JPH06192309A - Sensitizing pigment for photo-polymerization initiation system - Google Patents

Abstract

PURPOSE:To obtain a new sensitizing pigment composed of a coumarin derivative, having high sensitivity to enable the high-speed scanning recording with visible laser such as argon ion laser and useful for photo-sensitive microcapsule, hologram-recording material, etc. CONSTITUTION:The coumarin derivative expressed by the formula (R1 to R4 are independently 1-3C alkyl; X is 5-membered heterocyclic group which may have condensed ring). In the formula, X is 2-thiazolyl group, 2-oxazolyl group, etc. The pigment may be incorporated with a photo-polymerization initiator.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photopolymerization initiation sensitizing dye comprising a novel coumarin derivative.

[0002]

2. Description of the Related Art A photopolymerizable composition is a material which shows changes in physical properties in a light-irradiated portion and a non-irradiated portion upon receiving light energy.
Printing, fine processing of ultra LSI, printed circuit formation, U
It has been put to practical use in a wide range of fields such as V-curing paints, inks, and hologram recording, and its applications are expanding more and more. This composition is basically composed of a photopolymerization initiator, a photopolymerizable compound and a binder resin, and usually has a spectral sensitivity in the ultraviolet region, and it has a g-line, an i-line of a mercury lamp and a high-power argon laser. An image is recorded using an ultraviolet oscillation line or the like. In recent years, the development of a technique for recording an image using visible laser light has been actively pursued, and the use of a sensitizing dye has become an indispensable technical element in order to give the recording light spectral sensitivity. The characteristics of such sensitizing dyes include:
(1) It has excellent solubility in a solvent, (2) it has a large absorption coefficient at the wavelength of recording light, (3) the photosensitive wavelength is in good agreement with the wavelength of recording light, and (4) high sensitivity. And (5) good storage stability, and (6) good compatibility with other components. from now on,
Many types of photopolymerization initiation sensitizing dyes have been proposed. For example, JP-A-54-151024 has a merocyanine dye, JP-A-58-29803 has a cyanine dye, JP-A-59-56403 has a stilbene derivative, and JP-A-58-1983 has a 63.
-23901 is a coumarin compound, and 64-33104.
Describes methylene blue derivatives. In reality, it is difficult to find a dye having all of the above-mentioned required properties among these known dyes.

[0003]

[Problems to be Solved by the Invention] In the technical field of image recording using a photopolymerizable composition, sensitizing dyes with higher sensitivity are demanded due to the need for high-speed recording and low-power laser recording. . However, the relationship between the molecular structure of the sensitizing dye and various properties, particularly the sensitivity, has not been sufficiently clarified, and by analogy with known materials, by selecting,
Finding a highly sensitive dye is not easy.

[0004]

[Means for Solving the Problems] As a result of intensive investigations by the present inventors, it was found that the novel coumarin derivative represented by the following general formula (I) exhibits extremely high sensitization property to a photopolymerizable composition. Found and completed the present invention.

Embedded image (I) In the above formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent an alkyl group consisting of a methyl group, an ethyl group and a propyl group. X represents a 5-membered heterocyclic group which may have a condensed ring. Examples of this include 2-thiazolyl group, 2-oxazolyl group, 2-imidazolyl group, 2- (1,3,4-thiadiazolyl) group, 2- (1,3,4-oxadiazolyl) group, 2-benzothiazolyl group, 2-benzoxazolyl group, 2-benzoselenazolyl group, 2-indorenyl group, 2-pyridothiazolyl group, 2-benzimidazolyl group, 2- (4,5-benzo) benzothiazolyl group, 2-
(6,7-benzo) benzoxazolyl group, 2- (4,
5-benzo) indolenyl group and the like, and in the vacant position of these groups, an alkyl group which may be branched, an alkoxy group which may be substituted with an alkoxy group, a halogen such as fluorine and chlorine, a cyano group, an alkyl group and an alkoxy group. A phenyl group which may have a substituent such as a group, a halogen-substituted alkyl group, an amino group which may be substituted with an alkyl group, an alkylsulfonyl group, a carboxylic acid ester group, or an alkyl or arylcarbonyloxy group. It may have one or more substituents.

As the photopolymerization initiator used in combination with the sensitizing dye of the present invention, various organic peroxides, triazine compounds represented by 2,4,6-trichloromethyl-s-triazine, benzoin alkyl ethers, and bisimidazoles. ,
Examples thereof include iron-allene chain products, N-phenylglycine and diphenyliodonium salts. Also, a multi-component initiator obtained by combining these several kinds may be used. As an example of the organic peroxide, as the peroxy ester, di-t-
Butyldiperoxyisophthalate 3,3'4,4 '
-Tetrakis (t-butyldioxycarbonyl) benzophenone, 2,5-as dialkyl peroxide
Dimethyl-2,5-bis (t-butyldioxy) -3-
Hexane, di-t-butyl peroxide, and hydroperoxide include 2,5-bis (hydroperoxy)
-2,5-dimethylhexane, t-butyl hydroperoxide, butyl-4 as a peroxyacetal,
4-bis (t-butyldioxy) valerate, 1,1-
Examples of bis (t-butyldioxy) -3,3,5-trimethylcyclohexane include ketone peroxides such as ethylmethylketone peroxide.

The photopolymerizable compound is composed of a photopolymerizable or photocrosslinkable monomer, oligomer, prepolymer or a mixture thereof having at least one ethylenically unsaturated double bond in one molecule. Examples of such compounds include ethyl acrylate, hydroxyethyl acrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, polyester methacrylate, polyurethane methacrylate, epoxy methacrylate, etc. The compound used for can be mentioned.

Examples of the binder resin include poly-N-vinylpyrrolidone, polyvinyl acetate, polyvinyl butyral, polyvinylcarbazole, polystyrene, polymethylmethacrylate, polyethylene oxide,
Examples thereof include polybutylmethacrylate, styrene-maleic acid ester, polymethylmethacrylate-methacrylic acid-based resin, poly-N-vinylpyrrolidone-glycidylmethacrylate-based resin, and the like.

The sensitizing dye according to the present invention is used in a proportion of 0.1 to 10 times that of the photopolymerization initiator, and a binder resin is added in a proportion of 0 to several hundred times to the mixture thereof. A polymerizable composition is prepared. If necessary, additives such as a thermal polymerization inhibitor and a plasticizer may be added to this composition.

Next, the present invention will be described in more detail with reference to examples. Specific examples of the sensitizing dye of the present invention include the following dyes.

[Chemical Formula 2] Dye 1

[Chemical Formula 3] Dye 2

[Chemical 4] Dye 3

[Chemical 5] Dye 4

Embedded image Dye 5

Embedded image Dye 6

Embedded image Dye 7

Embedded image Dye 8

Embedded image Dye 9

Embedded image Dye 10

Embedded image Dye 11

Embedded image Dye 12

Embedded image Dye 13

Embedded image Dye 14

The dye according to the present invention is a dye according to British Patent 86759.
2. It can be manufactured based on the method described in German Patent 1098125 or Japanese Patent Publication No. 51-7488. The production of Dye 1 is described in Reference Example.

[Reference example]

[Chemical 16] 9-formyl-8-hydroxy-1,1, represented by
5 g of 7,7-tetramethylurolidine, 3.7 g of orthoaminothiophenol and 10 ml of dimethylformamide
And heated at an internal temperature of 110 to 120 ° C. for 6 hours. Dispersion of ammonia gas is observed on the cooling pipe on the way. After the reaction, the mixture is cooled, 30 ml of isopropyl ether is added to crystallize, and then collected by filtration. 200 g of 4.1 g of the obtained crude crystals
After heat-dissolving in 1 liter of atocene and natural filtration, 1/2 amount of acetone is distilled off, and after cooling, the precipitated crystals are collected by filtration and washed with isopropyl ether. It has an absorption maximum wavelength of 480 mm and a melting point of 228-9 ° C. in methylene chloride.

Next, sensitivity measurement will be described. Photosensitive solution formulation: Binder resin (HSP-621) 100 parts Polyfunctional monomer (PETA) 100 parts Organic peroxide (BTTB) 8 parts Sensitizing dye 6 parts Ethyl cellosolve 1000 parts Grain-finished aluminum plate surface-treated with the above photosensitive solution Was spin coated to form a photosensitive layer. An overcoat layer of polyvinyl alcohol was provided to avoid polymerization inhibition by oxygen. Light from a 3 kW ultra-high pressure mercury lamp is passed through a sharp cut filter (Y-47) and an interference filter (KL-49) into this photosensitive layer to extract light of 490 nm close to the oscillation wavelength of an argon laser, and this light is grayed out. The scale was brought into close contact and irradiated. After that, it was developed with an alkaline developer. The sensitivity is based on the gray scale method,
It was calculated from the number of steps of photo-cured steps. The results are shown in Table 1.

Embedded image Dye 15

Embedded image Dye 16

It can be seen from Table 1 that the dye of the present invention has a high sensitivity which is several times to ten times higher than that of the conventionally known dye (comparative example).
This sensitivity was considered to be a result of matching the irradiation wavelength and the wavelength of the dye, but it was found that the dye of the present invention exhibits high sensitivity even when compared with the amount of absorbed light for comparison. Other dyes according to the present invention also show similar effects. The reason why sensitivity is shown in this way is currently unknown,

Since it has a tetraalkyl-substituted urolidine ring represented by the formula: in the molecule, the dye molecule also has the required characteristics as the above-mentioned sensitizing dye, and is considered to exhibit unpredictable high sensitivity. To be Similarly good effects can be expected in the derivative of the general formula (I) in which X is —CO—Y. Here, Y is a substituted or unsubstituted alkyl group; a substituted or unsubstituted alkoxy group;
It represents a substituted or unsubstituted phenyl group, an aryl group such as a naphthyl group or a heterocyclic group; a substituted or unsubstituted styryl group; and a substituted or unsubstituted 3'-coumarino group.

[0013]

Since the dye of the present invention has high sensitivity, it is possible to perform high-speed scanning recording with a visible laser such as an argon ion laser, a PS plate for laser direct plate making, a dry film resist, a digital color proof, and a hologram. It is extremely useful as a sensitizing dye for materials such as recording materials and photosensitive microcapsules.

Claims (1)

[Claims] 1. A photopolymerization initiation sensitizing dye comprising a coumarin derivative represented by the following general formula (I): (I) (In the above formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent an alkyl group having 1 to 3 carbon atoms, and X represents a 5-membered heterocyclic group which may have a condensed ring. .).