JPH07292012A - Preparation of photosensitive resin composition - Google Patents

Abstract

PURPOSE: To obtain a method for preparing a photosensitive resin composition in the form of an aqueous solution or an aqueous dispersion free of an organic solvent which is developable with a diluted alkali aqueous solution.

CONSTITUTION: A method for preparing a photosensitive resin composition developable with a diluted alkali solution and having, as the essential components, (a) an aqueous emulsion of a polymeric compound having an acid value of 80-250 mg-KOH/g, a glass transition temperature of 50-200°C and at least one carboxyl group per molecule; (b) a compound having at least one ethylenically unsaturated bond per molecule; and (c) a photopolymerization catalyst which generates free radicals by actinic light irradiation and component (b) being absorbed in component (a) comprises adding component (b) and a surfactant to component (a) in the absence of organic solvent and stirring the mixture to allow the particles of component (a) to absorb component (b) therein.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a photosensitive resin composition containing no organic solvent. More specifically, the present invention relates to a method for producing a photosensitive resin composition in the form of an aqueous solution or an aqueous dispersion, which enables development processing with a dilute alkaline aqueous solution.

[0002]

2. Description of the Related Art Photosensitive resin solutions and films are used as resist materials for chemical and electrochemical processing of base materials such as etching and plating in the fields of printed circuit board manufacturing, precision processing of metals and the like. It is widely used. Conventional photosensitive resin is an organic solvent solution,
Most are processed into a film from an organic solvent solution. In the developing step after exposure, an organic solvent has been mainly used as a developing solution in the past, but in recent years, a dilute alkaline aqueous solution has been used as a developing solution in view of environmental problems, health problems and the like. However, even if the developing solution is replaced with an aqueous solution, volatilization of the organic solvent is inevitable during application of the resist, drying, or processing into a film, which causes air pollution and health problems.

In order to solve such a problem, JP-A-54-91585 proposes a photosensitive resin composition comprising a water-dispersible latex and a water-soluble or water-dispersible unsaturated compound. However, the composition using a water-soluble, dispersible unsaturated compound has high hydrophilicity, so etching,
There is a possibility that problems may occur in the characteristics when processing with an aqueous system such as plating. Therefore, it is desirable to add a water-insoluble unsaturated compound, but it was difficult to stably mix the water-insoluble unsaturated compound with the water-dispersible latex.

Further, in US Pat. No. 5,045,435, a part of the acid of a water-insoluble carboxylated (meth) acrylate latex having an acid value of 80 or more is neutralized with amines, inorganic alkali, etc., The composition is stabilized and the rheology during coating is adjusted. According to such a method, although a stable composition can be obtained, problems such as bad odor during work due to volatilization of amines and contamination of electronic devices with inorganic alkali cannot be avoided.

[0005]

It is an object of the present invention to solve the above-mentioned problems, to cause no problem of organic solvent scattering because the resist solution is an aqueous solution, and to stably mix a water-insoluble unsaturated compound. And a method for preparing a photosensitive resin composition having high etching resistance and plating properties.

[0006]

DETAILED DESCRIPTION OF THE INVENTION Here, the present inventors have added a compound having at least one ethylenically unsaturated bond in one molecule and a surfactant to an aqueous emulsion of a polymer compound for curing. It was later found that it becomes possible to stably mix a water-insoluble unsaturated compound capable of exhibiting excellent properties into an aqueous emulsion. Further, the present inventors have found that in an aqueous emulsion of a polymer compound having an acid value of 80 to 250 mg-KOH / g and a glass transition temperature of 50 to 200 ° C. and having at least one carboxyl group in one molecule. When a compound having at least one ethylenically unsaturated bond in the molecule (hereinafter referred to as “unsaturated compound”) and a surfactant are added, the unsaturated compound is first dispersed in water by the surfactant, By adding this water-dispersed unsaturated compound to an aqueous emulsion of a polymer compound,
It has been found that a stable emulsion is formed by being absorbed in an aqueous emulsion particle of a polymer compound having at least one carboxyl group in one molecule, and exhibits excellent film forming property. The present invention has been completed based on these findings.

That is, in one aspect of the present invention, (a) an acid value of 80 to 250 mg-KOH / g and 50 to
(B) an aqueous emulsion of a polymer compound having a glass transition temperature of 200 ° C. and having at least one carboxyl group in one molecule; (b) a compound having at least one ethylenically unsaturated bond in one molecule; and c) a photopolymerization initiator capable of generating a free radical upon irradiation with active light; as an essential component, at least 1 in each molecule in the particles of the aqueous emulsion (a) of the polymer compound.
A method for preparing a developable photosensitive resin composition using a dilute alkaline solution, wherein the compound (b) having a number of ethylenically unsaturated bonds is absorbed.
An aqueous emulsion (a) of the polymer compound, which comprises the compound (b) having at least one ethylenically unsaturated bond in one molecule and a surfactant in the absence of an organic solvent.
A compound (b) having at least one ethylenically unsaturated bond in one molecule is absorbed into the particles of the aqueous emulsion (a) of the polymer compound by adding and stirring the mixture thereinto. It is about how to do it.

[0008] In another aspect, the present invention provides (a) an acid value of 80 to 250 mg-KOH / g and 50 to 2
An aqueous emulsion of a polymer having a glass transition temperature of 00 ° C. and having at least one carboxyl group in one molecule; (b) a compound having at least one ethylenically unsaturated bond in one molecule; c) a photopolymerization initiator capable of generating a free radical upon irradiation with active light; as an essential component, at least 1 in each molecule in the particles of the aqueous emulsion (a) of the polymer compound.
A method for preparing a developable photosensitive resin composition using a dilute alkaline solution, wherein the compound (b) having a number of ethylenically unsaturated bonds is absorbed.
A compound (b) having at least one ethylenically unsaturated bond in one molecule and a surfactant are added to water to prepare an aqueous dispersion, and the aqueous dispersion is prepared in the absence of an organic solvent. A compound having at least one ethylenically unsaturated bond in one molecule in the particles of the aqueous emulsion (a) of the polymer compound, by adding and stirring in the aqueous emulsion (a) of the polymer compound. It relates to a method characterized by absorbing (b).

The polymer compound having at least one carboxyl group in one molecule used as the component (a) in the composition of the present invention is solubilized, dispersed, suspended or emulsified in water to give an aqueous emulsion. That is, a high molecular compound having at least one carboxyl group in one molecule is dissolved in water using a surfactant called an emulsifier.
It is also possible to disperse, suspend, or emulsify, but in order to obtain a more stable aqueous resin composition solution, a monomer having at least one carboxyl group and at least one double bond in the molecule is used. It is preferable to prepare an aqueous emulsion of a polymer compound prepared by polymerizing a body and a monomer copolymerizable therewith by a method such as emulsion polymerization or suspension polymerization.

A monomer having at least one carboxyl group and at least one double bond in the molecule used for such purpose, that is, for preparing the component (a) in the composition of the present invention. Examples of the body include acrylic acid, methacrylic acid, maleic acid, itaconic acid, crotonic acid, cinnamic acid and the like. You may use these monomers in mixture of 2 or more types.

These monomers have a carboxyl group content of 1.43 mm per 1 g of the polymer compound having at least one carboxyl group in one molecule produced.
It is desirable to use it in such an amount that the ol to 4.46 mmol.

In addition, another monomer copolymerizable with the monomer having at least one carboxyl group and at least one double bond in the molecule, which is used in the preparation of the component (a) of the composition of the present invention, can be used. As the monomer, methyl acrylate,
Use of acrylic acid ester such as ethyl acrylate, methacrylic acid ester such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, etc., and known polymerizable monomer such as styrene, vinyltoluene, acrylamide, acrylonitrile, butadiene, etc. Is possible.

Polymerization methods such as emulsion polymerization and suspension polymerization in the preparation of the component (a) of the composition of the present invention are carried out by known methods and conditions. That is, a monomer having at least one or more carboxyl group and at least one double bond in one molecule and another monomer are converted into an alkyl sulfonate, an alkylbenzene sulfonate, an alkyl diphenyl ether disulfonate. , Naphthalene sulfonic acid formalin condensate, anionic surfactants such as polyoxyethylene alkyl ether sulphate, nonionic surfactants such as polyethylene glycol ether, polyoxyethylene sorbitan ester, etc. The polymerization reaction is carried out using a water-soluble polymerization initiator such as potassium sulfate, hydrogen peroxide, ammonium persulfate. During the reaction, known additives may be added to the solution after the reaction in order to enhance the stability. In order to control the molecular weight of the polymer, it is preferable to use a known chain transfer agent such as 1-dodecanethiol and 3-dodecanethiol.

The acid value of the polymer compound having at least one carboxyl group in one molecule obtained by the above method is preferably 80 to 250 mg / g. When the acid value is less than 80 mg / g, it is difficult to carry out development processing using a dilute aqueous alkali solution, while 250 m
If it is larger than g / g, water resistance as a resist film,
Characteristics such as etching resistance are impaired.

The glass transition temperature of the polymer compound having at least one carboxyl group in one molecule obtained by the above method is preferably 50 to 200 ° C. If the glass transition temperature is lower than 50 ° C., it remains tacky even after being applied as a resist solution to a substrate and dried, which is inconvenient when the negative mask is closely contacted and exposed. Further, if the glass transition temperature exceeds 200 ° C., it is difficult to obtain a uniform film after coating the resist solution on the substrate and drying.

The particle size of the particles of the aqueous emulsion of the polymer compound having at least one carboxyl group in one molecule obtained by the above method is preferably in the range of 0.02 to 0.3 μm. . In order to absorb the unsaturated compound into the seed particles by the seed polymerization method or the like, it is common to use an organic solvent such as acetone together, but with this method, the acetone has to be removed later, The work is complicated. However, if the particle size of the particles of the aqueous emulsion of the polymer compound having at least one carboxyl group in one molecule of the present invention is within the range of 0.02 to 0.3 μm, an auxiliary agent such as an organic solvent is used. Unsaturated compounds can be absorbed into the emulsion particles without the need to use.

An unsaturated compound which is the component (b) of the present invention,
That is, as a compound having at least one ethylenically unsaturated bond in the molecule, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,
N-vinylpyrrolidone, acroylmorpholine, methoxytetraethylene glycol acrylate, methoxypolyethylene glycol acrylate, polyethylene glycol diacrylate, N, N-dimethylacrylamide, N-methylolacrylamide, N, N-dimethylaminopropylacrylamide, N, N- Dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, melamine acrylate, or methacrylates corresponding to the above acrylates, diethylene glycol diacrylate, triethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, phenoxyethyl Acrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, trimethylolpropane triacrylate, glycerin diglycidyl ether diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, pentaerythritol hexaacrylate, isoborneolyl acrylate, cyclopentadiene Mention may be made of mono- or diacrylates and methacrylates corresponding to the above acrylates.

The component (c) of the composition of the present invention, that is, a photopolymerization initiator capable of generating a free radical upon irradiation with actinic light, includes 2-ethylanthraquinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1,2. -Quinones such as benzanthraquinone, benzoin,
Α-Ketaldonyl alcohols such as pivaloin and acyloin ether, and ethers, ketones such as α-phenylbenzoin, α, α′-diethoxyacetophenone, benzophenone and 4,4′-bisdialkylaminobenzophenone Or thioxanthone derivative, 2,4
The 5-triarylimidazolyl dimer can be mentioned. These may be used alone or in combination of two or more.

A known polymerization inhibitor may be added to the photosensitive resin composition of the present invention in order to prevent thermal polymerization during storage. Examples of these inhibitors include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tertiary butyl catechol, and phenothiazine. In the photosensitive resin composition of the present invention, if necessary, known fillers such as barium sulfate, silicon oxide, talc, clay and calcium carbonate, known conventional colorants such as phthalocyanine green, titanium oxide and carbon black. , Leveling agent, adhesion improver, thixotropic agent,
Fillers and the like can be added.

The photosensitive resin composition according to the present invention is prepared by using a compound having at least one ethylenically unsaturated bond in one molecule as described above and a surfactant.
80-250 m prepared by the method as shown above
An unsaturated compound is added to an aqueous emulsion of a polymer compound having an acid value of g-KOH / g and a glass transition temperature of 50 to 200 ° C. and having at least one carboxyl group in one molecule, and stirred to form an unsaturated compound in the emulsion. It is carried out by dispersing in. It should be noted here that it is necessary to add a new surfactant together with the unsaturated compound. As explained above, the surfactant is also used in the preparation of the aqueous emulsion of the polymer compound, and therefore it is considered that the surfactant used in the preparation of the polymer compound remains in the aqueous emulsion. To be
However, since most of these surfactants are adsorbed on the surface of the aqueous emulsion particles,
It is considered to be ineffective for dispersing the unsaturated compounds newly added to the system. Further, even if an excessive amount of surfactant is used when preparing an aqueous emulsion of a polymer compound, in this case, the size of the emulsion particles becomes smaller, the number of particles increases, and the surface area of the entire particles increases. In addition, the surfactant does not remain excessively in the produced aqueous emulsion, and a surfactant for dispersing the unsaturated compound must be newly added to the system.

As the surfactant to be added to the aqueous emulsion together with the unsaturated compound, any of known anionic, cationic and nonionic surfactants may be used, which were used when preparing the aqueous emulsion of the polymer compound. The same surfactant may be used, or different surfactants may be used. These surfactants may be used alone or as a mixture of two or more kinds. The amount of the surfactant added is 0.1 based on the amount of the unsaturated compound added.
It may be in the range of 15% by weight to 15% by weight, and 1% by weight to
6% by weight is more preferred. When the amount of the surfactant is less than the above range, the dispersion stability is insufficient, and when it exceeds the above range, the water resistance of the final resist film is adversely affected.

The surfactant may be first dissolved in the unsaturated compound and then added to the aqueous emulsion, or the surfactant for dispersing the unsaturated compound may be added first to the aqueous emulsion of the polymer compound. You may dissolve in it and may add an unsaturated compound to this. Alternatively, the surfactant may be added to the aqueous emulsion at the same time as the unsaturated compound.

After the unsaturated compound and the surfactant have been added to the aqueous emulsion as described above, the mixture is vigorously stirred (however, it is not necessary to stir the mixture at a high shearing force that causes destruction of the aqueous emulsion particles). No), it is necessary to disperse the unsaturated compound in the aqueous emulsion and keep the dispersion until the unsaturated compound is completely absorbed by the aqueous emulsion particles. Usually, the time required to absorb the unsaturated compound into the aqueous emulsion particles varies depending on the aqueous emulsion used, but is 5 minutes to 1 day at room temperature and 50 ° C to 50 ° C.
It can be achieved in a few minutes at a temperature of about 100 ° C.

When the photopolymerization initiator is solid, it is convenient to dissolve it in an unsaturated compound in advance and then to make it into a water dispersion state together with a surfactant. When the photopolymerization initiator is a liquid, it can be added to the system at any stage of the preparation of the photosensitive resin composition. For example, pre-added in unsaturated compound; added in aqueous emulsion with unsaturated compound and surfactant; made into water dispersion state with unsaturated compound and surfactant; water dispersion of unsaturated compound and surfactant And the like are possible. The amount of the photopolymerization initiator is selected within the range of 0.5 to 15% by weight, preferably 1 to 10% by weight, based on the weight of the total solid content of the resin composition.

The amount of the ethylenically unsaturated compound in the resin composition of the present invention is preferably 5 to 65% by weight of the solid content in the aqueous emulsion of the polymer compound. If it is below this range, it is difficult to obtain a uniform coating film after drying, and if it exceeds this range, there is stickiness after drying, and the coating film becomes unsuitable for exposing a negative mask in close contact.

Further, in the second aspect of the present invention, the method of the present invention comprises homogenizing an unsaturated compound having at least one ethylenically unsaturated bond in one molecule in water in which a surfactant is dissolved. After dispersing using ultrasonic waves, etc., at least one carboxyl group in one molecule having an acid value of 80 to 250 mg-KOH / g and a glass transition temperature of 50 to 200 ° C. And a step of adding the polymer compound to an aqueous emulsion.

As the surfactant used for dispersing the unsaturated compound in the second aspect, the same kind as that used in the first aspect can be used in the same concentration as described above. The unsaturated compound is dispersed by previously dissolving the surfactant in water at a concentration of 0.1 to 15% by weight of the unsaturated compound to be added, and then adding the unsaturated compound. The ratio (weight ratio) of water / unsaturated compound used is water / unsaturated compound = 5/95 to 95/5.
It is selected in the range of.

Further, in such an embodiment, it is convenient that the photopolymerization initiator is previously dissolved in the unsaturated compound before the unsaturated compound is dispersed in water. The amount of the photopolymerization initiator is 0.5 with respect to the total solid content of the resin composition.
To 15% by weight.

The unsaturated compound dispersed in water using a surfactant as described above is added in an amount of 80 to 250 mg-KOH / g.
With an acid value of and a glass transition temperature of 50-200 ° C.,
The photosensitive resin composition of the present invention can be more easily prepared by adding it to an aqueous emulsion of a polymer compound having at least one carboxyl group in one molecule.

The advantages of the preparation method in which the unsaturated compound is previously dispersed in water in which a surfactant is dissolved by using a homogenizer, ultrasonic waves, etc. and then added to an aqueous emulsion of a polymer compound are as follows. Is mentioned.

(1) Since the unsaturated compound can be absorbed in the aqueous emulsion particles without stirring or after gentle mixing after mixing the unsaturated compound dispersion and the aqueous emulsion of the polymer compound. , Can minimize disruption of the aqueous emulsion.

(2) Since the unsaturated compound is dispersed separately from the aqueous emulsion, it can be dispersed quickly and efficiently by a homogenizer having a high shearing force.

(3) Absorption efficiency is high, and absorption can be performed in a shorter time.

The aqueous solution of the photosensitive resin composition obtained as described above did not produce a precipitate or the like even after being left for several weeks or longer.

[0035]

According to the method for preparing a photosensitive resin composition of the present invention, since no organic solvent is used, the problem of organic solvent scattering does not occur at all, and high etching resistance,
A water-insoluble unsaturated compound that imparts a plating property to the composition can be stably mixed.

[0036]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto.

(Synthesis Example 1) (Preparation of Emulsion Polymer Aqueous Emulsion "EM01") The components used in this Synthesis Example and the amount ratio of each component are shown in the following table. A 500 ml separable flask equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was charged with a surfactant, polyethylene glycol nonylphenyl ether, sodium dodecylbenzenesulfonate and deionized water, and the temperature of the flask was raised to 75 ° C. Raised. A monomer mixture was prepared by mixing methyl methacrylate, butyl acrylate, methacrylic acid and 1-dodecanethiol. A portion (10% by weight) of this monomer mixture was added to the flask and dispersed. Next, ammonium persulfate (A
A solution of 0.2 g of PS) in 6 g of deionized water was added. The remaining portion of the monomer mixture was added dropwise from the dropping funnel over about 2 hours. After completion of the dropping, the reaction was continued for another 2 hours at the same temperature to obtain a translucent aqueous emulsion solution. This aqueous emulsion solution is referred to as "EM01".

Ingredients Parts by weight Monomer 100.0 (breakdown) Methyl methacrylate (71.0) Butyl acrylate (9.0) Methacrylic acid (20.0) 1-Dodecanethiol (chain transfer agent) 0.1 Polyethylene glycol nonyl phenyl ether (surfactant) (Kao, Emulgen 920) 2.0 Sodium dodecylbenzene sulfonate 2.0 Deionized water 390.0 APS (ammonium persulfate) (initiator) 0.2 Deionized water for dissolving APS 6.0 (Synthesis examples 2 to 6) (Emulsion polymer aqueous emulsion EM02, 03, 04,
Preparation of 05 and 06) In the same manner as in Synthesis Example 1, by changing the ratio of methacrylic acid (or acrylic acid), the acid value (A.V.) was different, and the ratio of butyl acrylate was changed. Various aqueous emulsions with different Tg were prepared in the solid content range of 25% to 40% by weight. The results are summarized in the table below.

(Synthesis example 7) Aqueous emulsion E was prepared in the same manner as in synthesis example 1 except that a double amount of surfactant was used.
M01 'was prepared.

Composition weight ratio of monomer Solid content Acid value Tg External appearance Particle size (wt%) (℃) (μm) EM01 MMA / BA / MAA = 71/9/20 25 130 100 White translucent 0.054 EM02 MMA / BA / MAA = 58/12/30 25 196 100 White translucent 0.060 EM03 MMA / BA / MAA = 41.3 / 28.7 / 30 25 196 70 White translucent 0.038 EM04 MMA / BA / AA = 71/9/20 25 156 82 White translucent 0.071 EM05 MMA / BA / MAA = 65.5 / 10 / 24.5 40 160 100 White translucent 0.045 EM06 MMA / AA = 80/20 25 156 105 White translucent 0.181 EM01 'MMA / BA / MAA = 71/9 / 20 25 130 100 White translucent- * MMA: Methyl methacrylate, BA: Butyl acrylate, MAA: Methacrylic acid, AA: Acrylic acid, * Measurement (Synthesis example 8) (Dispersion solution of unsaturated compound (M1) Preparation) Part I was prepared by dissolving Irgacure 651 and butylhydroxytoluene in ethoxylated trimethylolpropane triacrylate at the ratio shown in the table below at 50 ° C. Separately, Part B was prepared by dissolving two types of surfactants and defoamers shown in the table below in deionized water. Next, mix Part A1 and Part B, and using a homogenizer,
The mixture was stirred at 8,000 rpm for 1 minute to obtain a milky white dispersion liquid. This dispersion is referred to as "M1".

Dispersion M1 of compound having at least one ethylenically unsaturated bond in one molecule (Synthesis example 8)Parts by weight Part A1 Ethoxylated trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd. A-TMPT-3EO) 50.0 2,2-dimethoxy-2-phenylacetophenone [Photoinitiator (Ciba Geigy, IRGACURE 651)] 7.1 Butylhydroxytoluene (Polymerization Inhibitor) 0.1Part B Deionized water 40.7 Polyethylene glycol nonyl phenyl ether (Emulgen 920, Kao Corporation) 1.0 Sodium dodecylbenzene sulfonate 1.0Silicone defoamer, TSA750S (Toshiba Silicone Co., Ltd.) 0.1  (Synthesis Examples 9 to 11) (Preparation of dispersion solution of unsaturated compound (M2 to M4))
Change the A1 into parts A2 to A4 shown in the table below,
With Part B as it is,
Saturated compound dispersions (M2), (M3) and (M4)
Prepared. M2 and M3 were milky white. M4 is a little yellow
It had a milky white color.

Dispersion M2 of compound having at least one ethylenically unsaturated bond in one molecule (Synthesis example 9)Parts by weight Part A2 Trimethylolpropane triacrylate (Shin-Nakamura Chemical Co., Ltd. A-TMPT) 50.0 2,2-dimethoxy-2-phenylacetophenone [Photoinitiator (Ciba Geigy, Irgacure 651)] 7.1Butyl hydroxytoluene (polymerization inhibitor) 0.1  Dispersion M3 of compound having at least one ethylenically unsaturated bond in one molecule (Synthesis example 10)Parts by weight Part A3 Propoxylated trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd. A-TMPT-3P0) 50.0 2,2-dimethoxy-2-phenylacetophenone [photoinitiator (Ciba Geigy, Irgacure 651)] 7.1Butyl hydroxytoluene (polymerization inhibitor) 0.1  Dispersion M4 of compound having at least one ethylenically unsaturated bond in one molecule (Synthesis Example 11)Parts by weight Part A4 Ethoxylated trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd. A-TMPT-3EO) 50.0 2-Methyl- [4- (methylthio) phenyl] -2-morpholine-1-propanone [Photoinitiator (Ciba Geigy, Irgacure 907)] 7.1 Diethylthioxanthone (photosensitizer) 2.4Butyl hydroxytoluene (polymerization inhibitor) 0.1  (Example 1) 200 g of an aqueous emulsion EM01 (white
(Translucent color) has at least one ethylenic group in one molecule.
54 g of a dispersion liquid (M1) of a compound having a saturated bond was added.
After stirring lightly, the mixture was left at each temperature shown in Table 1.
It was milky immediately after mixing, but after standing at room temperature for 30 minutes
The dispersion (M1) of the unsaturated compound is emulsion particles.
Completely absorbed by the same as the original aqueous emulsion
It became white and translucent. This solution does not undergo phase separation
No, it was stable for a long time.

Next, this solution was coated on a copper-clad substrate so that the thickness after drying was about 15 μm, and 8
It was dried in an oven at 0 ° C. for 5 minutes to obtain a transparent and uniform film. 200mJ / c through a negative mask on this substrate
It was irradiated with m ² of ultraviolet rays. After that, 1% sodium carbonate aqueous solution was sprayed for 30 seconds to develop,
An image having a line and space pattern of μm / 50 μm was obtained.

Example 2 Aqueous emulsion EM01
In addition, a dispersion M4 of a compound having at least one ethylenically unsaturated bond in one molecule is mixed in a weight ratio of solids thereof of 65/35, and the mixture is placed in an oven at 70 ° C. The dispersion of the compound was absorbed into emulsion particles. After about 5 minutes, the dispersion of the unsaturated compound was completely absorbed by the aqueous emulsion particles and became white and translucent, similar to the original aqueous emulsion. This solution was treated in the same manner as in Example 1 to give 50 μm / 50 μm.
An image having a line and space pattern of m was obtained.

(Example 3) EM as an aqueous emulsion
A solution in which a dispersion liquid M4 of a compound having at least one ethylenically unsaturated bond in one molecule was absorbed by emulsion particles was obtained in the same manner as in Example 2 except that 05 was used. This solution was treated in the same manner as in Example 1 to give 50
An image having a line and space pattern of μm / 50 μm was obtained.

(Example 4) To 200 g of the aqueous emulsion EM01, 0.54 g of polyethylene glycol nonylphenyl ether and 0.54 g of sodium dodecylbenzene sulfonate as surfactants were added, and 31 g of Part A1 in Synthesis Example 1 was further added. The unsaturated compound was dispersed by stirring. Then, while stirring at room temperature for 30 minutes, the unsaturated compound was absorbed into emulsion particles of a polymer compound having at least one carboxyl group in one molecule to obtain a translucent solution. By the same method as in Example 1, an image having a line and space pattern of 50 μm / 50 μm was obtained.

(Comparative Example 1) To 200 g of an aqueous emulsion EM01, 31 g of Part A1 in Synthesis Example 1 was added, and the mixture was vigorously stirred and left to stand. The compound having at least one ethylenically unsaturated bond in one molecule was not absorbed by the emulsion particles, and phase separation occurred after a few minutes, so that coating could not be performed.

Comparative Example 2 200 g of an aqueous emulsion EM01 ′ (Synthetic Example 7) synthesized in the same manner as in Synthetic Example 1 except that the surfactant was used in an amount twice that of the aqueous emulsion EM01 was used. 31g of Part A1 in
In addition, the mixture was vigorously stirred and then left to stand. The compound having at least one ethylenically unsaturated bond in one molecule was not absorbed by the emulsion particles and phase separated after a few minutes,
Could not be coated.

[0049]

[Table 1] (Examples 5 to 12) In the same manner as in Example 1, various aqueous emulsions and dispersions of unsaturated compounds were mixed at different ratios as shown in Table 2. Immediately after mixing, it became milky white, but within 20 minutes after standing at 25 ° C., the dispersion of the unsaturated compound was completely absorbed by the emulsion particles, resulting in a white translucent color similar to the original aqueous emulsion. became. This solution is coated on a copper-clad substrate and the temperature is 80 ° C.
And dried for 5 minutes. A transparent, uniform coating was obtained on the substrate. The results are shown in Table 2.

[0050]

[Table 2]

Claims (2)

[Claims] 1. (a) An aqueous emulsion of a polymer compound having an acid value of 80 to 250 mg-KOH / g and a glass transition temperature of 50 to 200 ° C. and having at least one carboxyl group in one molecule; b) a compound having at least one ethylenically unsaturated bond in one molecule; and (c) a photopolymerization initiator capable of generating a free radical upon irradiation with active light; At least 1 in each molecule in the particles of the aqueous emulsion (a).
A method for preparing a developable photosensitive resin composition using a dilute alkaline solution, wherein the compound (b) having one ethylenically unsaturated bond is absorbed. In the absence of an organic solvent, a compound (b) having at least one ethylenically unsaturated bond, and an aqueous emulsion of the polymer compound (a) in the absence of an organic solvent.
A compound (b) having at least one ethylenically unsaturated bond in one molecule is absorbed into the particles of the aqueous emulsion (a) of the polymer compound by adding and stirring the mixture thereinto. how to. 2. (a) An aqueous emulsion of a polymer compound having an acid value of 80 to 250 mg-KOH / g and a glass transition temperature of 50 to 200 ° C. and having at least one carboxyl group in one molecule; b) a compound having at least one ethylenically unsaturated bond in one molecule; and (c) a photopolymerization initiator capable of generating a free radical upon irradiation with active light; At least 1 in each molecule in the particles of the aqueous emulsion (a).
A method for preparing a developable photosensitive resin composition using a dilute alkaline solution, wherein the compound (b) having one ethylenically unsaturated bond is absorbed. To at least one ethylenically unsaturated bond-containing compound (b) and a surfactant in water to prepare an aqueous dispersion, and the aqueous dispersion is prepared in the absence of an organic solvent. The compound (b) having at least one ethylenically unsaturated bond in one molecule is added to the particles of the aqueous emulsion (a) of the polymer compound by adding to the aqueous emulsion (a) and stirring. A method characterized by absorption.