Patent ID: 12248251

EXAMPLES

Synthesis Example 1

A 300-ml flask was charged with 22.3 g of tetraethoxysilane, 6.5 g of methyltriethoxysilane, 3.2 g of triethoxysilylpropyldiallyl isocyanurate, and 48.5 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.2 g of 0.2 M aqueous nitric acid solution and 0.32 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-1). The polymer was found to have a weight average molecular weight Mw of 1,500 as determined by GPC in terms of polystyrene.

Synthesis Example 2

A 300-ml flask was charged with 23.1 g of tetraethoxysilane, 6.8 g of methyltriethoxysilane, 1.9 g of glycidoxypropyltrimethoxysilane, and 48.1 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.8 g of 0.2 M aqueous nitric acid solution and 0.32 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-2). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 3

A 300-ml flask was charged with 22.6 g of tetraethoxysilane, 6.6 g of methyltriethoxysilane, 2.7 g of phenylsulfonylpropyltriethoxysilane, and 48.4 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.4 g of 0.2 M aqueous nitric acid solution and 0.32 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-3). The polymer was found to have a weight average molecular weight Mw of 1,800 as determined by GPC in terms of polystyrene.

Synthesis Example 4

A 300-ml flask was charged with 23.0 g of tetraethoxysilane, 6.8 g of methyltriethoxysilane, 2.0 g of bicyclo(2,2,1)hept-5-en-yltriethoxysilane, and 48.2 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.7 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-4). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 5

A 300-ml flask was charged with 23.1 g of tetraethoxysilane, 6.8 g of methyltriethoxysilane, 1.9 g of cyclohexylepoxyethyltrimethoxysilane, and 48.1 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.8 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-5). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 6

A 300-ml flask was charged with 22.7 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.5 g of phenylsulfonamidopropyltrimethoxysilane, and 48.1 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.5 g of 0.2 M aqueous nitric acid solution and 0.32 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-6). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 7

A 300-ml flask was charged with 23.2 g of tetraethoxysilane, 6.8 g of methyltriethoxysilane, 1.6 g of cyclohexyltrimethoxysilane, and 48.0 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.9 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes.

Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-7). The polymer was found to have a weight average molecular weight Mw of 1,500 as determined by GPC in terms of polystyrene.

Synthesis Example 8

A 300-ml flask was charged with 23.4 g of tetraethoxysilane, 8.3 g of methyltriethoxysilane, and 48.0 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 20.0 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-8). The polymer was found to have a weight average molecular weight Mw of 1,700 as determined by GPC in terms of polystyrene.

Synthesis Example 9

A 300-ml flask was charged with 22.9 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.2 g of trifluoroacetamidopropyltriethoxysilane, and 48.2 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.6 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-9). The polymer was found to have a weight average molecular weight Mw of 1,800 as determined by GPC in terms of polystyrene.

Synthesis Example 10

A 300-ml flask was charged with 22.8 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.4 g of succinic anhydride-propyltriethoxysilane, and 48.3 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.5 g of 0.2 M aqueous nitric acid solution and 0.32 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-10). The polymer was found to have a weight average molecular weight Mw of 1,600 as determined by GPC in terms of polystyrene.

Synthesis Example 11

A 300-ml flask was charged with 22.9 g of tetraethoxysilane, 6.7 g of methyltriethoxysilane, 2.2 g of p-ethoxyethoxyphenyltrimethoxysilane, and 48.2 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.6 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-11). The polymer was found to have a weight average molecular weight Mw of 1,600 as determined by GPC in terms of polystyrene.

Synthesis Example 12

A 300-ml flask was charged with 23.5 g of tetraethoxysilane, 6.9 g of methyltriethoxysilane, 1.2 g of vinyltrimethoxysilane, and 47.9 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 20.2 g of 0.2 M aqueous nitric acid solution and 0.33 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-12). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 13

A 300-ml flask was charged with 23.1 g of tetraethoxysilane, 5.7 g of methyltriethoxysilane, and 48.0 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 20.0 g of 2 M aqueous nitric acid solution and 3.3 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-8). The polymer was found to have a weight average molecular weight Mw of 2,800 as determined by GPC in terms of polystyrene.

Synthesis Example 14

A 300-ml flask was charged with 18.3 g of tetraethoxysilane, 15.1 g of triethoxysilylpropyldiallyl isocyanurate, and 50.6 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 15.7 g of 0.2 M aqueous nitric acid solution and 0.26 g of dimethylaminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-13). The polymer was found to have a weight average molecular weight Mw of 1,500 as determined by GPC in terms of polystyrene.

Synthesis Example 15

A 300-ml flask was charged with 22.3 g of tetraethoxysilane, 6.6 g of methyltriethoxysilane, 3.2 g of triethoxysilylpropyldiallyl isocyanurate, and 48.5 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.2 g of 0.2 M aqueous nitric acid solution and 0.27 g of aminopropyltrimethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-14). The polymer was found to have a weight average molecular weight Mw of 2,500 as determined by GPC in terms of polystyrene.

Synthesis Example 16

A 300-ml flask was charged with 22.3 g of tetraethoxysilane, 6.5 g of methyltriethoxysilane, 3.2 g of triethoxysilylpropyldiallyl isocyanurate, and 48.6 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.1 g of 0.2 M aqueous nitric acid solution and 0.42 g of 4,5-dihydroxyimidazole propyltriethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was100%. The resultant polymer corresponds to Formula (A-15). The polymer was found to have a weight average molecular weight Mw of 2,000 as determined by GPC in terms of polystyrene.

Synthesis Example 17

A 300-ml flask was charged with 22.2 g of tetraethoxysilane, 6.5 g of methyltriethoxysilane, 3.2 g of triethoxysilylpropyldiallyl isocyanurate, and 48.6 g of acetone. While the mixture was stirred with a magnetic stirrer, a mixture of 19.1 g of 0.2 M aqueous nitric acid solution and 0.47 g of bishydroxyethylaminopropyltriethoxysilane was added dropwise to the flask. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 64 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. while a solvent proportion of propylene glycol monomethyl ether was 100%. The resultant polymer corresponds to Formula (A-16). The polymer was found to have a weight average molecular weight Mw of 1,800 as determined by GPC in terms of polystyrene.

Synthesis Example 18

A 500-ml flask was charged with 91.16 g of water. While the mixture was stirred with a magnetic stirrer, 22.23 g of dimethylaminopropyltrimethoxysilane and 8.16 g of triethoxysilylpropylsuccinic anhydride were added dropwise to the mixture. After completion of the dropwise addition, the flask was transferred to an oil bath set at 40° C., and reaction was allowed to proceed for 240 minutes. Thereafter, the reaction mixture was cooled to room temperature, and 91.16 g of water was added to the reaction mixture. Methanol (i.e., a reaction by-product) and water were then distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polysiloxane). Subsequently, water was added to the aqueous solution so as to achieve a solid residue content of 20% by mass at 140° C. while a solvent proportion of water was 100% (solvent: water only). The resultant polymer corresponds to Formula (A-17). The polymer was found to have a weight average molecular weight Mw of 3,300 as determined by GPC in terms of polyethylene glycol.

Synthesis Example 19

A 500-ml flask was charged with 16.84 g of acetic acid, 70.11 of water, and 70.11 g of acetone. While the mixture was stirred with a magnetic stirrer, 23.26 g of dimethylaminopropyltrimethoxysilane was added dropwise to the mixture. Thereafter, the resultant mixture was added to 15.58 g of tetraethoxysilane. The flask was then transferred to an oil bath set at 110° C., and reaction was allowed to proceed for 240 minutes. Thereafter, the reaction mixture was cooled to room temperature, and 116.51 g of water was added to the reaction mixture. Ethanol (i.e., a reaction by-product) and water were then distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polysiloxane). Subsequently, water was added to the aqueous solution so as to achieve a solid residue content of 20% by mass at 140° C. while a solvent proportion of water was 100% (solvent: water only). The resultant polymer corresponds to Formula (A-18). The polymer was found to have a weight average molecular weight Mw of 1,000 as determined by GPC in terms of polyethylene glycol.

Synthesis Example 20

A 500-ml flask was charged with 25.24 g of 70% nitric acid, 70.11 g of water, and 70.11 g of acetone. While the mixture was stirred with a magnetic stirrer, 23.26 g of dimethylaminopropyltrimethoxysilane was added dropwise to the mixture. Thereafter, the resultant mixture was added to 15.58 g of tetraethoxysilane. The flask was then transferred to an oil bath set at 110° C., and reaction was allowed to proceed for 240 minutes. Thereafter, the reaction mixture was cooled to room temperature, and 143.87 g of water was added to the reaction mixture. Ethanol (i.e., a reaction by-product) and water were then distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polysiloxane). Subsequently, water was added to the aqueous solution so as to achieve a solid residue content of 20% by mass at 140° C. while a solvent proportion of water was 100% (solvent: water only). The resultant polymer corresponds to Formula (A-19). The polymer was found to have a weight average molecular weight Mw of 800 as determined by GPC in terms of polyethylene glycol.

Synthesis Example 21

A 500-ml flask was charged with 10.78 g of acetic acid, 44.90 g of water, and 44.90 g of acetone. While the mixture was stirred with a magnetic stirrer, 14.89 g of dimethylaminopropyltrimethoxysilane was added dropwise to the mixture. Thereafter, the resultant mixture was added to 34.92 g of tetraethoxysilane. The flask was then transferred to an oil bath set at 110° C., and reaction was allowed to proceed for 240 minutes. Thereafter, the reaction mixture was cooled to room temperature, and 149.43 g of water was added to the reaction mixture. Ethanol (i.e., a reaction by-product) and water were then distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polysiloxane). Subsequently, water was added to the aqueous solution so as to achieve a solid residue content of 20% by mass at 140° C. while a solvent proportion of water was 100% (solvent: water only). The resultant polymer corresponds to Formula (A-18). The polymer was found to have a weight average molecular weight Mw of 1,200 as determined by GPC in terms of polyethylene glycol.

Synthesis Example 22

A 500-ml flask was charged with 16.16 g of 70% nitric acid, 44.90 g of water, and 44.90 g of acetone. While the mixture was stirred with a magnetic stirrer, 14.89 g of dimethylaminopropyltrimethoxysilane was added dropwise to the mixture. Thereafter, the resultant mixture was added to 34.92 g of tetraethoxysilane. The flask was then transferred to an oil bath set at 110° C., and reaction was allowed to proceed for 240 minutes. Thereafter, the reaction mixture was cooled to room temperature, and 149.43 g of water was added to the reaction mixture. Ethanol (i.e., a reaction by-product) and water were then distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polysiloxane). Subsequently, water was added to the aqueous solution so as to achieve a solid residue content of 20% by mass at 140° C. while a solvent proportion of water was 100% (solvent: water only). The resultant polymer corresponds to Formula (A-19). The polymer was found to have a weight average molecular weight Mw of 1,000 as determined by GPC in terms of polyethylene glycol.

Comparative Synthesis Example 1

A 300-ml flask was charged with 24.1 g of tetraethoxysilane, 1.8 g of phenyltrimethoxysilane, 9.5 g of triethoxymethylsilane, and 53.0 g of acetone. While the mixture was stirred with a magnetic stirrer, 11.7 g of 0.01 M aqueous hydrochloric acid solution was added dropwise to the mixture. After completion of the dropwise addition, the flask was transferred to an oil bath set at 85° C., and the mixture was refluxed for 240 minutes. Thereafter, 70 g of propylene glycol monomethyl ether was added to the mixture, and then acetone, methanol, ethanol, and water were distilled off under reduced pressure, followed by concentration, to thereby prepare an aqueous solution of a hydrolysis condensate (polymer). Subsequently, propylene glycol monomethyl ether was added to the aqueous solution so as to achieve a solid residue content of 13% by weight at 140° C. The resultant polymer corresponds to the following Formula (E-1). The polymer was found to have a weight average molecular weight Mw of 1,400 as determined by GPC in terms of polystyrene.

(Preparation of Resist Underlayer Film-Forming Composition)

Each of the polysiloxanes (polymers) prepared in the aforementioned Synthesis Examples, an acid, and a solvent were mixed in proportions shown in Table 1, and the resultant mixture was filtered with a fluororesin-made filter (0.1 μm), to thereby prepare a resist underlayer film-forming composition. The amount of each polymer shown in Table 1 corresponds not to the amount of the polymer solution, but to the amount of the polymer itself.

The water used in Examples was ultrapure water. In the following Tables, the amount of each component is represented by “parts by mass.” In the following Tables, MA denotes maleic acid; NfA, nonafluorobutanesulfonic acid;

APTEOS, aminopropyltrimethoxysilane; TPSCS, triphenylsulfonium camphorsulfonate; TPSNO3, triphenylsulfonium nitrate; PGMEA, propylene glycol monomethyl ether acetate; PGEE, propylene glycol monoethyl ether, PGME, propylene glycol monomethyl ether; and DIW, water.

TABLE 1Si polymersolutionAdditive 1Additive 2SolventExample 1SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 10.03401038121Example 2SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 20.03401038121Example 3SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 30.03401038121Example 4SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 40.03401038121Example 5SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 50.03401038121Example 6SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 60.03401038121Example 7SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 70.03401038121Example 8SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 80.03401038121Example 9SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 90.03401038121Example 10SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 100.03401038121Example 11SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 110.03401038121Example 12SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 120.03401038121

TABLE 2Si polymersolutionAdditive 1Additive 2SolventExample 13SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 130.03401038121Example 14SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 140.03401038121Example 15SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 150.03401038121Example 16SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 160.03401038121Example 17SynthesisMAPGEEPGMEAPGMEDIW(parts by mass)Example 170.03401038121Example 18SynthesisNfADIW(parts by mass)Example 180.011001Example 19SynthesisNfADIW(parts by mass)Example 190.011001Example 20SynthesisNfADIW(parts by mass)Example 200.011001Example 21SynthesisNfADIW(parts by mass)Example 210.011001Example 22SynthesisNfADIW(parts by mass)Example 220.011001ComparativeComparativeMAPGEEPGMEAPGMEDIWExample 1Synthesis0.0340103812(parts by mass)Example 11ComparativeComparativeMATPSNO3PGEEPGMEAPGMEDIWExample 2Synthesis0.030.0540103812(parts by mass)Example 11
(Preparation of Organic Resist Underlayer Film)

In a nitrogen atmosphere, a 100-ml four-necked flask was charged with 6.69 g (0.040 mol) of carbazole (available from Tokyo Chemical Industry Co., Ltd.), 7.28 g (0.040 mol) of 9-fluorenone (available from Tokyo Chemical Industry Co., Ltd.), 0.76 g (0.0040 mol) of p-toluenesulfonic acid monohydrate (available from Tokyo Chemical Industry Co., Ltd.), and 6.69 g of 1,4-dioxane (available from Kanto Chemical Co., Inc.), and the resultant mixture was stirred. The mixture was heated to 100° C. for dissolution, to thereby initiate polymerization. After the elapse of 24 hours, the mixture was left cool to 60° C. The mixture was then diluted with 34 g of chloroform (available from Kanto Chemical Co., Inc.) and reprecipitated in 168 g of methanol (available from Kanto Chemical Co., Inc.). The resultant precipitate was filtered and dried with a reduced pressure dryer at 80° C. for 24 hours, to thereby yield 9.37 g of a target polymer (Formula (F-1), hereinafter abbreviated as “PCzFL”).

The results of1H-NMR analysis of PCzFL were as follows:1H-NMR (400 MHz, DMSO-d6): δ 7.03-7.55 (br, 12H), δ 7.61-8.10 (br, 4H), δ 11.18 (br, 1H).

PCzFL was found to have a weight average molecular weight Mw of 2,800 as determined by GPC in terms of polystyrene and a polydispersity Mw/Mn of 1.77.

Subsequently, 20 g of the resultant resin was mixed with 3.0 g of tetramethoxymethyl glycoluril (trade name: Powderlink 1174, available from Mitsui Cytec Ltd.) serving as a crosslinking agent, 0.30 g of pyridinium p-toluenesulfonate serving as a catalyst, and 0.06 g of MEGAFAC R-30 (trade name, available from Dainippon Ink and Chemicals, Inc.) serving as a surfactant, and the mixture was dissolved in 88 g of propylene glycol monomethyl ether acetate, to thereby prepare a solution. Thereafter, the solution was filtered with a polyethylene-made microfilter (pore size: 0.10 μm), and then filtered with a polyethylene-made microfilter (pore size: 0.05 μm), to thereby prepare a solution of an organic resist underlayer film-forming composition used for a lithography process using a multilayer film.

(Tests for Solvent Resistance and Developer Solubility)

Each of the Si-containing resist underlayer film-forming compositions prepared in Examples 1 to 22 and Comparative Examples 1 and 2 was applied onto a silicon wafer with a spinner, and then heated on a hot plate at 215° C. for one minute, to thereby form an Si-containing resist underlayer film. Thereafter, a solvent of propylene glycol monomethyl ether/propylene glycol monomethyl ether acetate (=7/3) was applied onto the Si-containing resist underlayer film and then spin-dried for determining a change in film thickness between before and after application of the solvent. Solvent resistance was evaluated as “Good” when a change in film thickness was less than 1%, or evaluated as “Not cured” when a change in film thickness was 1% or more.

Similarly, each of the Si-containing coating liquids prepared in Examples 1 to 22 and Comparative Examples 1 and 2 was applied onto a silicon wafer with a spinner, and then heated on a hot plate at 215° C. for one minute, to thereby form an Si-containing resist underlayer film. Thereafter, an alkaline developer (2.38% aqueous TMAH solution) was applied onto the Si-containing resist underlayer film and then spin-dried for determining a change in film thickness between before and after application of the solvent. Developer resistance was evaluated as “Good” when a change in film thickness was less than 1%, or evaluated as “Not cured” when a change in film thickness was 1% or more.

TABLE 3Solvent  resistanceDeveloper  resistanceExample 1GoodGoodExample 2GoodGoodExample 3GoodGoodExample 4GoodGoodExample 5GoodGoodExample 6GoodGoodExample 7GoodGoodExample 8GoodGoodExample 9GoodGoodExample 10GoodGoodExample 11GoodGoodExample 12GoodGood

TABLE 4Solvent  resistanceDeveloper  resistanceExample 13GoodGoodExample 14GoodGoodExample 15GoodGoodExample 16GoodGoodExample 17GoodGoodExample 18GoodGoodExample 19GoodGoodExample 20GoodGoodExample 21GoodGoodExample 22GoodGoodComparative Example 1Not curedNot curedComparative Example 2GoodGood
(Measurement of Dry Etching Rate)

Dry etching rate was measured with the following etchers and etching gases.

Lam 2300 (available from Lam Research Co., Ltd.): CF4/CHF3/N2

RIE-10NR (available from SAMCO Inc.): O2

Each of the resist underlayer film-forming compositions prepared in Examples 1 to 22 and Comparative Example 2 was applied onto a silicon wafer with a spinner, and then heated on a hot plate at 215° C. for one minute, to thereby form an Si-containing coating film (thickness: 0.02 μm (for measurement of etching rate with CF4gas), thickness: 0.02 μm (for measurement of etching rate with O2gas)). Similarly, the organic resist underlayer film-forming composition was applied onto a silicon wafer with a spinner, to thereby form a coating film (thickness: 0.20 μm). The dry etching rate of the coating film was measured by using CF4/CHF3/N2gas and O2gas serving as etching gases, and was compared with the dry etching rate of the Si-containing coating film formed from each of the compositions of the Examples.

TABLE 5Fluorine-Oxygen-containing gascontaining gasResistanceetching rate(relative to organic resist(nm/min)underlayer film)Example 1460.03Example 2500.02Example 3460.02Example 4430.02Example 5380.03Example 6430.03Example 7430.02Example 8460.02Example 9490.02Example 10490.03Example 11430.02Example 12460.02

TABLE 6Fluorine-Oxygen-containing gascontaining gasResistance (relativeetching rateto organic resist(nm/min)underlayer film)Example 13530.02Example 14400.06Example 15460.03Example 16460.03Example 17460.03Example 18530.06Example 19500.04Example 20500.04Example 21480.03Example 22480.03Comparative  Example 2300.02

[Formation of Resist Pattern by EUV Exposure: Positive Alkali Development]

The aforementioned organic underlayer film (layer A)-forming composition was applied onto a silicon wafer, and then baked on a hot plate at 215° C. for 60 seconds, to thereby form an organic underlayer film (layer A) having a thickness of 90 nm. Each of the resist underlayer film-forming composition solutions prepared in Examples 1 to 22 of the present invention and Comparative Example 2 was applied onto layer A by spin coating, and then heated at 215° C. for one minute, to thereby form a resist underlayer film (layer B) (20 nm). An EUV resist solution (methacrylate resin resist) was applied onto the hard mask by spin coating, and then heated to form an EUV resist layer (layer C). The EUV resist layer was exposed to light with an EUV exposure apparatus (NXE3300B, available from ASML) under the following conditions: NA: 0.33, a: 0.67/0.90, Dipole. After the light exposure, PEB was performed, and the resultant product was cooled on a cooling plate to room temperature, followed by development with an alkaline developer (2.38% aqueous TMAH solution) for 60 seconds and rinsing treatment, to thereby form a resist pattern. The resist pattern was evaluated for formation of a 20 nm line and space. The pattern shape was evaluated by observation of a cross section of the pattern.

In Table 7, “Good” indicates a shape between footing and undercut and a state of no significant residue in a space portion; “Collapse” indicates an unfavorable state of peeling and collapse of the resist pattern; and “Bridge” indicates an unfavorable state of contact between upper portions or lower portions of the resist pattern.

TABLE 7Pattern shapeExample 1GoodExample 2GoodExample 3GoodExample 4GoodExample 5GoodExample 6GoodExample 7GoodExample 8GoodExample 9GoodExample 10GoodExample 11GoodExample 12Good

TABLE 8Pattern shapeExample 13GoodExample 14GoodExample 15GoodExample 16GoodExample 17GoodExample 18GoodExample 19GoodExample 20GoodExample 21GoodExample 22GoodComparative Example 2Good

[Formation of Resist Pattern by EUV Exposure: Negative Solvent Development]

The aforementioned organic underlayer film (layer A)-forming composition was applied onto a silicon wafer, and then baked on a hot plate at 215° C. for 60 seconds, to thereby form an organic underlayer film (layer A) having a thickness of 90 nm. Each of the resist underlayer film-forming composition solutions prepared in Examples 1 to 22 of the present invention and Comparative Example 2 was applied onto layer A by spin coating, and then heated at 215° C. for one minute, to thereby form a resist underlayer film (layer B) (20 nm). An EUV resist solution (methacrylate resin resist) was applied onto the hard mask by spin coating, and then heated to form an EUV resist layer (layer C). The EUV resist layer was exposed to light with an EUV exposure apparatus (NXE3300B, available from ASML) under the following conditions: NA: 0.33, σ: 0.67/0.90, Dipole. After the light exposure, PEB was performed, and the resultant product was cooled on a cooling plate to room temperature, followed by development with an organic solvent developer (butyl acetate) for 60 seconds and rinsing treatment, to thereby form a resist pattern. The resist pattern was evaluated for formation of a 22 nm line and space. The pattern shape was evaluated by observation of a cross section of the pattern.

In Table 9, “Good” indicates a shape between footing and undercut and a state of no significant residue in a space portion; “Collapse” indicates an unfavorable state of peeling and collapse of the resist pattern; and “Bridge” indicates an unfavorable state of contact between upper portions or lower portions of the resist pattern.

TABLE 9Pattern shapeExample 1GoodExample 2GoodExample 3GoodExample 4GoodExample 5GoodExample 6GoodExample 7GoodExample 8GoodExample 9GoodExample 10GoodExample 11GoodExample 12Good

TABLE 10Pattern shapeExample 13GoodExample 14GoodExample 15GoodExample 16GoodExample 17GoodExample 18GoodExample 19GoodExample 20GoodExample 21GoodExample 22GoodComparative Example 2Good
(SPM, SC-1 Solubility Test)

Each of the Si-containing resist underlayer film-forming compositions prepared in Example 18 and Comparative Example 2 was applied onto a silicon wafer with a spinner, and then heated on a hot plate at 180° C. for one minute, to thereby form an Si-containing resist underlayer film. Thereafter, RS-30 (mixture of hydrogen peroxide and sulfuric acid) (available from Rasa Industries, LTD.) or hydrogen peroxide-aqueous ammonia was applied onto the Si-containing resist underlayer film and then spin-dried for determining a change in film thickness between before and after application of the solvent. Solubility was evaluated as “Good” when a change in film thickness was 90% or more, or evaluated as “Not dissolved” when a change in film thickness was less than 90%.

TABLE 11SPM solutionSC-1 solutionExample 18GoodGoodComparative Example 2Not dissolvedNot dissolved

INDUSTRIAL APPLICABILITY

The present invention provides a resist underlayer film material that achieves a high etching rate during etching with halogen gas by a hydrolysis condensate (polysiloxane) containing a curing catalyst when a resist pattern is transferred onto an underlayer film in accordance with a reduction in the thickness of a resist film in a tri-layer process, and forms a resist underlayer film capable of being removed with a chemical after processing of a substrate.