JPH08179503A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

PURPOSE: To provide a photosensitive resin compsn. which satisfies various requirements, is low in COD and BOD at the time of a waste water treatment and has the lower flocculating property of the photosensitive layers in a developer by using a specific urethane compd. having an ethylene glycol group and a propylene glycol group as a blocked group in the molecule as an ethylene unsatd. compd. and a photosensitive element formed by using this compsn. CONSTITUTION: This compsn. contains (A) a binder polymer having a carboxyl group, (B) a photopolymn. initiator and (C) a photopolymerizable compd. having at least one polymerizable ethylenic unsatd. groups within the molecule. The component (C) contains the compd. expressed by the formula (where, R<1> denotes a hydrogen atom or <=3C alkyl group, X denotes an ethylene oxide, Y denotes -CH2 CH2 CH2 O-, etc., Z denotes 2 to 16C hydrocarbon group, (n), (m), (p) and (q) are respectively independently an integer from 1 to 14), etc.

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 suitable for metal working, more particularly for producing a printed circuit board, and a photosensitive element using the same.

[0002]

2. Description of the Related Art Conventionally, in the field of printed circuit board manufacturing, as a resist material used for etching, plating, etc., a photosensitive resin composition and a photosensitive element obtained by using a support and a protective film therefor are widely used. Has been. The printed circuit board is formed by laminating a photosensitive film on a copper substrate, pattern-exposing it, removing the unexposed part with a developing solution, performing etching or plating treatment to form a pattern, and then curing the part. It is manufactured by a method of peeling and removing from the substrate.

As a developing solution for removing the unexposed portion, an alkaline developing type using a sodium hydrogen carbonate solution is mainly used. The developing solution is usually used as long as it has the ability to dissolve the photosensitive layer to some extent, and the photosensitive resin composition is dissolved or dispersed in the developing solution at the time of use.

Along with the recent increase in the density of printed wiring boards, the occurrence of aggregates in a developing solution in which a photosensitive resin composition is dissolved or dispersed has been regarded as a problem. This aggregate is dispersed in the developer and adheres to the printed wiring board redeveloped by a spray pump or the like, which causes unnecessary defects in the subsequent etching and plating steps. . In order to prevent the occurrence of this defect, good dispersion stability of the photosensitive resin composition in the developing solution is required.

The photosensitive layer is required to have excellent adhesion to a copper substrate, mechanical strength, acid resistance, flexibility and the like in the subsequent etching or plating process.

Further, in the peeling process after the circuit is formed,
It is necessary to subdivide the feed roll so that it does not get caught.

The developing solution and the stripping solution used for these are neutralized with an acid, the dissolved photosensitive layer is aggregated and removed by filtration to remove BOD (biochemical oxygen demand) and COD (wastewater) of the waste solution. Chemical oxygen demand).
At this time, if the solubility in water is high, BOD and COD are high, and the cost required for wastewater treatment is high.

This kind of photosensitive resin composition or photosensitive element is disclosed in JP-A-58-1142 and JP-A-58-8.
No. 8741 is disclosed. However, no invention related to wastewater treatment has been made and COD is high.
There are problems such as a large amount of aggregation in the developing tank. In addition, JP-A-54
JP-A-153624 exemplifies a photosensitive resin composition having a good adhesive force, but has a problem such as a large amount of sludge in a developing tank. Further, JP-A-61-77844, JP-A-1-224747 and the like disclose photosensitive resin compositions in which a peeling piece is difficult to dissolve. However, these contain ethylene glycol or propylene glycol alone. Alternatively, since the diisocyanate groups are reacted by mixing, COD becomes high when ethylene glycol is alone, and cohesiveness becomes high in the developing solution when propylene glycol is alone, and ethylene glycol and propylene glycol were mixed. In this case, microscopically different compounds are present in a mixed state, and cohesiveness and waste liquid treatment are not satisfied.

[0009]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and is a specific urethane compound having an ethylene glycol group and a propylene glycol group as a blocked group in the molecule. By using as an ethylenically unsaturated compound, various requirements are satisfied, COD and BOD at the time of wastewater treatment are low, and a photosensitive resin composition having a less cohesive property of a photosensitive layer in a developer and a photosensitive resin composition using the same To provide a sex element.

[0010]

The present invention has (A) a binder polymer having a carboxyl group, (B) a photopolymerization initiator, and (C) at least one polymerizable ethylenically unsaturated group in the molecule. A photopolymerizable compound is contained, and the component (C) is represented by the general formula (I).

[Chemical 9] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X represents

[Chemical 10] And Y is

[Chemical 11] , Z represents a hydrocarbon group having 2 to 16 carbon atoms, n,
m, p and q are each independently an integer of 1 to 14)
A compound represented by the general formula (II)

[Chemical 12] (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)), the compound represented by formula (II
I)

[Chemical 13] (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)) or the formula (IV)

Embedded image The invention relates to a photosensitive resin composition containing a compound represented by the formula (wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)). The present invention also relates to a photosensitive element obtained by applying the photosensitive resin composition on a support and drying the composition.

Examples of the (A) carboxyl group-containing binder polymer used in the present invention include (meth) acrylic acid ((meth) acrylic acid means methacrylic acid and acrylic acid. The same applies hereinafter). Examples thereof include copolymers with vinyl monomers that can be copolymerized with. These copolymers are used alone or in combination of two or more.

Examples of the vinyl monomer include (meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester,
(Meth) acrylic acid 2-ethylhexyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, (meth) acrylic acid diethylaminoethyl ester, methacrylic acid glycidyl ester, 2,2,2- Examples thereof include trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene and vinyltoluene, but there is no particular limitation.

The binder polymer (A) having a carboxyl group is preferably soluble or swellable in an alkaline aqueous solution (for example, 1 to 3 wt% sodium carbonate or potassium carbonate aqueous solution), and has an acid value of 100 to 500. Preferably, the weight average molecular weight is 20,000 to 3
It is preferably 0,000. If the acid value is less than 100, the developing time tends to be delayed, and if it exceeds 500, the developer resistance of the photocured resist tends to decrease. Further, if the weight average molecular weight is less than 30,000, the developing solution resistance tends to be lowered, and the weight average molecular weight is 300,0.
If it exceeds 00, the developing time tends to be long.

In the present invention, the compounding amount of the component (A) is
It is preferable that the total amount of the components (A) and (C) is 100 parts by weight, and the range is 40 to 80 parts by weight. If the blending amount is less than 40 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating property tends to be poor, and if it exceeds 80 parts by weight, the sensitivity tends to be insufficient. is there.

Examples of the photopolymerization initiator (B) used in the present invention include aromatic ketones (benzophenone, N,
N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetramethyl-4,
4'-diaminobenzophenone, 4-methoxy-4'-
Dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrenequinone, etc.) Benzoin (benzoin methyl ether, benzoin ethyl ether, benzoin ether such as benzoin phenyl ether, methylbenzoin, ethylbenzoin etc.), benzyl derivative (benzyldimethylketal etc.), 2, 4,5-Triarylimidazole dimer (2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-Chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
-Diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer,
2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, etc., acridine derivative (9-phenylacridine) ,
1,7-bis (9,9'-acridinyl) heptane etc.)
And the like. These are used alone or in combination of two or more.

In the present invention, the blending amount of the component (B) is
The total amount of the components (A) and (C) is preferably 0.1 to 20 parts by weight based on 100 parts by weight. If the blending amount is less than 0.1 parts by weight, the sensitivity tends to be insufficient, and if it exceeds 20 parts by weight, the absorption on the surface of the composition is increased during exposure and the internal photocuring is insufficient. Tends to be sufficient.

In addition, the compound represented by the above general formula (I), the compound represented by the general formula (II), and the general formula (III) which are essential components in the component (C) used in the present invention. )
As the component other than the compound represented by and the compound represented by the general formula (IV), for example, α, β-
Compounds obtained by reacting unsaturated carboxylic acids (polyethylene glycol di (meth) acrylate (having 2 to 14 ethylene groups), trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, polypropylene glycol di (meth) acrylate (having 2 to 14 propylene groups), dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, etc., a compound obtained by adding α, β-unsaturated carboxylic acid to a glycidyl group-containing compound (bisphenol A dioxyethylene di (meth) acrylate, bisphenol A trioxyethylene) Di (meth) acrylate,
Bisphenol A decaoxyethylene di (meth) acrylate and other bisphenol A dioxyethylene di (meth) acrylate, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether acrylate and the like), alkyl ester of (meth) acrylic acid ( (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester, etc.) and the like.

Suitable compounds include general formula (V)

[Chemical 15] (Wherein R ² and R ³ each independently represent a hydrogen atom or a methyl group) or a compound represented by the general formula (VI)

Embedded image (In the formula, R ⁴ represents a hydrogen atom or a methyl group, and r is 3 to
It is a compound represented by the formula (20 is an integer of 20), and by using these in combination, appropriate curability, flexibility, shortening of peeling time, etc. can be achieved without increasing COD and BOD.

In the compound represented by the general formula (I), the compound represented by the general formula (II), the compound represented by the general formula (III) and the compound represented by the general formula (IV),
R ¹ is a hydrogen atom or an alkyl group having 3 or less carbon atoms,
It is preferably a methyl group. X needs to be an ethylene oxide group, which improves dispersibility in the developer and reduces the generation of aggregates. Y needs to be a propylene oxide group, a butylene oxide group, a pentylene oxide group or a hexylene oxide group. When there are a plurality of Ys, the plurality of Ys may be the same or different. M + n / p + q, which is the ratio of X and Y
Is preferably 0.5 to 10. This ratio is 1
If it exceeds 0, the dispersion stability in the developer tends to decrease and aggregates and the like are likely to occur. When this is done, the BOD value in the filtrate tends to increase. Also,
m, n, p and q are each independently an integer of 1 to 14, m and n are preferably 1 to 5, p and q
Is preferably 2 to 14. When m, n, p and q exceed 14, the curability tends to decrease.

Z is a divalent hydrocarbon group having 2 to 16 carbon atoms, preferably hexamethylene group, 2,4,4-trimethylhexamethylene group, tolylene group and the like. These general formula (I), general formula (II), general formula (III) and general formula (I
The compound represented by V) is, for example, a compound represented by the general formula (VII-1),
General formula (VII-2), general formula (VII-3), general formula (VII
-4), a compound represented by the general formula (VII-5), a general formula (VII-6), a general formula (VII-7) or a general formula (VII-8) and a general formula (VIII). Obtained by reaction with a compound.

[Chemical 17] (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms, m, n, p, and q are integers of 1 to 14, and k
Is an integer of 3 to 6) In the above general formula (VII-1), general formula (VII-2), general formula (VII-3) and general formula (VII-4),

Embedded image Shows a block segment consisting of a propylene oxide unit. Further, in the propylene oxide unit of this block segment, the bonding position of the methyl group is on the carbon atom two adjacent to the oxygen atom for convenience of description, but it is not limited to this structure.

[Chemical 19] Etc. are also included. The same applies to the block segment composed of the propylene oxide unit in the general formula (VI).

Embedded image (In the formula, Z represents a hydrocarbon group having 2 to 16 carbon atoms)

General formula (VII-1), general formula (VII-2),
General formula (VII-3), general formula (VII-4), general formula (VII
-5), the compound represented by the general formula (VII-6), the general formula (VII-7) or the general formula (VII-8), polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene Glycol (meth) acrylate and the like are listed, and examples of commercially available products thereof include Nissan Bremmer PEP series (polyethylene glycol polypropylene glycol mono (meth) acrylate), PE manufactured by NOF Corporation.
Examples include T series (polyethylene glycol polybutylene glycol mono (meth) acrylate) and the like.

In the present invention, the compounding amount of the component (C) is
With respect to 100 parts by weight of the total amount of the components (A) and (C),
It is preferably 20 to 60 parts by weight. If the amount is less than 20 parts by weight, the sensitivity tends to be insufficient,
If it exceeds 60 parts by weight, the photocured product tends to become brittle.

Further, the compound represented by the general formula (I), the compound represented by the general formula (II), the compound represented by the general formula (III) and the general formula which are the essential components in the component (C). (I
The compounding amount of the compound V) is preferably 3 parts by weight or more, and more preferably 5 to 30 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (C). . If the amount is less than 3 parts by weight, sensitivity, adhesion, plating resistance, etc. tend to be poor.

Dyes, color formers, plasticizers, pigments, flame retardants, stabilizers, adhesion promoters and the like may be added to the photosensitive resin composition of the present invention as required.

In the photosensitive resin composition of the present invention, the above components are dissolved in a solvent such as toluene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, A homogeneous solution can be obtained by dissolving and mixing in methyl alcohol, ethyl alcohol, or the like.

The photosensitive resin composition of the present invention can be used as a photosensitive element by coating it on a support and drying it. As the support, a polymer film, for example, a film made of polyethylene terephthalate, polypropylene, polyethylene or the like is used, and a polyethylene terephthalate film is preferable. Since these polymer films must be removable from the photosensitive layer later, they must not be surface-treated or made of a material that makes them impossible to remove. The thickness of these polymer films is preferably 5 to 100 μm, more preferably 10 to 30 μm. Further, one of these polymer films may be laminated on both sides of the photosensitive layer as a support film for the photosensitive layer and the other as a protective film for the photosensitive layer.

In producing a photoresist image using the photosensitive element of the present invention, if the above-mentioned protective film is present, the protective film is removed, and then the photosensitive layer is pressed against the substrate while heating. By doing so. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive layer is preferably 90 to 130 ° C., and the pressure bonding is preferably 3 kg / cm ² , but these conditions are not particularly limited. Further, if the photosensitive layer is heated as described above, it is not necessary to preheat the substrate in advance, but the substrate may be preheated in order to further improve the stacking property.

The photosensitive layer thus laminated is
It is then imagewise exposed to actinic light using a negative or positive film. At this time, when the polymer film existing on the photosensitive layer is transparent, it may be exposed as it is, and when it is opaque, it is of course necessary to remove it. From the viewpoint of protecting the photosensitive layer, it is preferable that the polymer film is transparent, and the polymer film is allowed to remain and exposed through it.

As the active light, light generated from a known active light source, for example, carbon arc, mercury vapor arc, xenon arc or the like is used. The sensitivity of the photoinitiator contained in the photosensitive layer is usually maximum in the UV region, in which case the actinic light source should be one which emits UV radiation effectively. Also, the photoinitiator is sensitive to visible light,
For example, in the case of 9,10-phenanthrenequinone or the like, visible light is used as the active light, and as the light source thereof, a photographic flood light bulb, a sun lamp, or the like is also used. Then, after exposure, if a polymer film or the like is present on the photosensitive layer, after removing it,
Using an alkaline aqueous solution, the unexposed portion is removed and developed by a known method such as spraying, rocking dipping, brushing, scraping, or the like. Examples of the base of the alkaline aqueous solution include alkali hydroxide (lithium, sodium or potassium hydroxide, etc.), alkali carbonate (lithium, sodium or potassium carbonate, bicarbonate, etc.),
Alkali metal phosphates (potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.) are used, and an aqueous solution of sodium carbonate is preferred. The pH of the alkaline aqueous solution used for development is preferably in the range of 9 to 11,
The temperature is adjusted according to the developability of the photosensitive layer. Further, a surface active agent, a defoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

Further, when manufacturing a printed wiring board, the exposed surface of the substrate is treated by a known method such as etching or plating using the developed photoresist image as a mask. The photoresist image is then typically
The peeling is performed with an aqueous solution having a stronger alkaline property than the alkaline aqueous solution used for the development. As the strong alkaline aqueous solution, for example, a 1 to 5 wt% sodium hydroxide aqueous solution or the like is used.

[0031]

EXAMPLES The present invention will be described below with reference to examples. Synthesis example 1

[Table 1]

[Chemical 21] The materials shown in Table 1 are used for the dropping funnel, cooling tube, thermometer,
The mixture was placed in a 2 liter flask equipped with a dry air inlet tube and a stirrer, and then the materials shown in Table 1 were gradually dropped from the dropping funnel so that the temperature became 40 to 50 ° C., and after dropping. The mixture was kept warm at 50 ° C. for 3 hours with stirring, and the product (C-
1) was obtained. In order to confirm the completion of the reaction of the obtained product (C-1), its infrared absorption spectrum was 2,270 cm ^-1.
After confirming the disappearance of the characteristic absorption of the isocyanate group in the vicinity, 1 g of the product (C-1) was precisely weighed on a metal Petri dish and 1
It was heated at 05 ° C. for 3 hours, the dry weight was measured, and the solid content (NV) was calculated to be NV = 93% by weight.

Synthesis Example 2 Instead of the hexamethylene diisocyanate of Synthesis Example 1,
2,2,4-Trimethylhexamethylene diisocyanate (TMDI: VEBA-CHEMIE)

[Chemical formula 22] Was performed in the same manner as in Synthesis Example 1 except that 1 mol equivalent was used,
The product (C-2) was obtained. The solid content (NV) of the obtained product (C-2) was NV = 92% by weight.

Synthetic Examples 3 to 6 and Comparative Synthetic Examples 1 and 2 The same processes as in Synthetic Example 1 were carried out except that the materials shown in Table 2 were used, and the products (C-3), (C-4), (C -5), (C
-6), (H-1) and (H-2) were obtained. The solid content (NV) of each product obtained is also shown in Table 2.

[0034]

[Table 2]

Synthesis Example 7 Instead of the diethylene glycol nonapropylene glycol monomethacrylate of Synthesis Example 1, nonapropylene glycol monomethacrylate (manufactured by NOF CORPORATION, PP-5) was used.
00) (1.6 molar equivalent)

[Chemical formula 23] And nona ethylene glycol monomethacrylate (PE-350 manufactured by NOF CORPORATION) (0.5 molar equivalent)

[Chemical formula 24] A product (H-3) was obtained in the same manner as in Synthesis Example 1 except that a mixture of was used. The obtained product (H-
The solid content (NV) of 3) was NV = 92% by weight.

Examples 1 to 7 and Comparative Examples 1 to 4 Materials shown in Tables 3 and 4 were blended to obtain solutions.

[Table 3]

[Table 4]

The component (C) shown in Table 5 was dissolved in this solution to obtain a solution of a photosensitive resin composition.

[Table 5]

Then, a solution of this photosensitive resin composition was added to
It was uniformly coated on a polyethylene terephthalate film having a thickness of 5 μm and dried in a hot air convection dryer at 100 ° C. for about 10 minutes to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer after drying was 50 μm.

On the other hand, the copper surface of a copper-clad laminate (trade name: MCL-E-61 manufactured by Hitachi Chemical Co., Ltd.), which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both surfaces, is # 60
Polishing using a polishing machine having a brush equivalent to 0 (manufactured by Sankeisha Co., Ltd.), washing with water, drying with an air stream, heating the obtained copper-clad laminate to 80 ° C., and applying the above to the copper surface. The photosensitive resin composition layer was laminated while being heated to 120 ° C.

Then, using an exposing machine (Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp, a 21-step Stofer step tablet was placed on the test piece as a negative and exposed at 60 mJ / cm ² . . Next, the polyethylene terephthalate film was peeled off, and a 1 wt% sodium carbonate aqueous solution was sprayed at 30 ° C. for 60 seconds,
The unexposed part was removed. Furthermore, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step tablets of the photocured film formed on the copper-clad laminate, and the results are shown in Table 6. The light sensitivity is indicated by the number of steps of the step tablet, and the higher the number of steps of this step tablet, the higher the light sensitivity.

The adhesiveness was expressed by the line width (μm) remaining after the development without peeling. The smaller the adhesiveness number, the more closely the thin line adheres to the copper-clad laminate without peeling from the copper-clad laminate, indicating that the adhesiveness is high.

The plating resistance was determined by laminating as described above and exposing with a predetermined exposure amount. Then, after development with the above developing solution, degreasing (PC-455 (manufactured by Meltex Co., Ltd.) 25% by weight) 5 minutes immersion → water washing → soft etch (ammonium persulfate 150 g / liter) 2 minutes immersion → water washing → 10
Pre-treatment is performed in the order of dipping in 1% by weight sulfuric acid for 1 minute, and copper sulfate plating bath (copper sulfate 75 g / liter, sulfuric acid 190 g / liter, chlorine ion 50 ppm, copper greem PCM (Meltex)
5 ml / liter), and copper sulfate plating was performed at room temperature at 3 A / dm ² for 40 minutes. After that, it is washed with water and immersed in 10 wt% borofluoric acid for 1 minute, and a solder plating bath (45 wt% tin borofluoride 64 ml / liter, 45 wt% lead borofluoride 2
2 ml / liter, 42 wt% borofluoric acid 200 ml / liter, Pultin LA Conductivity Salt (Meltex) 20 g / l, Pultin LA Starter (Meltex) 40 ml / l), and solder plating at room temperature It was carried out at 1.5 A / dm ² for 15 minutes.

After washing with water and drying, cellophane tape was immediately applied to check the plating resistance, and this was peeled in the vertical direction (90 ° peel-off test) to observe whether the resist was peeled. In addition, after the resist was peeled off, the presence or absence of chipping of the solder plating was observed with an optical microscope from above. When the solder plating is removed, the solder deposited by plating is observed under the transparent resist through the transparent resist.

The sludge and oily material generation rate in the developing tank is 1
The resin of the photosensitive film is dissolved in an area of 0.4 m ^{2 in} 1 liter of an aqueous solution of sodium carbonate having a weight of 0.4%, and spray-circulated for 1 hour without a defoaming agent using a small developing machine having a spray pump and a nozzle. At this time, if foaming becomes high and overflows, W2369 is used as an antifoaming agent.
10 ml (manufactured by Nichika Chemical Co., Ltd.) was added. At this time, the amount of oily substances generated on the wall surface or liquid surface of the small-sized developing tank was examined and used as a measure of the dispersibility of the developing solution. ◎ indicates no oily substance, ○
Indicates that there is a small amount of oil, and x indicates that there is a large amount of oil.

Next, regarding the waste liquid processability, the above-mentioned developing solution was adjusted to about pH = 2 with sulfuric acid to agglomerate the photosensitive resin component, and the agglomerate was filtered through a 5 μm quantitative filter paper, and COD and BOD of the filtrate were obtained.
The value was measured. The results are shown in Table 6.

[0046]

[Table 6]

As is clear from Table 6, Examples 1 to 7 within the scope of the present invention produced less oily substances in the developer,
In addition, the waste liquid treated product has little COD and BOD and is excellent in other characteristics.

[0048]

EFFECT OF THE INVENTION The photosensitive resin composition of the present invention and the photosensitive element using the same have the dispersibility of the photosensitive resin composition developed and removed when developed with an alkali developing solution, It is excellent in reduction of COD and BOD, adhesion and plating resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Taku Kawaguchi 13-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture Hitachi Chemical Co., Ltd. Yamazaki Plant (72) Inventor Takuya Kajiwara, 4-13 Higashicho, Hitachi City, Ibaraki Prefecture No. 1 Hitachi Chemical Co., Ltd. Yamazaki Factory

Claims (6)

[Claims] 1. A binder polymer having (A) a carboxyl group, (B) a photopolymerization initiator, and (C) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated group in the molecule, The component C) has the general formula (I): (In the formula, R ¹ represents a hydrogen atom or an alkyl group having 3 or less carbon atoms, and X represents And Y is , Z represents a hydrocarbon group having 2 to 16 carbon atoms, n,
m, p and q are each independently an integer of 1 to 14)
A compound represented by the general formula (II): (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)), the compound represented by formula (II
I) [Chemical 5] (Wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)) or a compound represented by formula (IV): A photosensitive resin composition containing a compound represented by the formula (wherein R ¹ , X, Y, Z, n, m, p and q have the same meanings as in formula (I)). 2. The use ratio of component (A), component (B) and component (C) is such that the total amount of component (A) and component (C) is 100.
40 to 80 parts by weight of the component (A), (B)
0.1 to 20 parts by weight of component and 20 to 60 of component (C)
In parts (C), the compound represented by the general formula (I), the compound represented by the general formula (II), the general formula (II)
The photosensitive resin composition according to claim 1, wherein the compound represented by I) or the compound represented by the general formula (IV) is contained in an amount of 3 parts by weight or more. 3. A compound represented by the general formula (I), a compound represented by the general formula (II), a compound represented by the general formula (III) or a compound represented by the general formula (IV), m and n are each independently an integer of 1 to 5, p and q are each independently an integer of 2 to 14, and m + n / p + q
Is 0.5-10, The photosensitive resin composition of Claim 1 or 2. 4. A thermoplastic linear polymer in which the component (A) is soluble or swellable in an alkaline aqueous solution, has an acid value of 100 to 500, and has a weight average molecular weight of 20,000 to 300,000. The photosensitive resin composition according to claim 1, 2 or 3. 5. The component (C) has the general formula (V): (Wherein R ² and R ³ each independently represent a hydrogen atom or a methyl group) or a compound represented by the general formula (VI): (In the formula, R ⁴ represents a hydrogen atom or a methyl group, and r is 3 to
The photosensitive resin composition according to claim 1, which comprises a compound represented by the formula (which is an integer of 20). 6. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1, 2, 3, 4 or 5 on a support and drying it.