JPS59178449A - Photopolymerizable image forming composition - Google Patents

Abstract

PURPOSE:To shorten exposure time and to execute sufficient cross-linking and color development of a reducing dye by incorporating a photopolymn. initiator, and an aromatic diazonium type light activating agent having a light absorption wavelength region different from that of the photopolymn. initiator in a photoresist compns. for manufacturing a printing plate and a printed circuit board. CONSTITUTION:A photopolymerizable image forming compsn. is prepared by incorporating a polymer binder, such as poly(meth)acrylate, a photopolymerizable monomer, a photopolymn. initiator, a reducing dye, such as lactone or lactam type triarylmethane type dye, and moreover, an aromatic diazonium salt type light activating agent having a light absorption wavelength region different from that of said initiator, such as diphenylamine-4,4'-bisdiazonium-tetrafluoroborate represented by the formula shown here in which Ar is aryl and X is an anionic component of a Lewis acid in a wide sense. As a result, crosslinking reactivity is enhanced without deteriorating photopolymerizability, color developability is improved, color retention time is extended, and further, discrimination of exposed areas from unexposed areas is made easy.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a photopolymerizable image forming composition. By shining light through a negative or other means onto the surface of the material coated on the base material and concatenating the image, the areas exposed to the light polymerize or crosslink, making them insoluble in solvents, and the areas not exposed to light are eluted. It is known that the above images can be developed, and this principle is applied to the production of plate materials and printed wiring boards.

Alternatively, a photocoloring agent such as a leuco dye may be added to the above composition, and areas exposed to light and areas not exposed to light may be clearly identified.
It is known that it can discriminate between m and K.

However, when polymerizing or crosslinking a composition coated on a substrate or coloring the composition using ultraviolet light such as a commonly used high-pressure mercury lamp as a light source, the presence of a coloring agent reduces the polymerization or crosslinking rate. However, the 9th disadvantage is that you have to make the happy time longer for that purpose;bj
This is presumed to be due to the fact that the light energy absorbed by the sensitizer, polymerization initiator, etc. in the composition is divided into both color development and polymerization or crosslinking.

The present invention solves the above-mentioned drawbacks, and produces color development at the same time as polymerization or crosslinking, but the sensitivity decreases and there is no need to lengthen the exposure time, and it has good photosensitivity and excellent workability. The present invention was made for the purpose of providing an image forming composition suitable for multiple PK light.

That is, the present invention comprises a binder made of a polymeric material, a photopolymerizable heptadone monomer polymerization initiator, a reduced dye, and an aromatic 4f group diazonicum salt whose light absorption wavelength range is different from that of the photopolymerization initiator. The present invention relates to a photo-indentable image-forming composition comprising a photoactivator.

The binder used in the present invention is made of a polymeric feather, and any binder that has been conventionally used as a binder for image-forming compositions can be used, such as acetyl cellulose, acetyl butyl cellulose, etc. , polymethyl acrylate, polymethacrylic acid, methacrylic acid-methyl methacrylate copolymer, halogenated polyolefin, and the like.

In addition, the photopolymerizable monomer in the present invention refers to a monomer that is activated by light irradiation and starts polymerization in the presence of a photopolymerization initiator, and has a boiling point of 100°C or more at normal pressure. Monomers having at least one ethylene terminal group are preferably used. Polyethylene glycol, acrylate, triethylene glycol diacrylate, polyethylene glycol dimethacrylate, polymethylene diacrylate, polymethylene dimethacrylate, trimethylolpropane triacrylate,
Polyacrylate or polymethacrylate yarn threads such as trimethylolpropane trimethacrylate and oligomerized monomers of these monomers are preferably used.

As the photopolymerization initiator used in the present invention, conventionally known photopolymerization initiators are widely used, and phenylketone-based photopolymerization initiators are particularly preferably used.

Specific examples of the polymerization initiator include benzophenone 1.1.
p+-His (dimethylamino)penone-noenone (
(hereinafter referred to as Tomichler's ketone), P-aminone enzymes, pezin, pen/in methyl ether, he/soin ethyl needle, and benzene/buhi.
ether, benzine isofuroyl ether,
Benzyl anthraquinone, 2-nonal anthraquinone, 2-ethyl anthraquinone, 2-ter/yarylic anthraquinone, 2-amino anthraquinone, etc. are quenched, and many of these have an fI of 320 to 370. n
By absorbing the energy of light in the range of m, it acts as an initiator for synthesis.

゛These photopolymerization initiators may be used in combination with 24 fli or more, and in particular, when a mixture of penphenol and Michler's ketone is used, it has excellent polymerization initiation kinetics when exposed to light, This is suitable because it allows for the transfer of knowledge.

In the composition of the present invention, a combination of an aromatic dye and an aromatic anochloride photoactivator whose light absorption wavelength range is different from the photopolymerization initiation range is used as a coloring agent.

That is, the reduced dye in the present invention refers to a dye that is colorless or light colored and develops color when oxidized by a diazonicum salt type photoactivator, which will be described in detail later.A typical example thereof is a lactone type or lactam type triarylmethane. Examples include Song Mu 1, lactone type or lactam type fluoran dyes, and more specifically, crystal violet lactone,
Lactone-type amino-substituted triphenylmethane dyes such as methyl violet lactone; lactam-type amino-substituted triphenylmethane dyes; lactone-type fluoran dyes such as rhodamine lactone and compounds represented by the structural formula - lactams such as rhodamine lactam; Examples include fluoran type dyes.

In the present invention, the aromatic diazonicum salt type photoactivator having a light absorption wavelength range different from that of the 1311 photopolymerization initiator has the general formula A r N2X (A r is an aryl group, and K is a compound represented by the formula K, which is activated by irradiation with actinic light and releases an acid, thereby having the effect of oxidizing the above-mentioned reduced dye and developing color.

The photoactivator is prepared by reacting an aromatic amine capable of providing the aryl group with nitrous acid in the presence of an excess of the broad range Lewis acid described above.

Examples of the Lewis acids used at this time include hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, etc., and narrowly defined Lewis acids that do not contain hydrogen, such as zinc chloride, zinc bromide, and boron trifluoride. However, Lewis acids in the narrow sense, particularly fluorine trifluoride, are preferably used. When obtaining a diazonium salt having a Lewis acid component in the narrow sense, prepare the aromatic diazonium salt in advance by reacting the above mineral acid with the aromatic amine described below, and add the Lewis acid component to the diazonium salt. Special VC involves reacting salts to obtain the desired diazonium salt.
preferable.

Specific examples of the aromatic amine that can provide the above aryl group include 1-amino-4-dimethylamine naphthalene, 2
-Amino-7-dimethylaminofluorene, 1-amino-2,5-jetoki/-4-(N-1,4-oxazine)benzene, 1-amino-4-dimethylbenzene, 1-
Examples include aminopyrene, 4,4'-diaminodiphenylamine, and the like.

Particularly preferred examples of the photoactivator include diphenylamine-4,4'-bis-diazonicum tetrafluoroborate, 4-dimethylaminonaphthalene-
1-Diazonicum tetrafluoroborate, 7-dimethylaminofluorene-2-diazonicum tetrafluoroborate, 4-phenylaminobenzenediazonicum tetrafluoroborate, 4-phenylaminobenzenediazonicum tetrafluoroborate, etc. can be mentioned.

These aromatic cya/nium salt type photoactivators are selected from among the photopolymerization initiators and have a light absorption wavelength range different from that of the initiator to be actually used. Generally, the difference in the light absorption wavelength range between the two is required to be about 20 nm or more, which is the difference in the wavelength showing the shortest peak of the absorption spectrum.

However, if the absorption spectrum distributions of the photoactivator and the polymerization initiator are both narrow, the difference in peak wavelength is 10
nm may also be used; conversely, if the distribution is wide, for example l-1:50
nm or more, the researchers considered the wavelength and distribution of the spectral peaks and determined that the light at the wavelength mainly used for the polymerization initiator activates the photoactivator and releases the acid. By doing so, a dye having a difference in the wavelength range that does not substantially inhibit the polymerization and curing of the composition is appropriately selected so as to be used for the coloring of the reduced dye of No. 11.

To prepare the composition of the present invention, the binder, photopolymerizable monomer, photopolymerization initiator, reduced dye, and aromatic diazonium salt type photoactivator may be added and mixed uniformly. Since it is usually used by forming a thin layer on the surface of a substrate made of synthetic resin or other materials, it has a viscosity that allows it to be mixed with methyl ethyl ketone or other appropriate solvent and applied to the substrate, etc. It is preferable to use a liquid composition that can be dried by volatilization of the agent.

In addition, as for the quantitative relationship of the above components, the photopolymerizable monomer lθ~
300 parts by weight, 0.1 to 20 parts by weight of photopolymerization initiator, 0.01 to 10 parts by weight of reduced dye, more preferably 0.1 to 10 parts by weight.
5-fold-1-fold and aromatic diazonium salt type photoactivator o
It is preferable to use 0.05 to 0.5 parts by weight, preferably 0.05 to 0.5 parts by weight.

The composition of the present invention can be used for making relief printing plates and photoresists, and usually a solution of the composition of the present invention dissolved in a solvent is coated on a transparent notebook support and dried. Forming a coating layer on an object, laminating this on the surface of the object on which an image such as a photoresist image is to be formed by heat fusion, etc., and irradiating active light from above through a negative or the like to expose the exposed part, After that, if any transparent notebook-like support remains, it is peeled off, the unexposed 1.1 minute portion is removed with a solvent or the like, development is carried out, and thereafter, etching or the like is carried out as necessary.

The composition of the present invention is activated by the aromatic diazonium salt type photoactivator contained therein, and the dye acts as a coloring agent to develop color in the exposed area. During the exposure process, it is easy to distinguish the tlftlft color part from the light part, and it is very convenient when performing multiple exposures or checking the exposure state. The workability of coloring is improved.

Furthermore, when leuco dye-based color formers have been used in the past, the energy of the irradiated light is split into both polymerization of the composition and color development, which slows down the polymerization curing speed and reduces sensitivity. In contrast, the composition of the present invention does not have such drawbacks and can be used for short poems 1 and 2.
It also has excellent photosensitivity since exposure of 6" is sufficient.

Example 1-0 Synthesis Example 1 0.1 mole of 4.4'-diazodiphenylamine salt was dissolved in 500 d of water, and at room temperature the excess sodium fluoride was dissolved in an amount of 30%. An aqueous solution was added and mixed. After several hours, the precipitated crystals were filtered, washed, and dried to obtain diphenylamine-4,4'-bis-diazonic mutetrafluoroborate with a yield of about 90%. was a yellow crystal, and its light absorption spectrum had maximum values at 420 nm and 520 nm, and the sand value in the former was larger than that in the latter.

Example 1 Polymethyl methacrylate 6
0y trimethylolpropane triacrylate
33y× Penzofufun (input max 330nm)
3.5F Michler Ketone (max. 370n)
m) 1. sy crystal violet lactone 1.0y' baud rate (human ma
x420nm) 0.1fX person m a
x represents the wavelength of the highest peak of the optical absorption spectrum. same as below.

A light yellow bath solution prepared by dissolving the above compound in methyl ethyl ketone to make a total amount of 3002 was applied to a polyethylene/terephthalate film support so that the thickness after drying was 50/I, and the film was dried. Thereafter, this was laminated on a copper-coated epoxy/glass fiber board at a temperature of 115 DEG C. so that the coating was in contact with the copper surface.

Next, the photosensitive laminate prepared above was placed 1 m from a 400W high-pressure mercury lamp in a vacuum frame, and a test negative (
21v'-2 step exposure step guide) and 90 millijoules/square centimeter (m J/ly &
exposure was performed. This time was 20 seconds. After exposure, peel off the film support and expose IvJ for 40 seconds.
It was developed by immersion in trichloroethane and dried. In the test negative image, a 9-step image remained on the board, and the resolution in the printed wiring image was 50 microns.

Before the above development, yellow appears clearly in the unexposed area and purple appears clearly in the exposed area of the printed circuit (absorbance 0y5), and the contrast between the different colors is clear, making it extremely convenient for inspecting the exposure status. The exposed printed circuit board was left overnight, and the next day it was developed and etched, and the film was removed to form a printed circuit, but the exposed area remained clearly colored until the film was removed. It was convenient for inspecting the state of printing, development, etching, and film removal.

Example 2 Rhodamine lactam instead of crystal violet lactone as tJ1 archetypal dye 1. OEl was used as an aromatic diazonicum salt type photoactivator with diphenylamine-4,4'-4 instead of diazonicum borate.
-Dimethylaminonaphthalene-1-diasonium tetrafluoroborate (input max. 420 nm) 0.
1 fi! In the same manner as in Example 1 except for using
1J developed the test negative image and created a printed wiring circuit.The results were as follows: 19I
? It was observed that both the image power and the degree of color development were the same as in Example 1.

Comparative Examples 1 to 5 Photosensitive laminates were prepared in the same manner as in Example 1 using the materials shown in the respective columns of Comparative Examples 1 to 5 in Table 1, and exposed and exposed in the same manner as in Example 1. I developed it. The results were as shown in Table 1. Regarding the resolution, Comparative Example 1 was approximately 200/I, and Comparative Examples 2.3 were even worse.

Table 1 Note 1): means 2-(0-chlorophenyl)-4,5-dimethoxynylimidazolyl dimer.

Note 2): 1. 3. 3-) Tumethylindolino-
8'-Methoxybenzobilyl subirane.

Note 3): A test negative image (exposed to 90 mJ/d after passing through 2i (ff stepwise exposure step guide) in the same manner as in Example 1 was developed in the same manner as in Example 1, and the image remaining on the board was The number of steps is displayed. (The degree of hardening in Example 1 is 9.) Patent applicant Mototoshi Fujinuma, representative of Sekisui Chemical Co., Ltd.

Claims (1)

[Claims] 1. A binder made of a polymeric material, a photopolymerizable monomer, a photopolymerization initiator, a reduced dye, and an aromatic diazonium salt type photoactivator whose light absorption wavelength range is different from that of the photopolymerization initiator. Photo-combinable image-forming composition 02, characterized in that it contains Qiken.The composition according to item 1, wherein the reduced dye is a lactone-type or lactam-type triarylmethane dye. 3. The composition according to item 1 or 2, which is used as a photoresist.