JP2003202667A - Photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having high sensitivity, high resolution, a tenting property, a low scumming property, a high following property, low edge fusibility and good removability and useful as alkali- developable DFR for production of a printed circuit board, a lead frame and a semiconductor package. <P>SOLUTION: The photosensitive resin composition is prepared which comprises (a) 20-90 mass% binder resin comprising a linear polymer having a carboxyl group content of 100-600 (expressed in terms of acid equivalent) and a weight average molecular weight of 20,000-500,000, (b) 3-70 mass% photopolymerizable unsaturated compound including a specified compound and (c) 0.1-10 mass% 2,4,5-triarylimidazole dimer as a photopolymerization initiator. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive resin composition and a photosensitive resin laminate, and more particularly to an alkali developable photosensitive material suitable for manufacturing printed circuit boards, lead frames, semiconductor packages and the like. -Related resin composition and photosensitive resin laminated body.

[0002]

2. Description of the Related Art Conventionally, as a resist for manufacturing a printed circuit board, a lead frame and a semiconductor package, a photosensitive resin laminate, which is a so-called dry film resist (hereinafter abbreviated as DFR), comprising a supporting layer and a photosensitive resin layer. Is used. DFR is generally prepared by laminating a photosensitive resin composition on a support layer, and in many cases, further laminating a protective layer on the photosensitive resin composition. As the photosensitive resin composition used here, at present, an alkali developing type using a weak alkaline aqueous solution as a developing solution is generally used.

In order to manufacture a printed circuit board using DFR, first, after peeling off the protective layer, the DFR is laminated on a permanent circuit-forming substrate such as a copper clad laminate using a laminator or the like, Exposure is performed through a wiring pattern mask film or the like. Next, if necessary, the support layer is peeled off, and the photosensitive composition in the unexposed portion is dissolved or dispersed by a developing solution and developed to form a cured resist pattern on the substrate. Using the formed resist pattern as a mask, the metal surface of the substrate is subjected to etching or plating treatment, and then the resist pattern is peeled off using an alkaline aqueous solution stronger than the developing solution to form a printed wiring board or the like. Particularly, in recent years, a so-called tenting method in which a through-hole (through-hole) is covered with a cured film and then etched is widely used because of the simplicity of the process. In the etching process, cupric chloride, ferric chloride, copper ammonia complex solution, etc. are used.

With the recent miniaturization of printed wiring boards, the DFR used is required to have high resolution, and from the viewpoint of productivity, high sensitivity is desired to shorten the exposure time. Also, in the developing process, aggregates (scum) in the unexposed area in the developing tank.
If such a phenomenon occurs, it leads to a defect such as a wiring short, and the frequency of cleaning increases, so that a DFR having less scumming and less generation of aggregates is desired. When the DFR is used for tenting, the cured film covering the through-hole is tough, and good tenting property without film breakage is required.
Further, if there are minute scratches on the substrate or if the following ability of the photosensitive resin layer is poor, the etching method leads to disconnection, so high following ability is required.

In order to improve the followability, the viscosity of the photosensitive resin layer may be lowered. However, if the viscosity is lowered, the photosensitive resin layer exudes from the end face of the roll when the DFR is stored. -Missing occurs. When the edge fuse occurs, not only the life of the product roll is shortened, but also
During lamination, the photosensitive resin layer scatters as chips and reattaches to the substrate, which causes a reduction in product yield. DF used to produce products with high yield
It is required that R has a good edge-fuse property and high followability. Further, considering productivity in the peeling process, it is required that the peeling time is short, the peeling piece is thin, and there is no entanglement with the ring roll in the peeling machine.

[0006]

An object of the present invention is to provide excellent sensitivity in exposure and resolution of a resist pattern after development, low scum during development, good tenting property, and film breakage. Photosensitive resin composition having a tough cured film having no scratch, high followability for high yield, low edge fuse property, and good peeling property, photosensitive resin laminate, and resist pattern using the same It is to provide a method of forming.

[0007]

As a result of extensive studies to solve the above problems, it was found that the above problems can be solved by using a specific photosensitive resin composition.
The present invention has been completed. That is, the present invention is as follows. (1) (a) Carboxyl group content is 100 in terms of acid equivalent
To 600 and a binder resin composed of a linear polymer having a weight average molecular weight of 20,000 to 500,000, 20 to 90% by mass, and (b) containing a compound represented by the following general formula (I). A photopolymerizable unsaturated compound, 3 to 70% by mass, and (c) as a photopolymerization initiator, 2,4,5-triallyl-imidazole dimer is contained in an amount of 0.1 to 10% by mass. And a photosensitive resin composition.

[0008]

[Chemical 4]

(In the formula, R ₁ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an aromatic ring, a cyclic hydrocarbon or an aliphatic hydrocarbon.)

(2) The photopolymerizable unsaturated compound (b) further contains at least one selected from the group consisting of compounds represented by the following general formulas (II) and (III). The photosensitive resin composition as described in (1) above.

[0011]

[Chemical 5]

(Wherein R ₃ and R ₄ are H or CH ₃ ,
These may be the same or different, A is C ₂ H ₄ ,
B is C ₃ H ₆ , n ₁ + n ₂ is an integer of ₂ to 30, and n ₃ + n ₄ is 0.
Is an integer from 30 to 30, n ₁ and n ₂ are integers from _{1 to} 29, and n ₃ and n ₄ are integers from 0 to 29. -(A-O)-and-(B-
The arrangement of O) -repeating units may be random or block. )

[0013]

[Chemical 6]

(In the formula, R ₅ and R ₆ are H or CH ₃ and these may be the same or different. N ₅ , n ₆ and n ₇
Is an integer of 3 to 20. )

(3) A photosensitive resin laminate comprising a support layer and a layer comprising the photosensitive resin composition according to (1) or (2) provided on the support layer. (4) A method for forming a resist pattern, which comprises forming a photosensitive resin layer on a substrate using the photosensitive resin laminate according to (3), exposing the photosensitive resin layer, and developing the resist pattern.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The amount of the carboxyl group contained in the linear polymer constituting the binder resin (a) used in the present invention is 10 in terms of acid equivalent.
It must be 0 to 600, preferably 300 to 40
It is 0. The acid equivalent means the mass of a linear polymer having 1 equivalent of a carboxyl group in it. The carboxyl group in the linear polymer is necessary for giving the photosensitive resin layer developability and releasability to an alkaline aqueous solution. When the acid equivalent is less than 100, the development resistance is lowered and the resolution and the adhesion are adversely affected, and when it exceeds 600, the developability and the peelability are lowered.

The molecular weight of the linear polymer constituting the (a) binder resin used in the present invention must be 20,000 to 500,000. When the molecular weight of the linear polymer exceeds 500,000, the developability decreases, and when it is less than 20,000, the tenting film strength decreases and the edge fuse becomes remarkable. The molecular weight of the linear polymer is preferably from 20,000 to 300,000 in order to further exert the effects of the present invention.

The acid equivalent was measured at 0.1 m using an Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd.
It is carried out by potentiometric titration using ol / L sodium hydroxide. As for the molecular weight, gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gu
Lliver, PU-1580 type, column: Shodex (registered trademark) (KF-807, K, manufactured by Showa Denko KK)
F-806M, KF-806M, KF-802.5) 4
The weight average molecular weight (in terms of polystyrene) is determined by the main series, moving layer solvent: tetrahydrofuran, using a calibration curve based on a polystyrene standard sample.

The linear polymer (a) constituting the binder resin used in the present invention is obtained by copolymerizing one or more monomers from the following two kinds of monomers. can get. The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. For example, (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester and the like can be mentioned.

The second monomer is non-acidic, has one polymerizable unsaturated group in the molecule, developability of the photosensitive resin layer, resistance in etching and plating steps, and flexibility of the cured film. Etc. are selected to retain various properties such as. For example, methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylates such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate,
There are 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth) acrylonitrile and the like. Further, a vinyl compound having a phenyl group (for example, styrene) can also be used.

The (a) binder resin used in the present invention is a solution prepared by diluting a mixture of the above monomers with a solvent such as acetone, methyl ethyl ketone, and isopropanol.
It is preferable to add an appropriate amount of a radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile and to carry out the synthesis by stirring with heating. In some cases, a part of the mixture is added dropwise to the reaction solution to carry out the synthesis. After completion of the reaction, a solvent may be further added to adjust the concentration to a desired value. As the synthesizing means, bulk polymerization, suspension polymerization and emulsion polymerization may be used other than solution polymerization.

The ratio of the (a) binder resin used in the present invention to the entire photosensitive resin composition is 20 to 90.
It is in the range of mass%, preferably 30 to 70 mass%. (A) When the proportion of the binder resin is less than 20% by mass or more than 90% by mass, the resist pattern formed by exposure and development has characteristics as a resist, such as tenting and etching. And does not have sufficient resistance in various plating processes.

A compound represented by the following general formula (I) is an essential component of the (b) photopolymerizable unsaturated compound used in the present invention.

[0024]

[Chemical 7]

(In the formula, R ₁ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an aromatic ring, a cyclic hydrocarbon or an aliphatic hydrocarbon.)

Examples of compounds containing the compound represented by the general formula (I) include Aronix (registered trademark) M-7100, M in which R ₁ is an ethyl group and R ₂ is a benzene ring.
-8060, M-8100, M-8560 (manufactured by Toagosei Co., Ltd.) and the like can be mentioned. As the photopolymerizable unsaturated compound (b), the following general formulas (II) and (II
At least one selected from the group consisting of the compounds represented by formula (I) is contained, and the total amount of the compounds represented by formula (I) is 3 to 70% by mass. This is a preferred embodiment.

[0027]

[Chemical 8]

(Wherein R ₃ and R ₄ are H or CH ₃ ,
These may be the same or different, A is C ₂ H ₄ ,
B is C ₃ H ₆ , n ₁ + n ₂ is an integer of ₂ to 30, and n ₃ + n ₄ is 0.
Is an integer from 30 to 30, n ₁ and n ₂ are integers from _{1 to} 29, and n ₃ and n ₄ are integers from 0 to 29. -(A-O)-and-(B-
The arrangement of O) -repeating units may be random or block. )

[0029]

[Chemical 9]

(In the formula, R ₅ and R ₆ are H or CH ₃ and they may be the same or different. N ₅ , n ₆ and n
₇ is an integer of 3 to 20. )

In the compound represented by the general formula (II), the compound in which n ₁ + n ₂ and n ₃ + n ₄ exceeds 30 is DF
When used for R, sufficient sensitivity cannot be obtained. Also,
₄ to 14 are preferable for n ₁ + n _{2, and} 0 to 14 are preferable for n ₃ + n ₄ . Specific examples of the compound represented by the general formula (II) include dimethacrylate of polyalkylene glycol in which an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide are added to both ends of bisphenol A, and , Bisphenol A with 5 moles of ethylene oxide added to both ends of the polyethylene glycol dimethacrylate (NK, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Ester BPE-500).

In the compound of general formula (III),
When n ₅ , n ₆ and n ₇ are smaller than 3, the boiling point of the compound is lowered, the odor of the resist becomes strong, and the work becomes extremely difficult. If n ₅ , n ₆ and n ₇ exceed 20, practical sensitivity cannot be obtained. As a specific example of the compound represented by the general formula (III), a dimethacrylate of polyalkylene glycol in which an average of 3 mol of ethylene oxide is further added to both ends of polypropylene glycol in which an average of 12 mol of propylene oxide is added, respectively. There is

As the photopolymerizable unsaturated compound (b) used in the present invention, the photopolymerizable unsaturated compounds shown below can be used together. Examples of such compounds include 1,6-hexanedioldi (meth) acrylate, 1,4-cyclohexanedioldi (meth) acrylate, polypropylene glycol di (meth) acrylate, and polyethylene. Glycol di (meth) acrylate, 2-di (p-hydroxyphenyl) propane di (meth) acrylate,

Glyceryl tri (meth) acrylate,
Trimethyl propane tri (meth) acrylate, polyoxypropyl trimethyl propane tri (meth)
Acrylate, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether -Tertoli (meth) acrylate, Bispheno-
Le A diglycidyl ether (meth) acrylate and β-hydroxypropyl-β '-(acryloyloxy) propyl phthalate, phenoxy polyethylene glycol acrylate, 4-normalnonyl phenoxy polyethylene glycol (meth) acrylate , 4-normalnonylphenoxy polyethylene glycol polypropylene glycol (meth) acrylate and the like monofunctional monomers.

From the standpoint of tenting property, it is preferable that a compound having a urethane group is further contained as the (b) photopolymerizable unsaturated compound used in the present invention because flexibility is imparted to the cured film. It is preferable. As such a compound having a urethane group, there is a compound represented by the following general formula (IV).

[0036]

[Chemical 10]

(In the formula, R ₇ is a diisocyanate residue having 4 to 12 carbon atoms, R ₈ and R ₉ are H or CH ₃ , and these may be the same or different. N ₈ And n ₉ is 1 to
It is an integer of 15. )

In the compound represented by the general formula (IV), when n ₈ and n ₉ exceed 15, practical sensitivity cannot be obtained. Examples of the compound represented by the general formula (IV) include hexamethylene diisocyanate, tolylene diisocyanate, and diisocyanate such as 2,2,4-trimethylhexamethylene diisocyanate. Compound and a compound having a hydroxyl group and a (meth) acryl group in one molecule (2-hydroxypropyl acrylate,
Polyurethane compounds with oligo propylene glycol monomethacrylate etc.). Specifically, hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (Bremmer-PP10 manufactured by NOF CORPORATION).
00).

The ratio of the photopolymerizable unsaturated compound containing the compound represented by the general formula (I) to the whole photosensitive resin composition is in the range of 3 to 70% by mass. This ratio is
If it is less than 3% by mass, the sensitivity is not sufficient, and 70% by mass
If it exceeds, the protrusion of the photopolymerizable layer during storage becomes remarkable, which is not preferable. It is preferably 10 to 60% by mass, more preferably 15 to 55% by mass. Based on the whole photosensitive resin composition, when the compound represented by the general formula (I) and at least one selected from the group consisting of the compounds represented by the general formulas (II) and (III) are contained. The proportion of the photopolymerizable unsaturated compound is 3 to 70% by mass, preferably 10 to 60% by mass.

When the compound represented by the general formula (I) is used in combination with a photopolymerizable unsaturated compound other than the compounds represented by the general formulas (II) and (III), and the compound represented by the general formula (II ) And (III) together with at least one selected from the group consisting of compounds represented by the general formula (I),
Furthermore, even when a photopolymerizable unsaturated compound other than the compounds represented by the general formulas (II) and (III) is simultaneously used, the ratio of the photopolymerizable unsaturated compound to the entire photosensitive resin composition Is 3 to 70% by mass,
It is preferably 10 to 60% by mass.

It is essential that the (c) photopolymerization initiator used in the present invention contains a 2,4,5-triallyl-imidazole dimer represented by the following general formula (V).

[0042]

[Chemical 11]

(In the formula, X, Y and Z represent any of hydrogen, an alkyl group, an alkoxy group and a halogen group,
p, q, and r are integers of 1-5. )

In the compound represented by the general formula (V), the covalent bond connecting two lophine groups is 1,1 '.
-, 1,2'-, 1,4'-, 2,2'-, 2,4'-
Alternatively, the compound at the 4,4′-position, but the compound at the 1,2′-position is preferred. Examples of the 2,4,5-triallyl-imidazole dimer include 2- (O-chlorophenyl) -4,5-diphenylimidazole dimer and 2- (O-chlorophenyl) -4,5-diphenylimidazole dimer.
There are (O-chlorophenyl) -4,5-bis- (m-methoxyphenyl) imidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer and the like. , Especially 2- (O-chlorophenyl) -4,5
-Diphenylimidazole dimer is preferred.

As the photopolymerization initiator (c) used in the present invention, a system in which 2,4,5-triallyl-imidazole dimer represented by the general formula (V) and p-aminophenyl ketone are used in combination is preferable. , P-aminophenyl ketone,
For example, p-aminobenzophenone, p-butylaminophenone, p-dimethylaminoacetophenone, p-dimethylaminobenzophenone, p, p'-bis (ethylamino) benzophenone, p, p'-bis (dimethylamino) benzophenone [Michler's ketone ], P, p '
-Bis (diethylamino) benzophenone, p, p'-
Examples thereof include bis (dibutylamino) benzophenone.

In addition to the compounds shown above, other photopolymerization initiators may be used in combination. The photopolymerization initiator here is a known compound that is activated by various actinic rays such as ultraviolet rays to initiate polymerization. Examples of other photopolymerization initiators include quinones such as 2-ethylanthraquinone and 2-tert-butylanthraquinone, aromatic ketones such as benzophenone, benzoin, and the like.
Benzoin ethers such as benzoin methyl ether and benzoin ethyl ether, benzyl dimethyl ketone
And benzyl diethyl ketal. Also, for example, thioxanthone, 2,4-diethylthioxanthone, 2-
There is also a combination of a thioxanthone such as chlorothioxanthone and a tertiary amine compound such as a dimethylaminobenzoic acid alkyl ester compound. Further, for example, acridines such as 9-phenylacridine, 1-phenyl-1,
2-propanedione-2-o-benzoyl oxime, 1
There are oxime esters such as -phenyl-1,2-propanedione-2- (ο-ethoxycarbonyl) oxime. It is also possible to use N-aryl-α-amino acid compounds, and among these, N-phenylglycine is particularly preferable.

The proportion of the 2,4,5-triallyl imidazole dimer represented by the general formula (V) in the whole photosensitive resin composition is 0.1 to 10% by mass, preferably 0. It is 0.5 to 5 mass%. When the content of the 2,4,5-triallyl imidazole dimer exceeds 10% by mass, fogging due to diffraction of light passing through the photomask during exposure is likely to occur, resulting in deterioration of resolution. Conversely, 0.1
If it is less than mass%, sufficient sensitivity cannot be obtained.

The photosensitive resin composition of the present invention may contain coloring substances such as dyes and pigments. Examples of the coloring substance used include fuchsin, phthalocyanine green, olamine base, chalcoxide green S,
Paramagenta, Crystal Violet, Methyl Orange, Nile Bull-2B, Victoria Bull-, Malachite Green (Hodogaya Chemical Co., Ltd. Eisen (registered trademark) MALACHITE GREEN), Basic Bull-20, Diamond Green (Hodogaya Chemical Co., Ltd.) ) Aizen (registered trademark) DIAMOND G
REEN GH) and the like.

The photosensitive resin composition of the present invention may contain a color-forming dye that develops color when irradiated with light. Examples of the coloring dye used include a combination of a leuco dye or a fluorane dye and a halogen compound. Examples of leuco dyes include tris (4-dimethylamino-2-methylphenyl) methane [leuco crystal violet] and tris (4-dimethylamino-2).
-Methylphenyl) methane [leucomalachite
]] And the like.

As the halogen compound, amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzal bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris ( 2,3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide,
Examples include 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, hexachloroethane, triazine compounds and the like.

Examples of the triazine compound include 2,4,6-
Tris (trichloromethyl) -s-triazine, 2-
(4-Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine may be mentioned. Among such color-forming dyes, a combination of tribromomethylphenyl sulfone and a leuco dye and a combination of a triazine compound and a leuco dye are useful.

In order to improve the thermal stability and storage stability of the photosensitive resin composition of the present invention, it is preferable to add a radical polymerization inhibitor to the photosensitive resin composition. Examples of such radical polymerization inhibitors include:
p-methoxyphenol, hydroquinone, pyrogallo-
, Naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis (4-ethyl-6-te)
rt-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.

If necessary, the photosensitive composition of the present invention may contain additives such as a plasticizer. Examples of such additives include phthalic acid esters such as diethyl phthalate, p-toluenesulfonamide,
Examples thereof include polypropylene glycol and polyethylene glycol monoalkyl ether. In the case of forming a photosensitive resin laminate for DFR, the above-mentioned photosensitive resin composition is coated on the support layer. As the support layer, a transparent layer that transmits active light is desirable. As the support layer which transmits active light, a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film,
Vinylidene chloride copolymer film, polymethylmethacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film,
Examples thereof include a polyamide film and a cellulose derivative film. These films may be stretched if necessary.

The haze of the support layer is preferably 5.0 or less. The thinner the thickness, the more advantageous it is in terms of image forming property and economy, but it is necessary to maintain the strength.
It is generally 0 μm. If necessary, a protective layer may be laminated on the surface opposite to the photosensitive resin layer laminated with the support layer. An important characteristic of this protective layer is that the protective layer has a sufficiently smaller adhesion to the photosensitive resin layer than the supporting layer and can be easily peeled off. As such a protective layer,
Examples thereof include polyethylene film and polypropylene film.

Although the thickness of the photosensitive resin layer varies depending on the use, it is 5 to 100 μm, preferably 5 to 50 μm for producing a printed circuit board, and the thinner the photosensitive resin layer, the higher the resolution. Further, the thicker the photosensitive resin layer, the higher the film strength. The process of producing a printed circuit board using this photosensitive resin laminate is performed by a known technique, which will be briefly described below. When there is a protective layer, first, the protective layer is peeled off, and then the photosensitive resin layer is laminated by thermocompression bonding to the metal surface of the substrate, that is, the printed circuit board substrate. The heating temperature at this time is generally 40 to 160 ° C.

Then, if necessary, the support layer is peeled off and imagewise exposed to actinic light through a mask film. Next, if there is a supporting layer on the photosensitive resin layer, the supporting layer is removed if necessary, and subsequently, the unexposed portion of the photosensitive resin layer is removed by development using an alkaline aqueous solution. As an alkaline aqueous solution,
An aqueous solution of sodium carbonate, potassium carbonate or the like is used. These alkaline aqueous solutions are selected according to the characteristics of the photosensitive resin layer, but 0.5 to 3 mass% sodium carbonate aqueous solution is generally used.

Next, a metal image pattern is formed by performing a known etching method or a plating method on the metal surface exposed by the development. Then, the cured resist pattern is peeled off with an alkaline aqueous solution which is generally stronger than the alkaline aqueous solution used in the development. The alkaline aqueous solution for stripping is not particularly limited, but an aqueous solution of 1 to 5 mass% sodium hydroxide or potassium hydroxide is generally used.

[0058]

The present invention will be described in detail below. <Photosensitive resin composition> Table 1 shows the composition of the photosensitive resin composition used in Examples and Comparative Examples. Further, the components constituting the photosensitive resin composition represented by the abbreviations (P-1 to B-3) in Table 1 are shown in <symbol description>.

Next, a method for forming the photosensitive resin laminate will be described. In Examples and Comparative Examples, the components shown in Table 1 were mixed and uniformly dissolved to prepare a solution of a photosensitive resin composition, and a polyethylene terephthalate film having a thickness of 20 μm was coated with a bar coater. It was applied uniformly and dried in a dryer at 95 ° C. for 4 minutes. The thickness of the photosensitive resin layer at this time was 40 μm. Then, 25μ on the photosensitive resin layer
The polyethylene film of m was laminated to obtain a laminated film. In order to evaluate the sensitivity and the resolution, a resist pattern was prepared by the following steps using the photosensitive resin laminate obtained above.

The surface of a copper-clad laminate having laminated 35 μm rolled copper foil was wet-buffled polished (manufactured by 3M Co., Ltd., trade name ScotchBright (registered trademark) # 600, 2 series), and a polyethylene film of this laminated film was obtained. While peeling off, remove the photosensitive resin layer by hot roll laminator at 105 ° C.
Laminated with. A mask film is passed through this laminate to form a super high pressure mercury lamp (HMW- manufactured by Oak Manufacturing Co., Ltd.).
The light-sensitive resin layer was exposed to 40 mJ / cm ² with 201 KB). Then, the polyethylene terephthalate support layer was peeled off, and a 1% by mass aqueous sodium carbonate solution at 30 ° C. was sprayed for about 45 seconds to dissolve and remove the unexposed portion, followed by development.

(1) Sensitivity test The laminated body laminated on the copper clad laminate was placed on
It was exposed and developed through a 21-step step tablet manufactured by K.K. The maximum number of remaining film steps of the obtained cured resist was taken as the sensitivity. (2) Resolution The laminate laminated on the copper clad laminate was exposed through a mask film having a line and space of 1: 1 and developed. The minimum line width of the obtained cured pattern that can be separated was defined as the resolution. Tenting test, development cohesion test,
The follow-up test, the edge fuse test and the peeling test were performed by the following methods.

(3) Tenting Property Test A laminated body laminated on a copper clad laminate having a 100 mm hole and a 6 mm diameter through hole was placed in an ultra high pressure mercury lamp (HMW manufactured by Oak Manufacturing Co., Ltd.). -201 KB) 4
It was exposed at 0 mJ / cm ² . Then, after peeling off the polyethylene terephthalate support layer, a 1 mass% sodium carbonate aqueous solution at 30 ° C. was sprayed for about 45 seconds. Thereafter, as a severe evaluation, water was sprayed in a water washing tank at a pressure of 0.3 MPa for 30 seconds, the number of film breakages was counted, and the film breakage rate was calculated according to the following formula. Film breakage rate (%) = (number of film breakages / 1008 holes) × 100 The tenting property was evaluated from the film breakage rate according to the following ranks. (Tenting Rank) A: The film breakage rate is 0%. ◯: Film breakage occurs and the film breakage rate is less than 1.0%. Δ: The film breakage rate is 1.0% or more and less than 3.0%. X: The film breakage rate is 3.0% or more.

(4) Development cohesiveness (scum) test 50 μm in 30 ° C., 1 mass% sodium carbonate aqueous solution
0.5m in terms of film thickness ²/ L unexposed photosensitive resin layer
Dissolve and sprinkle 200 mL of solution at a pressure of 0.2 MPa.
While circulating, the solution was circulated for 3 hours. Then in the tank
The state of generation of aggregates (scum) of
Ranked as. ◯: There is no suspended matter on the liquid surface, and it is completely on the bottom of the tank after removing the solution.
No generation of aggregates (scum). Δ: Very slightly solid agglomerates (sca
) Occurrence is recognized. ×: Large amount of solid aggregate (scum) is generated on the liquid surface or the bottom of the tank
Raw is recognized.

(5) Follow-up test A commercially available dry film resist was used in advance on a copper-clad laminate in which rolled copper foil of 35 μm was laminated, and the process of laminating-exposure-developing-etching-resist stripping was performed. Width 100, 110, 120, 130, 14
A linear groove having a diameter of 0 and 150 μm was formed to form a grooved substrate. The depth of the groove was about 10 μm.

Using the prepared grooved substrate, a photosensitive resin laminate was laminated by the same method as described above. A cured pattern was obtained by exposing and developing through a mask film using a line pattern (line width: 125 μm) perpendicular to the groove of the substrate. Further, a cupric chloride solution at 50 ° C. was sprayed for 70 seconds to etch the copper in the resist-free area. Finally, a 3 mass% sodium hydroxide aqueous solution at 50 ° C. was sprayed for about 80 seconds to remove the cured resist.

On the copper line thus produced, the number of points where the grooved portion was not broken was counted, and the number was defined as x. On the other hand, the number of locations where etching was caused and disconnection was counted, the number was defined as y, the disconnection rate (%) was calculated by the following calculation formula, and ranked by the following method. Wire breakage rate (%) = 100y / (x + y) ◎; Wire breakage rate is less than 10% ○; Wire breakage rate is 10% or more and less than 30% △; Wire breakage rate is 30% or more and less than 50% ×; Wire breakage rate is 50% or more

(6) Edge fuse test The roll was stored at 23 ° C. and a humidity of 50% and evaluated by the following ranking depending on whether or not the photosensitive resin layer exudes from the end face. ◎: Can be stored for 100 days or more without exuding from the edge. ○: 30 days or more and less than 100 days Can be stored without exuding from the end face. Δ: 15 days or more but less than 30 days Can be stored without exuding from the end surface. X: Exudation from the end face occurs in less than 15 days.

(7) Peelability test While the polyethylene film (protective layer) of the dry film resist was peeled off, the photosensitive resin layer was hot-rolled on the copper-clad laminate laminated with 35 μm rolled copper foil.
Laminated at 105 ° C. An ultrahigh pressure mercury lamp (HMW-201 manufactured by Oak Manufacturing Co., Ltd.) was added to the laminated body.
The photosensitive resin layer was exposed at 40 mJ / cm ^{2 according} to KB). Subsequently, the polyethylene terephthalate film (support layer) was peeled off, and then a 1% by mass sodium carbonate aqueous solution at 30 ° C. was sprayed for about 45 seconds.

The obtained laminated plate was cut into a 5 cm square and 50
It was dipped in a 3% by mass aqueous solution of sodium hydroxide at 0 ° C., and the time of peeling from the laminate was measured, and the time was taken as the minimum peeling time. In addition, the shape of the cured film peeled from the laminate (shape of peeled piece) was ranked as follows. LL: There is no crack when the cured film is peeled off from the laminated plate.
Peeled off. L: When the cured film is peeled off from the laminated plate, cracks are generated and after peeling, the shape is about 10 mm to 20 mm square. M: When the cured film is peeled off from the laminated plate, cracks are generated and peeled off to form strips of about 5 mm to 10 mm square. S: When the cured film is peeled from the laminated plate, a large number of cracks are generated and after peeling, it becomes a fine piece of 5 mm square or less.

[0070]

Examples 1 to 8 and Comparative Examples 1 and 2 The components of the photosensitive resin composition and the results evaluated by the above methods are summarized in Table 1.
Shown in. In addition, Comparative Example 1 lacks the requirement (c), and Comparative Example 2 lacks the requirement (b).

<Symbols> P-1: Methyl ethyl ketone solution of terpolymer of 65% by weight of methyl methacrylate, 25% by weight of methacrylic acid and 10% by weight of butyl acrylate (solid content concentration 35%, weight average molecular weight 7 Methyl acid equivalent 344) P-2: Methyl ethyl ketone solution of terpolymer of 67% by weight of methyl methacrylate, 23% by weight of methacrylic acid and 10% by weight of butyl acrylate (solid content concentration 25%, weight average molecular weight 200,000). , Acid equivalent 374) P-3: Methyl ethyl ketone solution of terpolymer of methyl methacrylate 50% by weight, methacrylic acid 25% by weight, styrene 25% by weight (solid content concentration 35%, weight average molecular weight 50,000, acid equivalent weight 344)

M-1: Aronix (registered trademark) manufactured by Toagosei Co., Ltd. containing a compound represented by the general formula (I), wherein R ₁ is an ethyl group and R ₂ is a benzene ring. M-8060 M-2: a compound represented by the general formula (II), which is a polyalkylene glycol in which an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide are added to both ends of bisphenol A, respectively. Dimethacrylate M-3: a compound represented by the general formula (II), which is a polyethylene glycol dimethacrylate (Shin Nakamura) in which an average of 5 mol of ethylene oxide is added to both ends of bisphenol A. NK BP manufactured by Chemical Industry Co., Ltd.
E-500) M-4: a compound represented by the general formula (III),
Polyalkylene glycol obtained by adding 3 mol of ethylene oxide to both ends of polypropylene glycol added with 12 mol of propylene oxide on average.
Dimethacrylate

M-5: a compound represented by the general formula (IV), which is hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (BREMMA (registered trademark of NOF CORPORATION) ) PP1000) reaction product M-6: 4-normalnonylphenoxyheptaethyleneglycol dipropyleneglycol acrylate M-7: 4-normalnonylphenoxyoctaethyleneglycol acrylate (manufactured by Toagosei Co., Ltd. M -11
4) M-8: trimethylolpropane triacrylate M-9: trioxyethyl trimethylolpropane triacrylate (NK ester A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.) M -10: Nonaethylene glycol diacrylate M-11: β-hydroxypropyl-β ′-(acryloyloxy) propyl phthalate (Biscoat # 2 manufactured by Osaka Organic Chemical Industry Co., Ltd.)
323)

A-1: 4,4′-bis (diethylamino) benzophenone A-2: benzophenone A-3: 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer B-1: malachite Green (Hodogaya Chemical Co., Ltd.)
Eisen (registered trademark) M ALACHITE GREEN B-2: Leuco Crystal Violet B-3: Tribromomethylphenyl sulfone

[0075]

[Table 1]

[0076]

EFFECT OF THE INVENTION DF using the photosensitive resin composition of the present invention
R has high sensitivity and high resolution, has good tenting property, low scum property, high followability, low edge fuse property and good peeling property, and is suitable for alkaline development type printed circuit boards and -Useful as a DFR for the production of dframes and semiconductor packages.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/031 G03F 7/031 7/033 7/033 H05K 3/00 H05K 3/00 F F term (reference) ) 2H025 AA01 AA02 AA16 AB11 AB15 AB16 AB17 AC01 AD01 BC14 BC42 CA28 CB13 CB14 CB43 CB51 CB55 FA03 FA17 4F100 AH03A AH03H AK01A AK25 AK25 CA07 CA07 CA01 CA05 CA07 CA01 CA05 JA01 J05A04 J01A01 J05A04 A01 AL05A AT00B BA02 CA30A GB43 J07A14A4 DA02 FA01 FA07 FB01 PA65 PA69 PA70 PB40 PC02 PC08 QA12 QA22 QB16 SA78 UA01 VA01 WA01 4J026 AA16 AA43 AA45 AA48 AC09 AC23 AC33 BA28 BB01 BB02 DB06 DB11 DB36 GA06 GA07 GA10

Claims (4)

[Claims] 1. (a) The carboxyl group content is from 100 to 600 in terms of acid equivalent, and the weight average molecular weight is from 20,000 to.
Resin for binder composed of 500,000 linear polymers, 20 to 20
90% by mass, (b) a photopolymerizable unsaturated compound containing a compound represented by the following general formula (I), 3 to 70% by mass,
(C) A photosensitive resin composition comprising, as a photopolymerization initiator, 0.1 to 10% by mass of a 2,4,5-triallyl-imidazole dimer. [Chemical 1] (In the formula, R ₁ represents hydrogen or an alkyl group having 1 to 4 carbon atoms, and R ₂ represents an aromatic ring, a cyclic hydrocarbon or an aliphatic hydrocarbon.) 2. The photopolymerizable unsaturated compound (b) further contains at least one selected from the group consisting of compounds represented by the following general formulas (II) and (III). The photosensitive resin composition according to claim 1. [Chemical 2] (In the formula, R ₃ and R ₄ are H or CH ₃ , and these may be the same or different, A is C ₂ H ₄ , B is C ₃ H ₆ ,
n ₁ + n ₂ is an integer of ₂ to 30, n ₃ + n ₄ is an integer of 0 to 30, n ₁ , n ₂ are integers of _{1 to} 29, and n ₃ and n ₄ are integers of 0 to 29. The arrangement of repeating units of-(A-O)-and-(B-O)-may be random or block. ) [Chemical 3] (In the formula, R ₅ and R ₆ are H or CH ₃ and these may be the same or different. N ₅ , n ₆ and n ₇ are integers of 3 to 20.) 3. A photosensitive resin laminate comprising a support layer and a layer comprising the photosensitive resin composition according to claim 1 or 2 provided on the support layer. 4. A method for forming a resist pattern, which comprises using the photosensitive resin laminate according to claim 3 to form a photosensitive resin layer on a substrate, exposing it, and developing it.