JPS5934292B2 - photoresist material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photoresist materials, and more particularly to photoresist materials having a layer of a photopolymerizable composition on a support.

Conventional photoresist materials for producing printed wiring boards include photosensitive liquids that combine dichromate and glue, dichromate and polyvinyl alcohol, etc., and photosensitive liquids that mainly contain polyvinyl cinnamate and a sensitizer. So-called "solution type" photoresist materials, such as photosensitive liquids containing natural rubber or cyclized rubber and a crosslinking agent as main components, have been widely used. Still other photoresist materials include "film-type" photoresist materials in which a photosensitive layer is interposed between two plastic films.

To use this material, the user peels off one plastic film to expose the photosensitive layer, laminates this photosensitive layer on a copper substrate for printed wiring, performs image exposure from the remaining plastic film side, and then The film is removed and developed with a suitable developer such as an organic solvent or an alkaline aqueous solution. The portions cured by light irradiation remain on the copper substrate, and the unirradiated portions are dissolved and removed by a developer. In this way, a resist pattern for the intended printed wiring circuit is formed. However, both the above-mentioned "solution type" and "film type" photoresist materials are undesirable because the development process is complicated because they use liquids such as organic solvents and alkaline water, and there is a risk of harming public health. In recent years, dry-developable recording materials have been proposed in place of such solution-developable recording materials.
That is, Japanese Patent Publication No. 38-9663, U.S. Patent No. 3,353
No. 1955 (Special Publication No. 43-22901) and No. 3
, No. 770, No. 438 (Japanese Unexamined Patent Publication No. 47-7728), the difference in adhesive strength between the exposed portion and the non-exposed portion of the photosensitive (photopolymerizable) composition is determined. This is a method of forming images by using This method is
Generally, a layer of a photopolymerizable composition whose main components are a binder polymer, an unsaturated monomer, and a photopolymerization initiator is provided on a base material such as a plastic film, metal, or paper, and then a thin transparent Place the film as a cover, expose the cover to light using an original, and peel off the cover to leave either the exposed or unexposed part of the photosensitive layer on the base material and cover the remaining part. negative and positive (or positive and negative) on the base material and cover respectively.
This is a method of forming an image. When this recording material is used, compared to the case where the solution-developable recording material described above is used, a so-called liquid development step is omitted, and a resist pattern can be created simply by peeling off the cover film. This method is called "peel development," and the photoresist material produced by this method is called a "peel development type" photoresist material. If this method is used in the manufacturing process of printed wiring boards, significant labor savings are expected. Furthermore, compared to conventional solution-developable photoresist materials, the resist can be peeled off and removed much more easily, so it goes without saying that this is a very advanced technology that has almost solved the problems in use.

When producing a resist pattern using such a "peel-and-develop" photoresist material, it is necessary to destroy the photosensitive layer at the boundary line between exposed and unexposed areas.

The properties of the polymer binder and monomer used for this purpose are particularly important. Among them, the properties of the polymer binder,
For example, molecular weight, softening point, crystallinity, mixability with other materials,
Adhesion to the base material is an important point. Furthermore, the formed image is used for various subsequent uses, and it is preferable that the image has properties required during its use, such as abrasion resistance and weather resistance. The importance of materials used in photosensitive materials consisting of a combination system of a polymeric substance for a binder, a monomer, and a polymerization initiator has been explained above. However, few of them have satisfactory performance, and image formation has not been achieved satisfactorily.

For example, in Japanese Patent Publication No. 38-9663, a polymeric substance for a binder is used as a part of the tackifying agent, but some of these include polyvinyl butyral, polyvinyl acetate, polyvinylpyrrolidone, gelatin, Maron indene resin, silicone resin, rubber, etc. are used. Further, in US Pat. No. 3,770,438, examples of "binding agents" include vinylidene chloride copolymers, cellulose ethers, synthetic rubbers, polyvinyl acetate copolymers, polyacrylates, polyvinyl chloride, etc. It is stated that is used. However, even when tests were actually conducted using combination systems of these polymeric substances, various monomers, and their polymerization initiators, satisfactory results were not necessarily obtained. The present inventors have conducted various studies to overcome the drawbacks of the prior art, and have discovered that chlorinated polyolefin has excellent performance as a polymeric material for binders. In a recording material having a layer of a polymerizable composition and optionally a protective film on the layer, the photopolymerizable composition contains a chlorinated polyolefin, a monomer having an addition-polymerizable unsaturated bond, and a photopolymerizable composition. He invented a photoresist material consisting of a polymerization initiator (JP-A-49-123021, corresponding German Patent Application No. 2,414,240).

However, the layer of the photopolymerizable composition in the above-mentioned invention is laminated on the surface of a base material such as a copper plate or aluminum plate, imagewise exposed, and peeled and developed to form a good pattern on the surface of the base material. It has been found that in some cases, a portion of the resist pattern that should remain on the surface of the substrate may be removed together with the support during peeling, resulting in breakage or partial loss of the resist pattern on the surface of the substrate. This phenomenon is thought to be due to the fact that the layer of the photopolymerizable composition does not have sufficient uniformly strong adhesion to the substrate. The present inventors have focused on the fact that rosin and rosin esters are used as softeners and adhesives for rubber. When mixed with chlorinated polyolefin, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral, polyvinyl acetate, vinyl chloride monovinyl acetate copolymer, vinylidene chloride.
It can be mixed well with a wide range of polymeric materials such as acrylonitrile copolymers, polyisoprene, chlorinated rubber and poly(chlorosulfonated ethylene), and the mixtures exhibit good adhesion to the surfaces of a variety of materials. I found out that it shows.

Based on the above-mentioned knowledge, the present inventors further included a rosin-based tackifier in the photopolymerizable composition system of the above-mentioned invention, thereby creating a photoresist layer made of the photopolymerizable composition. The photopolymerizable composition must adhere firmly and uniformly to the substrate (e.g., copper plate, aluminum plate, etc.) after exposure, and the resist pattern on the substrate surface will not be cut or partially damaged during peeling and development, and the photopolymerizable composition must be photosensitive. The present inventors have discovered that the sensitivity is higher than that of a photopolymerizable composition that does not contain a rosin-based tackifier, and have completed the present invention.

An object of the present invention is to provide a peel-and-develop type photoresist material in which the hardened portion adheres firmly and uniformly to a substrate after exposure, and the resist pattern is not cut or partially damaged during peel-and-develop. .

Another object of the present invention is to provide a peel-and-develop type photoresist material having high photosensitivity.

Yet another object of the present invention is to provide a peel-and-developable photoresist material that provides a resist pattern with sharper edges. Still another object of the present invention is that the layer of the photosensitive composition uniformly adheres to the substrate before exposure;
Another object of the present invention is to provide a peel-and-develop type photoresist material in which the uncured, unexposed portions can be completely removed from the substrate during peel-off development after exposure.

In the present invention, a layer of a photopolymerizable composition containing at least a film-forming polymeric substance, a monomer having at least one addition-polymerizable unsaturated bond, and a photopolymerization initiator is provided on a support. A peel-and-develop photoresist material that is developed by peeling off a support, characterized in that the photopolymerizable composition further contains a rosin-based tackifier. .

Examples of the rosin-based tackifier that can be used in the present invention include rosin as a natural resin (for example, gum rosin, oil rosin, tall oil rosin, etc.), polymerized rosin, partially hydrogenated rosin, pentaerythritol ester of partially hydrogenated rosin, Glycerin ester rosin, pentaerythritol ester rosin, monoethylene glycol ester rosin, methyl abietate,
Examples include hydrogenated methyl abuetate, diethylene glycol abietate, diethylene glycol 2-hydroabietate, and the like. The ability to increase the photosensitivity of the photopolymerizable composition, the adhesion of the resultant resist pattern to the substrate and the resistance to etching liquids, the ease of availability, low price, and ease of preparing the photopolymerizable composition, etc. Considering these, preferred rosin-based tackifiers include rosin as a natural resin (for example, gum rosin, uddrosin, tall oil rosin, etc.), polymerized rosin, partially hydrogenated rosin, and partially hydrogenated rosin pentaerythritol. ester, glycerin ester-based rosin, and nopentaerythritol ester-based rosin.

Among these, particularly preferred rosin-based tackifiers are glycerin esters of partially hydrogenated rosins, pentaerythritol esters of partially hydrogenated rosins, and pentaerythritol esters of rosin. The above-mentioned substances can be used alone or in a mixture of two or more of them in the photopolymerizable composition. The content of the rosin-based tackifier is 0.1wt in the total solid content of the photopolymerizable composition.
% to 30wt01),
Preferably, it can be used in a range of 1w1% to 10wt%. If the content of the rosin-based tackifier is less than the above range, the layer of the photopolymerizable composition will lose its ability to adhere uniformly and firmly to the surface of the substrate, resulting in peeling after image exposure. During development, the resist pattern on the surface of the substrate is likely to be cut or partially damaged, and at the same time, no increase in photosensitivity of the photopolymerizable composition is observed. On the other hand, if the content of the rosin-based tackifier exceeds the above-mentioned range, it becomes difficult to prepare and apply the photosensitive composition, its photosensitivity increasing effect is lost, and ultimately The resulting resist pattern on the surface of the substrate is not sufficiently solidified, resulting in problems such as tackiness remaining and the strength of the resist pattern being reduced. Film-forming polymeric substances used in the present invention include chlorinated polyolefins (e.g., chlorinated polyethylene, chlorinated polypropylene),
Polymethyl methacrylate, polymethyl acrylate, polyvinyl chloride, polyvinylidene chloride, polyvinyl butyral, polyvinyl acetate, vinyl chloride vinyl acetate copolymer, vinylidene chloride-atarylonitrile copolymer, polyisoprene, chlorinated rubber, polychloroprene, Examples include polychlorosulfonated ethylene and polychlorosulfonated propylene.

Among these, preferred film-forming polymeric materials are chlorinated polyethylene, chlorinated polypropylene and polymethyl methacrylate. Next, examples of the monomer having at least one addition-polymerizable unsaturated bond that can be used in the present invention include a wide range of addition-polymerizable monomers. Examples include acrylic esters, acrylamides, methacrylic esters, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes, crotonic esters, and the like. Specific examples of compounds having one addition-polymerizable unsaturated bond include acrylic esters, such as
Acrylic acid, alkyl acrylates (e.g. propyl acrylate, butyl acrylate, amyl acrylate, ethylhexyl acrylate, octyl acrylate), methacrylic esters such as methacrylic acid, alkyl methacrylates (e.g. methyl methacrylate,
Ethyl methacrylate, propyl methacrylate,
isopropyl methacrylate), acrylamides,
For example, acrylamide, N-alkylacrylamide,
(The alkyl group includes, for example, a methyl group, an ethyl group,
Examples include butyl group, isopropyl group, t-butyl group, and ethylhexyl group. ), methacrylamides, such as methacrylamide, N-alkylmethacrylamide (the alkyl groups include methyl, ethyl, isopropyl, t-butyl, ethylhexyl, etc.), allyl compounds, such as allyl esters vinyl ethers such as alkyl vinyl ethers (such as hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether), vinyl ethers, Examples include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl caproate, and the like. In addition, styrenes such as styrene,
Examples include methylstyrene, chloromethylstyrene, alkoxystyrene, halogenated styrene, and styrene benzoate. Crotonate esters include methyl crotonate,
Examples include ethyl crotonate, butyl crotonate, hexyl tarotonate, and isopropyl crotonate. next,
Specific examples of compounds having two or more addition-polymerizable unsaturated bonds are shown below.
It is more preferably used than individual compounds. First, as acrylic esters and 4-methacrylic esters, there are polyacrylates and polymethacrylates of polyhydric alcohols (herein, "Polymer" refers to diacrylate or higher).The above polyhydric alcohols as,
Polyethylene glycol, polypropylene oxide, polybutylene oxide, bis(β-hydroxyethoxy)
Benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane, triethylolpropane, pentaerythritol, dipentaerythritol, sorbitan, sorbitol, 1,4-butanediol, 1,2,4-butanetriol, 2-butene- 1,
4-diol, 2-butyl-2-ethyl-propanediol, 2-butene-1,4-diol, 1,3-propanediol, triethanolamine, decalindiol, 3-chloro-1,2-propanediol, etc. There is. Among these acrylic esters and methacrylic esters, preferred are ethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, pentaerythritol triacrylate, pentaerythritol dimethacrylate, and dipentaerythritol pentaacrylate. These include acrylate, glycerol triacrylate, diglycerol dimethacrylate, 1,3-propanediol diacrylate, and triacrylic acid ester of trimethylolpropane added with ethylene oxide.

Two or more types of such monomers having at least one addition-polymerizable unsaturated bond can also be used in combination.

These monomers are used in an amount of 10 to 500 parts by weight, preferably 30 to 200 parts by weight, based on 100 parts by weight of the film-forming polymeric substance. On the other hand, as the photopolymerization initiator used in the present invention, conventionally known initiators can be suitably used. Written by Hajime Kosa [Light Sensitive Systems G. KOsar：゛Light
t-Sensitive Systems55 (JOhn
Wiley & SOns, Inc. ,l965,NewY
Ork) carbonyl compounds, organic sulfur compounds, peroxides, redox compounds as described in Chapter 5,
Examples include azo and diazo compounds, halogen compounds, and photoreducible dyes.

Typical specific examples include carbonyl compounds such as benzoin, benzoin methyl ether, benzophenone, anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, 9,10-phenanthrenequinone, diacetyl, benzyl, and Compounds represented by the following general formula are useful. In the formula, R1 represents an alkyl group commonly known in cyanine dyes, such as unsubstituted lower alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and isopropyl group, hydroxyalkyl group, alkoxyalkyl group, and carboxy group. alkyl group,
Indicates a sulfoalkyl group and an aralkyl group.

R2 is an alkyl group (for example, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, or an isopropyl group is preferable), an aryl group (for example, a phenyl group, a p-
Hydroxyphenyl group, p-methoxyphenyl group, p-
Chlorophenyl group, naphthyl group, etc. are preferred. ) or thienyl group. Z is a non-containing compound necessary to form a nitrogen-containing heterocyclic ring usually used in cyanine dyes, such as a benzothiazoly heptad ring, a naphthothiazoline ring, a benzoselenazoline ring, a naphthoselenazoline ring, a benzoxazoline ring, and a naphthoxazoline ring. Hail metal atoms. Specific examples of the compound represented by the above general formula include 2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-benzoylmethylene-3-ethyl-β
-Naphthothiazoline, 3-ethyl-2-(2-thenoino(c)methylene-β-naphthothiazoline, 3-ethyl-
2-propionylmethylene-β-naphthothiazoline, 5
-chloro-3-ethyl-2-p-methoxybenzoylmethylenebenzothiazoline and the like.

Examples of organic sulfur compounds include dibutyl disulfide, dioctyl disulfide, dibenzyl sulfide, diphenyl disulfide, dibenzoyl disulfide, and diacetyl disulfide.

Examples of peroxides include hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. Redox compounds consist of a combination of a peroxide and a reducing agent, and include ferrous ions and water peroxide, ferrous ions and persulfate ions, ferric ions and peroxides, and the like.

Examples of azo and diazo compounds include α,α5-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azo-bis-cyclohexanecarbonitrile, and diazonium salt of p-aminodiphenylamine. be.

Examples of the halogen compound include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, β-naphthalenesulfonyl chloride, and xylene sulfonyl chloride.

Examples of photoreducible pigments include rose bengal, erythrosin, eosin, atariflapine, riboflavin, and thionin.

Among these photopolymerization initiators, preferred are 2-methylanthraquinone, 2-ethylanthraquinone, and 2-methylanthraquinone.
Anthraquinone derivatives such as isopropylanthraquinone and 2-t-butylanthraquinone, benzoin derivatives such as 9,10-phenanthrenequinone, benzoin methyl ether, and 2-benzoylmethylene-3-methyl-β-naphthothiazoline, 2-benzoylmethylene Naphthothiazoline derivatives such as -3-ethyl-β-naphthothiazoline, 3-ethyl-2-(2-tenoino(ha)methylene-β-naphthothiazoline) and 3-ethyl-2-propionylmethylene-β-naphthothiazoline. .

These photoinitiators are generally used alone, but
Two or more types can be used in combination if necessary.

These photopolymerization initiators are 0% per 100 parts by weight of monomer.
．． It is used in a range of 1 to 20 parts by weight, preferably in a range of 1 to 10 parts by weight.

The photopolymerizable composition used in the present invention consists of the above-mentioned components, but a thermal polymerization inhibitor can be further added thereto.

Specific examples of thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous chloride, phenothiazine, chloranil, naphthylamine, β-naphthol, 2,6-di -t-Butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene to p-toluidine, methylene blue, organic acid copper (
For example, copper acetate). These thermal polymerization inhibitors are preferably contained in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the monomer. The photopolymerizable composition used in the present invention can further contain various additives such as colorants and plasticizers.

Examples of colorants include pigments such as carbon black, iron oxide, phthalocyanine pigments, and azo pigments, and dyes such as methylene blue, crystal violet, rhodamine B1 fuchsin, auramine, azo dyes, and anthraquinone dyes. It is preferable that the colorant used does not absorb light at the absorption wavelength of the photopolymerization initiator. Such a coloring agent has a total amount of film-forming polymeric substance and monomer of 10
0.1 to 30 parts by weight in the case of pigments to 0 parts by weight;
In the case of a dye, it is preferably contained in a range of 0.01 to 10 parts by weight, preferably 0.1 to 3 parts by weight. Examples of plasticizers include phthalate esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, and diotatylphthalate;
Glycol esters such as dimethyl glycol phthalate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, butylphthalyl butyl glycolate, triethylene glycol dicaprylate, tricresyl phosphate, triphenyl phosphate, etc. These include phosphoric acid esters, triethyl citrate, glycerin triacetyl ester, and butyl laurate. The photopolymerizable composition used in the present invention is dissolved in a solvent to form a coating solution, which is coated on a suitable support and dried. Examples of the solvent for the coating solution include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diisobutyl ketone, etc., such as ethyl acetate, butyl acetate, amyl acetate, methyl formate, ethyl propionate, dimethyl phthalate, and ethyl benzoate. esters such as toluene, xylene, benzene, ethylbenzene, etc., aromatic hydrocarbons such as carbon tetrachloride, trichlorethylene, chloroform,
1,1,1-trichloroethane, monochlorobenzene,
Examples include halogenated hydrocarbons such as chlornaphthalene, ethers such as tetrahydrofuran, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, dimethylformamide, dimethyl sulfoxide, and the like.

If necessary, other coating layers and/or antihalation layers necessary for good bonding between the photopolymerizable composition layer and the support can be provided on the surface of the support.
The support used in the present invention needs to have good transmittance to light that can photopolymerize the photopolymerizable composition and a uniform surface.

For example, in the wavelength range from 290 nm to 500 nm, it is necessary that the light transmittance is at least 3001), preferably at least 65%, and that the surface is uniform. Specifically, polyethylene terephthalate, polypropylene, polyethylene,
Cellulose triacetate, cellulose diacetate, polyvinyl chloride, polyvinyl alcohol, polycarbonate, polystyrene, cellophane, polyvinylidene chloride copolymer, polyamide (e.g. 6-nylon, 6,6-nylon, 6
, 10-nylon, etc.), polyimide, vinyl chloride monovinyl acetate copolymer, polytetrafluoroethylene, polytrifluoroethylene, and the like can be used. Furthermore, a composite material consisting of two or more of these types can also be used. The support is generally of a thickness of 10 to 150 μm, preferably 20 to 50 μm.
A thickness of m is used, but thicknesses outside the above range can also be used. provided on a support.

The thickness of the layer of the photopolymerizable composition is set such that the finally formed image performs the desired function,
Generally, the thickness after drying, ie in the absence of solvent, is in the range of 5 to 100 μm, more preferably in the range of 10 to 60 μm. The recording material of the present invention is
Although it consists of a layer of a photopolymerizable composition provided on a support, a protective film can be provided on the layer of the photopolymerizable composition if necessary.

Such a protective film can be appropriately selected from those used for the support and paper such as paper laminated with polyethylene, polypropylene, etc. The thickness is generally in the range of 8 to 80 μm, and 10
More preferably, the range is from 50 μm to 50 μm. At that time, it is necessary to make sure that the adhesive force A between the photopolymerizable composition and the support and the adhesive force B between the photopolymerizable composition and the protective film satisfy A>B.
For example, the support and the protective film can be used in combinations as shown in Table 1 below. In addition to the method of selecting the support and the protective film from mutually different types as described above, it is also possible to surface-treat at least one of the support and the protective film so as to satisfy the adhesive force relationship as described above. I can do it.

The surface treatment of the support is generally performed to increase the adhesive strength with the photopolymerizable composition, such as applying an undercoat layer, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, and high frequency treatment. Examples include irradiation treatment, glow discharge irradiation treatment, active plasma irradiation treatment, and laser beam irradiation treatment. In addition, the surface treatment of the protective film is generally carried out in order to reduce the adhesive force with the photopolymerizable composition, contrary to the surface treatment of the support described above. There is a method of providing an undercoat layer of polyfluoroethylene or the like.

Next, an image forming method using the photoresist material of the present invention will be explained.

When the photoresist material of the present invention has a protective film, the protective film is peeled off, and then the layer of the photosensitive composition of the photoresist material is pressed onto a desired substrate.

Next, image exposure is carried out through the transparent support. As the light source, a light source containing light with a wavelength in the range of 350 to 450 nm, such as a high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, a fluorescent tube for copying, etc., can be used. In addition, laser beams, electron beams, X-rays, etc. may be used as light sources. When the support is peeled off after image exposure, the exposed portions in the image exposure are cured and remain on the substrate, but the unexposed portions are removed together with the support without being cured, and an image is formed on the substrate. The recording material of the invention is particularly advantageously used for the production of resist images, but can also be used for photography, optical reproduction, production of relief molds, production of printing plates such as lithography and letterpress printing, etc.

The photoresist material of the present invention provides a resist pattern with sharper edges than conventional solution type photoresist materials, and can also form fine patterns well.

Compared to photoresist materials having a photopolymerizable composition system that does not contain a rosin-based tackifier, the sensitivity is higher and the adhesion of the photopolymerizable composition layer to the substrate after exposure is enhanced. The photoresist material of the present invention has the excellent effect of not causing defects such as disconnection or partial defects in the resist pattern that can be obtained. It has been found that the resist produced using the photoresist material of the present invention has particularly excellent performance as a resist for producing printed wiring circuit boards. It was also found that the resist produced using the photoresist material of the present invention has excellent wear resistance and chemical resistance. The present invention will be specifically explained below using Examples, but the present invention is not limited to these Examples.

TO (U.S. Super Chron CPE-907LTN 40% by weight
The compound has a toluene solution having a viscosity of about 90 cps at 25° C. and a chlorine content of 66% by weight or more.

) The above composition was dissolved in a mixed solvent consisting of methyl ethyl ketone 1001f11 and dimethyl formamide 20d to prepare a solution of the photopolymerizable composition.

A portion of this liquid was applied onto a polyethylene terephthalate film having a thickness of 25 μm and dried at 80° C. for 20 minutes.
The thickness of the layer of the photopolymerizable composition after drying was 15 μm. Next, we made a cleaned copper board for printed wiring (a board made by laminating a 35 μm thick copper plate on a 1.21 m thick epoxy resin board reinforced with glass fiber, and the size was 10 cm x 15 CI! It was laminated under pressure on top of the copper layer of L). In this state, a negative original having a wiring circuit pattern was brought into close contact with the surface of the support made of photoresist material, and the negative original was exposed to light for 1 minute from a 2 KW high-pressure mercury lamp light source at a distance of 50 cm. When the support polyethylene terephthalate film is immediately peeled off, a layer of photocured photopolymerizable composition corresponding to the negative original remains on the copper layer of the copper substrate, forming a positive image, corresponding to the negative original. The uncured portion of the photopolymerizable composition layer was removed together with the polyethylene terephthalate film. The resist pattern formed on the copper substrate had no defects such as disconnections or defects. Copper substrate 9 of the same size and made of the same material with similar treatment
When the process was repeated for each sheet, a resist pattern with no defects was similarly formed. Next, the copper substrate having the resist pattern formed in this way was 38wt%
The copper layer was etched using an aqueous iron chloride solution at a temperature of 40°C. Even during this treatment, the photosensitive layer adhered firmly to the copper surface, and no peeling or pinholes occurred. The photosensitive layer was easily peeled off using methylene chloride. Conventional photoresist films (for example, DuPOnt's Riston)
When using "RlstOn)", there was a drawback that it was difficult to remove the final resist, but in the case of this example, it was easy to remove, and it has excellent performance in that respect as well. discovered. Comparative Example 1 A photopolymerizable composition was prepared by removing the glycerin ester of the partially hydrogenated rosin from the composition of Example 1, and coating and drying were carried out in the same manner.

The thickness of the layer of the photopolymerizable composition after drying was 15 μm. Furthermore, a resist pattern was created on a copper substrate under the same conditions. Resist patterns were formed on 10 copper substrates, and as a result of evaluating the resist patterns, it was found that an average of two copper substrates had one damage (mainly breakage) at one point of force.

However, the etching treatment (4'C) using a 38 wt % iron chloride (Ili) aqueous solution did not further increase the number of defects. Example 2 In the composition of Example 1, pentanylitritol ester of rosin (manufactured by Arakawa Forestry Chemical Industry Co., Ltd., Pencell 1A) was used instead of glycerin ester of partially hydrogenated rosin.
A photopolymerizable composition was prepared in the same manner as in Example 1 with the same composition as in Example 1 using Pencel-A), applied on a polyethylene terephthalate film (thickness: 25 μm), and dried at 80° C. for 20 minutes. After that, a cleaned flexible copper board (a board with a 35 μm thick copper thin plate laminated on the surface of a 100 μm thick polyimide resin board, which has flexibility as a whole, and the size is 20 crr L x 20 Cff)
It was laminated under pressure on top of the copper layer of L).

Next, exposure and peeling of the photoresist material support were carried out in the same manner as in Example 1, except that the exposure time was 40 seconds, and a positive resist pattern corresponding to the negative original was formed on the copper layer of the flexible copper substrate. formed. The resist pattern was clearly formed down to a fine line of 100 μm, and was able to withstand the subsequent etching treatment (38 wt % iron chloride (treated with aqueous solution at 40°C)). The same resist pattern was formed on each of nine flexible copper substrates.

When the resist patterns on a total of 10 copper substrates obtained were investigated, it was found that there were very few defects such as disconnections and defects in the resist patterns. That is, there was an average of one damage point per copper substrate. On the other hand, a photopolymerizable composition was prepared by removing the pentaerythritol ester of rosin from the composition of this example, and using it, a resist pattern was formed on 10 flexible copper substrates in the same manner as in this example. formed. When the resist patterns on the 10 copper substrates obtained were examined, it was found that there were breaks at an average of 5 force points per copper substrate. As is clear from the above comparison results, it was found that the effect of the pentaerythritol ester of rosin in the photoresist material of the present invention is large. Example 3 The following composition liquid was prepared.

(U.S. Super Chron CPP-306 has a viscosity of 40% by weight toluene solution at 25°C, approximately 95 cps, and a chlorine content of 6
6% by weight or more of the compound.

) Among the above compositions, methylene blue was dissolved in 1 d of ethanol, and the others were dissolved in 50 ml of ethylene chloride, and both were mixed to prepare a viscous solution of a colored photopolymerizable composition. This was uniformly applied onto a polyethylene terephthalate film having a thickness of 25 μm and dried to obtain a photoresist material having a layer of the photopolymerizable composition of 10 μm. Next, the same copper substrate used in Example 1 was heated to a temperature of 25°C.
The distance from the 2KW high pressure mercury lamp is 40? A resist pattern was produced on the copper substrate layer by exposing and peeling off the polyethylene terephthalate film in the same manner as in Example 1, except that the resist was exposed for 40 seconds.

The copper substrate having the resist pattern thus obtained was treated at 45°C with an etching solution having the composition shown below.

Etching liquid composition: Solution A: Ammonium peroxonisulfate 2199 to water 11
Aqueous solution dissolved in.

Solution B: An aqueous solution of sodium chloride 1469 dissolved in water 11.

When used, liquid A and liquid B are mixed at a 1:I ratio.

It was found that the resist did not change at all in response to this treatment, maintained good etching resistance, and had very little side etching in the resulting wiring circuit made of the copper layer.

On the other hand, a photoresist material was prepared using a photopolymerizable composition in which only gum rosin was removed from the composition of this example,
When a wiring circuit consisting of a copper layer was prepared in the same manner as in this example, there were disconnections and side etching of the copper layer was observed. The results of this comparison revealed that the resist pattern formed from the layer of the photopolymerizable composition of the photoresist material of this example exhibited very good adhesion to the copper substrate. A: As in Example 1, a layer of the photopolymerizable composition (thickness after drying: 30 μm) coated on a polyethylene terephthalate film (thickness: 25 μm) was laminated on a copper substrate for printed wiring. .

Using a positive manuscript opposite to that used in Example 1, exposure was carried out for 40 seconds from a distance of 40CTfL using a 2KW ultra-high pressure mercury lamp, and the polyethylene terephthalate film was immediately peeled off to form a photocured negative type resist pattern on the copper substrate. It was done. It was found that this pattern had higher clarity than a pattern obtained using a partially hydrogenated rosin without the addition of glycerin ester, and the lines of the pattern were clearly formed. The exposed copper portions of this resist pattern were solder-plated using a borofluoride bath having the following composition.

A solder rod (tin to lead weight ratio of 6:4) was used as the anode, bath temperature was 30°C, and current density of the cathode was 3.0 amperes/DTr.
It was plated for 30 minutes under the conditions of I. As a result, plating was performed satisfactorily, and no defects such as peeling off of the resist pattern or generation of pinholes were observed. Example 5 A solution of a photopolymerizable composition having the following composition was prepared.

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V. v. ．． ．． , -1 53 The above composition liquid was applied onto a polyethylene terephthalate film and dried at 80°C for 10 minutes. The thickness of the photopolymerizable composition layer after drying is 30μ
It was m. This photosensitive layer was laminated under pressure at 25° C. on a copper substrate for printed wiring.

Thereafter, a resist pattern for plating was created using a positive original in the same manner as in Example 4 except that the exposure time was changed to 20 seconds. Next, the exposed copper portions were tin-plated, but the resist portions adhered firmly to the copper surface against the plating solution, and no peeling phenomenon was observed. A photopolymerizable composition was prepared by removing pentaerythritol ester (ester gum HP) of partially hydrogenated rosin from the above composition solution, and a resist pattern was prepared using the photoresist material in the same manner as in this example. , an exposure time of 40 seconds was required. That is, it has been found that the sensitivity of the photopolymerizable composition can be doubled by incorporating pentaerythritol ester of partially hydrogenated rosin. Example 6 A photoresist material was prepared in the same manner as in Example 1, and immediately after the layer of the photopolymerizable composition had dried, a low-density polyethylene film with a thickness of 25 μm and a smooth surface without surface treatment was prepared. A photoresist material with a protective film was obtained by laminating the photoresist material as a protective film on a layer of the photopolymerizable composition using a laminator.

This product is in the temperature range of 18℃ to 25℃, 45% to 7
It was stored for 3 months in a dark room at a relative humidity of 0%. Thereafter, the protective film was peeled off, and a layer of the photopolymerizable composition was laminated under pressure on the copper substrate in the same manner as in Example 1, and a resist pattern was produced in the same manner as in Example 1. Example 1
Similar results were obtained. Example 7 A photoresist material was prepared in the same manner as in Example 3, and immediately after the layer of the photopolymerizable composition had dried, a cellulose triacetate film with a thickness of 38 μm and a smooth surface without surface treatment was prepared. A photoresist material with a protective film was obtained by laminating the photoresist material as a protective film on a layer of the photopolymerizable composition using a laminator.

Claims (1)

[Claims] 1 A layer of a photopolymerizable composition containing at least a film-forming polymeric substance, a monomer having at least one addition-polymerizable unsaturated bond, and a photopolymerization initiator is provided on a support; 1. A peel-and-develop photoresist material that is developed by peeling off a body, characterized in that the photopolymerizable composition further contains a rosin-based tackifier.