Photobase generator

Abstract

Provided are a photobase generator having higher sensitivity to light than do conventional photobase generators, and a photosensitive resin composition containing the photobase generator. The present invention is a photobase generator characterized in containing a salt represented by general formula (1). (In formula (1), R.sup.1-R.sup.4 are mutually independent groups represented by general formula (2), C1-18 alkyl groups, or Ar, with at least one being a group represented by general formula (2); in formula (2), (D) is a divalent group bonded on at least one side to elemental boron, and Ar.sup.1 is the same as the aforementioned Ar; and Q.sup.+ is a monovalent onium cation.) ##STR00001##

Claims

1. A photobase generator, comprising a salt represented by general formula (3): ##STR00023## [wherein in general formula (3), R.sup.1 to R.sup.4 independently represent a group represented by general formula (2) below, an alkyl group having 1 to 18 carbon atoms or Ar, wherein at least one of R.sup.1 to R.sup.4 represents a group represented by general formula (2) below, Ar represents an aryl group having 6 to 14 carbon atoms (excluding carbon atoms contained in a substituent as mentioned below), some of hydrogen atoms in the aryl group may be independently substituted by an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkynyl group having 2 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group or aryloxy group represented by OR.sup.39, an acyl group represented by R.sup.40CO, an acyloxy group represented by R.sup.41COO, an alkylthio group or arylthio group represented by SR.sup.42, an amino group represented by NR.sup.43R.sup.44, or a halogen atom, R.sup.39 to R.sup.42 independently represent an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R.sup.43 and R.sup.44 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 14 carbon atoms; in formula (2), (D) represents a divalent group having at least one bond through which a boron element is bonded, and Ar.sup.1 is the same as the above-mentioned Ar; Y.sup.+ represents an ammonio group represented by any one of general formulas (4) to (6) and (8) below; in formula (4), R.sup.5 to R.sup.8 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be bonded to one another to form a ring structure; in formula (5), R.sup.9 to R.sup.15 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be bonded to one another to form a ring structure, and p represents an integer of 0 to 6; in formula (6), R.sup.16 to R.sup.18 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be bonded to one another to form a ring structure, R represents a group represented by general formula (7), and q represents an integer of 0 to 3; in formula (7), R.sup.19 to R.sup.24 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be bonded to one another to form a ring structure; in formula (8), R.sup.25 to R.sup.27 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be bonded to one another to form a ring structure; and E represents a group represented by general formula (9) below, R.sup.28 to R.sup.32 independently represent hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a nitro group, a hydroxyl group, a cyano group, an alkoxy group represented by OR.sup.39, an acyl group represented by R.sup.40CO, an acyloxy group represented by R.sup.41COO, an alkylthio group represented by SR.sup.42, an amino group represented by NR.sup.43R.sup.44 or a halogen atom, R.sup.28 to R.sup.32 may be the same as or different from one another and may be bonded to one another to form a ring structure, in general formula (9), (G) represents a divalent group represented by general formula (10) or general formula (11), and R.sup.33 to R.sup.36 independently represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, and may be the same as or different from one another,]
-(D)-Ar.sup.1(2) ##STR00024##

2. The photobase generator according to claim 1, wherein an absorption wavelength which Ar as one of R.sup.1 to R.sup.4 in general formula (1) has and an absorption wavelength which Ar.sup.1 in general formula (2) has satisfy an inequality of Ar<Ar.sup.1.

3. The photobase generator according to claim 1, wherein Ar as one of R.sup.1 to R.sup.4 in general formula (1) represents a phenyl group or a naphthyl group.

4. The photobase generator according to claim 1, wherein Y.sup.+ in general formula (3) represents an ammonio group selected from the group of general formulas (12) to (18) below: ##STR00025## [wherein in formula (18), R.sup.37 represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms or an aryl group having 6 to 14 carbon atoms, R.sup.38 represents an alkyl group having 1 to 18 carbon atoms, and R.sup.37 and R.sup.38 may be bonded to each other to form a ring structure].

5. A photocurable composition, comprising the photobase generator according to claim 1 and a basic reactive compound.

6. A cured product obtained by curing the photocurable composition according to claim 5.

7. The photobase generator according to claim 1, wherein Y.sup.+ represents an ammonio group represented by any one of general formulas (4) to (6).

8. The photobase generator according to claim 1, wherein the divalent group of the (D) is selected from an ether, a sulfide, a ketone, an imine, a sulfoxide, a sulfone, an amide, an imide, a carboxylic acid ester, a thiocarboxylic acid ester, a carbonate ester, an acid anhydride, a urea, a thiourea, an acetal, a thioacetal, a carbodiimide, a carbamoyl, a thiocarbamoyl, a silylene and a siloxy, an alkylene having 1 to 18 carbon atoms which may have a substituent, an alkenylene having 2 to 18 carbon atoms, an alkynylene having 2 to 18 carbon atoms, and an arylene having 6 to 14 carbon atoms which may contain a hetero atom.

9. The photobase generator according to claim 1, wherein the divalent group of the (D) is selected from an alkylene having 1 to 18 carbon atoms, an arylene with 6 to 14 carbon atoms which may contain a hetero atom, ether, a sulfide and a carboxylic acid ester.

Description

EXAMPLES

(1) Hereinafter, the present invention will be further described by reference to examples, but the present invention is not intended to be limited thereto. It should be noted that % means % by weight unless otherwise stated.

Production Example 1 Synthesis of thioxanthone-3-carboxylic acid (Intermediate a)

(1) Synthesis of 2-(phenylthio)-dimethyl terephthalate (Intermediate a-1)

(2) In a reaction vessel, the inside of which was replaced with nitrogen, 43 g of dimethyl 2-nitroterephthalate (available from Tokyo Chemical Industry Co., Ltd.) and 100 mL of DMF were placed, and cooled to 10 C. with an ice-salt bath. To this, separately, a sodium thiophenolate solution prepared with 22 g of thiophenol, 8 g of sodium hydride and 60 mL of DMF was added dropwise over a period of 1 hour. The contents were stirred for 3 hours at room temperature, and then, charged into water. After being extracted with ethyl acetate and removed from the aqueous layer, water washing was performed three times and the organic layer was concentrated. The concentrated organic layer was treated with hexane to obtain 45 g of a white solid. It was confirmed by .sup.1H-NMR that this white solid was (Intermediate a-1).

(2) Synthesis of 2-(phenylthio)-terephthalic acid (Intermediate a-2)

(3) In a reaction vessel equipped with a condenser, 50 g of (Intermediate a-1) and 600 mL of methanol were placed and stirred. To this, 52 g of potassium hydroxide was gradually added. The contents were refluxed for 3 hours and then concentrated. To the resultant white solid, 600 g of water was added, and the solid was heated to 70 C. and dissolved. To this, 150 g of 4N hydrochloric acid was gradually added, whereupon a solid precipitated. Filtration and drying were performed to obtain 40 g of a white solid. It was confirmed by 1H-NMR that this white solid was (Intermediate a-2).

(3) Synthesis of thioxanthone-3-carboxylic acid (Intermediate a)

(4) In a reaction vessel, 27 g of (Intermediate a-2) and 300 g of polyphosphoric acid were placed and stirred for 18 hours at 160 C. The reaction liquid was charged in small portions into 3 L of water under stirring to precipitate a solid. The obtained solid was recrystallized from DMF/water to obtain 20 g of a yellow solid. It was confirmed by: .sup.1H-NMR that this yellow solid was (Intermediate a).

Production Example 2 Synthesis of 2-mercaptothioxanthone (Intermediate b)

(5) In a reaction vessel, 300 mL of concentrated sulfuric acid was placed, and to this, 16 g of dithiosalicylic acid (available from Wako Pure Chemical Industries, Ltd.) was added in small portions. The contents were stirred for 30 minutes, and cooled to 5 C. with an ice bath. To this, 120 g of thiophenol was added dropwise. After being stirred for 1 hour at room temperature, the contents were allowed to undergo a reaction for 5 hours at 80 C., and then, again cooled to room temperature. To 5 L of water at 80 C., the reaction liquid was added in small portions under stirring. After being cooled to room temperature, a solid precipitated was filtered. The solid was recrystallized from dioxane/water to obtain 22 g of a yellow solid. It was confirmed by 1H-NMR that this solid was (Intermediate b).

Production Example 3 Synthesis of 2-bromomethylthioxanthone (Intermediate c)

(1) 2-Methylthioxanthone (Intermediate c-1)

(6) In a reaction vessel, 70 mL of concentrated sulfuric acid was placed, and to this, 10 g of dithiosalicylic acid (available from Wako Pure Chemical Industries, Ltd.) was added and stirred at room temperature for 1 hour. The contents were cooled with an ice bath and 25 g of toluene was added dropwise while keeping the temperature thereof at 20 C. or lower. After dropping, the temperature thereof was returned to room temperature, and furthermore, stirring was performed for 2 hours. This reaction liquid was poured into 800 g of ice water. A yellow solid precipitated was filtered off and dissolved in 200 g of dichloromethane, after which water washing was performed. The organic layer was concentrated to obtain 9 g of a yellow solid. It was confirmed by: .sup.1H-NMR that this yellow solid was Intermediate (c-1).

(2) Synthesis of 2-bromomethylthioxanthone (Intermediate c)

(7) In a reaction vessel equipped with a reflux tube, 2 g of Intermediate (c-1) was dissolved in 100 mL of cyclohexane, and to this, 8 g of N-bromosuccinimide (available from Wako Pure Chemical Industries, Ltd.) and 0.1 g of benzoyl peroxide were added. The contents were allowed to undergo a reaction for 4 hours under reflux. The solvent was distilled off, and to this, 50 mL of chloroform was added to dissolve the residue, after which water washing was performed three times. The organic layer was concentrated to obtain 2 g of a brown solid. The brown solid was recrystallized from ethyl acetate to obtain 1.8 g of a yellow solid. It was confirmed by .sup.1H-NMR that this yellow solid was Intermediate (c).

Production Example 4 Synthesis of potassium (4-hydroxyethyloxy)phenyltriphenylborate (Intermediate d)

(1) Synthesis of 4-(trimethylsiloxyethyloxy)bromobenzene (Intermediate d-1)

(8) In a reaction vessel, the inside of which was replaced with nitrogen, 15 g of 4-bromophenoxy ethanol (available from Tokyo Chemical Industry Co., Ltd.), 200 mL of THF and 8 g of triethylamine were placed. While the contents were cooled with an ice bath, 8.5 g of trimethylsilyl chloride (available from Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the completion of dropping, the contents were allowed to undergo a reaction for 2 hours at room temperature, and the reaction liquid was charged into 300 mL of water. The liquid was extracted with 50 g of ethyl acetate three times and the organic layer was washed with 20 mL of water two times, after which the organic layer was concentrated to obtain 19 g of a pale brown liquid. This liquid was purified by silica gel column chromatography to obtain a colorless liquid. It was confirmed by .sup.1H-NMR that this liquid was (Intermediate d-1).

(2) Synthesis of potassium (4-trimethylsiloxyethyloxy)phenyltriphenylborate (Intermediate d-2)

(9) In a four-necked reaction vessel, the inside of which was replaced with nitrogen, 100 mL of a 0.25 molL.sup.1 tetrahydrofuran solution of triphenylborane (available from Aldrich) was placed, and cooled to 20 C. To this, 26 mL of a 1.0 molL.sup.1 Grignard reagent prepared by a routine procedure from (Intermediate d-1) was gradually added dropwise. After dropping, the contents were stirred for 2 hours at room temperature, after which to this solution, 100 ml of a saturated aqueous potassium bicarbonate solution was added, the organic layer was separated and subjected to solvent removal, and the residue was washed with hexane two times and then dried under reduced pressure to obtain a white solid.

(3) Synthesis of potassium (4-hydroxyethyloxy)phenyltriphenylborate (Intermediate d)

(10) To Intermediate (d-2) obtained in (2), 100 mL of tetrahydrofuran was added, and to this, an aqueous potassium fluoride solution was gradually added. After being stirred overnight, 100 mL of a saturated aqueous potassium bicarbonate solution was added, and furthermore, the liquid was extracted with 100 mL of diethyl ether three times. The organic layer was concentrated to obtain 7 g of a white solid. It was confirmed by 1H-NMR that this white solid was (Intermediate d).

Production Example 5 Synthesis of potassium (4-hydroxyethyl)phenyltriphenylborate (Intermediate e)

(11) According to the method described in Production Example 4, Intermediate e, which is an aimed product, was obtained in the same manner except that the starting material was changed.

Production Example 6 Potassium styryltriphenylborate (Synthesis of Intermediate f)

(12) In the production of Intermediate d-2 in Production Example 4, in place of the Grignard reagent prepared from Intermediate d-1, 26 mL of a 1.0 molL.sup.1 Grignard reagent prepared by a routine procedure from 4-bromostyrene was used, and an aimed product was obtained according to the method described in Production Example 4 (2).

Production Example 7 Potassium 3-butenyl-triphenylborate (Synthesis of Intermediate g)

(13) In the production of Intermediate d-2 in Production Example 4, in place of the Grignard reagent prepared from Intermediate d-1, 26 mL of a 1.0 molL.sup.1 Grignard reagent prepared by a routine procedure from 4-bromo-1-butene was used, and an aimed product was obtained according to the method described in Production Example 4 (2).

Production Example 8 Synthesis of potassium (4-hydroxyethyloxy)phenyltrinaphthylborate (Intermediate h)

(14) In the synthesis of Intermediate d-2 in Production Example 4, in place of the 0.25 molL.sup.1 tetrahydrofuran solution of triphenylborane (available from Aldrich), a 0.25 molL.sup.1 trinaphthylborane solution was prepared in the following way.

(15) In a reaction vessel, the inside of which was replaced with nitrogen, 7.1 g of a boron trifluoride-ether complex and 100 mL of THF were placed, and cooled to 0 C. To this, 100 mL of a 0.5 molL.sup.1 THF solution of 2-naphthylmagnesium bromide (available from Aldrich) was added dropwise. After dropping, the contents were allowed to undergo a reaction for 6 hours at room temperature, and added with 100 mL of hexane to perform filtration. The organic layer was concentrated to obtain a white solid. This solid was added with 200 mL of THF to prepare a 0.25 molL.sup.1 tetrahydrofuran solution of trinaphthylborane.

(16) Thus, an aimed product was obtained according to the method described in Production Example 4 except that the 0.25 molL.sup.1 tetrahydrofuran solution of trinaphthylborane was used.

Production Example 9 Synthesis of 2-mercaptomethylthioxanthone (Intermediate i)

(17) In 150 mL of DMF, 15 g of (Intermediate c) obtained in Production Example 3 was dissolved, and to this, 7 g of potassium thioacetate (available from Wako Pure Chemical Industries, Ltd.) was added, and stirred for 6 hours under room temperature. The reaction liquid was charged into 500 g of water, and extracted with ethyl acetate. In 80 mL of methanol, 6 g of a yellow solid obtained by concentrating the organic layer was dissolved, and to this, 4 g of potassium carbonate was added. After being stirred for 1 hour at room temperature, 20 mL of 1N HCL was added. In 100 mL of chloroform, a solid precipitated was dissolved, and the organic layer was washed with water and then concentrated. This liquid was purified by silica gel column chromatography to obtain 5 g of a yellow solid. It was confirmed by .sup.1H-NMR that this yellow solid was (Intermediate i).

Production Example 10 Synthesis of Potassium Salt A-1

(18) In a reaction vessel, 10 g of (Intermediate d) obtained in Production Example 4 was dissolved in 50 mL of DMF, and to this, 2 g of potassium hydroxide was added and stirred. To this, a solution prepared by dissolving 8 g of (Intermediate c) obtained in Production Example 3 in 50 mL of DMF was gradually added. After being stirred for 20 hours, the reaction liquid was poured into 500 mL of water, and a yellow solid precipitated was filtered. After being dried under reduced pressure, 11 g of a yellow solid was obtained. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-1.

Production Example 11 Synthesis of Potassium Salt A-2

(19) In a reaction vessel, 15 g of (Intermediate a) obtained in Production Example 1, 20 mL of dioxane and 20 mL of thionyl chloride were placed, and allowed to undergo a reaction for 6 hours under reflux. After being cooled to room temperature, the reaction liquid was concentrated, 50 mL of dichloromethane was added to the residue, and to this, a solution prepared from 20 g of (Intermediate d) obtained in Production Example 4, 0.5 g of dimethylaminopyridine (available from Tokyo Chemical Industry Co., Ltd.), 50 mL of triethylamine and 50 mL of dichloromethane was added. The contents were allowed to undergo a reaction for 20 hours under room temperature, and the reaction liquid was concentrated. To this, 100 mL of dichloromethane was added, and the liquid was washed with 1N hydrochloric acid two times, after which the organic layer was concentrated. This liquid was purified by silica gel column chromatography to obtain 10 g of a yellow solid. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-2.

Production Example 12 Synthesis of Potassium Salt A-3

(20) An aimed product was obtained according to the method described in Production Example 10 except that 10 g of (Intermediate e) was used in place of 10 g of (Intermediate d) in Production Example 10. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-3.

Production Example 13 Synthesis of Potassium Salt A-4

(21) An aimed product was obtained according to the method described in Production Example 11 except that 20 g of (Intermediate e) was used in place of 20 g of (Intermediate d) in Production Example 11. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-4.

Production Example 14 Synthesis of Potassium Salt A-5

(22) In a reaction vessel, 3 g of (Intermediate b), 4 g of (Intermediate f) and 100 mL of cyclohexane were placed, and allowed to undergo a reaction for 24 hours under reflux with heating. This liquid was concentrated, and the obtained brown solid was purified by silica gel column chromatography to obtain a yellow solid. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-5.

Production Example 15 Synthesis of Potassium Salt A-6

(23) An aimed product was obtained according to the method described in Production Example 14 except that 3 g of (Intermediate g) was used in place of 4 g of (Intermediate f) in Production Example 14. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-6.

Production Example 16 Synthesis of Potassium Salt A-7

(24) An aimed product was obtained according to the method described in Production Example 10 except that 14 g of (Intermediate h) was used in place of 10 g of (Intermediate d) in Production Example 10. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-7.

Production Example 17 Synthesis of Potassium Salt A-8

(25) An aimed product was obtained according to the method described in Production Example 11 except that 14 g of (Intermediate h) was used in place of 10 g of (Intermediate d) in Production Example 11. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-8.

Production Example 18 Synthesis of Potassium Salt A-9

(26) An aimed product was obtained according to the method described in Production Example 11 except that 13 g of anthraquinone-2-carboxylic acid (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 15 g of (Intermediate a) in Production Example 11. It was confirmed by .sup.1H-NMR that this pale yellow solid was Potassium salt A-9.

Production Example 19 Synthesis of Potassium Salt A-10

(27) An aimed product was obtained according to the method described in Production Example 11 except that 20 g of (Intermediate e) was used in place of 20 g of (Intermediate d) and 13 g of anthraquinone-2-carboxylic acid (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 15 g of (Intermediate a) in Production Example 11. It was confirmed by .sup.1H-NMR that this pale yellow solid was Potassium salt A-10.

Production Example 20 Synthesis of Potassium salt A-11

(28) An aimed product was obtained according to the method described in Production Example 14 except that 3 g of (Intermediate i) was used in place of 3 g of (Intermediate b) in Production Example 14. It was confirmed by .sup.1H-NMR that this yellow solid was Potassium salt A-11.

Example 1 Synthesis of Compound B-1

(29) (1) Synthesis of Intermediate (CA-1 Chloride)

(30) In 100 g of chloroform, 23 g of benzyl chloride was dissolved, and to this, 27 g of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU, available from San-Apro Ltd.) was added dropwise. The contents were stirred under room temperature. After 2 hours, the disappearance of the raw materials was confirmed by HPLC, and a 50% chloroform solution of an intermediate (CA-1 Chloride) was obtained.

(31) (2) Synthesis of Compound B-1

(32) To 10 g of the 50% chloroform solution of an intermediate (CA-1 Chloride) obtained in (1), 11 g of (Potassium salt A-1) obtained in Production Example 10 and 50 g of ion-exchanged water were added and stirred for 3 hours at room temperature. An organic layer was washed with 50 g of ion-exchanged water three times. The organic layer was concentrated and the solvent was evaporated, after which the residue was subjected to silica gel chromatography to obtain a yellow solid. It was confirmed by .sup.1H-NMR that this yellow solid was Compound B-1. The structure of Compound B-1 was described in Table 1.

Example 2 Synthesis of Compound B-2

(33) An aimed product was prepared according to the method described in Example 1 except that 12 g of (Potassium salt A-2) obtained in Production Example 11 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-2 was described in Table 1.

Example 3 Synthesis of Compound B-3

(34) An aimed product was prepared according to the method described in Example 1 except that 11 g of (Potassium salt A-3) obtained in Production Example 12 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-3 was described in Table 1.

Example 4 Synthesis of Compound B-4

(35) An aimed product was prepared according to the method described in Example 1 except that 11 g of (Potassium salt A-4) obtained in Production Example 13 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-4 was described in Table 1.

Example 5 Synthesis of Compound B-5

(36) An aimed product was prepared according to the method described in Example 1 except that 11 g of (Potassium salt A-5) obtained in Production Example 14 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-5 was described in Table 1.

Example 6 Synthesis of Compound B-6

(37) An aimed product was prepared according to the method described in Example 1 except that 10 g of (Potassium salt A-6) obtained in Production Example 15 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-6 was described in Table 1.

Example 7 Synthesis of Compound B-7

(38) An aimed product was prepared according to the method described in Example 1 except that 14 g of (Potassium salt A-7) obtained in Production Example 16 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-7 was described in Table 1.

Example 8 Synthesis of Compound B-8

(39) An aimed product was prepared according to the method described in Example 1 except that 14 g of (Potassium salt A-8) obtained in Production Example 17 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-8 was described in Table 1.

Example 9 Synthesis of Compound B-9

(40) An aimed product was prepared according to the method described in Example 1 except that 12 g of (Potassium salt A-9) obtained in Production Example 18 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-9 was described in Table 1.

Example 10 Synthesis of Compound B-10

(41) An aimed product was prepared according to the method described in Example 1 except that 11 g of (Potassium salt A-10) obtained in Production Example 19 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-10 was described in Table 1.

Example 11 Synthesis of Compound B-11

(42) An aimed product was prepared according to the method described in Example 1 except that 11 g of (Potassium salt A-11) obtained in Production Example 20 was used in place of 11 g of (Potassium salt A-1) in Example 1. The structure of Compound B-11 was described in Table 1.

Example 12 to Example 22 Synthesis of Compound B-12 to Compound B-22

(43) (1) Synthesis of Intermediate (CA-2 Chloride)

(44) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 14 g of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN, available from San-Apro Ltd.) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-2 Chloride) was obtained.

(45) (2) Synthesis of Compound B-12 to Compound B-22

(46) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-2 Chloride) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-12 to Compound B-22 were described in Table 1.

Example 23 to Example 33 Synthesis of Compound B-23 to Compound B-33

(47) (1) Synthesis of Intermediate (CA-3 Chloride)

(48) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 10 g of 1-methylimidazole (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-3 Chloride) was obtained.

(49) (2) Synthesis of Compound B-23 to Compound B-33

(50) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-3 Chloride) in Examples 1 to 11. It was confirmed by: .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-23 to Compound B-33 were described in Table 1.

Example 34 to Example 44 Synthesis of Compound B-34 to Compound B-44

(51) (1) Synthesis of Intermediate (CA-4 Bromide)

(52) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 37 g of phenacyl bromide (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 23 g of benzyl chloride in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-4 Bromide) was obtained.

(53) (2) Synthesis of Compound B-34 to Compound B-44

(54) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-4 Bromide) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-34 to Compound B-44 were described in Table 1.

Example 45 to Example 55 Synthesis of Compound B-45 to Compound B-55

(55) (1) Synthesis of Intermediate (CA-5 Bromide)

(56) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-4 Bromide) except that 14 g of DBN was used in place of 17 g of DBU in Synthesis of intermediate (CA-4 Bromide) of Example 31, and a 50% chloroform solution of an intermediate (CA-5 Bromide) was obtained.

(57) (2) Synthesis of Compound B-45 to Compound B-55

(58) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-5 Bromide) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-45 to Compound B-55 were described in Table 1.

Example 56 to Example 66 Synthesis of Compound B-56 to Compound B-66

(59) (1) Synthesis of Intermediate (CA-6 Bromide)

(60) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-4 Bromide) except that 10 g of 1-methylimidazole (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 17 g of DBU in Synthesis of intermediate (CA-4 Bromide) of Example 31, and a 50% chloroform solution of an intermediate (CA-6 Bromide) was obtained.

(61) (2) Synthesis of Compound B-56 to Compound B-66

(62) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-6 Bromide) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-56 to Compound B-66 were described in Table 1.

Example 67 to Example 77 Synthesis of Compound B-67 to Compound B-77

(63) (1) Synthesis of Intermediate (CA-7 Chloride)

(64) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 17 g of 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (available from Tokyo Chemical Industry Co., Ltd.) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-7 Chloride) was obtained.

(65) (2) Synthesis of Compound B-67 to Compound B-77

(66) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-7 Chloride) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-67 to Compound B-77 were described in Table 1.

Example 78 to Example 88 Synthesis of Compound B-78 to Compound B-88

(67) (1) Synthesis of Intermediate (CA-8 Chloride)

(68) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 19 g of 2-tert-butyl-1,1,3,3-tetramethylguanidine (available from Aldrich) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-8 Chloride) was obtained.

(69) (2) Synthesis of Compound B-78 to Compound B-88

(70) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-8 Chloride) in Examples 1 to 11. It was confirmed by: .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-78 to Compound B-88 were described in Table 1.

Example 89 to Example 99 Synthesis of Compound B-89 to Compound B-99

(71) (1) Synthesis of Intermediate (CA-9 Chloride)

(72) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 35 g of tert-butylimino-tri(pyrrolidino)phosphorane (available from Aldrich) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-9 Chloride) was obtained.

(73) (2) Synthesis of Compound B-89 to Compound B-99

(74) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-9 Chloride) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-89 to Compound B-99 were described in Table 1.

Example 100 to Example 110 Synthesis of Compound B-100 to Compound B-110

(75) (1) Synthesis of Intermediate (CA-10 Chloride)

(76) An aimed product was prepared according to the method described in Synthesis of intermediate (CA-1 Chloride) except that 35 g of N-(ethylimide)-N,N-tetramethyl-N-(tris(dimethylamino)phosphoranylidene)phosphoric triamide (available from Aldrich) was used in place of 17 g of DBU in Synthesis of intermediate (CA-1 Chloride) of Example 1, and a 50% chloroform solution of an intermediate (CA-10 Chloride) was obtained.

(77) (2) Synthesis of Compound B-100 to Compound B-110

(78) Respective compounds were obtained by the methods described in Examples 1 to 11 respectively except that the intermediate (CA-1 Chloride) was changed to the intermediate (CA-10 Chloride) in Examples 1 to 11. It was confirmed by .sup.1H-NMR that the respective compounds were aimed products. The structures of Compound B-100 to Compound B-110 were described in Table 1.

(79) ##STR00013## ##STR00014## ##STR00015## ##STR00016##

(80) TABLE-US-00001 TABLE 1 Example Compound Cation Anion 1 B-1 CA-1 A-1 2 B-2 CA-1 A-2 3 B-3 CA-1 A-3 4 B-4 CA-1 A-4 5 B-5 CA-1 A-5 6 B-6 CA-1 A-6 7 B-7 CA-1 A-7 8 B-8 CA-1 A-8 9 B-9 CA-1 A-9 10 B-10 CA-1 A-10 11 B-11 CA-1 A-11 12 B-12 CA-2 A-1 13 B-13 CA-2 A-2 14 B-14 CA-2 A-3 15 B-15 CA-2 A-4 16 B-16 CA-2 A-5 17 B-17 CA-2 A-6 18 B-18 CA-2 A-7 19 B-19 CA-2 A-8 20 B-20 CA-2 A-9 21 B-21 CA-2 A-10 22 B-22 CA-2 A-11 23 B-23 CA-3 A-1 24 B-24 CA-3 A-2 25 B-25 CA-3 A-3 26 B-26 CA-3 A-4 27 B-27 CA-3 A-5 28 B-28 CA-3 A-6 29 B-29 CA-3 A-7 30 B-30 CA-3 A-8 31 B-31 CA-3 A-9 32 B-32 CA-3 A-10 33 B-33 CA-3 A-11 34 B-34 CA-4 A-1 35 B-35 CA-4 A-2 36 B-36 CA-4 A-3 37 B-37 CA-4 A-4 38 B-38 CA-4 A-5 39 B-39 CA-4 A-6 40 B-40 CA-4 A-7 41 B-41 CA-4 A-8 42 B-42 CA-4 A-9 43 B-43 CA-4 A-10 44 B-44 CA-4 A-11 45 B-45 CA-5 A-1 46 B-46 CA-5 A-2 47 B-47 CA-5 A-3 48 B-48 CA-5 A-4 49 B-49 CA-5 A-5 50 B-50 CA-5 A-6 51 B-51 CA-5 A-7 52 B-52 CA-5 A-8 53 B-53 CA-5 A-9 54 B-54 CA-5 A-10 55 B-55 CA-5 A-11 56 B-56 CA-6 A-1 57 B-57 CA-6 A-2 58 B-58 CA-6 A-3 59 B-59 CA-6 A-4 60 B-60 CA-6 A-5 61 B-61 CA-6 A-6 62 B-62 CA-6 A-7 63 B-63 CA-6 A-8 64 B-64 CA-6 A-9 65 B-65 CA-6 A-10 66 B-66 CA-6 A-11 67 B-67 CA-7 A-1 68 B-68 CA-7 A-2 69 B-69 CA-7 A-3 70 B-70 CA-7 A-4 71 B-71 CA-7 A-5 72 B-72 CA-7 A-6 73 B-73 CA-7 A-7 74 B-74 CA-7 A-8 75 B-75 CA-7 A-9 76 B-76 CA-7 A-10 77 B-77 CA-7 A-11 78 B-78 CA-8 A-1 79 B-79 CA-8 A-2 80 B-80 CA-8 A-3 81 B-81 CA-8 A-4 82 B-82 CA-8 A-5 83 B-83 CA-8 A-6 84 B-84 CA-8 A-7 85 B-85 CA-8 A-8 86 B-86 CA-8 A-9 87 B-87 CA-8 A-10 88 B-88 CA-8 A-11 89 B-89 CA-9 A-1 90 B-90 CA-9 A-2 91 B-91 CA-9 A-3 92 B-92 CA-9 A-4 93 B-93 CA-9 A-5 94 B-94 CA-9 A-6 95 B-95 CA-9 A-7 96 B-96 CA-9 A-8 97 B-97 CA-9 A-9 98 B-98 CA-9 A-10 99 B-99 CA-9 A-11 100 B-100 CA-10 A-1 101 B-101 CA-10 A-2 102 B-102 CA-10 A-3 103 B-103 CA-10 A-4 104 B-104 CA-10 A-5 105 B-105 CA-10 A-6 106 B-106 CA-10 A-7 107 B-107 CA-10 A-8 108 B-108 CA-10 A-9 109 B-109 CA-10 A-10 110 B-110 CA-10 A-11

Comparative Example 1 Synthesis of Photobase Generator (H-1) Below

(81) According to the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(82) ##STR00017##

Comparative Example 2 Synthesis of Photobase Generator (H-2) Below

(83) According to the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(84) ##STR00018##

Comparative Example 3 Synthesis of Photobase Generator (H-3) Below

(85) According to the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(86) ##STR00019##

Comparative Example 4 Synthesis of Photobase Generator (H-4) Below

(87) Based on the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(88) ##STR00020##

Comparative Example 5 Synthesis of Photobase Generator (H-5) Below

(89) Based on the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(90) ##STR00021##

Comparative Example 6 Synthesis of Photobase Generator (H-6) Below

(91) Based on the method described in Patent Document 7 (WO 2009/122664 A), an aimed product was synthesized.

(92) ##STR00022##

Examples 111 to 198

Comparative Examples 1 to 3

(93) By uniformly mixing 10 g of a bisphenol A type epoxy resin (Epikote 828, available from Mitsubishi Chemical Corporation), 9 g of an acid anhydride (HN5500E, available from Hitachi Chemical Company, Ltd.) and 0.5 g of a photobase generator, a mixture was prepared. The mixture was coated on a glass substrate (76 mm52 mm) by means of an applicator (40 m) and then subjected to exposure with a belt conveyor type UV irradiation device (EYE GRAPHICS Co., Ltd. ECS-151U) to generate a base, immediately after which subsequently, the glass substrate was placed on a hot plate heated to 120 C. and the time required for the tackiness of the coated surface to be eliminated was measured. These results were shown in Table 2.

Examples 199 to 220, Comparative Examples 4 to 6

(94) By uniformly mixing 10 g of a bisphenol A type epoxy resin (Epikote 828, available from Mitsubishi Chemical Corporation) and 0.5 g of a photobase generator, a curable composition was prepared.

(95) This curable composition was coated on a glass substrate (76 mm52 mm) by means of an applicator (40 m) and then subjected to exposure with a belt conveyor type UV irradiation device (EYE GRAPHICS Co., Ltd. ECS-151U) to generate a base, and the gel time at 150 C. was measured in accordance with the procedure of JISK5909. These results were shown in Table 3.

(96) TABLE-US-00002 TABLE 2 Tack-free time Example Compound (min) 111 B-1 13 112 B-2 20 113 B-3 10 114 B-4 16 115 B-5 12 116 B-6 10 117 B-7 13 118 B-8 18 119 B-9 16 120 B-10 15 121 B-11 10 122 B-12 12 123 B-13 21 124 B-14 11 125 B-15 15 126 B-16 12 127 B-17 10 128 B-18 13 129 B-19 18 130 B-20 16 131 B-21 14 132 B-22 10 133 B-34 15 134 B-35 22 135 B-36 12 136 B-37 18 137 B-38 14 138 B-39 12 139 B-40 15 140 B-41 20 141 B-42 18 142 B-43 17 143 B-44 12 144 B-45 14 145 B-46 24 146 B-47 13 147 B-48 17 148 B-49 14 149 B-50 13 150 B-51 15 151 B-52 24 152 B-53 20 153 B-54 18 154 B-55 13 155 B-67 15 156 B-68 25 157 B-69 13 158 B-70 18 159 B-71 15 160 B-72 13 161 B-73 15 162 B-74 22 163 B-75 19 164 B-76 17 165 B-77 13 166 B-78 12 167 B-79 19 168 B-80 10 169 B-81 15 170 B-82 11 171 B-83 9 172 B-84 12 173 B-85 17 174 B-86 15 175 B-87 14 176 B-88 9 177 B-89 15 178 B-90 22 179 B-91 12 180 B-92 18 181 B-93 14 182 B-94 12 183 B-95 15 184 B-96 20 185 B-97 18 186 B-98 17 187 B-99 12 188 B-100 14 189 B-101 21 190 B-102 11 191 B-103 17 192 B-104 13 193 B-105 11 194 B-106 14 195 B-107 19 196 B-108 17 197 B-109 16 198 B-110 11 Comparative Example 1 H-1 120< 2 H-2 Not cured 3 H-3 90

(97) TABLE-US-00003 TABLE 3 Example Compound Gel time (Sec) 199 B-23 100 200 B-24 120 201 B-25 90 202 B-26 110 203 B-27 95 204 B-28 80 205 B-29 105 206 B-30 120 207 B-31 115 208 B-32 110 209 B-33 80 210 B-56 115 211 B-57 145 212 B-58 100 213 B-59 130 214 B-60 110 215 B-61 90 216 B-62 120 217 B-63 140 218 B-64 130 219 B-65 125 220 B-66 90 Comparative Example 4 H-4 600 5 H-5 Not gelated 6 H-6 400

(98) The results in Tables 2 and 3 reveal that the photobase generator according to the present invention has higher sensitivity to light compared with photobase generators for comparison, and is useful as a photobase generator.

INDUSTRIAL APPLICABILITY

(99) The photobase generator according to the present invention is suitably used for a paint, a coating agent, various kinds of covering materials (a material for hard coat, a stain-resistant covering material, a defogging covering material, a corrosion-resistant covering material, an optical fiber and the like), a backside treating agent for a pressure-sensitive adhesive tape, a release coating material of a releasable sheet for a pressure-sensitive adhesive label (release paper, a release plastic film, release metal foil and the like), a printing plate, dental materials (a dental formulation, a dental composite), an ink, an inkjet ink, a positive type resist (a connecting terminal, wiring pattern formation, or the like in the production of electronic components such as a circuit board, CSP and an MEMS element), a resist film, a liquid resist, a negative type resist (a permanent film material such as an interlayer insulating film, a flattening film and a surface protective film such as a semiconductor element and a transparent electrode for FPD (ITO, IZO, GZO) and the like), a resist for MEMS, a positive type photosensitive material, a negative type photosensitive material, various kinds of adhesives (temporary fixing agents for various kinds of electronic components, an adhesive for HDD, an adhesive for pickup lens, an adhesive for a functional film for FPD (a deflection plate, an antireflection film or the like), insulator films for circuit formation and for semiconductor sealing, an anisotropic conductive adhesive (ACA), film (ACF) or paste (ACP), and the like), a resin for holography, FPD materials (a color filter, a black matrix, a partition wall material, a photospacer, a rib, an oriented film for liquid crystal, a sealing agent for FPD and the like), an optical member, molding materials (ones for building materials, an optical component, a lens), a casting material, putty, an impregnant for glass fiber, a filling material, a sealing material, a flip chip, a chip sealing material for COF or the like, a sealing material for package such as CSP and BGA, an optical semiconductor (LED) sealing material, an optical waveguide material, a nanoimprint material, materials for photofabrication and for micro-photofabrication, and the like while utilizing a base generated by photoirradiation.