JP2000171970A - Photosensitive resin composition and photosensitive element using the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a photosensitive element having excellent tent reliability and good stripping property. SOLUTION: This composition contains (A) a binder polymer having a carboxyl group, (B) a photo-polymerizable compound having a polymerizable ethylenic unsaturated group in a molecule, which contains an acrylate compound expressed by a formula CH2=CHCO(OCH2CH2)n-OCH((CH2)k-CH3)2, wherein n is an integer of 1-15 and k is an integer of 1-10 and (C) a photo-polymerization initiator. And a photosensitive element is formed by laminating this photosensitive resin composition layer on a substrate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition and a photosensitive element using the same.

[0002]

2. Description of the Related Art Conventionally, there are two methods of manufacturing a printed wiring board, a tenting method and a plating method. The tenting method protects copper through-holes for chip mounting with resist, forms electrical circuits through etching and resist stripping, whereas the plating method deposits copper in through-holes by electroplating and solder plating In this method, an electric circuit is formed by peeling off the resist and etching. A photosensitive resin composition and a photosensitive element using the same are used as the resist, and an alkali developing type in which an uncured portion is removed with an alkaline aqueous solution is mainly used. Therefore, the photosensitive resin composition to be used is required to have a tenting property, that is, a tent reliability, which is not broken by a developing solution or a spray pressure of water washing.

[0003] JP-A-5-271129 discloses a photosensitive resin composition having good tent reliability using a vinyl urethane compound represented by the following general formula (II) for such a purpose. . However, such a photosensitive resin composition has a problem that the peeling time is long and the peeled pieces are hard to be divided. The stripping time is short, and it is more effective to separate the stripped pieces in terms of workability. CH ₂ ＣC (R ₃ ) COO (X) ₁ (Y) _p CO—NH——Z—NH—COO (Y) _q (X) _m COC (R ₃ ) = CH ₂ (II) R ₃ represents a hydrogen atom or an alkyl group, the two R ₃ may be the same or different, X is -CH ₂ CH ₂
O- are shown, Y is _{-CH 2 CH (CH 3) -O} -, - CH
_{(CH 3) -CH 2 -O -} , - CH 2 -CH 2 -CH 2 -O
_{-, - CH 2 -CH 2 -CH} 2 -CH 2 -O -, - CH 2 -
CH ₂ —CH ₂ —CH ₂ —CH ₂ —O— or —CH ₂ —CH ₂
—CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—, Z represents a divalent hydrocarbon group, and l, m, p and q each independently represent 1
It is an integer of ~ 14. It is presumed that the reason for using a vinyl urethane compound represented by the general formula (II) to increase the peeling time is that the crosslinking density is high because it has two functional groups. Further, the peeled piece is represented by the general formula (II)
It is presumed that the skeleton of Y of the vinyl urethane compound represented by the formula (1) hardly swells in an alkali release liquid (for example, an aqueous solution of 1 to 5% by weight of sodium hydroxide).

[0004] Conventionally, the number of functional groups has been reduced (use of a monofunctional monomer) to shorten the stripping time, and a skeleton (hydrophilicity) which easily swells in an alkali stripping solution to fragment the stripped pieces. It has been known that it is effective to introduce a base or the like into the structure, but it has been difficult and difficult to maintain the reliability of the tent while shortening the separation time and segmenting the separation pieces.

[0005]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and provides a photosensitive resin composition having excellent tent reliability and good peelability, and a photosensitive element using the same. Things.

[0006]

Means for Solving the Problems The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, they have been found to be monofunctional and have a hydrophilic group (polyethylene glycol group:
(OCH ₂ CH ₂ ) _n ) having the following general formula (I)
By using an acrylate compound represented by
It has been found that the peelability can be improved while maintaining the tent reliability, and the present invention has been completed based on this finding.

That is, the present invention relates to (A) a binder polymer having a carboxyl group, (B) an acrylate compound represented by the general formula (I) (b1) CH ₂ ＣＨCHCO (OCH ₂ CH ₂ ) _n -O- A polymerizable ethylenically unsaturated group in a molecule containing CH ((CH ₂ ) _k —CH ₃ ) ₂ (I) (where n is an integer of 1 to 15 and k is an integer of 1 to 10); The present invention provides a photosensitive resin composition characterized by comprising a photopolymerizable compound and a photopolymerization initiator (C).

[0008] The present invention also provides a photosensitive element obtained by laminating a layer of the photosensitive resin composition on a support.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The binder polymer having a carboxyl group as the component (A) in the present invention includes, for example, copolymers of alkyl acrylate or alkyl methacrylate, acrylic acid or methacrylic acid, and a vinyl monomer copolymerizable therewith. Coalescence and the like.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like. These acrylic acid alkyl esters are used alone or in combination of two or more.

Examples of the alkyl methacrylate include:
For example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned. These methacrylic acid alkyl esters are used alone or in combination of two or more.

The acrylic acid and methacrylic acid may be used as a mixture.

Examples of the vinyl monomer include tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, dimethylaminomethyl acrylate, dimethylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, , 2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl acrylate, acrylamide, 2,2
Examples include 3,3-tetrafluoropropyl methacrylate, methacrylamide, diacetacrylamide, styrene, vinyltoluene and the like. These vinyl monomers are used alone or in combination of two or more.

The above copolymer is obtained by mixing the above components,
It can be synthesized according to a known polymerization method (solution polymerization method or the like).

The mixing ratio of the above-mentioned alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid and vinyl monomers copolymerizable therewith is not particularly limited. From the viewpoint of the balance between developability and alkali resistance, it is preferable that the carboxyl group content of the component (A) described later (the ratio of the monomer having a carboxyl group to all the monomers used) is 15 to 50 mol%. . These copolymers are used alone or in combination of two or more.

The weight average molecular weight of the component (A) is not particularly limited, but is preferably 20,000 to 300,000, and more preferably 40,000 to 200, from the viewpoint of mechanical strength and alkali developability. , More preferably 60,000 to 120,000. If the weight average molecular weight is less than 20,000, the mechanical strength tends to be inferior, and 300,000
If it exceeds, the alkali developability tends to be poor.

The weight average molecular weight referred to here is a value measured by gel permeation chromatography and converted by a calibration curve prepared using standard polystyrene.

The content of the carboxyl group of the component (A) (the ratio of the monomer having a carboxyl group to all the monomers used) is not particularly limited, but from the viewpoint of the balance between alkali developability and alkali resistance, 15 to 50 mol. %
Is preferably set to 15 to 30 mol%, more preferably 15 to 25 mol%. When the carboxyl group content is less than 15 mol%, alkali developability tends to be poor, and when it exceeds 50 mol%, alkali resistance tends to be poor.

The photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention is:
It contains the acrylate compound (b1) represented by the general formula (I). _{CH 2 = CHCO (OCH 2 CH} 2) n -O-CH ((CH 2) k -CH 3) 2 (I) ( wherein, n is 1 to 15 and k is an integer of 1 to 10.) In the general formula (I), when n is an integer of more than 15, the hydrophilicity becomes too high, and the resulting resist has poor developer resistance. In the case of a compound in which k is an integer greater than 10, the hydrophilicity is lowered, the swellability of the obtained resist is reduced, and the peeled pieces are not fragmented.

Specific examples of the acrylate compound (b1) represented by the general formula (I) include, for example, an acrylate compound in which n is 9 and k is 5 (manufactured by Shin-Nakamura Chemical Co., Ltd .;
K ester A-SAL-9E) and an acrylate compound in which n is 3 and k is 5 (NK ester A-SAL-3E, manufactured by Shin-Nakamura Chemical Co., Ltd.).

Further, the photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule of the component (B) in the present invention comprises an acrylate compound represented by the general formula (I) and a acrylate compound represented by the general formula (II). Vinyl urethane compound (b2) represented
It is preferable that they also contain CH ₂ ＣC (R ₃ ) COO (X) ₁ (Y) _p CO—NH——Z—NH—COO (Y) _q (X) _m COC (R ₃ ) = CH ₂ (II) R ₃ represents a hydrogen atom or an alkyl group, the two R ₃ may be the same or different, X is -CH ₂ CH ₂
O- are shown, Y is _{-CH 2 CH (CH 3) -O} -, - CH
_{(CH 3) -CH 2 -O -} , - CH 2 -CH 2 -CH 2 -O
_{-, - CH 2 -CH 2 -CH} 2 -CH 2 -O -, - CH 2 -
CH ₂ —CH ₂ —CH ₂ —CH ₂ —O— or —CH ₂ —CH ₂
—CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—, Z represents a divalent hydrocarbon group, and l, m, p and q each independently represent 1
It is an integer of ~ 14. In formula (II), the alkyl group for R ₃ is preferably an alkyl group having 1 to 3 carbon atoms. Z is preferably a divalent hydrocarbon group having 2 to 16 carbon atoms, and examples thereof include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. When a hydrocarbon group having 17 or more carbon atoms is used, the sensitivity of the obtained photosensitive resin composition tends to decrease. Also,
In the case where l, m, p or q is an integer of 15 or more in the general formula (II), the obtained resist becomes brittle.

Vinyl urethane represented by the general formula (II)
Specific examples of the compound (b2) component include, for example, two
R₁Is a methyl group, Y is -CH_TwoCH (CH_Three) -O-,
1 and m are 1, p and q are 9, Z is a hexylene group
Vinyl urethane compound (Shin-Nakamura Chemical Co., Ltd., trade name UΑ-
13) Two R₁Is a methyl group, Y is -CH_TwoCH (C
H_Three) -O-, 1 and m are 1, p and q are 3, 5 or 1.
2, a vinyl urethane compound in which Z is a hexylene group,
Two R₁Is a hydrogen atom, Y is -CH_TwoCH (CH _Three) -O
-, L and m are 1, p and q are 9, Z is a hexylene group
Certain vinyl urethane compounds are exemplified.

The photopolymerizable compound of the component (B) in the present invention always contains the component (b1). In addition, (b)
2) It is preferable to contain a component. As long as the component (b1) is contained, a photopolymerizable compound having a polymerizable ethylenically unsaturated group in another molecule may be contained.

Examples of such a photopolymerizable compound include a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, bisphenol-bis (polyoxyethylene diacrylate), bisphenol-bis (Polyoxyethylene dimethacrylate), a compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound, an alkyl acrylate, an alkyl methacrylate and the like.

Examples of the polyhydric alcohol include polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, trimethylolpropane diacrylate, and trimethylolpropane. Dimethacrylate, trimethylolpropane triacrylate,
Trimethylolpropane trimethacrylate, tetramethylol methane triacrylate, tetramethylol methane trimethacrylate, tetramethylol methane tetraacrylate, tetramethylol methane tetramethacrylate, the number of propylene groups is 2 to 14 polypropylene glycol diacrylate, the number of propylene groups 2-14, such as polypropylene glycol dimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

Examples of the α, β-unsaturated carboxylic acid include acrylic acid and methacrylic acid.

Examples of bisphenol bis (polyoxyethylene diacrylate) include, for example, bisphenol bis (dioxyethylene diacrylate), bisphenol bis (trioxyethylene diacrylate),
Bisphenol-bis (pentaethyleneoxyacrylate), bisphenol-bis (decaoxyethylene diacrylate) and the like can be mentioned.

Examples of bisphenol bis (polyoxyethylene dimethacrylate) include bisphenol bis (dioxyethylene dimethacrylate), bisphenol bis (trioxyethylene dimethacrylate), bisphenol bis (pentaethyleneoxy methacrylate), Bisphenol @ bis (decaoxyethylene dimethacrylate) and the like are exemplified, and bisphenol @ bis (pentaethyleneoxymethacrylate) is exemplified by BPE-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.).

Examples of the glycidyl group-containing compound include trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate, bisphenol bis (diglycidyl ether acrylate), bisphenol bis (diglycidyl ether methacrylate), and the like. Is mentioned.

Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like.

Examples of the alkyl methacrylate include:
For example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and the like can be mentioned.

These are used alone or in combination of two or more.

The photopolymerization initiator used as the component (C) in the present invention includes, for example, benzophenone,
Aromatic ketones such as N, N-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, phenanthrequinone, benzoin methyl ether, benzoin ethyl Ether, benzoin ether such as benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, benzyl derivative such as benzyl dimethyl ketal, 2,2'-bis (o-chlorophenyl) -4,5,4 ', 5'-tetra Phenyl-1,2'-biimidazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer Isomer, 2- (o-fluorophenyl) -4, - diphenyl imidazole dimer, 2-(o-methoxyphenyl) -4,5-diphenyl imidazole dimer, 2-(p-methoxyphenyl)
-4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) -4,5
2,4,5-triarylimidazole dimer such as -diphenylimidazole dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,7- Acridine derivatives such as bis (9-acridinyl) heptane; These are used alone or in combination of two or more.

In the photosensitive resin composition of the present invention,
The amount of the component (A) is preferably from 40 to 80 parts by weight based on 100 parts by weight of the total of the components (A) and (B) from the viewpoint of the balance between the coating properties and the photocurability. , 5
More preferably 0 to 70 parts by weight, 55 to 65 parts by weight
It is particularly preferred to use parts by weight.

If the amount is less than 40 parts by weight, the resulting photosensitive element tends to have poor coating properties. If it exceeds 80 parts by weight, the photocurability tends to be insufficient.

(B) in the photosensitive resin composition of the present invention
The total amount of the components is preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, and more preferably 35 to 50 parts by weight, based on 100 parts by weight of the total amount of the components (Α) and (B). It is particularly preferable that the content be 45 parts by weight. If the amount is less than 20 parts by weight, the photocurability tends to be insufficient, and if it exceeds 60 parts by weight, the coating properties tend to deteriorate.

(B) in the photosensitive resin composition of the present invention
The amount of the component (b1) in the component is 10% in total.
It is preferably 25 to 75 parts by weight, more preferably 35 to 65 parts by weight, and more preferably 4 to 0 parts by weight.
It is particularly preferred that the amount be 5 to 55 parts by weight. If the amount is less than 25 parts by weight, the tent reliability tends to be insufficient, and if it exceeds 75 parts by weight, the resolution tends to deteriorate.

(B) in the photosensitive resin composition of the present invention
The amount of the component (b2) in the component is preferably 25 to 75 parts by weight, more preferably 35 to 65 parts by weight, and more preferably 45 to 65 parts by weight, per 100 parts by weight of the component (B).
It is particularly preferred that the amount be from 55 to 55 parts by weight. If the amount is less than 25 parts by weight, the resolution tends to be insufficient, and if it exceeds 75 parts by weight, the tent reliability tends to deteriorate.

(C) in the photosensitive resin composition of the present invention
The amount of the components is determined from the balance between sensitivity and resolution.
The amount is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B), and is preferably 0.0 to 5 parts by weight.
It is more preferably 5 to 4 parts by weight, particularly preferably 0.1 to 3 parts by weight. If the amount is 0.0
If the amount is less than 1 part by weight, the sensitivity tends to be insufficient.
When the amount exceeds the weight part, the resolution tends to be deteriorated.

The photosensitive resin composition of the present invention may contain, if necessary, a dye, a pigment, a color former, a plasticizer, a burning agent, in addition to the above components (A), (B) and (C). Additives such as stabilizers and adhesion promoters may be included.

Examples of the dye, pigment and color former include leuco crystal violet, malachite green and the like. Examples of the plasticizer include p-toluenesulfonic acid amide. Examples of the stabilizer include Antage 500 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.). Examples of the adhesion-imparting agent include benzotriazole and the like. These additives can be used alone or in combination of two or more.

The photosensitive element of the present invention is obtained by laminating a layer of the photosensitive resin composition of the present invention on a support.

As a method of laminating a layer of the photosensitive resin composition of the present invention on a support, for example, dissolving the photosensitive resin composition of the present invention in an organic solvent, coating the solution on the support,
Drying method may be mentioned.

Examples of the organic solvent include toluene, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, dimethylformamide, methanol, ethanol and the like.
Used in combination of more than one type.

The support is not particularly limited as long as it has heat resistance and solvent resistance required for the production of the photosensitive element, and a known film can be used.

Examples of such a support include polymer films (polyethylene terephthalate film, polypropylene film, polyethylene film, etc.). Among these polymer films, polyethylene terephthalate film is preferred from the viewpoint of transparency. Is preferred.

Since these polymer films must be removable from the photosensitive layer (photosensitive resin composition layer) in a later step, the polymer film to be used cannot be removed. Or surface treatment has not been performed.

The coating method is not particularly limited, and a known method can be used, and examples thereof include a knife coating method, a roll coating method, and a spray coating method.

Drying can be carried out, for example, by applying a coating operation on a support and then heating using a dryer.

The heating temperature is preferably from 50 to 175 ° C., more preferably from 70 to 110 ° C.
If the heating temperature is less than 50 ° C., a large amount of the organic solvent tends to remain in the photosensitive layer, and if it exceeds 175 ° C., the photosensitive layer tends to discolor.

The heating time is preferably from 30 to 900 seconds, more preferably from 30 to 600 seconds.
If the heating time is less than 30 seconds, the amount of the organic solvent remaining in the photosensitive layer tends to increase, and if it exceeds 900 seconds, the photosensitive layer tends to discolor.

The thickness of the photosensitive layer is appropriately selected depending on the intended use, and is generally about 10 to 100 μm after drying.

The amount of the residual organic solvent in the photosensitive layer is preferably 2% by weight or less from the viewpoint of preventing the diffusion of the organic solvent in a later step.

The photosensitive element of the present invention is preferably one in which the photosensitive layer is covered with a protective film or the like in order to prevent external damage or attachment of foreign matter to the photosensitive layer on the support.

The protective film is not particularly limited as long as the adhesive strength between the photosensitive layer and the protective film is smaller than the adhesive strength between the photosensitive layer and the support. Known protective films can be used. , Polyolefin films (polyethylene film, polypropylene film, etc.), polyester films and the like.

By using the photosensitive resin composition and the photosensitive element of the present invention, a layer of the photosensitive resin composition of the present invention can be laminated on a substrate.

As a method of laminating the layer of the photosensitive resin composition of the present invention on a substrate, a method of dissolving the photosensitive resin composition of the present invention in an organic solvent, directly applying the solution to the substrate, and drying, When a protective film is present using the photosensitive element of the present invention, a method of removing the protective film and then pressing the protective layer on the substrate while heating the photosensitive layer is exemplified. Examples of the substrate include a copper substrate, a nickel substrate, and a chromium substrate.

In the method of dissolving the photosensitive resin composition of the present invention in an organic solvent, directly applying the composition to a substrate, and drying, the organic solvent used in the method for producing the photosensitive element is, for example, the organic solvent used in preparing the photosensitive element. Is mentioned.

The coating method is not particularly limited, and a known method can be used, and examples thereof include a dip coating method and a flow coating method.

Drying can be carried out, for example, by applying a coating operation on a substrate and then heating it using a dryer. The heating temperature and time can be in accordance with the heating temperature and time in the drying operation after the coating operation in producing the photosensitive element.

Further, the thickness of the photosensitive layer and the amount of the residual organic solvent in the photosensitive layer can be determined according to the thickness of the photosensitive layer and the amount of the residual organic solvent in the photosensitive layer when the photosensitive element is prepared.

Further, it is preferable that the obtained photosensitive layer is covered with a protective film or the like, as in the case of the preparation of the photosensitive element.

When a protective film is present using the photosensitive element of the present invention, and after removing the protective film, the photosensitive layer is pressed against a substrate while heating the photosensitive layer. , 90 to 130 ° C., and the compression pressure is usually 3 kgf / cm ² , but these conditions are not particularly limited.

If the photosensitive layer is heated as described above, it is not necessary to pre-heat the substrate in advance, but it is preferable to pre-heat the substrate in order to further improve the lamination property.

The photosensitive layer laminated on the substrate is imagewise exposed to actinic light through a negative or positive film. At this time, if the support existing on the photosensitive layer is transparent, the exposure may be performed as it is. However, if the support is opaque, it is necessary to remove the support before exposure. From the viewpoint of protecting the photosensitive layer, it is preferable that the support is transparent and the photosensitive layer is exposed through the support while the support is left.

As the actinic ray, known actinic rays can be used, and usually, light having a wavelength of 300 to 450 nm is used.
As the light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a xenon arc lamp, or the like is used.

Since the sensitivity of the photopolymerization initiator contained in the photosensitive layer is usually maximum in the ultraviolet region, when a photopolymerization initiator having high sensitivity in the ultraviolet region is used, ultraviolet light can be effectively used as an active light source. Preferably, they emit. On the other hand, when a photopolymerization initiator highly sensitive to visible light is used in combination (e.g., 9,10-phenanthrenequinone, etc.), the active light is preferably visible light, and the light source is as described above. Other than the above, a flood lamp for photography, a sun lamp and the like can be mentioned.

After the exposure, if a support is present on the photosensitive layer, it is removed and developed. The developer is not particularly limited as long as it is safe and stable and has good operability, but it is preferable to use an alkaline aqueous solution from the viewpoint of little influence on the environment.

Examples of the alkaline aqueous solution include alkali hydroxide (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali carbonate (lithium carbonate or bicarbonate, sodium carbonate). Or bicarbonate, potassium carbonate or bicarbonate), alkali metal phosphate (eg, potassium phosphate, sodium phosphate), alkali metal pyrophosphate (eg, sodium pyrophosphate, potassium pyrophosphate, etc.) and the like are used. Among them, sodium carbonate is preferable.

The pH of the aqueous alkali solution needs to be adjusted to an appropriate pH range since the photosensitive layer in the unexposed portion is removed and the photosensitive layer in the exposed portion remains on the substrate as a resist.
To 11, and the temperature is adjusted according to the developability of the photosensitive layer.

Further, a surfactant, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.

The developing method is not particularly limited, and a known developing method can be used. Examples of such a developing method include a dip method, a battle method, a high-pressure spray method, brushing, and scrubbing. However, a high-pressure spray method is preferable from the viewpoint of increasing resolution.

By this developing operation, the photosensitive layer in the unexposed area is removed, and the photosensitive layer in the exposed area remains on the substrate as a resist.

Further, when manufacturing a printed wiring board, after development, treatment is performed by a known method such as etching and plating.

Examples of the plating method include copper plating (copper sulfate plating, copper pyrophosphate plating, etc.), solder plating (high throw solder plating, etc.), nickel plating (watt bath (nickel sulfate-nickel chloride) plating, nickel sulfamate). Plating) and gold plating (hard gold plating, gold plating, etc.).

Next, the resist is stripped from the substrate on which the resist remains. In order to remove the resist, for example, the substrate may be immersed in an aqueous solution that is more alkaline than the aqueous alkaline solution used for development. Examples of such a strongly alkaline aqueous solution include 1 to 5
% By weight of an aqueous sodium hydroxide solution.

[0078]

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 3 and Comparative Example 1 Materials shown in Table 1 (component (A), component (C), additives and solvents) were blended, and component (B) shown in Table 2 was dissolved therein. Thus, a solution of the photosensitive resin composition was obtained.

[0080]

[Table 1]

[0081]

[Table 2] * 1: γ-chloro-β-hydroxypropyl-β′-methacryloyloxyethyl-o-phthalate (manufactured by Hitachi Chemical Co., Ltd.) * 2: Polypropylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) Using a coating method, a solution of the photosensitive resin composition was uniformly applied on a 25 μm-thick polyethylene terephthalate film (manufactured by Teijin Limited, GS type) at 100 ° C.
And dried with a hot air convection dryer for 10 minutes to obtain a photosensitive element. The film thickness of the photosensitive resin composition layer after drying is 40
μm.

Next, the copper surface of a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., trade name: MCL-E-61), which is a glass epoxy material in which copper foil (thickness: 35 μm) is laminated on both sides, is set to $ 600.
Polishing using a polishing machine (manufactured by Sankeisha) having a considerable brush, washing with water, drying with an air stream, heating the obtained copper-clad laminate to 80 ° C., and then obtaining the photosensitive obtained above By using an element, a layer of the photosensitive resin composition was
Lamination was performed at 0 ° C. and 4 kgf / cm ² .

After lamination, the copper-clad laminate was cooled, and when the temperature of the copper-clad laminate reached 23 ° C., a photo tool (a 21-step step tablet of a stofer was brought into close contact with the polyethylene terephthalate surface, Using an exposure machine (model HMW-201GX, 5kW ultra-high pressure mercury lamp)
A 21-step tablet of the stofer is closely attached to a photo tool having a wiring pattern having a line / space of 30/400 to 250/400 (adhesion, unit: μm), and the stofer remains after development of the 21-step tablet. Exposure was performed with an energy amount such that the number of steps was 8.0.

After exposure, the film was allowed to stand at room temperature for 15 minutes, then the polyethylene terephthalate film was peeled off from the copper-clad laminate, and developed by spraying a 1.0% by weight aqueous solution of sodium carbonate at 30 ° C.

Thereafter, based on the result, the exposure amount (sensitivity) at which the number of remaining steps after development was 8.0 was accurately obtained.

Then, a base material in which three holes each having a diameter of 4 mm are continuously formed in a copper-clad laminate having a thickness of 1.6 mm (see FIG. 1).
Were laminated on both sides, and exposed at the above-mentioned energy amount (exposure amount at which the number of remaining steps after development becomes 8.0 steps), and development was performed twice for 60 seconds.

After the development, the portions shown in FIG.
The number of broken holes in each of the three (φ4 mm holes) was measured and evaluated as a deformed tent tear rate (the following formula), which was considered as tent reliability. Deformation tent tear rate (%) = (number of hole tears (pieces) / 18
(Pieces)) × 100 The peelability was determined by laminating the copper-clad laminate for which the exposure amount (sensitivity) was determined as described above, and performing solid exposure with the above energy amount. Next, after development with the above developer, the plate was cut into 5 cm × 5 cm to obtain test pieces. Thereafter, the test piece was immersed in a 3% by weight aqueous solution of sodium hydroxide heated to 50 ° C., and the time required for the resist to peel off and the size of the peeled piece were measured.

Table 3 summarizes the above results.

[0089]

[Table 3] As is clear from Table 3, the photosensitive resin composition used in Comparative Example 1 had very poor peelability, and it was expected that workability would deteriorate.

On the other hand, the photosensitive resin composition used in Example 1 has good tent reliability because the deformed tent has no breakage, and the peeling time is short and the peeled pieces are finely divided. It had peeling properties.

The photosensitive resin composition used in Example 2 was slightly inferior in peelability as compared with Example 1, and the photosensitive resin composition used in Example 3 was different from Example 1. In comparison, although the deformed tent was somewhat torn, the tent reliability was superior to that of the photosensitive resin composition used in the comparative example, and the peelability was good.

[0092]

The photosensitive resin composition of the present invention has excellent tent reliability and good peelability.

The photosensitive element of the present invention has excellent tent reliability and good peelability.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an evaluation board for evaluating a deformed tent tear rate in an example, and shows a portion of a portion where the deformed tent tear rate was evaluated.
One of the eight pieces is shown enlarged.

[Explanation of symbols]

 1 evaluation points

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H025 AA00 AA04 AA13 AA16 AB15 AC01 AD01 BC13 BC34 BC45 BC65 BC83 CA00 CB13 CB14 CB43 FA17 FA39

Claims (4)

[Claims] (A) a binder polymer having a carboxyl group; (B) an acrylate compound represented by the general formula (I) (b)
_{1) CH 2 = CHCO (OCH} 2 CH 2) n -O-CH ((CH 2) k -CH 3) 2 (I) ( wherein, n is 1 to 15 and k is an integer of 1 to 10 ) Comprising a photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule thereof, and (C) a photopolymerization initiator. 2. The acrylate compound (b1) represented by the general formula (I) wherein the photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule of the component (B) is CH ₂ ＣＨCHCO (OCH ₂ CH). represented by _{2) n -O-CH ((} CH 2) k -CH 3) 2 (I) ( wherein, n 1 to 15 and k is an integer of from 1 to 10.) and the general formula (II) Vinyl urethane compound (b2) CH ₂ ＣC (R ₃ ) COO (X) ₁ (Y) _p CO—NH——Z—NH—COO (Y) _q (X) _m COC (R ₃ ) = CH ₂ (II) (wherein, R ₃ represents a hydrogen atom or an alkyl group, and two R _{3 s} may be the same or different, and X is —CH ₂ CH ₂
O- are shown, Y is _{-CH 2 CH (CH 3) -O} -, - CH
_{(CH 3) -CH 2 -O -} , - CH 2 -CH 2 -CH 2 -O
_{-, - CH 2 -CH 2 -CH} 2 -CH 2 -O -, - CH 2 -
CH ₂ —CH ₂ —CH ₂ —CH ₂ —O— or —CH ₂ —CH ₂
—CH ₂ —CH ₂ —CH ₂ —CH ₂ —O—, Z represents a divalent hydrocarbon group, and l, m, p and q each independently represent 1
It is an integer of ~ 14. The photosensitive resin composition according to claim 1, comprising: 3. A binder polymer having a carboxyl group as the component (A) in an amount of 40 to 80 parts by weight, an acrylate compound (b1) represented by the general formula (I) and a general formula (II) as the component (B). 20 to 60 parts by weight of the photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule containing the vinyl urethane compound (b2) (provided that the total amount of the components (A) and (B) is 100 parts by weight The amount of the component (b1) in the photopolymerizable compound (B) is 25 to 75 parts by weight based on 100 parts by weight of the component (B), b2)
The component is 25 to 75 parts by weight. 4. The photosensitive resin according to claim 1, wherein the photopolymerization initiator is contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Composition. 4. A photosensitive element obtained by laminating a layer of the photosensitive resin composition according to claim 1, 2 or 3 on a support.