JPH01142547A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To enable the formation of a permanent coating film having superior resolution and heat resistance and maintaining stability over a long period by incorporating a specified photopolymerizable compd., a specified polymerizable compd., a specified initiator and sensitizer, an epoxy hardening agent and a finely powdered filler. CONSTITUTION:This photosensitive resin compsn. contains at least one kind of photopolymerizable compd. represented by formula I and having at least one (meth)acryl modified epoxy group, a polymerizable compd. having at least two terminal ethylene groups, an initiator and sensitizer generating radicals under active rays of light, an epoxy hardening agent and a finely powdered filler. In formula I, R is 1-3C alkyl and n=3 or 4. When the amt. of the polymerizable compd. used is <=1pt.wt. per 100pts.wt. of the photopolymerizable compd. represented by formula I, the heat resistance of a hardened coating film is reduced. In case of >=30pts.wt., the thermal shock resistance is reduced. By using the resin compsn., a permanent protective coating film having superior resolution and heat resistance can be formed.

Description

Detailed Description of the Invention (Industrial Field of Application) The invention of Section 1 relates to a photosensitive resin composition, and more specifically to a photosensitive resin assembly J & product for forming a permanent protective film that can be used in the production of printed wiring boards. .

The invention of Section 2 relates to a photosensitive resin composition, and more specifically to a photosensitive resin composition for forming a vine interlayer insulation coating used in the production of multilayer printed wiring boards.

(Prior Art) Resin compositions having excellent properties that can be used for solder masks and the like have been known in the printed wiring board industry.

However, these are mainly composed of thermosetting resins such as epoxy resins and amino resins, and are usually used in screen printing methods.

However, in recent years, the wiring density of printed wiring boards has increased and a high degree of electrical insulation is required, and the solder masks used are also required to be thick and have excellent dimensional accuracy.
Conventional screen printing methods are no longer compatible.

Therefore, a photosensitive resin composition is coated or coated on a substrate, and active light such as ultraviolet rays is irradiated through a negative mask film, etc., and the exposed portions are polymerized or crosslinked to make them insolubilized in solvents. Photographic methods have been widely used in which images are formed on substrates by removing areas that are not exposed to light through development.

Conventionally, this type of photosensitive resin composition for solder masks includes (1) a photosensitive resin composition containing an acrylic polymer and a photopolymerizable hexamer as main components, and (2) an epoxy resin composition with a photoreactive group added. Photosensitive resin compositions containing resin as a main component are known.

However, although the resin composition of (1) can be developed with a flame-retardant developer (for example, 1.1.1-trichloroethane) and can form a highly accurate solder mask,
Because it contains a large amount of acrylic polymer, the cured film does not have sufficient heat resistance.

Since the resin composition (2) above is based on a novolac flat epoxy resin, the heat resistance of the cured film is sufficient, but it has the problem that the molecular weight distribution of the resin is large and sufficient resolution cannot be obtained. ing.

Furthermore, in recent years, multilayer printed wiring boards in which wiring circuits are formed in multiple layers have been used for the purpose of increasing the density of printed wiring boards. Conventionally, multilayer printed wiring boards have been used in which multiple circuit boards on which inner layer circuits have been formed are laminated and pressed together using prepreg as an insulating layer, and then the inner layer circuits are connected through through holes. Ta. However, since such multilayer printed wiring boards connect desired inner layer circuits by forming through holes that pass through the board, each inner layer circuit becomes a complex circuit that bypasses through holes that do not require connection, resulting in high density. It was fixed.

Recently, as a multilayer printed wiring board capable of solving this difficulty, development of a multilayer printed wiring board in which conductor circuits and organic insulating layers are alternately built up has been actively promoted. Although this multilayer printed wiring board is suitable for ultra-high density, it is difficult to form an organic insulating layer that can firmly adhere the plating film, so the conductor circuit of this type of multilayer printed wiring board is difficult to form. is formed by a PVD method or a combination of a PVD method and a plating method. However, forming conductor circuits by such a PVD method has the drawbacks of poor productivity and high cost. Therefore, the development of a photosensitive resin composition capable of forming an organic insulating layer to which a plating film can be firmly adhered has been awaited.

(Problems to be Solved by the Invention) The first object of the present invention is to eliminate the drawbacks of the above-mentioned prior art, to provide a photosensitive film that has excellent resolution and heat resistance, and is capable of forming a permanent film that is stable over a long period of time. An object of the present invention is to provide a resin composition.

The object of the wS2 of the present invention is to eliminate the drawbacks of the prior art, and to be able to form an organic insulating layer that has excellent heat resistance and electrical insulation properties, and can firmly adhere to the paint film. An object of the present invention is to provide a synthetic resin composition.

(Means for solving the problem) As a result of intensive research, the present inventor has developed a photosensitive resin composition based on an epoxy resin that has excellent heat resistance and electrical insulation properties and has an extremely small molecular weight distribution. , the above problem has been solved. That is, the invention of this Ml is (a
) at least one compound represented by formula l (R is an alkyl group having 1 to 3 carbon atoms, n is 3 or 4);
(b) a polymerizable compound having at least two or more terminal ethylene groups; (C) an initiator and sensitizer that generate radicals when exposed to actinic rays; (d) epoxy curing agent, (
e) A photosensitive resin composition containing a fine particle filler.

The photosensitive resin composition of the present invention contains as an essential component at least one compound represented by formula 1 (R is alkyl having 1 to 3 carbon atoms, 5, and n is 3 or 4) and at least one epoxy group. Contains a (meth)acrylic-modified photopolymerizable compound (hereinafter referred to as essential component (a)).

The epoxy resin used in the present invention is a heat-resistant polyfunctional epoxy resin represented by the general formula 1. These are commercially available, and include, for example, Epicoat 1031S manufactured by Yuka Shell, IDYL-931 manufactured by Yuka Shell, and YL-933 manufactured by Yuka Shell. These resins have an extremely small molecular weight distribution compared to novolac type epoxy resins, which do not have a small molecular weight distribution during synthesis.It is also possible to refine resins with a large molecular weight distribution and reduce the molecular weight distribution. However, there are many commercially available resins that are impractical due to the extremely high cost of loading, and which inherently have a small molecular weight distribution (e.g., glycidylamine type epoxy resin, bisphenol A9 epoxy resin, etc.). However, it became clear that it could not be used due to problems with its heat resistance and electrical properties when wet. For this reason, the inventors of the present invention investigated various resins and found that the above-mentioned problems could be solved by using a group of heat-resistant polyfunctional te epoxy resins represented by formula 1. Furthermore, these resins are subjected to (meth)acrylic modification in a conventional manner using acrylic acids or methacrylic acids to obtain the essential component (a). Generally known acrylic acids or methacrylic acids can be used here, but! ! It is desirable to use acrylic acid from the viewpoints of strength and resolution.

In the present invention, the degree of (meth)acrylic modification is 20 to
It is preferably 90%, more preferably 30 to 80%. If the degree of (meth)acrylic modification is less than 20%, the photocured film will easily swell and peel off during the development process after image exposure, and if it is more than 90%, heat resistance, adhesion, etc. will decrease. The polymerizable resin composition contains as an essential component a polymerizable compound having at least two or more terminal ethylene groups (hereinafter referred to as essential component (b)). Generally known compounds can be used for this compound, such as dipentaerythritol hexaacrylate, 1,6-hexanediol diacrylate, tris(2-acryloxyethyl)in cyanurate, and neopentyl glycol diacrylate.

Diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, diallyl terephthalate, N,
Examples include N-methylenebisacrylamide. If the amount of the polymerizable compound of essential component (b) used is less than 100 parts by weight of the photopolymerizable compound of essential component (a), the heat resistance of the cured film will decrease, and if it is more than 30 parts by weight, Thermal shock resistance deteriorates. Therefore, the amount of the polymerizable compound used as the essential component (b) is 1 to 30 gL parts, preferably 5 to 20 parts by weight, per 1 part of the photopolymerizable compound as the essential component (a). It is.

The photosensitive resin composition of the present invention contains as essential components an initiator and a sensitizer (hereinafter referred to as essential component (C)) that generate radicals when exposed to actinic rays. As this initiator, conventionally used photopolymerization initiators can be used. For example, benzophenone, 1-hydroxycyclohexylphenyl ketone, benzyl dialkyl ketal, 2-hydroxy-2-methylpropiophenone, Michler's ketone. , benzoin ethyl ether, 2,4-dialkylthioxanthone, 2-methyl-1[4-(methylthio)phenyl]
-2-MoJ lephorinolobanone and the like. Furthermore, by combining the photopolymerization initiator with a sensitizer having a different absorption wavelength of actinic rays, the polymerization initiation efficiency can be improved and the sensitivity can be further increased.For example, benzophenone and triethanolamine, 2-methyl- Examples include combinations of 1[4-(methylthio)phenyl]-2-moJ lepronolobanone and thioxanthone, and benzyl dialkyl ketal and Michler's ketone.

The amount of initiator and sensitizer of essential component (c) is determined by the amount of initiator and sensitizer of essential component (c).
0.1 to 2 per 100 parts by weight of the photocombinant compound a)
01f! parts by weight, preferably 1 to 15 parts by weight.

The photosensitive resin composition of the present invention contains 1 to 10 parts by weight of an epoxy curing agent (hereinafter referred to as essential component (d)) as an essential component. Examples of the epoxy curing agent include imidazoles such as l-methylimidazole, 1-phenylimidazole, and l-benzyl-2-methylimidazole;
Examples include 3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, boron trifluoride monoethylamine, adipic acid, dihydrazide, and dicyandiamide. However, from the viewpoint of electrical properties, it is preferable to use imidazoles or dicyanamide.

The photosensitive resin composition of the present invention contains a fine particle filler (hereinafter referred to as essential component (e)) as an essential component. Examples of the particulate filler include silica, alumina, talc, antimony trioxide, antimony pentoxide, aluminum hydroxide, and calcium carbonate. *The particle size of the particle filler is preferably 0.01 to 15 ILm, more preferably 0.001 to 2.0 ILm, from the viewpoint of resolution, adhesion of the cured film, etc.
It is 5JLm. The amount of the fine particle filler used as the essential component (e) is 10 to 60 parts by weight based on 100 parts by weight of the photopolymerizable compound as the essential component (a).

It is desirable that the particulate filler is uniformly dispersed in the photosensitive resin composition, and for this purpose, the surface of the particulate filler can be treated with a coupling agent having a functional group such as an amino group or a hydroxyl group. Examples of the coupling agent include γ-aminopropyltriethoxysilane, β-aminoethyl-γ-aminopropyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components, such as thermal polymerization inhibitors, pigments, coloring agents, coating properties improvers, antifoaming agents, etc. agents, adhesion improvers, leveling agents, etc.

The photosensitive resin composition of the present invention can be applied onto a substrate by a conventional method such as a dip coating method, a flow coating method, or a screen printing method. When applying, the composition can be diluted with a solvent if necessary. Examples of solvents include butyl cellosolve and methyl cellosolve acetate.

Butyl cellosolve acetate, methyl ethyl ketone, cyclohexanone, etc. can be avoided.

Concerning the second invention, the inventor has first made the resin composition of the invention contain a particulate filler that can be dissolved and removed by chemical conversion treatment, and conducts chemical conversion treatment on the surface of the completely cured insulating layer and dissolves it by chemical conversion treatment. By dissolving and removing the removable particulate filler and roughening the surface of the insulating layer, we succeeded in significantly improving the adhesion strength between the insulating layer and the plating film formed on the L, which was pointed out in the above problem. did. In other words, the invention of the youngest brother 2 is that (a) at least one compound represented by formula 1 (R is an alkyl group having 1 to 3 carbon atoms, n is 3 or 4) has at least one epoxy group (meth). ) an acrylic-modified photopolymerizable compound, (b) a polymerizable compound having at least 2 m or more of terminal ethylene groups, (C) an initiator and sensitizer that generates radicals by actinic rays, (d) an epoxy curing agent, (e ) A particulate filler; and (f) a particulate filler that can be dissolved and removed by chemical conversion treatment.

The photosensitive resin composition of the present invention contains as an essential component at least one compound represented by formula 1 (R is an alkyl group having 1 to 3 carbon atoms, n is 3 or 4), and at least one compound is Photopolymerizable compound with (meth)acrylic modified group (
(hereinafter referred to as essential component (a)).

The details are the same as the essential component (a) of the invention of youngest brother 1.

The photosensitive resin composition of the present invention contains as an essential component a polymerizable compound having at least two terminal ethylene groups.The details are the same as the essential component (b) of the invention of the youngest brother 1.

The photosensitive resin composition of the present invention contains as essential components an initiator and a sensitizer that generate radicals when exposed to actinic rays.

The details are the same as the essential component (c) of the invention of youngest brother 1.

The photosensitive resin composition of the present invention has as an essential component.

Contains 1 to 10 parts by weight of an epoxy curing agent.

The details are the same as the essential component (d) of the invention of youngest brother 1.

The photosensitive resin composition of the present invention contains a fine particle filler as an essential component.

The details are the same as the essential component (e) of the invention of youngest brother 1.

The photosensitive resin composition of the present invention has a fine particle filler (hereinafter referred to as essential component (f)) which can be dissolved and removed by chemical conversion treatment as an essential component.
). Particulate fillers that can be dissolved and removed by chemical conversion treatment include inorganic particulates such as silica and calcium carbonate, and heat-resistant resin particulates. When using heat-resistant resin fine particles, it is preferable to use heat-resistant resin fine particles that have been cured in advance. This is because if resin fine particles are used, they will dissolve in the resin liquid when dispersed in the photosensitive resin composition, making it impossible to selectively dissolve and remove them by chemical conversion treatment. By using heat-resistant resin fine particles that have been cured in advance, it is possible to form an insulating layer in which the heat-resistant resin fine particles are uniformly dispersed without dissolving in the resin liquid even when dispersed in a photosensitive resin composition. By applying a chemical conversion treatment to the heat-resistant resin particles and dissolving and removing the heat-resistant resin particles, the surface of the insulating layer can be uniformly roughened, and a plating film can be reliably formed on the insulating layer.

The material of the heat-resistant resin fine particles is a resin that has excellent heat resistance and electrical properties, does not dissolve even when dispersed in a photosensitive resin composition by curing treatment, and has the property of being soluble in a specific chemical solution used for chemical conversion treatment. For example, epoxy resin, polyester resin.

Examples include bismaleimide-triazine resin. Methods for the curing treatment include a method of curing by heating and a method of curing by adding a catalyst. Further, as the specific chemical solution used for the chemical conversion treatment, for example, oxidizing agents such as chromic acid, chromate, permanganate, hydrofluoric acid, hydrochloric acid, etc. can be used.

The particle size of the heat-resistant resin fine particles is preferably 15 μm or less, more preferably 5 ILm or less.

The reason for this is that the roughened surface formed by dissolving and removing fine particles having a particle size of 15 ILm or more becomes non-uniform, making it impossible to form a plating film with good reliability.

The amount of the fine particle filler that can be dissolved and removed by the chemical conversion treatment of the essential component (f) is 100% of the photopolymerizable compound of the essential component (a).
The amount is 10 to 60 parts by weight.

Furthermore, the photosensitive resin composition of the present invention may contain other subsidiary components, such as a thermal polymerization inhibitor,
Examples include pigments, color formers, coating and workability improvers, antifoaming agents, adhesion improvers, and leveling agents.

The photosensitive resin composition of the present invention can be applied onto a substrate by a conventional method such as a dip coating method, a flow sheet method, or a screen printing method. When making ramie, the composition can be diluted with a solvent if necessary. Examples of the solvent include butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, methyl ethyl ketone, cyclohexanone, etc.
(Function of the invention) The photosensitive resin composition of Mizuo 1's invention has an extremely small molecular weight distribution of the photopolymerizable compound constituting the main part compared to conventional photosensitive resin compositions, and therefore, it is possible to precisely form the desired part. A film can be easily formed using a photographic method. Furthermore, since the composition contains a polymerizable compound having two or more functionalities, the crosslinking density is increased during curing, and the heat resistance and chemical resistance of the cured film are improved.

Furthermore, the curing of the invention by the first photosensitive resin composition, which suppresses thermal expansion and has excellent adhesion to the underlying conductor due to the fine particle filler contained therein, occurs for the reasons described above. Presumed.

The photosensitive resin composition according to the invention of Suiden 2 contains a fine particle filler that can be dissolved and removed by chemical conversion treatment in the photosensitive resin composition according to the first invention. It has an effect. By subjecting the cured film of the photosensitive resin composition of the second invention to a chemical conversion treatment, minute irregularities are formed on the surface of the cured film.

When plating is applied to such a surface, the plating film penetrates into the minute irregularities. When you try to peel off this plating film, the minute irregularities get caught,
The plating film formed on the cured film of the photosensitive resin composition of the second invention, which acts as a so-called anchor,
It is presumed that the effect of the invention due to the zero second photosensitive resin composition that firmly adheres to the cured film occurs for the reasons described above.

(Example) The present invention will be explained in more detail with reference to an example below.
The present invention is not limited to these, and the parts used as numerical units in the examples mean the highlighted parts.

Example 1 1) 100 m of a 50% acrylate of a polyfunctional epoxy resin (manufactured by Yuka Shell Co., Ltd., trade name: Epicoat 1031s) and 15 parts of diallyl terephthalate.

2-Methyl-1-(4-(methylthio)phenylgo2)
- Morpholinopropanone (manufactured by Ciba Geigy, product name:
Isorgacure-907) 4 parts, imidazole (Shikoku Kasei-Sou, trade name: 2 parts 4MH2), 4 parts, benzoguanamine resin fine powder (Nippon Shokubai Chemical Co., Ltd., trade name: Eposter S-6, average particle size 0.5 μm) 50 While adding butyl cellosolve, the mixture was adjusted to a viscosity of 250 cps using a homodisper stirrer, and then kneaded using three rolls to prepare a solution of the photosensitive resin composition.

2) Next, a solution of the photosensitive resin set rR, ￥S was applied using a knife coater onto the printed wiring board obtained by photoetching the surface of the copper-clad 8IN board using a conventional method, and the solution was left in a horizontal position for 20 minutes. Thereafter, it was dried to the touch at 70° C. to form a photosensitive resin layer with a thickness of about 501 Lm.

3) Next, a photomask film on which a black line with a line width of 100#Lm was formed was closely attached to this, and ultra-high pressure mercury etc.
00 mj/cm" exposure. This was subjected to ultrasonic development treatment with a mixed solution of equal amounts of chlorocene/butyl cellosolve to form a line pattern of 1100p on the printed wiring board. Next, this wiring board was exposed to ultra-high pressure. About 3 mercury lamps
000 mj/cm' exposure and further 100°C
By heat-treating at 150° C. for 1 hour and 10 hours at e150° C., a permanent coating with excellent dimensional accuracy, which corresponds to a photomask film, was obtained.

Since the fine particles included in this permanent coating are resin fine powder, they have good dispersibility in the coating, so that the fine particles do not settle to the bottom of the coating, and the resin is in sufficient upper contact with the underlying copper conductor, so that the underlying copper conductor and resin are in sufficient upper contact. Particularly excellent adhesion to conductors. In addition, diallyl terephthalate contained in the resin solution increases the crosslinking density during curing, so the cured film has excellent heat resistance and
A soldering heat resistance test was conducted at 0° C. for 30 seconds, but no peeling or discoloration of the film was observed. Also, MIL-5TD-2
02Method 107 Candition
In a thermal shock test similar to B, no peeling of the film or occurrence of cracks was observed even after 100 cycles, and it was revealed that the film had excellent long-term reliability. This coating also has excellent alkali resistance, and is
No peeling or discoloration of the film was observed even after immersion for a long time.

Electroless copper plating bath sulfuric acid jjl (CuSO4e 5Ht O) 0.06
mol/liter Formalin 0.05 mol/1 Caustic soda 0.32 mol/I
E D T A 0.12
Mol/1 additive A little plating temperature 70℃ plating liquid P H
12.4 Example 2 The only difference from Example 1 was that the resin composition was changed as follows.

l) 100 parts of 75% acrylate of polyfunctional epoxy resin (manufactured by Yuka Shell, trade name: Epicote 1031S), 20 parts of dipentaerythritol hexaacrylate, benzyl alkyl ketal (manufactured by Chiha Geigy, trade name Coil Gacure 651) 5 part, imidazole (manufactured by Shikoku Kasei,
Product name: 2 parts 4 MHz) 3 parts, fine silica powder (manufactured by Nippon Shokubai Chemical Co., Ltd., product name 2NS Silica X-05, average particle size 0
．． After mixing 50 parts of 5 μm), the viscosity was 250 cp using a homodisper stirrer while adding butyl cellosolve.
s, and then kneaded with three rolls to prepare a solution of the photosensitive resin composition.

The obtained permanent coating is characterized by particularly excellent thermal shock resistance because the fine particles to be encapsulated are inorganic silica particles, so the coating has high hot hardness and suppresses thermal expansion. MIL-STD-202Method 10
7. In a thermal shock test based on Condition B, no peeling of the film or generation of cracks was observed even after 500 cycles, and it was revealed that the film had excellent long-term reliability. Furthermore, since the dipentaerythritol hexaacrylate contained in the resin solution is hexafunctional, it significantly improves the crosslinking density during curing and makes the cured IIt film excellent in heat resistance. A soldering heat resistance test was conducted at 260° C. for 30 seconds, but no peeling or discoloration of the film was observed.

Real mN3 1) Multifunctional epoxy resin (manufactured by Yuka Shell, product name: YL
-933), 100 parts of diallyl terephthalate, 2-hydroxy-2-methylpropiophenone (manufactured by Merck & Co., trade name: Darocure-11)
73) 4fi% 1゜3-bis(hydrazinocarboethyl)-5-isoprobylhytontoin (manufactured by Ajinomoto, trade name: Amicure-VDH) 30 parts, talc fine powder (manufactured by Fuji Talc Industries, trade name: LNS) #200, average particle size 1
．． After mixing 40m of 5#Lm), the viscosity was 250c using a homodisper stirrer while adding butyl cellosolve.
ps and knead with one and three wooden rolls to form a solution of the photosensitive resin composition. ! did.

2) Next, a solution of the photosensitive resin composition was applied using a knife coater to a printed wiring board obtained by photo-etching the surface of the copper-clad laminate using a conventional method, and after being left in a horizontal position for 20 minutes, It was dried to the touch at 70°C to form a photosensitive resin layer with a thickness of about 50 m.

3) Next, a photomask film on which a black line with a line width of about 100 lm has been formed is attached closely to this, and the film is heated with an ultra-high pressure mercury lamp for 8
00 mj/crn' exposure. This was subjected to ultrasonic development treatment using a mixed solution of equal amounts of chlorocene/butyl cellosolve to form a loOpm line pattern on the printed wiring board. Next, this wiring board is exposed to approximately 3000 mj/crrr' using an ultra-high pressure mercury lamp, and then heat-treated at 100°C for 1 hour and then at 150°C for 1 hour to form a permanent film with excellent 1-dimensional accuracy equivalent to a photomask film. I got it.

The photosensitive resin layer uses 1,3-bis(hydrazinocarboethyl)-5-isobrobylhydontoin as the epoxy curing agent, so the curing speed is fast, and the final heating time is sufficient for one hour, improving productivity. increases significantly. Furthermore, since YL-933 is used as the polyfunctional epoxy resin, it has high flexibility, and since it contains fine talc powder that has excellent heat resistance and impact resistance, the cured film has particularly excellent thermal shock resistance. Furthermore, since it contains diallyl phthalate, it also has excellent heat resistance as shown in Example 1. A soldering heat resistance test was conducted at 260° C. for about 30 seconds, but no peeling or discoloration of the film was observed. M
IL-STD-202METHOD 107 Co
In a thermal shock test according to ndition B, no peeling or cracking of the film was observed even after 500 cycles, and it was revealed that the film had excellent long-term reliability.

1) Methyl methacrylate 93χ, 63 parts of a copolymer of 7% methacrylic acid, 371 parts of 2,2-bis(4-dimethacryloxydithoxyphenyl)propane, 6 parts of benzophenone, and methyl ethyl ketone 408B were uniformly mixed. ,
A solution of a photosensitive resin composition was obtained.

2) Next, using a flow coater, a solution of the photosensitive resin composition is applied onto the printed wiring board obtained by photoetching the surface of the copper-clad laminate using a conventional method! I! After leaving it in a horizontal position for 20 minutes, dry it to the touch at 70°C to a thickness of 40. A photosensitive resin layer of Bm was formed.

3) Next, a photomask film on which a black line with a line width of 100p and m was formed was attached closely to this, and the film was heated with an ultra-high pressure mercury lamp for 8
00 mj/cm" exposure. This was subjected to ultrasonic development treatment with a chlorocene solution to form a 100p!11 pattern on a printed wiring board.

Next, this wiring board was heated for about 3000mj using an ultra-high pressure mercury lamp.
/ crn' exposure and then heat treatment at 150° C. for 1 hour to obtain a film corresponding to a photomask film.

When this wiring board was immersed in a solder bath at 260°C, 20
A bulge appeared in seconds.

Cresol novolac type epoxy resin (manufactured by Asahi Kasei,
Product name: ECN299 ioo% acrylate 100
part, 2-methyl-1-[4-(methylthio)phenyl]
-2-MoJ Refuorinobanon (manufactured by Chiha Geigy,
After mixing 4 parts (trade name: Niirgacure 907) and 50 parts of benzoguanamine resin fine powder (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name: Epostor S-6° average particle size 0-51 parts m), while adding butyl cellosolve, , to a viscosity of 200 CPS using a homodisbur stirrer. ! Then, the mixture was kneaded using three rolls to prepare a solution of the photosensitive resin composition.

Although the same processing as in Comparative Example 1 was carried out, it was not possible to resolve the 1100p pattern. Next, examples will be described regarding a photosensitive resin composition that can be used as a living room insulation material according to the second invention.

Example 4 1) 100 parts of 50% acrylate of polyfunctional epoxy resin (manufactured by Yuka Shell Co., Ltd., trade name: Epicote 1031S), 15 parts of diallyl terephthalate, 2-methyl-1-[4-(
Methylthio)phenyl]-2-morpholinopropanone-1 (manufactured by Chiha Geigy, trade name: Niirgacure 90)
7) 4f1. Imidazole (manufactured by Shikoku Kasei, product name: 2)
Part 4MH2) 4 parts, silica fine powder (manufactured by Nippon Shokubai Chemical Industry Co., Ltd. 5 Trade name: NS Silica X-05, average particle size 0.5JL1
11) 25 parts, epoxy resin fine powder (manufactured by Toshi, product name:
While adding butyl cellosolve mixed with 25 parts of Treval EP-B (average particle size 0.5 ILm), the viscosity was adjusted to 250 cps using a homodisbur stirrer, and kneaded with one and three rolls to form a photosensitive resin composition. Get the liquid.

2) Next, a solution of the photosensitive resin composition was applied using a knife coater onto the printed wiring board obtained by photoetching the surface of the copper-clad laminate using a conventional method, and after being left in a horizontal position for 20 minutes, Dry to the touch at 70℃ to a thickness of approx.
A photosensitive resin layer of 0#Lm was formed.

3) Next, a foot mask film with a black circle of 100 gmΦ was tightly attached to this, and the film was heated at 800 gm using an ultra-high pressure mercury lamp.
This was exposed to 100p, mΦ via holes on the printed wiring board by ultrasonic development treatment with a mixed solution of equal amounts of chlorocene/butyl cellosolve.Next, this wiring board was exposed to ultra-high pressure. Approximately 3 with a mercury lamp
000 m j / cr n' exposure, then 100
By heat-treating at 150° C. for 1 hour and then 10 hours at 150° C., an interlayer insulating film with excellent one-dimensional accuracy corresponding to a photomask film was obtained.

This coating is made of silica particles that are insoluble in chromic acid.

Because it contains soluble epoxy particles, the coating surface becomes a roughened surface with a very complex shape when treated with chromic acid.
When a conductor is formed on the film, it is characterized by high adhesion. In addition, since it contains fine silica particles of the S carrier, the coating has high hot hardness and suppresses thermal expansion, so it has particularly excellent thermal shock resistance.

For example, this interlayer insulating film is coated at a temperature of 70°C and a concentration of 500°C.
It is roughened with g/l chromic acid for 15 minutes, immersed in a neutralizing solution (manufactured by Sibley, trade name: PM950), and washed with water.

Next, as a pretreatment for chemical plating, a palladium catalyst (manufactured by Sibley Co., Ltd., trade name: Catabosite 44) was applied to activate the surface, and the surface was immersed in chemical copper plating with the following composition for 15 minutes, followed by electrolytic copper plating solution with the following composition. When 201 Lm of copper was deposited in the via hole, the beer strength under normal conditions was 1.80 kg/cm. Also, MIL-
STD-202Method 107Conditi
In a thermal shock test similar to on B, it was revealed that the wire did not break even after 500 cycles and had excellent long-term reliability. In addition, diallyl terephthalate contained in the resin solution increases the crosslink density during curing, so the cured film has excellent heat resistance, and when a soldering heat resistance test was conducted at 260 ° C. for 30 seconds, no peeling or discoloration of the insulating film was observed.

Chemical plating liquid composition Manufactured by Sibley 328A 12-51 Sibley company 328L 12.5 Manufactured by Sibley
32aC1,5! Pure water temperature at 73.5
25℃ Electrolytic copper plating liquid composition CUSO, 5 Hz 0 150g/AC Ht
S Oa 40g/view Cl -21
1 ppm Additive Predetermined amount Temperature 25°C Cathode current density 2A/drn' Example 5 ■) Epoxy resin (manufactured by Yuka Shell, trade name: Epicoat 11001) 100 and epoxy curing agent (manufactured by Shikoku Kasei, trade name: 2PZ) 5 1 part added resin in a hot air dryer
It was cured by drying at 00° C. for 1 hour and then at 150° C. for about 10 hours. This hardened epoxy resin is roughly pulverized, then pulverized using a supersonic jet pulverizer while being frozen with liquid nitrogen, and further classified using a wind classifier.The epoxy resin has an average particle size of 1.6 gm. Made a fine powder.

2) 100 parts of 75% acrylate of polyfunctional epoxy resin (manufactured by Yuka Shell, trade name: Epicote 1031S), 25 parts of dipentaerythritol hexaacrylate, benzyl alkyl ketal (manufactured by Ciba Geigy, trade name: Nilgacure 651) 5 part, imidazole (Shikokuka #r
, product name: P4MH2), 3 parts, benzoguanamine fine powder (H-catalyst chemical industry grade, product name: Epostor S-
6. After mixing 15 parts (average particle size: 0.5 gm) and 35 parts of the epoxy resin fine powder, the viscosity was 250 cps using a homodisbur stirrer while adding butyl cellosolve.
The solution of the photosensitive resin composition was prepared by firstly kneading the photosensitive resin composition using a three-piece roll.

3) Next, a solution of the photosensitive resin composition was applied using a knife coater onto the printed wiring board obtained by photo-etching the surface of the copper-clad laminate using a conventional method, and the solution was left in a horizontal position for 20 minutes. The photosensitive resin layer was dried to the touch at 70° C. to form a photosensitive resin layer having a thickness of about 501 Lm.

4) Next, a photomask film with a black circle of 11,001 LΦ was attached tightly to this, and an 800 mm
0 mj/cm' exposure. This was subjected to ultrasonic development treatment with a mixed solution of equal amounts of chlorocene/butyl cellosolve to form via holes with a diameter of 100 mΦ on the printed wiring board.Next, this wiring board was processed using an ultra-high pressure mercury lamp to form a via hole of approximately 3000 mj/cm. ' : Jl light, and then heat-treated at 100° C. for 1 hour and then at 150° C. for 10 hours to obtain a living room insulation coating with excellent dimensional accuracy and equivalent to a photomask film.

This insulating layer contains fine benzoguanamine resin powder that is insoluble in chromic acid and fine epoxy resin powder that is soluble in chromic acid. Furthermore, since the contained fine particles are resin powder, the fine particles have good dispersibility and do not settle to the bottom of the fine particles. Since this does not occur, a very complex roughened surface can be obtained by treating the surface with chromic acid. Therefore, when a conductor is formed on the insulating layer E, an extremely high adhesion force can be obtained.

When this interlayer insulating film is roughened with chromic acid according to the method of Example 4, chemical steel plating is thinly applied, and 201 Lm of copper is deposited in the pipe hole by electrolytic copper plating, the beer strength in the normal state is 2.3 kg. /cm. Also, MIL-3TD-202Method 107
In the thermal shock test according to Condition B,
It was revealed that even after 500 cycles, no wire breakage occurred and long-term reliability was excellent. Furthermore, since the dipentaerythritol hexaacrylate contained in the resin solution is hexafunctional, it significantly improves the crosslinking density during curing and makes the cured film excellent in heat resistance. A soldering heat resistance test was conducted at 260° C. for 30 seconds, but no peeling or discoloration of the insulating M coating was observed.

Tomoaki ■Al), polyfunctional epoxy resin (manufactured by Yuka Shell, product name:
100 parts of 50% acrylated product of YL-933), 15m diallyl terephthalate, 4 parts of 2-hydroxy-2-2-methylpropiophenone (manufactured by Merck & Co., trade name: Rilocure-1173), 1,3-bis( hydrazinocarboethyl)-5-isobrobylhytontoin (manufactured by Ajinomoto,
Product name: Amicure-VDH) 30 parts, talc fine powder (
Fuji Talc Kogyo Co., Ltd., product name: LMS #200, average particle size 1.54 m) 25 parts, epoxy resin fine powder (Toshi Co., Ltd., product name: Treval EP-B, average particle size 0.5 u-m)
), and while adding butyl cellosolve, the viscosity was adjusted to 250 cps using a homodisper stirrer, and the solution was mixed using a wooden roll once and then three times to prepare a solution of the photosensitive resin composition.

2) Next, a coating of the photosensitive resin IIi composition was applied to the printed wiring board obtained by photoetching the surface of the copper-clad 8M board by a conventional method using a knife coater,
After being left in a horizontal state for 20 minutes, it was dried to the touch at 70°C to form a photosensitive resin layer with a thickness of about 50 gm.

3) Next, a photomask film on which a black circle of loOILmΦ was formed was closely attached to this, and it was heated with an ultra-high pressure mercury lamp.
00 mj/c was exposed. this.

A via hole of 1,100 pΦ was formed on the printed wiring board by ultrasonic development treatment with a mixed solution of equal amounts of chlorocene/butyl cellosolve.Then, this wiring board was exposed to approximately 3,000 m j/c rrr' with an ultra-high pressure mercury lamp. Further heat treatment was performed at 100° C. for 1 hour and then at 150° C. for 1 hour to obtain an interlayer insulating film with excellent dimensional accuracy, which corresponds to a photomask film.

The photosensitive resin layer uses 1,3-bis(hydrazinocarboethyl)-5-isobrobyrhytontoin as the epoxy curing agent, so the curing speed is fast, and the final heating time is sufficient for 1 hour, improving productivity. increases significantly. In addition, since YL-933 is used as the polyfunctional epoxy resin, it has high flexibility.
Furthermore, since it contains fine talc powder which has excellent heat resistance and impact resistance, the cured film has particularly excellent thermal shock resistance. Furthermore,
Since it contains diallyl phthalate, it also has excellent heat resistance as shown in Example 4. A soldering heat resistance test was conducted at 260° C. for 30 seconds, but no peeling or discoloration of the insulating layer was observed. MIL-5TD-202Method 107
In a thermal shock test according to Condition B, no peeling of the coating or generation of cracks was observed even after 1000 cycles, and it was revealed that the long-term reliability was excellent. This insulating layer coating contains fine talc particles that are insoluble in chromic acid and fine epoxy particles that are soluble in chromic acid, so by treating the Si surface with chromic acid, it becomes a roughened surface with a very complex shape, and the surface of the insulating layer coat is roughened. When a conductor is formed, it is characterized by high adhesion. When this interlayer insulating film is roughened with chromic acid according to the method of Example 4, applied thinly with chemical copper plating, and further 201 Lm of copper is deposited in the pipe hole by electrolytic copper plating, the beer strength in the normal state is 2.2 kg. /cm.

(Effect of the invention) The protective film obtained using the photosensitive resin composition of the invention of Mizuo 1 has excellent heat resistance and thermal shock resistance, and is also resistant to all alkaline aqueous solutions, so it can be used as a resist for plating and as a solder. It can be used as a permanent protective coating on masks, etc. Furthermore, the protective film obtained using the photosensitive resin composition of the invention of Suihiro 1 has excellent adhesion to the base, and is therefore extremely useful in making printed wiring boards with high tonality.

If the interlayer insulating film obtained using the photosensitive resin composition of the invention of the youngest brother 2 is used, the adhesion between the conductor circuit made of the plating film and the insulating layer is extremely excellent, and the multilayer film has excellent heat resistance *thermal shock resistance. It is useful for making printed wiring boards.

that's all

Claims (1)

[Scope of Claims] 1.a) At least one compound represented by formula 1 (R is an alkyl group having 1 to 3 carbon atoms, n is 3 or 4) containing at least one epoxy group (meth) ) Acrylic modified photopolymerizable compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Formula 1 b) A polymerizable compound having at least two terminal ethylene groups. c) An initiator and sensitizer that generate radicals by actinic rays. d) Epoxy curing agent e) Fine particle filler A photosensitive resin composition comprising at least the above a) to e). 2.a) Photopolymerization in which at least one epoxy group is (meth)acrylic modified with at least one compound represented by formula 1 (R is an alkyl group having 1 to 3 carbon atoms, n is 3 or 4) sexual compound. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Formula 1 b) A polymerizable compound having at least two terminal ethylene groups. c) An initiator and sensitizer that generate radicals by actinic rays. d) Epoxy hardener. e) Particulate filler. f) Particulate filler that can be dissolved and removed by chemical conversion treatment. A photosensitive resin composition comprising at least the above a) to f).