JPS5875148A - Photosensitive resin composition and photosensitive element - Google Patents

Abstract

PURPOSE:To obtain a composition having superior resistance to heat, thermal shock, solvent, etc. and suitable for use in the formation of a solder mask, etc. by blending specified urethane di(meth) acrylate with a linear high molecular compound having a specified glass transition point and a photopolymerizable sensitizer (system). CONSTITUTION:A photosensitive composition is obtd. by blending 20-75pts.wt. urethane di(meth) acrylate compound (a) prepared by reacting lysine isocyanate with dihydric alcohol and (meth)acrylic monoester of dihydric alcohol with 20- 75pts.wt. linear vinyl copolymer compound (b) having about 40-150 deg.C glass transition point and a sensitizer (system) forming free radicals under active light. In the composition the components (a), (b) are compatible with each other. The composition is suitable for use as a material for a photosensitive element with superior resistance to heat and cold-hot shock for forming a solder mask, etc. Tribromophenyl acrylate or the like may be added to the component (b) and a flame retarding compound such as Sb2O3 may be added to the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photosensitive resin compositions and photosensitive elements. For more details, please refer to printed wiring board manufacturing.

A material with excellent properties that can be used in metal precision processing, etc.
The present invention relates to a photosensitive resin composition for forming an i'I11 film and a photosensitive element comprising a layer of the composition and a support film supporting a wrinkled layer.

It is well known that photosensitive elements, ie, layers of substantially dry photosensitive resin compositions on support films, are used as photoresists for producing printed wiring boards. Furthermore, it is well known that photosensitive resin compositions having excellent properties and properties that can be used for solder masks, resists for chemical plating, etc. are very useful.

The main purpose of a solder mask is to limit the area during soldering and prevent solder bridging.

The purpose is to prevent corrosion of bare copper conductors and to maintain electrical insulation between conductors over the long term.

For these purposes, conventionally, thermosetting ink such as epoxy resin, IB or photocurable ink has been screen printed. However, in recent years, the wiring density of printed wiring boards has increased, and it has become difficult to form the solder masks used therein in terms of precision using the screen printing method. 9. As wiring density increases, requirements for electrical insulation between conductors become stricter.

It is desirable that the thickness of the conductor protective film 9 be at least about 20 μm or more. In the screen printing method, the average thickness of the resist that can be formed at one time is at most 30 μm, and the thickness of the thinnest part of the resist formed on the conductor convex portion is 10 μm.
−m or less. Although it is possible to make the film thicker by repeating printing twice or thrice, it is practically very l- due to the printing precision and the complexity of the process.

Therefore, the emergence of a photosensitive element for forming a half-Tsukuda mask is desired. The thickness of the layer of photosensitive resin composition is 20p
Photosensitive elements of m or more are useful. Since the conductor thickness of most printed wirings is 18 μm or more, the photosensitive element #i having a photosensitive resin layer thickness of 40 pm or more is particularly useful. ' It is generally called a photosensitive dry film and is used for forming conductor patterns on printed wiring boards.

Photosensitive elements for etching or electrolytic plating do not have sufficient heat resistance and cannot be used for forming solder masks.

Therefore, proposals have been made for photosensitive resin compositions for photosensitive elements that are heat resistant and can be used for forming solder masks.
-43092, 4I Kosho 53-44346). , they have excellent heat resistance, which is one of the purposes of the proposal, but 4
When forming a thick protective film of 0 μm or more, heat at 125°C.
Cracks occur within 5 cycles in a thermal shock test at -65°C. The occurrence of cracks becomes more severe in #1 as the film thickness increases. This becomes a major problem when long-term reliability of printed wiring boards must be considered.

Among the solder masks formed by the screen printing method, there are four types that have good resistance to cold and heat shock.

This is mainly because the thickness of the solder mask formed by the screen printing method is 10 to 30 μm. Another reason is that printing inks generally contain large amounts of filler. It is known that the inclusion of a filler contributes to improving thermal shock resistance. However, in the case of a photosensitive element, the layer of the photosensitive resin composition must already be substantially dry before irradiation with actinic light and must have some film properties. This means that the layer of the photosensitive resin composition must contain a linear polymer compound for the purpose of imparting film properties. For this reason,
It is difficult to contain a large amount of filler in addition to the linear polymer compound, active photosensitive compound, and sensitizer.

Furthermore, the present inventors have conducted various studies.

In the case of a photosensitive element, if the layer of the photosensitive resin composition contains a filler of about 10% by weight or more, the cold and thermal shock resistance of the solder mask formed thereby will certainly improve, but the main properties will be It was found that the soldering heat resistance, which is one of the properties, deteriorated, making it impractical.

Nine different urethane (meth)acrylate compounds (urethane acrylate compounds or urethane methacrylate compounds, hereinafter the same) have been proposed as compounds for use in photocurable inks for screen printing, as they have excellent heat resistance. However, they are different from photocurable inks.
When attempting to apply the present invention to a photosensitive element which normally involves imagewise exposure and development, difficulties arise when k is thick. The first difficulty is that many of the urethane (meth)acrylate compounds that have been proposed are either incompatible or incompatible with linear polymer compounds, especially vinyl copolymer linear polymer compounds that are suitable for various properties. The solubility is extremely poor. The second difficulty is that the proposed urethane (meth)acrylated metals are difficult to use when using the nonflammable solvents used in the production of photosensitive elements, especially the commonly used 1,1.1-)lichloroethane solvents. Most of them are insoluble.

Japanese Patent Publication No. 51-15733 discloses a nine-rethane (meth)acrylate compound that overcomes these difficulties. However, the composition disclosed therein cannot be used for forming a solder mask due to its flexibility and heat resistance.

The object of the present invention is to provide a photosensitive resin composition that can be used in the formation of a solder mask and has excellent heat resistance and cold shock resistance, and a photosensitive resin composition that is composed of a layer of the composition and a support film that supports the layer. It is to provide elements.
1 The present invention comprises (a) (a) lysine diisocyanate, (b) dihydric alcohol, and (c) 2
(Meth)acrylic acid monoester of alcohol (refers to acrylic acid monoester or methacrylic acid monoester).

Urethane di(meth)acrylate compound (referring to a urethane diacrylate compound or urethane dimethacrylate compound, the same hereinafter) obtained by reacting 2
0 to 75 weight 1 part (b) Glass transition temperature is approximately 40〒1
The present invention relates to a photosensitive resin composition containing 20 to 75 parts by weight of a linear polymer compound at 50° C. and (C) a sensitizer that generates free radicals upon actinic light (and) a sensitizer system.

Furthermore, the present invention a, (1) (a) urethane diacrylate obtained by reacting (a) lysine diisocyanate, (b) dihydric alcohol, and (c) acrylic acid monoester or methacrylic acid monoester of dihydric alcohol; 20 to 75 parts by weight of a compound or urethane dimethacrylate compound (bl) 20 to 75 parts by weight of a linear polymer compound with a glass transition temperature of about 40 to 150°C, and (C) sensitization that generates free radicals by actinic light. The present invention relates to a photosensitive element comprising a layer of a photosensitive resin composition containing an agent or/and a sensitizer system and a support film supporting the layer.

The photosensitive resin composition proposed by the present invention will be explained in detail below.

The photosensitive resin composition proposed by the present invention is obtained by reacting (a) lysine diisocyanate, (b) dihydric alcohol, and (c) (meth)acrylic acid monoester of dihydric alcofur. ) Contains an acrylate compound as an essential component.

(a) Lysine diisocyanate is a known compound.For example, the carboxyl group of lysine (1,5-diaminopencune-1-carboxylic acid), a type of amino acid, is converted into methanol or ethanol.

After esterification with lower alcohol such as butanol,
Refers to a divalent isocyanate compound obtained by modifying an amino group into an incyanate group by the action of phosgene etc.9
For example, there is LDI-M100 (methyl λ6-dicyanate caproate) manufactured by Toshi.

The dihydric alcohols (b) and (c) include methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and propylene glycol.

Diglobylene glycol, 1,4-butanediol, L
3-butanediol, 2,3-butanediol, L5-
Bentanediol, L6-bentanediol, 1.10
-Decanediol, neopentyl glycol, 1.4-
Examples include cyclohexane dimetatool, bis(2-hydroxyethyl) terephthalate, s-2-bis(4-hydroxyethoxyphenyl)propane, and s-2-bis(4-hydroxyjetoxyphenyl)propane.

As the (meth)acrylic acid monoester of dihydric alcohol (c), ti2-hydroxyethyl (meth)acrylate, 2-human p-xyglopyl (meth)acrylate, etc. are used.

The dihydric alcohol (b) and the dihydric alcohol (c) may be the same dihydric alcohol or different dihydric alcohols. The resulting urethane di(meth)acrylate compound has the formula! It is expressed as

ζ where & is H or CHl, R4 is a dihydric alcohol residue, & is a dihydric alcohol residue, and X is a lysine diisocyanate residue. n is O or a positive integer, and the reaction products actually obtained are urethane di(meth) with different values of n.
It is a mixture of acrylate compounds.

When synthesizing the urethane di(meth)acrylate compound of the present invention, the isocyanate equivalent of the lysine diisocyanate (a), the dihydric alcohol (b), and the dihydric alcohol (c)
React so that the total alcohol equivalent of the (meth)acrylic acid monoester of the alcohol is equal to the amount of (meth)acrylic acid monoester (
It is preferable to determine the amounts of lysine diisocyanate (a), dihydric alcohol (b), and (meth)acrylic acid monoester of dihydric alcohol (c), but the incyanate equivalent is in slight excess relative to the alcohol equivalent. It doesn't matter if you are a little short on ton. When the isocyanate equivalent is in slight excess over the alcohol equivalent, the excess inocyanate groups can be finally reacted with a monohydric alcohol such as methanol to eliminate free inocyanate groups.

If the ratio of the alcohol equivalent of the dihydric alcohol to be reacted (1) to the alcohol equivalent of the (meth)acrylic acid monoester of the dihydric alcohol (c) is 1 (provided that 1 of the lysine diisocyanate to be reacted is The isocyanate equivalent and the total alcohol equivalent are approximately equal) The number average value of n is IK.

When a dihydric alcohol having a large number of constituent carbon atoms is used, the cold shock resistance of the formed solder mask improves, but the heat resistance decreases. On the other hand, if a dihydric alcohol having a small number of carbon atoms is used, the heat resistance of the formed solder mask will be further improved, but the cold shock resistance will be lowered. The number of carbon atoms constituting the dihydric alcohols (b) and (c) is preferably 1 to 23. It is possible to improve the decrease in heat resistance when using a dihydric alcohol having a large number of constituent carbon atoms. i.e. 1
The alcohol equivalent of the dihydric alcohol to be reacted (1) should be less than the alcohol equivalent of the (meth)acrylic acid monoester of the dihydric alcohol (3) (provided that the total (The alcohol equivalents are equal to #1) By setting the number average value of n to 1 or less, the decrease in heat resistance can be improved.

The decrease in cold shock resistance when using a dihydric alcohol having a small number of constituent carbon atoms can be similarly improved. That is, alcohol a of dihydric alcohol to be reacted (1)
Quantity t, G"to 2 valence 7 Ru: F-Ru's (meta)
The alcohol equivalent of acrylic acid monoester is larger (
However, the incyanate equivalent of the lysine diincyanate to be reacted and the total alcohol equivalent are approximately equal.) By setting the number average value of n to 1 or more, the decrease in cold shock resistance can be improved. That is, in consideration of the balance between heat resistance and cold shock resistance, there is a preferable range of the concentration of the (meth)acryloyl group (referring to an acryloyl group or a methacryloyl group, the same applies hereinafter).

The inventors conducted various studies and found nine results *lX10-s~4.5
Urethane di(meth)acrylate compound (mixture) containing a (meth)acryloyl group of X10 equivalent/P
It was found that the solder mask formed using the resin composition with good and bad photonic properties has an excellent balance of heat resistance and cold shock resistance.

Considering that the conductor is protected by the solder paste and the electrolytic corrosion resistance of the printed wiring board is considered, the dihydric alcohol to be reacted is 1,4-butanediol.

1.3-butanediol, 1.5-bentanediol
Dihydric alcohols that do not contain a hydrophilic group such as an ether bond in their residues are preferred, such as 1,6-hexanediol and 1,4-cyclohexane dimetatool.

The content of the urethane di(meth)acrylate compound is in the range of 20 to 75 parts by weight from the viewpoint of heat resistance and cold shock resistance.

The photosensitive resin composition of the present invention contains as an essential component a linear polymer compound having a glass transition temperature of about 40 to 150°C.

When the glass transition temperature is less than about 40° C., the formed solder mask has low heat resistance. If the glass transition temperature exceeds about 150°C, the compatibility with the urethane di(meth)acrylate compound will be poor and it will be impossible to form a layer of the photosensitive resin composition on the support film or substrate. The vinyl copolymerized linear polymer compound is preferable in terms of compatibility with the urethane di(meth)acrylate compound and adhesion between the printed wiring board and the layer of the photosensitive resin composition. Various vinyl monomers can be used as the copolymerization component of the linear polymer compound.

A suitable example of a vinyl monomer is methyl methacrylate.

Butyl methacrylate, ethyl acrylate, styrene, α
-Methylstyrene, vinyltoluene.

2-hydroxyethyl acrylate, 2-hydroxyglybyl methacrylate, 2-hydroxyethyl acrylate, acrylic acid, methacrylic acid, glycidyl methacrylate, t-butylaminoethyl methacrylate, 2.
&-dibromopropyl methacrylate, 3-crocou2
-Hydroxyethyl acrylate, acrylamide and acrylonitrile, to name a few.

If flame retardancy is required for the solder paste formed, it is possible to use monomers containing bromine atoms as copolymerization components.

The content of bromine atoms in the linear polymer compound is 40
The weight limit is appropriate; if the weight exceeds 40, the thermal shock resistance decreases. As the monomer containing a bromine atom, triprophenol(meth)acrylate (hereinafter referred to as tribromophenyl acrylate or tripromophenyl methacrylate) is suitable. The copolymerization amount of tribromophenyl (meth)acrylate is as follows:
If the amount is less than 5% by weight, the effect on flame retardancy is not much different from that without copolymerization, and if it exceeds 65% by weight, the thermal shock resistance decreases. For flame retardancy, the combined use of antimodium trioxide is effective.

However, if the content of antimony trioxide in the photosensitive resin composition exceeds 5% by weight, the heat resistance of the formed solder mask will be adversely affected.

The content of the linear polymer compound in the photosensitive resin composition is in the range of 20 to 75 parts by weight from the viewpoint of heat resistance, isobaric properties, and cold/hot shock resistance.

The photosensitive resin composition proposed by the present invention contains as an essential component a sensitizer (and) a sensitizer system that generates free radicals upon activation of active light.

Sensitizers that can be used include substituted or unsubstituted polynuclear quinones, such as 2-ethylanthrone, 2-1-
Butylanthraquinone, octamethylanthraquinone,
1.2-benzanthraquinone, 2.3-diphenylanthraquinone, etc.

Ketoaldonyl compounds such as diacetyl and benzyl;
a-ketal vinyl alcohols and ethers such as benzoin and vivalon, a-hydrocarbon substituted aromatic acylins 9 such as α-phenyl-benzoin, (X, a-jethoxyacetophenone, etc., benzophenone, 44'
Examples include aromatic ketones such as -bisdialkylaminobenzophenol, which may be used singly or in combination.

Sensitizer systems that can be used include combinations of 2.45-) realarylimidazole dimer and 2-mercaptobenzoquinazole, leuco crystal bijolet, tris(4-diethylamino-2-methylphenyl)methane, etc. I can give an example. For example, for benzophenone, it is possible to use additives which do not have photoinitiating properties by themselves, but when used in combination with the above-mentioned substances, result in a sensitizer system with better photoinitiation performance as a whole. These include tertiary amines such as triethanolamine. These sensitizers or (and) sensitizer systems include (a) urethane di(
meth) acrylate and (b)! It is preferably contained in an amount of 0.5 to 10% by weight based on the I-shaped bulky polymer compound.

The photosensitive resin composition of the present invention may further contain other photopolymerizable unsaturated compounds. Examples of other photopolymerizable unsaturated compounds include trimethyl IC1 triacrylate, hentaerythritol triacrylate, and tetraethylene glycol diacrylate.

Furthermore, photopolymerizable unsaturated compounds disclosed in JP-A-53-56018 can also be used. However, the content of these other photopolymerizable unsaturated compounds is determined by the balance between heat resistance and cold shock resistance.

The above aa) urethane di(meth)acrylate and (b)
) It is preferably 20 weight or less, particularly preferably 10 weight or less, based on the linear polymer compound. Other photopolymerizable unsaturated compounds can be added to further improve other properties such as solvent resistance and adhesion, but (meth)acrylic esters (acrylic esters or Methacrylic acid ester (hereinafter the same) is preferable because it further improves the adhesion between the formed solder mask and the printed wiring board.

As a (meth)acrylic acid ester containing a phosphate group in the molecule, PM of the KAYAMER' series manufactured by Nippon Kayaku ■ is used.
-1, PM-2, PA-1 or PA-2, oil and fat products ■
Hosmer M” (acid phosphoxyethyl methacrylate) manufactured by Co., Ltd.

*xv-CL (3-chloro-2-acid phosphoxypropyl methacrylate), etc.

The content of (meth)acrylic acid ester containing a phosphoric acid group in these molecules is 0.0 with respect to the above-mentioned (a) urethane di(meth)acrylate and (b) II-type bulky polymer compound.
A weight of 1 to 5 weight is preferred.

Ingredients include thermal polymerization inhibitors, dyes, pigments, coating properties improvers, etc. - Their selection is made based on the same considerations as for conventional photosensitive resin compositions.

Next, the photosensitive element proposed by the present invention will be explained in detail below.

The photosensitive element proposed by the present invention is obtained by forming a layer of the photosensitive resin composition described in detail above on a support film. A layer of the photosensitive resin composition can be formed on the support film by a conventional method.

For example, a photosensitive resin composition is uniformly dissolved in an organic solvent such as methyl ethyl ketone, toluene, or methylene chloride (however, antimony trioxide, pigments, etc. are uniformly dispersed), and this solution is coated on the support film using a knife coating method. , apply by roll coating method etc.

It is done dry. The amount of residual solvent in the photosensitive layer is preferably kept to 2 parts by weight or less, particularly preferably 1 part by weight or less, in order to maintain properties.

The support film used in the present invention preferably has the heat resistance and solvent resistance necessary for manufacturing the photosensitive element, but a release film such as Teflon film or release paper may be used as temporary support A layer of a photosensitive resin composition is formed on top of the body film, and after eating, a film with low heat resistance or solvent resistance is laminated on top of this layer, and the temporary support film is peeled off to form a layer of a photosensitive resin composition. Alternatively, it is also possible to produce photosensitive elements having a support film with low solvent resistance. Further, the support film may be transparent or opaque to actinic light. Examples of support films that can be used are polyester films, polyimide films, polyamide-imide films.

Known films such as polyglupylene film and polystyrene film can be mentioned.

When manufacturing long photosensitive elements.

In the final stage of manufacture, the element is wound up into a roll.

In this case, by using a pressure-sensitive adhesive tape or the like to treat the back side using a known method and using a support film, the layer of the photosensitive resin composition can be transferred to the back side of the support film when it is wound into a roll. It is possible to prevent wear. Same purpose.

It is preferable to laminate a removable cover film on the photosensitive resin composition layer of the element for the purpose of preventing dust from adhering to the element.

Examples of removable cover films include polyethylene film and polypropylene film.

Teflon film, surface treatment and good paper etc. are not damaged.

It also improves the adhesion between the photosensitive resin composition layer and the support film when the cover film is peeled off.

It is sufficient that the adhesive force between the layer of the photosensitive resin composition and the cover film is smaller.

The thickness of the layer of the photosensitive resin composition constituting the photosensitive element of the present invention is determined to maintain a high degree of electrical insulation between the conductors of the printed wiring board to which it is applied.

Further, from the viewpoint of resolution of the solder mask pattern to be formed, the thickness is preferably 20 to 200 sm.

Next, an example of how to use the photosensitive element proposed by the present invention will be described.

The photosensitive element proposed by the present invention can be easily laminated onto a substrate. That is, when there is no cover film, the lamination is carried out as is, and when there is a cover film, the cover film is peeled off or while being peeled off while being laminated under heat and pressure. Heat and pressure lamination can be carried out using an atmospheric pressure laminator well known to printed wiring board manufacturers. When the substrate is a substrate having conductor wiring lines and unevenness of 10 #m or more, such as a printed wiring board, it is preferable to laminate under reduced pressure or vacuum.

Examples of this rounding device include the laminating device described in Japanese Patent Publication No. 53-31670 and Japanese Patent Publication No. 55-13341.

Exposure and development treatments after lamination can be carried out by conventional methods.

That is, if the support film is opaque to actinic light, the support film is peeled off and then exposed through a negative mask using a light source such as a high-pressure mercury lamp or ultra-high pressure mercury lamp. Heat treatment at 50° C. to 100° C. before and after exposure is preferred in order to improve the adhesion between the substrate and the photosensitive resin layer.

#'i1.1.1-) A solvent such as dichloroethane is used as the current solution. It is preferable to use a nonflammable solvent for safety reasons. 10 The image-like protective film obtained by this method becomes a corrosion-resistant film for ordinary etching, plating, etc., but the
Heat treatment at 0° C. to 200° C. and exposure to actinic light results in a protective coating with even better properties. The heat treatment after development and the exposure to active light may be performed first.

Further, each step may be performed several times.

The protective film obtained by heat treatment after development and exposure to actinic light is sufficiently resistant to organic solvents such as tricrene, methyl ethyl ketone, isopropyl alcohol, and toluene, and also resistant to acidic or alkaline aqueous solutions. Furthermore, since it has excellent heat resistance and excellent cold and heat shock resistance, it is suitable as a permanent protective coating for solder masks and the like that require long-term reliability.

In addition, 9, a solution of the photosensitive resin composition proposed by the present invention is directly applied to a substrate by a dip coating method, a full coating method, etc., and after drying with a solvent, either directly or after laminating a film transparent to active light such as a polyester film, the above-mentioned imagewise through a negative mask in the same manner as for the photosensitive element.

By developing, heat-treating and exposing to actinic light, a Kuho eel coating with excellent % properties can be obtained in the same manner as described above.

As described above, the photosensitive resin composition of the present invention has a coating formed using a photosensitive element that has excellent chemical and physical properties.

It is also used for printing plate materials, glass reliefs, etc.

Next, the embodiments of the present invention will be described. The embodiments shown here are a book showing the practical aspects of the present invention, and are not limited by this.

In Examples and Comparative Examples, "1 part" indicates parts by weight.

Example 1 a) Synthesis of urethane diacrylate compound Toluene (
Solvent) 1200 parts B 1,6-hexanediol 472 parts (8) C2-hydroxyethyl acetate 928 parts (8 equivalents) Lylate toluene (solvent) 95 parts Methanol (terminator) 32 parts Stir the above A with a thermometer. The reactor, a cooling tube, a nitrogen gas inlet tube, and a dropper were added to a reactor with a volume of 51 which can be heated and cooled, and the temperature was raised to 60° C. with stirring. B was uniformly added dropwise over about 3 hours while maintaining the reaction temperature at 55 to 65°C. After dropping B, keep at a temperature of 55 to 65°C for about 2 hours.

Thereafter, C was uniformly added dropwise at a temperature of 55 to 65° C. over a period of about 3 hours. After dropping C, the reaction temperature was gradually increased to 80°C over about 5 hours.
The temperature was raised to ℃. Thereafter, the temperature was lowered to 60°C, D was added, and stirring was continued for about 1 hour. In this way, the non-volatile content is 70
A solution (1) of a urethane diacrylate compound by weight was obtained.

b) Production of photosensitive element A solution of the nine-urethane diacrylate compound obtained by the above method (1170 parts (49 parts as non-volatile content)).

47 parts of methyl methacrylate/methacrylic acid/tetrahydrofurfuryl methacrylate (78/2/20 weight ratio) copolymer (molecular weight approximately 150,000, glass transition temperature 95°C).

5 parts of benzophenone.

p-methoxyphenol 0.1 part.

Crystal violet 0.1 part.

Methyl ethyl ketone 80 parts.

A solution of the photosensitive resin composition was prepared according to the above formulation, and applied onto a polyimide film with a thickness of about 50 μm.
t'20 minutes, dried at 80°C for 10 minutes, and at 105°C for 5 minutes,
A photosensitive element was obtained in which the layer of the photosensitive resin composition had a thickness of about 60 μm.

C) Formation of solder mask Six test boards having the steel pattern shown in Figure 1 were formed by etching a glass epoxy copper clad laminate with a base material thickness of 1.6 mm and a steel foil thickness of 18 μm. Got nine. 1 indicates the copper pattern portion, 2 indicates the layered portion of the base material, and the unit of the number is the sieve.

On this test substrate, the photosensitive element obtained in b) above was laminated using an A-500 model atmospheric pressure laminator manufactured by Akebono Dogyo. After lamination, the polyimide film of the support film was peeled off and exposed using a test negative mask shown in Figure 2.
Exposure was performed at mJ/cam. 3 indicates the opaque part of the negative mask, 4 indicates the transparent part of the negative mask, and the unit of the number is ■
It is. After being left for 30 minutes after exposure, the film was developed by spraying with 1,1,1-trifluorethane at 20° C. for 90 seconds. After incubation, it was heated and dried for one part at 80°C, and then irradiated at 2.5J151 using an ultraviolet irradiation device manufactured by Toshiba Denzai.

Thereafter, heat treatment was performed at 150° C. for 30 minutes.

In this way, a protective film was formed, and 4 of the 96 test substrates were immersed in Ingropanol, toluene, trichlene, or 10La acid aqueous solution at 25°C for 10 minutes each. No change was observed.

The other sheet was immersed in a solder bath at 255-265°C for 30 seconds, but the protective film remained stable.

No cracking or peeling from the board was observed, indicating that it can be used satisfactorily as a solder mask.

Furthermore, on the remaining one test board, using a-jin type flux A-226 (manufactured by Tamura Kaken ■), 255 to 26
After soldering for 3 seconds in a 5℃ solder bath, MIL-
8TD-202E107D A thermal shock test was conducted for 50 cycles under condition B (-65°C, 30 minutes = within 5 minutes at room temperature, 2125°C, 30 minutes), but there were no cracks in the protective coating, and the long-term reliability is extremely high. It turned out to be excellent.

Example 2 a) Synthesis of urethane diacrylate compound A LD
I-Mloo (1696 parts (16 equivalents) diisocyanate) Toluene 800 parts didiuric acid 1 part tin (catalyst) B 1,4-cy/a 360 parts (5
MMa) Methanol 2-hydroxyethyl urea 348 parts (3M) Acrylate methyl ethyl ketone (solvent 520i1S agent) C2-hydroxyethyl urea 928 parts (8M) Acrylate toluene (solvent) 80 parts p-methoxyphenol 0.3 parts (thermal polymerization Inhibitor) D Ethanol (terminating agent) 23 parts A solution of the urethane diacrylate compound was obtained using the above formulation in the same manner as in Example 1-m). after that.

A viscous urethane diacrylate compound was obtained by drying under reduced pressure.

b) Production of photosensitive element Nine urethane diacrylate compounds obtained by the above method (40 parts).

Methyl methacrylate, methyl acrylate, 2- and diethyl methacrylate φ acrylonitrile (80/1
015 parts 6 weight ratio) copolymer (molecular weight approximately 10,000, glass transition temperature approximately 90° C.) 57 parts.

27 parts of benzophenone.

Michler Ketone 0.3 parts.

p-methoxyphenol 0.1 part.

Victoria Pure Blue O, OS Department.

780 parts of methyl ethyl keto.

Toluene 40 parts.

Using the apparatus shown in FIG. 3, a solution 10 of the photosensitive resin composition of the above formulation is uniformly applied onto a 25 μm thick polyethylene terephthalate film 16, and then heated in a hot air convection dryer 11 at 80 to 100° C. for about 10 minutes. Dry. The dry thickness of the photosensitive resin composition layer was approximately 100 μm. On the layer of the photosensitive resin composition, a polyethylene film 17 having a thickness of about 25 μm was further laminated as a cover film as shown in FIG.

In FIG. 3, 5 is a polyethylene terephthalate film (roll), 6, 7.8 is a roll, 9 is a knife, polyethylene film manufactured by 12 is a roll (roll), 13.
14 is a roll, and 15 is a roll for winding up the photosensitive element.

C) Formation of solder mask The photosensitive element obtained above was used as a test printed wiring board (glass epoxy board) on which the steel pattern (copper thickness: about 70 μm) shown in FIG. 1 was formed.

Thickness: 1.6 mm) with a Hitachi Chemical vacuum laminator (
Vacuum degree 3911111 (g, lamination temperature 100℃,
Lamination was carried out under heat and pressure using a net speed of 1 m 1 minute). After lamination, heat at 60°C for 5 minutes.

After leaving it at room temperature for 3 hours, a second sample was prepared in the same manner as in Example 1-C).
156 mJ 7 through the test negative mask shown in the figure.
cm- exposed.

After exposure, the film was heated at 80°C for 5 minutes, left at room temperature for 20 minutes, and then the support film was peeled off.
Spray development was performed at 20° C. for 150 seconds using IJ dichlorothane.

After development, heat dry at 80℃ for 10 minutes, &OJ/c
tm'' ultraviolet IIs irradiation and heat treatment at 130° C. for 2 hours.

The test substrate on which the protective film was formed in this way was treated with isopropanol at 25°C in the same manner as in Example 1-c).
A 10-minute immersion test was conducted in toluene, trichlene, or a 10-chloride hydrochloric acid aqueous solution.

No change was observed in the formed protective film.

t7t A 30-second immersion test was conducted in a solder bath at 255-265°C, and there were no problems, showing excellent heat resistance.

Furthermore, after the same soldering treatment as in Example 1-c).

No cracks were observed in the 9 coatings formed even in the thermal shock test of 50 cycles under MIL-8TD-202E 107D condition B.

Example 3 60 parts of the nine-urethane diacrylate compound (1) obtained in Example 2-1).

Methyl methacrylate/methacrylic acid (98 parts 2 weight ratio)
Copolymer (molecular weight approximately 100,000, glass transition temperature approximately 105℃
) 37 parts.

Benzophenone 2.7 parts.

Michler Ketone 0.3 parts.

p-methoxyphenol 0.1 part.

Victoria Pure Blue 0.02 parts.

Methyl ethyl ketone 60 parts.

70 parts of toluene.

Example 2-
A photosensitive element having a layer of photosensitive resin composition having a thickness of about 80 μm was obtained using the apparatus shown in FIG. 3 in the same manner as in b).

This photosensitive element was laminated under reduced pressure in the same manner as in Example 2-C) on a test printed wiring board on which the steel pattern shown in FIG. 1 (steel thickness: approximately 50 μm) was formed. Further, the same treatment as in Example 2-C) was carried out to form a highly protective film on the test substrate. The formed protective film is heated to 25°C.
No problems were found in a 10-minute immersion test with Impropatol, toluene, trichlene, methyl ethyl ketone, 10-hydrochloric acid aqueous solution or 1011101L aqueous solution (25
It has excellent heat resistance with no cracking or peeling from the base material in a 30 second immersion test in a 5-265°C solder bath. Furthermore, after the same soldering process as in Example 1-C), MIL
-8TD-202E107D Condition B, 50 cycles A thermal shock test did not cause 2 cracks.

Comparative Example 1 Urethane diacrylate compound (n) of Example 2-b)
The same operations as in Example 2-b) and Example 2-C) were carried out except that trimethylolpropane triacrylate was used instead. The final protective film was 255~
During a 30 second immersion test in a 265°C solder bath, some peeling from the board was observed. Furthermore, after soldering treatment similar to Example 1-c), MIL-8TD-202E 107
D: In the thermal shock test under condition B, cracks occurred within 5 cycles.

Comparative Example 2 Urethane diacrylate compound (If) 60 of Example 3
Pentaerythritol triacrylate 2
The same operation as in Example 3 was carried out except that 0 parts and 40 parts of bisphenol di(3-acryloxy-2-hydroxypropyl) ester were used. The finally obtained protective film was MI after the same soldering process as in Example-1-c).
L-8TD-202E 107D In the thermal shock test under condition B, cracks occurred within 5 cycles. Maku, 1
In a 10-minute immersion test in a 0% hydrochloric acid aqueous solution, part of the protective film was found to be lifted off the substrate.

Comparative Example 3 Trimethylolprobant reactor 17L/30 parts.

Polypropylene glycol (average molecular weight 100G) diacrylate 10 parts.

Methyl methacrylate/tetrahydrofurfuryl methacrylate (78/2/20 weight ratio) copolymer (molecular weight approximately 1,50,000, glass transition temperature approximately 95°C) 5
0 copies.

Benzophenone 2.7 parts.

Michler Ketone 0.3 parts.

p-methoxyphenol α5 parts.

200 parts of methyl ethyl ketone.

The same operation as in Example 3 was carried out except that the solution of the photosensitive resin composition having the above formulation was used. The finally obtained protective film had excellent solvent resistance and heat resistance.
MIL-8TD-202E after soldering process similar to c)
In the 107D condition B''t'O thermal shock test, two cracks occurred within 10 psi.

Example 4 a) Synthesis of urethane diacrylate compound.

A LDI-M100' (lysine 1696 parts (16
醋) Diisocyanate) Toluene (solvent) 1200 parts B Triethylene glycol 100 parts (2'MIk)・E Natsumi! '7 xyethylua 696 parts (6 equivalents) C2-1
=Do HJ? Shibu-a Building 1040 parts (8fi) Acrylate Toluene° (solvent) 190 parts Hydroquinone 0.4 part (thermal polymerization inhibitor) D Methanol (terminating agent) 32 parts Example 1-a)
A solution of the urethane diacrylate compound was obtained using the above formulation in the same manner as above. after that.

A viscous urethane diacrylate compound (button) was obtained by drying under reduced pressure.

b) Production of photosensitive element and formation of solder mask The urethane diacrylate compound (1
) 60 copies.

37 parts of methyl methacrylate/methacrylic acid/tribromophenyl acrylate (38/2/60 weight/1 ratio) copolymer (molecular weight approximately 120,000, glass transition temperature approximately 120°C, bromine content 37% by weight).

27 parts of benzophenone.

4.4'-bis(diethylamino)benzophenone0.
Part 3.

2.0.3 part of 2'-methylenebis(4-ethyl-6-t-butylphenol).

Part 02 to Victoria Pure Blue.

100 parts of methyl ethyl ketone.

Toluene 50 parts.

Using a solution of the photosensitive resin composition with the above formulation.

Otherwise, the same operations as in Example 2-b) and Example 2-C) were performed. The finally obtained protective film showed no problems in a 10-minute immersion test in isopropanol, toluene, trichloride, or 101G hydrochloric acid aqueous solution.
When immersed in a solder bath at ~265°C for 30 seconds, no changes such as peeling or cracking were observed. Furthermore, Example 1-
MIL-8TD-202E1 after soldering process similar to C)
07D Condition B: No cracks occurred even in 50 cycles of thermal shock test. In addition, 0 of the printed wiring board MCL-E-68 (UL flame retardant grade 94V-0) manufactured by Hitachi Chemical ■
．． 8. Form a protective film over the entire surface of the thick base material in the same manner as above.

This product satisfied UL's 94V-1 standard.

Example 5' a) Synthesis of urethane diacrylate compound A LD
I-Mloo (1696 parts (16 equivalents) diisocyanate) Toluene (solvent) 1000 parts Dilauric acid 1 part Tilttin (catalyst) B Ethylene glycol 310 parts (10 parts) C2
-Hydroxyethyl 696 parts (611) Acrylate Toluene (solvent) 150 parts Human cI Non 0.3 parts (thermal polymerization inhibitor), D Methanol (terminating agent) 32 parts! A solution of a urethane diacrylate compound was obtained using the above formulation in the same manner as in J-Example 1-1). after that.

The mixture was dried under reduced pressure to obtain a viscous urethane diacrylate compound (conversion).

b) Manufacture of photosensitive element and formation of solder mounds The urethane diacrylate compound (j
/) 50 copies.

Methyl methacrylate/Methyl acrylate Φacrylic acid/
Tetrahydrofurfuryl methacrylate) 177” Romophenylaque IJL/-) (40/23/2/10/
25% by weight) copolymer (molecular weight approximately 80,000, glass transition temperature approximately 75°C, bromine content 15% by weight) 47 parts.

4-ri four lepen\siphenon 6 parts.

Mihiraketone 0.1 part.

0.5 part of 42'-methylenebis(4-methyl-6-t-butylphenol).

Victoria Pure Blue 0.02 parts.

100 parts of methyl ethyl ketone.

Toluene 50 parts.

Using a solution of the photosensitive resin composition with the above formulation.

Otherwise, the same operations as in Example 2-b) and Example 2-C) were performed. The final protective coating showed no problems in a 10-minute immersion test with isoglopanol, toluene, trichlene, or 10% hydrochloric acid aqueous solution.
Although it was immersed in a 65°C solder bath for 30 seconds, no changes such as peeling or clutter were observed. Further Example 1-C)
MIL-8TD-202E107 after soldering process similar to
No cracking occurred even in the 50-cycle thermal shock test under D condition B. Also, printed wiring board MCL manufactured by Hitachi Chemical
A protective film was formed on the entire surface of the 1.6-inch thick substrate of -B-68 by the same operation as above. This one is UL's 94V-1
Satisfied the standards.

Example 6 The same operation as in Example 5-b) was carried out except that 1 part of antimony trioxide was further added to the solution of the photosensitive resin composition of Example 5-b. Solvent resistance of the final protective film,
The heat resistance and cold shock resistance were good with the same results as in Example 5-b). Also.

Hitachi Chemical printed wiring board MCL-E-68 t/3m
A protective film was formed on the entire surface of the thick substrate by the same operation as on the substrate. This product satisfied UL's 94V-0 standard.

Example 7 a) Synthesis of urethane dimethacrylate compound A LD
I-Mloo (Rigi 1696 parts (16 equivalents) di-inocyanate) Toluene (Solvent 3 1000 parts ・B1,4-I
/ Tanediol 270 parts (6) Toluene (solvent) 280 parts A solution of the above urethane dimethacrylate compound was obtained in the same manner as in Example 4). after that.

Dry under reduced pressure to obtain a viscous urethane dimethacrylate compound (
I got ■.

b) Production of photosensitive element and formation of solder mask 40 parts of the urethane dimethacrylate compound obtained by the above method.

Methyl methacrylate/Φtetrahydrofurfuryl methacrylate/acrylonitrile/tribromophenyl acrylate (43/2/2015/30 weight ratio) copolymer (molecular weight approximately 150,000, glass transition temperature approximately 10)
0″C, bromine content 18 wt) 57 parts.

27 parts of benzophenone.

Mihiraketone 0.3 parts.

p-methoxyphenol 0.05 part.

Victoria Pure Blue 0.05 part.

Toluene 150 parts.

The same operations as in Example 2-b) and Example 2-C) were carried out using the solution of the photosensitive resin composition having the above formulation.

The finally obtained protective film showed no problems in a 10-minute immersion test in iso7'opanol, toluene, and trichlene 5110 aqueous hydrochloric acid solution, and was immersed in a solder bath at 255-265°C for 30 seconds, but peeled off. No changes such as cracks were observed. Furthermore, after soldering treatment similar to Example 1-C), MIL-8TD-202E'107D condition B
No cranking occurred even in a 50-cycle thermal shock test. Also, printed wiring board MCL-E- manufactured by Hitachi Chemical ■
A protective film was formed on the entire surface of the No. 68 1.6-inch thick base material in the same manner as above. This product satisfied UL's 94V-1 standard.

Example 8 1) Synthesis of urethane diacrylate compound Toluene (
Solvent) 1000 parts dilauric acid
1 part Tilttin (catalyst) Tetraethylene glycol 291 parts (3 tbsp) Methyl ethyl ketone (solvent) 200 parts C2-hydroxyethyl acetate 1160 parts (10 equivalents) Toluene acrylate (solvent) 200 parts p-methoxyphenol 0.2 part (heat Polymerization inhibitor) D Methanol 32 parts A solution of a urethane diacrylate compound was obtained using the above formulation in the same manner as in Example 1). after that.

Dry under reduced pressure to obtain a viscous urethane diacrylate compound (■
Got nine.

b) Production of photosensitive element Urethane diacrylate (2) obtained by the above method 47
Department.

Methyl methacrylate, methyl acrylate, acrylic! !
-tetrahydrofurfuryl methacrylate/diethyl methacrylate/tribromophenyl acrylate in 2-hydro) (43/10/21515/35 weight ratio) copolymer (molecular weight approximately 150,000, glass transition temperature approximately 90°C, bromine content 22 Weight-) 50 parts.

27 parts of benzophenone.

Michler Ketone 0.3 parts.

p-methoxyphenol 0.05 part.

Victoria Pure Blue 0.02 parts.

KAYAMERPA-2 (El Honkayaku #I), 9
0.1 part of divalent acrylate containing an acid group).

Methyl ethyl ketone 50 parts.

Toluene 100 parts.

Using a solution of the photosensitive resin composition with the above formulation.

A photosensitive element having a layer of photosensitive resin composition having a thickness of about 50 μm was obtained using the apparatus shown in FIG. 3 in the same manner as in Example 2-b).

C) Formation of a solder mask The nine photosensitive elements obtained above were applied to a printed wiring board for testing on which a steel pattern (steel thickness approximately 184 ffl) as shown in FIG. Lamination was carried out under reduced pressure. After lamination, it was left at room temperature for 3 hours, and 200 mJ/
Exposure was made with cyy+1.

After exposure, the film was heated at 80°C for 5 minutes, allowed to cool at room temperature for 20 minutes, the support film was peeled off, and the film was developed by spraying with 1,1,1-trifluorethane at 20°C for 70 seconds.

After development, the film was dried by heating at 80°C for 30 minutes, then heated at 120°C for 30 minutes, and then at 150°C for 30 minutes. After dispersing and cooling at room temperature for 10 minutes, it was irradiated with ultraviolet rays at 10 J/cns'' and further heat-treated at 130°C for 2 hours.

After forming the protective film in this manner, the test substrate was subjected to a 10-minute immersion test in Improper Tool, toluene, trichlene, or 10-hydrochloric acid aqueous solution at 25°C in the same manner as in Example 1-C). , there were no problems. Also 2
Even in a 30-second immersion test in a solder bath at 55 to 265°C, there was no peeling of the protective film, and the heat resistance was good. Furthermore, Example 1-C) and MIL-8TD-2 after soldering treatment
02E 107D Condition B: No cracks occurred even after 50 cycles of thermal shock test.

Even in the cross-sectional test, there was no peeling of the protective film.

Adhesion was excellent. In addition, a protective film was formed on the entire surface of the printed wiring board MCL-E-68 manufactured by Hitachi Chemical (O) and S (S) thick materials using the same procedure as above.

This product satisfies UL's 94V-1 standard.

Comparative Example 4 LDI-Mloo (lysine diisocyaner) in Example 1-1) was replaced with >1696 parts (16 equivalents).

A urethane diacrylate compound was synthesized using 1344 parts (16 equivalents) of hexamethylene diisocyanate and in the same manner as in Example 4) except for the following.

The produced urethane diacrylate compound (■) is insoluble in the reaction solvent, toluene, and can be separated into a waxy state as it is produced. The obtained urethane diacrylate compound (1) was sparingly soluble in methyl ethyl ketone and 1,1.1-)lychloroethane, but soluble in acetone and lyoform.
.

50 parts of the obtained urethane diacrylate compound.

47 parts of the nine copolymer used in Example 1-b).

27 parts of benzophenone.

Den Hiller Ketone 0.3 parts.

p-methoxyphenol O, OS part.

Victoria Pure Blue 0.02 parts.

Acetone 50 parts.

100 parts of chloroform.

Example 2-b)
Similarly, it was coated on a polyethylene terephthalate film using the apparatus shown in FIG. I can't get it.9. Further, when the copolymers used in Examples 2 to 8 were used, the compatibility was poor as in the above case, and a preferred photosensitive electrode element could not be obtained.

The photosensitive elements obtained using the photosensitive resin compositions described in detail in the Examples and explained in detail above are as follows:
It forms a Kuho-ji film with excellent heat resistance, cold shock resistance, and solvent resistance, and the formed protective film is suitable for solder masks that require long-term reliability.

Of course, the above is only one example of the photosensitive resin composition and photosensitive element of the present invention.

Various modifications and methods of use are possible without departing from the spirit of the invention.

[Brief explanation of drawings]

Fig. 1 shows the steel pattern of the test substrate used in the example, Fig. 2 shows the negative mask for the test used in the example, and Fig. 3 shows the photosensitive element manufacturing apparatus used in the example. This is a schematic diagram. Explanation of symbols 1... Copper pattern portion 2... Exposed portion of base material 3... Opaque portion of negative mask 4... Transparent portion of negative blue mask 5... Polyethylene terephthalate film drawing roll 6.7. 8...p-ru 9...knife 10...solution of photosensitive resin composition 11...dryer 12...polyethylene film<fl roll 13.
14... Roll 15... Photosensitive element winding roll 16...
Polyethylene terephthalate film 17...Polyethylene film Figure 1

Claims (1)

[Claims] 14a), (a) lysine diisocyanate, (b)
(c) 20 to 75 parts by weight of a urethane diacrylate compound or urethane dimethacrylate compound obtained by reacting a dihydric alcohol and (c) an acrylic acid monoester or a methacrylic acid monoester of the dihydric alcohol; (b) a glass transition temperature of about 40 -150℃ linear ^
A photosensitive resin composition comprising 20 to 75 parts by weight of a molecular compound and (C) a sensitizer or/and a sensitizer system that generates two volumes of free light upon activation of actinic light. 2. The photosensitive resin composition according to claim 1, wherein the linear polymer compound is a vinyl copolymerized linear polymer compound. Claim 1, wherein the linear polymer compound is a linear polymer compound containing up to 40 bromine atoms by weight.
The photosensitive resin composition according to item 1 or 2. Table Claims 1, 2 or 2, wherein the linear molecular compound is a linear polymer compound containing 5 to 65 weight grams of tribromophenyl acrylate or tribromophenyl methacrylate as a copolymer composition. The photosensitive resin composition according to claim 3, wherein the dihydric alcohols (b) and (c) are dihydric alcohols containing 1 to 23 carbon atoms. The photosensitive resin composition according to item 3 or item 4. & (b) The dihydric alcohol is selected from the group consisting of 1,4-butanediol, 1,3-butanediol, 1.5-bentanediol, L6-hexanediol and 1,4-cyclohexane dimetatool. Claims 1, 2, 3, and 4 which are dihydric alcohols
The photosensitive resin composition according to item 1 or item 5. 7. Acrylic acid monoester or methacrylic acid monoester of dihydric alcohol is a compound selected from the group consisting of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxyethyl methacrylate, Claim 1 Section, Section 2, Section 3, Section 4. The photosensitive resin composition according to item 5 or 6. & Urethane diacrylate compound or urethane dimethacrylate compound is 1×10 ~t5×10-' equivalent/
? Claims 1, 2, and 3 are urethane diacrylate compounds or urethane dimethacrylate compounds containing an acryloyl group or a methacryloyl group.
The photosensitive resin composition according to item 1, 4, 5, 6 or 7. Claims 1, 2 and 3 containing up to 9.5% antimony trioxide by weight. The photosensitive resin composition according to item 4, 5, 6, 7 or 8. 1α(1) Urethane diacrylate compound or urethane dimethacrylate obtained by reacting (a) lysine diisocyanate, (b) dihydric alcohol, and (c) acrylic acid monoester or methacrylic acid monoester of dihydric alcohol 20 to 75 parts by weight of a compound (b) 20 to 75 parts by weight of a linear polymer compound having a glass transition temperature of about 40 to 150°C and K (C) a sensitizer or (and) a sensitizer that generates free radicals by actinic light; A photosensitive element comprising a layer of a photosensitive resin composition containing a sensitizer system and a support film supporting the layer. 11. The photosensitive element according to claim 10, wherein the linear polymer compound is a vinyl copolymerized fused polymer compound. 11 $I-shaped bulky polymer compound A special linear polymer compound containing up to 40% by weight of bromine atoms 1
A photosensitive element according to claim 10 or 11. 11. Claims 10, 11, or 11, wherein the linear polymer compound is a linear polymer compound containing 5 to 65 weight of tribromophenyl acrylate or tribromophenyl methacrylate as a copolymer composition. The photosensitive element according to item 12. 14. The photosensitive material according to claim 10, 11, 12 or 13, wherein the dihydric alcohol in (b) and (c) is a dihydric alcohol containing 1 to 23 carbon atoms. sexual element. 11 (W) dihydric alcohol is from the group consisting of 1,4-butanediol, 1,3-butanediol, 1,5-bentanediol, 1,6-hexanediol and 1,4-cyclohexane dimetatool A photosensitive element according to claim 10, 11, 12, 13 or 14, which is a selected dihydric alcohol. 16. Acrylic acid monoester or methacrylic acid monoester of divalent arsul is a good compound selected from the group consisting of hydroxyethyl acrylate, hydrodiethyl methacrylate, hydroxypropyl acrylate, and hydroxyethyl methacrylate. The photosensitive element according to item 10, item 11, item 12, item 13, item 14, or item 15. 17. Urethane diacrylate compound or urethane dimethacrylate compound is 1×1O-1-45X10”
Claims 10 and 11 are compounds containing an acryloyl group or a methacryloyl group with an equivalent amount of
Section, Section 12. The photosensitive element according to item 13, 14, 15 or 16. 1 & Claims 10 and 11, wherein the photosensitive resin composition contains antimony trioxide at 5 gbt by weight.
, 12, 13, 14, 15, 16, or 17. 19. Claims 10, 11, 12, 13, 14, 15, and 15, comprising a peelable cover film laminated on a layer of photosensitive resin composition. The photosensitive element according to item 16, 17 or 18. 2α Claims 10, 11, and 12, wherein the layer of the photosensitive resin composition has a thickness of 20 to 200 μm.
Section 13, Section 14, Section 15, Section 16, Section 17,
The photosensitive element according to item 18 or 19.