JPS63208838A - Image forming material - Google Patents

Abstract

PURPOSE:To improve developability and chemical resistance by incorporating a linear polymer contg. a carboxyl group into a film formable high-polymer material, incorporating a specific compd. into an ethylenic unsatd. polymerizable compd. and incorporating a specified nonionic surfactant into a photopolymerizable compsn. layer. CONSTITUTION:The film formable high-polymer material of an image forming material formed by providing the photopolymerizable compsn. layer contg. the film formable high-polymer material, the ethylenic unsatd. polymerizable compd. and a photopolymn. initiator contains the linear polymer contg. the carboxyl group and the ethylenic unsatd. polymerizable compd. contains the compd. expressed by formula (I); in addition, the nonionic surfactant expressed by formula (II) is incorporated into the photopolymerizable compsn. layer. In formula, Y1, Y2 denote a (meth)acryloyl group; (l), (m) denote integers to make l+m=8-40; R7 denotes an alkyl group of 8-12C; (n) denotes 8-12 integers. The image forming material satisfying the developability, chemical resistance, and the removability of the cured image part after a circuit forming process is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to an image-forming material that is developable with an alkaline aqueous solution and has a photopolymerizable composition layer provided on a transparent support.

[Conventional technology]

This type of image forming material is made by forming a conductive layer such as an aluminum film or an ITO film (indium oxide-tin oxide composite film) on a substrate on which an image is to be formed, such as an insulating base made of a glass plate or plastic film. The photopolymerizable composition layer is laminated on the surface of the conductive layer of the substrate by heating and pressing so that it is on the inside, and after this lamination, pattern exposure is performed from the transparent support side through a predetermined original image, and then the transparent support By peeling off only the body, removing the photopolymerizable composition layer of the unexposed part with an alkaline aqueous solution and developing it,
A photopolymerizable composition layer cured by exposure is formed as an image on the substrate.

After this development, a circuit forming process is performed, such as etching away the conductive layer exposed by removing the non-exposed areas with an etching solution, or forming a plating layer on this layer using an appropriate plating solution. As a result, a circuit board is obtained in which a patterned conductive layer or a patterned plating layer is formed on an insulating base. Here, the photopolymerizable composition layer cured by the exposure, that is, the cured image, functions as a mask material in the circuit forming treatment step, and after this treatment step, an alkaline aqueous solution that is more alkaline than that at the time of development is used. will be removed.

Conventionally, various image forming materials have been proposed for use in this purpose, but most of them relate to the material composition of the photopolymerizable composition layer provided on the transparent support. That is, the photopolymerizable composition layer is
It contains a film-forming polymeric substance, an ethylenically unsaturated polymerizable compound, and a photopolymerization initiator as main components. In addition, the image portions that have been hardened by exposure are finally removed with a strong alkaline aqueous solution to impart smooth developability. Efforts have been taken to impart chemical resistance to the parts so that they can withstand chemicals such as etching solutions and plating solutions and can sufficiently function as a mask material.

For example, in JP-A-58-1142, a film constituting a photopolymerizable composition layer is described as an image forming material having excellent developability, chemical resistance, and final removability of the cured image portion as described above. A linear polymer containing a carboxyl group in the molecule is used as the formable polymer substance, and after addition reaction of ethylene oxide or propylene oxide to bisphenol is performed as the ethylenically unsaturated polymerizable compound constituting the same composition layer. It has been proposed to use a (meth)acrylate compound obtained by subjecting (meth)acrylic acid to an esterification reaction.

Furthermore, in JP-A No. 61-213213, by using a copolymer of benzyl acrylate, alkyl methacrylate, (meth)acrylic acid, etc. as a film-forming polymer substance, properties such as developability with an alkaline aqueous solution are improved. It has been proposed to obtain an improved imaging material.

[Problem that the invention seeks to solve]

However, according to the experimental studies conducted by the present inventors, the conventionally known image forming materials as described above do not necessarily fully satisfy the above-mentioned characteristics such as developability and chemical resistance.
It has been found that there is still room for improvement as an image forming material that requires precise circuit formation for liquid crystal display devices, electrochromic display devices, and the like.

Therefore, the present invention further examines the material components of the photopolymerizable composition layer, improves the development characteristics such as developability and chemical resistance, and provides an alkaline aqueous solution that enables extremely precise circuit formation. The object of the present invention is to provide an image-forming material that can be developed by.

[Means for Solving the Problems] As a result of intensive studies to achieve the above object, the inventors used a carboxyl group-containing linear polymer as a film-forming polymer substance, and also used an ethylenic non-ethylene polymer. By using a specific difunctional (meth)acrylate compound as a saturated polymerizable compound and further including a specific nonionic surfactant in the photopolymerizable composition layer containing these components, development with an alkaline aqueous solution is possible. We learned that it is possible to obtain an image forming material with extremely high practical value, which has highly satisfactory properties, excellent chemical resistance to etching solutions, and good removability of the cured image area after circuit formation processing. The invention was completed.

That is, the present invention provides an image forming material comprising a photopolymerizable composition layer containing a film-forming polymeric substance, an ethylenically unsaturated polymerizable compound, and a photopolymerization initiator on a transparent support. The film-forming polymer substance contains a carboxyl group-containing linear polymer, and the above ethylenically unsaturated polymerizable compound has the following formula (■); [wherein R, and R2 are each hydrogen or a methyl group, X
is a group represented by the following formula; (in the formula, R3-R6 are halogen atoms), Yl r Y2 is a (meth)acryloyl group, l ,
m4t/+m is an integer of 8 to 40], and the photopolymerizable composition layer contains a compound represented by the following formula (ID; group, n is 8~
The present invention relates to an image-forming material characterized by containing a nonionic surfactant represented by:

In this specification, (meth)acrylic acid refers to acrylic acid and/or methacrylic acid, (meth)acrylate refers to acrylate and/or methacrylate, and (meth)acryloyl group refers to the following formula; R represents an acryloyl group and/or a methacryloyl group, respectively.

In addition, the term "weight average molecular weight" means a value measured by gel permeation chromatography (GPC).

[Structure and operation of the invention]

The film-forming polymer substance used in this invention contains a linear polymer containing a carboxyl group, and this polymer has excellent film-forming properties and is easily dissolved or swollen by an alkaline aqueous solution. By combining this with a specific ethylenically unsaturated polymerizable compound to be described later, particularly good results can be obtained in terms of developability and removability of the cured image portion after circuit formation processing.

Such carboxyl group-containing linear polymers include:
It is preferable that the acid value is 50 to 300, particularly preferably 70 to 200, and the weight average molecular weight is 5,000 to 300°,000, particularly preferably s,ooo to 250,000.

If the acid value is too low or the molecular weight is too high, developability with an alkaline aqueous solution will be poor, and if the acid value is too high, even the cured image will flow out during development with an alkaline aqueous solution, making it impossible to form the desired image. Furthermore, if the molecular weight is too low, film forming properties may deteriorate or the developer,
Resistance to etching solutions, plating solutions, etc. is impaired.

The above-mentioned carboxyl group-containing linear polymers include various conventionally known ones, but generally they are made by combining a carboxyl group-containing unsaturated monomer with another unsaturated monomer copolymerizable with it. A copolymer of 1 is used. Examples of the above carboxyl group-containing unsaturated monomers include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, propionic acid, itaconic acid, maleic acid, maleic anhydride, and maleic acid half ester. . In addition, the above-mentioned other unsaturated monomers have good developability in the photopolymerizable composition layer.

Monomers are selected that can impart flexibility and maintain the chemical resistance of the cured image.Specifically, methyl (meth)
Acrylate, ethyl (meth)acrylate, butyl (
(Meth)acrylates such as meth)acrylate, 2-ethylhexyl (meth)acrylate, styrene and α
Styrene derivatives having substituents at positions or aromatic rings are preferably used. In these copolymers, the acid value and weight average molecular weight can be easily adjusted within the above range by selecting the copolymerization ratio and polymerization conditions.

Among these carboxyl group-containing linear polymers, the most preferred is a styrene-maleic acid half ester copolymer. Maleic acid half ester is a half ester in which one free carboxyl group remains in the molecule by reacting maleic anhydride with an alcohol such as inpropyl alcohol. The copolymerization ratio of this half ester and styrene is such that the half ester in the copolymer is 40 to 8% so that the acid value of the copolymer is within the above range.
It is desirable that the proportion is about 0% by weight.

In this invention, the carboxyl group-containing linear polymer as described above can be used alone, and if necessary, other polymeric substances may be used in combination with this polymer. Examples of other polymeric substances include polyvinyl alcohol, polyvinylpyrrolidone, copolyamide, partial hydrolyzate of polymethyl methacrylate, polychloroprene, and styrene-butadiene copolymer rubber. In order not to impair the effect, it is preferable that the amount is 50% by weight or less of the total amount of the carboxyl group-containing rod-like polymer, that is, of the entire film-forming polymer material.

The ethylenically unsaturated polymerizable compound used in this invention is a bifunctional (meth)acrylate compound represented by the above formula (I), and this compound mainly has resistance to chemicals such as etching solutions for cured images. This contributes to improvement. However, this compound itself is lipophilic and has poor compatibility with the above-mentioned film-forming polymeric substance, so it tends to remain as it is on the substrate when developing with an alkaline aqueous solution. That is, even after development, a portion of the above-mentioned compound remains in the non-exposed areas, making it impossible to obtain good developability. The nonionic surfactant represented by the formula (0) described below is for avoiding the above problems,
By using this surfactant, the compatibility between the above compound and the film-forming polymer substance is improved, and the above compound does not remain on the substrate during development, resulting in good developability.

On the other hand, when using the above nonionic surfactant,
When a compound having no halogen substituents (R, ~Re) in the bisphenol skeleton in the above formula (I) (for example, the compound disclosed in the above-mentioned JP-A-58-1142 etc.) is used, the exposure-cured portion There is a risk that the adhesion or adhesion to the substrate surface may be reduced. However, when the compound represented by the formula (I) having a halogen substituent (R, to R6) on the bisphenol skeleton is used as in the present invention, the above-mentioned drawbacks do not occur, and the exposure-cured portion does not deteriorate. Resistance to chemicals such as etching solutions is significantly improved. The removability of the exposed and hardened portion after the circuit forming process, that is, the removability with a strong alkaline aqueous solution, is still maintained.

As described above, in the present invention, by using a combination of the film-forming polymer substance, the compound represented by the above formula +I>, and the nonionic surfactant represented by the formula (II) described below, , developability.

Good results can be obtained in both chemical resistance and removability of the cured image portion after circuit formation processing.

The difunctional (meth)acrylate compound represented by formula (I) is, for example, tetrabromobisphenol (R3-
8 to 40 moles of ethylene oxide or propylene oxide, preferably 13 to 1 mole (R6 is a bromine atom)
It can be obtained by carrying out an addition reaction at a ratio of ~30 moles and then carrying out an esterification reaction with (meth)acrylic acid. Here, the reason why the number of moles of ethylene oxide or propylene oxide added is 8 to 40 moles, that is, 10m in the above formula (I) is an integer of 8 to 40.
If it is less than 8 moles, it will be difficult to improve the compatibility with the film-forming polymer substance even if a specific nonionic surfactant described below is used in combination, and if it is more than 40 moles, the hydrophilicity will become too strong and This is because even the exposed and hardened portions peel off, making it impossible to obtain good developability.

The specific compound name of the bifunctional (meth)acrylate compound represented by the formula (I) having such an addition mole number is 2,2-bis(4-acryloxypolyethoxytetrabromophenyl). ) Propane, 2・2−
Bis(4-acryloxypolyflopoxytetrabromophenyl)propane, 2,2-bis(4-methacryloxypolyethoxytetrabromophenyl)propane, 2,2
-bis(4-methacryloxypolypropoxytetrabromophenyl)propane and the like. In these compounds, R3 to R6 in formula (I) are all composed of bromine atoms, but the bromine atoms may be replaced by other halogen atoms such as chlorine atoms.

In this invention, the difunctional (meth)acrylate compound represented by the above-mentioned formula fI) can be used alone or in combination with other ethylenically unsaturated polymerizable compounds.

In the latter combination system, the bifunctional (meth)acrylate compound represented by formula (I) is contained in an amount of 1% by weight or more, usually 10% by weight or more, of the entire ethylenically unsaturated polymerizable compound.
Particularly preferably, it is used in a proportion of 20% by weight or more.

Other ethylenically unsaturated polymerizable compounds mentioned above include (
Polyester (meth)acrylate synthesized from meth)acrylic acid, polyhydric alcohol and polybasic acid, especially polyester (meth)acrylate having at least one, preferably three or more (meth)acryloyl groups in the molecule and having a weight average molecular weight of 5, The above-mentioned polyester (meth)acrylate in the form of an oligomer of 000 or less is preferably used. Commercially available products include Aronix M8030 and M8030 manufactured by Toagosei Chemical Industry Co., Ltd.
80601 M6300, M6100, M5700
Examples include.

Moreover, other conventionally known ethylenically unsaturated polymerizable compounds can also be used in combination. This compound includes a compound having one ethylenically unsaturated bond and a compound having two or more ethylenically unsaturated bonds.

Examples of compounds having one ethylenically unsaturated bond include (meth)acrylic acid, its esters, (meth)
Acrylamides, allyl compounds, vinyl ethers, vinyl esters, N-vinyl compounds, styrenes,
Examples include crotonic acid esters.

Examples of the above (meth)acrylic esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate,
Examples of (meth)acrylamides include amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate.
meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-
Examples include t-butyl (meth)acrylamide and N-2-ethylhexyl (meth)acrylamide.

Allyl compounds include allyl esters such as allyl acetate, allyl cabroate, allyl caprylate, allyl laurate, and allyl balmitate. Vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, and ethylhexyl vinyl ether. Examples include alkyl vinyl ethers.

In addition, vinyl esters include vinyl butyrate,
vinyl isobutyrate, vinyl trimethyl acetate,
Examples of the styrene include vinyl diethyl acetate, vinyl valerate, and vinyl caproate. In addition to styrene, styrenes include methylstyrene, chloromethylated styrene, alkoxystyrene, halogenated styrene, and styrene benzoate. Furthermore, examples of crotonate esters include methyl crotonate, ethyl crotonate, butyl crotonate, hexyl crotonate, isopropyl crotonate, and the like.

Examples of compounds having two or more ethylenically unsaturated bonds include esters of polyhydric alcohols and (meth)acrylic acid, and di(meth)acrylates or higher poly(meth)acrylates are used. The polyhydric alcohols mentioned above include polyethylene glycol, polypropylene glycol, polybutylene oxide, (β-hydroxyethoxy)benzene, glycerin, diglycerin, neopentyl glycol, trimethylolpropane, trimethylolpropane, pentaerythritol, dipentaerythritol, and sorbitan. , nrubitol, 1,4-butanediol, 1,2,4-butanetriol, 2-butenoto-4-diol, 2-butyl-2-ethyl-propanediol, 2-butenoto-4-diol, 1,3-
Examples include propanediol, triethanolamine, decalindiol, and 3-chloroto-2-propanediol.

As a polyethylenically unsaturated polymerizable compound other than the above,
In addition to the adduct obtained by adding ethylene oxide or propylene oxide to bisphenol as disclosed in JP-A-58-1142, (meth)
Various known compounds such as di(meth)acrylates formed by esterifying acrylic acid can also be used.

In this invention, the amount of the ethylenically unsaturated polymerizable compound that essentially includes the bifunctional (meth)acrylate compound represented by the above formula (I) is determined by Formable polymer substance 100
The ratio is usually 10 to 300 parts by weight, preferably 50 to 200 parts by weight.

If the amount used is too little or too much, it becomes difficult to form a photopolymerizable composition layer with excellent developability and chemical resistance, which is not preferable.

Photopolymerization initiators used in this invention include carbonyl compounds, organic sulfur compounds, peroxides, redox compounds, azo and diazo compounds, halogen compounds, and thioxanthone compounds.

To give a typical example, as a carbonyl compound,
Benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether,
Examples include benzyl dimethyl ketal, benzophenone, anthraquinone, 2-methylanthraquinone, 2-t-butylanthraquinone, 9,10-phenanthrenequinone, diacetyl, and benzyl. Examples of organic sulfur compounds include dibutyl disulfide, dioctyl disulfide, dibenzyl disulfide, diphenyl disulfide, dibenzoyl disulfide, and diacetyl disulfide.

Examples of peroxides include hydrogen peroxide, di-t-butyl peroxide, benzoyl peroxide, and methyl ethyl ketone peroxide. Furthermore, redox compounds consist of a combination of a peroxide and a reducing agent, such as ferrous ions and hydrogen peroxide, ferrous ions and persulfate ions, and ferric ions and peroxides. be.

Examples of azo and diazo compounds include .alpha..alpha.'-azobisisobutyronitrile, 2-azobis-2-methylbutyronitrile, 1-azobis-cyclohexanecarbonitrile, and diazonium salts of p-aminodiphenylamine. Examples of halogen compounds include chloromethylnaphthyl chloride, phenacyl chloride, chloroacetone, and
-Naphthalenesulfonyl chloride, xylenesulfonyl chloride, etc. can be mentioned.

Furthermore, as thioxanthone compounds, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2
・4-dimethylthioxanthone, etc., which are usually p-dimethylaminobenzoic acid isoamyl ester, p-dimethylthioxanthone, etc.
-Used in a mixed system with dimethylaminobenzoic acid ethyl ester, etc.

These photopolymerization initiators may be used alone or in combination of two or more. The amount used is usually 0.5 to 100 parts by weight of the ethylenically unsaturated polymerizable compound.
It may be in the range of 20 parts by weight. If the amount is too small, the exposure curability of the photopolymerizable composition layer will be poor, and if it is used in excess of a predetermined amount, no further improvement in curability will be observed, which is economically disadvantageous.

In this invention, the photopolymerizable composition used to form a photopolymerizable composition layer on a transparent support contains the above film-forming polymeric substance, ethylenically unsaturated polymerizable compound, and photopolymerization initiator. The above formula (
It contains a specific nonionic surfactant represented by IID as an essential component.

As mentioned above, the nonionic surfactant represented by the above formula (II) is composed of the above film-forming polymeric substance and the formula (I).
) gives good results in compatibility with the bifunctional (meth)acrylate compound represented by the formula, and greatly contributes to improving the developability. This surfactant is made by adding 8 to 12 ethylene oxides to 1 mole of p-alkylphenol, for example.
It can be obtained by carrying out a molar addition reaction.

The number of moles added above is 8 to 12 moles, that is, n in the formula (D
is an integer of 8 to 12 because if it is less than 8 mol, it is difficult to expect the above-mentioned effect, and if it exceeds 12 mol, the hydrophilicity of the photopolymerizable composition layer will increase too much, and even the exposed and hardened portion will be damaged during formation and imaging. This is because the resin swells and flows during washing, making it impossible to form a desired cured image. Furthermore, R7 in formula (IN) is an alkyl group having 8 to 12 carbon atoms, but if the number of carbon atoms deviates from the above range, the balance between hydrophilicity and lipophilicity will be lost, making it difficult to obtain good results in developability. .

A particularly preferred alkyl group is a nonyl group (having 9 carbon atoms).

The nonionic surfactant represented by the formula (m) is based on 100 parts by weight of the ethylenically unsaturated polymerizable compound which essentially includes the difunctional (meth)acrylate compound represented by the formula (I). Usually 1 to 50 parts by weight, preferably 1
It is preferable to use it in a proportion of ~20 parts by weight. If the amount used is too small or too large, it is difficult to obtain good results in developability, and if the amount is too large, the resistance to chemicals such as etching solutions will deteriorate, which is not preferable.

In this invention, the photopolymerizable composition containing the above-mentioned essential components may contain the following thermal polymerization inhibitors and colorants, if necessary.

Thermal polymerization inhibitors include paramethoxyphenol, hydroquinone, alkyl- or aryl-substituted hydroquinone, t-butylcatechol, pyrogallol, cuprous salt, phenothiazine, floranil, naphthylamine, β
- Naphthol, 2,6-di-t-butyl-p-cresol, pyridine, nitrobenzene, dinitrobenzene, p
-) Examples include organic acid copper such as luidine, methylene blue, and copper acetate. These thermal polymerization inhibitors are usually used in an amount of 0.001 to 5 parts by weight per 100 parts by weight of the ethylenically unsaturated polymerizable compound.
Used in parts by weight.

Examples of colorants include carbon black, iron oxide,
Pigments such as phthalocyanine pigments and azo pigments, methylene blue, crystal violet, and rhodamine B1
There are dyes such as axin, auramine, azo dyes, and anthraquinone dyes, but those that do not absorb light at the absorption wavelength of the photopolymerization initiator are preferred. The amount of the coloring agent added is usually 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the film-forming polymeric substance and the ethylenically unsaturated polymerizable compound.

Furthermore, in addition to the above-mentioned components, the above-mentioned photopolymerizable composition can also contain various additives such as a plasticizer and an adhesion promoter, if necessary.

In the present invention, such a photopolymerizable composition is uniformly dissolved in a normal solvent, cast on a transparent support, and then dried to obtain a polymerization ratio of 5 to 100%.
A photopolymerizable composition layer having a thickness of about μ, particularly preferably about 10 to 50 μ is formed to provide an image forming material.

The above-mentioned solvent is not particularly limited as long as it can dissolve the photopolymerizable composition, and may be one type or a mixed solvent of two or more types. Specific examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, ethyl acetate, butyl acetate, dichloromethane, chloroform, methanol, ethanol, and the like.

On the other hand, the above-mentioned transparent support is desired to have excellent surface smoothness so that the photopolymerizable composition 1 having a uniform thickness can be formed thereon. It is desirable that the material is selected so that it can be easily peeled off from the layer and wrapped, and that it is not surface-treated.

Furthermore, in order to be able to photopolymerize the photopolymerizable composition layer well by exposure to light, it must have excellent light transmittance, for example, a light transmittance of 3 in the wavelength range of 290 to 500 nm.
It is required that it be 0% or more, particularly preferably 65% or more.

There are various kinds of transparent supports that satisfy these required characteristics, and representative examples include polyethylene terephthalate film, polyethylene film, and polyethylene film having a thickness of 5 to 100μ, particularly 10 to 30μ. Examples include polypropylene film, and among these, polyethylene terephthalate film is the most preferred.

The image-forming material of the present invention can be stored by winding it into a roll or stacking it in layers. In this case, in order to prevent the materials from adhering to each other, a transparent film formed by forming the photopolymerizable composition 1 Either perform a mold release treatment on the back side of the support with a mold release agent such as a silicone resin, or apply a protective film with a mold release effect, such as a polyethylene film, polypropylene film, or polytetrafluoroethylene film, on the photopolymerizable composition layer. It is best to attach it to

The above-mentioned protective film is also useful for preventing deterioration of the photopolymerizable composition layer over time.

In order to form an image of a predetermined pattern using the image forming material of the present invention, a conventionally known method may be used. That is, first, an I.D.
An image forming material is applied to the surface of the conductive layer of a substrate formed with a conductive layer such as a TO film or an aluminum film, and after peeling off the protective film if it has a protective film, the photopolymerizable composition layer side is on the inside. The layers are laminated by heat-pressure bonding under conditions of usually 90 to 130°C so that the results are as follows. Next, the laminate is exposed to actinic light in a pattern through the original image from the side of the transparent support.

The active light is 200 to 700 nm, preferably 25 nm.
There are ultraviolet rays and visible rays of 0 to 500 nm, and suitable light sources include low pressure, high pressure, and ultra-high pressure mercury lamps, xenon lamps, carbon arc lamps, halogen lamps, germicidal lamps, and the like.

After the above-mentioned exposure, the transparent support is peeled off, and only the non-exposed areas are selected using a known method such as spray method, rocking dipping method, brushing method, scraping method, etc. using an alkaline aqueous solution as a developer. Develop by removing. As a result, a photopolymerizable composition layer cured by exposure is formed on the substrate as a clear image.

The above alkaline aqueous solution used as a developer contains, as an alkaline component, an alkali hydroxide such as a hydroxide of lithium, sodium or potassium, an alkali carbonate such as a carbonate or bicarbonate of lithium, sodium or potassium, and potassium phosphate. Alkali metal phosphates such as or sodium phosphate, alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate are used, and among these, sodium carbonate is particularly preferred.

The concentration of the alkali component in the aqueous solution is about 0.5 to 3% by weight, and if it is higher than this, there is a risk that even the exposed areas will be partially removed, resulting in poor developability. The temperature during development is appropriately adjusted depending on the type of each component of the photopolymerizable composition layer, but is generally about 20 to 30°C.

After forming the image in this manner, a circuit forming process is performed in which the exposed conductor layer is etched away using an etching solution using the cured image as a mask material.

In this process, for example, a hydrochloric acid-nitric acid mixed aqueous solution having a volume ratio of hydrochloric acid:water:nitric acid of 1:1:0.08 is used as an etching solution, and the substrate on which the image has been formed is placed in this solution for 30 minutes.
This can be done by a method of rocking immersion for 0 to 120 seconds.

Alternatively, the same process as above may be performed using a mixed aqueous solution having a volume ratio of phosphoric acid: nitric acid: acetic acid: water of about 20:1:0.5 as the etching solution. Note that instead of the above etching process, a plating layer may be formed on the exposed conductive layer using a known plating solution. In these various circuit forming processing steps, the cured image exhibits sufficient resistance to chemicals such as etching solutions and plating solutions, and fully functions as a mask material.

After this circuit forming process, the cured image is removed with an alkaline aqueous solution that is more alkaline than the developer, for example, a 2 to 7% by weight aqueous sodium hydroxide solution, so that a patterned conductive layer or A circuit board on which a patterned plating layer is precisely formed can be obtained.

〔Effect of the invention〕

As described above, in the present invention, as a photopolymerizable composition layer provided on a transparent support, a combination of the above-mentioned specific film-forming polymeric substance and a specific ethylenically unsaturated polymerizable compound is used. , by further including the specific nonionic surfactant, the developability is improved.

It is possible to obtain an image forming material that highly satisfies various performances such as chemical resistance and removability of the cured image portion after circuit forming treatment. Therefore, this imaging material
It can also be advantageously applied to applications that require precise circuit formation, such as liquid crystal display devices and electrochromic display devices.

〔Example〕

EXAMPLES Below, examples of the present invention will be described in more detail. In addition, in the following, parts mean parts by weight.

Example 1 2,4-diethylthioxanthone 8 parts p
-Dimethylaminobenzoic acid isoamyl ester 3
Part Victoria Pure Blue 0.08 part Hydroquinone 0.04 part The above composition was uniformly dissolved and mixed in ethyl acetate to prepare a photopolymerizable composition solution having a solid content concentration of 40% by weight. This solution,
Coated with an applicator onto a 25μ thick transparent polyethylene terephthalate film as a transparent support,
A photopolymerizable composition layer having a thickness of about 25 μm was formed by heating and drying at 0° C. for 5 minutes, and was used as an image forming material of the present invention. Next, this image forming material was used as an insulating base to a thickness of 125 μm 200A thick indium oxide as a conductor layer on a transparent polyethylene terephthalate film.
On the surface of the conductive layer of a substrate made of a 500Ω/d type transparent conductive film formed with a tin oxide composite film, the photopolymerizable composition layer was placed on the inside at 90°C. They were laminated by heat and pressure bonding.

A negative original is brought into close contact with the surface of the transparent support of this laminate,
This manuscript was exposed to light for 20 seconds at a distance of 60 meters from the light source using a 3Kl ultra-high pressure mercury lamp.

After that, the transparent support was peeled off and developed by immersion in a 1% by weight sodium carbonate (Na2CO3) aqueous solution at 25°C for 3 minutes with rocking, resulting in a clear image with a line width resolution of up to 75μ. was gotten.

The substrate with this cured image is then treated with phosphoric acid: nitric acid:
It was immersed for 30 seconds in an etching solution consisting of a mixed aqueous solution with a volume ratio of acetic acid:water of 20:1:0.5, and the exposed conductor layer was etched away using the cured image as a mask material.

After that, it was washed with water for 10 minutes, and then heated and dried in a hot air dryer at 100°C. During this etching and water washing process, the cured image did not peel off and showed very good resistance.

Finally, the cured image is removed by treatment with a 3% by weight aqueous sodium hydroxide solution, and further washed with water and dried.
Resolution 75 with patterned conductor layer on insulating base
A μ circuit board was obtained. The removability of the cured image at this time was good and could be easily and completely removed using the aqueous solution.

Comparative Example 1 A photopolymerizable composition solution was prepared in the same manner as in Example 1, except that 13 parts of nonylphenyl polyoxyethylene ether was not used, and an image was formed in the same manner as in Example 1 using this solution. I got the material.

Using this image forming material, image formation and circuit formation were carried out in the same manner as in Example 1. The solubility was poor, and even after development with an alkaline aqueous solution and washing with water, the polymerizable compound remained in non-exposed areas. Furthermore, for this reason, the conductive layer in non-exposed portions could not be completely etched away in the etching process, making it impossible to form a desired circuit.

Example 2 2,4-diethylthioxanthone 8 parts p
-Dimethylaminobenzoic acid isoamyl ester 3
Part Victoria Pure Blue o, os
sHydroquinone 0.04 parts A photopolymerizable composition solution was prepared in the same manner as in Example 1 using the above composition, and an image forming material was obtained in the same manner as in Example 1 using this solution. Using this, circuit formation was attempted in the same manner as in Example 1. As a result, at the development stage, the line width was 751
It is possible to form clear images with a resolution of up to Tln, and the cured image shows good resistance without peeling during the etching process for circuit formation and the subsequent water washing process, resulting in a clear pattern on the insulating base. It was possible to obtain a circuit board having a conductive layer.

Comparative Example 2 As a nonionic surfactant, nonylphenyl polyoxyethylene ether [R,=nonyl group in formula (II),
A photopolymerizable composition solution was prepared in the same manner as in Example 2, except that 5 parts (n=5) was used, and an image forming material was obtained in the same manner as in Example 1 using this solution.

Using this image forming material, image formation and circuit formation were carried out in the same manner as in Example 1. The solubility was poor, and even after development with an alkaline aqueous solution and washing with water, the polymerizable compound remained in non-exposed areas. Furthermore, for this reason, the conductive layer in non-exposed portions could not be completely etched away in the etching process, making it impossible to form a desired circuit.

Example 3 2,4-diethylthioxanthone 8 parts p
-Dimethinogeminobenzoic acid isoamyl ester 3
Part Victoria Pure Blue 〇, OS
Part Hydroquinone 0.04 part Using the above composition, a photopolymerizable composition solution was prepared in the same manner as in Example 1, and using this solution, an image forming material was obtained in the same manner as in Example 1. Using this, circuit formation was attempted in the same manner as in Example 1. As a result, it is possible to form a clear image with a resolution of up to 50 μm in line width in the development stage, and the cured image shows good resistance without peeling during the etching process for circuit formation and the subsequent water washing process, and the final It was possible to obtain a circuit board with a sharply patterned conductive layer on an insulating base.

Comparative Example 3 As a nonionic surfactant, nonylphenyl polyoxyether [R in formula (IIl, = nonyl group, n = 15
A photopolymerizable composition solution was prepared in the same manner as in Example 3, except that 14 parts was used, and an image forming material was obtained in the same manner as in Example 1 using this solution.

An attempt was made to form an image using this image forming material in the same manner as in Example 1, but when washing with water after development with an alkaline aqueous solution, the cured image washed away after about 15 minutes.
A desired image could not be formed.

Example 4 As an ethylenically unsaturated polymerizable compound, 2,2-bis(
4-Acryloxypolypropoxytetrabromophenyl)propane [R in formula (I), R2=CH3 group, R
3~R6=Br, YHY2=acryloyl group, l+m
A photopolymerizable composition solution was prepared in the same manner as in Example 1 except that 83,100 parts was used, and an image forming material was obtained in the same manner as in Example 1 using this solution. Circuit formation was attempted in the same manner as in Example 1. As a result, a clear image with a resolution of up to 75/'1 line width can be formed during the development stage, and the cured image will not peel off during the etching process for circuit formation and the subsequent water washing process, and has good durability. Finally, a circuit board with a sharply patterned conductive layer on an insulating base could be obtained.

Claims (7)

[Claims] (1) An image forming material comprising a layer of a photopolymerizable composition containing a film-forming polymer substance, an ethylenically unsaturated polymerizable compound, and a photopolymerization initiator on a transparent support, which has the film-forming properties described above. The polymeric substance contains a linear polymer containing a carboxyl group, and the above ethylenically unsaturated polymerizable compound has the following formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) [ In the formula, R_1 and R_2 are hydrogen or methyl groups, respectively, and X is the following formula; ▲ There are mathematical formulas, chemical formulas, tables, etc. (meth)acryloyl group, l
, m is an integer such that l + m = 8 to 40], and the photopolymerizable composition layer has the following formula (II): ▲Mathematical formula, chemical formula, table, etc.▼・...(II) (In the formula, R_7 is an alkyl group having 8 to 12 carbon atoms, and n is 8
An image forming material characterized by containing a nonionic surfactant represented by: (2) Claim No. 1 in which the carboxyl group-containing linear polymer is a styrene-maleic acid half ester copolymer (
The image forming material described in section 1). (3) Carboxyl group-containing linear polymer has an acid value of 50 to 3
00, and a weight average molecular weight of 5,000 to 300,000. (4) Claims in which the ethylenically unsaturated polymerizable compound includes, in addition to the compound represented by formula (I), polyester (meth)acrylate synthesized from (meth)acrylic acid, polyhydric alcohol, and polybasic acid. Parts (1) to (3)
) The image-forming material according to any one of the items. (5) Any one of claims (1) to (4) in which the ethylenically unsaturated polymerizable compound is present in a proportion of 10 to 300 parts by weight per 100 parts by weight of the film-forming polymeric substance. Imaging materials as described. (6) The nonionic surfactant represented by formula (II) is 1 to 1 parts by weight per 100 parts by weight of the ethylenically unsaturated polymerizable compound.
Claims Nos. (1) to (20 parts by weight)
The image forming material according to any of item 5). (7) Photopolymerization initiator is ethylenically unsaturated polymerizable compound 1
The image forming material according to any one of claims (1) to (6), wherein the image forming material is in a proportion of 0.5 to 20 parts by weight per 0.00 parts by weight.