing composition, and a contact lens containing the silicone hydrogel. The silicone hydrogel obtained from the silicone-containing composition of this application and the contact lens containing the silicone hydrogel have a desired water content and excellent dimensional stability due to the low rate of expansion that occurs in the hydration process, and also have excellent oxygen permeability.

Description

Technical Field

[0001] The present invention relates to a silicone-containing composition, a silicone hydrogel obtained from the silicone-containing composition, and a contact lens containing the silicone hydrogel.

Background Art

[0002] Generally, contact lenses are manufactured by a casting method using a polypropylene (PP) mold. The contact lens formed into the shape of a lens by the casting process is produced by polymerizing a silicone-containing composition into a silicone gel, and then formed into a silicone hydrogel through a hydration reaction. At this time, expansion occurs during the process of hydrating the silicone gel into a silicone hydrogel. Therefore, since the final dimensions such as the power, diameter, curvature, and thickness of the contact lens are the values after expanding into a hydrogel, the silicone gel must be manufactured using a PP mold in consideration of such expansion.

[0003] The process of expanding the silicone gel into a hydrogel should be predicted as three-dimensional expansion. Therefore, reducing the error in the predicted value in the actual process has an important impact on improving productivity. If the dimensions of the silicone gel and the hydrogel are not predicted correctly, the problem of having to repeat redesign and remanufacture will occur. The hydrogel has spaces between polymer chains and can contain water in these spaces. However, in the hydration process of being hydrated in the state of the silicone gel, it is not easy to expand uniformly in all directions. For this reason, the problem occurs that the shape of the hydrogel does not expand uniformly but becomes elliptical during the process of hydrating the silicone gel. Therefore, in order to solve such problems, it is necessary to use a silicone hydrogel having excellent water content and excellent dimensional stability and oxygen permeability, and a contact lens containing the silicone hydrogel.

Summary of the Invention

Problems to be Solved by the Invention

[0004] The present invention aims to provide a silicone-containing composition having excellent moisture content, and excellent dimensional stability and oxygen permeability, a silicone hydrogel obtained from the silicone-containing composition, and a contact lens containing the silicone hydrogel.

Means for Solving the Problems

[0005] The present invention has been made to achieve the above problems, and the silicone-containing composition according to the present invention contains a silicone macromer and a non-reactive diluent, and the Hansen solubility parameter (HSP) of the silicone macromer is 10.0 MPa 1 / 2 ~20.0 MPa 1 / 2 and is.

[0006] The silicone-containing composition has a dispersion force δD of 13.3 MPa 1 / 2 ~15.0 MPa 1 / 2 and is, the dipole attraction δP is 4.5 MPa 1 / 2 ~6.6 MPa 1 / 2 and is, and the hydrogen bonding force δH may be 6.8 MPa 1 / 2 ~12.0 MPa 1 / 2 and is.

[0007] Further, the silicone-containing composition can have a polymer-solvent interaction coefficient χ of 0.30 to 0.99.

[0008] Further, the silicone-containing composition can have a Gibbs free energy change ΔG of -9×10 23 ~-3.5×10 22 and is.

[0009] Further, the silicone macromer can be represented by the following Chemical Formula 1.

[0010]

Chemical formula

[0011] Furthermore, the non-reactive diluent may be one or more selected from the group consisting of organic acid solvents, alcohol-based solvents, hydrocarbon-based solvents, and ketone-based solvents.

[0012] Furthermore, the non-reactive diluent can be an aliphatic alcohol having 1 to 13 carbon atoms.

[0013] Furthermore, the non-reactive diluent has a molar volume of 20 cm³. 3 / mol~800cm 3 It may also be / mol.

[0014] Furthermore, the non-reactive diluent may be included in an amount greater than 0% by weight and less than 50% by weight.

[0015] Furthermore, the silicone-containing composition may further contain one or more selected from the group consisting of silicone monomers, hydrophilic monomers, hydrophilic additives, amphiphilic polymers, crosslinking agents, UV blocking agents, and initiators.

[0016] Furthermore, the silicone hydrogel of the present invention is obtained by polymerizing a silicone-containing composition and hydrating it.

[0017] Furthermore, the silicone hydrogel can have an expansion coefficient E of 9% or less, as shown in Formula 1 below.

[0018]

number

[0019] Furthermore, the silicone hydrogel may have a water content of 10% or more.

[0020] Furthermore, the silicone hydrogel has an oxygen permeability of 60 × 10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)]~160×10 -11 (cm 2 It can be / s)[mLO2 / (mL·mmHg)].

[0021] Furthermore, the method for producing the silicone hydrogel of the present invention includes a polymerization step of polymerizing the silicone-containing composition and a hydration step of hydrating the polymerized silicone gel.

[0022] Furthermore, during the hydration stage, the non-reactive diluent contained in the silicone gel can be replaced by water through a hydration reaction.

[0023] Furthermore, the contact lens of the present invention contains the silicone hydrogel. [Effects of the Invention]

[0024] The silicone hydrogel obtained from the silicone-containing composition of the present invention, and the contact lens containing the silicone hydrogel, have a desired water content and excellent dimensional stability due to the low expansion rate that occurs during the hydration process, and also have excellent oxygen permeability. [Modes for carrying out the invention]

[0025] The present invention relates to a silicone-containing composition. The silicone-containing composition comprises a silicone macromer and a non-reactive diluent, wherein the Hansen solubility parameter (HSP) of the silicone macromer is 10.0 MPa. 1 / 2 ~20.0 MPa 1 / 2 Specifically, the Hansen solubility parameter of the aforementioned silicone macromer is 11.0 MPa. 1 / 2 ~18.0MPa 1 / 2 or 11.0 MPa 1 / 2 ~16.0MPa 1 / 2 This may also be the case. The silicone-containing composition containing the aforementioned components satisfies the aforementioned range of Hansen solubility parameters of the silicone macromer, and in the process of forming a silicone hydrogel described later through a hydration reaction, it has the desired water content and excellent dimensional stability due to the low expansion rate that occurs in the hydration step, and also has excellent oxygen permeability.

[0026] In this specification, the "Hansen solubility parameter (HSP)" refers to an index indicating the solubility of a substance, specifically how much of it dissolves in another substance. The Hansen solubility parameter is derived from the solubility parameter introduced by Hildebrand, which is divided into three components: dispersion force δD, dipole attraction force δP, and hydrogen bonding force δH, and represented in three-dimensional space. The specific definition and calculation of the Hansen solubility parameter are described in the following literature.

[0027] Charles M. Hansen, *Hansen Solubility Parameters: A Users Handbook* (CRC Press, 2007).

[0028] The dispersion force δD reflects the van der Waals force, the dipole attraction force δP reflects the dipole moment, and the hydrogen bonding force δH reflects the action of water or alcohol, etc. In this case, the Hansen solubility parameter (HSP) of the silicone-containing composition is the sum of the three components and can be calculated by the following formula 2.

[0029]

number

[0030] The Hansen solubility parameters (HSP[δD,δP,δH]) can be easily estimated from their chemical structure, for example, using the computer software Hansen Solubility Parameters in Practice (HSPiP). Specifically, the Hansen solubility parameters can be determined from the chemical structure using the Y-MB method implemented in HSPiP. Furthermore, if the chemical structure is unknown, the Hansen solubility parameters can be determined from the results of dissolution tests using multiple solvents using the sphere method implemented in HSPiP. In this specification, the Hansen solubility parameters are determined by the type of silicone macromer and non-reactive diluent used, as well as their content.

[0031] The Hansen solubility parameter (HSP) of the silicone-containing composition is 15.5 MPa. 1 / 2 ~20.7MPa 1 / 2 , 16.2 MPa 1 / 2 ~20.5MPa 1 / 2 Or 16.3 MPa 1 / 2 ~20.0 MPa 1 / 2The silicone-containing composition may also have a desired water content and excellent dimensional stability due to a low rate of expansion during the hydration process, as the Hansen solubility parameter satisfies the aforementioned range, and has excellent oxygen permeability.

[0032] The aforementioned silicone-containing composition has a dispersion force δD of 13.3 MPa. 1 / 2 ~15.0 MPa 1 / 2 Therefore, the dipole attraction force δP is 4.5 MPa. 1 / 2 ~6.6MPa 1 / 2 Therefore, the hydrogen bonding force δH is 6.8 MPa. 1 / 2 ~12.0MPa 1 / 2 It may also be the case that the silicone-containing composition has a dispersion force δD of 13.5 MPa. 1 / 2 ~14.5 MPa 1 / 2 Therefore, the dipole attraction force δP is 4.8 MPa. 1 / 2 ~6.3MPa 1 / 2 Therefore, the hydrogen bonding force δH is 7.1 MPa. 1 / 2 ~11.5 MPa 1 / 2 The silicone-containing composition satisfies the aforementioned ranges for dispersion force, dipole attraction force, and hydrogen bonding force, thereby having a desired water content, low expansion rate during the hydration process, excellent dimensional stability, and excellent oxygen permeability.

[0033] In one embodiment, the silicone-containing composition has a polymer-solvent interaction coefficient χ of 0.30 to 0.99. Specifically, the silicone-containing composition can have a polymer-solvent interaction coefficient χ of 0.34 to 0.98. By satisfying the above-mentioned range for the polymer-solvent interaction coefficient of the silicone-containing composition, it can have a desired water content during the process of forming a silicone hydrogel via a hydration reaction, and can have excellent dimensional stability due to a low expansion rate during the hydration step, as well as excellent oxygen permeability.

[0034] In this specification, "polymer solvent interaction coefficient" refers to a coefficient indicating the affinity between the silicone macromer contained in the silicone-containing composition and the non-reactive diluent. The polymer solvent interaction coefficient χ of the silicone-containing composition can be calculated using the following formula 3.

[0035]

number

[0036] In another embodiment, the silicone-containing composition has a Gibbs free energy change ΔG of -9 × 10 23 ~-3.5 × 10 22 It can be, specifically, -8.9 × 10 23 ~-3.6 × 10 22 or -8.8 × 10 23 ~-3.7 × 10 22 This can be the case. The silicone-containing composition can improve the morphology of the silicone gel during the polymerization reaction by satisfying the above-mentioned range for the change in Gibbs free energy. For this reason, in the process of forming a silicone hydrogel described later through the hydration reaction, it can have the desired water content and excellent dimensional stability due to the low expansion rate that occurs in the hydration step, and it can have excellent oxygen permeability.

[0037] In this specification, "Gibbs free energy" means the maximum useful energy that a thermodynamic system can release during a reversible process while maintaining a constant temperature and pressure. The change in the Gibbs free energy of the silicone-containing composition can be calculated using the following equation 4, based on the Flory-Huggins solution theory.

[0038]

number

[0039] The aforementioned silicone macromer is a chain that forms the main backbone of a three-dimensional structure, such as a siloxane bond composed of silicon and oxygen. It has functional groups at its ends, which can copolymerize with other monomers to create polymers with a wider molecular weight range. This macromer is a major component of the contact lenses described later. For example, this silicone macromer may have a molecular weight of 500 g / mol to 2000 g / mol. By having the aforementioned molecular weight, the silicone macromer can improve the oxygen permeability, water content, and tensile strength of the silicone hydrogel described later.

[0040] As the aforementioned silicone macromer, a silicone macromer consisting of the following chemical formula 1 can be used in order to improve the oxygen permeability of the silicone hydrogel described later and to obtain the desired water content by appropriate crosslinking.

[0041] [ka] In the above chemical formula 1, n is 5 to 20, R1 is a (meth)acryloyl group, R2 is an alkylene group having 1 to 40 carbon atoms, and the methylene group contained in the alkylene group may be substituted with -O-, -N(R9)- or a carbonyl group, R9 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R3 to R6 are each independently a hydrogen, hydroxyl group, amino group, carboxyl group, halogen atom, or alkyl group having 1 to 3 carbon atoms, and the alkyl group may be substituted with a hydroxyl group, isocyanate group, halogen atom, carboxyl group or alkoxy group having 1 to 8 carbon atoms, R7 is a single bond or an alkylene group having 1 to 30 carbon atoms, and the methylene group contained in the alkylene group may be -O-, -N(R 10 )- or may be substituted with a carbonyl group, R 10 R8 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R8 is a hydrogen atom, a hydroxyl group, an isocyanate group, an amino group, a carboxyl group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a (meth)acryloyl group.

[0042] Furthermore, in the above chemical formula 1, n may be 5 to 15 or 5 to 10.

[0043] The aforementioned R2 may be an alkylene group having 1 to 30 carbon atoms, or an alkylene group having 1 to 25 carbon atoms.

[0044] The alkyl groups R3 to R6 may be methyl or ethyl groups, or they may be methyl groups. Furthermore, the alkoxy group as a substituent on the alkyl group may have 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0045] The aforementioned R7 may be a single bond or an alkylene group having 1 to 20 carbon atoms, or a single bond or an alkylene group having 1 to 15 carbon atoms.

[0046] The alkyl group of R8 may have 1 to 6 carbon atoms. The alkoxy group of R8 may have 1 to 6 carbon atoms, or 1 to 4 carbon atoms.

[0047] The above R9 and R 10 These may each be an alkyl group having 1 to 4 carbon atoms, and may be a methyl group or an ethyl group.

[0048] The non-reactive diluent, while present between polymer chains during the polymerization of the silicone macromer, does not substantially react with the silicone macromer, specifically the components contained in the silicone-containing composition, and plays a role in maintaining a space that can be replaced by water during the hydration reaction. The non-reactive diluent has no reactive groups and does not react with the silicone macromer or the crosslinking agent described later during polymerization and crosslinking reactions, and can remain in its original state. That is, when the non-reactive diluent polymerizes with the silicone macromer, the silicone macromer is formed from polymer chains, and the compatibility between the polymer chains and the non-reactive diluent changes, causing alcohol molecules to accumulate within the polymer chains at the nanometer level, and phase separation occurs between the polymer chains and the non-reactive diluent, creating a space that can be replaced by water. The phase-separated nanometer-sized non-reactive diluent can be extracted by the hydration process, and water can be replaced in its place. During the polymerization process, the morphology formed by the non-reactive diluent maintains its form even after extraction, and the hydration reaction allows the non-reactive diluent to be replaced by water, determining the water content of the silicone hydrogel. In this case, the water content is determined by water displacement in the morphology rather than by expansion of the network due to water absorption, thus allowing for a desired water content. Furthermore, the silicone hydrogel exhibits excellent dimensional stability due to its low expansion rate during the hydration process, and also has excellent oxygen permeability.

[0049] The non-reactive diluent is not particularly limited in type, as long as it does not react with the components contained in the silicone-containing composition, and can be, for example, one or more solvents selected from the group consisting of organic acid solvents, alcohol-based solvents, hydrocarbon-based solvents, and ketone-based solvents.

[0050] As the organic acid solvent, an organic acid solvent having 1 to 16 or 1 to 9 carbon atoms can be used. Specifically, solvents such as formic acid, acetic acid, propionic acid, acrylic acid, propiolic acid, butyric acid, valeric acid, β-hydroxyβ-methyl butyric acid, caproic acid, heptanoic acid, or caprylic acid, or nonanoic acid can be used.

[0051] As the aforementioned alcohol-based solvent, an aliphatic alcohol having 1 to 13 carbon atoms or an aromatic alcohol solvent having 6 to 12 carbon atoms can be used. Specifically, as the aliphatic alcohol (n-aliphatic alcohol) having 1 to 13 carbon atoms, methanol, ethanol, 1-propanol, 2-propanol, isopropyl alcohol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, tripropylene glycol monobutyl ether, ethylene glycol, propylene glycol, or butoxyethanol can be used. Furthermore, specifically, aromatic alcohols having 6 to 12 carbon atoms can be benzyl alcohol, methyl benzyl alcohol, or phenethyl alcohol, etc.

[0052] As the hydrocarbon solvent, an aliphatic hydrocarbon solvent having 1 to 20 carbon atoms, an alicyclic hydrocarbon solvent having 3 to 20 carbon atoms, or an aromatic hydrocarbon solvent having 6 to 20 carbon atoms can be used, for example, benzene or toluene can be used.

[0053] Examples of ketone-based solvents that can be used include acetone or methyl ethyl ketone.

[0054] Specifically, the non-reactive diluent may be an alcohol-based solvent, or an aliphatic alcohol having 1 to 13 carbon atoms. By using the non-reactive diluent, the expansion rate can be further reduced.

[0055] In one embodiment, the non-reactive diluent has a molar volume of 20 cm³. 3 / mol~800cm 3 The amount can be / mol. Specifically, the nonreactive diluent has a molar volume of 20 cm³. 3 / mol~650cm 3 / mol, 30cm³ 3 / mol~500cm 3 / mol, 40cm³ 3 / mol~350cm 3 / mol or 50cm² 3 / mol~200cm 3 The molar volume may be / mol. The non-reactive diluent, by having the aforementioned molar volume, can form the desired morphology, thereby reducing the expansion rate that occurs in the hydration step.

[0056] Furthermore, the non-reactive diluent can be included in the silicone-containing composition in an amount greater than 0% by weight and less than 50% by weight, specifically in an amount of 2% or more by weight, 3% or more by weight, or 5% or more by weight, and preferably in an amount of 48% or less by weight, 45% or less by weight, 43% or less by weight, or 40% or less by weight. By including the non-reactive diluent in the silicone-containing composition in the aforementioned amounts, the silicone-containing composition satisfies preferred numerical ranges for the Hansen solubility parameter, polymer-solvent interaction coefficient, Gibbs free energy change, etc., and as a result, in the process of forming a silicone hydrogel through a hydration reaction, the silicone hydrogel has a desired water content and has excellent dimensional stability due to the low expansion rate that occurs in the hydration step, and has excellent oxygen permeability.

[0057] In one embodiment, the silicone-containing composition may further include, in addition to the silicone macromer, one or more selected from silicone monomers, hydrophilic monomers, hydrophilic additives, amphiphilic polymers, crosslinking agents, ultraviolet blocking agents, and initiators. Here, the initiator may be at least one of a photoinitiator and a thermal initiator.

[0058] Specifically, the silicone monomer is a monomer having a molecular weight of 200 g / mol to less than 500 g / mol, and can be included in the silicone-containing composition to improve the elongation, strength, and elastic modulus of the contact lens described later. For example, as the silicone monomer, methacryloxypropyl-terminated polydimethylsiloxane; 2-propenoic acid, 2-methyl-2-hydroxy-3-3-1,3,3,3-tetramethyl-1-(trimethylsilyl)oxydisiloxanyl-propoxypropyl ester; and / or [tris(trimethylsiloxy)silyl]propyl methacrylate can be used.

[0059] The hydrophilic monomer is a monomer with a molecular weight of 100 g / mol to 800 g / mol and may be included in the silicone-containing composition to improve hydrophilicity and flexibility. For example, 2-hydroxyethyl (meth)acrylate and / or hydroxybutyl (meth)acrylate can be used as the hydrophilic monomer.

[0060] Furthermore, the hydrophilic additive may be included in the silicone-containing composition to increase the wettability and water content of the lens. For example, polyvinylpyrrolidone, N-vinylpyrrolidone, and / or N,N-dimethylacrylamide can be used as the hydrophilic additive.

[0061] Furthermore, the type of amphiphilic polymer is not particularly limited, and any amphiphilic polymer known in the industry can be used without restriction.

[0062] Furthermore, the crosslinking agent may be included in the silicone-containing composition in order to improve strength and elasticity by having monomers bond to each other to form a network structure. For example, triallyl isocyanurate, tetraethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate and / or allyl(meth)acrylate can be used as the crosslinking agent.

[0063] Furthermore, the UV-blocking agent may be included in the silicone-containing composition to prevent ultraviolet rays from directly entering the eyes. For example, the UV-blocking agent may be 2-(4-Benzyoyl-3-hydroxyphenoxy)ethyl acrylate, 2,4-dihydroxybenzophenone, 2-ethylhexyl-trans-4-methoxycinnamate, or 2-hydroxy-4-(methacryloyloxy)benzophenone. You can use substances such as ethacryloyloxy(benzophenone), 2-(2'-Hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole, and 2-[3-(2Hbenzotriazol-2-yl)-4-hydroxyphenyl]ethylmethacrylate.

[0064] Furthermore, the photoinitiator may be included in the silicone-containing composition in order to initiate polymerization in response to light. For example, aromatic α-hydroxyketones, alkoxybenzoin, acetophenone, acylphosphine oxide, tertiary amines and / or diketones can be used as the photoinitiator. Specifically, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (DMBAPO), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819), 2,4,6-trimethylbenzyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoin methyl ester, and / or a combination of camphorquinone and ethyl 4-(N,N-dimethylamino)benzoate can be used as the photoinitiator.

[0065] This application also relates to a silicone hydrogel. The silicone hydrogel is obtained from the silicone-containing composition described above, and details regarding the silicone-containing composition described later are omitted because the same information described for the silicone-containing composition can be applied to them.

[0066] The silicone hydrogel is obtained by polymerizing the silicone-containing composition described above and subjecting it to a hydration reaction. Specifically, during polymerization of the silicone-containing composition, polymer chains are formed, and the compatibility between these polymer chains and the non-reactive diluent changes. As a result, phase separation occurs within the polymer chains, with alcohol molecules gathering at the nanometer level, thereby forming a silicone gel in which spaces for water substitution are provided. Subsequently, the phase-separated nanometer-sized non-reactive diluent is extracted from the silicone gel through a hydration reaction, and water is substituted for it to obtain a silicone hydrogel. The silicone hydrogel maintains its morphology formed by the non-reactive diluent during the polymerization process even after extraction, and because the non-reactive diluent is replaced by water through the hydration reaction, it has a desired water content and excellent dimensional stability due to the low expansion rate that occurs during the hydration process, as well as excellent oxygen permeability. In this specification, the term "silicone gel" refers to the polymer state of the silicone-containing composition after polymerization but before hydration.

[0067] In one embodiment, the silicone hydrogel may have an expansion rate E of 9% or less in the following formula 1, specifically 7% or less, 5% or less, 3% or less, or 1% or less. The lower limit of the expansion rate E of the silicone hydrogel is not particularly limited, as a lower expansion rate in the following formula 1 results in superior dimensional stability.

[0068]

number

[0069] The silicone hydrogel can exhibit excellent dimensional stability because the expansion rate of formula 1 has the aforementioned range. The silicone gel and silicone hydrogel can be polymerized by a mold during the manufacturing process to take the form of a contact lens. Thus, the area of ​​the silicone gel and silicone hydrogel can be calculated using the diameter measured in the polymerized state.

[0070] Furthermore, the silicone hydrogel may have a water content of 10% or more. While there is no particular upper limit, as a higher water content indicates superior water content, it can be, for example, 50% or less, 45% or less, 40% or less, or 35% or less. The silicone hydrogel exhibits superior water content due to its water content being within the aforementioned range.

[0071] Furthermore, the silicone hydrogel has an oxygen permeability of 60 × 10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)]~160×10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)] can be, specifically, 65 × 10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)]~153×10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)] or 70×10 -11 (cm 2 / s)[mLO2 / (mL·mmHg)]~145×10 -11 (cm 2The value can be / s)[mLO2 / (mL·mmHg)]. Because the silicone hydrogel has the aforementioned oxygen permeability, when it is included in the contact lens described later, the amount of oxygen supplied to the cornea of ​​the eyeball increases, resulting in a comfortable fit and the ability to maintain a healthy eyeball. The oxygen permeability can be expressed by the diffusion coefficient D, which is the ability to pass through the silicone hydrogel, and the solubility coefficient k, which indicates the degree to which oxygen dissolves in the silicone hydrogel, and can be measured using the polarographic method in accordance with ISO 18369.

[0072] This application also relates to a method for producing a silicone hydrogel. The method for producing the silicone hydrogel is the same as the method for producing the silicone hydrogel described above, and the details regarding the silicone hydrogel described later will be omitted because the same information described for the silicone hydrogel can be applied to them. The method for producing the silicone hydrogel described above includes a polymerization step and a hydration step. According to the method for producing the silicone hydrogel of the present invention, it is possible to produce a silicone hydrogel that has a desired water content, excellent dimensional stability due to the low expansion rate that occurs in the hydration step, and excellent oxygen permeability.

[0073] The polymerization step involves polymerizing the aforementioned silicone-containing composition to produce a cone gel. For example, the silicone-containing composition can be polymerized by a cast molding method, specifically at a wavelength of 350 nm to 500 nm at 2 mW / cm². 2 ~40mW / cm 2 Polymerization can be achieved by irradiating with ultraviolet light at this illuminance.

[0074] The hydration step is a step in which the silicone gel polymerized in the polymerization step is subjected to a hydration reaction to produce a silicone hydrogel. For example, the hydration step can be carried out by placing the polymerized silicone gel in purified water for 1 to 3 hours to extract residual monomers and replacing the non-reactive diluent with water.

[0075] This application also relates to contact lenses. The contact lenses relate to contact lenses comprising the silicone hydrogel, and the details of the contact lenses described later are omitted because the same information described for the silicone hydrogel can be applied to them.

[0076] The aforementioned contact lens contains a silicone hydrogel. According to the present invention, the contact lens can not only have excellent water content but also excellent dimensional stability.

[0077] In one embodiment, the contact lens may further include a hardware device inserted inside. Specifically, the contact lens is useful for incorporating a hardware device inside due to having the aforementioned physical properties. The hardware device is not particularly limited, but for example, an electronic device or the like can be used.

[0078] If the contact lens has the aforementioned physical properties, it is useful for incorporating hardware devices inside. Specifically, the contact lens containing the silicone hydrogel can be manufactured through a hydration step. The silicone-containing composition forming the lens body of the contact lens generally has the property of expanding during the hydration process, whereas the hardware device incorporated into the contact lens may not expand. In particular, if the expansion rate is not controlled, the expansion rate of the contact lens containing the silicone hydrogel may fall outside the predicted range, and the silicone hydrogel may undergo irregular expansion or distortion during the hydration stage.

[0079] When hardware devices are incorporated into the contact lens, the hardware devices can be incorporated before the hydration stage. Specifically, the hardware devices can be incorporated into the aforementioned silicone-containing composition and polymerized to produce a silicone gel with the hardware devices incorporated. Subsequently, the polymerized silicone gel can be subjected to a hydration reaction to produce a silicone hydrogel with the hardware devices incorporated. In this case, the silicone gel with the hardware devices incorporated is called a dry lens, and the silicone hydrogel with the hardware devices incorporated is called a wet lens. Therefore, if the silicone composition undergoes a hydration process after the polymerization stage with hardware devices such as electronic elements incorporated, the silicone composition expands and deforms as it becomes a silicone hydrogel, and external forces are applied to the hardware devices incorporated within it. At this time, the expansion of the silicone hydrogel can lead to distortion, failure, or a decrease in performance of the hardware devices incorporated inside. Therefore, unless the rate of change in the area, size, thickness, shape, and volume of the contact lens before and after hydration is small, it will be impossible to reduce the defect rate of contact lenses with incorporated hardware and maintain their performance.

[0080] Here, the rate of change in the area, size, thickness, shape, and volume of the contact lens before and after hydration is affected by the expansion rate of the silicone composition, so it is important to control the expansion rate to be below a certain level.

[0081] For example, the contact lens may include a lens body, a protective layer, and hardware components. Specifically, the lens body is the body of the contact lens formed to be wearable on the cornea and may include the silicone hydrogel described above. The protective layer is a layer laminated on the lens body to protect the hardware components and may also include the silicone hydrogel described above. The hardware components may be hardware components such as the electronic elements described above, and may be incorporated between the lens body and the protective layer.

[0082] In one embodiment, the silicone hydrogel may have an expansion coefficient E of 9% or less in the following formula 1.

[0083]

number

[0084] In another embodiment, the contact lens may further contain an ophthalmic drug carried inside it. Specifically, the contact lens is useful for carrying an ophthalmic drug inside it by having the aforementioned physical properties. The ophthalmic drug is not particularly limited, but for example, drugs capable of diagnosing and treating eye diseases can be used.

[0085] This is applicable not only to embodiments in which an ophthalmic drug-carrying device is incorporated into the contact lens, but also to cases where the material of the contact lens directly carries the drug. In other words, if a space for carrying the drug in a silicone gel state is provided in advance, a drug-containing ophthalmic lens can be manufactured without any deformation of volume or shape by filling the space with the drug.

[0086] In one embodiment, after polymerizing the silicone-containing composition, the drug-containing ophthalmic lens can be manufactured through a hydration step in which the polymerized silicone gel is reacted with water and / or the drug, while in the hydration step, some or all of the non-reactive diluent is replaced with the ophthalmic drug.

[0087] For example, the contact lens may include a lens body, a protective layer, and an ophthalmic drug. Specifically, the lens body is the body of a contact lens formed to be wearable on the cornea and may include the silicone hydrogel described above. The protective layer is a layer laminated onto the lens body to protect the hardware device and may also include the silicone hydrogel described above. The ophthalmic drug is the ophthalmic drug described above and may be inserted between the lens body and the protective layer. [Examples]

[0088] The present invention will be described in more detail below with reference to the embodiments of this application, but the scope of the present invention is not limited to the embodiments presented below.

[0089] <Evaluation Method 1> Evaluation of Hansen solubility parameter (HSP), dispersion force (δD), dipole attraction force (δP), and hydrogen bonding force (δH) The Hansen solubility parameter (HSP) of the silicone macromer used in each example was determined by the Y-MB method implemented in HSPiP. The dispersion force δD, dipole attraction force δP, and hydrogen bonding force δH of each silicone-containing composition used in the production of the silicone gel in each example were determined by the sphere method implemented in HSPiP, and then the Hansen solubility parameter (HSP) of the silicone-containing composition was calculated and evaluated using the following formula 2.

[0090]

number

[0091] <Evaluation Method 2> Evaluation of Polymer-Solvent Interaction Coefficient (χ) In each example, the polymer-solvent interaction coefficient χ between the silicone macromer and the non-reactive diluent contained in the respective silicone-containing composition used during the production of the silicone gel was calculated and evaluated using the following formula 3.

[0092]

number

[0093] <Evaluation Method 3> Evaluation of Gibbs Free Energy Change (ΔG) In each example, the change in Gibbs free energy of each silicone-containing composition used in the production of the silicone gel was calculated and evaluated using the following formula 4.

[0094]

number

[0095] <Evaluation Method 4> Evaluation of Expansion Rate (E) The area of ​​the silicone gel and silicone hydrogel produced in each example was measured, and the expansion rate E of the silicone hydrogel was calculated and evaluated using the following formula 1.

[0096]

number

[0097] <Evaluation Method 5> Moisture Content (W H20 )evaluation Water content W of the silicone hydrogel produced in each example H20 The evaluation was performed by calculating using the following formula 5 with gravimetric analysis. In this case, the weight of each silicone hydrogel was measured after removing surface moisture, and then the weight was measured again after drying at 105°C until there was no further change in weight.

[0098]

number

[0099] <Evaluation Method 6> Evaluation of Oxygen Permeability (Dk) The oxygen permeability (Dk) of the silicone hydrogels produced in each example was measured and evaluated using polarographic methods in accordance with ISO-18369.

[0100] (Preparation Example 1) Preparation of Silicone Macromer 1 As a silicone macromer, the Hansen solubility parameter (HSP) is 12.0 MPa. 1 / 2 A silicone macromer 1 with the following chemical formula 2 was prepared.

[0101] [ka] In the above chemical formula 2, a is 3, b is 3, and c is 5, with R1 to R4 being methyl groups and R5 being a butyl group.

[0102] (Preparation Example 2) Preparation of Silicone Macromer 2 As a silicone macromer, the Hansen solubility parameter (HSP) is 13.4 MPa. 1 / 2 A silicone macromer 2 with the following chemical formula 3 was prepared.

[0103] [ka] In the above chemical formula 3, a is 3, b is 7, and R1 to R4 are each methyl groups.

[0104] (Preparation Example 3) Preparation of Silicone Macromer 3 As a silicone macromer, the Hansen solubility parameter (HSP) is 22.5 MPa. 1 / 2 A silicone macromer 3 with the following chemical formula 4 was prepared.

[0105] [ka] In the above chemical formula 4, a is 1, b is 1, and R1 to R4 are each methyl groups.

[0106] (Preparation Example 4) Preparation of Silicone Macromer 4 As a silicone macromer, the Hansen solubility parameter (HSP) is 22.0 MPa. 1 / 2 A silicone macromer 4 with the following chemical formula 5 was prepared.

[0107] [ka] In the above chemical formula 5, a is 1, b is 3, and R1 to R4 are each methyl groups.

[0108] (Preparation Example 5) Preparation of Silicone Macromer 5 As a silicone macromer, the Hansen solubility parameter (HSP) is 7.5 MPa. 1 / 2 A silicone macromer 5 with the following chemical formula 6 was prepared.

[0109] [ka] In the above chemical formula 6, a is 10, b is 22, and R1 to R4 are each methyl groups.

[0110] (Preparation Example 6) Preparation of Silicone Macromer 6 As a silicone macromer, the Hansen solubility parameter (HSP) is 5.1 MPa. 1 / 2 A silicone macromer 6 with the following chemical formula 7 was prepared.

[0111] [ka] In the above chemical formula 7, a is 12, b is 25, and R1 to R4 are each methyl groups.

[0112] (Example 1) Manufacturing of silicone gel After mixing the components shown in Table 1 below, the mixture is placed in a mold and exposed to a wavelength band of 430 nm and a power output of 20 mW / cm². 2 A silicone gel was manufactured by curing under these conditions using a cast molding method.

[0113] [Table 1]

[0114] (Examples 2-8) Manufacturing of silicone gel Each of the silicone gels in Examples 2 to 8 was prepared in the same manner as in Example 1, except that the components shown in Table 2 below were mixed.

[0115] [Table 2]

[0116] (Examples 9-15) Examples 9 to 15 are examples in which the expansion rate, water content, and oxygen permeability of the silicone gel were evaluated in each of the above Examples 1 to 7, and the results are shown in Table 3 below.

[0117] [Table 3]

[0118] (Examples 16 and 17) Examples 16 and 17 are examples in which the expansion rate, water content, and oxygen permeability of the silicone gels produced in Examples 7 and 8 were evaluated, and the results are shown in Table 4 below.

[0119] [Table 4]

[0120] (Examples 18-24) Examples 18 to 24 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attractive force δP, and hydrogen bonding force δH of each silicone-containing composition used in the production of the silicone gel in each of the aforementioned Examples 1 to 7 were evaluated, and the results are shown in Table 5 below.

[0121] [Table 5]

[0122] (Examples 25-28) Manufacturing of silicone gel The silicone gels of Examples 25 to 28 were prepared in the same manner as in Example 1, except that a non-reactive diluent was further added to the silicone gel composition of Example 8 and mixed with the components shown in Table 6 below. The expansion rate and water content of the silicone gels prepared in Examples 25 to 28 were evaluated and compared with the results of the evaluation of the expansion rate and water content of the silicone gel prepared in Example 8, and the results are shown in Table 6 below.

[0123] [Table 6]

[0124] (Examples 29-32) Examples 29 to 32 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attraction force δP, hydrogen bonding force δH, polymer-solvent interaction coefficient χ, and Gibbs free energy change ΔG of each silicone-containing composition used in the production of the silicone gel in each of the aforementioned Examples 25 to 28 were evaluated, and the results are shown in Table 7 below.

[0125] [Table 7]

[0126] (Example 33) Manufacturing of silicone gel The gel of Example 33 was prepared in the same manner as in Example 1, except that the components shown in Table 8 below were mixed.

[0127] [Table 8]

[0128] (Examples 34-37) Manufacturing of silicone gel Each of the silicone gels in Examples 34 to 37 was prepared in the same manner as in Example 1, except that the components shown in Table 9 below were mixed.

[0129] [Table 9]

[0130] (Examples 38-41) Examples 38 to 41 are examples in which the expansion rate, water content, and oxygen permeability of the silicone gels produced in each of the above Examples 33 to 36 were evaluated, and the results are shown in Table 10 below.

[0131] [Table 10]

[0132] (Examples 42 and 43) Examples 42 and 43 are examples in which the expansion rate, water content, and oxygen permeability of the silicone gels produced in Examples 35 and 37 were evaluated, and the results are shown in Table 11 below.

[0133] [Table 11]

[0134] (Examples 44-47) Examples 44 to 47 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attractive force δP, and hydrogen bonding force δH of each silicone-containing composition used in the production of the silicone gel in each of the aforementioned Examples 33 to 36 were evaluated, and the results are shown in Table 12 below.

[0135] [Table 12]

[0136] (Examples 48-50) Manufacturing of silicone gel The silicone gels of Examples 48 to 50 were prepared in the same manner as in Example 1, except that a non-reactive diluent was further added to the silicone gel composition of Example 37 and mixed with the components shown in Table 13 below. The expansion rate and water content of the silicone gels prepared in Examples 48 to 50 were evaluated and compared with the results of the evaluation of the expansion rate and water content of the silicone gel prepared in Example 37, and the results are shown in Table 13 below.

[0137] [Table 13]

[0138] (Examples 51-53) Examples 51 to 53 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attraction force δP, hydrogen bonding force δH, polymer-solvent interaction coefficient χ, and Gibbs free energy change ΔG of each silicone-containing composition used in the production of the silicone gel in each of the aforementioned Examples 48 to 50 were evaluated, and the results are shown in Table 14 below.

[0139] [Table 14]

[0140] (Example 54) Manufacturing of silicone gel The gel of Example 54 was prepared in the same manner as in Example 1, except that a non-reactive diluent was further added to the silicone gel composition of Example 37 and mixed with the components shown in Table 15 below. The expansion rate and water content of the silicone gel prepared in Example 54 were evaluated and compared with the results of evaluating the expansion rate and water content of the silicone gel prepared in Example 37, and the results are shown in Table 15 below.

[0141] [Table 15]

[0142] (Example 55) Example 55 is an example in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attraction force δP, hydrogen bonding force δH, polymer-solvent interaction coefficient χ, and Gibbs free energy change ΔG of the silicone-containing composition used in the production of the silicone gel in Example 54 were evaluated, and the results are shown in Table 16 below.

[0143] [Table 16]

[0144] (Examples 56 and 57) Manufacturing of silicone gel The silicone gels of Examples 56 and 57 were prepared in the same manner as in Example 1, except that a non-reactive diluent was further added to the silicone gel composition of Example 8 and mixed with the components shown in Table 17 below. The expansion rate and water content of the silicone gels prepared in Examples 56 and 57 were evaluated and compared with the results of the evaluation of the expansion rate and water content of the silicone gel prepared in Example 8, and the results are shown in Table 17 below.

[0145] [Table 17]

[0146] (Examples 58 and 59) Examples 58 and 59 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attraction force δP, hydrogen bonding force δH, polymer-solvent interaction coefficient χ, and Gibbs free energy change ΔG of the respective silicone-containing compositions used in the production of the silicone gel in Examples 56 and 57 were evaluated, and the results are shown in Table 18 below.

[0147] [Table 18]

[0148] (Examples 60-63) Manufacturing of silicone gel The silicone gels of Examples 60 to 63 were prepared in the same manner as in Example 33, except that the components shown in Table 19 below were mixed.

[0149] [Table 19]

[0150] (Examples 64-67) Examples 64 to 67 are examples in which the Hansen solubility parameter (HSP), dispersion force δD, dipole attraction force δP, hydrogen bonding force δH, polymer-solvent interaction coefficient χ, and Gibbs free energy change ΔG of each silicone-containing composition used in the production of the silicone gel in each of Examples 60 to 63 were evaluated, and the results are shown in Table 20 below.

[0151] [Table 20]

[0152] (Examples 68-71) Examples 68 to 71 are examples in which the expansion rate, water content, and oxygen permeability of the silicone gels produced in each of the above Examples 60 to 63 were evaluated, and the results are shown in Table 21 below.

[0153] [Table 21]

Claims

1. It comprises a silicone macromer and a non-reactive diluent. The Hansen solubility parameter (HSP) of the aforementioned silicone macromer is 10.0 MPa. １／２ ~20.0 MPa １／２ A silicone-containing composition.

2. Dispersion force δD is 13.3 MPa １／２ ~15.0 MPa １／２ Therefore, the dipole attraction force δP is 4.5 MPa. １／２ ~6.6 MPa １／２ Therefore, the hydrogen bonding force δH is 6.8 MPa. １／２ ~12.0 MPa １／２ The silicone-containing composition according to claim 1.

3. The silicone-containing composition according to claim 1, wherein the polymer-solvent interaction coefficient χ is 0.30 to 0.

99.

4. The silicone-containing composition according to claim 1, wherein the Gibbs free energy change ΔG is from -9×10 ２３ to -3.5×10 ２２ .

5. The silicone-containing composition according to claim 1, wherein the silicone macromer is represented by the following chemical formula 1. 【Chemistry 1】 In the aforementioned chemical formula 1, n is between 5 and 20. R １ This is a (meth)acryloyl group, R ２ This is an alkylene group having 1 to 40 carbon atoms, and the methylene group contained in this alkylene group is -O-, -N(R ９ ) - or may be substituted with a carbonyl group, R ９ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ３ ~R ６ Each of these is independently a hydrogen atom, a hydroxyl group, an amino group, a carboxyl group, a halogen atom, or a C1-C3 alkyl group, and the alkyl group may be substituted with a hydroxyl group, an isocyanate group, a halogen atom, a carboxyl group, or a C1-C8 alkoxy group. R ７ This is a single bond or an alkylene group having 1 to 30 carbon atoms, and the methylene group contained in the alkylene group is -O-, -N(R １０ ) - or may be substituted with a carbonyl group, R １０ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ８ These are hydrogen, a hydroxyl group, an isocyanate group, an amino group, a carboxyl group, a halogen atom, a C1-C8 alkyl group, a C1-C8 alkoxy group, or a (meth)acryloyl group.

6. The silicone-containing composition according to claim 1, wherein the non-reactive diluent is one or more selected from the group consisting of organic acid solvents, alcohol-based solvents, hydrocarbon solvents, and ketone solvents.

7. The silicone-containing composition according to claim 1, wherein the non-reactive diluent is an aliphatic alcohol having 1 to 13 carbon atoms.

8. The aforementioned non-reactive diluent has a molar volume of 20 cm³. ３ / mol~800cm ３ The silicone-containing composition according to claim 1, wherein the amount is / mol.

9. The silicone-containing composition according to claim 1, wherein the non-reactive diluent is contained in an amount greater than 0% by weight and less than 50% by weight.

10. The silicone-containing composition according to claim 1, further comprising one or more selected from the group consisting of silicone monomers, hydrophilic monomers, hydrophilic additives, amphiphilic polymers, crosslinking agents, UV blocking agents, and initiators.

11. A silicone hydrogel obtained by polymerizing and hydrating a silicone-containing composition according to any one of claims 1 to 10.

12. The silicone hydrogel according to claim 11, wherein the expansion rate E of the following formula 1 is 9% or less. [Math 1] In the above formula 1, a is the area of ​​the silicone gel before the hydration reaction, and b is the area of ​​the silicone hydrogel after the hydration reaction.

13. The silicone hydrogel according to claim 11, wherein the water content is 10% or more.

14. Oxygen permeability is 60 x 10 －１１ (cm ２ / s) [mLO ２ / (mL・mmHg)]~160×10 －１１ (cm ２ / s) [mLO ２ The silicone hydrogel according to claim 11, wherein the concentration is [mL・mmHg].

15. A polymerization step of polymerizing the silicone-containing composition according to any one of claims 1 to 10, A hydration step in which the polymerized silicone gel is subjected to a hydration reaction, A method for producing a silicone hydrogel containing [the specified ingredient].

16. The method for producing a silicone hydrogel according to claim 15, wherein in the hydration step, the non-reactive diluent contained in the silicone gel is replaced with water through a hydration reaction.

17. A contact lens comprising the silicone hydrogel described in claim 11.

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