JP3452770B2 - Photosensitive resin composition and photosensitive element - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photosensitive resin composition 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 obtained by laminating a photosensitive element on a copper substrate, pattern-exposing it, removing the unexposed portion with a developer, and subjecting it to etching or plating treatment,
After the pattern is formed, the cured part is manufactured by peeling off from the substrate.

With the recent increase in the density of printed wiring boards, the area of the resist material and the base material becomes smaller. Therefore, the resist material has excellent adhesive strength to a copper substrate, mechanical strength, chemical resistance, flexibility and the like. Required. Further, along with this increase in density, generation of aggregates in the developer in which the 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. Further, in the peeling process after the circuit is made, it is necessary to subdivide the film so that it does not get caught in the feed roll. In addition, 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 the BOD (biochemical oxygen demand) or COD of the waste solution.
(Chemical oxygen demand) is reduced. At this time, if the solubility in water is high, BOD and COD are high, and the cost required for wastewater treatment is high.

As a resist having improved chemical resistance, for example, a resist using a polymer obtained by copolymerizing a styrene-based monomer is known. (JP-B-55-38961, JP-B-54-25957, JP-A-2-289607, JP-A-4-347859, JP-A-4-28)
However, this resist has a problem that a large amount of aggregation occurs in the developing tank. Further, regarding cohesiveness and waste liquid treatment property, JP-A-58-1142
It is disclosed in Japanese Patent Laid-Open No. 58-88741. However, no invention related to wastewater treatment has been made,
There are problems such as high COD and a large amount of aggregation in the developing tank.

Further, JP-A-54-153624 exemplifies a photosensitive resin composition having a good adhesive force, but there is a problem such as a large amount of sludge in the developing tank. further,
JP-A-61-77844 and JP-A-1-22474.
The photosensitive resin composition disclosed in Japanese Patent Publication No. 7 etc. does not satisfy the cohesiveness and the waste liquid processability.

[0006]

The invention described in claims 1 and 2 has excellent adhesion to copper and chemical resistance, low COD and BOD during wastewater treatment, and low cohesiveness in the developing tank. A photosensitive resin composition is provided. The invention according to claim 3 is provided with a layer of a photosensitive resin composition which is excellent in adhesive strength with copper and chemical resistance, has low COD and BOD during wastewater treatment, and has low cohesiveness in a developing tank, A photosensitive element having excellent workability is provided.

[0007]

The present invention provides (A) a carboxyl group-containing α, β-unsaturated monomer 1 having 3 to 15 carbon atoms.
5 to 35% by weight, general formula (I)

[Chemical 8] (In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom or 1 to 4 carbon atoms.
Is an alkyl group, n is an integer of 0 to 3, and n is 2
In the above case, a plurality of X may be the same or different from each other) 1 to 40% by weight of a styrene-based monomer and 10 to 70% by weight of a methacrylate having an alkyl group having 1 to 8 carbon atoms. % And 0-40% by weight of an acrylate having an alkyl group having 1 to 8 carbon atoms, (B) a photopolymerization initiator and (C) a polymerizable ethylenically unsaturated group. A photopolymerizable compound, wherein the component (C) has the general formula (II)

[Chemical 9] (In the general formula (II), R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y represents

[Chemical 10] (In YO or OY, a methylene group or a methine group is bonded to O),

[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 (III)

[Chemical 12] (In the general formula (III), R ² , Y, Z, n, m, p and q have the same meanings as in the general formula (II)), the general formula (IV)

[Chemical 13] (In the general formula (IV), R ² , Y, Z, n, m, p and q are the same as those in the general formula (II)) or the general formula (V)

[Chemical 14] The present invention relates to a photosensitive resin composition containing a compound represented by the general formula (V), R ² , Y, Z, n, m, p and q have the same meanings as in the general formula (II).

Further, according to the present invention, the proportion of the component (A), the component (B) and the component (C) used is such that the component (A) is added to 100 parts by weight of the total amount of the component (A) and the component (C). 40-80
Parts by weight, the component (B) is 0.1 to 20 parts by weight and the component (C) is 20 to 60 parts by weight, and the compound represented by the general formula (II) in the component (C), the general formula (III) ), A compound represented by the general formula (IV) or a general formula (V)
The present invention relates to the photosensitive resin composition containing 3 parts by weight or more of the compound represented by. The present invention also relates to a photosensitive element obtained by applying the photosensitive resin composition on a support and drying the composition.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the carboxyl group-containing α, β-unsaturated monomer constituting the thermoplastic polymer (A) in the present invention include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, There are sorbic acid, itaconic acid, propiolic acid, maleic acid, fumaric acid and the like, and these half esters or anhydrides can also be used, but acrylic acid and methacrylic acid are different from the viewpoint of copolymerizability and availability. preferable. These carboxyl group-containing α, β-unsaturated monomers can be used alone or in combination of two or more. The content of the carboxyl group-containing α, β-unsaturated monomer in the (A) plastic polymer is 15 to 35% by weight.
It is necessary to be, and 18 to 30% by weight is preferable. If the content is less than 15% by weight, it cannot be developed with an alkaline aqueous solution or the development time is too long, resulting in deterioration of resolution. On the other hand, if it exceeds 35% by weight, the development time is too short. However, in order to obtain a high resolution pattern, it becomes difficult to control the development, and the water resistance of the photo-cured portion also deteriorates.

Examples of the styrene monomer represented by the general formula (I) which constitutes the thermoplastic polymer (A) in the present invention include, for example, α-methylstyrene, styrene, p-methylstyrene and p-chloro. Although there are styrene and the like, styrene and p-methylstyrene are preferable from the viewpoint of easy availability. These styrene-based monomers are used alone or in combination of two or more. The content of these styrene-based monomers in the thermoplastic polymer (A) is required to be 1 to 40% by weight, and preferably 2 to 30% by weight. If the content is less than 1% by weight, the adhesiveness and chemical resistance will be poor, while if it exceeds 40% by weight, the time for development and peeling will be long and the aggregation of the developing tank will be large.

Examples of the (A) methacrylate having an alkyl group having 1 to 8 carbon atoms which constitutes the thermoplastic polymer in the present invention include, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate and n-. Butyl methacrylate, se
Examples thereof include c-butyl methacrylate, t-butyl methacrylate and 2 ethylhexyl methacrylate, and methyl methacrylate is preferable from the viewpoint of polymerizability and water resistance. These methacrylates having an alkyl group having 1 to 8 carbon atoms may be used alone or in combination of two or more. The content of the methacrylate having an alkyl group having 1 to 8 carbon atoms is 1 in the thermoplastic polymer (A).
It is necessary to be 0 to 70% by weight, and preferably 30 to 70% by weight. If the content is less than 10% by weight, the developability and releasability are poor, and if it exceeds 70% by weight, the adhesiveness becomes weak.

As the acrylate having an alkyl group having 1 to 8 carbon atoms which constitutes the thermoplastic polymer (A) in the present invention, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n- Examples thereof include butyl acrylate, sec-butyl acrylate, t-butyl acrylate, and 2-ethylhexyl acrylate, with methyl acrylate, ethyl acrylate, and n-butyl acrylate being preferred from the viewpoint of polymerizability and developability. These acrylates having an alkyl group having 1 to 8 carbon atoms may be used alone or in combination of two or more. The content of the acrylate having an alkyl group having 1 to 8 carbon atoms in the thermoplastic copolymer (A) is required to be 0 to 40% by weight, and preferably 0 to 30% by weight. . If this content exceeds 40% by weight, the adhesiveness will decrease.

To achieve the object of the present invention, the thermoplastic polymer (A) used in the present invention must be a polymer composed of the above-mentioned specific monomers. The weight average molecular weight (value measured by gel permeation chromatography and converted into standard polystyrene) of the thermoplastic polymer (A) is preferably in the range of 20,000 to 100,000. When the weight average molecular weight is less than 20,000, a cold flow phenomenon tends to occur when it is used as a photosensitive element, while when it exceeds 100,000, the unexposed portion has insufficient solubility in an alkaline developer, The developability is poor and the development time is too long, which tends to cause a decrease in resolution and a decrease in circuit pattern productivity. The blending amount of the (A) thermoplastic polymer is preferably 40 to 80 parts by weight, and more preferably 45 to 65 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (C). preferable. If the blending amount is less than 40 parts by weight, the film forming property of the photosensitive layer of the resulting photosensitive element is impaired, sufficient film strength cannot be obtained, and cold flow tends to occur. On the other hand, if it exceeds 80 parts by weight, the photocurable film becomes brittle,
Adhesion to the substrate is impaired, and sufficient chemical resistance, particularly plating resistance and etching resistance, tends not to be obtained.

Examples of the photopolymerization initiator (B) used in the present invention include aromatic ketones (benzophenone, 4,
4'-bis (dimethylamino) benzophenone (Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, etc.), anthraquinone (2-ethylanthraquinone, phenanthraquinone, etc.) , Benzoin (benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, and other benzoin ethers, methylbenzoin, ethylbenzoin, etc.), benzyl derivatives (benzyl dimethyl ketal, 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 so on. 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.

The component (C) used in the present invention includes a compound represented by the general formula (II), a compound represented by the general formula (III), a compound represented by the general formula (IV), and At least one compound represented by the general formula (V) is contained as an essential component. In the compound represented by the general formula (II), the compound represented by the general formula (III), the compound represented by the general formula (IV) and the compound represented by the general formula (V), R ² is A hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a methyl group. 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 abundance ratio of the ethylene oxide group and the group represented by Y, is 0.
It is preferably 5 to 10. If this ratio exceeds 10, the dispersion stability in the developing solution tends to decrease, and agglomerates and the like tend to occur. If it is less than 0.5, the developing solution and the release solution are treated as waste liquid. In addition, the BOD value in the filtrate tends to increase when filtered. Also, m, n, p
And q are each independently an integer of 1 to 14, m and n are preferably 1 to 5, and p and q are 2 to 14
Is preferred. When m, n, p and q exceed 14, photocurability tends to decrease.

Z is a divalent hydrocarbon group having 2 to 16 carbon atoms, preferably hexamethylene group, 2,2,4-trimethylhexamethylene group, tolylene group and the like. Examples of the compound represented by the general formula (II), the compound represented by the general formula (III), the compound represented by the general formula (IV) and the compound represented by the general formula (V) are as follows. The general formula of (VI
-1) or a compound represented by the general formula (VI-2) and a compound represented by the general formula (VII).

[0018]

[Chemical 15] (In the formula, R ² , Y, m and p have the same meanings as in formula (II))

[0019]

[Chemical 16] (In the formula, Z represents a hydrocarbon group having 2 to 16 carbon atoms)

Examples of the compound represented by the general formula (VI-1) and the compound represented by the general formula (VI-2) include polyethylene glycol-polypropylene glycol acrylate,
Examples thereof include polyethylene glycol-polybutylene glycol acrylate and methacrylates corresponding to these. Examples of commercially available products thereof include Nippon Oil & Fat Co., Ltd. Nissan Bremmer PEP series (polyethylene glycol polypropylene glycol monoacrylate, corresponding methacrylate). , PET series (polyethylene glycol polybutylene glycol monoacrylate, corresponding methacrylate) 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 (II), the compound represented by the general formula (III), the compound represented by the general formula (IV) and the general formula which are the essential components in the component (C). The compounding amount of the compound represented by (V), when used alone, is preferably 3 parts by weight or more based on 100 parts by weight of the total amount of the components (A) and (C), and 5 to Three
It is more preferably 0 part by weight. If the amount is less than 3 parts by weight, sensitivity, adhesion, plating resistance, etc. tend to be poor. When two or more kinds are used in combination, the total amount of the combination is (A) component and (C)
It 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.

Further, the compound represented by the general formula (II), the compound represented by the general formula (III), and the general formula (I) which are the essential components in the component (C) used in the present invention.
Examples of components other than the compound represented by V) and the compound represented by the general formula (V) include polyhydric alcohols containing α,
Compounds obtained by reacting β-unsaturated carboxylic acid (polyethylene glycol diacrylate (having 2 to 14 ethylene groups), trimethylolpropane diacrylate, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, tetra Methylolmethane tetraacrylate, polypropylene glycol diacrylate (having 2 to 14 propylene groups), dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc., α, β-unsaturated carboxylic acid to the glycidyl group-containing compound Compounds obtained by addition (trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether acrylate, etc.), bisphenol A
Polyoxyethylene diacrylate (bisphenol A
Dioxyethylene diacrylate, bisphenol A trioxyethylene diacrylate, bisphenol A decaoxyethylene diacrylate, etc.), alkyl acrylate (methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc.), methacrylate corresponding to the above, o Derivatives of monoesters of hydroxyalkyl acrylate of phthalic acid (β-hydroxypropyl-β′-acryloyloxyethyl-o-phthalate etc.), derivatives of monoesters of hydroxyalkyl methacrylate of o-phthalic acid (β-hydroxypropyl- β′-methacryloyloxyethyl-o-phthalate etc.) and the like.

The above-mentioned bisphenol A polyoxyethylene diacrylate and the corresponding methacrylate are represented by the following general formula (VIII)

[Chemical 17] (In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and r and s are each independently an integer of 1 to 30). The adhesiveness and chemical resistance can be improved, and when this compound is used, its amount is preferably 3 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) and (C). More preferably 5 to 15 parts by weight.

By using the above-mentioned derivative of a monoester of hydroxyalkyl acrylate of o-phthalic acid and the derivative of a monoester of hydroxyalkyl methacrylate of o-phthalic acid, the peelability of the photocured film can be improved. If you use
With respect to 100 parts by weight of the total amount of the components (A) and (C),
The amount is preferably 3 to 25 parts by weight, more preferably 5 to 20 parts by weight.

Dyes, color formers, plasticizers, pigments, flame retardants, stabilizers, adhesion promoters, etc. 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 also be used as a photosensitive element in which the support is coated and dried to form a photosensitive layer having a thickness of 3 to 300 μm on the support. As the support, for example, a polymer film made of polyethylene terephthalate, polypropylene, polyethylene or the like and having a thickness of 5 to 100 μm is used,
A polyethylene terephthalate film is preferred. Further, these polymer films may be laminated on the photosensitive layer formed on the support 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, after removing the protective film, 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 to 10 kgf / 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 emitted from a known active light source such as carbon arc, mercury vapor arc, xenon arc, photographic flood light bulb, and solar lamp is used. Then, after exposure, if a polymer film or the like is present on the photosensitive layer, after removing it, an alkaline aqueous solution is used as a developing solution, for example, spraying, rocking dipping,
The unexposed portion can be removed and developed by a known method such as brushing or scraping. Examples of the base of the aqueous alkali solution include alkali hydroxide (lithium, sodium or potassium hydroxide, etc.), alkali carbonate (lithium, sodium or potassium carbonate or bicarbonate, etc.), alkali metal phosphate (potassium phosphate). , Sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.) and the like are used, and sodium carbonate is preferred. The concentration of the base in the alkaline aqueous solution is preferably about 1 to 5% by weight, and p
H is preferably in the range of 9 to 11, and its 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.

In the production of a printed wiring board, the developed photoresist image is used as a mask and the exposed surface of the substrate is treated by a known method such as etching or plating. The photoresist image is then stripped, usually with an alkaline aqueous solution that is stronger than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, a 1 to 5 wt% sodium hydroxide aqueous solution or the like is used.

[0033]

EXAMPLES The present invention will be described below with reference to examples. Synthesis Example 1 [Synthesis of (A) Component Thermoplastic Polymer A] 100 g of a mixture of methyl cellosolve / toluene at a weight ratio of 3/2 (hereinafter referred to as mixture A) was put in a 300 ml flask under a nitrogen atmosphere and stirred. While heating to 80 ° C. After keeping the temperature for 30 minutes, a solution prepared by mixing 20 g of methacrylic acid, 10 g of styrene, 50 g of methyl methacrylate, 20 g of methyl acrylate, and 1.0 g of azoisobutyronitrile was dropped into the flask for 4 hours for reaction. Then, 8.3 g of the mixture A was added and the mixture was kept warm for 2 hours, and then a solution of 0.2 g of azobisisobutyronitrile dissolved in 16 g of the mixture A was added and kept warm for another 4 hours. Then, it cooled and the solution of the thermoplastic polymer A was obtained. The thermoplastic polymers B, C and D shown in Table 1 below were also synthesized by the same synthesis method as above except that the copolymerization component was changed.

[0034]

[Table 1]

Synthesis Example 2 [Synthesis of the compound represented by the general formula (II) as the component (C)]
The materials shown in Table 2 below were placed in a 2 liter flask equipped with a dropping funnel, a cooling tube, a thermometer, a dry air inlet tube and a stirrer, and then the materials shown in Table 2 were added from the dropping funnel. , Gradually add dropwise so that the temperature becomes 40 to 50 ° C,
After the dropping, the temperature was kept at 50 ° C. for 3 hours with stirring to obtain a product (C-1). In order to confirm the completion of the reaction of the obtained product (C-1), 2,27
Characteristic of isocyanate group around 0 cm ^-1 After confirming disappearance of absorption, 1 g of product (C-1) was precisely weighed on a metal Petri dish, heated at 105 ° C for 3 hours, and dried weight was measured to obtain solid. When the amount (NV) was calculated, NV was 93% by weight (in the general formula (II), R ² is a methyl group, Y is —CH ₂ —CH (CH ₃ ) —, n is 2 and p is 9, m is 2, q
Is 9 and Z is a compound of hexamethylene group).

[0036]

[Table 2]

[0037]

[Chemical 18]

Synthesis Example 3 Instead of the hexamethylene diisocyanate of Synthesis Example 2,
A product (C-2) was obtained in the same manner as in Synthesis Example 1 except that 1 mol equivalent of 2,2,4-trimethylhexamethylene diisocyanate (TMDI: manufactured by VEBA-CHEMIE) was used. The solid content (NV) of the obtained product (C-2) was NV = 92% by weight. (In the general formula (II), R ² is a methyl group and Y is —CH ₂ —CH.
(CH ₃₎ -, n is 2, p is 9, m is 2, q is 9, Z is a compound of 2,2,4-trimethyl hexamethylene group)

Examples 1 to 5 and Comparative Examples 1 to 3 The materials shown in Table 3 were blended to obtain solutions. Table 4
The components (A) and (C) shown in (1) were dissolved to obtain a solution of the photosensitive resin composition.

[0040]

[Table 3]

[0041]

[Table 4]

Then, a solution of this photosensitive resin composition is 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 this photosensitive layer was 50 μm.

On the other hand, the copper surface of a copper-clad laminate (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 sides, is # 6.
Polished using a polishing machine (manufactured by Sankei Co., Ltd.) with a brush equivalent to 00, washed with water, dried with an air stream, and heat the obtained copper-clad laminate to 80 ° C. Then, the photosensitive resin composition layer was laminated while being heated to 120 ° C.

Next, using an exposure machine (Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp, a negative Stouffer 21-step tablet was placed on the test piece 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 photosensitivity of the photosensitive resin composition was evaluated by removing the unexposed portion and 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 5. . 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 adhesion is evaluated by measuring the minimum width (μm) of the line remaining without peeling after development,
The results are shown in Table 5. 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.

Next, after development with the above-mentioned developing solution, degreasing (PC-455 (manufactured by Meltex Co., Ltd.) 25% by weight) 5 minutes immersion-washing-soft etching (ammonium persulfate 150
g / liter) Pretreatment is performed in the order of dipping for 2 minutes → washing with water → dipping for 10 minutes by 10 wt% sulfuric acid, and then copper sulfate plating bath (copper sulfate 75 g
/ Liter, sulfuric acid 190g / liter, chloride ion 50
ppm, Copper Gleam PCM (Meltex) 5 ml
/ L) and copper sulfate plating 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 then a solder plating bath (45 wt%
Tin borofluoride 64 ml / liter, 45 wt% lead borofluoride 22 ml / liter, 42 wt% borofluoric acid 2
00 ml / liter, Pultin LA Conductivity Salt (Meltex) 20 g / l, Pultin LA Starter (Meltex 40 ml / l), and solder plating at room temperature at 1.5 A / dm ² for 15 minutes. went.

After washing with water and drying, cellophane tape was immediately applied to check the plating resistance, and the tape was peeled in the vertical direction (90 ° peel-off test) to observe the presence or absence of peeling of the resist. 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, and the results are shown in Table 5. When the solder plating is removed, the solder deposited by plating is observed under the transparent resist through the transparent resist.

The height of foaming of the developing solution is a small developing tank (length 20 cm).
Small development with a spray pump and nozzle by dissolving the photosensitive layer of the photosensitive element in an area of 0.4 m ^{2 in} 1 liter of a developing solution (1% by weight sodium carbonate aqueous solution) put in a (width × 20 cm × height 15 cm) The height of the foamed layer formed on the liquid surface by foaming was measured by spray circulating for 1 hour using a machine, and the results are shown in Table 5. Then W as an antifoaming agent
10 ml of 2369 (manufactured by Nika Kagaku Kogyo Co., Ltd.) was added, and spray circulation was carried out for 1 hour. The developer dispersibility is the amount of sludge and oily substances generated on the wall surface and liquid surface of the small developing tank after spray circulating for 1 hour without adding the defoaming agent and after spray circulating for 1 hour after adding the defoaming agent. The ⊚ indicates that there is no sludge or oily substance, and the ∘ indicates that there is a small amount of sludge or oily substance. The results are shown in Table 5.

The waste liquid processability was such that 0.4 m ² of the photosensitive layer of the photosensitive element was dissolved in 1 liter of a developer (1 wt% sodium carbonate aqueous solution) and the pH was adjusted to 2 with sulfuric acid.
The photosensitive resin component was aggregated, the aggregate was filtered through a 5 μm quantitative filter paper, and the COD and BOD values of the filtrate were measured. The results are shown in Table 5.

[0050]

[Table 5]

As is clear from Table 5, Examples 1 to 5 within the scope of the present invention have good adhesion plating resistance, little generation of sludge and oily substances in the developing solution, and waste liquid. The processed product has little COD and BOD and is excellent in other characteristics.

[0052]

The photosensitive resin composition according to claims 1 and 2 has excellent adhesion to copper and chemical resistance, low COD and BOD at the time of wastewater treatment, and low cohesiveness in the developing tank. It is a thing. The photosensitive element according to claim 3 is excellent in adhesive strength with copper and chemical resistance, and has COD when treating wastewater,
It has a low BOD and is provided with a layer of a photosensitive resin composition having a low cohesive property in a developing tank, and is excellent in workability.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masataka Kushida               Hitachi, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture               Kasei Industry Co., Ltd. Yamazaki Factory (72) Inventor Takuya Kajiwara               Hitachi, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture               Kasei Industry Co., Ltd. Yamazaki Factory (72) Inventor Yuichi Kamakura               Hitachi, 4-13-1, Higashimachi, Hitachi City, Ibaraki Prefecture               Kasei Industry Co., Ltd. Yamazaki Factory                (56) Reference JP-A-8-179503 (JP, A)                 Japanese Unexamined Patent Publication No. 1-224747 (JP, A)

Claims (3)

(57) [Claims] 1. A) 15 to 35% by weight of (A) an α, β-unsaturated monomer having 3 to 15 carbon atoms and containing a carboxyl group, represented by the general formula (I): (In the general formula (I), R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a halogen atom or 1 to 4 carbon atoms.
Is an alkyl group, n is an integer of 0 to 3, and n is 2
In the above case, a plurality of X may be the same or different from each other) 1 to 40% by weight of a styrene-based monomer and 10 to 70% by weight of a methacrylate having an alkyl group having 1 to 8 carbon atoms. % And 0-40% by weight of an acrylate having an alkyl group having 1 to 8 carbon atoms, (B) a photopolymerization initiator and (C) a polymerizable ethylenically unsaturated group. The component (C) comprises a photopolymerizable compound, and the component (C) has the general formula (II): (In the general formula (II), R ² represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y represents (In YO or OY, a methylene group or a methine group is bonded to O), , 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 (III): (In the general formula (III), R ² , Y, Z, n, m, p and q are the same as those in the general formula (II)), a compound represented by the general formula (IV): (Wherein in the general formula (IV), R ² , Y, Z, n, m, p and q have the same meanings as in the general formula (II)) or the compound represented by the general formula (V) The photosensitive resin composition containing the compound represented by (in general formula (V), R < ² >, Y, Z, n, m, p, and q is the same meaning as general formula (II)). 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 the component (C), the compound represented by the general formula (II), the compound represented by the general formula (III) and the general formula (I
The photosensitive resin composition according to claim 1, wherein the compound represented by V) or the compound represented by the general formula (V) is contained in an amount of 3 parts by weight or more. 3. A photosensitive element obtained by applying the photosensitive resin composition according to claim 1 or 2 onto a support and drying it.