Double-terminal (METH)acrylic-modified silicone macromer having tertiary amino group or quaternary ammonium cation site in molecular chain, and method for producing same

Abstract

PROBLEM: To provide a silicone macromer having a high proportion of a (meth)acrylic group at both terminals, and having a quaternary ammonium cation site in a molecular chain. SOLUTION: The present invention provides a double-terminal (meth)acrylic-modified silicone macromer represented by general formula (1) and having a tertiary amino group in a molecular chain. The present invention further provides a double-terminal (meth)acrylic-modified silicone macromer represented by general formula (4) and having a quaternary ammonium cation site in a molecular chain. (In general formulas (1) and (4): each R is independently a group selected from a C1-10 alkyl group, a C6-10 aryl group, and a C7-10 aralkyl group; each R1 is independently a group selected from a C1-10 alkyl group, a C6-10 aryl group, and a C7-10 aralkyl group; each R2 is independently a C1-10 alkyl group, a 2-hydroxyethyl group, a C6-10 aryl group, and a C7-10 aralkyl group; each X is independently a hydrogen atom or a methyl group; Q is a divalent organic group; each a is independently an integer of 1-400, b is an integer of 1-50, and each n1 is independently an integer of 2-10; and Y is a chlorine atom, a bromine atom or an iodine atom.)

Description

(Meth)acrylic-modified silicone macromer at both ends having tertiary amino groups or quaternary ammonium cation moieties in the molecular chain and method for producing the same

[0001] The present invention relates to a (meth)acrylic-modified silicone macromer at both ends that has a tertiary amino group or a quaternary ammonium cation moiety in the molecular chain, and a method for producing the same.

[0002] Silicone is widely used as a contact lens material due to its high oxygen permeability. However, because silicone is hydrophobic, the introduction of hydrophilic groups has been investigated to hydrophilize the contact lens surface. Among these, the introduction of quaternary ammonium cation moieties into silicone chains has been reported (Patent Documents 1 to 4). In particular, Patent Document 1 describes a method for synthesizing a silicone macromer having polymerizable groups at both ends and a quaternary ammonium cation moiety in the molecular chain.

[0003] Special Table No. 2009-542855 Publication Special Publication No. 2009-533532 Publication Special Publication No. 2010-516873 Publication Special Publication No. 2009-521547

[0004] However, the manufacturing method described in Patent Document 1 is presumed to contain a certain amount of silicone without polymerizable groups as an impurity. It is generally undesirable for silicones used as contact lens materials to contain a large amount of compounds without polymerizable groups. Therefore, it is desirable to establish a manufacturing method for silicone macromers containing quaternary ammonium cation moieties in the molecular chain, which allows for the introduction of a high proportion of (meth)acrylic groups at both ends.

[0005] An object of the present invention is to provide a silicone macromer having a high proportion of (meth)acrylic groups at both ends and a quaternary ammonium cation moiety in the molecular chain.

[0006] As a result of extensive research conducted by the present inventors in order to achieve the above-mentioned object, they discovered that by reacting an organopolysiloxane having hydroxy groups or secondary amino groups at both terminals and tertiary amino groups in the molecular chain with an isocyanate having a (meth)acrylic group, followed by conversion to a quaternary ammonium group, it is possible to obtain a silicone macromer having a high proportion of (meth)acrylic groups at both terminals and having a quaternary ammonium cation moiety in the molecular chain, thereby completing the present invention.

[0007] That is, the present invention provides a (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain, represented by the following general formula (1). (In general formula (1), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; each X is independently a hydrogen atom or a methyl group; Q is a divalent organic group; each a is independently an integer of 1 to 400; each b is an integer of 1 to 50; and each n1 is independently an integer of 2 to 10.

[0008] Preferably, the (meth)acrylic-modified silicone macromer at both ends further satisfies the following constituent requirement [1]: [1] A (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain, wherein in the general formula (1), each Q is independently a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

[0009] The present invention further provides a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain, represented by the following general formula (4): (In general formula (4), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X are each independently a hydrogen atom or a methyl group; Q is a divalent organic group; a are each independently an integer of 1 to 400, b is an integer of 1 to 50, n1 are each independently an integer of 2 to 10; and Y is a chlorine atom, bromine atom, or iodine atom.

[0010] Preferably, the above-mentioned (meth)acrylic-modified silicone macromer at both ends further satisfies the constituent requirement [1] below: [1] A (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain, wherein in the above-mentioned general formula (4), each Q is independently a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

[0011] The present invention further provides a method for producing a (meth)acrylic-modified silicone macromer at both ends having a tertiary amine in the molecular chain, represented by the following general formula (1): (In general formula (1), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; each X is independently a hydrogen atom or a methyl group; each Q is a divalent organic group; each a is independently an integer of 1 to 400, each b is an integer of 1 to 50, and each n1 is independently an integer of 2 to 10. The present invention provides a method for producing a silicone macromer as described above, characterized by comprising the step of reacting an organopolysiloxane (A) having a tertiary amino group in the molecular chain, as represented by the following general formula (7), with an isocyanate (B) having a (meth)acrylic group, as represented by the following general formula (10), to obtain a silicone macromer modified at both ends with (meth)acrylic acid, as represented by the above general formula (1). (In formula (7), R, R １ , a, and b are as defined above, and Q １ is a group represented by the following formula (8) or (9): (In formula (8), n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (9), R １ is as above) (In the general formula (10), X and n1 are as defined above).

[0012] Preferably, the method for producing a (meth)acrylic-modified silicone macromer at both ends having a tertiary amine in the molecular chain, represented by the above general formula (1), further has at least one of the following constituent elements [1], [2], and [3]: [1] In the above general formula (1), each Q is independently a group represented by the following formula (2) or the following formula (3), (In formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and n2 and n3 are as defined above.) (In formula (3), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and R １is as described above.) [2] The aforementioned production method further comprises the step of reacting an organopolysiloxane having a hydrosilyl group at at least one terminal and a tertiary amino group in the molecular chain with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain organopolysiloxane (A) having tertiary amino groups in the molecular chain represented by the above general formula (7). [3] The aforementioned production method further comprises the step of reacting an organohydrogenpolysiloxane modified with hydrosilyl groups at both terminals with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain the organopolysiloxane described in [2] above having hydrosilyl groups at the terminals and tertiary amino groups in the molecular chain.

[0013] The present invention further provides a method for producing a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain, represented by the following general formula (4): (In general formula (4), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; each X is independently a hydrogen atom or a methyl group; each Q is a divalent organic group; each a is independently an integer of 1 to 400, each b is an integer of 1 to 50, each n1 is independently an integer of 2 to 10; and Y is a chlorine atom, bromine atom, or iodine atom. The present invention provides a method for producing a silicone macromer (a) having a tertiary amino group in the molecular chain, represented by the following general formula (1), reacting it with a halogenated hydrocarbon (b) represented by the following formula (14), to obtain a silicone macromer (a) having a tertiary amino group in the molecular chain, represented by the following general formula (1), with a halogenated hydrocarbon (b) represented by the following formula (14): (In general formula (1), R, R １ , X, Q, a, b, and n1 are as described above) (In formula (14), R ２ is as defined above, and Y is a chlorine atom, a bromine atom, or an iodine atom).

[0014] Preferably, the method for producing a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain, represented by the above general formula (4), further satisfies at least one of the following constituent elements [1] to [5]: [1] The above method, in which in the above general formulas (1) and (4), Q is a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, n2's are each independently an integer from 2 to 10, and n3's are each independently an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and R １ are each independently selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. [2] The above production method further comprises a step of reacting an organopolysiloxane having hydroxy groups and / or secondary amino groups at the terminals and tertiary amino groups in the molecular chain with an isocyanate having a (meth)acrylic group to obtain the (meth)acrylic-modified silicone macromer (a) at both ends represented by the above general formula (1). [3] The above production method, wherein the organopolysiloxane having hydroxy groups and / or secondary amino groups at the terminals and tertiary amino groups in the molecular chain according to the above [2] is represented by the following general formula (7): (In general formula (7), R, R １ , a, and b are as defined above, and Q １ are each independently a group represented by the following formula (8) or (9): (In formula (8), n2 and n3 are as defined above.) (In formula (9), R １is as described above.) [4] The aforementioned production method further comprising the step of reacting an organopolysiloxane having a hydrosilyl group at at least one terminal and a tertiary amino group in the molecular chain with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain an organopolysiloxane having a tertiary amino group in the molecular chain represented by general formula (7) described in [3] above. [5] The aforementioned production method further comprising the step of reacting an organohydrogenpolysiloxane modified with hydrosilyl groups at both terminals with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane having hydrosilyl groups at the terminals and a tertiary amino group in the molecular chain described in [4] above.

[0015] The present invention further provides a copolymer of the above-mentioned (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain and a polymerizable monomer having a group polymerizable with the (meth)acrylic-modified silicone macromer.The present invention further provides a copolymer of the above-mentioned (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain and a polymerizable monomer having a group polymerizable with the (meth)acrylic-modified silicone macromer.The present invention further provides a silicone hydrogel comprising the above-mentioned copolymer.The present invention further provides an ophthalmic lens comprising the above-mentioned silicone hydrogel.

[0016] In the present invention, a "silicone macromer" refers to a high molecular weight silicone monomer having a polymerizable group, and is a silicone monomer having the number of siloxane units in which a and b in the above general formulas (1) and (4) satisfy the ranges of the present invention.

[0017] In the present invention, "high purity" and "high proportion" mean that the silicone macromer represented by formula (1) or (4) having polymerizable groups introduced at both ends is contained in a high proportion, preferably 80% by weight or more, more preferably 90% by weight or more, and even more preferably 95% by weight or more, of the total of the silicone macromer and compounds without polymerizable groups (i.e., impurities). The smaller the amount of the impurities accompanying the silicone macromer represented by formula (1) or (4), the better.

[0018] The production method of the present invention allows for the introduction of a high proportion of (meth)acrylic groups at both ends and allows for the efficient production of highly pure silicone macromers having quaternary ammonium cation moieties in the molecular chain. Furthermore, silicone hydrogels containing polymers obtained from the silicone macromer of the present invention have high surface hydrophilicity.

[0019] FIG. 1 shows the structure of the (meth)acrylic-modified silicone macromer at both ends having tertiary amino groups in the molecular chain, synthesized in Example 1. １ 2 is a H-NMR spectrum chart of the (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain, synthesized in Example 2. １ 1 is a H-NMR spectrum chart.

[0020] The present invention will be described in detail below. [(Meth)acrylic-modified silicone macromer at both ends having tertiary amino groups in the molecular chain] The (meth)acrylic-modified silicone macromer at both ends having tertiary amino groups in the molecular chain of the present invention is represented by the following general formula (1): In the general formula (1), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X are each independently a hydrogen atom or a methyl group; Q is a divalent organic group; a is an integer of 1 to 400, b is an integer of 1 to 50; and n1 are each independently an integer of 2 to 10.

[0021] In the general formula (1), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. R is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0022] In the above general formula (1), R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. R １ is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0023] In the above general formula (1), X's are each independently a hydrogen atom or a methyl group.

[0024] In the general formula (1), each a is independently an integer of 1 to 400, preferably an integer of 1 to 100, and more preferably an integer of 5 to 50. Each b is independently an integer of 1 to 50, preferably an integer of 1 to 30, and more preferably an integer of 1 to 10. Each n1 is independently an integer of 2 to 10, and preferably an integer of 2 to 4.

[0025] In the above general formula (1), Q is a divalent organic group, and is preferably a group represented by the following formula (2) or (3). In the above formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10. In the above formula (3), the portion indicated by ** indicates that it is bonded to a silicon atom, and the portion indicated by * indicates that it is bonded to a carbonyl group. １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0026] In the above formula (2), n2 is an integer of 2 to 10, preferably an integer of 2 to 4, and n3 is an integer of 0 to 10, preferably an integer of 1 to 6.

[0027] In the above formula (3), R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group.

[0028] [(Meth)acrylic-Modified Silicone Macromer at Both Ends Having Quaternary Ammonium Cation Moieties in the Molecular Chain] The (meth)acrylic-modified silicone macromer at both ends having quaternary ammonium cation moieties in the molecular chain is represented by the following general formula (4). In the general formula (4), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ２are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X are each independently a hydrogen atom or a methyl group; Q is a divalent organic group; a is an integer of 1 to 400, b is an integer of 1 to 50; n1 are each independently an integer of 2 to 10; and Y is a chlorine atom, bromine atom, or iodine atom.

[0029] In the above general formula (4), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group. R is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0030] In the above general formula (4), R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group. R １ is preferably a methyl group or an ethyl group, more preferably a methyl group. ２ is preferably a methyl group or a 2-hydroxyethyl group, more preferably a methyl group.

[0031] In the above general formula (4), X's are each independently a hydrogen atom or a methyl group.

[0032] In the above general formula (4), Y is a chlorine atom, a bromine atom, or an iodine atom, and preferably a bromine atom or an iodine atom.

[0033] In the general formula (4), a is an integer of 1 to 400, preferably an integer of 1 to 100, and more preferably an integer of 5 to 50. b is an integer of 1 to 50, preferably an integer of 1 to 30, and more preferably an integer of 1 to 10. n1s are each independently an integer of 2 to 10, and preferably an integer of 2 to 4.

[0034] In the above general formula (4), Q is a divalent organic group, and is preferably a group represented by the following formula (2) or (3). In the above formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10. In the above formula (3), the portion indicated by ** indicates that it is bonded to a silicon atom, and the portion indicated by * indicates that it is bonded to a carbonyl group. １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

[0035] In the above formula (2), n2 is an integer of 2 to 10, preferably an integer of 2 to 4, and n3 is an integer of 0 to 10, preferably an integer of 1 to 6.

[0036] In the above formula (3), R １is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group.

[0037] [Method for producing a (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain] A method for producing a (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain, represented by the above general formula (1), is described in detail below. The method is characterized by comprising a step of reacting an organopolysiloxane (A) having a tertiary amino group in the molecular chain, represented by the following general formula (7), with an isocyanate (B) having a (meth)acrylic group, represented by the following general formula (10), to obtain a compound represented by the above general formula (1) (hereinafter referred to as a urethanization reaction). In the general formula (7), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; Q １ is a group represented by the following formula (8) or (9), in which a is an integer of 1 to 400, b is an integer of 1 to 50, and n1 are each independently an integer of 2 to 10. In the above formula (8), n2 is an integer of 2 to 10, and n3 is an integer of 0 to 10. In the above formula (9), R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. In the above general formula (10), X is a hydrogen atom or a methyl group, and n1 is an integer of 2 to 10.

[0038] In the general formula (7), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. R is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0039] In the above general formula (7), R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl; and cycloalkyl groups such as cyclopentyl and cyclohexyl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, methylphenyl, and ethylphenyl. Examples of the aralkyl group having 7 to 10 carbon atoms include phenylmethyl and phenylethyl. R １ is preferably a methyl group or an ethyl group, more preferably a methyl group.

[0040] In the above general formula (7), Q １ is a group represented by the above formula (8) or (9).

[0041] In the above general formula (7), a is an integer of 1 to 400, preferably an integer of 1 to 100, and b is an integer of 1 to 50, preferably an integer of 1 to 30.

[0042] In the above formula (8), n2 is an integer of 2 to 10, preferably an integer of 2 to 4, and n3 is an integer of 0 to 10, preferably an integer of 1 to 6.

[0043] In the above formula (9), R １are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group.

[0044] In the above general formula (10), X's are each independently a hydrogen atom or a methyl group.

[0045] In the above general formula (10), n1 is an integer of 2 to 10, preferably an integer of 2 to 4.

[0046] The isocyanate represented by the general formula (10) may be a commercially available product, such as 2-isocyanatoethyl acrylate (trade name: Karenz AOI, manufactured by Showa Denko K.K.) and 2-isocyanatoethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko K.K.).

[0047] In the urethanization reaction, the molar ratio of the isocyanate represented by the general formula (10) to the total number of moles of the hydroxy groups and secondary amino groups in the general formula (7) is preferably 1 to 2 times, more preferably 1.05 to 1.5 times.

[0048] The catalyst used in the urethanization reaction may be any known urethanization catalyst. Examples of the urethanization catalyst include tertiary amines such as triethylamine and 1,4-diazabicyclo[2.2.2]octane, and organometallic compounds such as iron(III) acetylacetonate, dibutyltin dilaurate, dioctyltin dilaurate, bismuth 2-ethylhexanoate, bismuth octanoate, tetrabutyl orthotitanate, titanium diisopropoxide bis(acetylacetonate), zirconium tetrabutoxide, and zirconium tetraacetylacetonate. Among these, iron(III) acetylacetonate is preferred.

[0049] The amount of catalyst used in the urethanization reaction is not particularly limited, but is preferably 10 to 1,000 ppm relative to the weight of the organopolysiloxane represented by general formula (7).

[0050] In the urethanization reaction, the reaction temperature in the step of reacting the organopolysiloxane represented by general formula (7) with the isocyanate represented by general formula (10) in the presence of a urethanization catalyst is not particularly limited, but is preferably 40°C or higher and 90°C or lower, and more preferably 50°C or higher and 70°C or lower.

[0051] In the urethanization reaction, the reaction conditions, such as the reaction time and the solvent used, are not particularly limited. The reaction time is preferably 1 to 24 hours, more preferably 1 to 12 hours, and most preferably 2 to 6 hours. The solvent is preferably an aromatic hydrocarbon solvent such as toluene or xylene.

[0052] In the urethane-forming reaction, it is preferable to add a radical polymerization inhibitor to suppress polymerization of the terminal (meth)acrylic groups.

[0053] The radical polymerization inhibitor may be any conventionally known one. Examples include dibutylhydroxytoluene, 4-methoxyphenol, and hydroquinone. Dibutylhydroxytoluene and 4-methoxyphenol are preferred. The radical polymerization inhibitor may be used alone or in combination of two or more types.

[0054] The amount of radical polymerization inhibitor added is preferably 0.01 to 0.1 parts by mass, and more preferably 0.02 to 0.08 parts by mass, per 100 parts by mass of the organopolysiloxane represented by the general formula (7).

[0055] The method for producing the organopolysiloxane represented by general formula (7) is not particularly limited. For example, it can be produced by addition reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in an excess amount of hydrosilyl groups in the presence of a platinum catalyst, followed by adding (poly)ethylene glycol monoallyl ether and continuing the addition reaction.

[0056] More specifically, the production method of the present invention further comprises the step of reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane (11) having a hydrosilyl group at at least one end and a tertiary amino group in the molecular chain. The organohydrogenpolysiloxane containing hydrosilyl groups at both ends is used in an excess amount relative to the tertiary amine having two allyl groups. The molar ratio determines the number of repetitions of the silicone chain and the tertiary amino group-containing moiety, b, in general formula (1). The blending ratio of the organopolysiloxane is preferably 1.05 to 2 times the number of moles of the tertiary amine. The organopolysiloxane (11) is preferably represented by the following structure: In the above formula, Q ３ are each independently a hydrogen atom or a group represented by the following formula (3) or (5), and at least one Q ３ is a hydrogen atom. In the general formula (11), R are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, a is an integer from 1 to 400, and b is an integer from 1 to 50. １ The details of a, a, and b are as defined for the above general formula (1). The organopolysiloxane (11) is more preferably represented by the following structure: The organopolysiloxane represented by the general formula (11) above may be one or a mixture of two or more compounds selected from the above organopolysiloxanes, and more preferably an organopolysiloxane having an average of 0 to 2, preferably 1 to 2, and more preferably 1.5 to 2 hydrogen atoms bonded to silicon atoms per molecule.

[0057] The production method of the present invention further comprises the step of reacting the organopolysiloxane (11) with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain an organopolysiloxane having a tertiary amino group in the molecular chain, as represented by the general formula (7). The platinum catalyst, reaction conditions, solvent, and other factors used in this production method may be selected as appropriate.

[0058] In the method for producing the organopolysiloxane represented by general formula (7), the intermediate product (11) may be isolated at each step before proceeding to the next step. Alternatively, the reaction at each step may be carried out without treatment, or the solvent and unreacted raw materials may be distilled off, and the next step may be carried out without isolating the intermediate product (11). A method for producing the organopolysiloxane represented by general formula (7) without isolating the intermediate product (11) involves, for example, reacting an organohydrogenpolysiloxane containing hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst, confirming that no tertiary amine raw material remains, and then adding a (poly)ethylene glycol allyl ether and a platinum catalyst to the reaction solution and heating and stirring. After the reaction is complete, the low-boiling fraction is removed and the mixture is washed to obtain the organopolysiloxane represented by general formula (7) having tertiary amino groups in its molecular chain.

[0059] The (poly)ethylene glycol monoalkenyl ether is represented by the following formula: In the general formula (6), n3 is an integer of 0 to 8, preferably an integer of 0 to 2. n4 is an integer of 0 to 10, preferably an integer of 1 to 6. The (poly)ethylene glycol monoalkenyl ether used in the production method of the present invention may be a commercially available product. Examples include allyl glycol, diethylene glycol monoallyl ether, and polyethylene glycol allyl ether (trade names: UNIOX PKA-5001 (average molecular weight: 200), UNIOX PKA-5002 (average molecular weight: 400), UNIOX PKA-5003 (average molecular weight: 450), UNIOX PKA-5004 (average molecular weight: 750), and UNIOX PKA-5005 (average molecular weight: 1,500), all manufactured by NOF Corporation). The blending ratio of the (poly)ethylene glycol monoalkenyl ether is preferably 1.05 to 1.4 times the number of moles of terminal hydrosilyl groups contained in the organopolysiloxane.

[0060] Preferably, the organopolysiloxane represented by the general formula (7) is represented by the following formula: (wherein Q′ is a group represented by the following formula (8)) The organopolysiloxane represented by the general formula (7) may be one or a mixture of two or more compounds selected from compounds having groups represented by the formula (8) at both ends, compounds having groups represented by the formula (9) at both ends, and compounds having a group represented by the formula (8) at one end and a group represented by the formula (9) at the other end. When the organopolysiloxane represented by the general formula (7) is a mixture of compounds having different terminal structures, it is more preferable to use an organopolysiloxane having an average of 0 to 2, preferably 0.5 to 2, preferably 1 to 2, more preferably 1.5 to 2 groups represented by the formula (8) per molecule and an average of 0 to 2, preferably 0 to 1.5, preferably 0 to 1, more preferably 0 to 0.5 groups represented by the formula (9) per molecule.

[0061] The general formula (7) can be used in the reaction as a mixture of compounds having different terminal structures. The (meth)acrylic-modified silicone macromer at both ends represented by the general formula (1) obtained using the organopolysiloxane as a raw material may be a mixture of two or more compounds with different Q. More specifically, the silicone macromer may be one in which Q has an average of 0 to 2, preferably 0.5 to 2, more preferably 1 to 2, and even more preferably 1.5 to 2 terminals per molecule having the structure represented by the formula (2), and Q has an average of 0 to 2, preferably 0 to 1.5, more preferably 0 to 1, and even more preferably 0 to 0.5 terminals per molecule having the structure represented by the formula (3).

[0062] [Method for producing a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain] A method for producing a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain represented by the above general formula (4) is described below. The method is characterized by comprising a step of reacting a silicone macromer (a) having a tertiary amino group in the molecular chain represented by the above general formula (1) with a halogenated hydrocarbon (b) represented by the following formula (14) to obtain a compound represented by the above general formula (4) (hereinafter referred to as the quaternary ammonium cationization reaction). (In formula (14), R ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and Y is a chlorine atom, a bromine atom, or an iodine atom.

[0063] In the above formula (14), R ２are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms. Examples of the alkyl group having 1 to 10 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, and an octyl group; and cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a methylphenyl group, and an ethylphenyl group. Examples of the aralkyl group having 7 to 10 carbon atoms include a phenylmethyl group and a phenylethyl group. R ２ is preferably a methyl group or a 2-hydroxyethyl group, more preferably a methyl group.

[0064] In the above formula (14), Y is a chlorine atom, a bromine atom, or an iodine atom, preferably a bromine atom or an iodine atom.

[0065] Preferred examples of the halogenated hydrocarbon represented by the above formula (14) include bromides such as bromoethane, 1-bromopropane, 1-bromobutane, 2-bromoethanol, and benzyl bromide; and iodides such as iodomethane, iodoethane, 1-iodopropane, 1-iodobutane, and 2-iodoethanol.

[0066] In the quaternary ammonium cationization reaction, the molar ratio of the halogenated hydrocarbon represented by the formula (14) to the tertiary amino group in the general formula (1) is preferably 1 to 5 times, more preferably 2 to 4 times.

[0067] In the quaternary ammonium cationization reaction, the reaction temperature is preferably 20°C or higher and 120°C or lower, more preferably 20°C or higher and 90°C or lower.

[0068] The reaction conditions for the quaternary ammonium cationization reaction, such as the reaction time and the solvent used, are not particularly limited. The reaction time is preferably 1 to 24 hours, more preferably 3 to 12 hours. Examples of the solvent include ether solvents such as tetrahydrofuran, alcohol solvents such as isopropanol, and aromatic hydrocarbon solvents such as toluene and xylene. Among these, tetrahydrofuran is preferred.

[0069] The silicone macromer represented by general formula (1) can be produced by reacting a hydrogen-terminated organopolysiloxane with a tertiary amine having two allyl groups in an excess equivalent of organopolysiloxane in the presence of a platinum catalyst, and then adding a (poly)ethylene glycol allyl ether to the reaction system to produce an intermediate, which is then reacted with an isocyanate having a (meth)acrylic group.

[0070] As mentioned above, the dual-end (meth)acrylic-modified silicone macromer represented by general formula (1) above may be a mixture of two or more compounds with different Q. Accordingly, the dual-end (meth)acrylic-modified silicone macromer having a quaternary ammonium cation moiety in the molecular chain represented by general formula (4) above, which is obtained using the dual-end (meth)acrylic-modified silicone macromer represented by general formula (1) as a raw material, may also be a mixture of two or more compounds with different Q, and more specifically, may be a silicone macromer in which Q has an average of 0 to 2, preferably 0.5 to 2, more preferably 1 to 2, and even more preferably 1.5 to 2, ends having the structure represented by formula (2) above per molecule, and Q has an average of 0 to 2, preferably 0 to 1.5, more preferably 0 to 1, and even more preferably 0 to 0.5, ends having the structure represented by formula (3) above per molecule.

[0071] The silicone macromer of the present invention represented by the above general formula (1) or (4) can be copolymerized with a polymerizable monomer having a group polymerizable with the silicone macromer, such as a polymerizable silicone monomer or a polymerizable hydrophilic monomer, to form a copolymer. The blend ratio of the silicone macromer of the present invention to the other polymerizable monomers in the copolymer is preferably 15 to 30 wt %. Two or more polymerizable monomers may be used in combination.

[0072] Preferred examples of the polymerizable silicone monomer include (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane (abbreviation: SiGMA) and 3-[tris(trimethylsilyloxy)silyl]propyl methacrylate (abbreviation: TRIS).

[0073] Preferred examples of the polymerizable hydrophilic monomer include acrylamide-based monomers such as acrylamide, methacrylamide, N,N-dimethylacrylamide, and N,N-dimethylmethacrylamide; vinylamide-based monomers such as N-methyl-N-vinylacetamide; N-vinyl cyclic amide-based monomers such as N-vinylpyrrolidone and N-vinylcaprolactam; hydroxy-based monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl acrylate, N-hydroxyethyl acrylamide, and N-hydroxyethyl methacrylamide; amino-based monomers such as N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminoethyl acrylate, and N,N-dimethylaminoethyl methacrylate; and carboxylic acid-based monomers such as acrylic acid and methacrylic acid.

[0074] Polymerization is carried out by heat or ultraviolet irradiation. These methods are well known in the art. Polymerization by ultraviolet irradiation is carried out by adding a photopolymerization initiator to the side-chain urethane-modified silicone macromer and the polymerizable hydrophilic monomer, followed by ultraviolet irradiation. A representative photopolymerization initiator includes, but is not limited to, 2-hydroxy-2-methyl-1-phenylpropanone (trade name: Omnirad-1173, manufactured by IGM Resins B.V.).

[0075] The present invention further provides a silicone hydrogel containing the copolymer. The silicone hydrogel can be manufactured by a conventional method. The silicone hydrogel obtained from the silicone macromer of the present invention has high surface hydrophilicity. The surface hydrophilicity of a silicone hydrogel can be evaluated by dropping a water droplet onto the gel surface. Generally, the angle between the tangent of the water droplet and the gel surface is called the contact angle; the smaller the contact angle, the greater the surface hydrophilicity, and the larger the contact angle, the less the surface hydrophilicity.

[0076] According to the manufacturing method of the present invention, it is possible to introduce polymerizable groups into both ends of the silicone macromer at a high rate, thereby reducing the amount of compounds (impurities) that do not have polymerizable groups. The introduction rate of polymerizable groups (hereinafter referred to as the crosslinking rate) is determined by curing the silicone macromer by radical polymerization, washing the uncured component with an organic solvent, drying the organic solvent, and calculating the uncured material content from the ratio of the weight of the cured material after washing to the weight of the cured material before washing, which is then used as the crosslinking rate. In other words, the rate of impurities that do not have polymerizable groups is evaluated. According to the manufacturing method of the present invention, it is possible to reduce the amount of impurities that do not have polymerizable groups and provide a polymerizable silicone macromer with high purity.

[0077] The silicone hydrogels obtained from the silicone macromer of the present invention have excellent surface transparency and are therefore suitable for producing medical materials such as ophthalmic devices, contact lenses, intraocular lenses, and artificial corneas.

[0078] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. １ H-NMR measurements were performed using an ULTRASHIELD 400 PLUS (manufactured by BRUKER).

[0079] Synthesis Example 1 A three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with a compound of the following formula: 50.0 g of an organohydrogenpolysiloxane containing hydrosilyl groups at both ends represented by the formula (I), 0.2 g of a toluene solution of a chloroplatinic acid neutralized with sodium bicarbonate and a vinylsiloxane complex (platinum content: 0.5 wt%), and 17 g of toluene were charged and heated to 70°C. 5.3 g of diallylmethylamine was added dropwise over 30 minutes, and the mixture was heated and stirred at 75°C for 2 hours. After completion of the reaction, low-boiling fractions were removed at 100°C under a reduced pressure of 0.2 kPa for 1 hour. Subsequently, 25 g of acetonitrile and 6.3 g of water were added, stirred, washed, and then allowed to stand to separate the silicone layer. This separation and washing procedure was repeated three times. Low-boiling fractions were removed at 85°C under a reduced pressure of 0.3 kPa for 1.5 hours, yielding 24 g of an organopolysiloxane represented by the following formula (a'). In formula (a'), each A is independently a hydrogen atom bonded to a silicon atom or a group represented by the following formula: The organopolysiloxane is a mixture of two or more compounds with different As, and has an average of 1.8 silicon-bonded hydrogen atoms per molecule and an average of 0.2 groups represented by the following formula per molecule.

[0080] [Synthesis Example 2] A three-necked flask equipped with a thermometer, a stirrer, and a reflux condenser was charged with 250.0 g of the organopolysiloxane represented by formula (a') obtained in Synthesis Example 1 above, 1.0 g of a toluene solution of a chloroplatinic acid neutralized with sodium bicarbonate and a vinylsiloxane complex (platinum content: 0.5 wt%), and 83 g of toluene, and heated to 70 ° C. 24.3 g of allyl glycol and 0.5 g of a toluene solution of a chloroplatinic acid neutralized with sodium bicarbonate and a vinylsiloxane complex (platinum content: 0.5 wt%) were added, and the mixture was heated and stirred at 75 ° C. for 1.5 hours. After the reaction was completed, the low-boiling fraction was removed under a reduced pressure of 0.3 kPa at 90 ° C. for 1 hour. Subsequently, 125 g of acetonitrile and 31 g of water were added, stirred, washed, and then allowed to stand, and the silicone layer was separated and collected. This separation and washing procedure was repeated three times. The low boiling fraction was removed under reduced pressure of 0.9 kPa at 100° C. for 1.5 hours, yielding 247 g of an organopolysiloxane represented by the following formula (a). In the above formula (a), Q １ are each independently a group represented by the following formula (b) or (c): １The compound is a mixture of two or more compounds having different structures, each molecule having an average of 1.8 groups represented by the following formula (b) and an average of 0.2 groups represented by the following formula (c):

[0081] Example 1: Method for producing a (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain, represented by the above general formula (1) 80.0 g of the organopolysiloxane represented by the above formula (a), 9.5 g of 2-isocyanatoethyl methacrylate (product name: Karenz MOI, manufactured by Showa Denko K.K.), 0.0024 g of iron(III) acetylacetonate, 0.024 g of dibutylhydroxytoluene, 0.024 g of 4-methoxyphenol, and 60 g of toluene were charged into a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was heated and stirred at 65°C for 1 hour. 5.9 g of methanol was added, and the mixture was heated and stirred at 65°C for 30 minutes. After completion of the reaction, 2.4 g of Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature (25°C) for 1 hour. The solid was removed by pressure filtration. The low-boiling fraction was removed under a reduced pressure of 0.3 kPa at 90°C for 1 hour. Subsequently, 80 g of acetonitrile was added, stirred, and then allowed to stand to separate the silicone layer. This separation and washing procedure was repeated three times. The low-boiling fraction was removed under a reduced pressure of 0.3 kPa at 80°C for 2.5 hours, yielding 58 g of organopolysiloxane (silicone macromer) represented by the following formula (d): In the above formula (d), Q ２ are each independently a group represented by the following formula (e) or (f): ２ The compound is a mixture of two or more compounds having different structures, and each molecule has an average of 1.8 groups represented by the following formula (e) and an average of 0.2 groups represented by the following formula (f):

[0082] The silicone macromer obtained in Example 1 is １ The H-NMR spectrum is shown. １ H-NMR (400MHz, CDCl ３):δ -0.17 to 0.22 (m, 264H), 0.38 to 0.55 (m, 16H), 1.37 to 1.65 (m, 16H), 1.92 (s, 6H), 2 .05-2.36 (m, 21.4H), 2.84 (s, 0.6H), 3.18 (t, J=7.7Hz, 0.4H), 3.40 (t, J=7.1Hz) , 3.6H), 3.47 (q, J = 5.5Hz, 3.6H), 3.50 to 3.55 (m, 0.4H), 3.59 (t, J = 4.6Hz, 3.6H) , 4.12-4.28 (m, 7.6H), 4.70 (s, 0.2H), 5.02 (s, 1.8H), 5.56 (s, 2H), 6.08 (s, 2H)

[0083] Example 2 (Meth)acrylic-Modified Silicone Macromer at Both Ends and Having a Quaternary Ammonium Cation Moiety in the Molecular Chain, Represented by General Formula (4) Above 25.0 g of the silicone macromer represented by Formula (d) above, 7.5 g of iodomethane, and 25.0 g of tetrahydrofuran were placed in a flask equipped with a stirrer and stirred for 8 hours at 20° C. After completion of the reaction, low-boiling fractions were removed under reduced pressure of 0.3 kPa at 60° C. for 3 hours, yielding 26 g of the silicone macromer represented by the following formula (g): In the above formula (g), Q ３ are each independently a group represented by the above formula (e) or (f). ３ and has an average of 1.8 groups represented by the above formula (e) per molecule and an average of 0.2 groups represented by the above formula (f) per molecule.

[0084] The silicone macromer obtained in Example 2 is １ The H-NMR spectrum is shown. １ H-NMR (400MHz, CDCl ３): δ -0.19 to 0.25 (m, 264H), 0.36 to 0.63 (m, 16H), 1.48 to 1.79 (m, 16H), 1.87 (s, 6H), 2.80 (s, 0.6H), 3.13 (t, J = 8.2 Hz, 0.4H), 3.21 to 3.77 (m, 41.2H), 4.08 to 4.23 (m, 7.6H), 4.70 (s, 0.2H), 4.98 (s, 1.8H), 5.52 (s, 2H), 6.04 (s, 2H)

[0085] [Production of Silicone Hydrogel] [Example 3] Production of Silicone Hydrogel from Silicone Macromer Represented by Formula (g) Above (a) Silicone macromer represented by formula (g) above, (b) (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, (c) N,N-dimethylacrylamide, and (d) isopropanol were mixed in a mass ratio of (a):(b):(c):(d) = 25:35:40:20. Furthermore, 0.02 g of 2-hydroxy-2-methyl-1-phenylpropanone (trade name: Omnirad-1173, manufactured by IGM Resins B.V.) was added and stirred until a homogeneous solution was obtained. After allowing to stand and degassing, the solution was sealed in a mold. UV irradiation (wavelength 365 nm, irradiation dose 95,000 mJ / cm) was performed using a metal halide lamp. ２ ) and cured at room temperature (20°C). The cured product was washed with isopropanol and then swollen in water. The resulting silicone hydrogel was a yellow, transparent solid.

[0086] Comparative Example 1 A silicone hydrogel was prepared in the same manner as in Example 3, except that a side-chain glycerin-modified silicone macromer containing methacryl groups at both ends (Mw=7843, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicone macromer represented by formula (g) above.

[0087] Comparative Example 2 A silicone hydrogel was prepared in the same manner as in Example 3, except that a side chain polyether-modified silicone macromer containing methacrylic groups at both ends (Mw=9450, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicone macromer represented by formula (g) above.

[0088] [Measurement of Crosslinking Rate of Cured Product] (a) The silicone macromer represented by formula (g) obtained in Example 2 above and (b) isopropanol were mixed in a mass ratio of (a):(b) = 5:1. This mixture was cured using the same procedure as in Example 3 above to obtain a cured product. The uncured components contained in the resulting cured product were washed with isopropanol, air-dried for 1 hour, and then heated and dried at 150°C for 2 hours. The mass of the cured product after washing was 95% of the mass of the cured product before washing. In other words, the content of compounds without polymerizable groups attached to the silicone macromer obtained in the above example was 5%, and the crosslinking rate (i.e., the content of compounds with polymerizable groups relative to the total mass of the product) was 95%. Therefore, the manufacturing method of the present invention can introduce (meth)acrylic groups into the terminals of the silicone macromer at a high rate of 95% or more.

[0089] [Surface Hydrophilicity Test of Silicone Hydrogels] A surface hydrophilicity test was conducted on the silicone hydrogels prepared in Example 3 and Comparative Examples 1 and 2 above. A 3.0 μL water droplet was dropped from above the horizontally fixed silicone hydrogel using a microsyringe, and the contact angle between the water droplet and the gel surface was measured. These operations were performed automatically using a fully automatic contact angle meter DMo-701 (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 1.

[0090]

[0091] As shown in Table 1, the silicone hydrogel obtained from the copolymer of the present invention, a silicone macromer modified at both ends with a (meth)acrylic acid moiety and having a quaternary ammonium cation moiety, has a smaller surface water contact angle than the silicone hydrogels obtained in Comparative Examples 1 and 2. In other words, the silicone hydrogel having a structure derived from the present invention, a silicone macromer modified at both ends with a (meth)acrylic acid moiety and having a quaternary ammonium cation moiety, has high surface hydrophilicity.

[0092] Copolymers containing the (meth)acrylic-terminated silicone macromer of the present invention have excellent hydrophilicity. Silicone hydrogels containing the copolymers have excellent transparency. Therefore, the (meth)acrylic-terminated silicone macromer of the present invention is suitable for producing medical materials such as ophthalmic devices, contact lenses, intraocular lenses, and artificial corneas.

Claims

1. A silicone macromer modified at both ends with a (meth)acrylic group and having a tertiary amino group in the molecular chain, represented by the following general formula (1): (In general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; X are each independently a hydrogen atom or a methyl group; Q is a divalent organic group; a are each independently an integer of 1 to 400, b is an integer of 1 to 50, and n1 are each independently an integer of 2 to 10.

2. The (meth)acrylic-modified silicone macromer having tertiary amino groups at both ends in the molecular chain according to claim 1, wherein in the general formula (1), Q is, independently of each other, a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, and R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

3. A silicone macromer modified at both ends with a (meth)acrylic acid and having a quaternary ammonium cation moiety in the molecular chain, represented by the following general formula (4): (In the general formula (4), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; each X is independently a hydrogen atom or a methyl group; each Q is a divalent organic group; each a is independently an integer of 1 to 400, each b is an integer of 1 to 50, each n1 is independently an integer of 2 to 10, and each Y is a chlorine atom, a bromine atom, or an iodine atom.

4. The (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain according to claim 3, wherein in the above general formula (4), Q is each independently a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, and R １ is a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms).

5. A method for producing a (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain, represented by the following general formula (1), comprising the steps of: (In general formula (1), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, each X is independently a hydrogen atom or a methyl group, each Q is a divalent organic group, each a is independently an integer of 1 to 400, each b is an integer of 1 to 50, and each n1 is independently an integer of 2 to 10. The above-mentioned production method, which comprises a step of reacting an organopolysiloxane (A) having a tertiary amino group in the molecular chain represented by the following general formula (7) with an isocyanate (B) having a (meth)acrylic group represented by the following general formula (10) to obtain a silicone macromer modified at both ends with (meth)acrylic represented by the above general formula (1). (In general formula (7), R, R １ , a, and b are as defined above; Q １ is a group represented by the following formula (8) or (9): (In formula (8), n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) (In formula (9), R １ is as above) (In the general formula (10), X and n1 are as defined above).

6. A method for producing a (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain at both ends thereof according to claim 5, wherein in the above general formula (1), Q is, independently of each other, a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates bonding to a silicon atom, the portion indicated by * indicates bonding to a carbonyl group, and n2 and n3 are as defined above.) (In formula (3), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, and R １ is as above).

7. A method for producing a (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain at both ends thereof according to claim 5, further comprising the step of reacting an organopolysiloxane having a hydrosilyl group at at least one end and a tertiary amino group in the molecular chain with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain organopolysiloxane (A) having a tertiary amino group in the molecular chain, as represented by the above general formula (7).

8. A method for producing a (meth)acrylic-modified silicone macromer having a tertiary amine at both ends in the molecular chain according to claim 7, further comprising the step of reacting an organohydrogenpolysiloxane modified with hydrosilyl groups at both ends with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane having hydrosilyl groups at the ends and tertiary amino groups in the molecular chain.

9. A method for producing a silicone macromer modified at both ends with a (meth)acrylic acid, which has a quaternary ammonium cation moiety in the molecular chain and is represented by the following general formula (4): (In the general formula (4), R is, independently of each other, a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms; R ２ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, a 2-hydroxyethyl group, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, each X is independently a hydrogen atom or a methyl group, each Q is a divalent organic group, each a is independently an integer from 1 to 400, b is an integer from 1 to 50, each n1 is independently an integer from 2 to 10, and Y is a chlorine atom, a bromine atom, or an iodine atom. The above-mentioned production method, which comprises a step of reacting a both-terminal (meth)acrylic-modified silicone macromer (a) having a tertiary amino group in the molecular chain represented by the following general formula (1) with a halogenated hydrocarbon (b) represented by the following formula (14) to obtain a both-terminal (meth)acrylic-modified silicone macromer represented by the above general formula (4): (In general formula (1), R, R １ , X, Q, a, b, and n1 are as defined above. (In formula (14), R ２ is as defined above, and Y is a chlorine atom, a bromine atom or an iodine atom).

10. A method for producing a silicone macromer modified at both ends with a (meth)acrylic acid, which has a quaternary ammonium cation moiety in the molecular chain, according to claim 9, wherein in the above general formulas (1) and (4), Q is a group represented by the following formula (2) or (3): (In formula (2), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, n2's are each independently an integer from 2 to 10, and n3's are each independently an integer from 0 to 10.) (In formula (3), the portion indicated by ** indicates a bond to a silicon atom, the portion indicated by * indicates a bond to a carbonyl group, and R １ are each independently a group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms.

11. A method for producing a silicone macromer modified at both ends with (meth)acrylic, according to claim 10, further comprising the step of reacting an organopolysiloxane having hydroxy groups or secondary amino groups at both ends and a tertiary amino group in the molecular chain with an isocyanate having a (meth)acrylic group to obtain the silicone macromer (a) modified at both ends with (meth)acrylic, represented by the above general formula (1).

12. A method for producing a (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain according to claim 11, wherein the organopolysiloxane having hydroxyl groups or secondary amino groups at both ends and a tertiary amino group in the molecular chain is represented by the following general formula (7): (In general formula (7), R, R １ , a, and b are as defined above; Q １ are each independently a group represented by the following formula (8) or (9): (In formula (8), n2 and n3 are as defined above.) (In formula (9), R １ is as above).

13. A method for producing a (meth)acrylic-modified silicone macromer at both ends and having a quaternary ammonium cation moiety in the molecular chain according to claim 12, further comprising the step of reacting an organopolysiloxane having a hydrosilyl group at at least one end and a tertiary amino group in the molecular chain with a (poly)ethylene glycol allyl ether in the presence of a platinum catalyst to obtain an organopolysiloxane having a tertiary amino group in the molecular chain represented by the above general formula (7).

14. A method for producing a silicone macromer modified at both ends with (meth)acrylic groups and having a quaternary ammonium cation moiety in the molecular chain according to claim 13, further comprising the step of reacting an organohydrogenpolysiloxane modified at both ends with hydrosilyl groups with a tertiary amine having two allyl groups in the presence of a platinum catalyst to obtain an organopolysiloxane having hydrosilyl groups at the ends and tertiary amino groups in the molecular chain.

15. A copolymer of the (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain as described in claim 1 and a polymerizable monomer having a group which polymerizes with said (meth)acrylic-modified silicone macromer.

16. A copolymer of the (meth)acrylic-modified silicone macromer at both ends having a quaternary ammonium cation moiety in the molecular chain according to claim 3 and a polymerizable monomer having a group which polymerizes with said (meth)acrylic-modified silicone macromer.

17. A silicone hydrogel comprising the copolymer according to claim 15 or 16.

18. An ophthalmic lens comprising the silicone hydrogel of claim 17.

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