JP2002099082A - Photosensitive resin composition, photosensitive element using the composition, method of producing resist pattern and method of producing printed-wiring board - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition excellent in photosensitivity, resolution, chemical resistance (plating resistance), close adhesion, mechanical strength and flexibility, and also provide a method of producing resist pattern. SOLUTION: The method of producing a resist pattern which is characterized by laminating a photosensitive element comprising a photosensitive element composition composed of (A) a binder polymer having a water absorption of 4<wt.% and a degree of dispersion of 1.0-6.0, (B) a photopolymerizable compound having at least one polimerizable ethylenically unsaturated bond having 2,2-bis(4-((meth) acryloxypolyethoxy)phenyl) propane as an essential component, and (C) a photopolymerization initiator, on a substrate for forming a circuit in a way that a photosensitive resin composition layer is adhered thereto, and carrying out exposure and development, and the method of producing a printed- wiring board characterized by etching or plating the substrate for forming the circuit in which the resist pattern is produced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photosensitive resin composition, a photosensitive element using the same, a method for producing a resist pattern, and a method for producing a printed wiring board.

[0002]

2. Description of the Related Art Conventionally, in the field of manufacturing printed wiring boards, a photosensitive resin composition and a photosensitive element obtained using a support and a protective film have been widely used as a resist material for etching, plating, and the like. Have been. Printed wiring board, after laminating the photosensitive element on a copper substrate, pattern exposure, remove the unexposed part with a developing solution, subjected to etching or plating,
It is manufactured by a method of peeling and removing a cured portion from a substrate after forming a pattern. As a developing solution for removing the unexposed portion, an alkali developing type using a sodium carbonate solution or the like has become mainstream, and the developing solution usually has a certain ability to dissolve the photosensitive resin composition layer. It can be used, and the photosensitive resin composition is dissolved or dispersed in a developer during development.

With the recent increase in the density of printed wiring boards,
Because the contact area between the copper substrate and the patterned photosensitive resin composition layer is reduced, excellent adhesive strength, mechanical strength, chemical resistance, flexibility, etc. are required in the development, etching or plating process steps, and Resolution is required. Among these types of properties, a method using a photopolymerizable compound having a bisphenol A skeleton to improve chemical resistance is disclosed in Japanese Patent Publication No. 7-27.
As described in Japanese Patent Publication No. 205, when the degree of dispersion of the binder polymer is large, the adhesion and the resolution tend to be reduced.

[0004]

The invention described in claim 1 provides a photosensitive resin composition having excellent photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility. This is useful for increasing the density and resolution of printed wiring. The invention of claim 2 provides the effect of the invention of claim 1 and provides a photosensitive resin composition having excellent chemical resistance. The invention described in claim 3 provides a photosensitive resin composition having excellent alkali developability in addition to the effects of the invention described in claim 1 or 2.

[0005] The invention according to claims 4 and 5 is based on claim 1,
It is intended to provide a photosensitive resin composition exhibiting the effects of the invention described in 2 or 3 and further having excellent peeling properties. Claim 6
The invention described provides the effects of the invention described in claims 1, 2, 3, 4 and 5, and provides a photosensitive resin composition having excellent adhesion. The invention according to claim 7 has the effects of the invention according to claim 1, 2, 3, 4, 5, or 6, and further has photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, and the like. An object of the present invention is to provide a photosensitive resin composition having excellent flexibility.

The invention according to claims 8 and 9 is to provide a photosensitive element having excellent photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility. It is useful for high density and high resolution. The invention according to claims 10 and 11 is the invention according to claim 8 or 9
It is an object of the present invention to provide a photosensitive element having the effects of the invention described in the description and further having excellent resolution. The twelfth aspect of the invention provides the effects of the eighth, ninth, tenth, or eleventh aspects of the invention, and provides a photosensitive element having an excellent resolution. The inventions according to the thirteenth and fourteenth aspects provide a photosensitive element having further excellent laminating properties in addition to the effects of the inventions according to the eleventh or twelfth aspects.

The invention according to claim 15 provides a method for producing a resist pattern excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility. It is useful for high density and high resolution. The invention according to claim 16 provides a method for manufacturing a printed wiring board having excellent light sensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, and flexibility, and has a high density of printed wiring. It is useful for high resolution and high resolution.

[0008]

According to the present invention, there are provided (A) a binder polymer having a water absorption of less than 4% by weight and a dispersity of 1.0 to 6.0, and (B) 2,2-bis ( (C) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing 4-((meth) acryloxypolyethoxy) phenyl) propane as an essential component;
The present invention relates to a photosensitive resin composition containing a photopolymerization initiator.

The present invention also relates to the photosensitive resin composition wherein the binder polymer (A) contains styrene or a styrene derivative as an essential copolymer component. The present invention also relates to the photosensitive resin composition wherein (A) the binder polymer contains methacrylic acid as an essential copolymer component. The present invention also relates to the photosensitive resin composition, which further comprises, as an essential component, a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule as the component (B).

[0010] The present invention also relates to the photosensitive resin composition, wherein the photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule has one phenyl group or phenylene group in the molecule. In addition, the present invention relates to the photosensitive resin composition, wherein the photopolymerization initiator (C) contains a 2,4,5-triarylimidazole dimer as an essential component. In addition, the present invention provides a method for preparing 2,2-bis (4-
The present invention relates to the photosensitive resin composition, wherein the content of ((meth) acryloxypolyethoxy) phenyl) propane is 3 to 90% by weight.

[0011] The present invention also relates to a photosensitive element having a layer of the photosensitive resin composition on a support. The present invention also relates to the photosensitive element having a protective film on the side of the photosensitive resin composition layer opposite to the support. The present invention also relates to the photosensitive element, wherein the support has a thickness of 5 to 25 μm. The present invention also relates to the photosensitive element, wherein the support has a haze of 0.001 to 5.0.

The present invention also relates to the photosensitive element, wherein the layer of the photosensitive resin composition has a transmittance of 5 to 75% for ultraviolet rays having a wavelength of 365 nm. The present invention also relates to the photosensitive element, wherein the protective film has a thickness of 5 to 30 μm. The present invention also relates to the photosensitive element, wherein the protective film has a tensile strength in the film longitudinal direction of 13 MPa or more and a tensile strength in the film width direction of 9 MPa or more.

[0013] The present invention also provides a photosensitive element, which is laminated on a circuit-forming substrate in such a manner that the photosensitive resin composition layer is in close contact with the photosensitive element while removing a protective film which may be present in some cases. The present invention relates to a method for producing a resist pattern, which comprises irradiating an exposed portion, photocuring an exposed portion, and removing an unexposed portion by development. Further, the present invention relates to a method for manufacturing a printed wiring board, wherein a circuit forming substrate on which a resist pattern is manufactured is etched or plated by the method for manufacturing a resist pattern.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, (meth) acrylic acid means acrylic acid and methacrylic acid corresponding thereto,
(Meth) acrylate means acrylate and its corresponding methacrylate, and (meth) acryloyl group means acryloyl and its corresponding methacryloyl group.

The photosensitive resin composition of the present invention comprises (A) a binder polymer having a water absorption of less than 4% by weight, and (B) a bisphenol A-based (meth) acrylate compound having at least one component in its molecule. It comprises a photopolymerizable compound having a polymerizable ethylenically unsaturated bond and (C) a photopolymerization initiator.

The water absorption of the binder polymer (A) must be less than 4% by weight,
4.0% by weight, preferably 0.3 to 3% by weight
Is more preferably less than 0.5% and particularly preferably less than 0.5 to 2% by weight. When the water absorption exceeds 4% by weight, the developability of the unexposed portion is greatly promoted, but the exposed portion exceeds the hydrophilicity limit and the photoresist image is exposed at the end (the exposed portion and the unexposed portion). At the boundary), the image is sharply affected by the developer and the sharpness of the image is poor, the resolution is reduced, and as a result, the apparent photosensitivity is also reduced. Further, the resistance to the plating solution and the etching solution is reduced, and phenomena such as peeling are caused. Get up.

The binder polymer (A) preferably has a degree of dispersion (weight average molecular weight / number average molecular weight) of 1.0 to 6.0, more preferably 1.0 to 3.0. If the degree of dispersion exceeds 6.0, the adhesiveness and the resolution tend to decrease. However, the weight average molecular weight and the number average molecular weight in the present invention are values measured by gel permeation chromatography and converted to standard polystyrene.

The weight average molecular weight of the binder polymer (A) is preferably from 20,000 to 300,000, more preferably from 40,000 to 150,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long.

The (A) binder polymer includes:
For example, acrylic resin, styrene resin, epoxy resin, amide resin, amide epoxy resin, alkyd resin, phenol resin and the like can be mentioned. From the viewpoint of alkali developability, an acrylic resin is preferred. These can be used alone or in combination of two or more.

The binder polymer (A) can be produced, for example, by radically polymerizing a polymerizable monomer.

Examples of the polymerizable monomer include polymerizable styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, p-methylstyrene, p-ethylstyrene, acrylamide, acrylonitrile, vinyl-n-butyl ether. Esters of vinyl alcohol, such as alkyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, (meth) acrylic acid Glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-bromo (meth) acrylic acid, α- Chlor (meth) acrylic acid, β Furyl (meth) acrylic acid, beta-
Styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate such as monomethyl maleate, monoethyl maleate, monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid,
Examples include itaconic acid, crotonic acid and propiolic acid. These are used alone or in combination of two or more.

Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and the like.
Butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, structural isomers thereof and the like Is mentioned. These can be used alone or in combination of two or more.

The (A) binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability. For example, the polymerizable monomer having a carboxyl group is radically polymerized with another polymerizable monomer. It can be manufactured by the following. The polymerizable monomer having a carboxyl group is preferably methacrylic acid.
The (A) binder polymer preferably contains styrene or a styrene derivative as a polymerizable monomer from the viewpoint of flexibility.

In order to improve both adhesion and peeling properties by using the styrene or styrene derivative as a copolymer component, the content is preferably 3 to 30% by weight, more preferably 4 to 28% by weight, and more preferably 5 to 28% by weight. It is particularly preferred to contain 27% by weight. If the content is less than 3% by weight, the adhesion tends to be poor, and if it exceeds 30% by weight, the peeled pieces tend to be large and the peeling time tends to be long. Further, the binder polymer may have a photosensitive group, if necessary.

These binder polymers are used alone or in combination of two or more. When two or more kinds are used in combination, examples of the binder polymer include two or more kinds of binder polymers composed of different copolymer components, two or more kinds of binder polymers having different weight average molecular weights, and two or more kinds of different dispersion degrees. Binder polymers and the like. In addition, JP-A-11-3
A polymer having a multi-mode molecular weight distribution described in Japanese Patent No. 27137 can also be used.

The acid value of the binder polymer (A) is as follows:
It is preferably 100 to 500 mgKOH / g,
More preferably, it is で 300 mgKOH / g. If the acid value is less than 100 mgKOH / g, the developing time tends to be slow, and if it exceeds 500 mgKOH / g, the photocured resist tends to have a reduced resistance to a developing solution.

The test piece (A) for measuring the water absorption of the binder polymer can be prepared, for example, by the following procedures 1 to 17. 1. A Teflon (registered trademark) sheet having a thickness of 0.5 mm is laid on a metal dish, a solid binder polymer having a thickness of 3 mm or less is placed thereon, and vacuum-dried at 150 ° C. for 6 hours. 2. After being allowed to cool out of the dryer, the plate-shaped binder polymer is pulverized using a pulverizer. 3. 250 μm using a 250 μm mesh sieve
To obtain less than one binder polymer particle.

4. As shown in FIG. 1, a metal petri dish 1 in which only the bottom surface is processed with Teflon 2 is washed with acetone and dried. (Hereinafter, the metal petri dish in this state is referred to as a lid.) As shown in FIG. 2, a metal petri dish 1 having a diameter of 50 mm, in which a Teflon 2 is processed inside, is washed with acetone and dried.
(Hereafter, the metal dish in this state is referred to as a container.)

6. About 7 g (calculated from the true specific gravity of the binder polymer and slightly larger than the weight at which the thickness becomes 3 mm) of the binder polymer particles selected in the above container is weighed. 7. Place the lid carefully so as not to spill the binder polymer particles, and gently put the lid on the lid so that the container comes to the position of the mark 3 attached to the lid beforehand so that the thickness of the test piece becomes 3 mm as shown in FIG. The lid is rotated while applying pressure so that the height of the binder polymer particles is uniform.

8. Using a hydraulic press machine used for IR tablet molding, pressure is applied from above the lid at 10 to 15 MPa, and the state is left for 1 minute. 9. After that, put 2kg weight on the lid and put it on the hot plate. 10. The temperature of the hot plate is set to 60 ° C., and after the temperature reaches 60 ° C., the plate is left for 30 minutes. 11. Next, the temperature of the hot plate was set to 80 ° C.
Leave at 0 ° C for 30 minutes. 12. Similarly, the temperature is set to 120 ° C., and after the temperature reaches 120 ° C., the apparatus is left for 30 minutes. 13. Further, the temperature is set to 150 ° C., and the temperature is raised to 150 ° C., and the apparatus is left for 3 hours.

14. After that, keep the weight on for 150
Place in an oven at ℃ for 4 hours. 15. Take it out and let it cool at room temperature, then take out the test piece from the container. 16. Check that the test piece is not thermally denatured. 17． Sample size is 50 ± 1mm in diameter and 3 ± thick
After confirming that it is 0.2 mm, save it in a desiccator.

The water absorption of the binder polymer (A) is, for example, the standard shown in JIS K 6911, that is, the diameter 50 ± 1 mm and the thickness 3 ± 0.
The weight increase rate is shown when a 2 mm test piece is immersed in distilled water at 23 ± 0.5 ° C. for 24 hours. The water absorption of the binder polymer (A) is an average value of three test pieces prepared and measured by the above method.

(B) 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl which is an essential component as a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in the molecule. ) As propane,
For example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxypentaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis (4
-((Meth) acryloxyheptaethoxy) phenyl)
Propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryl) Roxide decaethoxy) phenyl) propane, 2,2-
Bis (4-((meth) acryloxytridecaethoxy)
Phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane,
2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2,2-bis (4-
((Meth) acryloxyhexadecaethoxy) phenyl) propane and the like, and 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane is represented by B
It is commercially available as PE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd., product name), and 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane is
It is commercially available as BPE-1300 (product name, manufactured by Shin-Nakamura Chemical Co., Ltd.). Further, the total number of ethylene glycol chains in the molecule is preferably from 4 to 20, and more preferably from 8 to 15.

The compound may have a substituent as long as the effects of the present invention are not impaired. These are used alone or in combination of two or more.

As the photopolymerizable compound other than the 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane, for example, α, β-
A compound obtained by reacting an unsaturated carboxylic acid, a compound obtained by reacting an α, β-unsaturated carboxylic acid with a glycidyl group-containing compound, 2,2-bis (4-((meth) acryloxypolypropoxy) Phenyl) propane, 2,
Urethane monomers such as 2-bis (4-((meth) acryloxypolyethoxypolypropoxy) phenyl) propane and (meth) acrylate compounds having a urethane bond, γ-chloro-β-hydroxypropyl-β ′-(meth) Acryloyloxyethyl-o-phthalate, β-
Hydroxyethyl-β '-(meth) acryloyloxyethyl-o-phthalate, β-hydroxypropyl-
β '-(meth) acryloyloxyethyl-o-phthalate, alkyl (meth) acrylate, EO-modified nonylphenyl (meth) acrylate, etc., in which one polymerizable ethylenically unsaturated bond is present in the molecule. It is preferable to use a photopolymerizable compound having at least one phenyl group or a phenylene group in the molecule. These are used alone or in combination of two or more.

Examples of the photopolymerizable compound having at least one phenyl group or phenylene group in the molecule include, for example, nonylphenoxytetraethyleneoxyacrylate, nonylphenoxypentaethyleneoxyacrylate, nonylphenoxyhexaethyleneoxyacrylate, nonylphenoxyheptaethylene. Nonylphenoxypolyethyleneoxyacrylates such as oxyacrylate, nonylphenoxyoctaethyleneoxyacrylate, nonylphenoxynonaethyleneoxyacrylate, nonylphenoxydecaethyleneoxyacrylate, and nonylphenoxyundecaethyleneoxyacrylate.

Examples of the photopolymerization initiator (C) include benzophenone, N, N'-tetramethyl-4,
N, N'-tetraalkyl-4,4'-diaminobenzophenone such as 4'-diaminobenzophenone (Michler's ketone), 2-benzyl-2-dimethylamino-1-
Aromatic ketones such as (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1, quinones such as alkylanthraquinone, benzoin alkyl ethers and the like Benzoin ether compounds, benzoin compounds such as benzoin and alkyl benzoin, benzyl derivatives such as benzyl dimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer,
(O-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2-
(O-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5
2,4,5-triarylimidazole dimer such as -diphenylimidazole dimer, acridine derivative such as 9-phenylacridine, 1,7-bis (9,9'-acridinyl) heptane, N-phenylglycine, N-phenylglycine derivatives, coumarin-based compounds and the like can be mentioned.

The substituents of the aryl groups of the two 2,4,5-triarylimidazoles may be the same to give the target compound or different asymmetric compounds. Further, from the viewpoints of adhesion and sensitivity, 2, 4, 5
-Triarylimidazole dimers are more preferred. These are used alone or in combination of two or more.

The amount of the binder polymer (A) is preferably from 40 to 80 parts by weight, and more preferably from 45 to 80 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
More preferably, it is 70 parts by weight. This blending amount is 4
If it is less than 0 parts by weight, the photocured product tends to be brittle, and when used as a photosensitive element, the coating properties tend to be poor,
If it exceeds 80 parts by weight, the light sensitivity tends to be insufficient.

The amount of the photopolymerizable compound (B) is as follows:
The total amount of the components (A) and (B) is preferably 20 to 60 parts by weight based on 100 parts by weight, and 30 to 5 parts by weight.
More preferably, it is 5 parts by weight. When the blending amount is 20
If the amount is less than 10 parts by weight, the light sensitivity tends to be insufficient.
If the amount exceeds the weight part, the photocured product tends to become brittle. The compounding amount of the bisphenol A (meth) acrylate compound, which is an essential component in the photopolymerizable compound (B), is preferably 3 to 90% by weight, and more preferably 5 to 70% by weight in the component (B). Is more preferable. When the amount is less than 3% by weight, the resolution tends to be inferior.
If the amount is more than 10% by weight, the stripping time of the resist tends to be long.

The amount of the photopolymerization initiator (C) is as follows:
It is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total of the components (A) and (B),
More preferably, the amount is from 10 to 10 parts by weight. If the amount is less than 0.1 part by weight, the photosensitivity tends to be insufficient. If the amount is more than 20 parts by weight, absorption on the surface of the composition upon exposure increases, resulting in insufficient photocuring inside. It tends to be.

The photosensitive resin composition of the present invention may contain, if necessary, a dye such as malachite green, a photochromic agent such as tribromophenylsulfone or leucocrystal violet, a thermochromic inhibitor, p-toluenesulfone. Plasticizers such as amides, pigments, fillers, defoamers, flame retardants, stabilizers,
Adhesiveness-imparting agents, leveling agents, peeling accelerators, antioxidants, fragrances, imaging agents, thermal crosslinking agents, etc. are each added in an amount of 0.0 to 100 parts by weight of the total of components (A) and (B).
About 1 to 20 parts by weight may be contained. They are,
Used alone or in combination of two or more.

The photosensitive resin composition of the present invention may contain, if necessary, a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether or the like. And a solution having a solid content of about 30 to 60% by weight.

The photosensitive resin composition of the present invention is not particularly limited, but is preferably a metal surface, for example, an iron-based alloy such as copper, a copper-based alloy, nickel, chromium, iron, or stainless steel, and preferably copper or a copper-based alloy. Preferably, it is applied as a liquid resist on the surface of the iron-based alloy and dried, and then coated with a protective film if necessary, or used in the form of a photosensitive element.

The thickness of the photosensitive resin composition layer varies depending on the use, but is preferably from 1 to 100 μm, more preferably from 1 to 50 μm, after drying. If the thickness is less than 1 μm, it tends to be difficult to apply industrially, and if it exceeds 100 μm, the effect of the present invention is reduced, and the adhesive strength and resolution tend to be reduced.

The transmittance of the photosensitive resin composition layer to ultraviolet rays having a wavelength of 365 nm is preferably 5 to 75%, more preferably 7 to 60%, and more preferably 10 to 40%.
% Is particularly preferred. If the transmittance is less than 5%, the adhesion tends to be poor, and if it exceeds 75%, the resolution tends to be poor. The transmittance can be measured with a UV spectrometer, and examples of the UV spectrometer include a 228A W-beam spectrophotometer manufactured by Hitachi, Ltd.

When used as the photosensitive element, the support preferably has a thickness of 5 to 25 μm, more preferably 8 to 20 μm, and more preferably 10 to 1 μm.
Particularly preferably, it is 6 μm. If the thickness is less than 5 μm, the support tends to be broken at the time of peeling before development,
If it exceeds 25 μm, the resolution tends to decrease.

The haze of the above support is 0.001 to 5.0.
Is preferably, more preferably 0.001 to 2.0, and particularly preferably 0.01 to 1.8. If the haze exceeds 2.0, the resolution tends to decrease. The haze is measured according to JIS K 7105, and is, for example, NDH-100.
It can be measured with a commercially available turbidity meter such as 1DP (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.).

Examples of the support include a heat-resistant and solvent-resistant polymer film such as polyethylene terephthalate, polypropylene, polyethylene and polyester.

The protective film used as the photosensitive element preferably has a thickness of 5 to 30 μm, more preferably 10 to 28 μm, and more preferably 15 to 28 μm.
It is particularly preferable that the number is from 25 to 25. If the thickness is less than 5 μm, the protective film tends to be broken during lamination, and if it exceeds 30 μm, the cost tends to be poor.

The tensile strength of the protective film in the longitudinal direction of the film is preferably 13 MPa or more, and the tensile strength in the film width direction is preferably 9 MPa or more. The tensile strength in the longitudinal direction of the film is preferably 13 MPa or more, more preferably 13 to 100 MPa, and 14 MPa.
-100 MPa is particularly preferable, and 15-100 M
It is very preferable that the pressure be Pa, and it is extremely preferable that the pressure be 16 to 100 MPa. If the tensile strength is less than 13 MPa, the protective film tends to be broken during lamination.

The tensile strength in the film width direction is preferably 9 MPa or more, more preferably 9 to 100 MPa, particularly preferably 10 to 100 MPa, and very preferably 11 to 100 MPa. ,
It is very preferable that the pressure be 12 to 100 MPa. If the tensile strength is less than 9 MPa, the protective film tends to be broken during lamination. The tensile strength is JIS C23
It can be measured according to 18-1997 (5.3.3), for example, by a commercially available tensile strength tester such as Tensilon (trade name, manufactured by Toyo Baldwin Co., Ltd.).

These supports and protective films are
Since it must be removable from the photosensitive resin composition layer later, it must not have been subjected to a surface treatment that makes removal impossible, but there is no particular limitation and treatment is performed as necessary. You may. Further, these supports and protective films may be subjected to antistatic treatment as required.

The photosensitive element composed of two layers of the support and the photosensitive resin composition layer and the photosensitive element composed of three layers of the support, the photosensitive resin composition layer and the protective film are obtained as described above. For example, a protective film is further laminated as it is or on the other surface of the photosensitive resin composition layer and stored in a roll shape.

In producing a resist pattern using the photosensitive element, if the above-mentioned protective film is present, the protective film is removed and the photosensitive resin composition layer is heated while forming a circuit. For example, a method of laminating by press-bonding to a substrate may be mentioned, and it is preferable to laminate under reduced pressure from the viewpoint of adhesion and followability. The surface to be laminated is usually a metal surface, but is not particularly limited. The heating temperature of the photosensitive resin composition layer is preferably from 70 to 130 ° C., and the pressing pressure is preferably from about 0.1 to 1.0 MPa (about 1 to 10 kgf / cm ² ). There are no particular restrictions on the conditions. Further, if the photosensitive resin composition layer is heated to 70 to 130 ° C. as described above, it is not necessary to pre-heat the circuit formation substrate in advance,
In order to further improve the lamination property, a pre-heat treatment of the circuit forming substrate may be performed.

The photosensitive resin composition layer thus completed is irradiated with actinic rays imagewise through a negative or positive mask pattern. As the light source of the actinic ray, a known light source, for example, a carbon arc lamp, a mercury vapor arc lamp, a high-pressure mercury lamp, a xenon lamp, or the like that effectively emits ultraviolet light, visible light, or the like is used. It is also used for the laser direct writing exposure method.

Next, after the exposure, if a support is present on the photosensitive resin composition layer, the support is removed.
A resist pattern can be manufactured by removing unexposed portions and developing by wet development using a developer such as an alkaline aqueous solution, an aqueous developer, or an organic solvent, or dry development.

As the alkaline aqueous solution, for example,
Dilute solution of 0.1-5 wt% sodium carbonate, 0.1-
A dilute solution of 5% by weight of potassium carbonate, a dilute solution of 0.1 to 5% by weight of sodium hydroxide and the like can be mentioned. The pH of the alkaline aqueous solution is preferably in the range of 9 to 11, and the temperature is adjusted according to the developability of the photosensitive resin composition layer. Further, a surfactant, an antifoaming agent, an organic solvent and the like may be mixed in the alkaline aqueous solution. Examples of the developing method include a dip method, a spray method, brushing, slapping, and the like.

As processing after development, if necessary,
The resist pattern may be further cured by heating at about 250 ° C. or exposing at about 0.2 to 10 J / cm ² . For the etching of the metal surface performed after the development, for example, a cupric chloride solution, a ferric chloride solution, an alkali etching solution, or the like can be used.

When a printed wiring board is manufactured using the photosensitive element of the present invention, the surface of the circuit forming substrate is treated by a known method such as etching or plating using the developed resist pattern as a mask.

Examples of the plating method include copper plating, solder plating, nickel plating, and gold plating. Next, the resist pattern can be stripped with, for example, a more alkaline aqueous solution than the alkaline aqueous solution used for development. As the strong alkaline aqueous solution, for example, a 1 to 10% by weight aqueous solution of sodium hydroxide, a 1 to 10% by weight aqueous solution of potassium hydroxide or the like is used. Examples of the peeling method include a dipping method and a spray method. Further, the printed wiring board on which the resist pattern is formed may be a multilayer printed wiring board or may have a small diameter through hole.

[0062]

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

Examples 1 and 2 and Comparative Examples 1 to 7 The materials shown in Table 1 were blended to obtain a binder polymer (A) shown in Table 1.

[0064]

[Table 1]

The materials shown in Table 2 were blended to obtain a solution.

[0066]

[Table 2]

The component (B) shown in Table 3 was dissolved in the obtained solution to obtain a solution of the photosensitive resin composition.

[0068]

[Table 3]

The materials used are shown in Table 3 below. * 1: 2,2-bis (4- (methacryloxypentaethoxy) phenyl) propane, manufactured by Shin-Nakamura Chemical Co., Ltd. * 2: 2,2-bis (4- (methacryloxypentadecaethoxy) phenyl) propane * 3: Nonylphenoxyoctaethyleneoxy acrylate, manufactured by Kyoeisha Chemical Co., Ltd. * 4: Heptapropylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.

Next, a 16 μm thick polyethylene terephthalate film (haze: 1.7%, trade name: GS-16, manufactured by Teijin Limited) was applied to the obtained photosensitive resin composition solution.
And apply it uniformly on a hot air convection dryer at 100 ° C.
After drying for 10 minutes, a polyethylene protective film (tensile strength in the longitudinal direction of the film: 16 MPa, tensile strength in the width direction of the film: 12 MPa, trade name: NF-15, Tamapoli Co., Ltd.)
To obtain a photosensitive element. The dried film thickness of the photosensitive resin composition layer was 50 μm.

Next, a UV spectrometer (22 manufactured by Hitachi, Ltd.)
The transmittance of the layer of the photosensitive resin composition to ultraviolet rays having a wavelength of 365 nm was measured using an 8A-type W-beam spectrophotometer). The transmittance was measured by first placing a support film and a photosensitive element composed of a layer of the photosensitive resin composition on the measurement side, placing the support film on the reference side, and measuring the transmittance by 70% in T% mode.
It was measured by continuously measuring from 0 to 300 μm and reading the value at 365 nm. Table 4 shows the results.

On the other hand, 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 a copper foil (thickness: 35 μm) laminated on both sides, is # 6
Polishing using a polishing machine with a brush equivalent to 00 (manufactured by Sankei Co., Ltd.), washing with water, drying with an air stream, heating the obtained copper-clad laminate to 80 ° C. The photosensitive resin composition layer was laminated at a speed of 3 m / min using a heat roll at 120 ° C. while peeling off the protective film.

Next, using an exposure machine (manufactured by Oak Co., Ltd.) HMW-201B having a high-pressure mercury lamp, a 21-step stofer tablet as a negative was placed on the test piece and exposed at 60 mJ / cm ² . did.

Next, the polyethylene terephthalate film was peeled off, a 1% by weight aqueous solution of sodium carbonate was sprayed at 30 ° C. for 60 seconds to remove unexposed portions, and then the steps of the photocured film formed on the copper-clad laminate were carried out. The photosensitivity of the photosensitive resin composition was evaluated by measuring the number of tablets, and the results are shown in Table 4. The light sensitivity is indicated by the number of steps of the step tablet. The higher the number of steps of the step tablet, the higher the light sensitivity.

The resolution was as follows: a photo tool having a 21-step tablet of a stofer and a line width / space width of 10/10 to 100 as a resolution evaluation negative.
A phototool having a wiring pattern of / 100 (unit: μm) was brought into close contact, and exposure was performed with an energy amount such that the number of remaining steps after development of the 21-step tablet of the stofer was 8.0. Here, the resolution was evaluated based on the smallest value of the space width between the line widths in which the unexposed portions could be clearly removed by the development processing. The smaller the value of the evaluation of the resolution, the better the value. The results are shown in Table 4.

The plating resistance was evaluated by laminating as described above, exposing with a predetermined exposure amount, developing with the above developer, and then immersing in a degreasing bath (PC-455 (manufactured by Meltex Corporation) 25% by weight). It was immersed for 5 minutes and washed with water. Next, a soft etching bath (150 g of ammonium persulfate)
/ Liter) for 2 minutes and washed with water. Then 10
A pretreatment was performed in the order of immersion in a 1% by weight sulfuric acid bath for 1 minute, and a copper sulfate plating bath (copper sulfate 75 g / liter, sulfuric acid 1
90 g / l, chloride ion 50 ppm, Copperglyme PCM (manufactured by Meltex) 5 ml / l), and copper sulfate plating was performed at room temperature at 3 A / dm ² for 40 minutes.

Thereafter, the plate was washed with water, immersed in 10% by weight borofluoric acid for 1 minute, and subjected to a solder plating bath (45% by weight of tin borofluoride 64 ml / l, 45% by weight of lead borofluoride 22 ml / l, 42% by weight). % Borofluoric acid 200 ml / l, Plutin LA conductivity salt (manufactured by Meltex) 20 g / l, Plutin LA starter (manufactured by Meltex) 41 ml / l), and solder plating was carried out at room temperature. Performed at 5 A / dm ² for 15 minutes.

After washing with water and drying, a 90 ° peel-off test was immediately performed to check the plating resistance. The results are shown in Table 4. The 90 ° peel-off test is a method in which a cellophane tape is applied to a plated substrate, adhered well with a rubber roller, and immediately peeled off at a peel angle of 90 ° to observe the degree of transfer of the resist to the cellophane tape. is there. After the 90 ° peel-off test, the resist was peeled off, and the presence or absence of solder plating was observed from above using an optical microscope, a projector or the like. The results are shown in Table 4. When the solder plating is buried, solder deposited by solder plating is observed below the transparent resist through the transparent resist.

Further, another test piece was subjected to a cross cut test (JIS-K-5400) after exposure and development with an exposure amount indicating 8 steps using a 21-step stepper tablet, and the results are shown in Table 4. Was. The cross-cut test is to draw 11 perpendicular and 11 parallel lines at 1 mm intervals using a cutter guide at the center of the circuit-forming substrate on which the photosensitive elements are stacked, and 100 lines in 1 cm ² Is to make a grid-like cut so as to form a square, and evaluate the state of the scratch. In addition, the cut was made so that the cutting edge of the cutter knife was maintained at a fixed angle of 35 to 45 degrees with respect to the photosensitive element, and penetrated the photosensitive resin composition layer to reach the circuit forming substrate. The book is drawn at a constant speed over 0.5 seconds. The evaluation of the state of the flaw is as follows.

10 points: Each cut is thin, both sides are smooth, and the intersection of the cut and the square are not separated at every glance. Eight points: There is slight peeling at the intersection of the cuts, no peeling at a glance, and the area of the defect is within 5% of the area of the entire square. 6 points: Both sides of the cut and the intersection are peeled, and the area of the defective portion is 5 to 15% of the total square area. 4 points: The width of the peeling due to the cut is wide, and the area of the defective portion is 15 to 35% of the total square area. 2 points: The width of the peeling due to the cut is wider than 4 points, and the area of the defective portion is 35 to 65% of the area of the entire square. 0 point: The area of the defective portion is 65% or more of the area of the entire square.

[0081]

[Table 4]

As is clear from Table 4, Examples 1 and 2
Has excellent resolution and cross-cutting properties and good plating resistance.

[0083]

The photosensitive resin composition according to claim 1 is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility, and has a high density and high printed wiring. Useful for resolution. The photosensitive resin composition according to the second aspect has the effects of the invention according to the first aspect, and further has excellent chemical resistance. The photosensitive resin composition according to the third aspect has further excellent alkali developability in addition to the effects of the invention according to the first or second aspect.

The photosensitive resin compositions according to the fourth and fifth aspects exhibit the effects of the inventions according to the first, second or third aspects, and are further excellent in peeling properties. The photosensitive resin composition according to the sixth aspect has the effects of the invention according to the first, second, third, fourth or fifth aspect, and further has excellent adhesion. The photosensitive resin composition according to the seventh aspect has the effects of the invention according to the first, second, third, fourth, fifth or sixth aspect, and further has photosensitivity, resolution, chemical resistance (plating resistance), and adhesion. Excellent mechanical strength and flexibility.

The photosensitive elements according to claims 8 and 9 are excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility, and have high density and high resolution of printed wiring. It is useful for conversion. The photosensitive element according to claims 10 and 11 has the effects of the invention according to claim 8 or 9, and further has excellent resolution.

The photosensitive element according to the twelfth aspect has the effects of the invention according to the eighth, ninth, tenth or eleventh aspect, and is further excellent in resolution. The photosensitive element according to claims 13 and 14 has further excellent laminating properties in addition to the effects of the invention according to claim 11 or 12.

The method for producing a resist pattern according to the fifteenth aspect is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength and flexibility, high density of printed wiring and high resolution. It is useful for conversion. The method for manufacturing a printed wiring board according to claim 16 is excellent in photosensitivity, resolution, chemical resistance (plating resistance), adhesion, mechanical strength, and flexibility, and is suitable for high density and high resolution printed wiring. Useful.

[0088]

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a metal petri dish (lid) having a Teflon-processed bottom surface.

FIG. 2 is a cross-sectional view of a metal petri dish (container) on which Teflon processing is performed on the inside.

FIG. 3 is a cross-sectional view of a metal petri dish (lid and container) when a test piece is prepared.

[Explanation of symbols]

 1. Metal Petri dish 2. Teflon 3. Mark 4. Powdered binder polymer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03F 7/004 512 G03F 7/004 512 5E343 7/027 502 7/027 502 7/031 7/031 H05K 3 / 00 H05K 3/00 F 3/06 3/06 J 3/18 3/18 D (72) Inventor Osamu Hirai 4-3-1-1, Higashicho, Hitachi City, Ibaraki Pref. Hitachi Chemical Co., Ltd. Inventor Katsushi Ueno 4-3-1 Higashicho, Hitachi City, Ibaraki Prefecture Within Hitachi Chemical Co., Ltd. (72) Inventor Akihiro Unno 4-3-1-1, Higashimachi, Hitachi City, Ibaraki Prefecture F-term in the laboratory (reference) 2H025 AA00 AA01 AA02 AA06 AA07 AA08 AA13 AA14 AB11 AB15 AC01 AD01 BC32 BC42 BC43 CA28 CB13 CB16 CB51 CB56 DA01 DA18 DA20 FA03 FA17 FA40 FA43 4J011 PA65 PA69 PA85 PA86 PA 96 PC02 QA12 SA21 SA31 SA41 SA51 SA61 UA01 WA01 4J026 AA17 AA42 AB01 AB04 AB28 BA28 BB01 BB02 DB06 DB36 FA05 GA07 GA08 4J100 AL60P AL65P BC43P CA01 DA61 FA03 FA27 FA35 JA37 5E339 AD03 BC02 BE11 CC01 CC02 CC10 CD01 CF01 CF01 CF02 CF10 AA02 AA12 BB21 CC62 DD33 DD43 ER16 ER18 GG08

Claims (16)

[Claims] (A) a binder polymer having a water absorption of less than 4% by weight and a dispersity of 1.0 to 6.0,
(B) a photopolymerizable compound having at least one polymerizable ethylenically unsaturated bond in a molecule containing 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane as an essential component; C) A photosensitive resin composition containing a photopolymerization initiator. 2. The method according to claim 1, wherein (A) the binder polymer comprises styrene or a styrene derivative as an essential copolymer component.
The photosensitive resin composition as described in the above. 3. The photosensitive resin composition according to claim 1, wherein (A) the binder polymer contains methacrylic acid as an essential copolymerization component. 4. The photosensitive resin composition according to claim 1, further comprising, as an essential component, a photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule as the component (B). 5. The photosensitive resin composition according to claim 4, wherein the photopolymerizable compound having one polymerizable ethylenically unsaturated bond in the molecule has one phenyl group or phenylene group in the molecule. 6. The photosensitive resin composition according to claim 1, wherein (C) the photopolymerization initiator comprises 2,4,5-triarylimidazole dimer as an essential component. 7. The compound according to claim 1, wherein the amount of 2,2-bis (4-((meth) acryloxypolyethoxy) phenyl) propane in the component (B) is 3 to 90% by weight. ,
7. The photosensitive resin composition according to 5 or 6. 8. A photosensitive element having a layer of the photosensitive resin composition according to claim 1, on a support. 9. The photosensitive element according to claim 8, further comprising a protective film on the side of the layer of the photosensitive resin composition opposite to the support. 10. The photosensitive element according to claim 8, wherein the thickness of the support is 5 to 25 μm. 11. The support has a haze of 0.001 to 5.0.
The photosensitive element according to claim 8, 9 or 10, wherein 12. The wavelength of the photosensitive resin composition layer is 365 nm.
9. The ultraviolet light transmittance of 5 to 75%.
12. The photosensitive element according to 9, 10 or 11. 13. The photosensitive element according to claim 9, 10, 11 or 12, wherein the protective film has a thickness of 5 to 30 μm. 14. The photosensitive element according to claim 9, wherein the protective film has a tensile strength in the film longitudinal direction of 13 MPa or more and a tensile strength in the film width direction of 9 MPa or more. 15. The method of claim 8, 9, 10, 11, 12, 13.
Or, the photosensitive element according to 14 is laminated so that the photosensitive resin composition layer is in close contact with the circuit-forming substrate while peeling off the protective film that may be present in some cases, and is exposed to actinic rays in an image-like manner, and is exposed. A method for producing a resist pattern, comprising: photo-curing portions and removing unexposed portions by development. 16. A method for manufacturing a printed wiring board, comprising etching or plating a circuit-forming substrate on which a resist pattern has been manufactured by the method for manufacturing a resist pattern according to claim 15.