JPS604940A - Photopolymerizable image forming composition - Google Patents

Abstract

PURPOSE:To make a photopolymerizable image forming composition suitable for multiple exposure by adding an amino substituted triarylmethane dye and a cyanated aromatic compound type optical activator so as to decolor the exposed part of the composition when the composition is irradiated with light and to facilitate discrimination between the exposed and unexposed parts. CONSTITUTION:To 100pts.wt. binder are added 10-300pts.wt. photopolymerizable monomer or oligomer, 0.1-20pts.wt. photopolymn. initiator, 0.01-10pts.wt. amino substituted triarylmethane dye and 0.001-1pt.wt. cyanated aromatic compound type optical activator, and they are mixed with methyl ethyl ketone or other solvent to prepare a liq. composition. The combination of the triarylmethane dye with the optical activator is used as a decoloring agent which acts when irradiated with light. The triarylmethane dye colors the unexposed composition. The optical activator is different from the photopolymn. initiator in the light absorption wavelength range.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a polymerizable imaging composition.

Conventionally, a composition made of a polymeric material (Ingu, a photopolymerizable monomer or oligomer, a photopolymerization initiator, etc.) is coated on a substrate surface, and light is applied through six strokes, etc. It is known that an image is formed on the base material by polymerizing or crosslinking the exposed area and making it insoluble in the solvent, and eluting the non-exposed area. It is applied to the manufacturing of printed wiring boards.

It is also possible to add a photochromic agent, such as a leuco dye, to the above composition so that it is possible to clearly distinguish between areas that are exposed to light and areas that are not, thereby enabling leisurely exposure. Are known.

For example, in the method disclosed in Japanese Patent Publication No. 4g-38403, a leuco dye is mixed into a composition in which imidazolyl dimer and P-aminophenyl ketone are added to an ethylene monomer, but it is generally used as a light source. When using an ultraviolet light source such as a high-pressure mercury lamp to color a dye at the same time as photopolymerization or crosslinking in a composition, the presence of the dye reduces the rate of photopolymerization or crosslinking, and therefore the exposure time This has the disadvantage of requiring a longer length of time.

This is presumed to be due to the fact that the light energy absorbed by the photopolymerization initiator and the like is divided and used for both photopolymerization and crosslinking and color development of the dye.

The present invention solves the conventional drawbacks as described above.
Light 1 decolorizes the dyeing by irradiation, making it possible to distinguish it from the unexposed area, and the sensitivity decreases, resulting in j! The light time does not become long,
The purpose of this invention is to provide an image-forming composition that has good photosensitivity, excellent workability, and is suitable for multiple exposures.

The gist of the present invention is to provide a binder made of a polymeric material, a photopolymerizable monomer or oligomer, a photopolymerization initiator, an amino-substituted triarylmethane dye, and a cyanide having a light absorption wavelength range different from that of the photopolymerization initiator. g characterized by containing an aromatic compound type photoactivator:
It consists in an image-forming composition that is a polymeric material.

The binder used in the present invention is made of a polymeric material, and any binder conventionally used as a binder for image-forming compositions can be used. For example, in the case of a solvent-developable type, it is important that the binder is resistant to solvents. It is. Specifically, acetylcellulose, acetylglutylcellulose,
Examples include polymethyl acrylate, polyacrylic acid, and methacrylic acid-methyl methacrylate copolymer.

A photopolymerizable monomer used in the present invention.

The term “moshikake oligomer” refers to a substance that is activated by light irradiation in the presence of a photopolymerization initiator to initiate polymerization, has a boiling point of 100°C or higher at normal pressure, and has at least one ethylene thread end group. The one that you have individually is preferably used. Specifically, pen querythritol acrylate (
or methacrylate), polyethylene glyco-l diacrylate (or methacrylate), dielate (or methacrylate), σnibo+noalkylene glycol acrylate (or methacrylate) such as jO polymethylene diacrylate, trimethylolpropane triacrylate (or or methacrylate), or oligonucleotides thereof.

These photopolymerizable monomers or oligomers become entangled with the binder and become insolubilized through photopolymerization, or form a strong image by polymerizing or crosslinking with polymeric materials having photosensitive groups.

As the photopolymerization initiator used in the present invention, conventionally used initiators can be used, but phenylgtone-based photopolymerization initiators are particularly preferred. Specific examples of photopolymerization initiators include benzo-1 enone, (λmax=330 nm)
(λmax indicates the wavelength of the highest peak of the optical absorption spectrum), P + P'-bis(dimethylaminone benzophenone (hereinafter referred to as Michlagton)) (λmax =
P-amino 7 enyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin guthyl ether, penzoin isoglobyl ether (λmax = 325 nm), etc.
Benzyl anthraquinone, 2-methyl-anthraquinone, 2-ethyl-anthraquinone (λmax=325n
m), 2-tertbutyl-anthraxin (λ
max=325 nm), 2-aminoanthraquinone, etc., and most absorb light energy with a wavelength of 320 to 370 nm and act as a polymerization initiator.

In addition, two or more of these photopolymerization initiators Fi can be used as a mixture. For example, a mixture of benzophenone and Michlacton absorbs light at different wavelengths, improving the efficiency of polymerization initiation by irradiation light and shortening the exposure time. This is preferable because it can be further shortened.

Next, in the present invention, a combination of an amino-substituted triarylmethane dye and a cyanated aromatic compound type photoactivator is used as a photodecolorizer. By addition of amino-substituted triarylmethane dye, unexposed Jllll
It exists in high quality. The photoactivator has a light absorption wavelength range different from that of the photopolymerization initiator.

It is believed that the amino-substituted triarylmethane dye is reduced to a colorless or light-colored leuco dye by a cyanated aromatic compound type photoactivator. Specific examples of such amino-substituted triarylmethane dyes include: methyl violet, crystal violet, malachite green, bis(4-diethylamino-?
-tolyl)phenylmethane, tris(4-diethylaminogutolyl)methane, bis(4-diethylamino-θ
-tolyl)(p-penzylkeophenyl)methane, bis(4-jethylaminoketryl)(3,4-dimethoxyphenyl)methane, bis(p-diethylamino-α
-tolyl) (p-α-methoxyacetamidophenyl)
methane.

Among the above dyes, those below bis(4-diethylamino-?-tolylphenylmecune) can be used with hydrochloride, sulfate, chefate, zinc chloride, and double salt cedar.

Other agents are activated by irradiation with actinic light mainly in the wavelength range of 300 to 600 nm, reduce the above amino-substituted triarylmethane dye to a leuco form, and decolorize it to colorless or pale color for display. Apply pressure so that it can be clearly distinguished from the non-exposed areas.

Specific examples of the cyanated aromatic compound type photoactivator include 9-cyanoanthracene, 9.10-dicyanoanthracene, 1-cyanonaphthacene, 1-cyanonaphthalene, 2-cyanonaphthalene, and 4-acetylbenzonitrile. , 9-cyanophenanthrene and the like.

These cyanide aromatic compound type photoactivators are selected to have a light absorption wavelength range different from that of the above-mentioned photopolymerization initiator, but the difference in light absorption wavelength range between the two is generally one absorption. The difference in wavelength showing the highest peak in the spectrum is approximately 2
0 nm or more. However, if the distribution of absorption spectra of the above-mentioned photoactivator and photopolymerization initiator are both narrow, absorption will occur, and if the inverse hill distribution is EL/-, for example, 50 nm.
The light of the wavelength mainly absorbed and used by the initiator activates the photoactivated All to act as a reducing agent, and is also used to decolorize the amino-substituted triarylmethane dye, thereby preventing polymerization and curing of the composition. It is assumed that there is a difference in the wavelength range that does not qualitatively interfere.

Therefore, the present invention has the advantage that the cyanated aromatic compound photoactivating agent requires only a very small amount of photoactivating agent and dye compared to amino-substituted triaryl compounds. The aromatic cyanide compound must be mixed in solid form, and if used in large quantities, there is a risk that it may impede the adhesion with the copper laminated board (described later), but only a small amount is needed for mixing. This means that the occurrence of such problems can be suppressed.

Adhesion promoters may be mixed to improve adhesion.

Further, thermal polymerization inhibitors, plasticizers, flame retardants, and other agents may be added as necessary.

To obtain the composition of the present invention, a binder made of the above-mentioned polymeric material, a photopolymerizable monomer or an oligomer, a photopolymerization initiator, an amino-substituted triarylmethane dye, and a light absorption wavelength range different from that of the photopolymerization initiator are required. A cyanide aromatic compound type photoactivator with Therefore, it is preferable to use a liquid composition that has a viscosity that allows it to be mixed with methyl ethyl lactone or other appropriate solvent and applied to a substrate, etc., and that can be dried by volatilization of the solvent. .

In addition, the quantitative relationship of the components of the above composition is such that the amount of the photopolymerizable monomer or oligomer is 10 to 300 tFIL parts to 1001 tFIL parts of the binder made of the molecular material.
Parts by weight, 0.1 to 20 parts by weight of photopolymerization initiator, 0.01 to 10 parts by weight of amino/substituted triarylmethane dye, 0.001 to 1 part by weight of cyanide aromatic complex type photoactivator. It is better to use Furthermore, preferably the dye is 0.01
~0.2 parts by weight, photoactivator: o, o o s~(L
The full amount of XX is used.

The composition of the present invention can be used for making Relay-7 printing plates and for photoresist applications. Usually, a solution of the composition of the present invention dissolved in a solvent is applied onto a transparent sheet-like substrate, and then dried. Then, if necessary, a protective film is formed thereon.

Then, if necessary, the protective film is removed and the M layer is applied to the surface of a member on which an image such as an otoresist image is to be formed, for example, a copper AA layer plate with a thin copper foil pasted, by thermal fusion or the like. Then, irradiate active light from above through a negative film or the like to expose the exposed areas, then peel off the transparent sheet-like base material if it is cut, remove the unexposed areas with a solvent, etc., and develop. After that, the unprotected portion of the surface (the portion from which the composition of the present invention has been removed by a solvent) is etched or metal plated.

In addition, the composition of the present invention decolorizes the exposed area by photoactivating the cyanide aromatic complex type photoactivator contained therein and reducing the amide/substituted triarylmethane dye. It is easy to distinguish between exposed areas and non-exposed areas, which is very convenient when performing multiple exposures or when checking exposure conditions.

In addition, the amino-substituted triarylmethane dye and the cyanated aromatic compound type photoactivator can be used in extremely small quantities compared to conventional color-forming types, saving material and improving adhesion to copper-clad laminates. It has the advantage of not interfering with sexuality.

Furthermore, the photoquenching agent in the composition of the present invention, which is a combination of a mono-substituted triarylmethane dye and a cyanated aromatic compound type photoactivator, causes the colored image to disappear in a short time after exposure, as in the case of conventional photoquenching agents. Without this, the stability of the decolorized image is excellent and the workability is improved.

In addition, when a leuco dye-based coloring agent is conventionally used, it is presumed that the energy of the irradiated light is divided into both polymerization or crosslinking of the composition and color development, but the polymerization and curing reaction of the composition In contrast, the composition of the present invention does not have these drawbacks, requires only a short exposure time, and has excellent exposure workability. There is.

<Example 1> Polymethyl methacrylate (bustiness = 2.0X10)
60 F trimethylolpropane triacrylate
33f benzophenone (maximum input = 330 nm)
3.5 f Michler Ketone (input max = 370 nm)
1.51/Crystal Violet 0.08P 9.10-Tsukuano Ant 2sen (Max = 380
,400°425nm) 0,0 21! Dissolve the above compound in methyl ethyl ketone and add 3
00f solution was applied to a polyethylene terephthalate film support so that the thickness after drying would be 50 μmK, and after drying the film, the above film was applied to a copper-coated Gazis fiber-reinforced Evoki resin plate at a temperature of 160°C. The layers were stacked so that they were in contact with the copper surface.

Next, place the above photosensitive MN plate at 1 m from a 400W high-pressure water lamp.
At the place, test negatives (2h/T step exposure step guide = negatives are gradually made darker from a transparent state to 21 steps in steps of f) and printed wiring circuits arranged side by side so that they do not overlap. Exposures of 90 millijoules (mj)/cJ were made in a vacuum frame through the negative image. J14 original time was 20 seconds.

After exposure, the polyethylene terephthalate film support was peeled off, the exposed layer was immersed in l, l, t-) dichloroethane, developed, and the unexposed areas were removed) and dried. In the test negative images, a 9-step image remained on the copper coated glass fiber reinforced epoxy resin board, and the resolution in the printed wiring images was 50 μm.

Also, before the above development, the unexposed area is dark blue-purple with an absorbance of 1.0.
) The exposed area had a pale back color (absorbance 0.4) and the contrast was clear and sufficient for conducting an exposure test. Furthermore, after this exposure, the embryo was left overnight, and the next day it was developed and etched, and the film was removed to form a printed circuit. This was convenient for inspecting the state of membrane removal.

<Example 2> As a dye, 0.08 f of malachite green was used instead of the crystal violet of Example 1, and as a photoactivator, 1-noanonaphthacene (input max. =396nm) 0
．． A test negative image and a negative image for printed wiring were exposed and developed to create a printed wiring circuit in the same manner as in Example 1 except that 02f was used. The results show that the degree of hardening of the exposed area, resolution, and color contrast are
It was found that both cases were the same as in Example 1.

<Comparative Examples 1 to 4> Exposure, development, and formation of a printed circuit were performed in the same manner as in Example 1 using the compositions shown in the table below.

The results were as shown in the table below.

(Leaving space below) Table 1 Note 1) 2-Co-di-10-lofenyl)-4,5-dimethoxy/phynyl imidazole dimer Note 2) The image in the test negative described in Example 1 shows that photopolymerization and curing are not possible. Displays the number of remaining steps Note 3) Example means that the color absorbance of the unifted portion is 10 Note 4) Comparative Example 3.4 is larger than 200 μm, indicating poor resolution.

patent applicant Sekisui Chemical Co., Ltd. Representative: Mototoshi Fujinuma

Claims (1)

[Claims] L A photopolymerizable image-forming composition comprising a binder made of a polymeric material, a photopolymerizable monomer or oligomer, a photopolymerization initiator, an amino-substituted triarylmethane dye, and