Both terminal (METH)acryl-modified silicone macromer having tertiary amino group or quaternary ammonium cation part in molecular chain, and production method of the same

Abstract

To provide a silicone macromer having (meth)acryl groups on both terminals in a high ratio, and having a quaternary ammonium cation part in a molecular chain.SOLUTION: There is provided a both terminal (meth)acryl-modified silicone macromer having a tertiary amino group, or having a quaternary ammonium-cationized tertiary amino group in a molecular chain, which is expressed by general formula (1).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Silicone is widely used as a contact lens material due to its high oxygen permeability. However, since silicone is hydrophobic, the introduction of hydrophilic groups has been studied to hydrophilize the contact lens surface. Among them, 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. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2009-542855 [Patent Document 2] Special Publication No. 2009-533532 [Patent Document 3] Special Publication No. 2010-516873 [Patent Document 4] Special Publication No. 2009-521547 Summary of the Invention [Problem to be solved by the invention]

[0004] However, it is presumed that the manufacturing method described in Patent Document 1 contains a certain amount of silicone without polymerizable groups as an impurity. It is generally not preferable 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 that contain quaternary ammonium cation moieties in the molecular chain and that can introduce a high proportion of (meth)acrylic groups to both ends.

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

[0006] As a result of intensive research conducted by the present inventors in order to achieve the above-mentioned object, they discovered that by reacting an organopolysiloxane which has hydroxy groups or secondary amino groups at both terminals and which has a tertiary amino group in the molecular chain with an isocyanate which has a (meth)acrylic group, and then converting it into a quaternary ammonium group, it is possible to obtain a silicone macromer which has a high proportion of (meth)acrylic groups at both terminals and which has a quaternary ammonium cation moiety in the molecular chain, and thus completed 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, which is represented by the following general formula (1). [ka] (In the 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 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; 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.

[0008] Preferably, the silicone macromer modified at both ends by (meth)acrylic groups further satisfies the following constituent requirement [1]. [1] In the above general formula (1), each Q is independently a group represented by the following formula (2) or (3): [ka] (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.) [ka] (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).

[0009] The present invention further provides a silicone macromer modified at both ends by (meth)acrylic groups and having a quaternary ammonium cation moiety in the molecular chain, which is represented by the following general formula (4). [ka] 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 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; 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, a bromine atom, or an iodine atom).

[0010] Preferably, the silicone macromer modified at both ends by (meth)acrylic groups further satisfies the following constituent requirement [1]. [1] In the above general formula (4), each Q is independently a group represented by the following formula (2) or (3): [ka] (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.) [ka] (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).

[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): [ka] (In the 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. The present invention provides a method for producing a silicone macromer modified at both ends by (meth)acrylic acid and represented by the general formula (1), comprising the 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). [ka] (In formula (7), R, R 1 , a, and b are as above, and Q 1 is a group represented by the following formula (8) or (9): [ka] (In formula (8), n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) [ka] (In formula (9), R 1 is as above) [ka] (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, as 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), Q is each independently a group represented by the following formula (2) or the following formula (3), [ka] (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.) [ka] (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). [2] The above process further comprises a 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 a tertiary amino group in the molecular chain, represented by general formula (7) above. [3] The above process further comprises a step of reacting the 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 the organopolysiloxane having hydrosilyl groups at the ends and tertiary amino groups in the molecular chain as described in [2] above.

[0013] The present invention further provides a method for producing a silicone macromer modified at both ends by (meth)acrylic acid and having a quaternary ammonium cation moiety in the molecular chain, represented by the following general formula (4): [ka] 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 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; 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, a bromine atom, or an iodine atom. The production method includes a step of reacting (a), a silicone macromer modified at both ends by (meth)acrylic and having a tertiary amino group in the molecular chain and represented by the following general formula (1), with a halogenated hydrocarbon (b) represented by the following general formula (14), to obtain a silicone macromer modified at both ends by (meth)acrylic and represented by the above general formula (4). [ka] (In general formula (1), R, R 1 , X, Q, a, b, and n1 are as above. [ka] (In formula (14), R 2 is as above, and Y is a chlorine atom, a bromine atom, or an iodine atom).

[0014] Preferably, the method for producing a silicone macromer modified at both ends by (meth)acrylic and having a quaternary ammonium cation moiety in the molecular chain, as represented by the above general formula (4), further has at least one of the constituent elements [1] to [5] below. [1] The aforementioned production method, wherein in the above general formulas (1) and (4), Q is a group represented by the following formula (2) or (3): [ka] (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 of 2 to 10, and n3's are each independently an integer of 0 to 10.) [ka] (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. [2] The above process further comprises a step of reacting an organopolysiloxane which has hydroxy groups and / or secondary amino groups at its terminals and which has 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 by (meth)acrylic groups, represented by the above general formula (1). [3] The method for producing an organopolysiloxane having a hydroxy group and / or a secondary amino group at the terminal and a tertiary amino group in the molecular chain according to the above [2], which is represented by the following general formula (7): [ka] (In general formula (7), R, R 1 , a, and b are as above, and Q 1 are each independently a group represented by the following formula (8) or (9): [ka] (In formula (8), n2 and n3 are as defined above.) [ka] (In formula (9), R 1 is as above). [4] The above process further comprises a 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 above process further comprises a step of reacting the 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 the organopolysiloxane having hydrosilyl groups at the ends and tertiary amino groups in the molecular chain as described in [4] above.

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

[0016] In the present invention, a "silicone macromer" is a high molecular weight silicone monomer having a polymerizable group, and is a silicone monomer having the numbers 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 the above 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 not having polymerizable groups (i.e., impurities). The smaller the amount of the above impurities accompanying the silicone macromer represented by the above formula (1) or (4), the better. Effect of the Invention

[0018] The manufacturing method of the present invention can introduce a high proportion of (meth)acrylic groups to both ends and efficiently produce a silicone macromer with high purity and having a quaternary ammonium cation moiety in the molecular chain. Furthermore, silicone hydrogels containing polymers obtained from the silicone macromer of the present invention have high surface hydrophilicity. [Brief description of the drawings]

[0019] [Figure 1] FIG. 1 is a 1H-NMR spectrum chart of the (meth)acrylic-modified silicone macromer at both ends having tertiary amino groups in the molecular chain, synthesized in Example 1. [Diagram 2] FIG. 2 is a 1H-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. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The present invention will be described in detail below. [(Meth)acrylic-modified silicone macromer with tertiary amino groups at both ends in the molecular chain] The (meth)acrylic-modified silicone macromer having tertiary amino groups at both ends in the molecular chain of the present invention is represented by the following general formula (1). [ka] In the above 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 is an integer from 1 to 400, b is an integer from 1 to 50; and n1 are each independently an integer from 2 to 10.

[0021] In the above general formula (1), R is 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 groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. 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.

[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 groups; and cycloalkyl groups such as cyclopentyl and cyclohexyl groups. 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.

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

[0024] In the above 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). [ka] In the above formula (2), the portion indicated by ** indicates bonding to a silicon atom, and the portion indicated by * indicates bonding to a carbonyl group. n2 is an integer of 2 to 10, and n3 is an integer of 0 to 10. [ka] In the above formula (3), the portion indicated by ** indicates that the group is bonded to a silicon atom, and the portion indicated by * indicates that the group 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, and preferably an integer of 2 to 4; n3 is an integer of 0 to 10, and preferably an integer of 1 to 6.

[0027] 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.

[0028] [(Meth)acrylic-modified silicone macromer with quaternary ammonium cation moieties in the molecular chain] The silicone macromer modified at both ends with a (meth)acrylic group and having a quaternary ammonium cation moiety in the molecular chain is represented by the following general formula (4). [ka] In the above 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 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 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 is an integer from 1 to 400, b is an integer from 1 to 50; n1 are each independently an integer from 2 to 10; and Y is a chlorine atom, a bromine atom, or an iodine atom.

[0029] In the above general formula (4), R is 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 group, ethyl group, propyl group, butyl group, and octyl group; and cycloalkyl groups such as cyclopentyl group and 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 is preferably a methyl group or a phenyl group, and more preferably a methyl group.

[0030] In the above general formula (4), R 1 R 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 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 R 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 is preferably a bromine atom or an iodine atom.

[0033] In the above 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. n1 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). [ka] In the above formula (2), the portion indicated by ** indicates bonding to a silicon atom, and the portion indicated by * indicates bonding to a carbonyl group. n2 is an integer of 2 to 10, and n3 is an integer of 0 to 10. [ka] In the above formula (3), the portion indicated by ** indicates that the group is bonded to a silicon atom, and the portion indicated by * indicates that the group 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, and preferably an integer of 2 to 4; n3 is an integer of 0 to 10, and 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 silicone macromers modified with (meth)acrylic at both ends and having tertiary amino groups in the molecular chain] A method for producing the silicone macromer modified at both ends with a (meth)acrylic group and having a tertiary amino group in the molecular chain represented by the above general formula (1) is described in detail below. The production 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). [ka] In the above general formula (7), 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; 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. [ka] In the above formula (8), n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10. [ka] 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. [ka] In the above general formula (10), X is a hydrogen atom or a methyl group, and n1 is an integer of 2-10.

[0038] In the above general formula (7), R is 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 group, ethyl group, propyl group, butyl group, and octyl group; and cycloalkyl groups such as cyclopentyl group and 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 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 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.

[0040] In the above general formula (7), Q 1is 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, and preferably an integer of 1 to 100, and b is an integer of 1 to 50, and preferably an integer of 1 to 30.

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

[0043] In the above formula (9), 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. 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, and 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 molar number of the hydroxyl 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 a 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] In the urethanization reaction, the amount of the catalyst is not particularly limited, but it is preferable that the amount of the catalyst is 10 to 1,000 ppm based on the weight of the organopolysiloxane represented by the general formula (7).

[0050] In the above urethanization reaction, the reaction temperature in the step of reacting the organopolysiloxane represented by the above general formula (7) with the isocyanate represented by the above 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 urethane 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 above urethanization 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 known one. For example, dibutylhydroxytoluene, 4-methoxyphenol, and hydroquinone are included. Dibutylhydroxytoluene and 4-methoxyphenol are preferred. The radical polymerization inhibitor may be used alone or in combination of two or more.

[0054] The amount of the 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, based on 100 parts by mass of the organopolysiloxane represented by the above general formula (7).

[0055] The method for producing the organopolysiloxane represented by the general formula (7) is not particularly limited. For example, the organopolysiloxane can be produced by addition reaction of 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, and then adding (poly)ethylene glycol monoallyl ether and carrying out an addition reaction.

[0056] More specifically, the production method of the present invention further includes a 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 equivalent amount relative to the tertiary amine having two allyl groups. The molar ratio determines b in the above general formula (1), which is the number of repetitions of the silicone chain and the tertiary amino group-containing portion. 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: [ka] In the above formula, Q 3are 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. [ka] In the general formula (11), 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, a is an integer of 1 to 400, and b is an integer of 1 to 50. 1 The details of a and b are as defined for the above general formula (1). The organopolysiloxane (11) is more preferably represented by the following structure: [ka] The organopolysiloxane represented by the general formula (11) may be one or a mixture of two or more compounds selected from the above organopolysiloxanes. More preferably, the organopolysiloxane has an average of 0 to 2, preferably 1 to 2, more preferably 1.5 to 2 hydrogen atoms bonded to silicon atoms in one molecule.

[0057] The production method of the present invention further comprises a step of reacting the above 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 represented by the above general formula (7). The platinum catalyst, reaction conditions, and solvent used in the production method may be appropriately selected.

[0058] In the method for producing the organopolysiloxane represented by the general formula (7), each step may proceed to the next step after isolating the intermediate product (11) at each step, or after the reaction at each step, the intermediate product (11) may not be isolated or may be removed by distillation only. As a method for producing the organopolysiloxane represented by the general formula (7) without isolating the intermediate product (11), for example, an organohydrogenpolysiloxane containing hydrosilyl groups at both ends and a tertiary amine having two allyl groups are reacted in the presence of a platinum catalyst, and after confirming that no tertiary amine raw material remains, a (poly)ethylene glycol allyl ether and a platinum catalyst are added to the reaction solution and heated and stirred. After the reaction is completed, the low boiling point fraction is removed and washed to obtain an organopolysiloxane having a tertiary amino group in the molecular chain represented by the general formula (7).

[0059] The (poly)ethylene glycol monoalkenyl ether is represented by the following formula: [ka] In the above 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. For example, allyl glycol, diethylene glycol monoallyl ether, polyethylene glycol allyl ether (trade name: 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), UNIOX PKA-5005 (average molecular weight: 1,500), all manufactured by NOF Corporation) may be mentioned. The compounding ratio of the (poly)ethylene glycol monoalkenyl ether is preferably 1.05 to 1.4 times the number of moles of the terminal hydrosilyl group contained in the organopolysiloxane.

[0060] The organopolysiloxane represented by the above general formula (7) is preferably represented by the following formula: [ka] (wherein Q' is a group represented by the following formula (8)) [ka] The organopolysiloxane represented by the general formula (7) may be one or a mixture of two or more selected from a compound having a group represented by the formula (8) at both ends, a compound having a group represented by the formula (9) at both ends, and a compound 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 above general formula (7) can be used in the above reaction as a mixture of compounds having different terminal structures. The silicone macromer modified at both ends by (meth)acrylic represented by the above general formula (1) obtained by using the organopolysiloxane as a raw material may be a mixture of two or more compounds having different Q. More specifically, the silicone macromer may have 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 having the structure represented by the above formula (2) per molecule, and 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 having the structure represented by the above formula (3) per molecule.

[0062] [Method for producing silicone macromers modified with (meth)acrylic at both ends having quaternary ammonium cation moieties in the molecular chain] A method for producing the 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 above general formula (4) is described below. The production method is characterized by including 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 a quaternary ammonium cationization reaction). [ka] (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 2 are each independently 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 above quaternary ammonium cationization reaction, the molar ratio of the halogenated hydrocarbon represented by the above formula (14) to the tertiary amino group in the above general formula (1) is preferably 1 to 5 times, more preferably 2 to 4 times.

[0067] In the above 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 time of the quaternary ammonium cationization reaction and the reaction conditions such as 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 the general formula (1) is produced by reacting a hydrogen-terminated organopolysiloxane with a tertiary amine having two allyl groups in the presence of a platinum catalyst in an excess equivalent amount of organopolysiloxane, 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 described above, the silicone macromer modified at both ends by (meth)acrylic represented by the general formula (1) may be a mixture of two or more compounds having different Q. Therefore, the silicone macromer modified at both ends by (meth)acrylic represented by the general formula (1) having a quaternary ammonium cation moiety in the molecular chain represented by the general formula (4) obtained from the silicone macromer modified at both ends by (meth)acrylic represented by the general formula (1) may also be a mixture of two or more compounds having different Q, and more specifically, the silicone macromer may have 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 having the structure represented by the formula (2) in one molecule, and 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 having the structure represented by the formula (3) in one 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 and a polymerizable hydrophilic monomer, to form a copolymer. The blending ratio of the silicone macromer of the present invention to the other polymerizable monomer 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 BV).

[0075] The present invention further provides a silicone hydrogel comprising the copolymer. The silicone hydrogel may be produced by a conventional method. The silicone hydrogel obtained from the silicone macromer of the present invention has high surface hydrophilicity. The surface hydrophilicity of the silicone hydrogel is evaluated by dropping a water droplet onto the gel surface. In general, the angle between the tangent of the water droplet and the gel surface is called the contact angle, and the smaller the contact angle, the greater the surface hydrophilicity, and the greater the contact angle, the less the surface hydrophilicity.

[0076] According to the manufacturing method of the present invention, it is possible to introduce a high proportion of polymerizable groups to both ends of the silicone macromer, and to reduce the amount of compounds (impurities) that do not have a polymerizable group. The introduction rate of polymerizable groups (hereinafter referred to as crosslinking rate) is determined by curing the silicone macromer by radical polymerization, washing the uncured components with an organic solvent, drying the organic solvent, and calculating the uncured content rate from the ratio of the weight of the cured product after washing to the weight of the cured product before washing, and using this as the crosslinking rate. That is, the rate of impurities that do not have a polymerizable group is evaluated. According to the manufacturing method of the present invention, it is possible to reduce the amount of impurities that do not have a polymerizable group and provide a polymerizable silicone macromer with high purity.

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

[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. In the following 1 H-NMR measurements were performed using an ULTRASHIELD400 PLUS (BRUKER).

[0079] [Synthesis Example 1] In a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, add [ka] 50.0 g of organohydrogenpolysiloxane containing hydrosilyl groups at both ends represented by the formula (I), 0.2 g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and 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 the reaction was completed, low boiling point fractions were removed at 100°C for 1 hour under a reduced pressure of 0.2 kPa. Next, 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 operation was repeated three times. Low boiling point fractions were removed at 85°C for 1.5 hours under a reduced pressure of 0.3 kPa, and 24 g of organopolysiloxane represented by the formula (a') was obtained. [ka] 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 hydrogen atoms bonded to silicon atoms per molecule, and an average of 0.2 groups represented by the following formula per molecule. [ka]

[0080] [Synthesis Example 2] In a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, 250.0 g of the organopolysiloxane represented by formula (a') obtained in Synthesis Example 1 above, 1.0 g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5 wt%), and 83 g of toluene were charged and heated to 70 ° C. 24.3 g of allyl glycol and 0.5 g of a toluene solution of chloroplatinic acid neutralized with sodium bicarbonate and vinylsiloxane complex (platinum content 0.5 wt%) were added and heated and stirred at 75 ° C. for 1.5 hours. After the reaction was completed, the low boiling point fraction was removed at 90 ° C. for 1 hour under a reduced pressure of 0.3 kPa. Next, 125 g of acetonitrile and 31 g of water were added, stirred, washed, and then allowed to stand to separate the silicone layer. This separation and washing operation was repeated three times. The low boiling point 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). [ka] In the above formula (a), Q 1 are each independently a group represented by the following formula (b) or the following formula (c). 1 It is a mixture of two or more compounds having different structures, and has an average of 1.8 groups represented by the following formula (b) per molecule and an average of 0.2 groups represented by the following formula (c) per molecule. [ka] JPEG2025009288000044.jpg27170

[0081] [Example 1] A method for producing 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 above general formula (1). In a three-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, 80.0 g of the organopolysiloxane represented by the above formula (a), 9.5 g of 2-isocyanatoethyl methacrylate (trade 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 and heated and stirred at 65°C for 1 hour. 5.9 g of methanol was added and heated and stirred at 65°C for 30 minutes. After the reaction was completed, 2.4 g of Kyoward 2000 (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred at room temperature (25°C) for 1 hour. The solid was removed by pressure filtration. The low boiling point fraction was removed at 90°C for 1 hour under a reduced pressure of 0.3 kPa. Next, 80 g of acetonitrile was added, stirred, and then allowed to stand to separate the silicone layer. This liquid separation and washing operation was repeated three times. The low boiling fraction was removed under 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). [ka] In the above formula (d), Q 2 are each independently a group represented by the following formula (e) or the following formula (f). 2 It is a mixture of two or more compounds having different structures, and has an average of 1.8 groups represented by the following formula (e) per molecule and an average of 0.2 groups represented by the following formula (f) per molecule. [ka] JPEG2025009288000047.jpg26170

[0082] The silicone macromer obtained in Example 1 is 1 The H-NMR spectrum is shown. 1H-NMR (400MHz, CDCl3): δ -0.17~0.22(m,264H),0.38~0.55(m,16H),1.37~1.65(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),3.50~3.55(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] 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 above general formula (4). A flask equipped with a stirrer was charged with 25.0 g of the silicone macromer represented by the above formula (d), 7.5 g of iodomethane, and 25.0 g of tetrahydrofuran, and stirred for 8 hours at 20° C. After completion of the reaction, low boiling point 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). [ka] In the above formula (g), Q 3 are each independently a group represented by the above formula (e) or (f). 3 It is a mixture of two or more compounds having different structures, 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. 1H-NMR (400MHz, CDCl3): δ -0.19~0.25(m,264H),0.36~0.63(m,16H),1.48~1.79(m,16H),1.87(s,6H),2.80(s,0.6H),3.13(t,J=8.2 Hz,0.4H),3.21~3.77(m,41.2H),4.08~4.23(m,7.6H),4.70(s,0.2H),4.98(s,1.8H),5.52(s,2H),6.04(s,2H)

[0085] [Manufacturing silicone hydrogel] [Example 3] Preparation of silicone hydrogel from silicone macromer represented by formula (g) (a) Silicone macromer represented by the above formula (g), (b) (3-methacryloxy-2-hydroxypropoxy)propylbis(trimethylsiloxy)methylsilane, (c) N,N-dimethylacrylamide, and (d) isopropanol were mixed in amounts such that the mass ratio of (a):(b):(c):(d) was 25:35:40:20. Furthermore, 0.02 g of 2-hydroxy-2-methyl-1-phenylpropanone (product name: Omnirad-1173, manufactured by IGM Resins BV) was added and stirred until a homogeneous solution was obtained. The mixture was allowed to stand and degassed, and then 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 with 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 the above formula (g).

[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 methacryl groups at both ends (Mw=9450, manufactured by Shin-Etsu Chemical Co., Ltd.) was used instead of the silicone macromer represented by the above formula (g).

[0088] [Crosslinking rate measurement of cured product] (a) The silicone macromer represented by formula (g) obtained in Example 2 above and (b) isopropanol were mixed in amounts with a mass ratio of (a):(b)=5:1. The mixture was cured in the same manner as in Example 3 above to obtain a cured product. The uncured components contained in the prepared cured product were washed with isopropanol, then air-dried for 1 hour, and dried by heating 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. That is, the content ratio of the compound without a polymerizable group that was associated with the silicone macromer obtained in the above Example was 5%, and the crosslinking rate (i.e., the content ratio of the compound with a polymerizable group to the total mass of the product) was 95%. Therefore, the manufacturing method of the present invention can introduce a (meth)acrylic group to the end of the silicone macromer at a high ratio of 95% or more.

[0089] [Surface hydrophilicity test of silicone hydrogel] A surface hydrophilicity test was carried out 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 carried out 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] [Table 1]

[0091] As shown in Table 1, the silicone hydrogel obtained from the copolymer of the present invention's silicone macromer modified at both ends with (meth)acrylic and having quaternary ammonium cation moieties 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's silicone macromer modified at both ends with (meth)acrylic and having quaternary ammonium cation moieties has high surface hydrophilicity. [Industrial Applicability]

[0092] The copolymer containing the terminally (meth)acrylic-modified silicone macromer of the present invention has excellent hydrophilicity. The silicone hydrogel containing the copolymer has excellent transparency. Therefore, the terminally (meth)acrylic-modified 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): 【Chemistry 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 a tertiary amino group at both ends in the molecular chain according to claim 1, wherein in the general formula (1), Q is each independently a group represented by the following formula (2) or the following formula (3): 【Chemistry 2】 (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.) 【Chemistry 3】 (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): 【Chemistry 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 having a quaternary ammonium cation moiety in the molecular chain at both ends thereof according to claim 3, wherein in the general formula (4), Q is each independently a group represented by the following formula (2) or (3): 【Chemistry 5】 (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.) 【Chemistry 6】 (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 silicone macromer modified at both ends with a (meth)acrylic acid, which has a tertiary amine in its molecular chain and is represented by the following general formula (1): 【Chemistry 7】 (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 includes 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 by (meth)acrylic groups represented by the above general formula (1). 【Chemistry 8】 (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): 【Chemistry 9】 (In formula (8), n2 is an integer from 2 to 10, and n3 is an integer from 0 to 10.) 【Chemistry 10】 (In formula (9), R １ is as above) 【Chemistry 11】 (In the general formula (10), X and n1 are as defined above).

6. The 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 each independently a group represented by the following formula (2) or the following formula (3): 【Chemistry 12】 (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.) 【Chemistry 13】 (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. 6. The method for producing a (meth)acrylic-modified silicone macromer having a tertiary amine in the molecular chain at both ends according to claim 5, further comprising a 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 and represented by general formula (7).

8. 8. The 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 a 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, the silicone macromer having a quaternary ammonium cation moiety in the molecular chain, represented by the following general formula (4): 【Chemistry 14】 (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, b is an integer of 1 to 50, each n1 is independently an integer of 2 to 10, and Y is a chlorine atom, a bromine atom, or an iodine atom. The method includes a step of reacting a silicone macromer (a) modified at both ends with a (meth)acrylic group and having a tertiary amino group in the molecular chain, which is represented by the following general formula (1), with a halogenated hydrocarbon (b) represented by the following general formula (14), to obtain a silicone macromer modified at both ends with a (meth)acrylic group represented by the above general formula (4). 【Chemistry 15】 (In general formula (1), R, R １ , X, Q, a, b, and n1 are as defined above. 【Chemistry 16】 (In formula (14), R ２ is as defined above, and Y is a chlorine atom, a bromine atom or an iodine atom).

10. The 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): 【Chemistry 17】 (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.) 【Chemistry 18】 (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. 11. The 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 general formula (1).

12. The method for producing a (meth)acrylic-modified silicone macromer having quaternary ammonium cation moieties in the molecular chain at both ends 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): 【Chemistry 19】 (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): 【Chemistry 20】 (In formula (8), n2 and n3 are as defined above.) 【Chemistry 21】 (In formula (9), R １ is as above).

13. 13. The 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 having 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).

14. 14. The method for producing a (meth)acrylic-modified silicone macromer at both ends which has a quaternary ammonium cation moiety in the molecular chain according to claim 13, further comprising a 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 which has hydrosilyl groups at the ends and tertiary amino groups in the molecular chain.

15. 2. A copolymer of the (meth)acrylic-modified silicone macromer at both ends having a tertiary amino group in the molecular chain according to claim 1 and a polymerizable monomer having a group polymerizable with the (meth)acrylic-modified silicone macromer.

16. 4. 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 polymerizable with the (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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