Polyrotaxane-containing composition

Abstract

The present invention aims to provide a polyrotaxane-containing composition having excellent transparency. The present invention relates to a polyrotaxane-containing composition including: a polyrotaxane that has a cyclic molecule, a linear molecule threading through a cavity of the cyclic molecule in a skewered manner, and capping groups capping both ends of the linear molecule; and an alkyl (meth) acrylate that has a C4-C18 alkyl group, the polyrotaxane having at least one cyclic molecule that has a C4-C18 alkyl group.

Claims

1. A polyrotaxane-containing composition comprising: a polyrotaxane that has a cyclic molecule, a linear molecule threading through a cavity of the cyclic molecule in a skewered manner, and capping groups capping both ends of the linear molecule; and an alkyl (meth)acrylate that has a C4-C18 alkyl group, wherein the cyclic molecule is a cyclodextrin, the polyrotaxane has at least one cyclic molecule that has a C4-C18 alkyl group, a radical polymerizable group, and a solubility-imparting group, the solubility-imparting group is a polyester chain, and the C4-C18 alkyl group of the polyrotaxane is introduced to a terminal reaction point of the polyester chain by reacting a hydroxy group of the polyester chain with an alkyl isocyanate, wherein the alkyl isocyanate has an isocyanate group and the C4-C18 alkyl group, and the isocyanate group is reactive with the hydroxy group.

2. The polyrotaxane-containing composition according to claim 1, wherein the amount of the alkyl (meth)acrylate that has the C4-C18 alkyl group is 50% by mass or more.

3. The polyrotaxane-containing composition according to claim 1, wherein the alkyl isocyanate consists of the isocyanate group and the C4-C18 alkyl group.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention is more specifically described in the following with reference to, but not limited to, examples. The polyrotaxane used in preparation examples was prepared with reference to the method disclosed in Patent Literature 1.

PREPARATION EXAMPLE 1

(2) An amount of 300 g of a 35% by mass xylene solution of polyrotaxane (inclusion rate of cyclic molecule: 25%, mass average molecular weight: 470000, hydroxy value: 74 mgKOH/g) having polyethylene glycol (mass average molecular weight: 35000) as a linear molecule, a-cyclodextrin (substitution degree of hydroxypropyl group: 51%) in which a hydroxypropyl group is introduced and then -caprolactone was graft-polymerized as a cyclic molecule, and adamantane amine groups as capping groups was prepared. The solution was blended with 4.17 g of n-butyl isocyanate and stirred at 25 C. for 30 minutes, warmed to 60 C., and reacted at that temperature for four hours. The obtained reaction solution was cooled to 25 C., added to a large amount of methanol and stirred, and subjected to centrifugation for recovery of a precipitate. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol and stirred to be precipitated again, and centrifuged for recovery of the precipitate. The obtained precipitate was dried to give 104.7 g of polyrotaxane (PR-1) in which an n-butyl group was introduced into the cyclic molecule. The introduction rate of the n-butyl group in the polyrotaxane (PR-1) was 29%.

PREPARATION EXAMPLE 2

(3) An amount of 107.5 g of polyrotaxane (PR-2) in which an n-butyl group was introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 1, except that the amount of n-butyl isocyanate was changed to 6.94 g. The introduction rate of the n-butyl group in the polyrotaxane (PR-2) was 48%.

PREPARATION EXAMPLE 3

(4) An amount of 112.3 g of polyrotaxane (PR-3) in which an n-butyl group was introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 1, except that the amount of n-butyl isocyanate was changed to 9.72 g. The introduction rate of the n-butyl group in the polyrotaxane (PR-3) was 70%.

PREPARATION EXAMPLE 4

(5) An amount of 111.5 g of polyrotaxane (PR-4) in which an n-hexyl group was introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 1, except that 4.17 g of n-butyl isocyanate was changed to 8.90 g of n-hexyl isocyanate. The introduction rate of the n-hexyl group in the polyrotaxane (PR-4) was 49%.

PREPARATION EXAMPLE 5

(6) An amount of 112.2 g of polyrotaxane (PR-5) in which an n-octyl group was introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 1, except that 4.17 g of n-butyl isocyanate was changed to 10.9 g of n-octyl isocyanate. The introduction rate of the n-octyl group in the polyrotaxane (PR-5) was 47%.

PREPARATION EXAMPLE 6

(7) Part of the reaction solution obtained in Preparation Example 2 was taken out, purified using methanol and acetone in the same manner as in Preparation Example 2, and dried. The resulting polyrotaxane had an introduction rate of an n-butyl group of 48%. The remaining reaction solution was blended with 50 mg of dibutylhydroxytoluene and stirred at 25 C. for 15 minutes for dissolution of dibutylhydroxytoluene. The resulting solution was then blended with 10.5 g of 2-methacryloyloxyethyl isocyanate, stirred at 25 C. for 30 minutes, warmed to 60 C., and reacted at that temperature for four hours. The resulting reaction solution was cooled to 25 C., added to a large amount of methanol and stirred, and subjected to centrifugation for recovery of a precipitate. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol and stirred to be precipitated again, and subjected to centrifugation for recovery of the precipitate. The obtained precipitate was dried to give 115.3 g of polyrotaxane (PR-6) in which an n-butyl group and a methacryloyl group were introduced into a cyclic molecule. The introduction rate of the n-butyl group in the polyrotaxane (PR-6) was 48% as mentioned above and the introduction rate of the methacryloyl group therein was 51%.

PREPARATION EXAMPLE 7

(8) An amount of 115.7 g of polyrotaxane (PR-7) in which an n-hexyl group and a methacryloyl group were introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 6, except that part of the reaction solution obtained in Preparation Example 4 was used instead of the part of the reaction solution obtained in Preparation Example 2. The introduction rate of the n-hexyl group in the polyrotaxane (PR-7) was 49% and the introduction rate of the methacryloyl group therein was 49%.

PREPARATION EXAMPLE 8

(9) An amount of 119.5 g of polyrotaxane (PR-8) in which an n-octyl group and an acryloyl group were introduced into a cyclic molecule was prepared in the same manner as in Preparation Example 6, except that part of the reaction solution obtained in Preparation Example 5 was used instead of the part of the reaction solution obtained in Preparation Example 2 and that 9.87 g of 2-acryloyloxyethyl isocyanate was used instead of 10.5 g of 2-methacryloyloxyethyl isocyanate. The introduction rate of the n-octyl group in the polyrotaxane (PR-8) was 47% and the introduction rate of the acryloyl group therein was 48%.

PREPARATION EXAMPLE 9

(10) An amount of 300 g of a 35% by mass xylene solution of polyrotaxane (inclusion rate of cyclic molecule: 25%, mass average molecular weight: 470000, hydroxy value: 74 mgKOH/g) having polyethylene glycol (mass average molecular weight: 35000) as a linear molecule, -cyclodextrin (substitution degree of hydroxypropyl group: 51%) in which a hydroxypropyl group is introduced and then -caprolactone was graft-polymerized as a cyclic molecule, and adamantane amine groups as capping groups was prepared. The solution was added to a large amount of methanol, stirred, and subjected to centrifugation for recovery of a precipitate. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol and stirred to be precipitated again, and subjected to centrifugation for recovery of the precipitate. The obtained precipitate was dried to give 99.8 g of polyrotaxane (PR-9) in which no C4-C18 alkyl group was introduced into the cyclic molecule.

PREPARATION EXAMPLE 10

(11) An amount of 300 g of a 35% by mass xylene solution of polyrotaxane (inclusion rate of cyclic molecule: 25%, mass average molecular weight: 470000, hydroxy value: 74 mgKOH/g) having polyethylene glycol (mass average molecular weight: 35000) as a linear molecule, -cyclodextrin (substitution degree of hydroxypropyl group: 51%) in which a hydroxypropyl group is introduced and then -caprolactone was graft-polymerized as a cyclic molecule, and adamantane amine groups as capping groups was prepared. The solution was blended with 50 mg of dibutylhydroxytoluene and stirred at 25 C. for 15 minutes so that dibutylhydroxytoluene was dissolved. Then, the resulting solution was blended with 10.5 g of 2-methacryloyloxyethyl isocyanate, stirred at 25 C. for 30 minutes, warmed to 60 C., and reacted at that temperature for four hours. The obtained reaction solution was cooled to 25 C., added to a large amount of methanol and stirred, and subjected to centrifugation for recovery of a precipitate. The obtained precipitate was dissolved in a large amount of acetone, added to a large amount of methanol and stirred to be precipitated again, and subjected to centrifugation for recovery of the precipitate. The obtained precipitate was dried to give 113.4 g of polyrotaxane (PR-10) in which no C4-C18 alkyl group was introduced but a methacryloyl group was introduced into the cyclic molecule. The introduction rate of the methacryloyl group in the polyrotaxane (PR-10) was 50%.

PREPARATION EXAMPLE 11

(12) An amount of 116.5 g of polyrotaxane (PR-11) in which no C4-C18 alkyl group was introduced but a methacryloyl group was introduced into a cyclic molecule was prepared in the same manner as in Example 10, except that the amount of 2-methacryloyloxyethyl isocyanate was set to 15.2 g. The introduction rate of the methacryloyl group in the polyrotaxane (PR-11) was 71%.

EXAMPLES 1 to 15, COMPARATIVE EXAMPLES 1 to 5

(13) A 30-mL sample bottle equipped with a stirring element was charged with the materials each in an amount shown in Table 1, and the contents were stirred at 25 C. for one hour.

(14) In Table 1, 2-EHA refers to 2-ethylhexyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), BA refers to n-butyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.), and LA refers to dodecyl acrylate (produced by Tokyo Chemical Industry Co., Ltd.).

(15) <Evaluation>

(16) Each of the polyrotaxane-containing compositions obtained in the examples and comparative examples was subjected to the following evaluation. Table 1 shows the results.

(17) (Transparency)

(18) Each of the polyrotaxane-containing compositions obtained in the examples and comparative examples was visually observed at 25 C. and 40 C. The transparency was evaluated based on the following criteria: A composition with no turbidity at 25 C. and 40 C. was regarded to be excellent (oo); A composition with slight turbidity at 25 C. but no turbidity at 40 C. was regarded to be fair (o); A composition with turbidity or separation at both 25 C. and 40 C. was regarded to be poor (x).

(19) TABLE-US-00001 TABLE 1 Polyrotaxane C4-C18 Alkyl (meth)acrylate Introduction rate Amount Amount Amount Amount Amount (wt %) of each group Amount (g ) of (g) of (g) of (wt %) of of C4-C18 alkyl Kind in cyclic molecule (g) 2-EHA BA LA polyrotaxane (meth)acrylate Transparency Example 1 PR-1 n-Butyl: 29% 9.00 21.00 30 70 Example 2 PR-2 n-Butyl: 48% 9.00 21.00 30 70 Example 3 PR-3 n-Butyl: 70% 9.00 21.00 30 70 Example 4 PR-4 n-Hexyl: 49% 9.00 21.00 30 70 Example 5 PR-5 n-Octyl: 47% 9.00 21.00 30 70 Example 6 PR-6 n-Butyl: 48% 9.00 21.00 30 70 Methacryloyl: 51% Example 7 PR-2 n-Butyl: 48% 9.00 21.00 30 70 Example 8 PR-4 n-Hexyl: 49% 9.00 21.00 30 70 Example 9 PR-5 n-Octyl: 47% 9.00 21.00 30 70 Example 10 PR-3 n-Butyl: 70% 9.00 21.00 30 70 Example 11 PR-2 n-Butyl: 48% 3.00 27.00 10 90 Example 12 PR-5 n-Octyl: 47% 3.00 27.00 10 90 Example 13 PR-6 n-Butyl: 48% 6.00 12.00 12.00 20 80 Methacryloyl: 51% Example 14 PR-7 n-Hexyl: 49% 6.00 12.00 12.00 20 80 Methacryloyl: 49% Example 15 PR-8 n-Octyl: 47% 6.00 8.00 8.00 8.00 20 80 Acryloyl: 48% Comparative PR-9 9.00 21.00 30 70 x Example 1 Comparative PR-9 3.00 27.00 10 90 x Example 2 Comparative PR-10 Methacryloyl: 50% 9.00 21.00 30 70 x Example 3 Comparative PR-10 Methacryloyl: 50% 3.00 27.00 10 90 x Example 4 Comparative PR-11 Methacryloyl: 71% 9.00 21.00 30 70 x Example 5

(20) In the case of the polyrotaxanes having no C4-C18 alkyl group in the cyclic molecule as used in Comparative Examples 1 to 5, they each had poor compatibility with an alkyl (meth)acrylate that has a C4-C18 alkyl group so that the composition exhibited turbidity or separation. In contrast, in the case of the polyrotaxanes having a C4-C18 alkyl group in the cyclic molecule as used in Examples 1 to 15, they each had favorable compatibility with an alkyl (meth)acrylate that has a C4-C18 alkyl group to give a transparent composition.

INDUSTRIAL APPLICABILITY

(21) The present invention can provide a polyrotaxane-containing composition having excellent transparency.