JP2728665B2 - Photosensitive resin composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a photosensitive resin composition, and more particularly, to a novel photosensitive resin composition capable of removing finely divided photocured portions. (Prior art) When manufacturing a printed circuit board, a photosensitive resin composition is laminated on a copper substrate, and after pattern exposure, an unexposed portion is completely removed with a developing solution and subjected to etching or plating. Thereafter, the photocured portion (exposed resist layer) is removed (stripped) from the substrate. Conventionally, as a method of removing the photo-cured portion, a photo-cured portion is swelled and removed as it is by adding a stripping solution. However, according to this conventional method, if the stripped strip remains in the stripping solution as it is, it sticks to the stripping roll of the automatic stripping machine used in the manufacturing process of the printed circuit board, which significantly reduces workability. There are disadvantages. (Problems to be Solved by the Invention) It is an object of the present invention to provide a photosensitive resin composition which can eliminate the above-mentioned disadvantages of the prior art and can finely remove a photocured portion from a substrate. . (Means for Solving the Problems) The present inventors obtain a specific ethylenically unsaturated compound by adding it to a carboxyl group-containing film-imparting polymer and a photoinitiator and / or a photoinitiator system. The present inventors have found that the photo-cured portion is finely removed by a specific photosensitive resin composition with an appropriate peeling liquid, and as a result, troubles such as sticking to a roll of an automatic peeling machine are eliminated, and the present invention has been reached. The first invention is as follows: (a) Formula (I) (Wherein n is an integer of _{1 to} 23, R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a methyl group) with respect to 100 parts by weight of the total amount of (a) and (b) 20 to 90 parts by weight (b) a carboxyl group-containing film-imparting polymer having a weight average molecular weight of 10,000 or more is added to a total amount of (a) and (b) of 10
(C) 0.1 to 10 parts by weight of an organic halogen compound having a tribromomethyl group per 100 parts by weight of the total of (a) and (b).
And (d) 0.1 to 10 parts by weight of a photoinitiator or a photoinitiator system based on 100 parts by weight of the total of (a) and (b). The second invention is as follows: (a) Formula (I) (Wherein n is an integer of _{1 to} 23, and R ₁ , R ₂ and R _{3 each} represent a hydrogen atom or a methyl group). (B) A carboxyl group-containing film having a weight average molecular weight of 10,000 or more is imparted. 10 to 80 parts by weight of the polymer based on 100 parts by weight of the total of (a), (b) and the following (e). (C) The organic halogen compound having a tribromomethyl group is prepared by the steps (a), (b) and 0.1 to 10 parts by weight based on 100 parts by weight of (e), (d) photoinitiator or photoinitiator system based on 100 parts by weight of (a), (b) and the following (e) 0.1 to 10 parts by weight and (e) an ethylenically unsaturated compound, and (a) and (e) are 20 to 90 parts by weight based on 100 parts by weight of the total of (a), (b) and (e). The present invention relates to an alkali-developable photosensitive resin composition as a part. Examples of the compound represented by the formula (I) (component (a)) used in the present invention include ethylene glycol di (meth) acrylate (referring to methacrylate or acrylate, the same applies hereinafter), diethylene glycol di (meth) acrylate, Ethylene glycol di (meth)
Acrylate, polyethylene glycol di (meth) acrylate (n is 4 to 23), topylene glycol (meth) acrylate, dipropylene glycol di (meth)
Acrylate, tripropylene glycol di (meth) acrylate, and polypropylene glycol di (meth) acrylate (n is 4 to 23). Two or more compounds represented by the formula (I) may be used. The amount of component (a) is 20 to 90 parts by weight, preferably 30 to 80 parts by weight, per 100 parts by weight of the total of components (a) and (b). If the amount is less than 20 parts by weight, the photocured product is brittle and sufficient physical properties cannot be obtained. If the amount exceeds 90 parts by weight, other components become relatively small and sufficient light sensitivity is obtained. I can't. Examples of the carboxyl group-containing film-imparting polymer (component (b)) used in the present invention include (meth) acrylic acid (methacrylic acid or acrylic acid; the same applies hereinafter) alkyl ester and (meth) acrylic acid. Copolymer, alkyl (meth) acrylate and (meth) acrylate
Copolymers of acrylic acid and a vinyl monomer copolymerizable therewith are exemplified. Examples of the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and (meth) acrylic acid 2
-Ethylhexyl and the like. Vinyl monomers copolymerizable with alkyl (meth) acrylate or (meth) acrylic acid include tetrahydrofuryl (meth) acrylate, dimethylethyl (meth) acrylate,
Diethyl (meth) acrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl (meth) acrylate,
2,2,3,3-tetrafluoropropyl (meth) acrylate acrylamide, diacetone acrylamide, styrene, vinyltoluene and the like. Further, copolyesters, for example, polyesters such as terephthalic acid, isophthalic acid and sebacic acid, copolymers of butadiene and acrylonitrile, cellulose acetate, cellulose acetate butyrate, methyl cellulose, ethyl cellulose and the like can also be used. The use of the component (b) improves the coatability and the film strength of the obtained cured product. The amount of component (b) is 10 to 80 parts by weight, preferably 20 to 70 parts by weight, per 100 parts by weight of the total of components (a) and (b). When the amount is less than 10 parts by weight, the amount of ethylenically unsaturated compound is relatively increased, and the photosensitivity is lowered. When the amount exceeds 80 parts by weight, the photocured product becomes brittle and sufficient physical properties are obtained. I can't. The weight average molecular weight of the component (b) is set to 10,000 or more from the viewpoint of the coating properties and the film strength. Components (a) and (b) are used in amounts such that the total amount is 100 parts by weight within the range of parts by weight mentioned above. Examples of the organic halogen compound having a tribromomethyl group (component (c)) used in the present invention include tribromoacetophenone, bis- (tribromomethyl) sulfone, and tribromomethylphenylsulfone. Component (c) is added in an amount of 0.1 to 100 parts by weight of the total of components (a) and (b) due to the imaging properties of the photosensitive resin composition and the flexibility of the film obtained therefrom.
It is used in the range of 10 to 10 parts by weight, preferably 0.2 to 5.0 parts by weight. Examples of the photoinitiator or photoinitiator-based compound (component (d)) used in the present invention include benzophenone, N, N '
-Tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetramethyl-4,4'diaminobenzophenone, 4-methoxy-4'-dimethylaminobensophenone, 2 Aromatic ketones such as ethylanthraquinone and phenanthrenequinone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; benzoin such as methyl benzoin and ethyl benzoin; 2- (o-chlorophenyl) -4; 5-diphenylimidazole dimer, 2- (o-
Chlorophenyl) -4,5-di (m-methoxyphenyl)
Imidazole dimer, 2- (o-fluorophenyl) -4,
5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2-
(P-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer, 2- (2,4-dimethoxyphenyl) (Enyl) -4,5-diphenylimidazole dimer, 2- (p
2,4,5-triarylimidazole dimer such as -methylmercaptophenyl) -4,5-diphenylimidazole dimer. Component (d) is added in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 100 parts by weight of the total of components (a) and (b).
To 5.0 parts by weight. If the amount is less than 0.1 part by weight, sufficient photosensitivity cannot be obtained. If the amount exceeds 10 parts by weight, light absorption on the surface of the composition during exposure increases, and the internal photocuring Becomes insufficient. In the second invention, an ethylenically unsaturated compound as the component (e) is further used in the composition used in the first invention. Examples of the ethylenically unsaturated compound include compounds obtained by adding an α, β-unsaturated carboxylic acid to a polyhydric alcohol, such as trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolpropane tri (meth) acrylate. Glycidyl group-containing compounds such as methylol methane tri (meth) acrylate, tetramethylol methane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate Compounds obtained by addition, for example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether di (meth)
Esterified products of polyvalent carboxylic acids, such as acrylates, for example, phthalic anhydride, etc., and substances having a hydroxyl group and an ethylenically unsaturated group, for example, β-hydroxyethyl (meth) acrylate, alkyl esters of acrylic acid or methacrylic acid, for example, (Meth) acrylic acid methyl ester, (meth) acrylic acid ethyl ester, (meth) acrylic acid butyl ester, (meth) acrylic acid 2-ethylhexyl ester and the like are used, and trimethylhexamethylene diisocyanate, dihydric alcohol and A urethane diacrylate compound obtained by reacting a monoester of a (meth) acrylic acid with a polyhydric alcohol is also used. Two or more of these compounds may be used. The second invention is different from the first invention in that it contains the ethylenically unsaturated compound as the component (e). The components (a), (b), (c) and (d) are the same as those used in the first invention. The amount of components (b), (c) and (d) used depends on the amount of components (a), (b) and (e)
To the total amount of 100 parts by weight of the first invention. In the second invention, component (a) and component (e)
Is 20 to 90 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the total of components (a), (b) and (e), based on the properties of the photocured product and the photosensitivity of the photosensitive resin composition. Part of the range. There are no particular restrictions on the proportions of component (a) and component (e), but component (a) and component (e) must be used without fail. It is preferable that the ratio of (e) and (a) / (e) (weight ratio) be in the range of 0.1 or more. The photosensitive resin composition of the first and second inventions (hereinafter referred to as the photosensitive resin composition of the present invention) includes, for example, p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, t-butylcatechol and the like. Can be contained. Further, the photosensitive resin composition of the present invention may contain a coloring agent such as a dye or a pigment. As the coloring agent, for example, fuchsin, auramine base, crystal violet, Victoria Pure Blue, malachite green, methyl orange, acid violet RRH and the like are used. Further, a plasticizer, an adhesion promoter, talc and the like may be added to the photosensitive resin composition of the present invention. The photosensitive resin composition of the present invention comprises a solvent that dissolves the above-mentioned components, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, chloroform, methylene chloride, methyl alcohol,
By dissolving and mixing with ethyl alcohol or the like, a uniform solution can be used. The photosensitive resin composition of the present invention can be applied as a solution to a substrate such as a copper plate, dried, exposed to active light, and photocured before use. Alternatively, the composition in the form of a solution may be applied onto a polyethylene terephthalate film, dried, laminated on a substrate, and photocured before use. As the light source of the actinic ray used for photo-curing, those emitting light having a wavelength of 300 to 450 nm, for example, a mercury vapor arc, a carbon arc, and a xenon arc are preferably used. The cured film obtained by photocuring can be easily and finely removed with an aqueous alkali solution, for example, an aqueous sodium hydroxide solution. (Effects of the Invention) The photosensitive resin composition of the present invention has a cured part (exposed resist layer) which is not swelled and removed as it is, but is fragmented and removed in an alkaline aqueous solution, so that the printed circuit board is removed. The peeling pieces can be easily removed without being caught by the peeling roll of the automatic peeling machine used in the manufacturing process of (1), and the workability can be significantly improved. The photosensitive resin composition of the present invention can be used as a photoresist for etching or plating using a photocured film as a relief or using a copper-clad laminate as a substrate. (Examples) Hereinafter, the present invention will be described with reference to examples. As the carboxyl group-containing film imparting polymer, methacrylic acid / methyl methacrylate / butyl methacrylate /
2-ethylhexyl acrylate copolymer (weight ratio 25/50 /
5/20, 150 g of a 40% methylcellosolve / toluene (weight ratio 6/4) solution of weight average molecular weight ≒ 80,000 (polymer component 60 g),
Benzophenone / N, N'-tetraethyl-4,4'-diaminobenzophenone (40/1) mixture 6.0 g, malachite green 0.1 g, leuco crystal violet 1.0 g, tribromomethylphenylsulfon 0.5 g, methyl ethyl ketone 1
0 g, 20 g of toluene and 5.0 g of methanol to prepare solution A
I got In this solution A, the ethylenically unsaturated compound in the mixing ratio (unit: g) shown in Table 1 was dissolved to obtain a solution of the photosensitive resin composition. Next, this solution was uniformly applied on a 25 μm-thick polyethylene terephthalate film, and dried for about 10 minutes with a hot air convection dryer at 100 ° C. to obtain a photopolymerizable element. The film thickness of the photosensitive resin composition after drying was 50 μm. On the other hand, a copper-clad laminate (Hitachi Kasei Kogyo Co., Ltd.) is a glass epoxy material with copper foil (thickness: 35 μm) laminated on both sides.
The copper surface of the MCL-E-61) is polished with # 800 sandpaper, washed with water and dried in an air stream.
The photosensitive resin composition was heated to 120 ° C.
Lamination was performed while heating to ° C. Then, using a negative film on the substrate thus obtained, a 3KW high-pressure mercury lamp (HMW-201B, manufactured by Oak Manufacturing Co., Ltd.)
At 120 mJ / cm ² . At this time, a negative film made so that the amount of light transmission decreases stepwise so that the optical sensitivity can be evaluated (a stepper plate with an optical density of 0.05 as the first step and an optical density of 0.15 for each step). Was used. Next, the polyethylene terephthalate film was removed, and unexposed portions were removed by spraying a 2% aqueous solution of sodium carbonate at 30 ° C. for 50 to 150 seconds. Further, the photosensitivity of the photosensitive resin composition was evaluated by measuring the number of steps of the step blade of the photocured film formed on the copper-clad laminate. Table 1 shows the results. It shows that the higher the number of steps of the stepper bracket, the higher the light sensitivity. Next, the photocured portion (exposed resist layer) remaining on the copper surface was removed by treating with a 3% -NaOH aqueous solution at 50 ° C. Table 1 shows the results of examining the peelability of the light-cured portion with the naked eye. In the table, the symbol “剥離” means fine peeling, and × means non-fine peeling. The results in Table 1 show that when the photosensitive resin composition of the present invention is used, the peeled pieces are subdivided.

   ────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Hajime Kadomaru               4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi               Chemical industry inside Yamazaki factory (72) Inventor Daisuke Makino               4-13-1, Higashicho, Hitachi City, Ibaraki Prefecture Hitachi               Chemical industry inside Yamazaki factory                (56) References JP-A-59-113432 (JP, A)                 JP-A-61-22339 (JP, A)                 JP-A-54-100483 (JP, A)                 JP-A-60-236284 (JP, A)                 JP-A-60-91352 (JP, A)                 JP-A-61-138253 (JP, A)                 JP-A-61-56342 (JP, A)                 JP-A-61-56341 (JP, A)                 JP-A-63-44651 (JP, A)                 JP-A-63-78147 (JP, A)

Claims (1)

(57) [Claims] (A) Formula (I) (Wherein n is an integer of _{1 to} 23 and represents a hydrogen atom or a methyl group of R ₁ , R ₂ and R ₃ )
And (b) a carboxyl group-containing film-imparting polymer having a weight average molecular weight of 10,000 or more based on 100 parts by weight of the total amount of (a) and (b).
(C) 0.1 to 10 parts by weight of an organic halogen compound having a tribromomethyl group per 100 parts by weight of the total of (a) and (b).
An alkali-developable photosensitive resin composition containing 0.1 to 10 parts by weight of (d) a photoinitiator or a photoinitiator system based on 100 parts by weight of the total amount of (a) and (b). 2. (A) Formula (I) (N represents an integer of _{1 to} 23, and represents a hydrogen atom or a methyl group of R ₁ , R ₂ and R ₃ ) (b) a carboxyl group-containing film imparting polymer having a weight average molecular weight of 10,000 or more 10 to 80 parts by weight based on 100 parts by weight of the total of (a), (b) and the following (e). (C) An organohalogen compound having a tribromomethyl group is added to the (a), (b) and the following 0.1 to 10 parts by weight based on 100 parts by weight of (e), (d) photoinitiator or photoinitiator system based on 100 parts by weight of (a), (b) and the following (e) 0.1 to 10 parts by weight and (e) an ethylenically unsaturated compound, wherein (a) and (e) are 20 to 90 parts by weight based on 100 parts by weight of the total of (a), (b) and (e) Alkali-developing photosensitive resin composition,