JPH02289857A - Photosolder resist - Google Patents

Abstract

PURPOSE:To enhance developability, resolution, solvent resistance, and soldering adhesiveness by incorporating a specified vinyl type polymer compound, a compound having >= 2 polymerizable unsaturated double bonds in the molecule, a photopolymerization initiator, and fine inorganic particles. CONSTITUTION:The photosolder resist contains the vinyl type polymer compound having polymerizable units each represented by formula I (each of R<1> and R<2> being H or methyl, optionally same or different) and carboxylic groups, the compound having >= 2 polymerizable double bonds in the molecule, the photopol y-merization initiator, and the fine inorganic particles, thus permitting the obtained the alkali-developable type solder resist to be improved in developability and resolution and superior in solvent resistance and adhesiveness to copper circuits and solder circuits.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a new solgo resist, which has excellent properties particularly as a solgo resist for printed wiring boards 91I1 and for electroless plating resists. This article relates to a Solgool resist suitable for use as a permanent protective mask. More specifically, it relates to a seven-layer coating for printed wiring boards that is applied onto a circuit-formed printed wiring board, removes the solvent if necessary, and forms a desired pattern by image exposure and development. It is. [Junior's technology and its issues 1 The Jorubi screen printing method was used as a method for forming Solgur nost in the production of printed wiring boards. However, improvements in resolution were desired. As a method with excellent resolution, a liquid seductive composition is applied to the entire surface of the circuit-formed circuit board, the solvent is removed by heating if necessary, image exposure is carried out through a mask, and development processing is performed to form a renost. 7t} resist method. During this development process, an organic solvent such as Ll,1-}lichloroethane, trichlorethylene, modified 1jchloroethane, etc. is used as a developer. However, due to the damage caused by these developers to the substrate, the working environment, the waste, and the disposal of waste liquids, the organic solvent development type is being replaced by the alkaline development type. However, the alkaline development type solgo resist has the following characteristics compared to the melt-cut development type solgoresist:
Solgurnost properties such as developability, solvent resistance, and adhesion to copper circuits and solder circuits were inferior. [Means for Solving WN 1] The present inventors have developed an alkaline-developable Solgo resist-containing resin which has good developability and resolution, and has excellent solvent resistance and adhesion to copper circuits and solder paths. As a result of careful consideration to provide
We have arrived at the present invention. That is, the gist of the present invention is as follows: (a) a vinyl-based monomer compound containing a polymerized unit represented by the general formula (1) and having a carboxyl group, (wherein R1 and (/R'' are hydrogen atoms); or a methyl group, which may be the same or different.) (b) Compound containing two or more polymerizable double bonds in one molecule, (c) Polymerization initiator, (d) The present invention is described in detail below. The first component of the 7t} Sorgu resist of the present invention is represented by general formula (1). It is a vinyl polymer compound containing a polymerized unit represented by the formula and having a carboxyl group. Rl (wherein R1 and R1 represent a hydrogen atom or a methyl group,
They may be the same or different. ) This (.) vinyl-based molecular compound contains 5 to 50 mol%, more preferably 5 to 30 mol%, of polymerized units represented by general formula (1). The content of polymerized units represented by general formula (1) is 5 mol%
If it is lower than 50, Ushida's heat resistance tends to deteriorate;
If it exceeds mol%, gelation reaction tends to occur during storage and stability becomes a problem. Further, the content of carpotosyl groups is preferably 4'300 in terms of acid value, more preferably 50 to 250. If the carboxylic group content is lower than 4 in terms of acid value, it is difficult to develop with an alkaline developer, and if it is more than 300 in acid value, electrical insulation properties tend to deteriorate. (.) 1 kilo of vinyl! Introducing a carboxyl group into a molecular compound can be carried out by adding a monomer having a carboxyl group, such as acrylic acid or methacrylic acid, as a polymerization component in advance when preparing a polymer compound, or by adding a monomer having a carboxyl group in advance as a polymerizable component, or by adding a monomer having a carboxyl group as a polymerization potential in the commercial compound. This is carried out by a method in which a group such as a hydroxyl group or an amino group undergoes a molecular reaction with a nocarboxylic acid or an acid anhydride. Of these, the former method is superior in terms of ease of reaction and constraints. In addition, examples of the elliptic monomer contained in the vinyl polymer compound (a) include methyl (meth) acrylate, ethyl (meth) 7-acrylate, styrene, (meth)
Acrylonitrile, proyl (meth) 7 acrylate, butyl (meth) 7 acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, ethyl cellosolp (meth) acrylate, tribros 7 (/night)
Examples include 7 acrylate, a-methylstyrene, vinyl acetate, vinylphenol, vinyl benzoate, allyl benzoate, ethyl vinyl ether, and methyl vinyl ether. Among these, styrene, a-methylstyrene, and vinyl 7-hydroxyl are particularly preferred because they improve heat resistance. (a
) Vinyl type ^ molecular compound molecular size is 5000 ~ ioo, o
oo is preferable, more preferably 7000 to 50,00
It is 0. If the molecular size is smaller than sooo, the coating film forming ability tends to decrease and the heat resistance tends to deteriorate. 100 on the contrary
If the mackerel is larger than .000, delification reaction is likely to occur during storage, and stability becomes a problem. (a) Specific examples of the vinyl polymer compound include the following. Lllll t. r+= The second component is a polymerizable compound having two or more terminal (meth)acrylic groups. These can be either oligomers or polymers, and specifically, nools,
For example, ethylene glycol, tetraethylene glycol, nonaethylene glycol, polyethylene glycol, propylene glycol, butanediol, hexaneol, hexamethylene glycol, bis7enol, eightythyl ethyl ether, bis71tetrabromide. A1 Acrylic esters or methacrylic acid esters such as nohydroquine ethyl ether and cyclohexanesimethanol; divalent esters such as tri/tyrolpropane, pentaerythritol, noventaerythritol or derivatives thereof, glycerol, trihydroxyethyl isone 7 slate or derivatives thereof (Meth) acrylic esters of the above polyols; polyvalent engineering compounds, such as tosu-7-enol A-type epoxy compounds, 7-enol/borac-type epoxy compounds, cresol/borac-type evo-luxury compounds; Reaction products with meth)acrylic acid; Reaction products between noisocyanate compounds and diol mono-7 acrylates or methacrylates, reaction products between noisocyanate compounds, diol compounds, and nool mono(meth)acrylates, noisocyanate compounds and Possible reaction products between nool compounds and triolno(nota)7 acrylate; (nota)acrylate compounds having a phosphate ester group, specifically, bis(meth)7cryloxyethyl 7sueth, Bis(7 chloroethyl) 7 ethyl 7 eth, bis(methacryloxyethyl) butyl 7 eth, tris(meth) 7 chloroethyl 7 eth; silicone-based (meth)acrylates, etc. One or more of these may be used.Furthermore, a phosphoric acid (meth)7 acrylate compound having one (meth)acrylic group such as (meth)acrylic axyethyl 7 male heptaate may also be added. Preferably, the third component is (
e) It is a photopolymerization initiator. A-isomers include benzoin, penzoin alkyl ethers, 7-nthranone derivatives, penzanthrone derivatives, 2,2-cymethoxy-2-7-enylaceto 7-ethyl, 1-hy-Paquinyl-chlorhexyl-7
engineering diruketone, 2-methyl-[4-(methylthio)7 engineering:A,]-2 1 mol 7 surino 1-bropanone, ben ν
derivatives, benzo-7enone derivatives, 4,4゜bis-dimethyl-7mi/benzo-7enone, xanthone derivatives, thioxanthone derivatives, biimiguzoles, trichloromethyl-S-}ryanone, 3.4,3゜,4゛-tetra (t
-butylperoxycarponyl)benzo7enone, and these and pigments, amine compounds such as noalkylamine 7
Examples include combinations of benzoic acid alkyl ester, allylthiourea, N-7enylglycine, and the like. The fourth component is (d) inorganic fine particles. Examples of A-isomers include curk, silica, barium sulfate, calcium carbonate,
Clay, kaolin, bentonite, diatomaceous earth, alumina,
Examples include sintered talc, titanium dioxide, heptimony oxide, and zirconium silicate. These can also be used after surface treatment, such as by silane coupling machining. The vinyl polymer compound (a), which is an essential component of the 7 ton Legoulenost of the present invention described above, is 10 to 80% by weight, more preferably 2%, based on the total solid content excluding the coating solvent.
Contains 0 to 7011k%. The second essential component (b) is a compound containing two or more polymerizable double bonds in one molecule, which is 5 to 70% by weight based on the total solid content excluding the coating solvent.
, more preferably 10 to 50% by weight. The photopolymerization initiator (e), which is the third necessary H4 component, is contained in an amount of 0.05 to 10% by weight, preferably 0.5 to 6% by weight, based on the total solid content excluding the coating solvent. In addition, (d) inorganic fine particles, which are essential components of younger brother 4, are 2 to 80% by weight, preferably 10 to 50jlt%, based on the total solid content excluding the coating solvent.
Other polymers, preferably polymers soluble in an alkaline aqueous solution, may be added to the 7-year-old tonrugulenost of the present invention. Examples include polymers containing carpoquinyl groups, polymers containing phosphoric acid groups, and polymers containing sulfonic acid groups. It is also preferable to add a compound containing an epoxy group to improve heat resistance and strength, such as bisphenol A type epoxy resin, novolak type epoxy resin, triglycinol isocyanurate, etc. Particularly suitable is triglycinol isocyanate. In addition, there are other must-haves for the 7-year-old Tonguele Nost of the present invention! Depending on the requirements, thermal polymerization inhibitors, colorants, exposed visible image agents, development accelerators, flame retardants, antifoaming agents, adhesion improvers, coating properties improvers, etc. may be added. In the present invention, the above-mentioned components are mixed and, if necessary, dissolved or dispersed in a coating solvent to prepare a seven-year-old photosensitive solution. As a coating solvent, any solvent can be used as long as it has an appropriate boiling point and can dissolve or disperse MI and materials, but for example,
Methyl ethyl ketone, methyl isobrobyl ketone, methyl isobutyl ketone, methyl heptalosolp, ethyl cellosolve, butyl cellosolp, cyclohexanone, selon rub acetate, methyl selon lup acetate, butyl selon rub acetate, carbiF-ol, methyl carbitol, carbitol acetate, Methyl carbitol acetate, butyl carbitol acetate, xylene, toluene, brobylene glycol mono/notyl ether, propylene glycol monoethyl ether? Examples include pyrene glycol monomethyl ether acetate, butylene glycol monomethyl ether acetate, butylene glycol monoethyl ether acetate, and so on. A known method such as a roll coater, a curtain coater, or a screen printing method can be used to apply the 7 ton Legoulenost photosensitive liquid onto a substrate such as a printed wiring board. After the composition is applied to the entire surface of the substrate, the solvent is removed, if necessary, and the parts to which solder is not to be attached are masked by imagewise exposure and development. Weakly alkaline water is used as the developer in this case. [Examples] Next, the present invention will be specifically explained using examples, but the present invention is not limited to the following examples as long as the number of personnel is not exceeded. Synthesis Example 1 In a 7 flask equipped with a stirrer, a thermometer, a gas inlet tube, and a reflux condenser, 4 moles of styrene, 5 moles of methacrylic acid, and 1. 4 kg, azoisobutyronitrile 0.09
mol was added, and the mixture was heated and reacted on an oil bath at 80°C in a nitrogen stream for 6 hours. Add 0.18 mol of p-methoxy 7-enol and add 2
After a period of reaction, 1 mol of glycinol methacrylate,
9 g of dodecyl ammonium chloride was added. After reacting for 1 hour, the reaction product was reprecipitated in water to obtain the desired vinyl polymer compound. As a result of measuring the molecular weight of the obtained polymer compound using Delno's Chromatograph 7E, the weight average molecular weight was 30,000.
Example 1 35 kg of vinyl polymer compound obtained in Synthesis Example 1
, Beta Erythritol Tri-7 Acrylate 15kg, Beta Erythritol Tri-7 Acrylate 15kg, Beta Erythritol Tri-7 7-1. 6 kgs Michler Ketone 0
．． 1 kg of talocyanine green, 0.17 kg of 7 talocyanine green, and 17 kg of talc with an average particle size of 1 μm were dissolved or dispersed in methyl cellosolp to prepare a 7 ton le goulenost photosensitive solution. The resulting photosensitive solution was applied onto a printed wiring board using a curtain coater and dried at 80° C. for 60 minutes to form a 7 tonne resist film. The average film thickness on the substrate was 30μ. Next, the image mask film was exposed to light from a distance of 60cm using a 2km ultra-high pressure mercury lamp, and then spray developed using a 1% by weight sodium carbonate aqueous solution at 3kg/04'' for 1 minute to obtain a Lennost image. Developability was good.The sample for evaluation was then exposed to light using a high-pressure mercury lamp with a light intensity of 801/c@' from a distance of 20cm at a conveyor speed of 1s/min. A resist pattern formed with a width of 75 μm on the copper in the evaluation sample was immersed in trichlorethylene at room temperature for 60 minutes, and then rubbed vigorously, but no peeling of the Renost film was observed ( (hereinafter abbreviated as trichlorethylene test).Also, the same pattern part was immersed in a molten hang at 260°C for 20 seconds, but no peeling of the resist film was observed (hereinafter abbreviated as solder heat test). The resist formed on the copper in the evaluation sample was cross-cut into 100 square pieces with a razor, and an adhesive tape peeling test was performed, but all 100 pieces were completely adhered (hereinafter referred to as f). (abbreviated as cross-cut test).Example 2 In addition to the 7T Solgool resist sensitizer obtained in the same manner as in Example 1, triglycinolin cyanuride}15 was added.
kg was added to prepare a 7-year-old tongle nost photosensitive solution. A 7T} Solgool resist was applied onto the printed wiring board using a curtain footer, and then opened and dried at 80° C. for 60 minutes to form a 7R}Solgool resist film. The average film thickness on the substrate was 30μ. Next, the image mask film was exposed to light from a distance of 60 cm using a 2K ultra-high pressure mercury lamp, and then 3K was exposed using a 1% by weight sodium carbonate aqueous solution.
Spray development was performed for 1 minute using g/c size 2 to obtain a Renost image. Developability was good. Thereafter, it was heated at 150°C for 1 hour to thermally cure it to obtain a sample for evaluation. A trichlorethylene test, a solder heat resistance test, and a cross-cut test were conducted in the same manner as in Example 1, but no peeling of the Renost film was observed. Comparative Example 1 A copolymerized polymeric compound of notyl methacrylate and methacrylic acid (
A photosensitive solution containing a 7t) resin was prepared in the same manner as in Example 1, except that a molar ratio of 7:3 and a weight average molecular weight of io, ooo) were used. A photobulgoux film was formed on a printed wiring board in the same manner as in Example 1, exposed, developed, and post-exposed to obtain a sample for evaluation. When the Ushida-chu heat test was conducted in the same manner as in Example 1, peeling of the resist film was observed over the entire printed wiring board. [Effect of the invention 1] According to the present invention, it is possible to manufacture a 7-year-old tosorgoo mask that has excellent developability, resolution, solvent resistance, and Ushida adhesion, and the developer used is nonflammable and easy to work with. It is industrially useful because it has excellent properties, no pollution problems, and is inexpensive.

Claims (1)

[Claims] (1) (a) A vinyl polymer compound containing a polymerized unit represented by the general formula (I) and having a carboxyl group, ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (in the formula , R^1 and R^2 represent a hydrogen atom or a methyl group, and may be the same or different.) (b) A compound containing two or more polymerizable double bonds in one molecule, ( A photo solder resist comprising: c) a photopolymerization initiator; and (d) inorganic fine particles.