PHOTOSENSITIVE COMPOSITION

Abstract

The purpose of the present invention is to provide a photosensitive composition having excellent curability even when a colorant or other substance for attenuating or blocking radiated light is present at a high concentration, the film thickness thereof is large, and the light source is visible-to-infrared light, particularly infrared light having low energy. The present invention is a photosensitive composition characterized by containing as essential components (A) an onium salt represented by general formula (1), (B) a sensitizer, and (C) a radical polymerizable compound. (In formula (1), Rf each independently represents a C1-8 alkyl group, a C2-8 alkenyl group, or a C6-10 aryl group, 80% or more of hydrogen atoms bonded to the carbon atoms of each group being substituted with fluorine atoms, n represents an integer of 1 to 5, and A.sup.+ represents a monovalent onium cation.)

Claims

1. A photosensitive composition containing the following essential components: (A) an onium salt represented by the general formula (1); (B) a sensitizer, and (C) a radical polymerizable compound: ##STR00011## [in the formula (1), Rf each independently represents an alkyl group having a carbon number of 1 to 8, an alkenyl group having a carbon number of 2 to 8, or an aryl group having a carbon number of 6 to 10, where 80% or more of hydrogen atoms bonded to the carbon atoms of each group are substituted with fluorine atoms; n represents an integer of 1 to 5; and A.sup.+ represents a monovalent onium cation.]

2. The photosensitive composition according to claim 1, wherein A.sup.+ in the general formula (1) is sulfonium or iodonium.

3. The photosensitive composition according to claim 1, wherein Rf in the general formula (1) independently represents an alkyl group having a carbon number of 1 to 8 in which 90% or more of hydrogen atoms are substituted with fluorine atoms.

4. The photosensitive composition according to claim 1, wherein the sensitizer (B) is a polymethine-based dye.

5. A method for curing a photosensitive composition, the method comprising the step of irradiating the photosensitive composition according to claim 1 with light in a visible-to-infrared region having a wavelength of 400 nm to 1500 nm.

6. A method for curing a photosensitive composition, the method comprising the step of irradiating the photosensitive composition according to claim 1 with light in a near-infrared region having a wavelength of 700 nm to 1200 nm.

7. A cured product obtained by curing a photosensitive composition by the method according to claim 5.

8. A cured product obtained by curing a photosensitive composition by the method according to claim 6.

Description

EXAMPLES

[0094] Hereinafter, the present invention is more specifically described with reference to examples, which however are not intended to limit the invention. % means % by weight unless otherwise specified.

Production Example 1

Synthesis of Potassium Tris(nonafluorobutyl)trifluorophosphate (AN-1)

[0095] Tris(nonafluorobutyl)difluorophosphorane (gas chromatography purity: 90%, yield: 60%) was synthesized by electrolytic fluorination of tributylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Potassium fluoride of 18.0 g and dimethoxyethane of 600 ml were added in a 1 L reaction vessel, the mixture was stirred and suspended, and 202.6 g of the obtained tris(nonafluorobutyl)difluorophosphorane was added dropwise while the liquid was kept at a temperature of 20 to 30 C. The mixture was stirred at room temperature for 24 hours, the reaction liquid was then filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 136.0 g of a white powder. From .sup.19F and .sup.31P-NMR, this white powder was confirmed to be potassium tris(nonafluorobutyl)trifluorophosphate (AN-1).

Production Example 2

Synthesis of Potassium Tris(heptafluoropropyl)trifluorophosphate (AN-2)

[0096] Tris(heptafluoropropyl)difluorophosphorane (gas chromatography purity: 89%, yield: 52%) was synthesized by electrolytic fluoridation of tripropylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 161.0 g of tris(heptafluoropropyl)difluorophosphorane was used in place of 202.6 g of tris(nonafluorobutyl)difluorophosphorane in Production Example 1, the same procedure as in Production Example 1 was carried out to obtain potassium trisfheptafluoropropyl)trifluorophosphate (AN-2).

Production Example 3

Synthesis of Potassium Tris(pentafluoroethyl)trifluorophosphate (AN-3)

[0097] Tris(pentafluoroethyl)difluorophosphorane (gas chromatography purity: 97%, yield: 72%) was synthesized by electrolytic fluorination of triethylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 119.0 g of tris(heptafluoroethyl)difluorophosphorane was used in place of 202.6 g of tris(nonafluorobutyDdifluorophosphorane in Production Example 1, the same procedure as in Production Example 1 was carried out to obtain potassium tris(pentafluoroethyl)trifluorophosphate (AN-3).

Production Example 4

Synthesis of Potassium Tris(nonafluoroisobutyl)trifluorophosphate (AN-4)

[0098] Tris(nonafluoroisobutyl)difluorophosphorane (gas chromatography purity: 89%, yield: 47%) was synthesized by electrolytic fluorination of triisobutylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 202.6 g of tris(nonafluoroisobutyljdifluorophosphorane was used in place of 202.6 g of tris(nonafluorobutyl)difluorophosphorane in Production Example 1, the same procedure as in Production Example 1 was carried out to obtain potassium tris(nonafluoroisobutyl)trifluorophosphate (AN-4).

Production Example 5

Synthesis of Potassium Tris(heptafluoroisopropyl)trifluorophosphate (AN-5)

[0099] Tris(heptafluoroisopropyl)difluorophosphorane (gas chromatography purity: 89%, yield: 43%) was synthesized by electrolytic fluorination of triisopropylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 161.0 g of tris(heptafluoroisopropyl)difluorophosphorane wa3 used in place of 202.6 g of tris(nonafluorobutyl)difluorophosphorane in Production Example 1, the same procedure as in Production Example 1 was carried out to obtain potassium tris(heptafluoroisopropyl)trifluorophosphate (AN-5).

Production Example 6

Synthesis of Sodium Bis(heptafluoropropyl)tetrafluorophosphate (AN-6)

[0100] Bis(heptafluoropropyl)tetrafluorophosphorane (gas chromatography purity: 90%, yield: 53%) was synthesized by electrolytic fluorination of dipropylchlorophosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Then, 16.1 g of sodium fluoride and 600 ml of dimethoxyethane were added in a 1 L reaction vessel, the mixture was stirred and suspended, and 119.0 g of the obtained bis(heptafluoropropyl)tetrafluorophosphorane was added dropwise while the liquid is kept at a temperature of 20 to 30 C. The mixture was stirred at room temperature for 24 hours, the reaction liquid was then filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 115.5 g of a white powder. From .sup.19F and .sup.31P-NMR, this white powder was confirmed to be sodium bis(heptafluoropropyl)tetrafluorophosphate (AN-6).

Production Example 7

Synthesis of Sodium Bis(pentafluoroethyl)tetrafluorophosphate (AN-7)

[0101] Bis(pentafluoroethyl)trifluorophosphorane (gas chromatography purity: 96%, yield: 68%) was synthesized by electrolytic fluorination of diethylchlorophosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 91.0 g of bis(pentafluoroethyl)trifluorophosphorane was used in place of 119.0 g of bis(heptafluoropropyl)tetrafluorophosphorane in Production Example 6, the same procedure as in Production Example 6 was carried out to obtain sodium bis(pentafluoroethyl)tetrafluorophosphate (AN-7).

Production Example 8

Synthesis of Sodium Bis(nonafluorobutyl)tetrafluorophosphate (AN-8)

[0102] Bis(nonafluorobutyl)trifluorophosphorane (gas chromatography purity: 77%, yield: 67%) was synthesized by electrolytic fluorination of dibutylchlorophosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Except that 146.8 g of bis(nonafluorobutyl)trifluorophosphorane was used in place of 119.0 g of bis(heptafluoropropyl)tetrafluorophosphorane in Production Example 6, the same procedure as in Production Example 6 was carried out to obtain sodium bis(nonafluorobutyl)tetrafluorophosphate (AN-8).

Production Example 9

Synthesis of Lithium (Nonafluorobutyl)pentafluorophosphate (AN-9)

[0103] (Nonafluorobutyl)tetrafluorophosphorane (gas chromatography purity: 90%, yield: 53%) was synthesized by electrolytic fluorination of butyldichlorophosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Then, 8.1 g of lithium fluoride and 600 ml of dimethoxyethane were added in a 1 L reaction vessel, the mixture was stirred and suspended, and 91.0 g of the obtained (nonafluorobutyl)tetrafluorophosphorane was added dropwise while the liquid was kept at a temperature of 20 to 30 C. The mixture was stirred at room temperature for 24 hours, the reaction liquid was then filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 87.0 g of a white powder. From .sup.19F and .sup.31P-NMR, this white powder was confirmed to be lithium (nonafluorobutyl)pentafluorophosphate (AN-9).

Production Example 10

Synthesis of Lithium (Pentafluoroethyl)pentafluorophosphate (AN-10)

[0104] (Pentafluoroethyl)tetrafluorophosphorane (gas chromatography purity: 90%, yield: 53%) was synthesized by electrolytic fluorination of dichloroethylphosphine in accordance with a patent document (U.S. Pat. No. 6,264,818). Then, 8.1 g of lithium fluoride and 600 ml of dimethoxyethane were added in a 1L reaction vessel, the mixture was stirred and suspended, and 63.0 g of the obtained (nonafluorobutyl)tetrafluorophosphorane was added dropwise while the liquid was kept at a temperature of 20 to 30 C. The mixture was stirred at room temperature for 24 hours, the reaction liquid was then filtered, and dimethoxyethane was distilled off from the filtrate under reduced pressure to obtain 57.0 g of a white powder. From .sup.19F and .sup.31P-NMR, this white powder was confirmed to be lithium (pentafluoroethyl)pentafluorophosphate (AN-10).

Production Example 11

Synthesis of Onium Salt (Al-1): Diphenyliodonium Tris(nonafluorobutyl)trifluorophosphate

[0105] Added in a reaction vessel were 4.3 g of diphenyliodonium trifluoromethanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 30 g of dichloromethane. The potassium salt (AN-1) of 8.0 g synthesized in Production Example 1 was added while the mixture was stirred, 50 mL of water was further added, and the mixture was stirred at room temperature for 18 hours. The mixture was left standing, the aqueous layer was then removed by liquid separation, and the organic layer was washed with 50 mL of water five times. The organic solvent was distilled off under reduced pressure to obtain 9.7 g of a white solid. From .sup.1H, .sup.19F and .sup.31P-NMR, this white solid was confirmed to be an onium salt (Al-1).

Production Example 12

Synthesis of Onium Salt (Al-2): Di(tert-butylphenyl)iodonium Tris(nonafluorobutyl)trifluorophosphate

[0106] Except that 5.4 g of di(tert-butylphenyl) iodoniumhexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of 4.3 g of diphenyliodonium trifluoromethanesulfonate in Production Example 11, the same procedure as in Production Example 11 was carried out to obtain 10.9 g of a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this white solid was confirmed to be an onium salt (Al-2).

Production Example 13

Synthesis of Onium Salt (Al-3): (4-isopropylphenyl)tolyliodonium Tris(nonafluorobutyl)trifluorophosphate

[0107] Added in a reaction vessel was 20 g of 4-methyliodobenzene, and dissolved by adding 50 mL of acetic acid and 10 mL of sulfuric acid, and while the solution was cooled in an ice-water bath, 10 g of potassium persulfate was gradually added at 15 C. or lower. The mixture was reacted at 20 C for 4 hours, and 24.4 g of cumene was added dropwise thereinto at a temperature of not higher than 20 C. Thereafter, the mixture was reacted at room temperature for 20 hours. The reaction liquid was poured into a solution obtained by dissolving 60 g of the potassium salt (AN-1) in 500 mL of water, and the mixture was further stirred for 3 hours. Dichlororoethane of 500 mL was added thereto. The mixture was left standing, the aqueous layer was then removed by liquid separation, and the organic layer was washed with 100 mL of water five times. The dichloromethane was concentrated, and recrystallized from cyclohexane to obtain 95 g of a white solid. From .sup.1H, .sup.19F and .sup.31P-NMB, this white solid was confirmed to be an onium salt (Al-3).

Production Example 14

Synthesis of onium salt (Al-4): (4-isopropylphenyl)tolyliodonium Tris(pentafluoroethyl)trifluorophosphate

[0108] Except that 45 g of the potassium salt (AN-3) was used in place of 80 g of the potassium salt (AN-1) in Production Example 13, the same procedure as in Production Example 13 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-4).

Production Example 15

Synthesis of onium salt (Al-5): (4-isopropylphenyl)tolyliodonium Tris(heptafluoroisopropyl)trifluorophosphate

[0109] Except that 60 g of the potassium salt (AN-5) was used in place of 80 g of the potassium salt (AN-1) in Production Example 13, the same procedure as in Production Example 13 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-5).

Production Example 16

Synthesis of Onium Salt (Al-6): Di(tert-butylphenyl)iodonium Bis(pentafluoroethyl)tetrafluorophosphate

[0110] Except that 3.6 g of the sodium salt (AN-7) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 12, the same procedure as in Production Example 12 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-6).

Production Example 17

Synthesis of Onium Salt (Al-7): Di(tert-butylphenyl)iodonium Bis(heptafluoropropyl)tetrafluorophosphate

[0111] Except that 4.5 g of the sodium salt (AN-6) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 12, the same procedure as in Production Example 12 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-7).

Production Example 18

Synthesis of Onium Salt (Al-8): (4-octyloxyphenyl)phenyliodonium Tris(nonafluoroisobutyl)trifluorophosphate

[0112] A desired product was obtained in accordance with the method described in a patent document (JP-A-06-184170). From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-8).

Production Example 19

Synthesis of Onium Salt (Al-9): Di(tert-butylphenyl)iodonium (Nonafluorobutyl)pentafluorophosphate

[0113] Except that 4.0 g of the lithium salt (AN-9) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 12, the same procedure as in Production Example 12 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-9).

Production Example 20

Synthesis of Onium Salt (Al-10): Di(tert-butylphenyl)iodonium (Pentafluoroethyl)pentafluorophosphate

[0114] Except that 2.6 g of the lithium salt (AH-10) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 12, the same procedure as in Production Example 12 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (Al-10).

Production Example 21

Synthesis of Onium Salt (A2-1): Triphenylsulfonium Tris(nonafluorobutyl)trifluorophosphate

[0115] Added in a reaction vessel were 3.4 g of triphenylsulfonium bromide (manufactured by Tokyo Chemical industry Co., Ltd.) and 50 mL of dichloromethane. The potassium salt of 8.0 g (AN-1) synthesized in Production Example 1 was added while the mixture was stirred, 50 mL of water was further added, and the mixture was stirred at room temperature for 8 hours. The mixture was left standing, the aqueous layer was then removed by liquid separation, and the organic layer was washed with 50 mL of water five times. The organic solvent was distilled off under reduced pressure to obtain 9.2 g of a white solid. From .sup.1H, .sup.19F and .sup.31P-NMR, this white solid was confirmed to be an onium salt (A2-1).

Production Example 22

Synthesis of Onium Salt (A2-2): Tris(4-fluorophenyl)sulfonium Tris(heptafluoropropyl)trifluorophosphate

[0116] Bis(4-fluorophenyl)sulfoxide of 23.8 g was added in a reaction vessel, and 200 mL of THF was added. The mixture was cooled to 0 C. in an ice bath, and 50 g of trimethylsilyl chloride was added dropwise thereto. The mixture was stirred for 2 hours, and while the mixture was kept at 10 C or lower, 250 mL of a 1.0 mol/L THF solution prepared from 4-fluorobromobenzene by a normal method was added dropwise. After completion of the dropwise addition, the mixture was reacted at room temperature for 8 hours. The reaction liquid was poured into 1 L of water, and washed with 500 mL of toluene twice. The potassium salt of 65 g (AN-2) was added to the aqueous layer, and the mixture was further stirred for 4 hours. Dichloromethane of 700 mL was added, the aqueous layer was removed by liquid separation, and washing was performed with 500 mL of water five times. The dichlore-methane layer was concentrated, and crystallized with cyclohexane to obtain 88 g of a white solid. From .sup.1H, .sup.19F and .sup.31P-NMR, this white solid was confirmed to be an onium salt (A2-2).

Production Example 23

Synthesis of onium salt (A2-3): (4-phenylthio)phenyldiphenylsulfonium Tris(pentafluoroethyl)trifluorophosphate

[0117] A desired product was obtained in accordance with the method described in a patent document (WO 2005-116038). From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (A2-3).

Production Example 24

Synthesis of Onium Salt (A2-4): Thiodi-p-phenylene Bis(diphenylsulfonium)bis[tris(heptafluoroisopropyl)trifluorophosphate]

[0118] A desired product was obtained in accordance with the method described in a patent document (JP-A-2013-227368). From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (A2-4).

Production Example 25

Synthesis of Onium Salt (A2-5): (4-phenylthio)phenyldiphenylsulfonium Tris(nonafluoroisobutyl)trifluorophosphate

[0119] A desired product was obtained in accordance with the method described in a patent document (WO 2005-116038). From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (A2-5).

Production Example 26

Synthesis of Onium Salt (A2-6): Tris(4-tert-butylphenyl)sulfonium Bis(pentafluoroethyl)tetrafluorophosphate

[0120] Added in a reaction vessel were 5-8 g of tris(4-tert-butylphenyl)sulfonium triflate (manufactured by Aldrich) and 50 mL of dichloromethane. The sodium salt of 3.9 g (AN-7) synthesized in Production Example 7 was added while the mixture was stirred, 50 mL of water was further added, and the mixture was stirred at room temperature for 8 hours. The mixture was left standing, the aqueous layer was then removed by liquid separation, and the organic layer was washed with 50 mL of water five times. The organic solvent was distilled off under reduced pressure to obtain 6.2 g of a white solid. From .sup.1H, .sup.19F and .sup.31P-NMR, this white solid was confirmed to be an onium salt (A2-6).

Production Example 27

Synthesis of Onium Salt (A2-7): Tris(4-tert-butylphenyl)sulfonium Bis(nonafluorobutyl)tetrafluorophosphate

[0121] Except that 6.0 g of the sodium salt (AN-8) was used in place of 3.9 g of the sodium salt (AN-7) in Production Example 26, the same procedure as in Production Example 26 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31 P-NMR, this product was confirmed to be an onium salt (A2-7).

Production Example 28

Synthesis of Onium Salt (A2-8): Tris(4-fluorophenyl)sulfonium (Nonafluorobutyl)pentafluorophosphate

[0122] Except that 35 g of the lithium salt (AN-9) was used in place of 65 g of the potassium salt (AN-2) in Production Example 22, the same procedure as in Production Example 22 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (A2-8).

Production Example 29

Onium Salt (A2-9): Synthesis of Tris(4-fluorophenyl)sulfonium (Pentafluoroethyl)pentafluorophosphate

[0123] Except that 25 g of the lithium salt (AN-10) was used in place of 65 g of the potassium salt (AN-2) in Production Example 22, the same procedure as in Production Example 22 was carried out to obtain a desired product. From .sup.1H, .sup.19F and .sup.31P-NMR, this product was confirmed to be an onium salt (A2-9).

Comparative Production Example 1

Synthesis of Onium Salt (A-1) Below

[0124] Except that 3.5 g of the tetraphenyl borate sodium (manufactured by NACALAI TESQUE, INC.) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 12, the same procedure as in Production Example 12 was carried out to obtain a desired product. From .sup.1H-NMR, this product was confirmed to be an onium salt (A-1).

##STR00009##

Comparative Production Example 2

Synthesis of Onium Salt (A-2) Below

[0125] Except that 3.5 g of the tetraphenyl borate sodium (manufactured by NACALAI TESQUE, INC.) was used in place of 8.0 g of the potassium salt (AN-1) in Production Example 21, the same procedure as in Production Example 21 was carried out to obtain a desired product. From .sup.1H-NMR, this product was confirmed to be an onium salt (A-2).

##STR00010##

Examples 1 to 34 and Comparative Examples 1 to 16

[0126] [Preparation of Photosensitive Composition]

[0127] The radical-polymerizable compound (C) of 100 g, the onium salt (A) of 3 g and the sensitizer (B) of 0.3 g were homogeneously mixed to prepare photosensitive compositions (Q-1) to (Q-34) of the present invention, and comparative photosensitive compositions (Q-1) to (Q-16). The types of raw materials used are shown in Table 1. This photosensitive composition was applied to a glass substrate (76 mm52 mm) using an applicator (40 m), and exposed to light using an irradiator LIGHTNINGCURE Spot Light Source LC 8 (manufactured by Hamamatsu Photonics K.K.) as a light source, and curability was examined by the following evaluation method. The results are shown in Table 1.

[0128] [Raw Materials Used]

[0129] A1-1 to A2-9 (onium salt described above)

[0130] A-1: onium salt in Comparative Production Example 1

[0131] A-2: Onium salt in Comparative Production Example 2

[0132] A-3: di(tert-butylphenyl)iodonium hexafluorophosphate (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0133] A-4: triphenylsulfonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0134] B-1: B-201 (described above as a specific example of a polymethine dye)

[0135] B-2: B-204 (described above as a specific example of a polymethine dye)

[0136] B-3: 3,3-carbonylbis(7-diethylaminocoumarin)

[0137] C-1: dipentaerythritol pentaacrylate (NEOMER DA-600 manufactured by Sanyo Chemical Industries, Ltd.)

[0138] C-2: ethoxylated trimethylolpropane triacrylate (NEOMER TA-401 manufactured by Sanyo Chemical Industries, Ltd.)

[0139] C-3: polypropylene glycol diacrylate (NEOMER PA-305 manufactured by Sanyo Chemical Industries, Ltd.)

[0140] [Curability]

[0141] Curability-1: the composition was exposed to light through an infrared transmission filter R72 (cutting light having a wavelength of 700 nm or less) (manufactured by HOYA CORPORATION) to examine curability.

[0142] Evaluation of Curability: [0143] The surface has no tackiness, and is not scratched even when scraped with a nail. [0144] The surface has no tackiness, but is scratched with a nail. [0145] The surface remains tacky. [0146] x The composition remains liquid, and is not cured.

TABLE-US-00001 TABLE 1 Radical- Photosen- polym- sitive Onium Sensi- erizable compo- salt tizer compound Cur- sition (A) (B) (C) ability-1 Example 1 Q-1 A1-1 B-1 C-1 2 Q-2 A1-2 B-1 C-1 3 Q-3 A1-3 B-1 C-1 4 Q-4 A1-4 B-1 C-1 5 Q-5 A1-5 B-1 C-1 6 Q-6 A1-6 B-1 C-1 7 Q-7 A1-7 B-1 C-1 8 Q-8 A1-8 B-1 C-1 9 Q-9 A1-9 B-1 C-1 10 Q-10 A1-10 B-1 C-1 11 Q-11 A2-1 B-1 C-1 12 Q-12 A2-2 B-1 C-1 13 Q-13 A2-3 B-1 C-1 14 Q-14 A2-4 B-1 C-1 15 Q-15 A2-5 B-1 C-1 16 Q-16 A2-6 B-1 C-1 17 Q-17 A2-7 B-1 C-1 18 Q-18 A2-8 B-1 C-1 19 Q-19 A2-9 B-1 C-1 20 Q-20 A1-2 B-1 C-2 21 Q-21 A1-3 B-1 C-2 22 Q-22 A1-4 B-1 C-2 23 Q-23 A2-3 B-1 C-2 24 Q-24 A2-9 B-1 C-2 25 Q-25 A1-2 B-1 C-3 26 Q-26 A1-3 B-1 C-3 27 Q-27 A1-4 B-1 C-3 28 Q-28 A2-3 B-1 C-3 29 Q-29 A2-9 B-1 C-3 30 Q-30 A1-2 B-2 C-1 31 Q-31 A1-3 B-2 C-1 32 Q-32 A1-4 B-2 C-1 33 Q-33 A2-3 B-2 C-1 34 Q-34 A2-9 B-2 C-1 Compar- 1 Q-1 A-1 B-1 C-1 ative 2 Q-2 A-2 B-1 C-1 Example 3 Q-3 A-3 B-1 C-1 4 Q-4 A-4 B-1 C-1 X 5 Q-5 A-1 B-1 C-2 6 Q-6 A-2 B-1 C-2 7 Q-7 A-3 B-1 C-2 8 Q-8 A-4 B-1 C-2 X 9 Q-9 A-1 B-1 C-3 10 Q-10 A-2 B-1 C-3 11 Q-11 A-3 B-1 C-3 12 Q-12 A-4 B-1 C-3 X 13 Q-13 A-1 B-2 C-1 14 Q-14 A-2 B-2 C-1 15 Q-15 A-3 B-2 C-1 16 Q-16 A-4 B-2 C-1 X

Examples 35 to 39 and Comparative Examples 17 to 20

[0147] [Preparation of Photosensitive Composition]

[0148] The radical-polyroerizable compound (C) of 100 g, the onium salt (A)of 3 g and the sensitizer (B-3) of 0.3 g were homogeneously mixed to prepare photosensitive compositions (Q-35) to (Q-39) of the present invention, and comparative photosensitive compositions (Q-17) to (Q-20). The types of raw materials used are shown in Table 1. This photosensitive composition was applied to a glass substrate (76 mm52 mm) using an applicator (40 m), and exposed to light using an irradiator LIGHTNINGCURE spot Light Source LC 8 (manufactured by Hamamatsu Photonics K.K.) as a light source, and curability was examined by the following evaluation method. The results are shown in Table 2. The raw materials used are as described above.

[0149] [Curability]

[0150] Curability-2: the composition was exposed to light through a sharp-cut filter Y44 (cutting light having a wavelength of 430 nm or less) (manufactured by HOYA CORPORATION) to examine curability.

[0151] Evaluation of Curability: [0152] The surface has no tackiness, and is not scratched even when scraped with a nail. [0153] The surface has no tackiness, but is scratched with a nail. [0154] The surface remains tacky. [0155] x The composition remains liquid, and is not cured.

TABLE-US-00002 TABLE 2 Radical- Photosen- polym- sitive Onium Sensi- erizable compo- salt tizer compound Cur- sition (A) (B) (C) ability-2 Example 35 Q-35 A1-2 B-3 C-3 36 Q-36 A1-3 B-3 C-3 37 Q-37 A1-4 B-3 C-3 38 Q-38 A2-3 B-3 C-3 39 Q-39 A2-9 B-3 C-3 Compar- 17 Q-17 A-1 B-3 C-3 ative 18 Q-18 A-2 B-3 C-3 Example 19 Q-19 A-3 B-3 C-3 20 Q-20 A-4 B-3 C-3 X

[0156] It is apparent from Tables 1 and 2 that the photosensitive composition of the present invention is more sensitive than the comparative photosensitive composition. In addition, it is apparent that selection of a sensitizer appropriate to the wavelength of light to be radiated is important.

Examples 40 to 44 and Comparative Examples 21 to 24: Examples of Photosensitive Compositions Containing Pigment

[0157] [Preparation of Photosensitive Composition]

[0158] <Preparation of High-Concentration Dispersion (1)>

[0159] A mixture including 43 parts of titanium oxide (TIPAQUE R-930 manufactured by Ishihara Sangyo Kaisha, Ltd.) as a pigment, 4 parts of a pigment dispersant (SOLSPERSE 32000 manufactured by The Lubrizol Corporation) and 53 parts of tetrahydrofurryl acrylate LIGHT ACRYLATE THF-A manufactured by Kyoeisha Chemical Co., Ltd.) as a radical-polymerizable compound (C) was kneaded with a ball mill for 3 hours to prepare a pigment dispersant liquid having a pigment concentration of 43%.

[0160] <Preparation of Photosensitive Composition>

[0161] Said high-concentration pigment dispersant liquid of 47 parts, dipentaerythritol pentaacrylate of 46 parts (NEOMER DA-600 manufactured by Sanyo Chemical Industries, Ltd.), 0.5 parts of the sensitizer (B-2), and 5 parts of the onium salt (A) or 5 parts of the comparative onium salt (A) as shown in Table 2 were kneaded at 25 C. for 3 hours with a ball mill to produce photosensitive compositions (Q-40) to (Q-44) of the present invention and comparative photosensitive compositions (Q-21) to (Q-24), and coating film curability (curability-3) was evaluated by the following method. The results are shown in Table 3.

[0162] [Curability]

[0163] Curability-3: Each of these photosensitive compositions was applied to a surface-treated 100 m-thick PET (polyethylene terephthalate) film [COSMOSHINE A 4300 manufactured by Toyobo Co., Ltd.] with a thickness of 20 m using an applicator. The photosensitive composition was exposed to light using an irradiator LIGHTNINGCURE Spot Light Source LC 8 (manufactured by Hamamatsu Photonics K.K.) as a light source, and curability was examined by the following evaluation method.

[0164] Evaluation of Curability: [0165] The surface has no tackiness, and is not scratched even when scraped with a nail. [0166] The surface has no tackiness, but is scratched with a nail. [0167] The surface remains tacky. [0168] x The composition remains liquid, and is not cured.

TABLE-US-00003 TABLE 3 Onium Photosensitive salt Sensitizer composition (A) (B) Curability-3 Example 40 Q-40 A1-2 B-2 41 Q-41 A1-3 B-2 42 Q-42 A1-4 B-2 43 Q-43 A2-3 B-2 44 Q-44 A2-9 B-2 Comparative 21 Q-21 A-1 B-2 Example 22 Q-22 A-2 B-2 23 Q-23 A-3 B-2 24 Q-24 A-4 B-2 X

Examples 45 to 49 and Comparative Examples 25 to 28: Examples of photosensitive compositions containing pigment

[0169] [Preparation of Photosensitive Composition]

[0170] <Preparation of High-Concentration Dispersion (2)>

[0171] Except that the dye was changed to DIRECT BLUE 14 (manufactured by Tokyo Chemical Industry Co., Ltd.), the same procedure as in preparation of the above-described high-concentration dispersion (1) was carried out to prepare a dye dispersion.

[0172] <Preparation of Photosensitive Composition>

[0173] Said high-concentration dye dispersant liquid of 47 parts, dipentaerythritol pentaacrylate of 46 parts (NEOMER DA-600 manufactured by Sanyo Chemical Industries, Ltd.), 0.5 parts of the sensitizer (B-2), and 5 parts of the onium salt (A) or 5 parts of the comparative onium salt (A) as shown in Table 2 were kneaded at 25 C for 3 hours with a ball mill to produce photosensitive compositions (Q-45) to (0-49) of the present invention and comparative photosensitive compositions (Q-25) to (Q-28), and coating film curability (curability-4) was evaluated by the following method. The results are shown in Table 4.

[0174] [Curability]

[0175] Curability-4: Each of these photosensitive compositions was applied to a surface-treated 100 m-thick PET (polyethylene terephthalate) film [COSMOSHINE A 4300 manufactured by Toyobo Co., Ltd.] with a thickness of 20 m using an applicator. The photosensitive composition was exposed to light using an irradiator LIGHTNINGCURE Spot Light Source LC 8 (manufactured by Hamamatsu Photonics K.K.) as a light source, and curability was examined by the following evaluation method.

[0176] Evaluation of Curability: [0177] The surface has no tackiness, and is not scratched even when scraped with a nail. [0178] The surface has no tackiness, but is scratched with a nail. [0179] The surface remains tacky. [0180] x The composition remains liquid, and is not cured.

TABLE-US-00004 TABLE 4 Onium Photosensitive salt Sensitizer composition (A) (B) Curability-4 Example 45 Q-45 A1-2 B-2 46 Q-46 A1-3 B-2 47 Q-47 A1-4 B-2 48 Q-48 A2-3 B-2 49 Q-49 A2-9 B-2 Comparative 25 Q-25 A-1 B-2 Example 26 Q-26 A-2 B-2 27 Q-27 A-3 B-2 26 Q-28 A-4 B-2 X

[0181] The results in Tables 3 and 4 show that the photosensitive composition of the present invention can be efficiently cured even when a substance such as a colorant, which attenuates or blocks radiated light, is present in a high concentration, and the photosensitive composition of the present invention has sensitivity higher than that of the comparative photosensitive composition.

INDUSTRIAL APPLICABILITY

[0182] The photosensitive composition of the present invention utilizes light (particularly in a visible-to-infrared region), and is suitably used for coating agents, various coating materials (hard coats, anti-fouling coating materials, anti-fogging coating materials, anti-corrosion coating materials, optical fibers and the like), back surface treatment agents for pressure sensitive adhesive tapes, release coating materials of release sheets for pressure sensitive adhesive labels (release papers, release plastic films, release metal foils and the like), printing plates, dental materials (dental formulations and dental composites), ink compositions, inkjet ink compositions, positive resists (for formation of connection terminals and wiring patterns in production of electronic components such as circuit boards, CSP and MEMS elements), resist films, liquid resists and negative resists (permanent film materials of surface protecting films, interlayer dielectric films, planarizing films for semiconductor elements and transparent electrodes for FPD (ITO, IZO and GZO), etc.), resists for MEMS, positive photosensitive materials, negative photosensitive materials, various adhesives (various temporary fixing agents for electronic components, adhesives for HDD, adhesives for pick-up lenses, functional films for FPD (polarizing plates, antireflection films and the like), insulating films for circuit formation and semiconductor sealing, anisotropic electroconductive adhesives (ACA), films (ACF), pastes (ACP) and the like), holographic resins, FPD materials (color filters, black matrices, partition wall materials, photospacers, ribs, orientation films for liquid crystals, sealing agents for FPD and the like), optical members, molding materials (for building materials, optical components and lenses), casting materials, putty materials, glass fiber impregnating agents, fillers, sealing materials, flip-chips, chip sealants for COF etc., sealants for packages such as CSP or BGA, photosemiconductor (LED) sealants, optical waveguide materials, nano-imprint materials, stereolithography materials, and micro-stereolithography materials.