JPH11218909A - Photosensitive resin composition and photosensitive element using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive resin composition superior in tent reliability and good in plating resistance and the photosensitive element using this composition. SOLUTION: This photosensitive resin composition contains (A) 40-80 pts.wt. of a binder polymer having carboxy groups, (B) 20-60 pts.wt. of photopolymerizable compounds comprising an acrylate compound represented by CH2 =CHCOOCHRCH2 O-(C6 H4 )-C(CH3 )2 -(C6 H5 ), wherein R is an H atom or the like, and a vinyl-urethane compound represented by CH2 =C(R3 )COO(X)l (Y)p CO-NH-Z-NH-COO(Y)q (X)m COC(R3 )=CH2 , wherein R3 is an H atom or the like; X is -CH2 CH2 O-; Y is -CH2 CH(CH3 )-O-; and Z is a divalent hydrocarbon group, each of (l), (m), (p) and (q) is independently an integer of 1-14 and (C) 0.01-5 pts.wt. of a photopolymerization initiator. The photosensitive element is formed by laminating this photosensitive resin composition layer on a support.

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. JP-A-5-271129 discloses a photosensitive resin composition having good tent reliability using a vinyl urethane compound represented by the general formula (II) for such a purpose. However, such a photosensitive resin composition has a problem in terms of plating resistance. This is because the isocyanate residue portion having a urethane bond is
It is presumed that this is due to poor acid resistance. In the plating method, resistance to plating chemicals is required, but in the conventional technology, if this resistance is increased, the cured film becomes hard and brittle, and it is difficult to achieve compatibility with tent reliability.
Had been a problem.

[0003]

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 plating resistance, and a photosensitive element using the same. Is what you do.

[0004]

SUMMARY OF THE INVENTION The present invention relates to (A)
40 to 80% by weight of a binder polymer having a xyl group
Part, (B) an acrylate compound represented by the general formula (I)
(B1) CH_Two= CHCOOCHRCH_TwoO- (C₆H_Four) -C
(CH_Three)_Two− (C₆H _Five) (I) (wherein R represents a hydrogen atom or an alkyl group) and a vinyl urethane compound represented by the general formula (II)
(B2) CH_Two= C (R_Three) COO (X)_l(Y) pCO-NH-Z-NH-COO (Y) q (X) mCOC (R_Three) = CH_Two (II) (wherein, R_ThreeRepresents a hydrogen atom or an alkyl group;
R_ThreeMay be the same or different, and X is -CH_TwoC
H_TwoO-, Y is -CH_TwoCH (CH_Three) -O-,
-CH (CH_Three) -CH_Two-O-, -CH_Two-CH_Two−
CH_Two-O-, -CH_Two-CH_Two-CH_Two-CH_Two-O
-, -CH_Two-CH_Two-CH_Two-CH_Two-CH_Two-O-
Or -CH_Two-CH_Two-CH_Two-CH_Two-CH_Two-CH
_Two-O-; Z represents a divalent hydrocarbon group;
m, p and q are each independently an integer of 1 to 14)
The content of the component (b1) and the component (b2) is
With respect to 100 parts by weight of the total amount of the component (B),
The component (b1) is 25 to 75 parts by weight, and the component (b2) is 25 to 75 parts by weight.
Photopolymerizable compound having an ethylenically unsaturated group
20 to 60 parts by weight, and (C) a photopolymerization initiator, the total of the components (A) and (B)
0.01 to 5 parts by weight per 100 parts by weight
A photosensitive resin composition comprising: In addition, the present invention
Photosensitivity obtained by laminating a layer of the photosensitive resin composition on a support
Sexual element.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
Examples of (A) a binder polymer having a carboxyl group in the present invention include alkyl acrylate or alkyl methacrylate, acrylic acid or methacrylic acid, and a copolymer with a vinyl monomer copolymerizable therewith. 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,
Methacrylic acid methyl ester, methacrylic acid ethyl ester, methacrylic acid butyl ester, methacrylic acid 2-
Ethylhexyl ester and the like. These alkyl methacrylates are used alone or in combination of two or more. Further, 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, 2,2,2-trifluoroethyl methacrylate,
Examples thereof include 2,2,3,3-tetrafluoropropyl acrylate acrylamide, 2,2,3,3-tetrafluoropropyl methacrylate acrylamide, diacetacrylamide, styrene, and vinyl toluene. 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 alkyl acrylate, alkyl methacrylate, acrylic acid, methacrylic acid and the vinyl monomer copolymerizable therewith is not particularly limited, and may be mixed at any ratio.
From the viewpoint of the balance between alkali developability and alkali resistance, the content of the carboxyl group of component (A) described later (the ratio of the monomer having a carboxyl group to all the monomers used) may be 15 to 50 mol%. preferable. These copolymers are used alone or in combination of two or more.

The polymerization average molecular weight of the component (A) is not particularly limited, but is preferably from 20,000 to 300,000 from the viewpoint of balance between mechanical strength and alkali developability, and is preferably 40,000. It is more preferably set to 200,000, and particularly preferably set to 60,000 to 120,000. This weight average molecular weight is 2
If it is less than 000, the mechanical strength tends to be inferior,
If it exceeds 300,000, alkali developability tends to be poor. In addition, the weight average molecular weight mentioned here is a value measured by a gel permeation chromatography method 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 is preferably 15 to 5 in terms of the balance between alkali developability and alkali resistance.
The content is preferably 0 mol%, more preferably 15 to 30 mol%, and still 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. still,
In the present invention, the content of the carboxyl group of the component (A) and the content of the monomer unit having a carboxyl group with respect to the total number of monomer units in the component (A) are
It shows almost the same value.

In the present invention, (B) the photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule is an acrylate compound (b1) represented by the general formula (I) and a compound represented by the general formula (II). Vinyl urethane compound represented by (b
2) Contains components. The general formula (I) is as follows: CH ₂ 2CHCOOCHRCH ₂ O— (C ₆ H ₄ ) —C
(CH ₃ ) _2- (C ₆ H ₅ ) (I) (wherein R represents a hydrogen atom or an alkyl group). Specific examples of the acrylate compound (b1) component represented by the general formula (I) include:
For example, an acrylate compound in which R is a hydrogen atom (trade name, M-110, manufactured by Toa Gosei Chemical Co., Ltd.) and an acrylate compound in which R is a methyl group (Toa Gosei Chemical Co., Ltd.)
Manufactured, prototype name, TO-1430).

The general formula (II) is represented by the formula: CH ₂ ＣC (R ₃ ) COO (X) _l (Y) pCO-NH-Z-NH-COO (Y) q (X) mCOC (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 C
H ₂ O—, Y represents —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 represents —O—; Z represents a divalent hydrocarbon group;
m, p and q are each independently an integer of 1 to 14).

In the general formula (II), examples of the divalent hydrocarbon group represented by Z include hydrocarbon groups having 2 to 16 carbon atoms (ethylene, propylene, butylene, pentylene, pentylene, hexylene, heptylene) Octylene group etc.). 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 general formula (II), R ₃ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group. Y is preferably -CH ₂ CH
(CH ₃₎ is O-. In the general formula (II), l,
When m, p or q is an integer of 15 or more, the obtained resist becomes brittle. l and m are preferably each independently 1, and p and q are each independently preferably 3, 5, 9 or 1
2.

[0011] Vinyl urethane represented by the general formula (II)
Specific examples of the compound (b2) include, for example, two R_Three
Is a methyl group, Y is -CH_TwoCH (CH_Three) O-, l and
And m is 1, p and q are 9, and Z is a hexylene group.
Nylurethane compounds (Shin-Nakamura Chemical Co., Ltd. products, trade names,
UA-13) Two Rs_ThreeIs a methyl group, Y is -CH_TwoC
H (CH_Three) O-, l and m are 1, p and q are 3,
5, or 12, wherein vinyl urethane wherein Z is a hexylene group
Compound, two R_ThreeIs 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, and the like.
It is. (B) The photopolymerizable compound in the present invention must be
The component (b1) and the component (b2) are each composed of one or more kinds.
Used together.

In the present invention, the (B) photopolymerizable compound having a polymerizable ethylenically unsaturated group in the molecule is always an acrylate compound (b1) represented by the general formula (I) and a compound represented by the general formula (II) If the vinyl urethane compound (b2) component represented by the formula (1) is contained, other components may be contained. As such a component, for example, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a polyhydric alcohol, 2-2′-bis {4- (acryloxypolyethoxy) phenyl} propane, 2- 2'-bis ｛4
-(Methacryloxypolyethoxy) phenyl} propane, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound, alkyl acrylate, alkyl methacrylate and the like. As the polyhydric alcohol, for example, polyethylene glycol diacrylate having 2 to 14 ethylene groups, polyethylene glycol dimethacrylate having 2 to 14 ethylene groups, trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, Trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethanetrimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, polypropylene glycol diacrylate having 2 to 14 propylene groups , The number of propylene groups is 2 to 1
4, polypropylene glycol dimethacrylate,
Examples thereof include 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 2-2'-bis {4- (acryloxypolyethoxy) phenyl} propane include, for example, 2-
2'-bis {4- (acryloxydiethoxy) phenyl} propane, 2-2'-bis {4- (acryloxytriethoxy) phenyl} propane, 2-2'-bis} 4
-(Acryloxypentaethoxy) phenyl} propane, 2-2'-bis {4- (acryloxydecaethoxy) phenyl} propane and the like. Examples of 2-2'-bis {4- (methacryloxypolyethoxy) phenyl} propane include, for example, 2-2'-bis {4- (methacryloxydiethoxy) phenyl} propane, 2-2 '
-Bis {4- (methacryloxytriethoxy) phenyl} propane, 2-2'-bis {4- (methacryloxypentaethoxy) phenyl} propane, 2-2'-bis {4- (methacryloxydecaethoxy) phenyl {Propane and the like; 2-2′-bis {4- (methacryloxy pentaethoxy) phenyl} propane
BPE-500 (trade name, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like. As the glycidyl group-containing compound, for example,
Trimethylolpropane triglycidyl ether triacrylate, trimethylolpropane triglycidyl ether trimethacrylate, 2-2'-bis {4- (acryloxydiglycidyloxy) phenyl} propane,
2-2'-bis {4- (methacryloxydiglycidyloxy) phenyl} propane and the like. Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like. Examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, butyl methacrylate, and 2-ethylhexyl methacrylate.
These are used alone or in combination of two or more. The content of the components other than the components (b1) and (b2) in the component (B) is, for example, (B)
It may be 5 to 10 parts by weight based on 100 parts by weight of the total amount of the components.

The photopolymerizable initiator used as the component (C) in the present invention includes, for example, benzophenone,
N, N-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N-tetraethyl-
4,4'-diaminobenzophenone, 4-methoxy-
Aromatic ketones such as 4'-dimethylaminobenzophenone, 2-ethylanthraquinone and phenanthrenequinone;
Benzoin methyl ether, benzoin ethyl ether, benzoin ether such as benzoin phenyl ether, benzoin such as methyl benzoin, ethyl benzoin, benzyl derivatives such as benzyl dimethyl ketal,
2,2'-bis (o-chlorophenyl) -4,5
4 ', 5'-tetraphenyl-1,2'-biimidazole, 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-diphenyl Imidazole dimer,
2,4,5-triarylimidazole dimer such as 2- (p-methylmercaptophenyl) -4,5-diphenylimidazole dimer, 9-phenylacridine, 1,
Acridine derivatives such as 7-bis (9,9'-acridinyl) heptane; Preferably, 2- (o-
(Chlorophenyl) -4,5-diphenylimidazole dimer, N, N-tetraethyl-4,4'-diaminobenzophenone, or 9,10-phenanthrenequinone. 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 40 to 80 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B) from the viewpoint of the balance between the coating properties and the photocurability. Preferably, it is more preferably 50 to 70 parts by weight, and 55
It is particularly preferred that the content be up to 65 parts by weight. When the compounding amount of the component (A) is less than 40 parts by weight, the obtained photosensitive element tends to have poor coating properties. If it exceeds 80 parts by weight, the photocurability tends to be insufficient.

In the photosensitive resin composition of the present invention,
The compounding amount of the component (B) is preferably 20 to 60 parts by weight, more preferably 30 to 50 parts by weight, based on 100 parts by weight of the total of the components (A) and (B). It is particularly preferred that the amount is 35 to 45 parts by weight.
When the amount of the component (B) is less than 20 parts by weight, the photocurability tends to be insufficient, and when it exceeds 60 parts by weight, the coating properties tend to deteriorate.

The compounding amount of the component (b1) in the component (B) in the photosensitive resin composition of the present invention may be 25 to 75 parts by weight based on 100 parts by weight of the total amount of the component (B). It is more preferably from 35 to 65 parts by weight, particularly preferably from 45 to 55 parts by weight.
If the amount of the component (b1) is less than 25 parts by weight, the acid resistance tends to be insufficient, and if it exceeds 75 parts by weight, tent reliability tends to deteriorate. The amount of the component (b2) in the component (B) in the photosensitive resin composition of the present invention is preferably 25 to 75 parts by weight based on 100 parts by weight of the total amount of the component (B). ~ 6
It is more preferably 5 parts by weight, particularly preferably 45 to 55 parts by weight. If the amount of component (b2) is less than 25 parts by weight, tent reliability tends to be insufficient, and if it exceeds 75 parts by weight, acid resistance 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.
It is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B),
The amount is more preferably from 0.5 to 4 parts by weight, and from 0.1 to 3 parts by weight.
It is particularly preferred to use parts by weight. If the amount of the component (C) is less than 0.01 part by weight, the sensitivity tends to be insufficient, and if it exceeds 5 parts by weight, 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 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 burning agent include phosphoric acid esters such as triphenyl phosphate and halogen-containing organic compounds such as chlorinated paraffin. As the stabilizer, for example, Antage 500 (trade name, manufactured by Kawaguchi Chemical Industry Co., Ltd.)
And the like. 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, a method of dissolving the photosensitive resin composition of the present invention in an organic solvent, applying the solution on a support, and drying. No. 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. These may be used alone or in combination of two or more. Used in combination. 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, for example, a polymerized film (polyethylene terephthalate film, polypropylene film, polyethylene film, etc.), and among these polymerized films,
A polyethylene terephthalate film is preferred from the viewpoint of transparency.

Since these polymer films must be removable from the photosensitive layer (photosensitive resin composition layer) in a later step, the polymer film used is made of a material which cannot be removed. Or surface treatment has not been performed. As a coating method on the support,
There is no particular limitation, and a known method can be used, and examples thereof include a knife coating method, a low coating method, and a sley coating method. Drying, for example, after a coating operation on the support,
It can be performed by 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 be discolored. 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 support is
Although it is appropriately selected according to the application, it is preferably 5 to 100 μm, more preferably 10 to 30 μm. The thickness of the photosensitive layer is
Although it is appropriately selected depending on the application, the thickness after drying is usually
It is about 10 to 100 μm. Further, 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.

In the photosensitive element of the present invention, it is preferable that 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, and a known film can be used. For example, a polyolefin film ( Polyethylene film, polypropylene film, etc.), polyester film 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 a layer of the photosensitive resin composition of the present invention on a substrate, dissolving the photosensitive resin composition of the present invention in an organic solvent, directly,
A method of applying to a substrate and drying, a method of using the photosensitive element of the present invention, if a protective film is present, removing the protective film, heating the photosensitive layer while pressing the photosensitive layer, and the like. . 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 to a substrate, and drying, the organic solvent used includes, for example, the organic solvent used in preparing the photosensitive element. . The application 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 performed, for example, by heating using a dryer after the application operation on the substrate. The heating temperature and time can be in accordance with the heating temperature and time in the drying operation after the coating operation in preparing the photosensitive element. Also,
The thickness of the photosensitive layer and the amount of the remaining organic solvent in the photosensitive layer can also be determined according to the thickness of the photosensitive layer and the amount of the remaining 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 preparing the photosensitive element. Using the photosensitive element of the present invention, if a protective film is present, after removing it, in a method in which the photosensitive layer is pressed against a substrate while heating the photosensitive layer, the heating temperature of the photosensitive layer is usually 90 to 90. 13
The temperature is set to 0 ° C., and the pressing pressure is usually set to 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 lamination properties. The photosensitive layer laminated on the substrate is imagewise exposed to actinic radiation through a negative or positive film. At that time, if the support present on the photosensitive layer is transparent, it may be exposed as it is,
If 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. A known actinic ray can be used as the actinic ray, and usually has a wavelength of 300 to 45.
0 nm light 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 photopolymerizable initiator contained in the photosensitive layer is usually maximum in the ultraviolet region,
When a photopolymerizable initiator having high sensitivity in the ultraviolet region is used, it is preferable that the active light source emits ultraviolet light effectively. On the other hand, when a photopolymerizable initiator having high sensitivity to visible light is used in combination (for example, 9,10-phenanthrenequinone or the like), visible light is preferable as the active light, and the light source is:
In addition to the above, a flood lamp for photography, a sun lamp and the like can be mentioned.

After 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. However, 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). Salts, carbonates or bicarbonates of potassium), alkali metal phosphates (potassium phosphate, sodium phosphate, etc.), alkali metal pyrophosphates (sodium pyrophosphate, potassium pyrophosphate, etc.) and the like are used. Among them, sodium carbonate is preferred. The pH of the alkaline aqueous solution is preferably 9 to 11, since the photosensitive layer in the unexposed area is removed and the photosensitive layer in the exposed area needs to be in a proper pH range remaining on the substrate as a resist. The temperature is adjusted according to the developability of the photosensitive layer. Also, in the alkaline aqueous solution,
A surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed.

The developing method is not particularly limited, and a known developing method can be used. Such a developing method includes, for example, a dip method, a battle method, a high-pressure spray method, brushing, slapping, and the like, and a high-pressure spray method is preferable because resolution is increased. By this developing operation, the photosensitive layer in the unexposed portion is removed, and the photosensitive layer in the exposed portion remains on the substrate as a resist.

Further, when manufacturing a printed wiring board, after development, the printed wiring board is processed 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, etc.) And gold plating (hard gold plating, soft 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 an aqueous solution of 1 to 5% by weight of sodium hydroxide.

[0029]

The present invention will be described below with reference to examples.

Examples 1 to 3 and Comparative Examples 1 to 4 The component (A) shown in Table 1 was prepared by the following procedure. In a 3-liter separable flask equipped with a stirrer, a reflux condenser, and a thermometer, 40 g of toluene and 60 g of methylcellosolve are added as a solvent, and the temperature is raised to 90 ° C. Then, a mixed solution of 18 g of methacrylic acid, 52 g of methyl methacrylate, 30 g of ethyl acrylate, and 0.5 g of azobisisobutyronitrile was added dropwise over 4 hours. After the completion of the dropwise addition, the temperature was kept at 90 ° C. for 5 hours. Next, a solution prepared by dissolving 0.2 g of azobisisobutyronitrile in 10 g of toluene was added dropwise over 30 minutes. Thereafter, the temperature of the flask was maintained at 90 ° C. for 2 hours, then the temperature of the flask was lowered to 50 ° C. or lower, and the polymer taken out of the flask was used as the polymer of the component (A).
The carboxyl group content of the polymer (A) is 18%.
Met. Materials shown in Table 1 (component (A), component (C),
Additives and solvent), and (B)
The components were dissolved to obtain a solution of the photosensitive resin composition.

[0031]

[Table 1]

[0032]

[Table 2] * 1. Nonylphenol polyethylene glycol acrylate (manufactured by Toa Gosei Chemical Co., Ltd.). * 2. Polypropylene glycol diacrylate (Shin-Nakamura Chemical Co., Ltd.).

Next, using a knife coat 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), and heated with a hot air convection dryer at 100 ° C. for 10 minutes. After drying for a minute, a photosensitive element was obtained. The dried film thickness of the photosensitive resin composition layer was 40 μm. Then, copper foil (thickness 35μ)
Polishing machine with a brush equivalent to # 600 on 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 having m) laminated on both sides (manufactured by Sankeisha)
After polishing, washing with water and drying with an air stream, heating the obtained copper-clad laminate to 80 ° C., and using the photosensitive element obtained above, the photosensitive element The layer of the resin composition was laminated at 120 ° 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 stepper of Stofer) was brought into close contact with the polyethylene terephthalate surface, and an exposure machine manufactured by Oak Co., Ltd. was used. (Type HMW-2
01GX, 5kW ultra-high pressure mercury lamp), a 21-step tablet of stofer and 30 lines / space.
A photo tool having a wiring pattern of / 400 to 250/400 (adhesion, unit: μm) was brought into close contact, and exposed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0. . After exposure, the film was left at room temperature for 15 minutes, and then the polyethylene terephthalate film was peeled off from the copper-clad laminate.
The development was carried out by spraying a 1.0% by weight aqueous solution of sodium carbonate.

Thereafter, based on the result, an exposure amount (sensitivity) at which the number of remaining steps after development becomes 8.0 was accurately obtained. Then, a laminate of the photosensitive resin composition was laminated on both sides of a substrate having three holes of 4 mm in diameter in a 1.6 mm-thick copper-clad laminate as shown in FIG. Exposure was performed at (an exposure amount at which the number of steps remaining after development was 8.0), and development for 60 seconds was performed twice. After the development, the number of broken holes at the locations shown in 1 in FIG. 1 (a total of 18 triple-diameter φ4 mm holes) was measured and evaluated as a deformed tent breaking ratio (the following formula), and this was considered as tent reliability. Deformed tent tear rate (%) = (number of hole torn (pcs) / 18
(Pcs) x 100

The plating resistance was evaluated as follows. First, lamination was performed as described above, and exposure was performed using the above energy amount. Then, after developing with the above developer, degreased (PC-455 (manufactured by Meltex Co., Ltd.) 25% by weight) immersed for 3 minutes → rinsed with water → immersed in soft etch (ammonium persulfate 150 g / l) for 2 minutes → rinsed with water → 10% by weight sulfuric acid Pretreatment was performed in the order of immersion for 1 minute, and the resultant was placed in a copper sulfate plating bath (copper sulfate 75 g / liter, sulfuric acid 190 g / liter, chlorine ion 75 ppm, copper glyme PCM (manufactured by Meltex Co., Ltd.) 5 cc / liter). Copper plating was performed at room temperature for 40 minutes at 3 A / dm ^2. Then, the plate was washed with water, immersed in 10% by weight of hydrofluoric acid for 1 minute, and subjected to a solder plating bath (45% by weight of tin borofluoride 64 ml / liter, 45% by weight). % Lead borofluoride 22 ml / l, 42% by weight borofluoric acid 200 ml / l, Plutin LA Conductivity Salt (Meltec (Ltd.)
20 g / l) and 40 ml / l of Plutin LA starter (manufactured by Meltex Co., Ltd.), and subjected to solder plating at room temperature and 1.5 A / dm ² for 15 minutes.

Then, after washing with water and drying, a cellophane tape was immediately applied to check the plating resistance, and the cellophane tape was peeled off in a vertical direction (90 ° peel-off test) to determine whether or not the resist had peeled off. After the resist was peeled off, the presence or absence of the solder plating was observed from above using an optical microscope. When the solder plating is buried, solder deposited by plating is observed under the transparent resist via the transparent resist. Table 3 summarizes the above results.

[0037]

[Table 3]

As is evident from Table 3, the photosensitive resin compositions used in Comparative Examples 1 and 3 had poor plating resistance tape tests and very poor plating, and were unsuitable for producing high-density substrates. Was expected. Comparative Examples 2 and 4
In the photosensitive resin composition used in the above, the deformed tent was torn and the tent reliability was low. In contrast, Example 1
The photosensitive resin composition used in Example 1 had good tent reliability without breaking the deformed tent and excellent peel resistance in the tape test because there was no peeling or plating under the tape test. The photosensitive resin composition used in Example 2 had slightly poor plating resistance as compared with Example 1, and
The photosensitive resin composition used in Example 3 was slightly better than the photosensitive resin composition used in Comparative Example, although the deformed tent was slightly broken as compared with Example 1. High plating resistance.

[0039]

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

[Brief description of the drawings]

FIG. 1 is an example of a base material used for evaluating the rate of breaking a deformed tent of the photosensitive resin composition of the present invention.

Claims (2)

[Claims] 1. A binder having a carboxyl group (A)
(B) an acrylate compound (b) represented by the general formula (I)
1) CH_Two= CHCOOCHRCH_TwoO- (C₆H_Four) -C
(CH_Three)_Two− (C₆H _Five) (I) (wherein R represents a hydrogen atom or an alkyl group) and a vinyl urethane compound represented by the general formula (II)
(B2) CH_Two= C (R_Three) COO (X)_l(Y) pCO-NH-Z-NH-COO (Y) q (X) mCOC (R_Three) = CH_Two (II) (wherein, R_ThreeRepresents a hydrogen atom or an alkyl group;
R_ThreeMay be the same or different, and X is -CH_TwoC
H_TwoO-, Y is -CH_TwoCH (CH_Three) -O-,
-CH (CH_Three) -CH_Two-O-, -CH_Two-CH_Two−
CH_Two-O-, -CH_Two-CH_Two-CH_Two-CH_Two-O
-, -CH_Two-CH_Two-CH_Two-CH_Two-CH_Two-O-
Or -CH_Two-CH_Two-CH_Two-CH_Two-CH_Two-CH
_Two-O-; Z represents a divalent hydrocarbon group;
m, p and q are each independently an integer of 1 to 14)
The content of the component (b1) and the component (b2) is
With respect to 100 parts by weight of the total amount of the component (B),
The component (b1) is 25 to 75 parts by weight, and the component (b2) is 25 to 75 parts by weight.
Photopolymerizable compound having an ethylenically unsaturated group
20 to 60 parts by weight, and (C) a photopolymerization initiator, the total of the components (A) and (B)
A photosensitive resin composition comprising 0.01 to 5 parts by weight per 100 parts by weight. 2. A photosensitive element obtained by laminating a layer of the photosensitive resin composition according to claim 1 on a support.