JPH09146270A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain such a resin compsn. that a part not exposed to light or not hardened is soluble with an org. solvent and can be easily removed by cleaning with water while an exposed and hardened part has enough durability against washing with cleaning with water. SOLUTION: Polymn. of acryloylmorpholine, monomer having a hydroxy groups on the molecular end and another third monomer is performed in an org. solvent to obtain a copolymer, to which methacryloyl isocyanate is made to react. Thus, a copolymer high mol.wt. compd. comprising the main polymer containing a acryloylmorpholine component and side chains to which methacryloyl groups are introduced by urethane coupling is obtd. When the obtd. polymer compd. is used to prepare a photosensitive resin compsn., various kinds of compounding agent can be selected and mixed in wide ranges in an org. solvent, and an excellent photosensitive material which can be developed with water is obtd.

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 a urethane-bonded methacryloyl group in the side chain portion. The present invention relates to a photosensitive resin composition which is soluble in an organic solvent and can be easily washed and removed with water only in an unexposed portion during photocuring, and an exposed portion becomes insoluble. Used.

[0002]

2. Description of the Related Art Photosensitive resins have been used in a wide range of fields with the development of metal processing 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 resin plate for 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 to form a circuit using a partial etching solution such as a metal foil or a printing resin plate using these photosensitive resins. That is, a negative mask is placed on the thin film of the coated photosensitive resin composition, the exposed portion is photocured by light irradiation, and the non-exposed portion is removed by washing, and then the exposed metal portion is immersed in an etching solution. Elute and create 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, for example, 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, there has been a demand for the development of a new photosensitive resin composition capable of removing non-exposed and non-cured parts by washing with water without pollution and having good resolution without eroding the exposed and hardened parts. .

[0004]

SUMMARY OF THE INVENTION The present invention has been made under the background as described above. Although the non-exposed and non-cured parts are oil-soluble, they can be easily washed off with water, and the exposed and hardened parts can be easily washed away. Aims to provide a photosensitive resin composition that is sufficiently resistant to washing with water, and more specifically, a side chain having a photoreactive methacryloyl group is attached to a trunk polymer containing a water-soluble acryloylmorpholine. Accordingly, it is an object of the present invention to provide a photosensitive resin composition that forms a water-insoluble and hard film or image by exposure and can easily remove the unexposed portion by washing with water, and exhibits sufficient resolution.

[0005]

The present invention comprises 20 to 60 parts of acryloylmorpholine, and monomers 20 to 4 having a hydroxy group at the terminal and copolymerizable with acryloylmorpholine.
0 part, 20 to 40 parts of other copolymerizable monomers,
With respect to the copolymer obtained by polymerizing in an organic solvent, a part or all of the hydroxy groups of the side chain of the copolymer was polymer-reacted with methacryloyl isocyanate to introduce a methacryloyl group into the side chain. The present invention relates to a photosensitive resin composition containing a copolymerized polymer compound as a main component.

The copolymerizable polymer compound, which is the main component contained in the photosensitive resin composition of the present invention, is synthesized in two steps of synthesis of the copolymer and subsequent introduction of methacryloyl group by polymer reaction.

(1) Synthesis of Copolymer Acryloylmorpholine, a monomer having a hydroxy group at the terminal and other monomers are copolymerized in an organic solvent. The solvent used is not particularly limited,
When the reaction of methacryloyl isocyanate in the second step is also carried out in the solvent as it is, it needs to be isocyanate inactive. The polymerization initiator is α, which is soluble in the solvent.
α'-Azobisisobutyronitrile, benzoyl peroxide and the like are preferable. For the adjustment of the molecular weight and the control of the rate, a method which is carried out by a usual solution polymerization can be adopted.

The amount of acryloylmorpholine is preferably in the range of 20 to 60 parts, and above this amount, the polymer precipitates in the organic solvent. Further, since the amount of the monomer having a hydroxy group is reduced, the amount of the methacryloyl group introduced into the side chain during the reaction of the polymer is small, and the water swelling property is large after curing by exposure, which is unsuitable as a photosensitive resin due to its characteristics . Further, if the amount used is less than this, the characteristics of acryloylmorpholine are not sufficiently exhibited, and turbidity during copolymerization, turbidity upon introduction of a methacryloyl group, or separation upon standing at room temperature occurs.

As the comonomer having a hydroxy group which can be copolymerized with acryloylmorpholine, 2-hydroxyethyl ester or 2-hydroxypropyl ester of acrylic acid or methacrylic acid can be used. The number of parts of these monomers is preferably 20 to 40 parts,
Below this, crosslinking becomes insufficient, and above, turbidity occurs in the organic solvent, the swelling property of the exposed film becomes abnormally large, 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, methacrylic acid esters, styrene, etc. can be used. 20 to 40 in order to obtain a photosensitive resin having a uniform solubility of the resin liquid and an appropriate crosslinking density.
Parts is the preferred 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 methacryloyl group After synthesis of the copolymer, the remaining initiator is decomposed by heating, and if necessary, the solvent is replaced with an isocyanate inactive solvent, a polymerization inhibitor is added, and a predetermined amount of methacryloyl is added. Add isocyanate while stirring and at room temperature-40 ° C for 4
If the reaction is carried out for ~ 6 hours, the urethanization reaction between the hydroxy group in the copolymer and methacryloyl isocyanate 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. It may be preferable to add another solvent, because dissolution may become insufficient when other formulation is selectively added.

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-trimethylbenzenemethan ammonium chloride, Michler's ketone, α, α′-azobisisobutylnitrile, and benzoyl peroxide. Examples of the cross-linking agent include polyfunctional acrylates such as ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate and dipentaerythritol pentaacrylate, ethylenebisacrylamide. Etc. 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 tens of 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】

Example-1 An example of synthesis of a copolymer and introduction of a methacryloyl group is shown below.

[Table 1] The compound shown in A was weighed in a 500 ml four-necked flask, equipped with a cooling tube and a thermometer, and under a nitrogen atmosphere, 50 ° C. in an oil bath for 1 hour, 70 ° C. for 2 hours, and 90 ° C. for 1 hour. Finally, the temperature was raised to the reflux temperature and kept for 2 hours to finish. All were uniformly transparent and viscous liquids were obtained.

Similarly, the compound shown in B was weighed in the above copolymer and subjected to urethanization reaction at room temperature in a nitrogen atmosphere for 4 to 5 hours to give a uniform, slightly yellowish-brown transparent copolymer having a methacryloyl group introduced therein. A solution of the polymer compound was obtained. A
After the reaction, both the compounding and the compounding B were examined by high performance liquid chromatography for residual monomers. % Or less. In addition, as a result of IR measurement, it is 22 due to NCO.
The absorption at 60 cm ^-1 had disappeared.

Example-2 The following compounding ingredients were added to the above copolymerized polymer compound solution and ultrasonically stirred to prepare a photosensitive resin composition having a uniform solution.

This photosensitive resin composition was applied with a thickness of 3 mm, 30
A coated plate having a film thickness of about 30 μm was prepared on a glass substrate of × 30 mm using a spin coater, dried naturally, and then dried overnight at 50 ° C. under reduced pressure. 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, a petri dish having a diameter of 9 cm was filled with tap water, the irradiation coating plate was gently placed for 30 seconds, then shaken for 1 minute, and further washed vertically with a falling water stream.

As a result of the measurement, it was found that both compositions were cured in an air atmosphere with a resolution of 100 μm or more and with a sensitivity of 4 or more steps when exposed for 30 seconds.

Formulation Example Copolymer solution according to the present invention 4.0 g (No. 1 to No. 4) DPCA-60 * 0.6 g Benzoin isopropyl ether 0.12 g Michler's ketone 0.004 g dioxane 5.9 g * dipenta Hexaacrylate of ε-caprolactone adduct of erythritol (Nippon Kayaku)

[0022]

INDUSTRIAL APPLICABILITY The present invention is a photosensitive resin composition containing as a main component a copolymerized polymer compound containing acryloylmorpholine in a trunk polymer and having a methacryloyl group introduced into a side chain through a urethane bond. This photosensitive resin composition can be selectively compounded in a wide range with compounding agents such as a sensitizer, a polymerization initiator and a cross-linking agent in an organic solvent. It is extremely useful as a light-sensitive material which can be developed, the exposed and hardened part is not corroded, and has good resolution.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hikoji Yoshimura 4-27, Shibuya, Shibuya-ku, Tokyo Inside Amco Enterprise Co., Ltd.

Claims (1)

[Claims] 1. Acryloylmorpholine 20-60
Part, a copolymer having 20 to 40 parts of a monomer having a hydroxy group at the end and copolymerizable with acryloylmorpholine, and 20 to 40 parts of another copolymerizable monomer in an organic solvent. On the other hand, a part or all of the hydroxy group of the side chain of the copolymer is polymer-reacted with methacryloyl isocyanate, and the main component is a copolymerized polymer compound having a methacryloyl group introduced into the side chain. A photosensitive resin composition.