JPH0510367B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] This invention provides a novel photosensitive polyamide film that has extremely excellent solubility in organic solvents, and has photosensitive groups directly bonded to the polyamide main chain and has excellent photocuring performance. The present invention relates to a resin liquid composition that can be suitably used to form a film, and the above photosensitive polyamide film can be easily formed from the resin liquid composition, and the photosensitive polyamide film It has good resolution when photocuring to form relief patterns, etc., and the photocured film has good adhesion (especially edge adhesion) to the object to be coated (copper surface, resin surface, etc.). ) and has excellent heat resistance, dimensional stability, electrical and mechanical properties, so it can be suitably used as high precision solder resist, marking ink, solder leveler ink, etc. It can also be used to form insulating films (layers) for solid-state devices in the semiconductor industry, passivation films, and interlayer insulating materials for semiconductor integrated circuits, multilayer printed wiring boards, etc. [Prior Art] Materials for forming insulating films and passivation films on solid-state devices in the semiconductor industry, and interlayer insulating materials for semiconductor integrated circuits and multilayer printed wiring boards, are required to have high heat resistance and insulation properties. Furthermore, due to the demand for higher density and higher integration, photosensitive and heat-resistant materials have been sought. There have been many reports on photosensitive polyamides (resin compositions), but most of them are based on combinations of polyamides that do not have photosensitive groups and highly polymerizable unsaturated compounds (photosensitive monomers). The photosensitivity was not uniform and was not high enough (Japanese Patent Application Laid-Open No. 48-89004, JP-A No. 49-74739).
(See Japanese Patent Publication No. 56-93704, etc.). Polyamides having photosensitive groups directly in the polymer main chain have also been proposed (see JP-A-50-8605 and JP-A-56-122833, etc.), but these are related to aliphatic polyamides and have poor heat resistance. However, the amount of the photosensitive group was insufficient, or the photosensitive performance was low due to insufficient amount of the photosensitive group, so that the photosensitive properties were not fully satisfactory for practical purposes. Under the above-mentioned circumstances, the inventors have developed a variety of photosensitive resins with the aim of providing a photosensitive resin with excellent solubility and which can easily form a relief pattern with excellent heat resistance, electrical and mechanical properties. As a result of research, it was found that polyamide, which is made of a polymer of a dicarboxylic acid component mainly composed of aromatic dicarboxylic acids and an aromatic diamine component mainly composed of an aromatic diamine compound having a photosensitive group, has excellent solubility in organic solvents. It has been discovered that the photosensitive polyamide has excellent photosensitivity and that its photocured product retains excellent heat resistance, etc., and has already filed an application for an invention related to this photosensitive polyamide. However, although the photosensitive polyamide described above has excellent solubility in organic solvents, there are various problems when actually forming a photosensitive polyamide film from a solution of this polyamide in an organic solvent. In some cases, it may not be possible to form a photosensitive polyamide film with the desired performance, and the photosensitive polyamide film may not be able to be photocured with sufficiently satisfactory properties in terms of heat resistance, adhesion (particularly edge adhesion), dimensional stability, etc. In some cases, it is not possible to form a film (such as a relief pattern), which has been a problem in advanced technology fields that require precise performance, such as the semiconductor industry mentioned above. [Requirements and effects of the present invention] As a result of intensive research into a method for forming a photosensitive polyamide film free from the above-mentioned problems from the above-mentioned photosensitive polyamide, the inventors found that By adding specific amounts of photopolymerizable monomers, thermal polymerization inhibitors, and, if necessary, inorganic fillers to an organic solvent solution, a photosensitive polyamide film with stable performance can be formed. The present invention was completed based on the discovery that this is easily possible and that a photocured film with excellent properties can be obtained from the photosensitive polyamide film. That is, this invention comprises a dicarboxylic acid component containing at least 30 mol% of aromatic dicarboxylic acids based on the total dicarboxylic acid components, and an aromatic diamine component containing at least 30 mol% of an aromatic diamine compound having a photosensitive group. 100 parts by weight of a photosensitive polyamide which is soluble in an organic solvent and consists of a polymer, 1 to 150 parts by weight of a photopolymerizable monomer, 0.1 to 15 parts by weight of a photopolymerization initiator, 0.01 to 5 parts by weight of a thermal polymerization inhibitor, 100 to 100 parts by weight of an organic polar solvent. The present invention relates to a resin liquid composition for a photosensitive polyamide film comprising 200 parts by weight and 0 to 200 parts by weight of an inorganic filler. In particular, the resin liquid composition of the present invention is characterized in that (A) a polyamide film formed from this composition is obtained by polymerizing an aromatic diamine component containing an aromatic diamine compound having a photosensitive group with a dicarboxylic acid component; (b) Moreover, since a large number of photosensitive groups are introduced into the polymer main chain during the polymerization reaction, the polymer itself has extremely high photosensitivity.
Therefore, light transmittance and photocurability (photocrosslinkability)
(c) It also contains a photopolymerizable monomer in its composition, making it suitable for photosensitive polymers that use conventional non-photosensitive polymers as a polymer component. (B) It also contains a thermal polymerization inhibitor, so it can form a photosensitive polyamide film with superior curing speed and resolution compared to resin liquids for photosensitive films.
Many unsaturated photosensitive groups in the main chain of photosensitive polyamide are removed during the drying process by heating during film formation.
(C) Furthermore, it has excellent solubility in organic solvents, making it easy to prepare resin liquid for film formation, and After a thin film formed from the liquid is covered with a mask film and photocured, the uncured layer can be easily removed and washed, making it extremely suitable for forming relief patterns. Furthermore, the photocured film obtained by photocuring the photosensitive polyamide film formed from the resin liquid composition of the present invention by irradiation with light etc. mainly uses an aromatic monomer component as described above. The photocured product (film) is mainly composed of aromatic polyamide and inorganic filler obtained by
maintains a practical level of thermal properties,
Even when immersed in molten solder (approximately 260°C), the photocured film does not shrink or peel, and even after a thermal history at such high temperatures, the surface to be coated (resin It has excellent adhesion to surfaces (such as surfaces or copper wires), and also has excellent dimensional stability against changes in heat. [Description of each requirement of the present invention] The photosensitive polyamide soluble in the organic polar solvent used in the resin liquid composition of the present invention contains aromatic dicarboxylic acids at least 30 mol% based on the total dicarboxylic acid components; Preferably 50 mol% or more, more preferably 70 mol% or more, the dicarboxylic acid component contained and the aromatic diamine compound having a photosensitive group at least 30 mol%, preferably 40 mol% or more, more preferably 50 mol%. The organic solvent-soluble aromatic polyamide is composed of a homopolymer or copolymer obtained by polymerizing the aromatic diamine component contained above in an organic polar solvent. In addition to aromatic dicarboxylic acids, the dicarboxylic acid component may include dicarboxylic acids other than the aromatic dicarboxylic acids, such as alicyclic or aliphatic dicarboxylic acids. The aromatic dicarboxylic acids mentioned above may be any known aromatic dicarboxylic acids or acid derivatives thereof, as long as polyamide can be produced by polymerization reaction with an aromatic diamine component. Preferred examples include aromatic dicarboxylic acids and halides of these acids. Examples of the aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, 4,4'-dicarboxy-biphenyl, 4,4'-dicarboxy-diphenylmethane, and 4,4'-dicarboxy-diphenyl ether. Preferred examples include group dicarboxylic acids and halides of these acids. Among these aromatic dicarboxylic acids, acid halides, particularly acid chlorides, of the aromatic dicarboxylic acids mentioned above are most suitable. Furthermore, as the alicyclic or aliphatic dicarboxylic acids, any known alicyclic or aliphatic dicarboxylic acids or their It may be an acid derivative, and particularly preferred examples include alicyclic or aliphatic dicarboxylic acids, or acid halides thereof. Examples of the alicyclic or aliphatic dicarboxylic acids include alicyclic dicarboxylic acids such as 1,4-dicarboxy-cyclohexane, 1,2-dicarboxy-cyclopentane, and 1,5-dicarboxy-cyclooctane. compound, or general formula HOOC (-CH ₂ -) _o COOH (where n is 2
Suitable examples include aliphatic dicarboxylic acids represented by the formula (an integer of 8 to 8), or acid halides thereof (particularly acid chlorides). Examples of the aliphatic dicarboxylic acid compound represented by the above general formula include succinic acid, propanedicarboxylic acid, adipic acid, azelaic acid, and sebacic acid. In this invention, the aromatic diamine component is an aromatic diamine compound having a photosensitive group, or a molar ratio of the aromatic diamine having a photosensitive group to another aromatic diamine compound of 3:7 or more, preferably 4 : It is preferable that the aromatic diamine component is made of a mixture of aromatic diamine compounds of 6 or more. In the above-mentioned aromatic diamine component, if the content of the aromatic diamine having a photosensitive group is too low, the polyamide obtained from such a monomer will not have sufficient photocurability, which is not suitable. In addition, in this invention, in addition to the aromatic polyamide compound having a photosensitive group, the polyamide obtained from a monomer containing another aromatic diamine compound not having a photosensitive group as an aromatic diamine component is: It is preferable because the heat resistance of the photocured product (film) is stabilized or improved, and furthermore, it is preferable to use a monomer containing an aromatic diamine compound having a ketone group as another aromatic diamine compound not having a photosensitive group. The obtained polyamide is preferable because it improves the sensitivity to light when forming a photocured film. In this invention, if a diamine compound other than an aromatic diamine compound, such as an aliphatic diamine, is used, the target polyamide of this invention may not be obtained from such a monomer composition, or the polymer may not be obtained during polymerization. Even if polyamide is obtained, it is not preferable because the polyamide has poor heat resistance or is insoluble in organic solvents and tends to gel. Therefore, the aliphatic diamine compound is substantially Optimally, the polyamide is obtained from monomers that are not incorporated into the components. Examples of the aromatic diamine compound having a photosensitive group include aromatic diamine compounds having a photosensitive group that can be crosslinked by irradiation with light, for example, a carbon-carbon unsaturated group such as an ethylene group or an acryloyl group. Specifically, 3,
5-diaminobenzoic acid ethyl acrylate, 2,4-diaminobenzoic acid ethyl acrylate, 3,5-diaminobenzoic acid ethyl methacrylate, 2,4-diaminobenzoic acid ethyl methacrylate, 3,5- Diaminobenzoic acid glycidyl acrylate ester, 2,4
-Diaminobenzoic acid glycidyl acrylate ester, 3,5-diaminobenzoic acid glycidyl methacrylate ester, 2,4-diaminobenzoic acid glycidyl methacrylate ester, 3,5
-benzoic acid esters such as diaminobenzoic acid cinnamic ester and 2,4-diaminobenzoic acid cinnamic ester, benzyl acrylates such as 3,5-diaminobenzyl acrylate and 3,5-diaminobenzyl methacrylate, 4-acrylamide- 3,4'-diaminodiphenyl ether, 2-
Acrylamide-3,4'-diaminodiphenyl ether, 4-cinnamamide-3,4'-diaminodiphenyl ether, 3,4'-diacrylamide-3',4-diaminodiphenyl ether, 3,
4'-Cinnamamide-3',4-diaminodiphenyl ether, 4-methyl-2'-carboxyethyl methacrylate ester-3,4'-diaminodiphenyl ether [``Carboxyethyl methacrylate'' is CH ₂ = C( _CH3 )COO・
Indicates CH ₂ CH ₂・OOC−. ], and 4,4'-diaminochalcone,
3,3'-diaminochalcone, 3,4'-diaminochalcone, 3',4-diaminochalcone, 4'-methyl-3',4-diaminochalcone, 4'-methoxy-3',
Chalcone compounds such as 4-diaminochalcone and 3'-methyl-3,5-diaminochalcone can be mentioned. Other aromatic diamine compounds that do not have a photosensitive group that can be used as aromatic diamine components include, for example, paraphenylenediamine, metaphenylenediamine, 2,4-diaminotoluene,
4,4'-diaminodiphenyl ether, 4,4'-
Diaminodiphenylmethane, o-toluidine,
Examples include 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenoxyphenyl)propane, and o-toluidine sulfone. Furthermore, other aromatic diamine compounds that do not have a photosensitive group and are used as the aromatic diamine component are:
In addition to or instead of the other aromatic diamine compounds mentioned above, an aromatic diamine compound having a ketone group and having sensitizing performance may be blended, and as such an aromatic diamine compound having a ketone group, , for example, 9,9-bis(4-aminophenyl)-10-anthrone, 1,5-diaminoanthraquinone, 1,4-diaminoanthraquinone, 3,3'-diaminobenzophenone, 4'-
N,N-dimethylamino-3,5-diaminobenzophenone, 1-dimethylamino-4-(3,5
-diaminobenzoyl)naphthalene, etc. Note that among the above-mentioned aromatic diamines having a photosensitive group, diaminodiphenyl ethers, diaminobenzoic acid esters, and diaminobenzyl acrylates are new compounds, and their synthesis methods include, for example, the following. Here are some methods. (1) Synthesis method of diaminodiphenyl ethers (Mono- or di)amino-dinitrophenyl ether obtained by hydrolyzing (mono- or di)astylamido-dinitrophenyl ether is reacted with acrylic acid chloride, etc. , and then reducing the reactants to synthesize the desired aromatic diamine compound. (2) Method for synthesizing diaminobenzoic acid esters A method for synthesizing the desired aromatic diamine compound by reacting dinitrobenzoic acid chloride with hydroxyethyl methacrylate, etc., and then reducing the reactant. be able to. (3) Method for synthesizing diaminobenzyl acrylates Examples include a method for synthesizing the desired aromatic diamine compound by reacting dinitrobenzyl alcohol with acrylic acid chloride, etc., and then reducing the reactant. can. The photosensitive polyamide used in the present invention is prepared using the same mole of the above-mentioned dicarboxylic acid component and the aromatic diamine component containing the aromatic diamine compound having a photosensitive group, using the same mole as the known polymerization method. Polymerization conditions (e.g., in an organic polar solvent, ca.
In an organic solvent consisting of a high molecular weight polymer obtained by polymerization at a polymerization temperature of 100°C or less, particularly preferably 0 to 80°C, more preferably 5 to 60°C, and a polymerization time of about 0.1 to 48 hours, etc. It is a photosensitive polyamide that is soluble in The above photosensitive polyamide was measured at a temperature of 30°C using a dilute solution with a polyamide concentration of 0.5 g/100 ml (N-methyl-2-pyrrolidone), and the calculated logarithmic viscosity was 0.1. ~2.0, especially 0.2
A value within the range of approximately 1.5 is preferable. As the organic polar solvent used in this invention, the same organic polar solvent as the polymerization solvent used for producing the photosensitive polyamide can be used, such as N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2
-Pyrrolidone, dimethyl sulfoxide, hexamethylene phosphoramide, diglyme, etc. may be mentioned. In this invention, the amount of the organic polar solvent used is 100 to 100 parts by weight per 100 parts by weight of the photosensitive polyamide.
The amount is 2,000 parts by weight, preferably 150 to 1,500 parts by weight, and more preferably 200 to 1,000 parts by weight. If the amount of solvent used is too small, the rotational viscosity of the resin liquid composition increases and the production of the photosensitive polyamide film becomes difficult. This is not appropriate because the film will have an uneven thickness or the film formation itself will be difficult, or if too much solvent is used, it will take a long time to evaporate and remove the solvent during film formation. So it's not practical. Examples of the photopolymerizable monomer used in this invention include methyl methacrylate, tetrahydroxyfurfuryl methacrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or diethylaminoethyl ( Meta) acrylate, 2,
3,4-tribromobutyl acrylate, etc.
Mono(meth)acrylate compounds having hydroxy groups, 2-phenoxyethyl(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate
Acrylate, tetramethylolmethanetetra(meth)acrylate, N,N-methylenebis(meth)acrylate, 1,3,5-triacryloylhexahydro-S-triazine, triacryl formal, tris(acryloyloxyethyl)hydroxyethylisocyanur Other examples include N-vinyl-2-pyrrolidone and (meth)acrylic acid ester compounds containing phosphoric acid or urethane resin residues in the molecule. . In this invention, the amount of the photopolymerizable monomer used is 1 to 1 to 100 parts by weight of the photosensitive polyamide.
The amount is 150 parts by weight, preferably 3 to 120 parts by weight, and more preferably 5 to 100 parts by weight. If the amount of this photopolymerizable monomer used is too small, the photosensitivity obtained from the resin liquid composition After photo-curing the polyamide film, it may take a long time to remove the unexposed and uncured parts, and the photo-curing speed may be slow, so it is not suitable. It is not suitable because the mechanical properties of the material deteriorate. In this invention, examples of inorganic fillers used if necessary include mica, clay, mica, talc, alumina white, silica gel, calcium carbonate, diatomaceous earth, bentonite, wollastonite, quartz, aluminum hydroxide, water Calcium oxide, precipitated barium sulfate, calcium sulfate,
Examples include magnesium silicate, titanium oxide, zinc oxide, and silica alumina. The inorganic filler has an average particle size of about 50 μm or less,
In particular, it is preferably 20 μm or less. In the resin liquid composition of the present invention, when using an inorganic filler, the above-mentioned photosensitive polyamide
3 to 200 parts by weight, especially 5 to 100 parts by weight
The amount is preferably about 150 parts by weight, and if the amount of inorganic filler used is small, when the resin liquid is used to photocure a photosensitive poamide film formed on the surface of a printed wiring board, the light The cured film is
This is undesirable because it may cause curling up at the edge of the substrate, weaken the adhesive strength, or impair the thermal dimensional stability of the photocured film.On the other hand, if the amount of inorganic filler added is too large, This is not preferable since the photocurability (photocuring speed), photosensitivity, etc. of the photosensitive polyamide film decreases. Examples of photopolymerization initiators include Michler's ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, 2-tert-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, 4,4' -bis(diethylamino)benzophenone, acetophenone, benzophenone,
Examples include thioxanthone, methylthioxanthone, chlorothioxanthone, 1,5-acenaphthene, benzyl ketal, and anthranilic acid dimethylaminobenzoate. Further, examples of the thermal polymerization inhibitor used in this invention include hydroquinone, 2,6
Examples include -di-tert-butyl-4-methylphenol (BHT), methyl ether hydroquinone, benzoate, benzoquinone, and 4-hydroxymethyl-2,6-di-tert-butylphenol. In this invention, the amount of the thermal polymerization inhibitor used is, based on 100 parts by weight of the photosensitive polyamide,
It is about 0.01 to 5 parts by weight, preferably about 0.02 to 4 parts by weight, and the amount of photopolymerization initiator used is 0.01 to 15 parts by weight.
parts by weight, preferably 0.02 to 10 parts by weight. In this invention, the rotational viscosity of the resin liquid composition is about 50 to 100,000 centipoise, particularly preferably
It is preferably about 100 to 50,000 centipoise. In this invention, the resin liquid composition may contain coloring pigments/dyes such as phthalocyanine blue, phthalocyanine green, brilliant green, Victoria blue, Hansa yellow, lake red, and methyl violet, and further, sensitized As the agent, methyl N,N-dimethylanthranilate, ethyl ortho- or para-N,N-dimethylbenzoate, etc. may be contained in small amounts. The resin liquid composition of this invention can be prepared by the following operations.
Relief patterns can be formed. That is, first, a resin liquid composition containing the photosensitive polyamide and the like is applied to a printed wiring board, etc., by a method such as curtain coating, roll coating (rotary coater), silk screen, deep coating, or doctor knife method. Apply to the surface,
A coating film of resin liquid is formed, and the coating film is placed under hot air or in a heating furnace with a draft for about
The organic solvent is removed by drying at a drying temperature of 200°C or lower, preferably 150°C or lower, more preferably 120°C or lower, under normal pressure or reduced pressure, and the thickness is approximately 0.1 to 300 μm.
A solidified photosensitive polyamide film with a thickness of . Next, a negative type photomask chart is placed above the photosensitive polyamide film formed on the above-mentioned substrate, and through the mask chart,
A portion of the photosensitive polyamide film is photocured by irradiation with ultraviolet rays, visible rays, or actinic rays such as electron beams and X-rays from a high-pressure mercury lamp, xenon lamp, metal halide lamp, etc. Then, in the aforementioned photocuring process, the unexposed and non-photocured portions are washed away with a developer to form a relief pattern made of a photocured polyamide film. In addition, the relief pattern formed as described above is heated by hot air, infrared rays, etc.
At a heat treatment temperature of 250℃, especially 120-200℃, about 0.1~
A post-heat treatment for 6 hours, especially 0.2 to 2 hours, can further increase the heat resistance. It goes without saying that the above-described organic polar solvents for polyamide polymerization or polyamide solutions can be used as they are as the developer, and in particular, N,N-dimethylformamide, N,N-dimethylacetamide, etc. , N-methyl-2-pyrrolidone, dimethyl sulfoxide, bexamethylene phosphoramide, diglyme, or a mixed solvent of the solvent and methanol or ethanol can be used. In the resin liquid composition of the present invention, if the amount of the thermal polymerization inhibitor added is too small, the solvent may be evaporated and removed from the coating film of the resin liquid during the formation of the relief pattern described above. In the operation of forming a film, crosslinking of the photosensitive groups of the photosensitive polyamide is likely to occur when drying at high temperatures, and crosslinking of the polymer occurs when unexposed to light. This is not suitable because it dries and it becomes impossible to shorten the drying time. The photosensitive polyamide used in this invention is a polyamide that has excellent solubility in organic solvents and also has excellent photosensitivity, and it is possible to prepare a stable liquid resin composition. Therefore, the resin liquid composition of the present invention, which has this photosensitive polyamide as a main component, is extremely easy to form a photosensitive polyamide film, and the photocured film obtained by photocuring the photosensitive polyamide film is dimensionally stable. It has excellent properties such as strength, heat resistance, electrical and mechanical properties,
Due to these properties, it is possible to form a photocurable film that is effective as an insulating film for solid-state devices in the semiconductor industry and a passivation film. It can be used as Furthermore, since the photosensitive polyamide film formed from the resin liquid composition of the present invention has excellent light transmittance and photocurability (photosensitivity), it is possible to form a thick cured layer, and In addition, it can also be used for forming relief patterns for letterpress printing. Below, production examples of the photosensitive polyamide used in this invention, Examples of resin liquid compositions of this invention, and various physical property tests and their results are shown. Production Examples 1 to 3 "Dicarboxylic acid component containing dicarboxylic acids" consisting of the type and composition shown in Table 1
0.120mol [However, in Production Example 3, N-methyl-2
- used as a solution dissolved in 180 ml of pyrrolidone (NMP)] and the aromatic diamine component containing an aromatic diamine compound having a photosensitive group, etc., with the type and composition shown in Table 1. 0.120 mol of N-methyl-2-pyrrolidone (NMP) is dissolved in 240 ml of N-methyl-2-pyrrolidone (NMP).
The mixture was cooled to below 30°C, and the mixture, which generated heat during mixing and rose to about 30°C, was stirred for 30 minutes while cooling with ice water, and then stirred at room temperature for 1 hour to dissolve the dicarboxylic acid. A polymerization reaction between the component and the aromatic diamine component was carried out. Next, the polymerization reaction solution was diluted by adding 300 ml of N-methyl-pyrrolidone (NMP), and then the solution was added to a mixed solution of 6 methanol and 6 water to precipitate polyamide, and the precipitate was filtered. It was collected and dried to obtain a white polyamide powder. The following physical property tests were conducted on the polyamides obtained in Production Examples 1 to 3 above. (i) Solubility of polyamide: The solubility of polyamide in NMP was measured at room temperature.
Any polymer of about
It showed a solubility of 20% by weight or more. (ii) Logarithmic viscosity of polyamide: Measured at a temperature of 30° C. using a dilute solution of polyamide with a concentration of 0.5 g/100 ml (NMP). (iii) Thermal decomposition temperature of polyamide: The temperature at which weight loss starts when polyamide is heated was measured using a differential thermobalance TG-DSC manufactured by Rigaku Denki Co., Ltd. The test results for (ii) and (iii) are shown in Table 1.

[Table] Examples 1 to 3 Photosensitive polyamide obtained in Production Example 1 above
100g of N-methyl-2-pyrrolidone (NMP)
In addition, 20 g of photopolymerizable monomers of the types shown in Table 2, 4 g of Michler's ketone as a photopolymerization initiator, 0.5 g of methyl ether hydroquinone and 0.5 g of hydroquinone as thermal polymerization inhibitors,
and 0.5g of phthalocyanine green,
A resin liquid composition for a photosensitive polyamide film was prepared. The rotational viscosity, photosensitivity, and resolution of each resin liquid composition were measured using the following test methods, and the results are shown in Table 2. (1) Rotational viscosity: Measured at 25°C using an E-type viscometer manufactured by Tokyo Keiki Co., Ltd. (2) Photosensitivity: The resin liquid composition of each example was applied onto a glass plate using a rotational viscometer, and dried at 50°C for 5 hours under a reduced pressure of 1 to 2 mmHg to form the photosensitive polyamide shown in Table 2. Step Tablet No. 2 (manufactured by Kodak) was formed on the polyamide film.
Closely cover the lamp with an ultra-high pressure mercury lamp (jet light
2kw) at an illuminance of 5.0 J/cm ² (350 mμ) to photocure the polyamide film, and the amount of light irradiation (J/cm ² ) until photocuring was measured. (3) Resolution: In the photocuring of the photosensitive polyamide film mentioned above, as a test chart, the line width was
0.075, 0.10, 0.125, 0.15, 0.20, 0.25, 0.30,
Three thin lines with a length of 40 mm at 0.40 and 0.50 mm levels are drawn for each level of line width, so that both line parts and non-printing parts are equally spaced in width. A positive image mask pattern was used. The resin liquid composition obtained as described above is applied onto the copper side surface of a glass epoxy copper-clad substrate using a rotary coating machine to form a resin liquid coating film with a thickness of approximately 700 μm. Heat the coated film in a hot air dryer at 75°C.
The coating film was dried at a drying temperature of about 1.5 hours to remove the solvent and form a photosensitive polyamide film. The thickness of each photosensitive polyamide film is
60 μm (Example 1), 65 μm (Example 2) and
It was 58 μm (Example 3). The photosensitive polyamide film is exposed to 365mμ ultraviolet light using a 2kw ultra-high pressure mercury lamp (manufactured by Oak Seisakusho).
A photocured film was formed by exposure for 5 minutes under an illuminance of 10.5 mw/cm ² . The unexposed and uncured areas are
Each was washed away with NMP in a wash of approximately 1-1.5 minutes. The photocured film is further cured in a thermal oven.
Heat treatment was performed at 150°C for 30 minutes. The following tests were conducted on the photocured film.
The results are shown in Table 3. (1) Pencil hardness: The pencil hardness of the photocured film was measured according to test method 8-10 of JIS-D-0202. (2) Adhesion to copper surface (also called grid test): A photocured film formed on the copper side surface of a glass epoxy copper clad board according to test method 8-12 of JIS-D-0202. Adhesive strength is measured by the number of squares in the photocured film that come off when the adhesive tape is pasted on the surface of a grid with cut lines spaced at 1 mm intervals, and the tape is removed. (3) Solder heat resistance: After immersing the above photocured film in a molten solder bath (260°C) for 20 seconds, a test was conducted in the same manner as the adhesion test described above, and the adhesion was determined by heat history. Solder heat resistance was indicated by the number of missing squares. (4) Chemical resistance: 10% by weight sulfuric acid aqueous solution, 10% by weight
After the photocured film was immersed in a 5% by weight aqueous hydrochloric acid solution and a 5% by weight aqueous sodium hydroxide solution for 24 hours, abnormal changes in the photocured film were observed. Examples 4 to 9 A resin liquid having the same composition as in Example 1, except that the photopolymerizable monomer was replaced with 10 g of the compound shown in Table 2, and 15 g of the inorganic filler shown in Table 2 was added. A composition was prepared. The properties of the resin liquid composition are shown in Table 2. Further, a photosensitive polyamide film was formed in the same manner as in Example 1 except that the resin liquid composition was used, and a photocured film was further molded. Table 3 shows the properties of those photocured films. Examples 10-11 Production Example 2 (Example 10) or Production Example 3 (Example
Using the polyamide obtained in 11), the photopolymerizable monomer and inorganic filler shown in Table 2, Example 4
A resin liquid composition was prepared in the same manner as above. The properties of the resin composition are shown in Table 2. Example 4 except that the resin liquid composition was used.
A photosensitive polyamide film was formed in the same manner as above, and the photosensitive polyamide film was further photocured to produce a photocured film. Table 3 shows the properties of these photosensitive polyamide films and photocured films.

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Claims (1)

[Scope of Claims] 1. A dicarboxylic acid component containing at least 30 mol% of aromatic dicarboxylic acids based on the total dicarboxylic acid components; and an aromatic diamine component containing at least 30 mol% of an aromatic diamine compound having a photosensitive group. 100 parts by weight of a photosensitive polyamide soluble in an organic solvent consisting of a polymer of 1 to 150 parts by weight of a photopolymerizable monomer 0.1 to 15 parts by weight of a photopolymerization initiator 0.01 to 5 parts by weight of a thermal polymerization inhibitor 100 parts by weight of an organic polar solvent A resin liquid composition for a photosensitive polyamide film, comprising: ~2000 parts by weight and 0-200 parts by weight of an inorganic filler.