JP3399974B2 - Novel photoinitiator, photoinitiator system and photopolymerizable composition using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel photoinitiator, a photoinitiator system and a photopolymerization composition using the same.

[0002]

2. Description of the Related Art Photopolymerizable compositions are widely used for relief printing, relief images, photoresists and the like, generally using a UV light source, but a system having higher sensitivity is desired. If there is a light-sensitive material having sensitivity in the red and near-infrared region of 600 nm to 900 nm, a small-sized semiconductor laser that can be directly modulated can be used, and its utility is high. Although much research has been done in this field on photoinitiator systems for increasing sensitivity, none are known to have sufficient sensitivity at long wavelength light.

[0003]

The present invention provides a novel photoinitiator having a high sensitivity to near infrared light, a photoinitiator system, and a photopolymerizable composition using the same. .

[0004]

The present invention provides the following formula [I]:
Naphthalocyanine compound represented by

[Chemical 4] (In the formula, M represents H ₂ , a metal or metalloid, Y represents a substituent or a ligand, n = 0 when M is H ₂ , and M is a metal or metalloid, n = 0, 1 or 2,
When n = 2, two Ys may be the same or different, and
_The ring represented by ₁ , A ₂ , A ₃ and A ₄ represents a naphthalene ring to which a substituent may be bonded, and the substituent may be the same or different).

The present invention also relates to the above naphthalocyanine compound and an s-triazine compound represented by the following formula [II].

[Chemical 5] (Wherein R ₁ , R ₂ and R ₃ represent a substituent, at least one of which is a trihalomethyl group, and R ₁ , R ₂ and R ₃ may be the same or different) Photoinitiator system,
The above naphthalocyanine compound and an N-aryl-α-amino acid represented by the following formula [III]

[Chemical 6] (In the formula, R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a halogen atom, and R ₉ is a hydrogen atom, 1 to 12 carbon atoms. An alkyl group having 12 carbon atoms, a cycloalkyl group, a hydroxyalkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 2 to 12 carbon atoms, an aminoalkyl group or aryl group having 1 to 12 carbon atoms, R ₁₀ and R ₁₁ each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) And a photoinitiator containing the above naphthalocyanine compound and an organic peroxide. Regarding the system.

The present invention also provides a photopolymerizable composition containing these photoinitiators or photoinitiator systems and an addition polymerizable compound having a boiling point of at least 100 ° C. at atmospheric pressure, and these photoinitiators. Alternatively, a photoinitiator system, an addition polymerizable compound having a boiling point of at least 100 ° C. under normal pressure and a high molecular weight organic polymer are contained, and the high molecular weight organic polymer is added to The present invention relates to a photopolymerizable composition with 20 to 80% by weight as a standard.

In the formula [I], examples of the metal include aluminum, indium, copper, nickel and the like, and examples of the semimetal include boron, silicon, arsenic, tellurium and the like. Examples of Y as a substituent or a ligand include a trialkylsilyloxy group, a phenoxy group, a halogen, a hydroxy group and a phenyl group. Examples of the substituent which may be bonded to the naphthalene ring include an alkyl group, a halogen, an alkoxy group, a phenyl group, a carboxyl group, an acetyl group and a cyano group. R ₁ , R ₂ and R ₃ in the formula [II] are not particularly limited.

The naphthalocyanine compound represented by the formula [I] includes (1) [(n-C ₃ H ₇ ) ₃ SiO] ₂ SiNc (where Nc represents a naphthalocyanine skeleton. The same applies hereinafter) bis ( (Tri-n-propylsiloxy) naphthalocyano-
Silicon (2) _{[(n-C 6 H 13)} 3 SiO ] ₂ SINC bis (tri-hexyl-silyloxy) Nafutaroshiano - silicon (3) [(C ₂ H _{5) 3} SiO] ₂ GENC bis (triethylsilyl oxy) naphthalate Russia no germanium (4) _{[(n-C 4 H 9)} 3 SiO ] ₂ SnNc bis (tri -n- butylsilyloxy) naphthalate Russian North's ₍₅₎ C ₆ H 5 OA1Nc [Si (CH _{3) 3] 4} tetrakis (trimethylsilyl) Nafutaroshiano - phenoxy aluminum (6) _{[(n-C 3 H 7)} 3 SiO ] ₂ TINC [Si
(CH _{3) 3] 4} bis (tri -n- propyl silyloxy) - tetrakis (trimethylsilyl) Nafutaroshiano - titanium (7) C1A1Nc Nafutaroshiano - chloro aluminum (8) H ₂ Nc Nafutaroshiano - hydrogensulfate (9) [HO] ₂ SINC Nafutaroshiano - dihydroxy silicon (10) CONC cobalt naphthalocyanine (11) OA1Nc Nafutaroshiano - oxy aluminum (12) C ₆ H ₅ InNc [tert-C ₄ H _{9] 4} tetra -tert- butyl - Nafutaroshiano - phenyl indium (13) CuNc [(CN _{3) 3} Si] _4-tetra (trimethylsilyl) Nafutaroshiano - Copper (14) NINC [CH _{3) 3} Si] _4-tetra (trimethylsilyl) Nafutaroshiano - nickel (15) CONC [(CH ₃ ) ₃ Si] ₄ tetra (trimethylsilyl) naphthalocyano-cobalt (16) GeNc [(C ₂ H ₅ ) ₃ Si] ₄ tetra (triethylsilyl) naphthalocyano-germanium (17) PdNc [(CH ₃ ) ₃ Si] ₄ tetra (trimethylsilyl) Nafutaroshiano - palladium (18) PbNc [(CH _{3) 3} Si] _4-tetra (trimethylsilyl) Nafutaroshiano - lead (19) OVNc [(CH _{3) 2} PhSi] ₄ tetra (dimethylphenylsilyl) Nafutaroshiano - vanadyl (20 ) [(CH ₃ ) ₃ SiO] ₂ SiNc [Si (C
H _{3) 2} C ₆ H _{5] 4-bis} (trimethylsilyloxy) - tetrakis (dimethylphenylsilyl) Nafutaroshiano - silicon _{(21) (C 2 H 5} O) 2 SiNc [Si (C ₆ H _{5) 3]
4} Bisuetokishi - tetrakis (triphenylsilyl) Nafutaroshiano - silicon (22) [(C ₆ H _{5) 3} SiO] ₂ SINC [Si (C
₂ H ₅ ) ₃ ] ₄ Bis (triphenylsilyloxy) -tetrakis (triethylsilyl) naphthalocyano-silicon (23) [(C ₂ H ₅ ) SiO] ₂ GeNc [Si (C
_{H 3) 2 -n-C 14} H 29 ] _4-bis (triethylsilyl oxy) - tetrakis (dimethyl tetradecyl silyl) Nafutaroshiano - such as germanium and the like.

The s-triazine compound represented by the formula [II] is 2,4,6-tris (trichloromethyl)-
s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2,4-bis (dichloromethyl) -6-trichloromethyl-s-triazine, 2-propionyl-4,6-bis ( Trichloromethyl) -s-
Triazine, 2-benzoyl-4,6-bis (tribromomethyl) -s-triazine, 2- (p-cyanophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-nitro Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6- (trichloromethyl) -s-triazine, 2- (p-cumenyl) -4,6- Trichloromethyl-s-triazine, 2- (p-metrooxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-aminophenyl) -4,6-bis (trichlorolymethyl) -S-triazine, 2,4-bis (p-methoxyphenyl) -6-trichloromethyl-s
-Triazine, 2,4-bis (m-chlorophenyl)-
6-trichloromethyl-s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl)
-S-triazine, 2- (p-chlorostyryl) -4,
6-bis (trichloromethyl) -s-triazine, 2-
(P-Aminostyryl) -4,6-bis (dichloromethyl) -s-triazine, 2- (4'-methoxy-1'-
Naphthyl) -4,6-bis (trichloromethyl) -s-
Triazine, 2- (6'-chloro-1'-naphthyl)-
4,6-bis (trichloromethyl) -s-triazine,
2- (6'-nitro-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-
Cyano-1'-naphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned.

N-aryl-α represented by the formula [III]
-As amino acids, p-chloro-N-ethylphenylglycine, N-methylphenylglycine, p-chloro-
N-methylphenylglycine, p-bromo-N-methylphenylglycine, p-cyano-N-phenylglycine, p-chloro-N-phenylglycine, p-chloro-
Examples thereof include N-propylphenylglycine and p-cyano-N-methylphenylglycine.

Examples of organic peroxides include tertiary butyl oxylaurate, benzoyl peroxide, acetyl peroxide, t-butyl hydrolooxide, cumene hydroperoxide, and 2,5-dimethylhexane-2,5-dihydroperoxide. Oxide, 1, 1,
3,3-tetramethylbutyl hydroperoxide,
2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3, p-menthane hydroperoxide, di-t-butylperoxide, di-isopropylbenzene hydroperoxide, t-butylcumylper Oxide, α, α-bisa (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexane, 3,
3 ', 4,4',-tetra-(-t-butyroperoxycarbonyl) benzophenone, di-cumyl peroxide and the like can be mentioned. From the viewpoint of ease of use, it is preferable to use an organic peroxide having a 10-hour half-life temperature of 100 ° C. or higher.

The addition polymerizable compound contained in the photopolymerizable composition has a boiling point of at least 100 ° C. under normal pressure. When the boiling point is lower than 100 ° C. under normal pressure, the addition-polymerizable compound is volatilized when the solvent contained in the system is removed by drying or irradiated with an actinic ray, which is not preferable in terms of properties and workability. Because. Further, the addition-polymerizable compound is preferably soluble in the organic solvent used for forming a uniform composition with the photoinitiator and the like.

As the organic solvent, aromatic solvent, halogen solvent, ether solvent, ketone solvent, alcohol solvent, saturated hydrocarbon solvent, alicyclic hydrocarbon solvent, ester solvent and the like can be used. Examples of aromatic solvents include benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trimethylbenzene, 1-chloronaphthalene, quinoline, and the like.
Halogen-based solvents include methylene chloride, chloroform, carbon tetrachloride, trichloroethane, etc., ether-based solvents include diethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, etc., and ketone-based solvents include acetone. , Methyl ethyl ketone, methyl propyl ketone, cyclopentanone, acetone alcohol, etc., alcohol-based solvents include methanol, ethanol, isopropyl alcohol, etc., saturated hydrocarbon solvents such as hexane, heptane, octane,
There are nonane, decane, undecane, dodecane and the like, alicyclic hydrocarbon solvents include cyclooctane, cyclopentane, cyclohexane, cycloheptane and the like, and ester solvents include ethyl acetate, propyl acetate and the like.

As the addition-polymerizable compound having a boiling point of at least 100 ° C. under normal pressure, polyhydric alcohol and α,
Those obtained by condensing with β-unsaturated carboxylic acid, for example, diethylene glycol di (meth) acrylate (meaning diacrylate or dimethacrylate, the same applies hereinafter), triethylene glycol di (meth) acrylate, tetraethylene glycol di ( (Meth) acrylate, trimethylolpropane di (meth) acrylate,
1,3-propanediol di (meth) acrylate,
1,3-butanediol (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2,2-
Α to glycidyl group-containing compounds such as bis (4-acryloxydiethoxyphenyl) propane and 2,2-bis (4-methacryloxypentaethoxyphenyl) propane.
Those obtained by adding β-unsaturated carboxylic acid, for example, trimethylolpropane triglycidyl ether tri (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Shin Nakamura Chemical Co., Ltd.
Manufactured by BPE-500 (mixture of 2,2-bis (4-methacryloxypolyethoxyphenyl) propane)
, Unsaturated amides such as methylenebisacrylamide,
Ethylene bis acrylamide, 1,6-hexamethylene bis acrylamide and the like, vinyl esters such as divinyl phthalate, divinyl terephthalate, divinyl benzene-1,3-disulfonate and the like are used. Two or more kinds of this addition-polymerizable compound may be used.

In the present invention, 100 parts by weight of an addition-polymerizable compound having a boiling point of at least 100 ° C. under normal pressure (when a high-molecular-weight organic polymer is used, the addition-polymerizable compound and the high-molecular-weight organic polymer are 0.001 to 2.0 parts by weight of the naphthalocyanine compound represented by the above formula [I], the s-triazine compound represented by the above formula [II], and the formula [ II
It is preferable to use the N-aryl-α-amino acid represented by I] or the organic peroxide in an amount of 0.01 to 10 parts by weight.

The photopolymerizable composition according to the present invention may contain one or more high molecular weight organic polymers, if desired. The high molecular weight organic polymer is thermoplastic and has a molecular weight of 10,000.
Those having 0 to 700,000 are preferred. For example, the following is used. (A) Manufactured from copolyester polyhydric alcohol such as diethylene glycol, triethylene glycol, tetraethylene glycol, trimethylolpropane, naopentyl glycol and the like and polyvalent carboxylic acid such as terephthalic acid, isophthalic acid, sepacic acid and adipic acid. Copolyester (B) vinyl polymer methacrylic acid, acrylic acid, methacrylic acid or alkyl ester of acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate, Homopolymers or copolymers of vinyl monomers such as styrene, vinyltoluene, vinyl chloride and vinyl butyral (C) Polyformaldehyde (D) Polyurethane (E) Polycarbonate (F) Nylon or polyamide (G) cellulose esters such as methylcellulose,
Ethyl cellulose

By adding a high molecular weight organic polymer to the photopolymerizable composition, properties such as adhesion to a substrate, chemical resistance and film property can be improved. From the viewpoint of photocurability, the high molecular weight organic polymer is preferably in the range of 20 to 80% by weight based on the total weight of the high molecular weight organic polymer and the addition-polymerizable compound.

The photopolymerizable composition according to the present invention may contain coloring substances such as dyes and pigments, if necessary. The photopolymerizable composition according to the present invention may contain a radical polymerization inhibitor or a radical polymerization inhibitor in order to enhance stability during storage. Examples of such substances include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, and aryl phosphite. The photopolymerizable composition according to the present invention may contain other additives known to be used in the photopolymerizable composition, for example, additives such as a plasticizer and an adhesion promoter.

The photopolymerizable composition according to the present invention is used in the printing industry,
It can be used in a wide range of fields related to photoreaction such as electronics, paints, medical care, information recording, and ink. The actinic ray source used is one that mainly emits an actinic ray having a wavelength of 600 to 900 nm. Examples of such a light source include a mercury lamp, a xenon lamp, a dye laser, a Raman laser, a semiconductor laser, and a krypton laser. The photopolymerizable composition according to the present invention is coated on a support such as a polyethylene terephthalate film and dried, laminated on a substrate and exposed to actinic rays to produce a printing plate,
It can also be used as a photoresist for forming circuits by etching or plating. As the support, an organic polymer film such as polyethylene film, polypropylene film, polyethylene terephthalate film, or polyethylene naphthalate film is used, and as the substrate, a copper plate, an aluminum plate, a metal plate such as an iron plate, or a copper foil is used on the surface. A stretched laminated plate (glass epoxy base material, paper phenol base material, etc.) is used.

[0020]

The reason why the novel photoinitiator system according to the present invention provides high sensitivity to visible light and near infrared light is that the naphthalocyanine compound represented by the above formula [I] absorbs light and It is considered that the s-triazine compound represented by the above formula [II] receives energy in some form and decomposes to generate an active radical, but the detailed mechanism is not yet clear.

[0021]

EXAMPLES Examples of the present invention will be described. Where part,%
Means parts by weight and% by weight, respectively. Examples and Comparative Examples Preparation of Photopolymerizable Composition Acrylic polymer (methacrylic acid / methyl methacrylate / butyl methacrylate / 2-ethylhexyl acrylate = 23/51/6/20, copolymer by weight ratio, weight average molecular weight about 90 , 00) 40% ethyl cellosolve solution 120 parts Tetradiethylene glycol diacrylate 25 parts Hydroquinone 0.04 parts Photoinitiator system (with the formulation shown in Table 1) Methyl ethyl ketone 20 parts The components of the photopolymerizable composition shown above are Dissolve with stirring, 23μ
A polyethylene terephthalate film (trade name: “Lumirror” manufactured by Toray Industries, Inc.) having a thickness of m is coated with a bar coater and dried for about 10 minutes by a hot air convection dryer at 80 ° C. to obtain a photopolymerizable element. It was The thickness of the dried photopolymerizable composition layer was 20 μm. Next, using a laminator that pressurizes and heats with a rubber roll to laminate, a rubber roll temperature is set to 80 ° C. so that the photopolymerizable composition layer and the copper surface are in contact with each other on a 0.5 mm-thick aluminum plate having a clean surface. The polymerizable elements were laminated. From the polyethylene terephthalate film side of the laminated sample, static exposure was performed with a semiconductor laser having a beam diameter of 120 μm, a wavelength of 780 nm, and an optical output of 1.9 mW. After that, the polyethylene terephthalate film was removed and 1% Na was added at 30 ° C.
_The uncured portion was eluted by immersing it in a ₂ CO ₃ aqueous solution, and the irradiation time required for the diameter of the residual film to reach 0.3 mm was investigated, and this was taken as the sensitivity. The table shows a comparison of sensitivity.

[0022]

[Table 1]

[0023]

INDUSTRIAL APPLICABILITY According to the present invention, a photoinitiator, a photoinitiator system and a photopolymerizable composition having high sensitivity to near infrared light can be obtained.

Continuation of front page (56) References JP-A-60-199890 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 2/00-2/60

Claims (3)

(57) [Claims] 1. A naphthalocyanine compound represented by the following formula [I]: (In the formula, M represents H ₂ , a metal or metalloid, Y represents a substituent or a ligand, n = 0 when M is H ₂ , and M is a metal or metalloid, n = 0, 1 or 2,
When n = 2, two Ys may be the same or different, and
_The ring represented by ₁ , A ₂ , A ₃ and A ₄ represents a naphthalene ring to which a substituent may be bonded, and the substituents may be the same or different); and represented by the following formula [II] s-triazine compound (Wherein R ₁ , R ₂ and R ₃ represent a substituent, at least one of which is a trihalomethyl group, R ₁ , R ₂ and R ₃ may be the same or different), Photoinitiator system. 2. A photopolymerizable composition comprising the photoinitiator system according to claim 1 and an addition polymerizable compound having a boiling point of at least 100 ° C. under normal pressure. 3. A photoinitiator system according to claim 1 and an addition-polymerizable compound having a boiling point of at least 100 ° C. under normal pressure and a high molecular weight organic polymer, wherein A photopolymerizable composition in which the total weight of the polymer and the addition-polymerizable compound is 20 to 80% by weight.