JPS614038A - Novel photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a photoresist good in adhesion to a copper plate or the like and prevented from intruding plating by using a photopolymerizable compsn. consisting of a specified polymerizable non-gaseous unsatd. compd., a photopolymn. initiator, and a specified compd. CONSTITUTION:The intended photosensitive material consists of a non-gaseous unsatd. compd. which has at least one C=C double bond and is polymerizable with a photopolymn. initiator, the photopolymn. initiator, and a compd. represented by the formula in which X is 5-20C alkyl, cycloalkyl, 6-20C aryl, alkylaryl, or aralkyl; and Y is bivalent single- or double-bonded straight 2-3C or N or 6-14C aryl optionally substd. by 1-15C alkyl or aryl at the o- or p- position. The use of such a compsn. can improve close adhesion to a substrate, especially, copper, and prevent intrusion of plates, and it can be plated in various plating conditions. A printed circuit high in performance can be prepared with high reliability, and it can be used for printing ink and printing plates, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a novel photosensitive composition, and more specifically,
The present invention relates to a photopolymerizable composition with improved adhesion and plating resistance to substrates such as copper plates. As an application example of this composition,
Photoresist used to create printed wiring boards, etc.
Examples include solder resist.

[Conventional technology]

Methods of making printed wiring boards using photoresists are well known. First, a photoresist composition is coated or laminated on an image forming substrate such as a copper-clad laminate or a flexible copper-clad board to form a film, and then irradiation is performed with active light through a photomask. is polymerized and hardened. Next, the unexposed portions are dissolved and removed using a suitable developer such as an organic solvent or an alkaline aqueous solution to form a resist image. By performing various operations such as etching, copper plating, gold plating, and solder plating on this image forming substrate,
The copper surface that is not protected by resist is processed to create printed wiring boards.

At this time, when the adhesion between the resist and the substrate is sufficiently strong,
During etching, plating, and their pre-treatments, a processing solution permeates between the resist and the substrate, causing undercutting of the hardened resist, which tends to cause the resist to lift off the substrate. When such a phenomenon occurs, the edges of the resist are damaged due to etching, and the plating is peeled off (a phenomenon in which the plating extends to the bottom of the resist), resulting in loss of image lines and blurring of the image outline, which significantly reduces pattern accuracy. This will cause the product to be rejected.

For this reason, various adhesion aids have been developed. 0
Although it is disclosed in Japanese Patent Application Laid-open No. 9/77 and Japanese Patent Application Laid-open No. 33-70, etc., in recent years, plating methods and their pretreatment methods have become more diverse, and the conditions have become more severe. ,
Furthermore, the mounting density of electronic components and elements has been increasing year by year, and accordingly, printed circuit boards having increasingly finer and more complex wiring have been required.

For this reason, even the slightest amount of solder cannot be tolerated, as described above, such as the penetration of the processing solution and the lifting of the resist.
It has become. From this point of view, it cannot be said that the compositions disclosed in the publications cited above necessarily exhibit sufficient plating resistance.

[Problem that the invention seeks to solve]

Printed wiring boards created using the above process are exposed to light in order to avoid adhesion of solder to areas other than the desired parts when soldering components, and to protect the circuits on the surface of the wiring board. A solder resist is often applied. This solder resist) K is a material that remains on the product permanently, and solder bonding, which is immersed in a high-temperature solder bath, must not cause solder to bleed during the process. There is a high level of sexual need. It is known that it is effective to add adhesion aids such as those shown above to the solder resist, but there is a demand for adhesion aids with even higher performance.

Based on the above, as a result of intensive research, the present inventors have discovered a photopolymerizable composition that provides a photoresist that has high adhesion to metal substrates, especially copper surfaces, and does not cause problems such as plating peel-off during plating processing. Furthermore, it was confirmed that this composition is also effective for solder resists and shite.

[Failure to solve the problem]

The composition of the present invention comprises: (a) a non-gaseous unsaturated compound having at least one carbon-carbon double bond and capable of forming a polymer by means of a photoinitiator; initiator, (c
) A photopolymerizable composition comprising a compound represented by structural formula (T).

(Here, X is an alkyl group having 3 to 10 carbon atoms, S
- cycloalkyl group, aryl group having 6 to 5 carbon atoms,
an alkylaryl group, an alkyl group Y is unsubstituted,
or one or three carbons or nitrogens connected in a straight chain with a single or double bond, substituted with an alkyl group or aryl group having a total carbon number of 1 to 15, or a carbon number of 6 to 1I
(a covalent aryl group at the ortho or peri position of
CTT2-1-CH=CH-1-C=N-1-N=N-
1■ Specific compounds represented by structural formula (I) include /-
Phenyl-5-mercaptotetrazole, /-benzyl-5-mercaptotetrazole, /-cyclohexyl-
5-mercaptotetrazole, l-phenyl-comelcabutoimidazole, /-penzyl-comelcabutoimidazole, /-phenyl-mercabutimidazoline, l-phenyl-comelcabutopenzimidazole, l-phenyl-2-mercaptotriazole can be mentioned.

There is no limit to the amount of the compound represented by the structural formula CI+ (hereinafter referred to as compound I), but O, OS
Preferably from 2 to 1% by weight, and more preferably from 2 to 1% by weight.
I prefer 17. Furthermore, two or more types of compounds disclosed in the present invention may be used. Furthermore, the compound disclosed in the present invention, JP-A-5S-4 Left 9 Guku, JP-A-Sho! ;! r-A! 2
No. 02, Tokukai Sho&, 3-4. No. 2O2, Tokukai Sho Aid
-J/73! ; No., Tokukai Sho&A-471! :Dada, Tokukai Sho 4-A'/lg S, Toku Kai Shota r-ioor4t
Y issue, Tokukai Akira! ;7-/qco9'lA, 3- in Tokkai Sho
/2tl! Compounds disclosed in R9da publication etc. can also be used in combination.

These compounds specifically include phthalimide, phthalazine, indazole, acetoguanamine, benzoguanamine, monoazaindole, diphenylcarbazone,
．． Qd, −) rimercaptotrier, 7, f # /
<lk e 7- # II, -y- ep, yL
4y'l! can be mentioned.

The photoreactive composition is an ethylenically unsaturated compound (hereinafter referred to as
monomer] and a suitable binder thereto, the monomer has at least one carbon-carbon double bond, forms a polymer with a photoinitiator, is non-gaseous, and is resistant to atmospheric pressure. It has a boiling point of 700°C or higher.

Examples of such ethylenically unsaturated compounds are (meth)acrylic esters, (meth)acrylamides, allyl compounds, vinyl ether compounds, vinyl ester compounds,
These include cinnamic acid, maleic acid, fumaric acid, and their esters.

The (meth)acrylic acid ester is a polyhydric alcohol, poly(meth)acrylate (poly here refers to a compound higher than di(meth)acrylate), and the polyhydric alcohol is polyethylene glycol, polyfluorocarbon, etc. These include pyrene gelicol, neopentyl glycol, trimethylolpropane, pentaerythritol, butanediol, and trimethy4-ethane.

Moreover, urethane (meth)acrylate is mentioned as a preferable monomer. This is an addition product of (meth)acrylate or (meth)acrylamide having a hydroxyl group and a compound having one or more isocyanato groups.
These (meth)acrylates include -monohydroxyethyl (meth)acrylate, co-hydroxypropyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, dihydroxy-3-phenoxypropyl (meth)acrylate, etc. . Furthermore, as an amide, there is hydroxymethyl (meth)acrylamide.Furthermore, it has a hydroxyl group and a polyincyanate obtained by reacting a polyol such as polyethylene glycol or polypropylene gelicol with a diisocyanate in an amount more than the co-equivalent of the diisocyanate. Urethane (meth)acrylates obtained by reacting (meth)acrylates and the like are also effective.

Examples of compounds having two or more incyanato groups include hexamethylene diisocyanate, tolylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate, da, q'-diisocyanato diphenylmethane, etc. (Meth)acrylates and the like are detailed in Japanese Patent Application No. Shojt-za θaIIs. When these urethane (meth)acrylates are used,
It is noteworthy that the effect of the compound represented by structural formula (I) on plating resistance is further increased. In addition, monomers that can be used with phthalate include phthalic acid, adipic acid,
Diallyl esters of malonic acid, divinyl esters such as divinyl succinate, divinyl adipate, and divinyl phthalate, acid phosphooxydiethyl methacrylate, 3-chlorocoacid phosphoxyglobyl methacrylate, Corbis methacryloxyethyl phosphe-1, , Corbis acryloxyphosphate, cinnamic acid esters, maleic acid esters, fumaric acid esters, phenylmaleimide, and the like.

The amount of these monomers is preferably from 1 to 9 times (the same applies hereinafter), and more preferably from 20% to gθ, based on the weight of the entire composition.

There is no limit to the use of more than one of the above monomers.

Photoinitiators or sensitizers useful in photoreactive compositions may be those commonly used, but those suitable for polymerizing ethylenically unsaturated compounds include anthraquinone, λ-methylanthraquinone, coethylanthraquinone, etc. anthraquinone derivatives, benzoin, benzoin methyl ether,
These include benzoin derivatives such as benzine ethyl ether, thioxafure 1 conductors such as chlorothioxanthone and diisobrobylthioxanthone, benzophenone, phenanthrenequinone, and Michler's ketone (lI, 4/'-bis(dimethylamino)benzophenone). Although there is no limit to the amount of these photopolymerization initiators used, it is preferably θθ2 to 100, more preferably 01% to 10 cA.

It is also preferred that the composition of the present invention contains a thermoplastic organic polymer binder, such as '1''+
s″″″′f′1(tlNt!Ill”[+06B4c
If D is used, the combination will be determined automatically, but the binder used in the present invention is a vinyl such as polymethyl methacrylate, polystyrene, polyvinyl chloride, chlorinated polyethylene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, etc. Polymers and copolymers of monomers are preferred. In particular, when developing with an alkaline aqueous solution, copolymers of acrylic acid, methacrylic acid, itaconic acid, etc. are preferred. The amount used is preferably from left side to gθch, more preferably from 20 inches to LAθch. When using this composition as a solder resist, it is recommended not to use a binder or to use a small amount of binder.

In addition, polymerization inhibitors to prevent thermal polymerization of photoreactive compositions during storage, dyes and pigments to make the resist visible, pigments, photosensitive color change agents, plasticizers, and flame retardants may also be used. No problem. Examples of dyes include basic dyes such as Basic Pure Blue BO, Malachite Green, Victoria Blue, Brilliant Green GX, C, 1, Solvent Green, etc. , C,1, Solvent Blue J, C,1, Solvent Blue 36
Oil-based dyes such as

A method for forming a film of the photoreactive composition disclosed in the present invention on a substrate includes 1. coating a solution of the composition on a substrate; There is a method of drying, and a method of laminating the laminate obtained in step 17 of coating on a suitable film and drying on a substrate using a heating roll or the like. The latter laminate is generally referred to as a dry film, but it often has a structure in which a photosensitive composition is sandwiched between two layers of film, and when laminated onto a substrate, one film is peeled off while the other is removed. Laminate. This release film can be made of polyethylene, polypropylene, cellophane, or laminated with other films. ; There is a releasable film disclosed in Japanese Patent No. g-71190. The laminated resist is covered with another film called a support film, and generally a mask is placed on top of this film for exposure. Examples of the support film include films made of polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinyl chloride (IJ-Dene), polystyrene, polymethyl methacrylate, nylon, polyacrylonitrile, polyvinyl alcohol, and copolymers thereof. In particular, by using a material that dissolves in the developing solution used, it is possible to enjoy the advantages of automation of the process and no image floating during peeling, as disclosed in Japanese Patent Application Laid-Open No. 2002-17311.
It is disclosed in Publication No. 2.

The steps following the lamination of the photosensitive layer will be briefly described. That is, the support film is peeled off, if necessary, and imagewise exposed with actinic light through a halftone image, process negative, or positive. Next, add this to a suitable developer, such as an organic solvent.
/, /-) IJ chloroethane or the like, or an alkaline aqueous solution such as a sodium bicarbonate aqueous solution is used to remove the unexposed area and form an image pattern on the substrate. The exposed steel surface of this board is then melted using a solution such as ferric chloride, cupric ammonia, cupric chloride, or ammonium persulfate to form a copper image pattern, or solder plated. A typical process is to apply solder to the steel surface to form a solder pattern, but in the plating process, the steel surface is first chemically or electrochemically treated.
Copper plating using i4A- such as copper sulfate and pyrophosphoric acid, followed by solder plating.

〔Effect of the invention〕

By using the composition of the present invention, the adhesion to the substrate, especially the copper surface, was improved, and a significant improvement in plating damage was observed. Particularly noteworthy effects of the present invention are:
The fact is that the composition performs well under a variety of plating conditions. For example, typical copper plating methods include copper sulfate plating and copper pyrophosphate plating, and there are many methods for pretreating the substrate in the preceding stage, such as acid conditions, neutral conditions, and alkaline conditions. Conventional methods using adhesion aids show good results when plating under certain conditions, but under other conditions they often show very unsatisfactory results, making it difficult to choose a plating method. were often restricted. Furthermore, although the plating resistance is good, the adhesion of the photosensitive layer to the copper surface is insufficient, and the image lines flow during the development process.Chigi 4 □3! , t di□, wa, □ Atsue.

In contrast, the composition using multiple adhesion aids selected from the various compound groups disclosed in the present invention shows good results under a wide variety of plating conditions, broadening the range of conditions to choose from, and achieving higher plating conditions. It has become possible to create high-performance printed circuit boards with high reliability.

It should also be emphasized that the copper surface adhesive disclosed in this invention provides good effects on both organic solvent developed and alkaline aqueous developed types of dry film resists.

The basic life evaluation method for these various performances will be described in detail in the examples, but copper surface adhesion is measured by peeling off the photosensitive layer laminated on the copper surface using a tensile tester before exposure, and measuring the peeling force. It is obtained by measuring. In addition, regarding plating resistance, after forming the image, pre-plating treatment - Copper Metsukino.
After the damage is done, first, a visual inspection is performed to check whether there is any plating solution or plating metal in the resist area.

Furthermore, a tape peel test is performed to test for resist peeling. This tape peel test is an extremely harsh test.
Even if some peeling is observed, there is no problem in actual use. Of course, if higher reliability is sought, it is required that no peeling occurs at all.

Furthermore, when used as a solder resist, this composition is laminated on a printed circuit board by printing, coating, or a lamination method using a dry film, and is exposed to light directly or through a mask if necessary. Development is performed to form a hardened resist pattern. Thereafter, the terminals of the component were soldered by contacting them with a solder bath at, for example, 270° C. for about 10 seconds, and good results were obtained in terms of solder removal in this case as well.

Furthermore, this composition can be applied to the production of printing inks, printing plates, precision parts by photoetching, precision pattern plates, etc.

Examples are shown below.

〔Example〕

Reference example/ Hexamethylene diisocyanate 100 was added to a four-collar flask equipped with a dropping pot, a thermometer, and a stirrer.
g, dibutyltin dilaurate θ1-11 4 fots of methyl ethyl ketone were added, and while stirring, 2 ots of polyethylene glycol (average molecular weight θθ) was added dropwise over an hour. During this time, the temperature of the water bath and the dropping rate were adjusted so that the internal temperature did not exceed θ°C.

After further stirring at θ°C for 7 hours, cohydroxypropyl acrylate/3'lt was added dropwise so that the internal temperature did not exceed 1IO°C. Thereafter, after stirring at θ°C for 43 hours, methyl ethyl ketone of /309 was added to form a homogeneous solution. This mixture is called Nanatsuma/.

Reference Example/Reference Example/Tolylene diisocyaner) /7'lf and dry methyl ethyl ketone/!
Add 3f and dibutyltin dilaurate θ6gt,
6tx f pentaerythritol)
IJ acrylate (Aronix 1li4-305 manufactured by Toagosei Kagaku Kogyo ■) and! A mixed solution of methyl ethyl ketone was added dropwise so that the internal temperature did not exceed 35°C.

After the dropwise addition, stirring was continued for 30 hours at lIO°C, and it was confirmed in the infrared absorption spectrum that the characteristic absorption of the isocyanate group around 2270 on-' had almost disappeared. Next, methyl ethyl ketone at /rO9 was added. This mixture is called monomay.

Example 1 /θ0 as a solvent in a 300 ml separable flask
Add methyl ethyl ketone from Step 1, add qst of Delpetk θH (polymethyl methacrylate manufactured by Asahi Kasei Kogyo Co., Ltd.) as a binder, and heat to 0° C. to form a homogeneous solution. To this, 32 g of Monomer 7 prepared in Reference Example/ was added as a monomer, and further benzophenone 3? was added as an initiator. ,
Michlanuketone 0. Basic Pure Blue BO was added as a dye to prepare a homogeneous mixed solution.

The total amount of this solution is hereinafter referred to as a mixed solution.

After adding 7-phenyl-3-mercaptotetrazole OS to the mixture-1 and making it uniform, using a blade coater,
4 j ' m on 3 gμ polyethylene film
"#"*"L"CT"'10"1Se
y resist film is formed, -! A dry film registrar was prepared by laminating a μ-oriented polystyrene film onto the resist surface using a roller. Next, the polyethylene film was peeled off to the copper-clad laminate (glass epoxy board) prepared with this dry film resist, and then AL-7
Using a 00 type laminator (manufactured by Asahi Kasei Corporation), at 90℃
It was laminated under pressure. Three pieces of this laminate were created. One of the resist surfaces was cut into a width of 8 μm and the force required to peel the resist from the copper surface was measured at room temperature using an Instron universal tester. This value is defined as copper surface adhesion, but /
It was 200 f/2sm. Next, a mask in which 200 μm star lines were drawn at 1000 μm intervals was brought into close contact with the resist surface of the other laminated body, and exposure was performed using a high-pressure water lamp at an intensity of /θ0rrJ/−.

Next, development was performed with chlorocene to dissolve and remove the unexposed area (image area). After that, pre-plating treatment was performed under condition A (the contents of condition A are summarized in the notes at the end along with conditions B-F later) using a plating pre-treatment liquid and Shite "Nutra Clean C". After that, seven sheets were plated with copper sulfate (condition D), and the other seven sheets were plated with copper birophosphate (condition E). Next, after washing each board with water, solder plating (condition F) was performed. No plating was observed on the edge of the plated image (hereinafter referred to as appearance test). Next, a transparent adhesive tape was brought into close contact with the resist surface, and the tape was peeled off, but no peeling of the resist was observed (this test is hereinafter referred to as a tape peeling test).

Furthermore, tests were conducted combining various processing conditions.

The results are shown in Table 1.

Table 7 Comparative Example/A test sample was prepared using the liquid mixture-7 prepared in Example/in exactly the same manner as in Example/.

The adhesion strength to the copper surface was 1010972k, and no plating was observed in the cases where conditions A to F were performed, but in the tape peel test, the resist at the edge of the image line was Q! It was peeled off with a width of wx. Further conditions A-E-F
, B-D-F and B-E-F, the resist portions on both sides of the plated image were discolored, and plating was observed to fade. Furthermore, when a tape peeling test was conducted, most of the #1 resist portion between the images was peeled off.

Comparative Example 0.3-f of benzimidazole was added to the mixed solution-1, and the same test as in Example 1 was conducted. Copper surface adhesion is /θ
θ09/:lktrag. Further, Table 2 shows the appearance of the samples plated under each plating condition and the results of the tape peel test.

(The following is a blank space) =22- Comparative Example 3 The same test as in Example 1 was conducted by adding l-methyl-3-mercaptotetrazole of θS2 to the mixed solution -/. The adhesion to the copper surface was AOOt/2'rm, and the results of the plating test are shown in Table 3.

Table 3 Examples-~7. Comparative Examples q to 6 A3f methyl ethyl ketone was used as the solvent, 1IAf Delbet goN (manufactured by Mukasei Kogyo ■) was used as the binder, and the monomer co prepared in Reference Example q was used as the monomer.
Diisopropylthioxanthon f as a θ11 initiator
, methyl N,N-dimethylbenzoate l12, and Green C (manufactured by Mitsubishi Chemical Industries, Ltd.) as a dye were added at θ/2 to prepare a mixed solution in the same manner as in Example 1 (this is referred to as mixed solution-CO). . Various adhesive agents were added to this mixed solution = 2, and the same tests as in Example 1 were conducted. The results are shown in Table 1.

(Left below) Example g Ethyl acetate in SOI as a solvent, SO as a binder
2 Delvet 7θH (manufactured by Asahi Kasei Corporation), trimethylolpropane triacrylate qoy as a monomer
, penzophenone as an initiator? , Michler's ketone θ/! ft, Brilliant Green GX as dye
A mixed solution was prepared in the same manner as in Example 1 using o/f (this is referred to as mixed solution-3). After adding l-phenyl-2-J captotetrazole of θ5P and making it uniform, this mixture was applied to a polyethylene terephthalate film of Sμ using a blade coater, and the mixture was heated at 60°C for 30 minutes.
Dry for θ minutes to form a resist film with a thickness of 3Sμ, and
A μ polyethylene film was attached. This is 10
The same operations and tests as in Example 1 were performed except that the lamination was carried out under pressure at 0°C. The adhesion force to the copper surface was goθf7.23wm.

Table 5 shows the results of testing under each plating condition.

Comparative example 7. θIf to mixed solution-3 prepared in the same manner as in Example g.
A test similar to that in Example was conducted by adding benzotriazole and l-methyl-comelkabutotetrazole. Comparative examples of each are given as g.

The adhesion strength to the copper surface was θOf/koS■ in both cases, and the results of the plating test were as shown in Table 6.

(Leaving space below) Reference Example 3 Add 100-liter water at 60°C to a 1-liter separable flask, add 1-liter salt and methylcellulose (Metrose 8H90-/θ0, manufactured by Shin-Etsu Chemical Co., Ltd.) After dissolving by and making it homogeneous, add ice water of tθθ-. Raise the internal temperature to 60°C again and add styrene 52, methyl methacrylate/gOf, methacrylic acid 7si r, <z, +
Add a homogeneous mixture of '-azobisisobutyronitrile 13 and continue stirring at /30 rpm. The mixture was stirred at 60°C for 7 hours, further reacted at 70°C for 1 hour and at 0°C for 1 hour, poured into a sieve of θO mesh, thoroughly washed with warm water, and dried with hot air at -109°C. Obtained beads. This polymer is P-,? It is called.

Example 9 In a 300-ml separable flask, 100 f of Ingropanol and P-3 prepared in Reference Example 3 were added.

f, trimethylolpropane triacrylate as mo/mer 2! ;t, tetraethylene glycol cyacrylate 1-/jS', benzophenone 3 as an initiator, Michler's ketone 0.2t, green C as a dye.
Add O/39 to make a homogeneous solution. Mix this solution with -
It is called t. Add ay-y/-phenyl-comercaptotetrazole as a copper surface adhesive to this mixture,
After making it uniform, this solution was applied to a polyethylene terephthalate film of CoSμ using a blade coater, and 6
After drying at 0° C. for 30 minutes to form a resist film with a thickness of lIoμ, a 2Sμ polyethylene film was stretched over the resist film. Next, a resist was laminated on the copper-clad laminate at 703° C. using a pressure roll while peeling off the polyethylene film. Next, the film was exposed to light through a mask in the same manner as in Example 1, and the polyethylene terephthalate film was peeled off. After that, it was developed with a flathead IJium carbonate aqueous solution, washed with water, treated with aHb diluted hydrochloric acid, washed with water, and dried. I did this. Next, plating was performed under the combination of Condition 1 B, Condition D, and Condition F, but no abnormality was found in the appearance test, and peeling was only observed here and there in a tape peeling test with a width of 60 to 13[theta][mu].

Example 10 The same operations and tests as in Example D were carried out except that 13v monomer was used in place of tetraethylene glycol diacrylate. In the tape peel test, gθ~/2θμ
Only peeling was observed in some places along the width.

Comparative Example The same operations and tests as in Example t were carried out, except that a copper surface adhesive was added. In the tape peel test, koSO~, 300μ
Continuous peeling of the resist was observed over a width of .

31 Example // Epoxy ester 3002A (manufactured by Kyoeisha Yushi) θt and trimethylolpropane triacrylate 13f and 2
72/-phenyl-5-mercaptotetrazole was added to a mixed solution consisting of -hydroxyethyl methacrylate trf Exposure was carried out at Ik00mJ/aA using a high-pressure water lamp.

After exposure/I made a cross cut of IO x IO with a ■ width and performed a tape peeling test, but all 100 squares did not peel off and disappeared. Also, 2 other parts! ；Ni'c's solder bath/
Although the resist surface was brought into contact with liquid, no blistering was observed on the resist surface.

Comparative example i.

The same test as in Example 1 was conducted using the mixture-j prepared in Example 1. Among the 100 cross-cut squares, the gs portion peeled off, and blistering of the resist was observed after contact with the solder bath.

Remarks: The plating pretreatment conditions and plating conditions in Examples and Comparative Examples are as follows. However, there are cases in which washing with water and drying steps are added after the process, and such cases are simply indicated by (WD).

Condition A: Manufactured by Shitubley Far East Co., Ltd. [Nutra Clean CJ 2. Immersed in t% aqueous solution at 110°C for 3 minutes (WD).

Condition B: Manufactured by MacDamid Co., Ltd. [LkBJ] After immersion in a 30% aqueous solution at θ°C for 3 minutes (WD), immersion in a /s% ammonium persulfate aqueous solution for 7 minutes (WD), and further immersion in 2% dilute sulfuric acid for 1 minute (WD) .

Condition C: After electrolytic degreasing (WD) at 50°C for 1 minute in a Tachi aqueous solution of "Oakite 9O" manufactured by Diafloc, at a current density of 1/dd, 1 min in a 73% ammonium persulfate aqueous solution.
Immersed for 4 minutes (WD) in IIC, 10% diluted sulfuric acid.Condition D: Copper sulfate conc. made by Japan Metal Finishing Co., Ltd. in 9% sulfuric acid.
．． Plating is carried out at room temperature for 30 minutes at a current density of Qj A/d WI' in a plating solution diluted by a factor of A (WD).

Condition E: S of “Piroton Conch” manufactured by Barshaw Gyoda
O in ice water solution! kA/cllil for 30 minutes at f6℃
Plating is performed at a current density of (WD).

Condition F: Solder plating liquid manufactured by Makdamatsud Co., Ltd. (tin/lead =
10 at a current density of 1.2 A/dl11' using
Plating is performed for a minute (WD).

Claims (1)

[Claims] (1) (a) a non-gaseous unsaturated compound having at least two carbon-carbon double bonds and capable of forming a polymer with a photoinitiator; (b) a photopolymerizable compound that can be activated by actinic light; A photopolymerizable composition comprising: an initiator; (c) a compound represented by structural formula (I); ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) (where, X is an alkyl group having 5 to 20 carbon atoms, a cycloalkyl group, an aryl group having 6 to 20 carbon atoms, an alkylaryl group, an arylalkyl group, Y is unsubstituted, or substituted with an alkyl group or aryl group having a total of 1 to 15 carbon atoms, 2 or 3 carbons or nitrogen connected in a straight chain with a single or double bond, or 6 to 15 carbon atoms (Divalent aryl group at ortho or peri position of 14)