JPH033212B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photosensitive resin composition laminate, and more particularly to a photosensitive resin composition laminate that can be developed with an alkaline aqueous solution. Photoresists formed from photosensitive resin compositions are resistant to plating solutions and etching solutions, and are therefore used as resists when manufacturing printed wiring boards. These photosensitive resin compositions have conventionally been applied as a liquid film containing a solvent to a printed wiring board substrate (hereinafter simply referred to as a substrate), and then
The solvent contained therein is removed by heating and drying to form a dry film, which is then imagewise exposed to actinic light and developed to form a photoresist image. However, in recent years, in order to improve its low workability, air pollution, and low yield, flexible three-layer laminates have been developed, namely, a support film layer, a dried photosensitive resin composition layer (hereinafter simply referred to as photosensitive layer), A photosensitive resin composition laminate (hereinafter simply referred to as a photosensitive film) consisting of a protective film layer has come to be used. As photosensitive resin compositions, both the so-called alkali-developable type, in which unexposed areas are removed (developed) with an alkaline aqueous solution, and the so-called solvent-developable type, in which the unexposed areas are removed (developed) with an organic solvent are known. . The method of using an alkali-developable photosensitive film is to remove the protective film layer from the photosensitive film and create a laminate consisting of two layers, a photosensitive layer and a support film layer.
While heating to 90 to 130 degrees Celsius, the photosensitive layer is laminated by pressure bonding so that it is in contact with the metal surface heated to about 40 to 70 degrees Celsius. The metal surface is polished and moisture is removed by pretreatment. Next, after imagewise exposure using a negative film or the like, unexposed areas are removed (developed) using an alkaline aqueous solution to form a photoresist image. Using the formed resist image as a mask, the metal surface is etched or plated, and then the photoresist image is peeled off using an aqueous solution that is more strongly alkaline than a developer, thereby producing printed wiring boards and the like. Heating of the substrate during lamination is performed to improve adhesion (hereinafter referred to as lamination properties) when laminating the substrate and the photosensitive layer. However, if you take the board out of the heating machine and leave it for a while, the temperature will drop, and if it is heated too much, an oxide film will form on the polished metal surface, which may impair the lamination properties or affect the properties of the printed wiring. To avoid damage, it is necessary to control the heating time, standing time, heating temperature, etc. during work, or to use specific equipment.
For those skilled in the art, a photosensitive resin composition with good lamination properties that does not require heating of the substrate is desired in order to save such management effort and equipment. In order to improve lamination properties, it is a common method to soften a photosensitive resin composition, and conventionally known methods include adding an external plasticizer, increasing the amount of addition polymerizable substances, and adding a polymeric binder. There are means such as plasticization. However, with these methods, while the photosensitive film is wound up into a roll and stored, a phenomenon (edge fusing) occurs in which the photosensitive layer oozes out from the ends of the roll over time. The result is not satisfactory. Although it is possible to reduce the degree of edge fusing by adjusting the measures taken, it is difficult to reach a satisfactory compromise with lamination properties. Methods that soften the resin composition should be avoided as much as possible. Another way to improve lamination properties is to raise the heating temperature for the photosensitive layer during lamination (hereinafter referred to as lamination temperature) to a higher temperature, and this method requires special management as long as the temperature of the laminator is set. Does not require any special equipment,
It is in line with what the person in question wants. However, in conventionally known photosensitive resin compositions, even when the lamination temperature is within the normal operating temperature range (90 to 130°C), a considerable amount of the components evaporate and scatter.
Since the scattered gas is toxic, it is generally desired to exhaust it and remove it, and ducts are used. It is also naturally desired that the amount of components scattered is as small as possible. When the laminating temperature of a conventionally known photosensitive film is raised, a large amount of the components evaporate and scatter, producing smoke, which is difficult to evacuate. The properties of the photoresist, such as resistance to liquids, are significantly reduced. Therefore, the upper limit of the laminating temperature of conventionally known photosensitive films is 130 to 150 DEG C., and it is practically impossible to raise the temperature higher than that. The present invention solves the problems of conventional photosensitive films and provides an alkali-developable photosensitive film having the advantage that the amount of components evaporated and scattered due to heating during lamination is extremely small.
Furthermore, since it can be used at high lamination temperatures of 150 to 180℃, it has the advantage of omitting substrate preheating before lamination, and produces a good alkaline-developable photosensitive film with no deterioration of properties during that process. This is what we provide. If one simply wants to prevent or reduce the evaporation and scattering of components during lamination, this can be achieved by selecting a compound with a high boiling point and low volatility, that is, a compound with a larger molecular weight. However, since photosensitive films have the restriction that unexposed areas must be removed through development processing, new problems tend to arise, and this tendency is particularly strong in the case of alkaline-developed photosensitive films. Ta. That is, according to the study results of the present inventors, it was found that simply increasing the molecular weight of the entire composition of an alkali-developable photosensitive resin composition impairs the developability. It was done. For alkaline developable type, carboxyl group-containing linear copolymer (binder)
In contrast, other components with relatively low molecular weights are dissolved and removed by an aqueous alkaline solution in the presence of aqueous alkaline solution, whereas other components selected with the intention of having a high boiling point and low volatility increase in molecular weight and are removed by dissolution. It becomes a hindrance to doing so. The mechanism of alkaline development is that the carboxyl group-containing linear copolymer (binder) performs the same function as so-called soap. In other words, the carboxyl group undergoes a neutralization reaction with the base in the developer, so that the linear copolymer (binder) has both a hydrophilic group (neutral base) and a lipophilic group (alkyl group). A so-called stone ken was formed,
It is thought that it is dissolved and removed by forming a micelle structure that envelops the components of the addition polymerizable substance, etc., and if the molecular weight of the addition polymerizable substance increases, the formation of such a micelle structure is inhibited. It is estimated to be. Furthermore, if the molecular weight of addition polymerizable substances increases,
The compatibility with the linear copolymer (binder) decreases, and layer separation and turbidity are likely to occur in the photosensitive layer, which not only worsens the storage stability of the photosensitive layer itself, but also reduces lamination properties. I knew what was coming. This is because the main addition-polymerizable substance is selected to have an affinity for organic solvents for reasons explained later, whereas the linear copolymer (binder) has hydrophilic properties and is suitable for addition-polymerizable substances. This is presumed to be because an increase in molecular weight makes the difference in properties more noticeable. The reason why a substance with affinity for organic solvents is selected as the main addition polymerizable substance is that a substance with hydrophilicity is selected for the copolymer (binder) in order to maintain developability.
This is because the composition as a whole is preferably more hydrophobic in order to maintain resistance to plating solutions and etching solutions. Furthermore, even though the copolymer (binder) is hydrophilic, it must be water-insoluble from the viewpoint of resistance, and for this reason it is soluble in organic solvents, so it is difficult to make it into a composition. The main addition-polymerizable substance must be soluble in organic solvents, that is, must have an affinity for organic solvents. The various problems associated with an increase in molecular weight as described above are solved by the present invention. The present invention provides a photosensitive film in which a polymer film is laminated on at least one surface of a photosensitive resin composition layer, in which the photosensitive resin composition layer comprises (a) one or two of the following general formulas []. containing at least 10 parts by weight of one or more compounds;
One or more addition-polymerizable substances having a terminal ethylene group, having a molecular weight of 500 to 2000, a boiling point of 300°C or more at normal pressure, and soluble in an organic solvent capable of forming a high polymer20 to 60 Weight part (In the formula, R ₁ and R ₂ are H or CH ₃ , and n is
(b) Photoinitiator 0.2-10 parts by weight (c) Carboxyl group content 20-50 mol%, water absorption 4-30% by weight, weight average molecular weight 20,000-70
The present invention relates to a photosensitive film containing 40 to 80 parts by weight of a linear copolymer (binder). In the present invention, the photosensitive resin composition layer contains 20 to 50 parts by weight of an addition polymerizable substance. If it is less than 20 parts by weight, the photoreactive component is too small and a resist image with sufficient properties cannot be obtained by exposure. If the amount exceeds 60 parts by weight, the amount of photoreactive components will be too large, making it impossible to obtain images with sharp contours. And 20~
Of the 60 parts by weight, at least 10 parts by weight, preferably 15 to 40 parts by weight, must be a compound represented by the above general formula []. If it is less than 15 parts by weight, the above-mentioned problem associated with the increase in the molecular weight of the addition polymerizable substance tends to occur, and if it is less than 10 parts by weight, this tendency is particularly noticeable and it cannot be used practically. 40 again
If it exceeds 40 parts by weight, the water resistance of the resist film tends to decrease, resulting in a decrease in adhesion during development, so it is preferably 40 parts by weight or less. The compound represented by the general formula []

[Formula] Since it contains a base skeleton in the range of 14 to 23, it has both hydrophilic and lipophilic properties, and solves the problems associated with the increase in the molecular weight of addition polymerizable substances, that is, the problems of developability and compatibility. obtain. Of course, this is achieved not only by the compound represented by the general formula [], but also by the combination with the linear copolymer (binder) described below. General formula []
For example, the compound represented by CH ₂ =
CHCO−(−OCH ₂ CH ₂ )− ₁₄ OCOCH=CH ₂ (Trademark A-14G manufactured by Shin-Nakamura Chemical Co., Ltd.) CH ₂ =C
(CH ₃ )CO−(−OCH ₂ CH ₂ )− ₁₄ OCOC(CH ₃ )=
CH ₂ ((Trademark 14G manufactured by Shin Nakamura Chemical Co., Ltd.) CH ₂
=CHCO-(- _OCH2CH2 ) _-23 OCOCH= _CH2 (Trademark A-23G _manufactured by Shin-Nakamura Chemical Co., Ltd.), _CH2 =C
( _CH3 )CO( _−OCH2CH2 ) ₋₂₃ OCOC( _CH3 ) _{= CH2}
(Trademark 23G manufactured by Shin Nakamura Chemical Industry Co., Ltd.), CH ₂ =
CHCO[ _-OCH2 -C( _CH3 )H] _-14 OCOCH=
_CH2 , _CH2 =C( _CH3 )CO[ _-OCH2C ( _CH3 )H]
₁₄ OCOC (CH ₃ ) = CH ₂ etc. Addition-polymerizable substances are substances that have a terminal ethylene group, have a molecular weight of 500 to 2000, have a boiling point of 300°C or higher at normal pressure, and are soluble in organic solvents that can form high polymers through free radical-initiated polymerization. is used. The lower limits of molecular weight and boiling point are determined from the viewpoint of evaporation and scattering during lamination, and the upper limit of molecular weight is determined from the aforementioned problems associated with increased molecular weight. Furthermore, the reason why it must be soluble in organic solvents is that the linear copolymer (binder) contained in this photosensitive resin composition layer must be soluble in organic solvents. This is because the composition must be uniform. This addition polymerizable substance is liquid or semi-solid at room temperature, has two or more terminal ethylene groups, and has a plasticizing effect on the linear copolymer (binder). It is desirable to have Preferred compounds include those obtained by adding a polyhydric alcohol and an α,β-unsaturated carboxylic acid, such as 2,2′bis(4-acryloxydiethoxyphenyl)propane, 2,2′bis(4-acryloxydiethoxyphenyl)propane, - Addition of α,β-unsaturated carboxylic acid to glycidyl group-containing compounds such as (methacryloxydiethoxyphenyl)propane, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and glycidyl group-containing compounds. For example, trimethylolpropane triglycidyl ether triacrylate, bisphenol A diglycidyl ether diacrylate, etc. In particular, when using these low-volatility addition-polymerizable substances, the compound represented by the general formula [] is _CH2 =CHCO(-
OCH ₂ CH ₂ ) − ₁₄ OCOCH=CH ₂ or CH ₂ =C
(CH ₃ )CO−(−OCH ₂ CH ₂ )− ₁₄ OCOC(CH ₃ )=
CH ₂ 10-20 parts by weight, 2,2'bis(4-acryloxy diethoxyphenyl)propane or 2,
Favorable results are obtained when a mixture of 10 to 20 parts by weight of 2'bis(4-methacryloxydiethoxyphenyl)propane and 10 to 20 parts by weight of dipentaerythritol hexaacrylate is used. The photoinitiator contained in the photosensitive layer in the present invention is
Preferred are substances that are not thermally activated at temperatures below 200°C and have extremely low volatility. These substances include substituted or unsubstituted polynuclear quinones, such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, and 2-methylanthraquinone. Examples include enyl anthraquinone and 2,3-diphenylanthraquinone. Other useful compounds include ketone compounds such as diacetyl, benzyl, benzoin, and pivaloin, and α-hydrogencarbonate substituted aromatic acyloins such as α
Examples include -phenyl-benzoin, α,α-diethoxyacetophenone, and the like. Other aromatic ketones include 4,4'-bisdialkylamino-benzophenone. Furthermore, combinations of 2,4,5-triarylimidazole dimer and 2-mercaptobenzoxazole, leuco crystal, violet, tris(4-diethylamino-2-methylphenyl)methane, etc. can also be used. If the amount of the photoinitiator is less than 0.2 parts by weight, the photoreaction during exposure will be insufficient, resulting in the formation of a resist film with poor characteristics. Moreover, if the amount exceeds 10 parts by weight, the photosensitivity increases, resulting in a loss of resolution. In the photosensitive layer, a linear copolymer (binder) containing 40 to 80 parts by weight of carboxyl groups is present. If the amount is less than 40 parts by weight, the film properties of the system will be impaired, and if it exceeds 80 parts by weight, the system will become stiff and the lamination properties will be impaired. This linear copolymer is obtained by polymerizing two or more types of monomers, and the monomers are broadly classified into two types. The first monomer is the linear copolymer (binder)
It is a carboxylic acid having one unsaturated group or an acid anhydride. Examples include acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, propiolic acid, itaconic acid, maleic acid, maleic anhydride, and maleic acid half ester. Second to use for other
The monomer is selected in order to impart resistance to plating liquids, etching liquids, etc. to the core linear copolymer (binder), and to impart developer resistance, flexibility, and plasticity. Each monomer is selected so that the linear copolymer (binder) has a carboxyl group content of 20 to 50 mol% and a water absorption rate of 4 to 30% by weight. The water absorption rate in this case is expressed as the standard specified in JIS K6911, that is, the weight increase rate when a sample with a diameter of 50±1 mm and a thickness of 3±0.2 mm is immersed in water at 23° C. for 24 hours. Furthermore, the carboxyl group content herein refers to the percentage (mol%) of the number of moles of the first monomer relative to the number of moles of all monomers used in the linear copolymer (binder). . The second monomer used is one having one unsaturated group, and preferably has a water solubility of 2% by weight or less at 20°C, but 2% by weight or less. There is no problem even if a small amount of a monomer with hydrophilic properties exceeding the above is used as long as the water absorption of the produced polymer (linear copolymer binder) is within the above-mentioned range. The molecular weight of the second monomer is preferably 300 or less; if a monomer with a larger molecular weight is used, developability will be impaired. Examples of second monomers include alkyl acrylates or alkyl methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate; esters of vinyl alcohol. , such as vinyl-n-butyl ether; polymerizable styrene derivatives or styrene substituted in the α-position or in the aromatic ring. A preferred monomer among the first monomers mentioned above is acrylic acid or methacrylic acid;
Among the monomers, preferred are alkyl acrylates and alkyl methacrylates. The solubility (developability) of the linear polymer (binder) in an alkaline aqueous solution (developer) and the resistance to processing solutions including the developer depend on either its carboxyl group content or water absorption rate (hydrophilicity). It is not determined uniquely, but it is determined from both, and each must be within the above-mentioned range. The system developed with an alkaline aqueous solution was developed by JP-A-Sho.
53-40516, and the linear copolymer (binder) in that case is only specified to have a carboxyl group content of 20 to 50 mol% and to be water-insoluble. , if a monomer other than the carboxyl group-containing monomer, i.e., a second monomer, is chosen that is extremely hydrophobic, the water absorption of the linear copolymer (binder) is If it falls below 4%,
Even if the carboxyl group content is within the range of 20 to 50 mol%, development is impossible. This is because the developing solution does not penetrate sufficiently into the system, so the carboxyl groups of the linear copolymer (binder) in the system and the base of the developing solution cannot undergo a neutralization reaction, and therefore the original undesirable Due to the result of remaining water soluble. On the other hand, even if the carboxyl group content is 20 to 50 mol%, if the water absorption rate exceeds the upper limit of the above range, the developability of the unexposed areas is greatly promoted, but the exposed areas are hydrophilic. The edges of the photoresist image (the boundary between the exposed and unexposed areas) are most severely affected by the developer, resulting in poor image sharpness and reduced resolution, and as a result, the apparent sensitivity also decreases. Furthermore, the resistance to plating solution and etching solution decreases, and development such as peeling occurs. Similarly, the content of carboxyl groups is important as a determinant of developability. Even if the water absorption rate is within the above range, if the carboxyl group content is less than 20 mol%, the amount of development penetration into the unexposed area is sufficient, and even if a neutralization reaction may occur, the proportion of salt formation is small. It remains water-insoluble and cannot be developed. Conversely, if the carboxyl group content exceeds the upper limit of the above range, even if the water absorption rate is within the above range, the exposed area will be attacked by the developer from the surface layer, resulting in the resist image losing its surface gloss and becoming less durable. descend. In other words, if the carboxyl group content and water absorption exceed the upper limits of the respective ranges mentioned above, the photosensitive layer will become more hydrophilic, and even in exposed areas, resistance to plating solutions, etching solutions, and even developing solutions will decrease, resulting in poor practical use. On the other hand, below the lower limit of the range, the photosensitive layer becomes more hydrophobic or has a lower rate of salt formation, resulting in less solubility in a developer, making it difficult to develop. The molecular weight of the linear copolymer (binder) contributes to film-forming properties and is also a factor that secondarily determines developability and resistance to processing solutions. The molecular weight range must be 20,000 to 700,000, preferably 30,000 to 300,000 in weight average molecular weight. If it is less than this range, film forming properties will be impaired and resistance to processing solutions including developing solutions will be reduced. If this range is exceeded, film formation
Although the resistance becomes very good, the developability deteriorates. Generally, it is preferable to include a radical polymerization inhibitor in order to prevent thermal polymerization during the heating process and during storage. Examples of such thermal polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, phenothiazine, pyridine, nitrobenzene, dinitrobenzene, p-toluquinone, chloranil, and aryl phosphate.
Preferably low volatility in the following, such as alkyl-substituted hydroquinones, tert.
-Butylcatechol, cuprous chloride, 2,6-di-
tert-butyl p-cresol, 2,2-methylenebis(4-ethyl-6-t-butylphenol),
Examples include 2,2-methylenebis(2-methyl-6-t-butylphenol). The photosensitive layer may contain coloring substances such as dyes and pigments. The coloring substance is preferably one that does not affect the properties of the photoresist and does not decompose or volatilize at temperatures below 200°C. Colorants that can be used include, for example, fuchsin, auramine base, chalcoside green S, paramagenta, crystal violet, methyl orange,
Nile Blue 2B, Victoria Blue, Malachite Green, Basic Blue 20, Iosing Green, Night Green B, Tripalosan, New Magenta, Ashitu Violet RRH,
Red Violet 5RS, New Methylene Blue
There are GG etc. Furthermore, additives such as plasticizers and adhesion promoters may be added to the photosensitive layer. Examples of the polymer film laminated on at least one surface of the photosensitive layer include films made of polyethylene terephthalate, polypropylene, and polyethylene, and polyethylene terephthalate film is preferred. Since these must be removable from the photosensitive layer later, they must not be made of a material or have a surface treatment that makes it impossible to remove them. The thickness of these films is 5
~100 μm is suitable, preferably 10-30 μm. Further, one of these films may be laminated on both sides of the photosensitive layer as a support film for the photosensitive layer and the other as a protective film for the photosensitive layer. To prepare a laminate of a photosensitive resin composition, that is, a photosensitive film, the photosensitive resin composition is first uniformly dissolved in a solvent. Any solvent may be used as long as it dissolves the photosensitive resin composition, and one or more kinds of solvents may be used. As the solvent, common solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, dichloromethane, chloroform, methyl alcohol, and ethyl alcohol are used. Next, the photosensitive resin composition in solution form is uniformly applied onto the polymer film as the supporting film layer, and the solvent is removed by heating and/or hot air blowing to form a dry film. The thickness of the dry film is a normal thickness, and there is no particular restriction, and 10 to 100 μm is appropriate, and preferably
It is 20-60 μm. A laminate of a photosensitive resin composition consisting of two layers, a photosensitive layer and a polymer film, is stored as it is or after a protective film is further laminated on the other side of the photosensitive layer and wound into a roll. In the production of photoresist images, the protective film, if present, is removed and then the photosensitive layer is laminated by being pressed against the substrate while heating. The surface to be laminated is usually preferably a metal surface, but is not particularly limited. Heating of the substrate is not necessary depending on the temperature at which the photosensitive layer is heated (laminating temperature), but heating may of course be performed in order to further improve lamination properties. When the photosensitive film of the present invention is laminated at the lamination temperature of conventional photosensitive films (90 to 130°C), the amount of components evaporated and scattered is extremely smaller than that of conventional photosensitive films. Further, even when used at a high lamination temperature of 160 to 180°C, which is unbearable for conventional photosensitive films, the amount of evaporation and scattering is small, and the properties are not impaired. In the photosensitive film of the present invention, heating of the substrate can be omitted by increasing the lamination temperature to a high temperature. The laminated photosensitive layer is then imagewise exposed to actinic light using a negative or positive film. At that time, if the polymer film present on the photosensitive layer is transparent, it may be exposed as is. If it is opaque, it will of course need to be removed. In order to protect the photosensitive layer, it is preferable that the polymer film is transparent and that the exposure is carried out through it while the polymer film remains. As the active light, light emitted from a known active light source such as a carbon arc, a mercury vapor arc, a xenon arc, etc. is used. Since the sensitivity of the photoinitiator contained in the photosensitive layer is usually greatest in the ultraviolet region, the active light source should then be one that effectively emits ultraviolet radiation. Of course,
Photoinitiators sensitive to visible light e.g. 9,10
- If the active light is phenanthrenequinone, visible light is used as the active light, and the light source may be one of those mentioned above, a photographic flat light bulb, a solar lamp, etc. After exposure, the polymer film, if present, on the photosensitive layer is removed and the untreated film is removed using an aqueous alkaline solution by known methods such as spraying, oscillating dipping, brushing, scraping, etc. Develop by removing the exposed areas. As a base for an alkaline aqueous solution,
Alkali hydroxides, i.e. hydroxides of lithium, sodium and potassium; alkali carbonates, i.e.
Examples include carbonates and bicarbonates of lithium, sodium and potassium; alkali metal phosphates, such as potassium phosphate or sodium phosphate; alkali metal pyrophosphates, such as sodium pyrophosphate or potassium pyrophosphate; Particularly preferred is an aqueous solution of sodium carbonate. The pH of the alkaline aqueous solution used for development is preferably
The temperature is between 9 and 11, and the temperature can be adjusted depending on the developability of the photosensitive layer. A small amount of a surfactant, an antifoaming agent, or an organic solvent for accelerating development may be mixed into the alkaline aqueous solution. Furthermore, in the manufacture of printed wiring boards, the developed photoresist image is used as a mask to treat the exposed surface of the substrate by etching or plating in a known manner. Thereafter, the photoresist image is usually removed with an aqueous solution that is more strongly alkaline than the aqueous alkaline solution used for development, but there are no particular restrictions on this. As the strongly alkaline aqueous solution, for example, 2 to 10% by weight of sodium hydroxide is used. The present invention will be explained in more detail by the following examples. Here, % indicates weight %. Example 1 Solution A (solution 6 of photosensitive resin composition) was uniformly applied onto a 25 μm thick polyethylene terephthalate film using the apparatus shown in FIG. 7) for about 3 minutes. The thickness of the photosensitive layer after drying was approximately 25 μm.
A polyethylene film was further laminated as a protective film on the photosensitive layer as shown in FIG. Solution A 60% methyl methacrylate, 20% methacrylic acid
%, 20% 2-ethylhexyl acrylate copolymer (*1) 52g Ethylene glycol diacrylate (trademark A-14G, manufactured by Shin Nakamura Chemical Co., Ltd.) 13g 2,2'bis(4-methacryloxydiethoxyphenyl) Propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark BPE-4) 10 g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trademark DPHA) 15 g 2-ethylanthraquinone 2.5 g 2,2'-methylene-bis(4-ethyl- 6-t
-butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*1) Carboxyl group content 23 mol% Water absorption 7% Weight average molecular weight Approximately 80,000 Glass epoxy material with copper plates laminated on both sides The copper surface of a printed wiring board substrate (manufactured by Hitachi Chemical Co., Ltd., trademark MCL-E-61) was polished with a cleanser, washed with water, and dried with an air stream. The substrate was heated to 40°C, the photosensitive film removed the polyethylene film, and lamination was performed at a lamination temperature of 130°C so that the photosensitive layer was in contact with the copper surface. The scattering of the composition could not be visually recognized at all, and almost no odor could be observed. Furthermore, lamination was carried out at a lamination temperature of 160° C. while the substrate was kept at room temperature, and the lamination properties were good. The scattering of the composition during lamination was equal to or lower than that when conventional photosensitive films were laminated at 130°C. Using negative film, these samples were exposed to a 3kW high-pressure mercury lamp from a distance of 90cm for 60 seconds. After removing the polyethylene terephthalate film, development was carried out by spraying a 2% sodium carbonate aqueous solution at 25°C to approximately 40°C for both samples.
This was achieved in seconds, showing good developability. Furthermore, the obtained photoresist image has a line width of 80 μm.
It has good resolution that can resolve up to It had great resistance. In addition, a photosensitive film consisting of this composition was heated at 30°C.
The storage stability was examined by placing it in a constant temperature machine, but no abnormal changes were observed even after one month, and no abnormality in properties was observed even after reusing it, indicating good storage stability. Example 2 A photosensitive film was prepared using Solution B in the same manner as in Example 1. The thickness of the photosensitive layer after drying was 25 μm. Solution B 25% methacrylic acid, 45% methyl methacrylate
%, ethyl acrylate 30% copolymer (*
2) 52g ethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark A-14G) 13g 2,2'bis(4-methacryloxydiethoxyphenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark BPE-4) 10g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trademark DPHA) 15g 2-ethylanthraquinone 2.5g 2,2'-methylenebis(4-ethyl-6-t-
Butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*2) Carboxyl group content 28 mol% Water absorption 27% Weight average molecular weight Approximately 80,000 to 100,000 The obtained photosensitive film was used as an example. After lamination exposure and development was carried out in the same manner as in 1, the resistance to etching solution and plating solution was examined. For lamination, the laminating temperature is 160℃ while the substrate is at room temperature.
However, the lamination properties were good. The odor at that time was the same or lower than that when conventional photosensitive films were laminated at 130°C. Development was achieved by spraying a 2% aqueous sodium carbonate solution at 25° C. for 40 seconds for 60 seconds of exposure, and good developability was achieved. Under normal processing conditions, no abnormalities were observed with respect to etching solutions and plating solutions, and the resistance was sufficient. Furthermore, the photosensitive film was placed in a thermostat at 30°C to examine its storage stability, but no abnormal changes were observed even after one month, and no abnormality in properties was observed even after reusing it. Example 3 A photosensitive film was prepared using Solution C, Solution D, and Solution E in the same manner as in Example 1. The film thickness of the photosensitive layer after drying was in the range of 23 to 26μ. Solution C shows the composition of the present invention, solution D, solution E
indicates a comparative example. Solution C methacrylic acid 25%, methyl methacrylate 53
%, butyl acrylate 22% copolymer (*
3) 52g ethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark A-14G) 13g 2,2'bis(4-methacryloxydiethoxyphenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark BPE-4) 10g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trademark DPHA) 15g 2-ethylanthraquinone 2.5g 2,2'-methylenebis(4-ethyl-6-t-
Butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*3) Carboxyl group content 32 mol% Water absorption 6% Weight average molecular weight Approximately 80,000 to 100,000 solution D Methacrylic acid 15%, methyl methacrylate 60
%, ethyl acrylate 25% copolymer (*
4) 52g ethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark A-14G) 13g 2,2'-bis(4-methacryloxydiethoxyphenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark BPE-4) ) 10g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trademark DPHA) 15g 2-ethylanthraquinone 2.5g 2,2'-methylene-bis(4-ethyl-6-t)
-butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*4) Carboxyl group content 17 mol% Water absorption 12% Weight average molecular weight Approximately 80,000 to 100,000 solution E Methacrylic acid 20%, methyl methacrylate 46
%, 34% 2-ethylhexyl methacrylate copolymer (*5) 52g Ethylene glycol diacrylate (trademark A-14G, manufactured by Shin Nakamura Chemical Co., Ltd.) 13g 2,2'-bis(4-methacryloxy diethoxyphenyl) ) Propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark BPE-4) 10 g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., trademark DPHA) 15 g 2-ethylanthraquinone 2.5 g 2,2'-methylene-bis(4-ethyl) -6-t
-butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*5) Carboxyl group content 32 mol% Water absorption 3% Weight average molecular weight Approximately 80,000 to 100,000 Until exposure according to Example 1 I did it. During lamination, solution A in Example 1 was used in both cases.
It showed the same effect as the photosensitive film obtained from. Development was also carried out in the same manner as in Example 1, by removing the polyethylene terephthalate film and spraying a 2% sodium carbonate aqueous solution at 25°C, but a photosensitive film was obtained from solution C in about 60 seconds. Although good developability was exhibited, the photosensitive films obtained from solutions D and E were not developed even after being sprayed for 180 seconds, and their developability was poor. The photoresist image obtained from solution B exhibited the good properties shown in Example 1 and had good storage stability. Example 4 A photosensitive film was prepared in the same manner as in Example 1 using Solution F, Solution G, and Solution H. In each case, the film thickness of the photosensitive layer after drying was in the range of 23 to 26 μm. Solution F has the composition of the present invention, and solution G and solution H
indicates a comparative example. Solution F 25% methacrylic acid, 37% methyl methacrylate
%, copolymer of 8% 2-ethylhexyl acrylate and 30% butyl methacrylate (*6)
52g Ethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark A-14G) 13g 2,2'bis(4-acryloxydiethoxyphenyl)propane (manufactured by Shin-Nakamura Chemical Co., Ltd., trademark ABPE-4) 10g Di Pentaerythritol hexaacrylate (DPHA manufactured by Nippon Kayaku Co., Ltd.) 15g 2-ethylanthraquinone 2.5g 2,2'-methylene-bis(4-ethyl-6-t)
-butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g (*6) Carboxyl group content 22 mol% Water absorption 6% Weight average molecular weight Approximately 80,000 to 100,000 solution G Copolymer in solution F 52g 2,2'-bis(4-acryloxydiethoxyphenyl)propane (trademark A-BPE-4, manufactured by Shin-Nakamura Chemical Co., Ltd.) 38g 2-ethylanthraquinone 2.5g 2,2'-methylenebis(4-ethyl- 6-t-
Butylphenol) 0.6g Victoria Pia Blue 0.09g Ethyl cellosolve 130g Methyl ethyl ketone 10g Chloroform 10g Solution H Copolymer in solution F 52g Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd. trademark DPHA) 38g 2-ethylanthraquinone 2.5g 2, 2'-methylene-bis(4-ethyl-6-t
-butylphenol) 0.6 g Victoria Pia Blue 0.09 g Ethyl cellosolve 130 g Methyl ethyl ketone 10 g Chloroform 10 g The photosensitive film obtained from solution F was prepared in Example 1.
After laminating, exposing, and developing in the same manner as above,
Resistance to etching solution and plating solution was investigated. Lamination was carried out at a lamination temperature of 160°C while the substrate was kept at room temperature, and the lamination properties were good. The odor at that time is compared to when conventional photosensitive film is laminated at 130℃.
It was the same or lower. For 60 seconds of exposure, development was achieved with a 2% aqueous sodium carbonate solution at 25° C. for about 60 seconds and washing with water for 30 seconds, indicating good developability. No abnormalities were observed under normal processing conditions for etching solutions and plating solutions, and the resistance was sufficient. Furthermore, the storage stability of the photosensitive film was examined by placing it in a thermostat at 30°C, but no abnormal changes were observed even after one month, and no abnormality in properties was observed even after reusing the film. On the other hand, the lamination properties of the photosensitive film obtained from Solution G were extremely poor, and although it was possible to laminate with difficulty at a lamination temperature of 160°C and a substrate surface temperature of approximately 70°C, under the same exposure conditions and developer as described above, On the other hand, development was not possible even after 180 seconds. When the storage stability of the photosensitive film was examined by placing it in a thermostat at 40°C, separation of the photosensitive layer occurred in about one week. Furthermore, the photosensitive film obtained from Solution H also showed almost the same tendency as the photosensitive film obtained from Solution G. Example 5 and Example 6 Solution I (comparative example), solution J, and solution K were prepared with the compositions shown in Table 1. Each of these was applied uniformly onto a 23 μm thick polyethylene terephthalate film using the apparatus shown in Figure 1, and dried for about 3 minutes in a hot air convection dryer at 100°C.
1, Film-2, and Film-3 were obtained. The thickness of each dry film (photosensitive layer) was 25 μm. On the other hand, the copper surface of a printed wiring board substrate (manufactured by Hitachi Chemical Co., Ltd., trademark MCL-E-61) was polished with a cleanser, washed with water, and dried with an air stream. Each of the above-mentioned films was laminated onto a substrate at 25° C. by pressing it with a laminating roll heated to 160° C. so that the photosensitive layer was in contact with the copper surface. At this time, fuming was observed in Film-1 obtained from Solution I (Table 2). Furthermore, these samples are coated with negative film.
Exposure was performed using a 3 kW ultra-high pressure mercury lamp at 150 mJ/cm ² in each case. After removing the polyethylene terephthalate film by development, this was carried out by spraying a 20% aqueous sodium carbonate solution at 25°C. The developing time for Film-1 and Film-2 was acceptable, but Film-3, although practical, was a little long. The adhesion of fine lines was also examined for the image after development. A negative film was used in which the resist spacing was 400 μm and the resist width was variable, and Table 2 shows the narrowest width of the resist in close contact. The smaller the number, the better the adhesion of the fine line.
Furthermore, the plating resistance was evaluated under normal conditions using a commercially available solder plating bath, and the results were good. From the results of Table 2 regarding these evaluation items, film-1 using n = 9 compounds was heated at 160°C.
This indicates that the laminate produces smoke and is a practical problem.

【table】

[Table] As explained in detail in the examples above, the photosensitive resin composition laminate of the present invention has the advantage that the amount of components scattered during lamination is small. Further 160-180
Since there is no problem in terms of properties even at high temperatures of .degree. C., high-temperature lamination can be carried out at temperatures within this range, and there is an advantage in that preheating of the substrate can be omitted. Incidentally, the above is only one example of the photosensitive resin composition laminate according to the present invention, and naturally, various modifications and usage methods are possible without departing from the spirit of the present invention.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram showing the production of a photosensitive film carried out in Examples. Explanation of symbols, 1...Polyethylene terephthalate film feed roll, 2, 3, 4, 9, 1
0... Roll, 5... Knife, 6... Solution of photosensitive resin composition, 7... Dryer, 8... Polyethylene film feeding roll, 11... Photosensitive film winding roll.

Claims (1)

[Scope of Claims] 1. In a photosensitive resin composition laminate formed by laminating a polymer film on at least one surface of a photosensitive resin composition layer, the photosensitive resin composition layer (a) has the following general formula [ ] Containing at least 10 parts by weight of one or more compounds represented by
One or more addition-polymerizable substances having a terminal ethylene group, having a molecular weight of 500 to 2000, a boiling point of 300°C or more at normal pressure, and capable of forming a high polymer and soluble in an organic solvent, 20 to 60% by weight Department (In the formula, R ₁ and R ₂ are H or CH ₃ , and n is
(b) Photoinitiator 0.2-10 parts by weight (c) Carboxyl group content 20-50 mol%, water absorption 4-30% by weight, weight average molecular weight 20,000-70
A photosensitive resin composition laminate containing 40 to 80 parts by weight of a linear copolymer (binder). 2 The addition polymerizable substance is CH ₂ =CHCO(-
OCH ₂ CH ₂ ) ₁₄ −OCOCH=CH ₂ or CH ₂ =C
(CH ₃ )CO−(−OCH ₂ CH ₂ )− ₁₄ OCOC(CH ₃ )=
CH ₂ 10-20 parts by weight, 2,2'bis(4-acryloxy diethoxyphenyl)propane or 2,
The photosensitive resin composition laminate according to claim 1, which is a mixture of 10 to 20 parts by weight of 2'bis(4-methacryloxydiethoxyphenyl)propane and 10 to 20 parts by weight of dipentaerythritol hexaacrylate. .