JPH07238122A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin compsn. which is water-sol. and becomes water-resistant when cured by light exposure by attaching specific photoreactive side chains to a water-sol. chain polymer having groups derived from acryloylmorpholine. CONSTITUTION:A copolymer is prepared by copolymerizing 20-90 pts. acryloymorpholine, 5-40 pts. monomer having a terminal carboxyl or epoxy group and copolymerizable with acryloylmorpholine, and 5-40 pts. other copolymerizable monomer in a solvent mainly comprising water. Theme the polymer reaction of carboxyl groups of the side chains of the copolymer with glycidyl (meth)acrylate or of epoxy groups of the side chains of the copolymer with (meth)acrylic acid is conducted to convert at least a part of the carboxyl or epoxy groups into epoxy ester groups, giving a copolymer having (meth) acryloyl groups introduced into side chains. Thus obtd. copolymer is used as the main component of the title compsn.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition, and more specifically, it has a polyacryloylmorpholine structure in the main polymer portion of the main component resin and has an epoxy ester-bonded acryloyl group in the side chain portion. Alternatively, the present invention relates to a photosensitive resin composition which is soluble in an aqueous solvent having a methacryloyl group, and can be easily washed and removed with water only in an unexposed area during photocuring, and an exposed area becomes insoluble.

[0002]

2. Description of the Related Art Photosensitive resins have been widely used in a wide range of fields, along with the development of metal working industry, electronics industry, printing industry, paint / ink industry and the like. The main applications are (a) copper-clad laminate by partial etching of metal, creation of precise electronic circuits such as LSI,
(B) Preparation of plate for resin printing, (c) Ink for screen printing. Therefore, the modification of the photosensitive resin composition is naturally required in view of the final purpose of use, conditions, simplification of the process on the side of the creator, environmental consideration, and the like. At present, various types of photosensitive resins with different characteristics are on the market and on the market.
The following steps are used when a circuit is formed using a partial etching solution such as a metal foil using these photosensitive resins, or a resin printing plate is formed. That is, a negative mask is placed on the thin film of the coated photosensitive resin composition,
After irradiating light to photo-cure the exposed part and removing the non-exposed part by washing, the exposed metal part is dissolved by immersion in an etching solution to form a circuit. Further, in the plate making for printing, the etching step is unnecessary.

Conventionally, a photosensitive resin composition generally comprises a photosensitive resin, a photosensitizer, an initiator, a cross-linking agent, etc., and is diluted with an organic solvent or used as it is.
There are many resin components such as those containing an acryloyl group and cured by polymerization, those containing a cinnamoyl group and forming a cyclobutane ring and curing. Of these, those containing an acryloyl group are relatively easy to manufacture, and are inexpensive and easy to use, and are therefore widely used for those that do not require ultra-precision resolution. However, most of the cleaning liquid used for cleaning and removing the non-cured part is an organic solvent or an alkaline aqueous solution, and these cleaning liquids gradually remove the non-cured part and at the same time cause erosion of the cured part, which limits the resolution. Occurs. Further, when an organic solvent or an alkaline aqueous solution is used, the influence of the used cleaning liquid on the environment is regarded as a problem. Therefore, the non-exposed and non-cured parts can be removed with water that does not cause pollution, and
There has been a demand for the development of a new photosensitive resin composition which has good resolution without being eroded by the exposure-cured portion.

[0004]

SUMMARY OF THE INVENTION The present invention has been made under the background as described above, and the unexposed and uncured portions are water-soluble, and the exposed and cured portions are sufficiently resistant to washing with water. For the purpose of providing a water-soluble resin composition, more specifically, by attaching a side chain having a photoreactive acryloyl group or a methacryloyl group to a trunk polymer containing a water-soluble acryloylmorpholine, water-insoluble by exposure. An object of the present invention is to provide a photosensitive resin composition which forms a hard film or an image, and the unexposed portion is easily dissolved by water to exhibit sufficient resolution.

[0005]

The present invention comprises 20 to 90 parts of acryloylmorpholine, 5 to 40 parts of a monomer having a terminal carboxyl group or epoxy group and copolymerizable with acryloylmorpholine, and other copolymerizable monomers. For a copolymer obtained by polymerizing 5 to 40 parts in a solvent containing water as a main component, glycidyl acrylate or glycidyl methacrylate is used for the carboxyl group of the side chain of the copolymer, and epoxy group is used for the epoxy group. Acrylic acid or methacrylic acid are respectively polymer-reacted, a part or all of a carboxyl group or an epoxy group is epoxyesterified, and a copolymerized polymer compound in which an acryloyl group or a methacryloyl group is introduced into a side chain is used as a main component. The present invention relates to a photosensitive resin composition.

The copolymerizable polymer compound, which is the main component contained in the photosensitive resin composition of the present invention, is prepared by synthesizing the copolymer and subsequently introducing an acryloyl group by polymer reaction.
It is synthesized in stages.

(1) Synthesis of Copolymer Acryloylmorpholine, a monomer having a carboxyl group or an epoxy group at the terminal and other monomers are water, or water and water soluble, for example, N, N-dimethylformamide, dioxane, etc. Are copolymerized in a mixed solvent. The polymerization initiator is preferably potassium persulfate, ammonium persulfate, α, α′-azobisisobutyronitrile, etc. which are soluble in these solvents. For the adjustment of the molecular weight and the control of the speed, a method which is usually carried out by solution polymerization can be adopted. The introduction of the acryloyl group, which is the second-stage reaction, can be carried out continuously in the same solvent and in the same reactor.

The amount of acryloylmorpholine is preferably in the range of 20 to 90 parts. Above this amount, the amount of acryloyl group introduced into the side chain in the next step becomes small, and after curing by exposure, water swellability is large and the photosensitive resin is characteristically sensitive. Is unsuitable as
In addition, if the amount used is less than this, the characteristics of acryloylmorpholine will not be fully exhibited, and turbidity during copolymerization, turbidity upon introduction of an acryloyl group, or separation upon standing at room temperature will occur.

Acrylic acid, methacrylic acid, itaconic acid, glycidyl acrylate, glycidyl methacrylate and the like can be used as the carboxyl group- or glycidyl group-containing comonomer copolymerizable with acryloylmorpholine. The number of parts of these monomers is preferably from 5 to 40 parts, and if it is less than this, the crosslinking becomes insufficient, and if it is more than this, turbidity occurs in water or a water main solvent, insoluble matter occurs, and it becomes unsuitable as a photosensitive resin.

Acrylamide, diacetone acrylamide as other comonomer for adjusting physical properties such as solubility of the synthesized copolymerized polymer compound in a solvent, softening and hardening of resin at the time of curing, and ease of washing with water, Acrylic acid esters and the like can be used. In order to obtain a photosensitive resin having a uniform solubility of the resin liquid and an appropriate crosslinking density, 5 to 40 parts is a preferable range. If it exceeds this, the crosslinking density is rapidly reduced, and the cured product is washed off with water, which is not preferable.

(2) Introduction of acryloyl group After synthesis of the copolymer, the residual initiator is decomposed by heating, and a polymerization inhibitor and a predetermined amount of acrylic acid, methacrylic acid or glycidyl acrylate, glycidyl methacrylate are added, and further, When amines, ammonium salts or ammonia is added as a catalyst for epoxy esterification and the mixture is reacted under reflux for several hours, the epoxy esterification of carboxyl groups and epoxy groups in the copolymer is almost completed.

For the preparation of the photosensitive resin composition of the present invention, the resin solution obtained as described above can be used as it is, but it is more preferable to selectively add other chemicals. When other additives are selectively added, dissolution may be insufficient. Therefore, the solvent of the resin solution is partially removed by distillation, and other solvents such as dioxane, tetrahydrofuran, N, N-
It is also possible to add and use a substance such as dimethylformamide, N, N-dimethylacetamide, and dimethyl sulfoxide, which is freely soluble in water.

The photosensitive resin composition is obtained by uniformly mixing the above resin solution and the compounding ingredients. As the compounding ingredients, there are a sensitizer, a polymerization initiator, a cross-linking agent and the like, which are selected and used if necessary. Examples of the sensitizer and the polymerization initiator include benzoin alkyl ethers such as benzoin isopropyl ether, benzyl, 4-benzoyl-N,
Examples include N, N-trimethylbenzenemethanoammonium chloride, Michler's ketone, α, α′-azobisisobutylnitrile, and benzoyl peroxide. As the cross-linking agent, for example, a polyfunctional acrylate such as ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, or ethylene bisacrylamide can be used. In addition, a high-molecular weight water-soluble compound may be used in combination to improve smoothness during film formation and to improve water washability.

The photosensitive resin composition of the present invention is uniformly applied to a substrate to a film thickness of several to several + μm, and the solvent is volatilized in a dark place,
Place a negative film and irradiate it with an ultra-high pressure mercury lamp or a high-pressure mercury lamp to cross-link the light-irradiated portion. After that, the unexposed portion is washed away only by washing with water, whereby an image having precise resolution is obtained.

[0015]

Example 1 An example of synthesis of a copolymer and introduction of an acryloyl group is shown below.

[Table 1] The compound shown in A was weighed into a 300 or 500 ml four-necked flask, equipped with a cooling tube and a thermometer, and under a nitrogen atmosphere,
In an oil bath, the temperature was 60 ° C. for 1 hour, 70 ° C. for 2 hours, and 90 ° C. for 1 hour. All were uniformly transparent and slightly viscous liquids were obtained.

Similarly to the above copolymer, the compound shown in B was weighed and reacted for 4 to 5 hours under reflux in an air atmosphere to break the epoxy ester bond and introduce an acryloyl or methacryloyl group. A uniform and slightly yellowish brown transparent solution of the copolymerized polymer compound was obtained. A combination, B
After the reaction, the mixture was examined for residual monomer by high performance liquid chromatography. % Or less.

[0016]

[Example 2] No. 1 obtained in Example 1 3 and N
o. Excess ethanol was added to the 4 copolymer polymer solution to remove most of the water with an evaporator, and then a powdery resin was obtained.

The following compounding ingredients were added to these and dissolved by ultrasonic agitation to prepare a uniform solution of a photosensitive resin composition.

This product was coated on a glass substrate having a thickness of 3 mm and a size of 30 × 30 mm with a spin coater to prepare a coating plate having a film thickness of about 30 μm, which was naturally dried and dried under reduced pressure at 50 ° C. overnight. All these operations were performed in the dark.

On the dried coating plate, Kodak Step Tablet No. 2 Negative film was placed, and a quartz glass plate was placed on the film so that they were sufficiently adhered. This was set in a light irradiation device, and light was irradiated from a distance of 50 cm with a parallel light flux type 250 W ultra-high pressure mercury lamp. For development, fill a petri dish with a diameter of 9 cm with tap water, gently place the irradiation coating plate for 30 seconds, and then 1
Shaking for a minute and further washing with a falling water stream in the vertical direction.

As a result of measurement, both compositions have a resolution of about 200 μm or more in an air atmosphere and a sensitivity of 5 after exposure for 30 seconds.
It has been found that the above steps cure.

Compounding Agent Copolymer Polymer Compound According to the Present Invention 2.0 g (No. 3 or No. 4 Powder) DPCA-60 * 0.6 g N, N-Dimethylformamide 6.0 g Acryloylmorpholine 1.0 g Benzoin isopropyl Ether 0.125 g Michler's ketone 0.0082 g 2,6-ditertiary butyl cresol 0.0073 g Polyvinylpyrrolidone 0.7 g (as solid matter, Mw ~ 160,000) Water 1.1 g * Dipentaerythritol epsilon-caprolactone adduct hexa Acrylate (Nippon Kayaku)

[0022]

EFFECT OF THE INVENTION Photosensitization containing, as a main component, a copolymerized polymer compound containing acryloylmorpholine in a backbone polymer and having an acryloyl group or a methacryloyl group introduced into a side chain in water or a mixed solvent containing water as a main component. The resinous composition was able to be developed only by washing the unexposed portion, which was conventionally considered difficult, with water. A photosensitive resin composition having good resolution without being eroded in the exposure-cured part was obtained.

Claims (1)

[Claims] 1. Acryloylmorpholine 20-90
5 to 40 monomers having a carboxyl group or an epoxy group at the end thereof and copolymerizable with acryloylmorpholine
Parts, and 5 to 40 parts of other copolymerizable monomers in a solvent containing water as a main component, the glycidyl acrylate is contained in the carboxyl group of the side chain of the copolymer. Alternatively, glycidylmethacrylate is polymerized with acrylic acid or methacrylic acid as an epoxy group, and a part or all of a carboxyl group or an epoxy group is epoxyesterified to introduce an acryloyl group or a methacryloyl group into a side chain. A photosensitive resin composition comprising a copolymerized polymer compound as a main component.