JPS59152439A - Photosensitive composition having improved adhesive property to metal - Google Patents

Abstract

PURPOSE:To obtain the titled composition having an improved adhesive property to metal by adding a specified 2-substituted-4,6-dithiol-S-triazine deriv. to a photosensitive resin. CONSTITUTION:To a photosensitive composition consisting of a photosensitive resin, an org. binder such as polyvinyl chloride, and a photopolymn. initiator such as anthraquinone is added 0.1-10wt% 2-substituted-4,6-dithiol-S-triazine deriv. represented by the formula [where R1 is SR2 or R2; each of R2 and R3 is H, -NHR or -N(R2); and R is H, hydroxyl, alkyl, phenyl, benzyl, naphthyl, cyclohexyl, alkoxyl or phenoxyl]. Said photosensitive resin is made from a nongaseous ethylenic unsatd. compound having two or more terminal ethylene groups and >=100 deg.C b.p. under atmospheric pressure, e.g., 2-hydroxyethyl methacrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to photosensitive compositions with improved adhesion to metals. For example, dry film photoresists used in the manufacture of printed circuit boards have lower adhesion to metal surfaces than conventional solution-based photoresists, so they often cause underblating or underetching during plating or etching. It is often experienced that the desired pattern cannot be obtained due to peeling off and lifting from the substrate.

Therefore, in order to solve this problem, it has been proposed to add benzimidazole, benzotriazole, and derivatives thereof, such as hydrochloride. However, when a photosensitive composition containing such a heterocyclic nitrogen-containing compound or a hydrochloride thereof is used, red discoloration of the exposed copper surface of the substrate after development is observed, and problems such as plating, etching, etc. This has an unfavorable effect on post-processing.

The present inventors have arrived at the present invention as a result of intensive research to solve these problems and further improve the adhesion of photosensitive compositions to metals.

That is, the present invention provides an adhesion improver having the general formula [Bird is S R
2 or R2, R2 and R3 are hydrogen, -NHR
or -N (R)2, and R is hydrogen, hydroxyl group, alkyl group, phenyl group, benzyl group, naphthyl group, cyclohexyl group, alkoxyl group or phenoxy group] 2-substituted -4,6 It was discovered that a photosensitive composition containing a small amount of -dithiol-S-triazine derivative (both -'8M) forms images with extremely excellent adhesion to metals such as copper and aluminum, leading to the present invention.

Examples of dithiol-S-triazine derivatives useful in the present invention include: The amount of these dithiol-s-triazine derivatives added is 01 to 10% by weight, preferably 05 to 8% by weight, based on the weight of the photosensitive composition.

In the present invention, 2-substituted-4,6-sithio-S-
) It is thought that the riazine derivative contributes to improved adhesion by forming a mercaptide type complex with the metal9.

The photosensitive resin of the present invention may be a diazo type, an azide type, a cinnamoyl type, or an acryloyl ring type photosensitive resin, but a photosensitive resin of the photoheptapolymerization type is preferably used.

Among them, a photosensitive resin made of an ethylenically unsaturated compound having at least two terminal ethylene groups, non-gaseous, and having a boiling point of 100° C. or higher at atmospheric pressure is preferred.

A photosensitive composition comprising such an ethylenically unsaturated compound generally comprises the ethylenically unsaturated compound, an organic polymer binder, and additives such as a photopolymerization initiator.

Examples of such ethylenically unsaturated compounds are 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxyethyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolmethane triacrylate, tetramethylolmethane. Tetraacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetramethacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol diacrylate Methacrylate, 1. s-bentanediol diacrylate, 1,5-bentanediol dimethacrylate, 1,6-hexanethiol diacrylate), 1. ．． 6
'-hexanediol dimethacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, lauryl acrylate, lauryl methacrylate,
stearyl acrylate, stearyl methacrylate,
Examples include triallyl in cyanurate, diallyl phthalate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and tetrahydrofurfuryl methacrylate.

In addition, since the Ariiso polymer binder is compatible with the ethylene-1 biounsaturated compound, the combination is determined naturally, but the binder used in the present invention is polymethacrylate, polystyrene, polystyrene, etc. Vinyl chloride, chlorinated polyethylene, polyvinyl acetate,
These are polyvinyl alcohol, polyvinyl butyral, and copolymers thereof.

The photopolymerization initiator used in the photosensitive biocomposition is preferably one suitable for polymerizing ethylenically unsaturated compounds, such as anthraquinone, 2-methylanthraquinone, tonoanthraquinone derivatives, benzoin derivatives such as benzine and benzoin methyl ether, benzophenone, Michler's ketone, etc.

In addition, a thermal polymerization inhibitor may be used for the storage stability of the photosensitive composition, and dye pigments, plasticizers, etc. may be used to make it easier to check the resist.

Although the photosensitive composition of the present invention is a composition useful for forming photoresists, it is not necessarily limited to this use, and can also be applied to UU inks, printer resists, printing plates, and the like.

Examples are shown below.

Example 1 Trimethylolpropane triacrylate 45'' Benzophenone 5 Michler's ketone 0.5 Hydroquinone monomethyl ether 001 Crystal Violet 004
H A 10% methyl ethyl ketone solution of the above composition was added to a thickness of 25%.
It was applied onto a 25 μm polyethylene terephthalate film and dried to form a 25 μm film. Also, for comparison,
2.4,6. -) IJ Thio-Lou S -) IJ
A coating film without the addition of acine was similarly prepared. These coating films were laminated onto a copper plate, and exposed stepwise for 5 to 60 seconds using a 2KW ultra-high pressure mercury lamp (JP-2ooo, manufactured by Oak Co., Ltd.) through a stenoptole (manufactured by Fuji Photo Film Co., Ltd., 15 stages).

Next, the polyethylene terephthalate film was peeled off and developed with chlorocene (], , ], 1-) using a spray developer for 90 seconds, then washed with water and dried. Table 1 shows the number of exposure seconds and the number of step tablets at this time.

In this way, a test was carried out in which Sellotape was attached to the resist remaining on the substrate during actual operation and it was rapidly peeled off, but the resist to which 24.6-) Lithio-R-S-triazine was added remained in close contact with the substrate. However, did the additive-free resist come off with cellophane tape? j “Shita.

Further, the steel substrate on which the resist was formed was immersed in ammonium persulfate for 3 minutes, then washed with water, and copper plated for 30 minutes using a copper pyrophosphate plating solution.

When this substrate is taken out, the additive-free resist floats up from the substrate and the plating solution has entered between the substrate and the substrate. No such phenomenon was observed with the added resist.

The steel-plated board is then solder plated using a fluoroborated solder plating solution, the resist is stripped from the board, and the copper is etched with an etching solution consisting of ammonium persulfate to obtain a solder pattern. The pattern obtained from the resist with no additives had unclear lines, but the lines were clear in the pattern obtained with the addition of 24.6-)lithio--S-triazine.

Table 1 5 8 stages 5 stages 10 11 720
12 1030 13
1140' 14 1.
150 15 1160
15 11 Example 2 A composition in which part by weight of 2-phenylamino-4,6-sithio-S-)riazine H was added instead of 24.6-)lithio-S-triazine in the composition of Example 1 was used. Exposure and development was performed at the same time. The copper plate on which the resist was formed was etched using a cupric chloride aqueous solution to obtain a resist pattern.

There were some parts of the additive-free product that were floating above the steel surface, but 2-phenylamino-4,6-sithio-S
-) The resist to which riazine was added had no lifting and the line widths of the copper pattern and the resist pattern corresponded well after the resist was peeled off.

Example 3 Polymethyl methacrylate 50 parts by weight (Sumipex B manufactured by Sumitomo Chemical) Trimethylolpropane triacrylate 20 parts by weight Tetraethylene glycol diacrylate 25
〃0, P-) Luenesulfonic acid amide
6 Hydroquinone monomethyl ether
001〃Crystal Violet
004〃A coating film was formed from the above composition in the same manner as in Example 1, and subjected to flashing, development, and plating. The formed circuit was sufficiently usable.

Example 4 Polyvinyl Nfumato 100
Part 3-Methyl-1,3-diaza-1,9-benzanthrone 10 Crystal violet
O05 Part H A coating film was formed from the above composition in the same manner as in Example 1, exposed and developed, and the resist was subjected to the Chromeno-Tsuchi test. As a result, 2.4.6-) Lithio-R-S-triazine was added. The resist remained in close contact with the substrate, but the additive-free resist was peeled off (Table 2).

Table 2 Cross hatch test example 1] 00/] 00 =I
O1/100// 2 100/ I O035
/100// 3 99/100 30/
100tt 4 100/100 50/1
00 Special liver applicant Daicel Chemical Industries, Ltd.

Claims (1)

[Claims] In the photosensitive resin, CR, is SR2 or R2, R2 and Karasu are hydrogen, -NHR or -N, (R)2, and R is hydrogen, a hydroxyl group, an alkyl group, a phenyl group. , benzyl group, naphthyl group, cyclohexyl group, alkoxyl group or phenoxyl group. ] A small amount of the 2-substituted-4,6-dithiol-S-triazine derivative represented by
A photosensitive composition with improved adhesion to metals due to its inclusion of % by weight.