JPS616646A - Novel photosensitive composition - Google Patents

Abstract

PURPOSE:To obtain a photopolymerizalbe composition having a high adhesive property and giving a photoresist by blending a nongaseous unsatd. compound with a photopolymn, initiator and a mixture of compounds selected out of at least two groups of compounds among groups of compounds represented by specified formulae. CONSTITUTION:A photopolymerizable composition is composed of a nongaseous unsatd. compound (a) having at least two carbon-carbon double bonds and capable of forming a polymer in the presence of a photopolymn. initiator, the photopolymn. initiator (b) which can be activated by active light,and a mixture (c) of compounds selected out of at least two groups of compounds among groups of compounds represented by formulae I -III. A thermoplastic org. polymer binder (d) may be added. The compounds represented by formulae I -III include 1- pheny-2-mercaptoimidazoline, thiadiazoles such as 3,5-dimercapto-1,2,4-thiadiazoles, and sulfenamides such as N-cyclohexyl-2-benzothiazylsulfenamide, respectively.

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. Application examples of this composition include photoresists, solder resists, etc. used in the production of printed wiring boards, etc. [Prior Art] Methods for producing 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, and solder plating on this image forming substrate, the copper surface not protected by the resist is processed to create a printed wiring board. At this time, if the adhesive strength of the resist substrate is not strong enough, the processing solution may leak during etching, plating, or their pretreatment.
It penetrates between the resist substrate and undercuts the hardened resist, causing a phenomenon in which the resist lifts up from the substrate. When such a phenomenon occurs, the edge of the resist will be damaged due to etching, and the plating will peel off (a phenomenon in which the plating extends to the bottom of the resist), leading to loss of image lines and blurring of the image outline, resulting in poor pattern accuracy. This results in a significant decrease in the quality of the product, resulting in a rejected product. For this reason, various adhesion aids have been developed, and
This method is disclosed in Japanese Patent Application Laid-Open No. 53-702, etc. [Problems to be Solved by the Invention] However, in recent years, plating technology and especially its pretreatment methods have become more diverse, and conventional compositions have poor adhesion to copper surfaces and poor plating resistance due to harsher conditions. At present, there are few methods that give satisfactory results. Printed wiring boards created using the above process include:
When soldering components, a photosensitive solder resist is often applied to prevent solder from adhering to areas other than desired areas and to protect circuits on the surface of wiring boards. This solder resist has a high degree of adhesion properties because it is a material that permanently remains on the product, and the soldering process involves soaking it in a high-temperature solder bath, so no solder leakage should occur. I have a request. It is known that it is effective to add adhesion aids as shown above to the solder resist for this purpose.
Furthermore, a high-performance adhesion aid is required. As a result of intensive research with the above in mind, the present inventors have discovered that a photopolymerizable photoresist provides a 7-to-resist that has high adhesion to metal substrates, especially copper surfaces, and does not cause problems such as plating peel-off during plating processing. The composition further comprises:
It was confirmed that it is also effective as a solder resist. [Means for Solving the Problems] The composition disclosed in the present invention comprises (a) an unsaturated exhaust gas having at least two carbon-carbon double bonds and capable of forming a polymer with a photopolymerization initiator; compound, (b) a photopolymerization initiator that can be activated by actinic light, (C) structural formula (1),
A photopolymerizable composition consisting of a mixture of nine compounds selected from at least two of the compound groups represented by (It) and (To), and optionally (d) heating. Add the plastic organic polymer binder ÷ (where ■ 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, and W is unsubstituted or completely Alkyl group having 1 to 15 carbon atoms, aryl group substituted with 2 or 3 carbons or nitrogens connected in a straight chain with a single bond or double bond, or in the ortho or peri position of 6 to 14 carbon atoms With divalent a or -N=C, -te, Ct
, Ct it are both bonded to carbon technology, and C, is N
Combine with. Xr, X! is hydrogen or R1 is hydrogen or R1 is hydrogen, R1 amino group, mercapto group, phenyl group, X? is hydrogen, R or phenylA4, and R is an alkyl group having 1 to 8 carbon atoms. ) chloroalkyl group, Yat'iR,
cycloalkyl group, Y4 is R, -f), and R is an alkyl group having 1 to 8 carbon atoms. ) The groups of compounds represented by structural formulas (1), (ff) and (sand) are referred to as Group 11 Group ■ and Group ■, respectively. In Group I, V is an aryl group having 6 to 14 carbon atoms, arylalkyl A group is preferable, and w is -C
H, -cn, -1-CH=CH-, -C=N-1 Specific compounds represented by structural formula (1) include 1-
Phenyl-5-mercaptotetrazole, 1-benzyl-5-mercaptotetrazole, 1-Schiftetrazole-
5-mercap) 7-trazole, 1-phenyl-2-mercaptoimidazole, 1-benzyl-2-mercaptoimidazole, 1-phenyl-2-mercaptoimidacillin, and the like. In the group, Xr and Xs are preferably hydrogen or a methyl group, and X is preferably hydrogen or an acetyl group. with people

[7] Hydrogen, a methyl group, an amino group, and a carboxyl group are preferable, and hydrogen, a methyl group, and a phenyl group are preferable. Furthermore, as K Furthermore, R is preferably an alkyl group having 1 to 6 carbon atoms. Preferred compound names included in Group M are specifically 2-mercaptothiazoline, 5,5-dimethyl-2-mercaptothiazoline, 4-methoxycarbonyl-5,5-dimethyl-2-
Mercagtothiazolines such as Mercagtthiazoline, 2-
Mercaptothiazole, 2-mercapto-4-methylthiazole, 2-mercapto-4-phenylthiazole,
2-mercaptothiazoles such as 2-mercapto-4,5-dimethylthiazole, 5-amino-2-mercaptothiazole, 2-mercapto-5-phenyl-1,3,4
-thiadiazole, 2,5-dimercapto-1,3,4
-thiadiazole, 5-avanor-2-mercapto-1,
3,4-thiadiazole, 5-methylamino-2-mercapto-1,3,4-thiadiazole, 5-methyl-2
-mercapto-1,3,4-thiadiazole, 3-phenyl 5-mercapto-1,2,4-thiadiazole, 3
, 5-dimercap) -1,2,4-thiadiazole and other thiadiazoles. Among these, mercaptothiazolines are more preferred. In group ■, Yl is a benzothiazyl group, a morpholif group, Y! , Yl is preferably hydrogen, methyl group, ethyl group, globyl group, butyl group, t-butyl group, cycloalkyl group, Y4 is preferably a methyl group, morpholino group, etc., and Y is particularly preferably -8Y. Further, R is preferably an alkyl group having 1 to 8 carbon atoms. Specific names of compounds included in group ■ include cyhenzothiazyl disulfide, 2-(4-morpholinodithio)
Disulfides such as benzothiazole, N, N-shefk
-2-benzothiazylsulfenamide, mido, N, N-tetravir-2-benzothiazylsulfenamide,
N,N-dicyclohexyl-2-benzothiazylsulfenamide)', N-t-butyl-2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N- Sulfenamides such as cyclohexyl-2-benzothiazylsulfenamide,
Further examples include 2-(S-methylmercapto)benzothiazole, among which disulfides are particularly preferred. Group 1. There is no limit to the total amount of the compounds selected from II and (2), but it is preferably 0.05 to 5% by weight, more preferably 0.2 to 2% by weight, based on the total composition. Moreover, two or more types of compounds from each group disclosed in the present invention may be used. Furthermore, the compound disclosed in the present invention, JP-A-55-65947, JP-A-55-65202, JP-A-55-65203-9, JP-A-56-51735,
JP 56-67844, JP 56-67845, JP 58-100844, JP 57-1929
Compounds disclosed in publications such as No. 46 and JP-A-53-124594j can also be used in combination. Specific examples include phthalimide, 7-talazone, indazole, acetoguanamine, benzoguanamine, monoazaindole, diphenylcarbazone, 2,4.6-)rimercaptotriazine, thiobarbital acid, and thiohydantoin. The photoreactive composition is an ethylenically unsaturated compound (hereinafter referred to as
monomer) and a suitable binder thereto, the monomer has at least two carbon-carbon double bonds, forms a polymer with a photoinitiator, is non-gaseous, and is resistant to atmospheric pressure. and has a boiling point of 100°C or higher. Examples of such ethylenically unsaturated compounds are (meth)acrylic acid esters, (methaneacrylamide, allyl compounds, vinyl ether compounds, vinyl ester compounds, cinnamic acid, maleic acid, hexamaric acid and esters thereof, etc.). (Meth)acrylic acid esters include polyhydric alcohols such as poly(meth)acrylates (poly here refers to compounds greater than di(meth)acrylates),
Polyhydric alcohols include polyethylene glycol, polypropylene glycol, neopentyl glycol, trimethylolpropane, pentaerythritol, butanediol, and trimethylolethane. Moreover, urethane (meth)acrylate is mentioned as a preferable monomer. This has a hydroxyl group (meta)
It is an addition product of acrylate or (meth)acrylamide and a compound having two or more incyanato groups, and these (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , polyethylene glycol mono(meth)acrylate, 2-hydroxy-3-phenoxyprobyl (meth)acrylate, and the like. Furthermore, as an amide, there is hydroxymethyl (meth)acrylamide. Furthermore, urethane (meth)acrylate obtained by reacting a polyisocyanate obtained by reacting a polyol such as polyethylene glycol, polypropylene glycol, etc. with a diisocyanate of twice or more equivalent amount and a (meth)acrylate having a hydroxyl group. etc. are also valid. Examples of compounds having two or more incyanato groups include hexamethylene diisocyanate, tolylene diisocyanate, inphorone diisocyanate, xylylene diisocyanate, 4,4'-diisocyanate diphenylmethane, and urethanes of these. (Meth)acrylates and the like are detailed in Japanese Patent Application No. 80445/1983. When these urethane (meth)acrylates are used,
It is noteworthy that the effect of the compound represented by structural formula (1) on plating resistance is further increased. Further examples of salts that can be used include phthalic acid, adipic acid,
Diallyl esters such as malonic acid, divinyl esters such as divinyl succinate, divinyl adipate, and divinyl phthalate, acid phosphoxydiethyl methacrylate, 3-chloro-2-acid phosphoxypropyl methacrylate, 2-bismethacryloxyethyl phosphate, -bisacryloxyphosphate, cinnamate esters, maleate esters, fumarate esters,
There are phenylmaleimide, etc. The amount of these monomers is preferably 10 to 99 by weight based on the total composition, and K is 20
There is no restriction on the use of two or more monomers having a preferable value of % or sob of 0 or more. Photopolymerization initiators or sensitizers useful for photoreactive compositions may be those commonly used, but ethylenic initiators or sensitizers may be used. Those suitable for the polymerization of saturated compounds include anthraquinone, anthraquinone derivatives such as 2-methylanthraquinone and 2-ethylanthraquinone, benzoin, benzoin derivatives such as benzoin methyl ether and benzoin ethyl ether, chlorthioxanthone,
Thioxanthone derivatives such as diisoprobyl thiogysanthone, benzophenone, phenanthrenequinone, Michler's ketone (4,4'-bis(dimethylamino)benzophenone), etc. There is no limit to the amount of these photopolymerization initiators used, but it is preferably 0.02% to 15%, more preferably 0.1%.
It is between 1 and 10. Preferably, the composition of the present invention contains a thermoplastic organic polymer binder, which is compatible with the ethylenically unsaturated compound.
The combination is determined naturally, but the binder used in the present invention is a polymer or copolymer of vinyl monomers such as polymethyl methacrylate, polystyrene, polyvinyl chloride, chlorinated polyethylene, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. is 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 5% to 80cm,
More preferably, it is 20% to 60%. When using this composition as a solder resist, it is recommended that no binder be used or that a small amount of binder be used. In addition, polymerization inhibitors to prevent thermal polymerization during storage of the photoreactive composition, dyes, pigments, photosensitive color change agents, plasticizers, flame retardants, etc. to make the resist visible may also be used. No problem. Here, as a dye, for example, basic dye
Pure Blue BO. Basic dyes such as Malachite Green, Victoria Blue, Brilliant Green α, C, 1, Solvent, etc.
Clean 3, C, 1, Solvent Blue 21, C) ■
and oil-based dyes such as Solvent Blue 36. The method of forming a film of the photoreactive composition of the present invention on a substrate includes a method of applying a solution of the composition onto a substrate and drying it;
There is a method in which a laminate obtained by coating on a suitable film and drying is laminated on a substrate using a heated roll or the like. The latter laminate is generally referred to as a dry film, but many books have a structure in which a photosensitive composition is sandwiched between two layers of film, and when laminating on a substrate, one film must be removed. Laminate while peeling. This release film may include polyethylene, polypropylene, cellophane, films laminated with other films, and
There are peelable films disclosed in Japanese Patent Application No. 76190. The laminated resist is covered with another film called a support film, and generally a mask is placed on top of this film and exposed. This supporting film includes polyethylene terephthalate, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polystyrene, polymethyl methacrylate,
Examples include films made of polyamide, polyacrylonitrile, polyvinyl alcohol, and copolymers of these, but in particular, using materials that dissolve the developer used can help automate the process and prevent image lifting during peeling. It is disclosed in JP-A-54-18732 that the advantages can be enjoyed. 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 to actinic light through a halftone image, process negative, or positive. Next, this is mixed with a suitable developer such as an organic solvent of 1,1
．． 1-) An image pattern is formed on the substrate by removing the unexposed portion using lychloroethane or the like, or an aqueous alkali solution such as a sodium bicarbonate solution. Then, the exposed copper surface of this substrate is dissolved using a ferric chloride solution, cupric ammonia solution, cupric chloride solution, ammonium persulfate solution, etc. to form a copper image pattern, or solder plating is applied. The typical process is to form a solder pattern, but in the plating process, the copper is first subjected to chemical or electrochemical treatment, then copper plating using copper sulfate, pyrophosphoric acid, etc. Solder plating is performed, and 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 penetration was observed. Particularly noteworthy as an effect of the present invention is the fact that the present composition achieves good results under various plating conditions. For example, typical copper plating methods include copper sulfate plating and copper birophosphate plating, and the pretreatment methods for the substrate in the previous stage include acid conditions, neutral conditions,
There are various methods such as 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 was good, the adhesion of the photosensitive layer to the copper surface was insufficient, and in some cases, undesirable phenomena such as image lines flowing during the development process were observed. [Effects of the Invention] On the other hand, the composition disclosed in the present invention using a plurality of adhesion aids selected from nine different compound groups shows good results under many plating conditions, and the range of conditions selection is wide. This has made it possible to create higher-performance printed circuit boards with higher reliability. Also noteworthy is the surprising fact that when multiple copper surface adhesives are used as disclosed in the present invention, greater adhesion to the copper surface is exhibited than when each component is used alone. It is. Furthermore, it should be emphasized that the copper surface adhesive disclosed in the present invention provides good effects on both organic solvent developed and alkaline aqueous developed types of dry film resists. The basic evaluation method of these various performances will be described in detail in the examples, but the adhesion to the copper surface was measured by peeling off the photosensitive layer laminated on the copper surface using a tensile tester before exposure. Required for measuring force. Regarding plating resistance, after forming an image and performing plating pre-treatment - copper metal key solder plating, the presence or absence of plating liquid and plating metal in the resist area is checked by visual inspection. Furthermore, a tape peel test is performed to test for resist peeling. This tape peeling test is an extremely severe test, and 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 printed, coated, or laminated using a dry film, and then laminated onto a printed circuit board and exposed directly or, if necessary, through a mask. Development is performed to form a hardened resist pattern. Thereafter, the terminals of the components were soldered by contacting them with a solder bath at 250° C. to 270° C. for several seconds, for example, and good results were obtained in terms of solder penetration 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 1 Tolylene diisocyaner (tolylene diisocyaner) 174 t was placed in a 2-volume four-cylinder flask equipped with a dropping pouch, a thermometer, and a stirrer.
Add 153% of dry methyl ethyl ketone and 0.8f of dibutyltin dilaurate, and add 656% of dry methyl ethyl ketone while stirring.
pentaerythritol triacrylate of f (Aloex M-305 manufactured by Toagosei Chemical Industry Co., Ltd.), and
A mixed solution of 0f methyl ethyl ketone was added dropwise so that the internal temperature did not exceed 35°C. Stirring was continued for 30 hours at 40° C. after the dropwise addition, and it was confirmed in the infrared absorption spectrum that the characteristic absorption of the isocyanate group near 2270 os−′ had almost disappeared. Next, 150
t of methyl ethyl ketone was added. This mixture is called Monomer 1. Reference Example 2 Into the 94 flask used in Reference Example 1, hexamethylene diyne cyanide (100F) and dibutyltin dilaure (100F) were added.
After stirring 0.12 f methyl ethyl ketone 40P, 20 f polyethylene glycol (average molecular weight 200) was added dropwise over 2 hours. During this time, the temperature of the water bath and the dropping rate were adjusted so that the internal temperature did not exceed 40°C. After further stirring at 40°C for 1 hour, 2-hydroxyethyl acrylate 13
4F was added dropwise so that the internal temperature did not exceed 40°C. Thereafter, after stirring at 40°C for 48 hours, 130f of methyl ethyl ketone was added to form a homogeneous solution. This mixture is called Monomer 2. Example 1 100f as a solvent was added to a 300mm separable flask.
methyl ethyl ketone was added as a binder, and polymethyl methacrylate (DELPERA) 8ON (manufactured by Asahi Kasei Kogyo C Co., Ltd.) was added thereto as a binder, and the mixture was heated to 70°C to form a homogeneous solution. Here, monomer 1 prepared in Reference Example 1 was used as a monomer of 68
．． 6 F plus benzophenone 39 as an initiator.
．． Michler's Ketone 0.1? A uniform mixed solution was prepared by adding 0.1 f of Basic Pure Flu BO as a dye. The total amount of this solution is hereinafter referred to as mixed solution-1. Mixed liquid-1 contains 0.15f of 2-mercaptothiazoline,
0.25 1-phenyl-5-mercaptotetrazole
? After adding it evenly, use a blade coater to coat it with 38μ
Coat this mixed solution on a polyethylene film and heat it at 60°C.
The resist was dried for 30 minutes to form a resist film with a thickness of 50 μm, and a 25 μm oriented polystyrene film was laminated onto the resist surface using a roller to prepare a dry film resist. Next, the polyethylene film was peeled off from the copper-clad laminate (glass epoxy board) prepared with this Dora/F film resist, and then the film was pressed at 90°C using an AL-70011 laminator (manufactured by Asahi Kasei Corporation). Laminated. Three pieces of this laminate were created. One of the resist surfaces was cut at 25 wm QK using an Instron universal tester, and the force required to peel the resist from the copper surface was measured at room temperature. This value is defined as the copper surface adhesion force, and is 900 f
/ 25 dew. Next, a mask in which positive lines of 200 μm were drawn at intervals of 1000 μm was brought into close contact with the resist surfaces of the other two laminates, and exposure was performed using a high-pressure mercury lamp at an intensity of 100 mJ/−. Next, development was performed with 1 chlorocene to dissolve and remove the unexposed area (image area). After that, after performing plating pretreatment under condition B using "L-5B'" as the plating pretreatment liquid (the contents of this condition are shown with a note (-) at the end along with other conditions A-F). , one sheet is copper sulfate plated (condition D), the other sheet is copper pyrophosphate plated (condition E).
) was carried out. Next, each plate was washed with water and solder plated (condition F). No plating was observed at the edge of the plated image. Next, the transparent adhesive tape was tightly adhered to the resist surface, and when the tape was peeled off, it was found that both sides of the image line were only peeled off in places with a width of 50-120μ (this test is hereinafter referred to as tape peeling test). ). Examples 2 to 7 Each test was conducted in the same manner as in Example 1 by adding a copper surface adhesive as shown in Table IK to the mixed solution-1 prepared in Example 1. The results are shown in Table 1. Comparative Example 1 A test sample was prepared in exactly the same manner as in Example 1 using the mixed liquid-1 manufactured by Allil in Example 1. The adhesion force to the copper surface is 80 f725m, condition B - condition D
- In the case where the operation under condition F was performed, no plating was observed, but in the tape peeling test, the resist at the edge of the image was peeled off in a width of 250 to 300 μ in some places. Further, in the case where the operations under conditions B-E-F were performed, the resist portions on both sides of the plated image were discolored, and plating stains were observed. Furthermore, when a tape peeling test was conducted, most of the resist portions between the images were peeled off. Comparative Example 2 A test similar to Example 2 was conducted by adding 0.5 f of benzotriazole to Mixed Liquid-1. Copper surface adhesion strength is 90 (1
It was f/25 m. Further, Table 2 shows the appearance of the samples plated under each plating condition and the results of the tape peel test. Table 2 Examples 8 to 10, Comparative Example 3 639 methyl ethyl ketone as the solvent, 40F Delpet 70H (manufactured by Asahi Kasei Corporation C) as the binder
, Monomer 2 prepared in Reference Example 2 was used as a monomer at 92
Diinpropylthioxanthone 2F7 as f1 initiator
! , N,N-dimethylbenzoate methyl 42, and 0.15 F of Green C (manufactured by Mitsubishi Chemical Corporation C Co., Ltd.) as a dye were added to prepare a mixed solution in the same manner as in Example 1 (this was mixed with mixed solution-2). ). 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 3. Reference Example 3 To a separable flask with a capacity of 2, add 600 - 60°C water, add 12 f of common salt and methyl cellulose (Shin-Etsu Chemical Co., Ltd. "Metrose" SH90-100) 6 f
Dissolve it and add 600ml of ice water after it becomes homogeneous. Raise the internal temperature to 60°C again, Styrene 452, Methyl methacrylate 180F, Methacrylic acid 752.4-4'-
Add a homogeneous mixture of 1.5 f of azobisisobutyronitrile and continue stirring at 150 rpm. Stir at 60°C for 1 hour, react at 70°C for 2 hours, and at 80°C for 1 hour, pour into a 400 mesh sieve, wash thoroughly with warm water, and dry with hot air at 80°C to obtain a 280r piece. Ta. This polymer is designated P-3. Example 11 300111/! In a separable flask, 1002 isopropanol, 502 P-3 prepared in Reference Example 3,
trimethylolpropane triacrylate 25P1 as a 7-mer; tetraethylene glycol cyacrylate 15; benzophenone 31° as an initiator;
- Zuketone 0.2F, green C0.15F as dye
Add to make a homogeneous solution. This solution is called mixed solution-3. Add 0.3F 2-[N
-morpholinomercaptocobenzothiazole and 0.2f
After adding 1-phenyl-5-mercagtoteto disol and making it uniform, this solution was applied to a 25μ polyethylene terephthalate film using a blade coater.
After drying at 0° C. for 30 minutes to form a resist film with a thickness of 40 μm, a 25 μm polyethylene film was laminated thereon. Next, while peeling off the polyethylene film, a resist was laminated on the copper-clad laminate at 105° C. using a pressure roll. 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, development was performed with a 2-liter aqueous sodium carbonate solution, followed by washing with water, treatment with 0.5% diluted hydrochloric acid, washing with water, and drying. . Next, plating was carried out under the combination of Condition B - Condition 1 Condition F, but there was no abnormality in the appearance test, and the tape peeling test showed 50 to 1
Only peeling was observed here and there at a width of 00μ. Example 12 25 in place of tetraethylene glycol diacrylate
The same operations and tests as in Example 11 were performed except that monomer 1 of f was used. 70-100μ in tape peel test
Only peeling was observed here and there along the width. Comparative Example 4 Same operation as in Example 1 except that copper surface adhesive was not added.
I conducted a test. 250-300μ in tape peel test
Continuous peeling of the resist was observed over a width of . Example 13 Epoxy ester 3002A (manufactured by Kyoeisha Yushi) 40f
and trimethylolpropane triacrylate 45f and 2
0.52 of 2-(4'-morpholino
dithio)benzothiazole and 0.52 1-phenyl-
Add 5-mercaptotetrazole, apply it to a thickness of 40μ on a copper-clad laminate, and apply 1500mJ/c using a high-pressure mercury lamp.
j exposure was performed. After exposure, a 10 x 10 cross cut was made with 1 sieve width and a tape peeling test was performed.
All 00 squares did not peel off. Further, other parts were brought into contact with a solder bath at 255° C. for 15 seconds, but no blistering on the resist surface was observed. Comparative Example 5 The same test as in Example 10 was conducted using Mixed Liquid-4 prepared in Example 13. Out of 100 cross-cut squares, 85 were 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. Condition A: Immersed in a 25% aqueous solution of "Nutra Clean C" manufactured by Silapray Far East Co., Ltd. at 40°C for 3 minutes. Condition B;
After immersion at 0°C for 3 minutes, 15 ammonium thipersulfate aqueous solution K
Immerse for 1 minute, then 2 minutes in 2% dilute sulfuric acid. Condition C: After electrolytic degreasing in a 50% aqueous solution of Diafloc's "Okite 90" at 50°C for 2 minutes at a current density of 4A/dm, electrolytic degreasing was carried out in a 15% ammonium persulfate aqueous solution for 1 minute, and then in a 20% dilute sulfuric acid solution for 2 minutes. Condition D: Plating was carried out at room temperature for 30 minutes at a current density of 2.5 A/d- in a plating solution prepared by diluting "Japan Metal Finishing QSR Copper Sulfate Conc" 3.6 times with 19-thiosulfuric acid. Condition E: 5 of “Piroton Conch” manufactured by Barshaw Murayama Co., Ltd.
2.5 k/d1r for 30 minutes at 55°C in 0-chi flood control solution?
Plating is carried out at a current density of . Condition F: Plating is performed for 10 minutes at a current density of 2 A/dttt' using a non-dammet plating solution (tin/lead = 4/6) manufactured by McDammet.

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 photoinitiator that can be activated by actinic light; (c) a mixture of compounds selected from at least two compound groups represented by structural formulas (I), (II), and (III). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (Here, V 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, and W is an arylalkyl group. Unsubstituted or substituted with an alkyl group or aryl group having 1 to 15 carbon atoms, 2 or 3 carbons or nitrogen connected in a straight chain with single or double bonds, or having 6 to 14 carbon atoms Divalent aryl group at the ortho or peri position.) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (Here, X is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and C_1
, C_2 are both carbon, C_1 is bonded to S, and C_2 is N
Combine with. X_1, X_2 are hydrogen or R, X_3 is hydrogen or R, X_4 is hydrogen, R, amino group, carboxyl group, X_5 is hydrogen, R, or phenyl group, X_6 is hydrogen, R, amino group, ▲ Numerical formula, chemical formula, There are tables etc.▼,
S-CH_2-COOH, mercapto group, phenyl group,
X_7 is hydrogen, R or a phenyl group, and R is an alkyl group having 1 to 8 carbon atoms. ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (Here, Y is -SY_1, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -Y_4, and Y_1 is ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc. ▼, Y_2 is hydrogen,
R is a cycloalkyl group, Y_3 is R, a cycloalkyl group, Y_4 is R, ▲numerical formula, chemical formula, table, etc.▼, and R is an alkyl group having 1 to 8 carbon atoms. )