JPS59178448A - Photopolymerizable image forming composition - Google Patents

Abstract

PURPOSE:To enable cross-linking and color development without deteriorating sensitivity by incorporating a binder, a photopolymerizable monomer, a photopolymn. initiator, a leuco dye, and further, a specified light activating agent having a light absorption wavelength region different from that of the photopolymn. initiator in order to manufacture a printing plate or a printed circuit board. CONSTITUTION:A compsn. contains a binder, such as poly(meth)acrylate or cellosic polymer, a monomer having at least one photopolymerizable ethylenic group, a photpolymn. initiator, such as benzophenone, a leuco dye, and further, a cyanoaromatic compd. type light activating agent having a light absorption wavelength region different fromthat of said initiator, such as coumarin type dyes represented by formulae I and II, etc. As said leuco dye, amino-substd. triarylmethane type dyes, etc. are used. As a result, the obtained image forming compsn. is enhanced in cross-linking reaction and color developing and color retentive performances of the leuco dye for discriminating exposed areas from unexposed areas without deteriorating photopolymn. sensitivity, that is, extending the exposure time.

Description

[Detailed description of the invention] The present invention relates to photopolymerizable imaging compositions.

Conventionally, a composition consisting of a binder made of a polymeric material, a photopolymerizable top layer, a photopolymerization initiator, a photosensitizer, etc. is applied to the surface of a base material, and images are produced by shining light through a negative or other means onto the surface of the base material. It is said that the image can be developed by tying them together, polymerizing or cross-linking the areas exposed to light and making them insoluble in solvents, and eluting the areas exposed to light.This principle is applied to plate materials and prints. It is applied to manufacturing wiring boards.

It is also known that by adding a photochromic agent such as a leuco dye to the above composition, it is possible to clearly distinguish between areas that are exposed to light and areas that are not.However, it is generally used as a light source. When polymerizing or crosslinking or coloring a composition coated on a substrate using an ultraviolet light source such as a Shimada mercury lamp, the presence of a coloring agent slows down the polymerization or crosslinking rate and requires longer exposure times. <There is a disadvantage that it has to be
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/crosslinking.

The present invention solves the above-mentioned drawbacks, and produces color development at the same time as polymerization or crosslinking, which reduces sensitivity and eliminates the need to lengthen the exposure time. This was made for the purpose of providing a composition for image enhancement that was subjected to multiple exposure Vc4.

That is, the gist of the present invention is to provide a binder made of a polymeric material, a photopolymerizable monomer, a photopolymerization initiator, a leuco dye, and a cyanated aromatic compound type photoactivator having a hardening light absorption wavelength range different from the photopolymerization initiator described above. The present invention relates to a photopolymerizable image-forming composition characterized by containing a photopolymerizable agent.

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, such as acetylcellulose, acetylbutylcellulose, polyacrylic Examples include methyl acid, polymethacrylic acid, methacrylic acid-methyl methacrylate copolymer, and 10-genated polyolefin.

Furthermore, the photopolymerizable monomer in the present invention refers to a monomer that is activated by light irradiation to initiate polymerization, as is known from the existence of photopolymerization initiators, and has a boiling point of 100°C or more at normal pressure. Monomers having at least one ethylene terminal group are preferably used, specifically, penquerythritol triacrylate, polyethylene glycol diacrylate, triethylene glycol diacrylate, and polyethylene glycol. Polyacrylate or polymethacrylate yarn threads such as dimethacrylate, polymethylene diacrylate, polymethylene dimethacrylate, trimethylolpropane triacrylate, and trimethylolpropane trimethacrylate, or oligomers of these seven threads are suitable. 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 and P.

P-aminophenicergtones such as P'-bis(dimethylamino)benzophenone (hereinafter referred to as Michler's ketone), benzoin, penzoinlopyl ether, benzyl anthraquinone, 2-methyl-anthraquinone, 2-ethyl-anthraquinone , 2-tertiary-glyanthraquinone, 2-aminoanthraquinone, etc., and many of these act as polymerization initiators by absorbing the energy of light in the wavelength range of about 320 to 370 nm. be. These photopolymerization initiators may be used in combination of two or more types, and in particular, when a mixture of benzophenone and Michler's ketone is used, the efficiency of polymerization initiation by irradiation light is improved1, and the exposure time is further shortened. suitable.

Further, in the present invention, a leuco dye and a cyanated aromatic compound type photoactivator having a light absorption wavelength range different from that of the photopolymerization initiator are used in combination as a coloring agent.

That is, the leuco dye in the present invention refers to a colorless or light-colored dye obtained by reducing a colored compound and which develops color when oxidized by a cyanide aromatic compound type photoactivator described below. It belongs to the leuco compound of 7-substituted triarylmethane dyes, but is not limited thereto. Specific examples of such leuco dyes include leuco crystal violet, tris(4-diethylamino-
Triaminotriphenylmethane such as Q(lyl)methane, leucomalachite green, bis(4-diethylamide/
-0-)lyl)phenylmethane, bis('4-)nylamino-〇-)lyl)(3,4-dimethoxy7enyl)methane, bis(4-diethylamino-0-tolyl)(P- Examples thereof include benzylthiophenyl)methane, bis(P-dinegative totylamino-tolyl)(P-α-methoxyacetamidophenyl)methane, and the like.

These leuco dyes may be converted into salts by reacting with acids, and the acids at this time include hydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid, phosphoric acid, 6D, succinic acid, etc. ,
Examples include organic acids such as P-tolenic acid and trichloroacetic acid, and Lewis acids in a narrow sense that do not contain hydrogen, such as zinc chloride, zinc bromide, ferric chloride, and boron tri7noide.

The cyanated aromatic compound type photoactivator in the wood 1ull ic has a light absorption wavelength range different from that of the photopolymerization initiator,
It is activated by irradiation with active light mainly in the wavelength range of 300 Dm to 600 Dm, and has the effect of oxidizing the above 1 teroico dye and developing color.

Specific examples include 3-benzothiazoyl-4-cyano-7-ethylaminocuprine and the structural formula (1) below.
- cyanogen-substituted coumarin dyes such as compounds represented by (4); cyanogen-substituted naphthalenes such as α-cyanonaphthalene and β-cyanonaphthalene; 9-cyanoanthracene;
Examples include cyan group-substituted anthracenes such as 9°10-dicyanoanthracene; 1-cyanotetracene, 9-cyano7-enanthrene, and particularly preferred examples include cyanocoumarin dyes.

These photoactivators can be selected from among the photopolymerization initiators that have a light absorption wavelength range different from that of the initiator that is actually used, and the light absorption of both can be selected. Generally, the difference in wavelength range is required to be about 20 nm or more, which is the difference in wavelength showing the highest 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 will be 10D.
On the other hand, if the distribution is wide, for example, 50 Dm or more is required. Therefore, considering the wavelength and distribution of the peak of the spectrum, it is necessary that the light of the wavelength mainly used for the polymerization initiator has the above-mentioned photoactivity. A dye that activates the activating agent and is also used for coloring the leuco dye and has a difference in wavelength range that does not substantially inhibit the polymerization and curing of the composition is appropriately selected.

To prepare the composition of the present invention, it is best to add and uniformly mix the binder, photopolymerizable monomer, photoinitiator, leuco dye, and photoactivator, but usually synthetic resin or Since it is used by forming a thin layer on the surface of a substrate made of other materials, it has a viscosity that allows it to be mixed with methyl ethyl/r)one or other appropriate solvent and applied to the substrate, etc. It is preferable to use a liquid composition that can be dried by volatilization.

In addition, the quantitative relationship of the above components is 10 to 3 parts by weight of the photopolymerizable monomer to 100 parts by weight of the polymeric material.
00 parts by weight, photopolymerization initiator a1-20 parts by weight, leuco dye 0.01-10 parts by weight.

More preferably 0.1 to 4 parts by weight and a photoactivator α00
It is good to use 1 to 10 parts by weight, more preferably 0.01 to 11 parts by weight.

The composition of the present invention can be used for making relief printing plates and photoresists, and is usually prepared by coating a solution of the present invention #1 in a solvent on a transparent sheet-like support and drying it. Form a coating layer of the composition of the invention and apply 7
．． It is laminated on the surface of an object on which an image such as an I-regist image is to be formed by heat fusion, etc., and the exposed area is exposed by irradiating active light through a negative, etc., after which a transparent sheet-like support remains. If so, it is peeled off, the unexposed areas are removed with a solvent or the like, developed, and then etched as necessary.

In the composition of the present invention, the leuco dye activated by the cyanated aromatic compound type photoactivator contained therein acts as a coloring agent and the exposed area develops color, so that it can be used during the exposure process. It is easy to distinguish between exposed and non-exposed areas, which is very convenient when performing multiple exposures or checking the exposure status. The color image does not disappear in a short period of time, and the durability of the color image is excellent, resulting in improved workability.

In addition, in the current case where leuco dye-based color formers have been used in the past, the polymerization curing speed is reduced, presumably because the energy of the irradiated light is divided into both polymerization of the composition and color development. Compared to the lower sensitivity and the need for longer exposure times, the zero-shot 1η set does not have these drawbacks and only requires a short exposure time, so it has excellent photosensitivity. The present invention will be explained below based on examples.

Synthesis Example I P -N N'3 is a condensate of diethylaminosalicylaldehyde and 2-cyanomethylbenzothiazole
-benzothiazoyl-7-diethylaminocoumarin 11
When 1 mol was dissolved in 500 d of dimethylformamide F at room temperature and an excess amount of 30% aqueous sodium cyanide solution was added and stirred, a transparent brown solution was immediately obtained.

This was cooled for 8 to 10'CK, bromine was directly added dropwise, and the resulting precipitate was filtered and dried to obtain 0.9 mol of 3-benzothiazoyl-4cyano-7-diethylaminocoumarin. This was a red crystal with a maximum optical absorption spectrum at 519 nm.

Example 1 Polymethyl methacrylate 60p trimethylolpropane triacrylate 33F benzophenone (max 330 nm) a5F
Michler Ketone (λmax370 nm)
15 y 'Leuco Crystal Violet
LOf3-penzthiazoyl-4-cyano-7
-diethylaminocoumarin (λmax520nm)
alf yellow λmax#is represents the wavelength of the highest peak of the optical absorption spectrum. same as below.

Dissolve the above compound in methyl ethyl ketone and prepare 9.
A pale red solution of 50y was applied to a polyethylene terephthalate film surface to a dry thickness of 50μ, and after the film was dried, it was coated with copper-coated epoxy-glass fibers at a temperature of 115°C. After laminating the above coating on the plate so that it is in contact with the steel surface, the photosensitive laminate prepared above was placed at a distance of 1 m from a 400W high pressure mercury lamp, and a test negative (
214 stair exposure step guide) and printed wiring circuit negatives placed side by side so as not to overlap.
Exposure was carried out at E radiules per square centimeter (mJ/cI!f). This fffl is 20 seconds long. After exposure, the film support was peeled off, the exposed layer was developed by immersing it in 1,1.degree. 1-trichloroethane for 40 seconds, and was dried. In the test negative image, both images of the 9 steps remain on the board,
Further, the resolution of the printed wiring image was 50μ.

In addition, before the development, red appears clearly in the unexposed area and purple appears clearly in the exposed area of the printed circuit (color absorbance 0.5), and the contrast between the different colors is clear, making it extremely convenient for exposure inspection. Met.

Also, after this exposure, the printed circuit board was left overnight,
The next day, after development, etching was performed and the film was further removed to form a printed circuit, but the coloring in the exposed areas remained good until the film was removed.

Example 2 Photoactivated larvae (3 used in Example 1 as arsenic)
The test sample was prepared in the same manner as in Example 1 except that 9,10-dicyanoanthracene (λmax 400 nm) (101f) was used instead of benzothiazoyl-4-cyano-7-ethylaminocoumarin 0.19. We developed the negative image and created a printed wiring circuit.The results are as follows.
It was observed that the degree of curing of the exposed area, the resolution, the degree of color development, and the persistence of color development were the same as in Example 1, with a difference of 9.
, Example 3 Polymethyl methacrylate 602 trimethylolpropane acrylate 33y benzophenone (λmax 330 nm) 3.5
P Michler Ketone (＾max370nm) o
, 5f leucomalachite green LO
99-cyano7 enanthrene 0.027
Dissolve the above compounds in methyl ethyl ketone to make a total amount of 3
The solution obtained by oop 7 was applied to a polyethylene terephthalate film support so that the strength after drying was 25μ,
Covered V! After drying, a photosensitive laminate was prepared in the same manner as in Example 1, and A et al. developed it using a test negative and created a printed wiring circuit in the same manner as in Example 1.
, As a result, the degree of hardening of the exposed area was the same as in Example 1,
The resolution of printed wiring images was 40μ. Before the development described above, the unexposed area was colorless, and the exposed area of the printed circuit had a clear green color, and the degree of color development (absorbance 0.5) and color retention were as good as in Example 1. Met.

A photosensitive laminate was 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 further exposed and developed in the same manner as in Example 1. The results of the lie were as shown in Table 1.

Regarding the resolution h, Comparative Example iH was about 200μ, and Comparative Examples 2.3 were even worse.

(The following is a blank space) Table 1 Note 1): Means 2-(0-chlorophenyl)-45 dimethoxynylimidazolyl dimer.

Note 2): Means 1,3,3-trimethylindolino-8'-methoxybenzopyrylspirane.

Note 3): A test negative image (214 exposure steps is ID) was exposed to 90 mJ/cd in the same manner as in Example 1, and it was developed in the same manner as in Example 1, and the stages of the image that remained on the board were displayed the number. (Note that the degree of curing in Example 1 is 1, which is 9.) Patent applicant Mototoshi Fujinuma, representative of Sekisui Chemical Co., Ltd.

Claims (1)

[Scope of Claims] t A binder made of a polymeric material, a photopolymerizable monomer, a photopolymerization initiator, a leuco dye, and a cyanated aromatic compound type photoactivator whose light absorption wavelength range is different from that of the photopolymerization initiator. A photopolymerizable image-forming composition comprising: 2. The composition according to item 1, wherein the leuco dye is an amine 7-substituted triarylmethane dye, 13. The composition according to item 1 or 2, wherein the cyanated aromatic compound type photoactivator is a coumarin dye. Composition 1 of