JPS629110B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel phthalazinone compound, a method for producing the compound, and a method for photopolymerizing unsaturated compounds using the compound. Methods of providing a cured coating film by irradiation with ultraviolet rays in the presence of a photopolymerization initiator are conventionally known, and in particular,
It is also well known that benzoin-based ether compounds, benzophenone-based compounds, or phenylazo-based compounds are used as photopolymerization initiators. However, as mentioned above, when using conventionally known photopolymerization initiators, those with a relatively fast curing rate, that is, those with good sensitivity, have poor storage stability in the dark; Photopolymerization initiators with good intensities have the disadvantage of poor sensitivity, and therefore, a photopolymerization initiator that exhibits good storage stability in the dark and high sensitivity during photopolymerization has been desired. As a result of intensive research to solve these problems, the present inventors found the general formula: (In the formula, R ¹ represents hydrogen or a di-lower alkylamino group such as a dimethylamino group, a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, or a halogen such as chlorine, and R ² represents hydrogen or a methyl group, It represents a lower alkyl group such as an ethyl group, and ^R3 represents a di-lower alkylamino group such as a dimethylamino group or a diethylamino group.)
The present invention was completed based on the discovery that when a novel phthalazinone compound represented by is used as a photopolymerization initiator for unsaturated compounds, it exhibits high sensitivity during photopolymerization and good storage stability in the dark. I decided to do it. The novel phthalazinone compound of the present invention is a dihydrophthalazinone compound represented by the above general formula,
Some examples of these are as follows. (1) 4,4-bis(p-dimethylaminophenyl)-7-dimethylamino-3,4-dihydrophthalazin-1-one. (2) 4,4-bis(p-dimethylaminophenyl)-7-dimethylamino- ^N2 -methyl-3,
4-dihydrophthalazin-1-one. (3) 4,4-bis(p-dimethylaminophenyl)-3,4-dihydrophthalazin-1-one. (4) 4,4-bis(p-diethylaminophenyl)-3,4-dihydrophthalazin-1-one. (5) 4,4-bis(p-dimethylaminophenyl)-7-methyl-3,4-dihydrophthalazin-1-one. (6) 4,4-bis(p-dimethylaminophenyl)-7-methoxy-3,4-dihydrophthalazin-1-one. (7) 4,4-bis(p-diethylaminophenyl)-7-chloro- ^N2 -methyl-3,4-dihydrophthalazin-1-one. (8) 4,4-bis(p-dimethylaminophenyl) ^-N2 -ethyl-3,4-dihydrophthalazin-1-one. The dihydrophthalazinone compound [] of the present invention can be synthesized by the following typical method. That is, a 3,3-disubstituted phthalide compound represented by the general formula [] and a hydrazine compound [],
Usually, it is synthesized by reaction in a solvent such as alcohol by heating under reflux. In the above formulas [], [], [], R ¹ ,
R ² and R ³ are the same groups as described above for the novel phthalazinone compound of the present invention. The novel phthalazinone compound of the present invention can be used for the photopolymerization of conventionally known photopolymerizable unsaturated compounds alone or in a mixture, and the amount used is usually as follows:
Preferably about 0.1 to 20% by weight in the photopolymerizable composition
The amount is approximately 0.5 to 15% by weight, and may be increased as appropriate if pigments that block ultraviolet rays are included. Examples of the above-mentioned photopolymerizable unsaturated compounds include alkyl acrylates, hydroxyalkyl acrylates, mono- or polyethylene glycol diacrylates, trimethylolpropane triacrylates, and corresponding methacrylates, maleic acid, fumaric acid, crotonic acid, and sorbin. acids, α,β-unsaturated carboxylic acids such as itaconic acid, and their alkyl and aryl esters, as well as styrene, alkylstyrene, halogenostyrene, divinylbenzene, N-vinylpyrrolidone, diallylphthalate, triallylisocyanurate, triallyl Examples include trimellitate. Furthermore, examples of compounds that can be photopolymerized include unsaturated oligomers of polymers and mixtures of these and the above-mentioned unsaturated monomers. Examples include saturated polyester resins, unsaturated acrylic resins, polyether acrylates, and isocyanate-modified or epoxide-modified acrylate oligomers. The novel phthalazinone compound of the present invention can be used alone as a photopolymerization initiator for unsaturated compounds, but it can also be used with conventionally used benzoin-based ether compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, Benzoin alkyl ethers such as benzoin butyl ether, benzophenone compounds such as benzophenone, benzoylbenzoic acid alkyl esters such as methyl o-benzoylbenzoate, methyl p-benzoylbenzoate, or phenylazo compounds such as phenylazoisobutyronitrile, 2-phenylazo -2,4-dimethylvaleronitrile, 4-methoxy-2,4-dimethyl-2-phenylazovaleronitrile can be used in combination with these conventional photopolymerization initiators alone or in combination. It exhibits the surprising effect of not only extremely high thermal stability in the dark, but also significantly faster photocuring speed than when used in the dark. This photopolymerization initiator is extremely useful for printing inks, paints, adhesives, etc. Examples are given below to further explain the present invention. Example 1 3,3-bis(p-dimethylaminophenyl)
-6-dimethylaminophenyl phthalide 4.2g
(0.01 mol) was added to 200 ml of ethanol, 5 g (0.1 mol) of hydrazine hydrate was added, and the mixture was heated under reflux for 2 hours. After cooling, the reaction solution is concentrated under reduced pressure, the precipitated crystals are collected, and when recrystallized from ethanol, the melting point is 266℃.
3.5 g of 4,4-bis-(p-dimethylaminophenyl)-7-dimethylamino-3,4-dihydrophthalazin-1-one was obtained as white crystals. Elemental analysis value (C ₂₆ H ₃₁ N ₅ O) Calculated value C: 72.68, H: 7.29, N: 16.30 Actual value C: 72.70, H: 7.30, N: 16.18 NMR (CDCl ₃ ) δ: 2.92 (s, 12H ,N( _CH3 ) ₂ )
3.00 (s, 6H, N(CH ₃ ) ₂ )
6.51～7.41(m, 11H,
aromatic) IRν ^KBr _nax cm ^-1 ; 1660

[Formula] UVλ ^EtoH _nax nm; 266 (ε: 57100) Mass (m/e): 429 (M ⁺ ) Example 2 3,3-bis(p-dimethylaminophenyl)
4.2 g (0.01 mol) of -6-dimethylaminophthalide and 4.6 g (0.1 mol) of methylhydrazine are heated under reflux in 150 ml of ethanol for 10 hours. After cooling, the reaction solution was concentrated under reduced pressure, dissolved in a small amount of chloroform, applied to a column of silica gel (Wakogel C-300), and eluted with chloroform. When recrystallized from ethanol, 4,4-bis(p-
dimethylaminophenyl)-7-dimethylamino- ^N2 -methyl-3,4-dihydrophthalazine-
1.5 g of 1-one was obtained as pale yellowish brown crystals. Elemental analysis value (C ₂₇ H ₃₃ N ₅ O) Calculated value C; 73.11 H; 7.50 N: 15.79 Actual value C; 72.95 H; 7.37 N; 15.59 NMR (CDCl ₃ ) δ: 2.90 (12H, s, N (CH ₃ ) ₂ ×
2) 2.98 (6H, s, N
(CH ₃ ) ₂ ) 3.16 (3H, s,
CH ₃ ) 6.51~7.11 (11H, m, p-N
−C ₆ H ₄ ×2, C ₆ H ₃ ) IRν ^KBr _nax cm ^-1 ; 1635 (〓C=0) UVλ ^EtoH _nax nm; 267 (ε; 27300) Example 3 3,3-bis(p-dimethyl aminophenyl)
-1.9 g (0.005 mol) of phthalide and hydrazine hydrate
2.5 g (0.05 mol) was heated under reflux in 150 ml of aqueous ethanol for 20 hours, and then the melting point was determined in the same manner as in Example 1.
1.5 g of 4,4-bis(p-dimethylaminophenyl)-3,4-dihydrophthalazin-1-one was obtained as pale yellow crystals at 245°C. Elemental analysis value (C ₂₄ H ₂₆ N ₄ O) Calculated value C: 74.57, H: 6.79, N: 14.50 Actual value C: 74.87, H: 6.80, N: 14.70 NMR (CDCl ₃ ) δ: 2.92 (s, 12H ,N
( _CH3 ) ₂ ), 6.51~7.48 (m,
12H, aromatic) IRν ^KBr _nax cm ^-1 ; 1655

[Formula] UVλ ^EtOH _nax nm; 264 (ε: 46000) Mass (m/e): 386 (M ⁺ ) Example 4 3,3-bis(p-diethylaminophenyl)
-0.4g (0.001mol) of phthalide and hydrazine hydrate
0.5 g (0.01 mol) was heated under reflux in 50 ml of ethanol for 10 hours, and then the melting point was 198 in the same manner as in Example 1.
0.2 g of 4,4-bis(p-diethylaminophenyl)-3,4-dihydrophthalazin-1-one at ~200°C was obtained as pale yellow crystals. Elemental analysis value (C ₂₈ H ₃₄ ON ₄ ) Calculated value C: 75.98, H: 7.74, N: 12.66 Actual value C: 75.88, H: 7.86, N: 12.53 NMR (CDCl ₃ ) δ: 0.96 (12H, t, N(CH ₂
CH ₃ ) ₂ × 2, J = 8Hz) 3.40
(8H, q, N( CH ₂ CH ₃ ) ₂ ×
2, J=8Hz) 6.51~7.11
(14H, m, aromatic) IRν ^KBr _nax cm ^-1 ; 1660

[Formula] UVλ ^EtoH _nax nm; 265 (ε: 56000) Mass (m/e): 442 (M ⁺ ) Example 5 3,3-bis(p-dimethylaminophenyl)
-6-Methylphthalide 0.8g (0.002mol) and hydrazine hydrate 1.0g (0.02mol) in 100ml of ethanol
4,4-bis(p-dimethylaminophenyl)-7-methyl-3,4-dihydrophthalazin-1-one having a melting point of 249°C was heated under reflux for 5 hours in the same manner as in Example 1. 0.5 as a pale yellow crystal
I got g. Elemental analysis value (C ₂₅ H ₂₈ N ₄ O) Calculated value C: 74.96 H: 7.05 N: 13.99 Actual value C: 75.09 H: 7.27 N: 13.79 NMR (CDCl ₃ ) δ: 2.48 (3H, s, CH ₃ ) ,2.92
(12H, s, N(CH ₃ ) ₂ × 2) 6.51~7.40 (11H, m,
aromatic) IRν ^KBr _nax cm ^-1 ; 1655

[Formula] UVλ ^EtOH _nax nm; 265 (ε: 46500) Mass (m/e): 400 (M ⁺ ) Example 6 3,3-bis(p-dimethylaminophenyl)
- 0.8 g (0.002 mol) of 6-methoxyphthalide and 1.0 g (0.02 mol) of hydrazine hydrate were added to 100 ml of ethanol.
4,4-bis(p-dimethylaminophenyl)-7-methoxy-3,4-cyhydrophthalazine-1 having a melting point of 238°C was heated under reflux for 5 hours in the same manner as in Example 1. −on as a pale yellow crystal
Obtained 0.4g. Elemental analysis value (C ₂₅ H ₂₈ N ₄ O ₂ ) Calculated value C: 72.09 H: 6.78 N: 13.45 Actual value C: 72.15 H: 6.90 N: 13.22 NMR (CDCl ₃ ) δ: 2.91 (12H, s, N ( _CH3 ） ₂ ×
2) 3.85 (3H, s, OCH ₃ ) 6.52~7.45 (11H, m,
aromatic) IRν ^KBr _nax cm ^-1 ; 1660

[Formula] UVλ ^EtOH _nax nm; 266 (ε: 55000) Mass (m/e): 416 (M ⁺ ) Example 7 3,3-bis(p-diethylaminophenyl)
-6-Chlorphthalide 0.9 g (0.002 mol) and methylhydrazine 1.0 g (0.02 mol) in 100 ml of ethanol
ml for 10 hours, and then treated in the same manner as in Example 1 to obtain 4,4-bis(p
-diethylaminophenyl)-7-chloro-N ² -
0.3 g of methyl-3,4-dihydrophthalazin-1-one was obtained as pale yellow crystals. Elemental analysis value (C ₂₉ H ₃₅ N ₄ OCl) Calculated value C: 70.93 H: 7.18 N: 11.41 Actual value C: 71.11 H: 7.31 N: 11.30 NMR (CDCl ₃ ) δ: 0.95 (12H, t, N (CH ₂
CH ₃ ) ₂ × 2, J = 8Hz) 3.16
(3H, s, NCH ₃ )3.40(8H,
q, N( CH ₂ CH ₃ ) ₂ ×2, J=
8Hz) 6.50~7.11 (11H, m,
aromatic) IRν ^KBr _nax cm ^-1 ; 1630

[Formula] UVλ ^EtOH _nax nm; 268 (ε: 26700) Mass (m/e): 491 (M ⁺ ) Example 8 3,3-bis(p-dimethylaminophenyl)
- 1.9 g (0.005 mol) of phthalide and 3.0 g (0.05 mol) of ethylhydrazine were heated under reflux in 200 ml of butanol for 20 hours, and then treated in the same manner as in Example 1,
0.7 g of 4,4-bis(p-dimethylaminophenyl)-N ^{2 -ethyl} -3,4-dihydrophthalazin-1-one having a melting point of 210°C was obtained as pale yellow crystals. Elemental analysis value (C ₂₆ H ₃₀ N ₄ O) Calculated value C: 75.33 H: 7.30 N: 13.52 Actual value C: 75.18 H: 7.47 N: 13.61 NMR (CDCl ₃ ) δ: 0.99 (3H, t, NCH ₂ CH ₃ ,
J=7Hz)2.90(12H,s,N
(CH ₃ ) ₂ × 2) 3.65 (2H, q,
N CH ₂ CH ₃ , J=7Hz) 6.51~7.10 (12H, m,
aromatic) IRν ^KBr _nax cm ^-1 ; 1635

[Formula] UVλ ^EtOH _nax nm; 267 (ε: 26000) Mass (m/e): 414 (M ⁺ ) Example 9 Methyl methacrylate in a Pyrex polymer tube
Add 100 parts and a predetermined amount of photopolymerization initiator, replace the inside of the system with nitrogen gas, melt seal, and place in a constant temperature bath at 10℃.
The polymerization rate was measured by irradiating it with a 100W mercury lamp for 10 minutes from a distance of 12cm. In addition, a polymerization tube prepared in the same manner was thermally polymerized for 20 hours in a constant temperature bath at 60°C under light shielding, and the polymerization rate was measured. Table 1 shows the amount of photopolymerization initiator added and the results obtained.

[Table] Example 10 1 mol of maleic anhydride and 1 mol of phthalic anhydride were added to 1 mol of diethylene glycol and 1.2 mol of propylene glycol, and esterification was carried out by a conventional method to obtain an unsaturated polyester resin with an acid value of 40. Next, this product was diluted with styrene to a resin content of 60%, and further, 0.1 part of paraffin having a melting point of 62°C was dissolved in 100 parts of this resin. Next, a photocurable composition was prepared by adding a predetermined amount of a photopolymerization initiator to 100 parts of this unsaturated polyester resin, and the composition was applied to a thickness of 200μ on a glass plate.
Irradiate light from a distance of 20cm with a 200W high-pressure mercury lamp,
The curing time was measured. Further, the gelation time of this composition was measured in a constant temperature bath at 40°C. Table 2 shows the amount of photopolymerization initiator added and the results obtained.

[Table] Example 11 Epichlorohydrin to 100 parts of bisphenol A
Then, 100 parts of a 40% caustic soda aqueous solution was added dropwise to obtain an epoxy resin having an epoxy equivalent of 190 using a conventional method. Acrylic acid is added to 190 parts of the resulting resin.
72 parts of the mixture were added and reacted at 110°C for 15 hours in the presence of 1 part of triethylamino and 0.3 parts of hydroquinone to obtain a viscous liquid prepolymer with an acid value of 2.6. Next, 30 parts of trimethylolpropane triacrylate was added to 70 parts of this liquid prepolymer to prepare a varnish with a resin content of 70%. Next, a photocurable composition was prepared by adding a predetermined amount of a photopolymerization initiator to 100 parts of this varnish, and the composition was coated on a glass plate to a thickness of 200 μm. The curing time was measured by irradiating light from a distance of . Further, the gelation time of this composition was measured in a constant temperature bath at 40°C. Table 3 shows the amount of photopolymerization initiator added and the results obtained.

[Table] Example 12 A polymerization reaction was carried out under the same conditions as in Example 9 using the phthalazinone compounds obtained in Examples 5 to 7 as a photopolymerization initiator. Table 4 shows the amount of photopolymerization initiator added and the results obtained.

【table】

Claims (1)

[Claims] 1. General formula: (In the formula, R ¹ represents hydrogen or a di-lower alkylamino group such as a dimethylamino group, a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, or a halogen such as chlorine, and R ² represents hydrogen or a methyl group, It represents a lower alkyl group such as an ethyl group, and ^R3 represents a di-lower alkylamino group such as a dimethylamino group or a diethylamino group.)
A dihydrophthalazinone compound represented by 2. The dihydrophthalazinone compound according to claim 1, which is 4,4-bis(p-dimethylaminophenyl)-7-dimethylamino-3,4-dihydrophthalazin-1-one. 3 4,4-bis(p-dimethylaminophenyl)-7-dimethylamino-N ² -methyl-3,4
-dihydrophthalazinone compound according to claim 1, which is -dihydrophthalazin-1-one. 4. The dihydrophthalazinone compound according to claim 1, which is 4,4-bis(p-dimethylaminophenyl)-3,4-dihydrophthalazin-1-one. 5. The dihydrophthalazinone compound according to claim 1, which is 4,4-bis(p-diethylaminophenyl)-3,4-dihydrophthalazin-1-one. 6 General formula: (In the formula, R ¹ represents hydrogen or a di-lower alkylamino group such as a dimethylamino group, a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, or a halogen such as chlorine, and R ³ represents a dimethylamino group or a diethylamino group) represents a di-lower alkylamino group such as a 3,3-
The di-substituted phthalide compound is reacted with a hydrazine compound represented by the general formula: H ₂ NNH-R ² (wherein R ² represents hydrogen or a lower alkyl group such as a methyl group or an ethyl group). General formula: (In the formula, R ¹ represents hydrogen or a di-lower alkylamino group such as a dimethylamino group, a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, or a halogen such as chlorine, and R ² represents hydrogen or a methyl group, It represents a lower alkyl group such as an ethyl group, and ^R3 represents a di-lower alkylamino group such as a dimethylamino group or a diethylamino group.)
A method for producing a dihydrophthalazinone compound represented by 7 General formula: (In the formula, R ¹ represents hydrogen or a di-lower alkylamino group such as a dimethylamino group, a lower alkyl group such as a methyl group, a lower alkoxy group such as a methoxy group, or a halogen such as chlorine, and R ² represents hydrogen or a methyl group, It represents a lower alkyl group such as an ethyl group, and ^R3 represents a di-lower alkylamino group such as a dimethylamino group or a diethylamino group.)
A photopolymerization initiator comprising a dihydrophthalazinone compound represented by: