TW201825453A - Resist substrate preprocessing composition and resist substrate manufacturing method - Google Patents

Abstract

Provided is a resist substrate preprocessing composition with which wetting and spreading of resist ink after application by an inkjet method can be suppressed, making it possible to form a fine resist pattern with high accuracy. The resist substrate preprocessing composition of the present invention is a resist substrate preprocessing composition which contains an ampholytic surface-active agent (A1), an anionic surface-active agent (A2), and water, characterized in that: a numerical value obtained by subtracting, from a numerical value of an isoelectric point of the ampholytic surface-active agent (A1), a numerical value of the pH of the resist substrate preprocessing composition ([numerical value of isoelectric point of ampholytic surface-active agent (A1)] - [numerical value of pH of resist substrate preprocessing composition]) is -3 to 4; and the ratio of the mole number of the ampholytic surface-active agent (A1) to a total mole number of the mole number of the ampholytic surface-active agent (A1) and the mole number of the anionic surface-active agent (A2)([mole number of ampholytic surface-active agent (A1)]/([mole number of ampholytic surface-active agent (A1)] + [mole number of anionic surface-active agent (A2)])) is 0.1 to 0.9.

Description

   Pretreatment composition for resist substrate and method for manufacturing resist substrate   

The invention relates to a resist substrate pretreatment composition and a method for manufacturing a resist substrate. Specifically, it relates to a resist substrate pretreatment composition used before forming a pattern on the surface of copper or a copper alloy using a solder resist, and a method for manufacturing a resist substrate using the resist substrate pretreatment composition.

In recent years, with respect to a solder resist for protecting a conductor circuit formed on a wiring board, a pattern formation using an inkjet method has been proposed (see Patent Documents 1 and 2). In the conventional screen printing method, after an insulating film is applied to form a pattern, a step of pre-drying, development of the coating film, post-curing treatment, and removal of uncured resist is required. On the other hand, if an inkjet method is used, a pattern can be formed by exposing an insulating film ink and then photosensitizing and curing the patterned film. Therefore, compared with the conventional screen printing method, the work becomes simpler and the work can be greatly improved. To reduce manufacturing costs.

However, when using the inkjet method, there is a problem that a resin composition having a lower viscosity than that of a photocurable resin composition used in a conventional screen printing method is required, and blurring is caused during the curing step.

In response to these problems, the following measures have been taken, namely, the reactivity improvement or the adhesion improvement of the solder resist ink used in the inkjet method, but these measures are relatively large wetting diffusion on the substrate. Fine patterning is not sufficient (see Patent Document 3 and Patent Document 4). In addition, a method for treating a copper surface as described in Patent Document 5 with an organic substance such as a fatty acid or a resin acid before printing has also been studied, but this method is not sufficient.

    Prior art literature         Patent literature    

Patent Document 1: Japanese Patent Application Laid-Open No. 7-263845

Patent Document 2: Japanese Patent Application Laid-Open No. 9-18115

Patent Document 3: Japanese Patent Laid-Open No. 2007-227715

Patent Document 4: Japanese Patent Application Publication No. 2012-64640

Patent Document 5: Japanese Patent No. 4485282

If a resist ink is applied to a substrate by an inkjet method, there is a problem that the resist ink wets and diffuses before the ink is hardened, and it is difficult to form a fine resist pattern with high precision.

An object of the present invention is to provide a substrate which is subjected to a resist ink application by pretreatment, thereby suppressing the wetting and diffusion after the inkjet application of the resist ink, so that a fine resist pattern can be formed with high accuracy. Pre-treatment composition of a resist substrate.

The present inventors have made intensive studies in order to solve the above problems, and as a result, have completed the present invention. That is, the present invention relates to a pretreatment composition for a resist substrate, which contains an amphoteric surfactant (A1), an anionic surfactant (A2), and water, and is characterized in that it is selected from the above-mentioned amphoteric surfactant (A1) and the like. The value obtained by subtracting the pH value of the above-mentioned resist substrate pre-treatment composition from the value of the electric point ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the pH value of the pre-treatment composition of the resist substrate [Value]] is -3 ~ 4. The Molar number of the amphoteric surfactant (A1) is relative to the Molar number of the amphoteric surfactant (A1) and the Molar number of the anionic surfactant (A2). The ratio of the total mole number ([Mole number of amphoteric surfactant (A1)] / ([Mole number of amphoteric surfactant (A1)] + [Mole number of anionic surfactant (A2) ])) Is 0.1 to 0.9; a method for manufacturing a resist substrate, which includes the following steps: a substrate preparation step, which prepares a substrate on which a circuit material is formed; a pre-processing step, which uses the above-mentioned substrate of the present invention on the substrate Resist the substrate pretreatment composition to pretreat the substrate; and a resist placement step, Above the substrate after the pretreatment step the resist configuration.

The resist substrate pretreatment composition of the present invention exhibits an effect in the manufacturing steps of the resist substrate that suppresses wetting and diffusion of the resist for inkjet. Therefore, a fine resist pattern can be produced with high accuracy, and the density of the wiring can be increased.

The resist substrate pretreatment composition of the present invention is used for a substrate.

Examples of the substrate include simple substrates such as phenol-based resins, epoxy resins, polyimide resins, polyethylene terephthalate, Teflon (registered trademark), and ceramics, or a combination of these with glass or paper A composite base material formed by arranging on the insulating base material and arranging a metal such as copper or aluminum as a circuit material.

The resist substrate pretreatment composition of the present invention contains an amphoteric surfactant (A1), an anionic surfactant (A2), and water, and is characterized in that the value of the isoelectric point of the amphoteric surfactant (A1) is reduced by The value obtained by removing the pH value of the above-mentioned resist substrate pretreatment composition ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the value of the pH value of the pretreatment composition of the resist substrate]) is -3 ~ 4, the molar number of the amphoteric surfactant (A1) relative to the molar number of the amphoteric surfactant (A1) and the molar number of the anionic surfactant (A2) The ratio ([Mole number of amphoteric surfactant (A1)] / ([Mole number of amphoteric surfactant (A1)] + [Mole number of anionic surfactant (A2)]) is 0.1 ~ 0.9.

In the resist substrate pretreatment composition of the present invention, a value obtained by subtracting the pH value of the resist substrate pretreatment composition from the value of the isoelectric point of the amphoteric surfactant (A1) ([amphoter interface surfactant The value of the isoelectric point of (A1)]-[the value of the pH value of the pretreatment composition of the resist substrate]) is -3 to 4. That is, the isoelectric point of the amphoteric surfactant (A1) is only a value smaller than 3 by the value of the pH value of the pretreatment composition of the resist substrate, and only larger than the value of the pH value of the pretreatment composition of the resist substrate. The value is 4 or less. That is, in the resist substrate pretreatment composition of the present invention, the amphoteric surfactant is preferably not excessively negatively charged, and preferably not excessively positively charged. The value obtained by subtracting the value of the pH value of the pretreatment composition of the resist substrate from the value of the isoelectric point of the amphoteric surfactant (A1) is preferably -2.5 to 3.8, and more preferably -2 to 3.6.

If the value obtained by subtracting the pH value of the pretreatment composition of the resist substrate from the value of the isoelectric point of the amphoteric surfactant (A1) is outside the range of -3 to 4, the amphoteric surfactant (A1) will It is positively or negatively charged excessively, and therefore, the performance of suppressing the wetting and diffusion of the resist ink is deteriorated.

In addition, in this specification, the "isoelectric point of an amphoteric surfactant (A1)" means the value measured by the following method.

That is, first, a 1% by weight aqueous solution of the amphoteric surfactant (A1) of four or more samples having different pH values was prepared.

Secondly, the correlation between pH and conductivity is made by measuring these conductivity.

In the correlation curve, when the minimum value of the electrical conductivity appears, the value of the pH value when the minimum value appears is the "isoelectric point of the amphoteric surfactant (A1)". When the minimum value of the electrical conductivity does not appear in the correlation curve, an aqueous solution of 1% by weight of the amphoteric surfactant (A1) having a different pH value is then prepared and the electrical conductivity is measured until the minimum value appears in the correlation curve.

In this specification, the pH value of the resist substrate pretreatment composition is a value measured using a pH meter (manufactured by HORIBA, Ltd.) at 25 ° C.

In the resist substrate pretreatment composition of the present invention, the molar number of the amphoteric surfactant (A1) is relative to the molar number of the amphoteric surfactant (A1) and the molar number of the anionic surfactant (A2). The ratio of the total number of moles ([Mole number of amphoteric surfactant (A1)] / ([Mole number of amphoteric surfactant (A1)] + [Mole of anionic surfactant (A2) The number])) is 0.1 to 0.9, preferably 0.15 to 0.85, and further preferably 0.2 to 0.8.

If the above value is less than 0.1, the performance of suppressing the wetting and diffusion of the resist ink will be deteriorated, and if it exceeds 0.9, the performance of suppressing the wetting and diffusion of the resist ink will be similarly deteriorated.

The resist substrate pretreatment composition of the present invention preferably further contains an organic solvent (S) having a boiling point of 100 ° C. or higher and an SP value of 8 to 20.

Examples of the organic solvent (S) include ethylene glycol (boiling point: 198 ° C, SP value: 17.8), diethylene glycol (boiling point: 244 ° C, SP value: 15.0), and propylene glycol (boiling point: 188 ° C, SP value). : 15.9), propylene glycol monomethyl ether (boiling point: 120 ° C, SP value: 11.3), glycerol (boiling point: 290 ° C, SP value: 20.0), and other alcohols; diethylene glycol dimethyl ether (boiling point: 162 ° C, SP value) : 8.1) isoether; monoethanolamine (boiling point: 171 ° C, SP value: 14.3), isopropanolamine (boiling point: 160 ° C, SP value: 13.1), 2- (2-aminoethylamino) ethanol (boiling point : 244 ° C, SP value: 13.1), alkanolamines such as ethylenediamine-N, N, N ', N'-tetraethanol (boiling point: 280 ° C, SP value: 15.2) and the like. From the viewpoint of suppressing an increase in the viscosity of the resist substrate pretreatment composition during use, the organic solvent (S) is preferably ethylene glycol, diethylene glycol, propylene glycol, glycerol, or 2- (2-amineethylamine). Group) ethanol, ethylenediamine-N, N, N ', N'-tetraethanol, more preferably diethylene glycol, propylene glycol, ethylenediamine-N, N, N', N'-tetraethanol.

By including the organic solvent (S) in the resist substrate pretreatment composition of the present invention, it is possible to suppress the composition of the resist substrate pretreatment generated over time when the resist substrate pretreatment composition is used in an open environment. The viscosity of the substance increases.

As a result, the stability of the resist substrate pretreatment composition in an open environment is improved, and the handleability is improved.

In the resist substrate pretreatment composition of the present invention, from the viewpoint of suppressing an increase in the viscosity of the resist substrate pretreatment composition during use, the content of the organic solvent (S) is larger than that of the resist substrate pretreatment composition. The weight is preferably 1 to 40% by weight, more preferably 3 to 30% by weight, and most preferably 5 to 20% by weight.

The SP value in this specification is calculated by a method described in the following documents proposed by Fedors and others.

`` POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pages 147 ~ 154) ''

In the resist substrate pretreatment composition of the present invention, the amphoteric surfactant (A1) is preferably a compound represented by the following general formula (1).

R ¹ in the general formula (1) is a monovalent saturated hydrocarbon group having 1 to 25 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 25 carbon atoms.

Examples of the monovalent saturated hydrocarbon group having 1 to 25 carbon atoms include methyl, ethyl, n-propyl, hexyl, cyclohexyl, n-butyl, octyl, nonyl, decyl, undecyl, and lauryl , Stearyl, n-tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, undecyl, eicosyl, behenyl Base, behenyl, behenyl, and behenyl.

Examples of the monovalent unsaturated hydrocarbon group having 2 to 25 carbon atoms include octadecenyl and octadecadienyl.

From the viewpoint of suppressing the wetting and diffusion of the resist ink, R ^{1 is} preferably octyl, nonyl, decyl, undecyl, lauryl, and stearyl, more preferably octyl and lauryl, and further Lauryl is preferred.

R ² in the general formula (1) is a divalent saturated hydrocarbon group having 1 to 25 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms.

Examples of the divalent saturated hydrocarbon group having 1 to 25 carbon atoms and the divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms include ethylene, propyl, butyl, isobutyl, pentyl, and isobutyl Pentyl, d-nepentyl, 1-methyl butyl, 2-methyl butyl, 1,2-dimethyl propyl, 1-ethyl propyl, hexyl, isohexyl, 1 -Methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 1,1-dimethyl-butyl-butyl, 1,2-dimethyl-butyl-butyl, 2,2-bis Methyl butyral, 1-ethyl butyral, 1,1,2-trimethyl butyral, 1,2,2-trimethyl butyral, 1-ethyl-2-methyl butyral And 1-ethyl-1-methylpropane.

From the viewpoint of solubility in water, R ^{2 is} preferably a divalent saturated hydrocarbon group having 1 to 25 carbon atoms, more preferably ethylene, propyl and butyl, and even more preferably ethyl and propylene. And particularly preferably ethyl.

R ³ in the general formula (1) is a divalent saturated hydrocarbon group having 1 to 25 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms.

Examples of the divalent saturated hydrocarbon group having 1 to 25 carbon atoms and the divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms include methylene, ethylene, propyl, butyl, isobutyl, and pentyl , Iso-pentyl, neo-pentyl, 1-methyl butyl, 2-methyl butyl, 1,2-dimethyl propyl, 1-ethyl propyl, hexyl, hexamethylene Base, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 1,1-dimethyl-butyl-butyl, 1,2-dimethyl-butyl-butyl, 2, 2-dimethyl-butylene, 1-ethyl-butylene, 1,1,2-trimethyl-propyl, 1,2-2-trimethyl-propyl, 1-ethyl-2-methyl Propylidene and 1-ethyl-1-methylidene.

From the viewpoint of solubility in water, R ^{3 is} preferably methylene, ethylene, propyl, and butylene, more preferably methylene and ethylene, and even more preferably methylene.

X in the general formula (1) is an integer of 1-20. From the viewpoint of suppressing the wetting and diffusion of the resist ink, it is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.

When x is 2 or more, each hydrocarbon group represented by R ² may be the same hydrocarbon group or different hydrocarbon groups.

M ⁺ in the general formula (1) is a counter ion. Anyone that can electrically neutralize the anion and form a water-soluble salt with the anion may be used, and examples thereof include cations, protons, protonated amines, and ammonium ions formed from alkali metals or alkaline earth metals.

Specific examples include the following counter ions: sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine, and butylamine, monoethanolamine, and guanidine); secondary amines (dimethylamine, diethylamine, and Dialkylamines such as dibutylamine and diethanolamine, etc.); tertiary amines {trialkylamines such as trimethylamine, triethylamine, and tributylamine, triethanolamine, N-methyldiethanolamine, and 1,4-diazepine Heterobicyclo [2.2.2] octane, etc.); 脒 {1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter, referred to as DBU), 1,5-diazabicyclo [4.3 .0] -5-nonene, 1H-imidazole, 2-methyl-1H-imidazole, 2-ethyl-1H-imidazole, 4,5-dihydro-1H-imidazole, 2-methyl-4,5 -Dihydro-1H-imidazole, 1,4,5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine, etc.), ammonium and quaternary ammonium (tetraalkylammonium, etc.), methylammonium , Isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium, and dimethylethylammonium.

Specific examples of the compound represented by the general formula (1) include sodium octylamine and 2 mol adduct sodium acetate, nonylamine and 2 mol adduct sodium acetate, and decyl Amine ethyleneimine 2 mol adduct sodium acetate, undecylamine ethyleneimine 2 mol adduct sodium acetate, laurylamine ethyleneimide 2 mol adduct sodium acetate, stearylamine Imine 2 mol adduct sodium acetate, laurylamine ethyleneimide 1 mol adduct sodium acetate, laurylamine ethyleneimine 3 mol adduct sodium sodium acetate, laurylamine ethymine 4 mol Addition Sodium Acetate, Laurylamine Ethylimine 5 Molar Addition Sodium Acetate, Laurylamine Ethylimine 2 Molar Addition Sodium Acetate, Laurylamine Butylimine 2 Molar Addition Sodium Acetate , Laurylamine Ethyleneimide 2 Molar Adduct Potassium Acetate, Laurylamine Ethylimine 2 Molar Adduct Monoacetate Acetate, Laurylamine Ethylimine 2 Molar Adduct DBU Salt, Laurel Amine ethyleneimine 2 mol adduct tetramethylammonium acetate, laurylamine ethyleneimide 1 mol adduct sodium propionate, laurylamine ethyleneimine 2 mol adduct sodium propionate, Laurylamine and ethyleneimine 2 mole Adduct sodium butyrate.

From the viewpoint of suppressing the wetting and diffusion of the resist ink, octylamine 2 mol adduct sodium acetate, laurylamine 2 mol adduct sodium acetate, lauryl adduct Ethylamine 3 Mole Adduct Sodium Acetate, Laurylamine Ethylimide 2 Mole Adduct Potassium Acetate, and Laurylamine Ethylimide 2 Mole Adduct Sodium Propionate, More preferably Laurylamine Ethyl Acetate The imine 2 mol adduct sodium acetate and the laurylamine ethimine 2 mol adduct potassium acetate, and further preferably the laurylamine ethylidene 2 mol adduct sodium acetate.

From the viewpoint of suppressing the wetting and diffusion effect of the resist ink, the isoelectric point of the amphoteric surfactant (A1) in the resist substrate pretreatment composition of the present invention is preferably 8.0 to 11.0, and more preferably 8.5 ~ 11.0.

In the resist substrate pretreatment composition of the present invention, the anionic surfactant (A2) is preferably a compound represented by the following general formula (2) and / or general formula (3).

R ⁴ in the general formula (2) is a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 25 carbon atoms or the unsaturated hydrocarbon group having 2 to 25 carbon atoms include methyl, ethyl, n-propyl, hexyl, cyclohexyl, n-butyl, octyl, nonyl, and decyl , Undecyl, lauryl, stearyl, n-tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, undecyl, di Decadecyl, behenyl, behenyl, behenyl, behenyl, behenyl, octadecenyl, and octadecadienyl.

From the viewpoint of suppressing the wetting and diffusion of the resist ink, R ^{4 is} preferably a saturated hydrocarbon group having 1 to 25 carbon atoms, more preferably octyl, nonyl, decyl, undecyl, lauryl, and stearin. Base, further preferably octyl and lauryl, and particularly preferably lauryl.

A ¹ in the general formula (2) is an alkylene group having 2 to 12 carbon atoms.

Specific examples of the alkylene group having 2 to 12 carbon atoms include ethylidene group, propylidene group, butylidene group, isobutylidene group, pentylyl group, isopropylidene group, denopentyl group, 1- Methyl butylene, 2-methyl butylene, 1,2-dimethyl butyral, 1-ethyl butyral, hexyl, isohexyl, 1-methyl butyl, 2-methyl Pentyl, 3-methyl pentyl, 1,1-dimethyl butyl, 1,2-dimethyl butyl, 2,2-dimethyl butyl, 1-ethyl butyl Butyl, 1,1,2-trimethylpropane, 1,2-2-trimethylpropane, 1-ethyl-2-methylpropane, and 1-ethyl-1-methyl Phenylene, etc.

From the standpoint of solubility in water, A ^{1 is} preferably ethylene, propyl, and butyl, more preferably ethyl and propyl, and even more preferably ethyl.

Y in the general formula (2) is an integer of 1-20. From the viewpoint of suppressing the wetting and diffusion of the resist ink, it is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5. When y is 2 or more, each alkylene group represented by A ¹ may be the same alkylene group or different alkylene groups.

M ⁺ in the general formula (2) is a counter ion. Anyone that can electrically neutralize the anion and form a water-soluble salt with the anion may be used. Examples include cations, protons, protonated amines, and ammonium ions formed from alkali metals or alkaline earth metals.

Examples of M ⁺ include sodium, potassium, and primary amines (such as alkylamines such as methylamine, ethylamine, and butylamine, monoethanolamine, and guanidine); and secondary amines (such as dimethylamine, diethylamine, and dibutylamine). Alkylamines and diethanolamines, etc.); tertiary amines {trialkylamines such as trimethylamine, triethylamine, and tributylamine, triethanolamine, N-methyldiethanolamine, and 1,4-diazabicyclo [2.2. 2] octane etc.}; 脒 {1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, 1H- Imidazole, 2-methyl-1H-imidazole, 2-ethyl-1H-imidazole, 4,5-dihydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4 , 5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine, etc.), ammonium and quaternary ammonium (tetraalkylammonium, etc.), methylammonium, isopropylammonium, butylammonium, diamine Relative ions such as propylammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium.

R ⁵ O-SO ₃ ^- M ⁺ (3)

R ⁵ in the general formula (3) is a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms.

Examples of the saturated hydrocarbon group having 1 to 25 carbon atoms or the unsaturated hydrocarbon group having 2 to 25 carbon atoms include methyl, ethyl, n-propyl, hexyl, cyclohexyl, n-butyl, octyl, nonyl, decyl, Undecyl, lauryl, stearyl, n-tridecyl, tetradecyl, pentadecyl, cetyl, heptadecyl, octadecyl, undecyl, icosyl Alkyl, behenyl, behenyl, behenyl, behenyl, behenyl, octadecenyl and octadecadienyl.

From the viewpoint of suppressing the wetting and diffusion of the resist ink, R ^{4 is} preferably a saturated hydrocarbon group having 1 to 25 carbon atoms, more preferably octyl, nonyl, decyl, undecyl, lauryl, and stearin. Base, further preferably octyl and lauryl, and particularly preferably lauryl.

M ⁺ in the general formula (3) is a counter ion. Anyone that can electrically neutralize the anion and form a water-soluble salt with the anion may be used. Examples include cations, protons, protonated amines, and ammonium ions formed from alkali metals or alkaline earth metals.

Examples of M ⁺ include sodium, potassium, and primary amines (such as alkylamines such as methylamine, ethylamine, and butylamine, monoethanolamine, and guanidine); and secondary amines (such as dimethylamine, diethylamine, and dibutylamine). Alkylamines and diethanolamines, etc.); tertiary amines {trialkylamines such as trimethylamine, triethylamine, and tributylamine, triethanolamine, N-methyldiethanolamine, and 1,4-diazabicyclo [2.2. 2] octane etc.}; 脒 {1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene, 1H- Imidazole, 2-methyl-1H-imidazole, 2-ethyl-1H-imidazole, 4,5-dihydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4 , 5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine, etc.), ammonium and quaternary ammonium (tetraalkylammonium, etc.), methylammonium, isopropylammonium, butylammonium, diamine Relative ions such as propylammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium.

In the resist substrate pretreatment composition of the present invention, examples of the anionic surfactant (A2) include alkyl sulfate esters (salts having a saturated hydrocarbon group of 1 to 25 carbon atoms or unsaturated hydrocarbon groups of 2 to 25 carbon atoms). ) (A2-1) and polyoxyalkylene alkyl ether sulfates (salts) (A2-2) of which the alkyl group is saturated with 1 to 25 carbon atoms or unsaturated hydrocarbon group with 2 to 25 carbon atoms.

Examples of the alkyl sulfate (salt) (A2-1) having a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms include mono- and diesters such as propanol, octanol, lauryl alcohol, and oleyl alcohol, and Its salt and so on.

Examples of the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) include mono- and diesters of alkylene oxide adducts of primary and secondary alcohols, and salts thereof.

The primary alcohol used as a raw material for the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) may be a straight chain, a branched chain or a cyclic chain, and may have a saturated or unsaturated bond. Specific examples of the primary alcohol include hexane-1-ol, heptane-1-ol, octane-1-ol, nonane-1-ol, decane-1-ol, and dodecane-1-ol Alcohols, tetradecane-1-ol, cetyl-1-ol, stearyl-1-ol, eicosane-1-ol, linear amines; branched chain alcohols such as isodecanol; rings such as cyclohexanol State alcohols; the first-grade alcohols of source vegetable oils such as tallow alcohol, hydrogenated tallow alcohol and coconut oleyl alcohol as a mixture of these.

The secondary alcohol used as a raw material for the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) may be linear, branched, or cyclic, and may have a saturated or unsaturated bond. Examples of the secondary alcohol include propane-2-ol, butane-2-ol, cyclohexanol, and decane-2-ol. The secondary alcohol may be used alone or as a mixture of two or more.

Examples of the alkylene oxide in the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) include alkylene oxides having 2 to 12 carbon atoms, such as ethylene oxide and 1,2-propylene oxide. , 1,2-butene oxide, 1,2-epoxyhexane, tetrahydrofuran and 3-methyltetrahydrofuran. When the number of added alkylene oxides is 2 or more, the oxyalkyl groups may be the same or different, and may be a random bond or a block bond.

Specific examples of the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) include lauryl alcohol ethylene oxide 3 mol adduct sodium sulfate (salt), and lauryl ethylene oxide 5 Moore propylene oxide 3 Moore adduct sodium sulfate (salt), Myristyl alcohol ethylene oxide 8 Moore adduct sodium (salt), Tetradecyl alcohol ethylene oxide 3 Moore adduct Sodium sulfate (salt), octanol ethylene oxide 2 mol adduct sodium (salt) and lauryl alcohol ethylene oxide 2 mol adduct sodium (salt) and the like.

In the resist substrate pretreatment composition of the present invention, examples of the water include ultrapure water, ion exchange water, reverse osmosis (RO) water, and distilled water. In terms of cleanliness, ultrapure water is preferred.

In the resist substrate pretreatment composition of the present invention, from the viewpoint of suppressing the wetting and diffusion of the resist, the weight ratio of the amphoteric surfactant (A1) to the anionic surfactant (A2) ([amphoteric interface The weight of the active agent (A1)] / [the weight of the anionic surfactant (A2)]) is preferably 0.1 to 5.0, further preferably 0.3 to 3.0, and more preferably 0.4 to 2.0.

In the resist substrate pretreatment composition of the present invention, from the viewpoint of suppressing the wetting and diffusion of the resist ink, the total weight of the amphoteric surfactant (A1) and the anionic surfactant (A2) and the resist substrate The ratio of the weight of the pretreatment composition (([total weight of the amphoteric surfactant (A1) and the anionic surfactant (A2)] / [weight of the resist substrate pretreatment composition]}) × 100 is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and still more preferably 1 to 10% by weight.

The resist substrate pretreatment composition of the present invention preferably has a pH of 7.0 to 12.0. From the viewpoint of suppressing the wetting and diffusion of the resist, it is preferably 7.5 to 11.5, more preferably 8.0 to 11.0, and even more preferably 8.5 to 11.0.

The resist substrate pretreatment composition of the present invention may also contain a pH adjuster (B), a preservative (C), and the like as other constituent substances.

Examples of the pH adjusting agent (B) include acids (inorganic acids and organic acids), and bases (inorganic bases such as sodium hydroxide and potassium hydroxide, amines such as diethanolamine and isopropanolamine).

As the preservative (C), a commercially available preservative can be used.

The method for manufacturing a resist substrate in the present invention includes the steps of using the resist substrate pretreatment composition of the present invention to perform substrate pretreatment before resist coating. That is, the method for manufacturing a resist substrate of the present invention is characterized by including the following steps: a substrate preparation step for preparing a substrate on which a circuit material is formed; and a preprocessing step for using the above-mentioned resist substrate pretreatment composition of the present invention to The substrate is subjected to pre-treatment; and the resist arrangement step is a step of placing the resist on the substrate after the above-mentioned pre-treatment step.

In the method for manufacturing a resist substrate of the present invention, the circuit material formed on the substrate is preferably composed of at least one selected from the group consisting of copper, aluminum, iron, tin, silver, and nickel. , Titanium, chromium and zinc.

The resist substrate manufactured by the manufacturing method of the resist substrate of this invention can be used as a board | substrate for printed wiring boards.

    Examples    

Hereinafter, the present invention will be described in more detail through examples and comparative examples, but the present invention is not limited to these. Unless otherwise specified, "part" means "part by weight" and "%" means "% by weight" in the following. In addition, the water system used in the Example and the comparative example used the specific resistance value of 18 MΩ or more.

<Manufacturing Example 1>

Put 205 parts of lauryl chloride and 103 parts of diethylene triamine into a stainless steel autoclave with stirring and temperature adjustment functions. After nitrogen substitution in the mixing system, the temperature is 80 ~ 120. The reaction was carried out at a temperature of about 1 hour. After the reaction, the reaction solution was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand and separate. After removing the lower layer (water layer), the gas layer portion was replaced with nitrogen and distilled under reduced pressure (distillation conditions of the main product: 185 to 240 ° C, 5 to 20 mmHg). 271 parts of water and the main product were put into a glass reaction container, while nitrogen gas was circulated in the gas layer part, while an aqueous solution of monochloroacetic acid (95 parts) was added at 50 to 100 ° C, and the reaction was performed at 90 to 110 ° C, and then hydrogen was used. The pH of the aqueous sodium oxide solution was adjusted to obtain sodium acetate (A1-1), a laurylamine and ethyleneimine 2 mol addition product.

<Manufacturing Example 2>

Put 205 parts of 1-chlorododecane and 60 parts of ethylenediamine into a stainless steel autoclave with stirring and temperature adjustment functions. After replacing nitrogen in the mixing system, perform a reaction at 80 to 120 ° C for about 1 hour. After the reaction, the reaction solution was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand and separate. After removing the lower layer (water layer), the gas layer portion was replaced with nitrogen and distilled under reduced pressure (distillation conditions of the main product: 185 to 240 ° C, 5 to 20 mmHg). 271 parts of water and the main product were put into a glass reaction vessel, and while nitrogen gas was circulated in the gas layer, an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100 ° C, and the reaction was performed at 90 to 110 ° C. The sodium hydroxide aqueous solution was adjusted to pH value, and sodium laurylamine and ethyleneimine 1 mol addition product sodium propionate (A1-2) was obtained.

<Manufacturing Example 3>

Put 205 parts of 1-chlorododecane and 103 parts of diethylene triamine into a stainless steel autoclave with stirring and temperature adjustment functions. After nitrogen substitution in the mixing system, perform about 1 at 80 to 120 ° C. Hour response. After the reaction, the reaction solution was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand and separate. After removing the lower layer (water layer), the gas layer portion was replaced with nitrogen and distilled under reduced pressure (distillation conditions of the main product: 185 to 240 ° C, 5 to 20 mmHg). 271 parts of water and the main product were put into a glass reaction vessel, and while nitrogen gas was circulated in the gas layer part, an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100 ° C, and the reaction was performed at 90 to 110 ° C. The sodium hydroxide aqueous solution was used for pH adjustment, and sodium laurylamine and ethyleneimine 2 mol addition product sodium propionate (A1-3) was obtained.

<Manufacturing Example 4>

186 parts of lauryl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were put into the same container as in Manufacturing Example 1. After nitrogen substitution was performed in the mixing system, the pressure was reduced to 1 (20 mmHg) and 120 ° C. Hours of dehydration. Then, 88 parts of ethylene oxide (hereinafter, also referred to as "EO") was introduced so that the gauge pressure became 1 to 3 kgf / cm ² at 150 ° C. The reaction product was transferred to a glass reaction container, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20 ° C. Dehydrochlorination was performed while blowing nitrogen at this temperature for 2 hours, and then the sulfate was neutralized with "an aqueous solution prepared by dissolving 41.2 parts of sodium hydroxide in 102 parts of water" to obtain lauryl alcohol ethylene oxide 3 Aqueous solution of sodium sulphate (A2-2-1).

<Manufacturing Example 5>

186 parts of lauryl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were put into the same container as in Manufacturing Example 1. After nitrogen substitution was performed in the mixing system, the pressure was reduced to 1 (20 mmHg) and 120 ° C. Hours of dehydration. Then, at 150 ° C, 220 parts of EO and 174 parts of propylene oxide (hereinafter, also referred to as "PO") were introduced so that the gauge pressure became 1 to 3 kgf / cm ² . The reaction product was transferred to a glass reaction container, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20 ° C. Dehydrochloric acid was carried out while blowing nitrogen at this temperature for 2 hours, and then the sulfate was neutralized with "an aqueous solution prepared by dissolving 41.2 parts of sodium hydroxide in 102 parts of water" to obtain lauryl alcohol ethylene oxide Aqueous solution of 5 mol propylene oxide 3 mol adduct sulfate sodium salt (A2-2-2).

<Manufacturing Example 6>

214 parts of myristyl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were put into the same container as in Production Example 1. After nitrogen substitution was performed in the mixing system, the reaction was performed under reduced pressure (20 mmHg) and 120 ° C. Dehydrate for 1 hour. Next, 235 parts of EO was introduced at 150 ° C. so that the gauge pressure became 1 to 3 kgf / cm ² . The reaction product was transferred to a glass reaction container, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20 ° C. Dehydrochloric acid was carried out for 2 hours while blowing nitrogen gas at this temperature, and then the sulfate was neutralized with "an aqueous solution prepared by dissolving 41.2 parts of sodium hydroxide in 102 parts of water" to obtain a myristyl alcohol epoxy. Aqueous solution of ethane 8 mol adduct sulfate sodium salt (A2-2-3).

<Examples 1 to 22> and <Comparative Examples 1 to 3>

Each component was blended so as to have the composition described in Tables 1 to 3, and was stirred at 25 ° C for 20 minutes with a magnetic stirrer at 40 rpm to obtain a resist substrate pretreatment composition (E1) to (E22) and comparative resistances. The substrate pre-treatment composition (H1) to (H3). The weight part of each component is a numerical value converted by pure content, and the water system in each component is included in pure water.

<Measurement of pH>

The pH of the resist substrate pre-treatment composition was measured at 25 ° C using a pH meter (manufactured by Horiba, Ltd.). The results are shown in Tables 1 to 3.

<Measurement of the contact angle between the resist and the substrate after surface treatment -1 (surface treatment of copper substrate)>

A copper test piece (C1020 oxygen-free copper, 20 mm × 50 mm × 1 mm) was used as a model substrate.

(1) A substrate was immersed in 100 ml of a 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, and then the resistivity of the substrate was 18 MΩ. Pure water of cm or more was washed for 10 seconds, immersed in 300 ml of pure water for 30 seconds, and then dried with nitrogen.

(2) Secondly, the substrate was immersed in a resist substrate pre-treatment composition at 25 ° C for 1 minute, and then the resistivity was 18MΩ. Pure water of cm or more was washed for 10 seconds, immersed in 300 ml of pure water for 30 seconds, washed, and then dried with nitrogen to prepare a substrate after surface treatment.

(3) Using triethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.) as model resists, using a fully automatic contact angle meter (Kyowa Interface Science) Manufactured by the company, "Automatic Contact Angle Meter DM700") measures the contact angle between the model resist and the substrate after surface treatment. The results are shown in Tables 1 to 3. When the contact angle is 40 ° or more, it indicates that the wetting and diffusion are good.

<Measurement of the contact angle between the resist and the surface-treated substrate-2 (surface treatment of a copper substrate on which a copper oxide film is formed)>

A copper test piece (C1020 oxygen-free copper, 20 mm × 50 mm × 1 mm) was used as a model substrate.

(1) A substrate was immersed in 100 ml of a 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, and then the resistivity of the substrate was 18 MΩ. Pure water of cm or more was washed for 10 seconds, immersed in 300 ml of pure water for 30 seconds, and then dried with nitrogen.

(2) Secondly, the substrate was immersed in 5% hydrogen peroxide for 1 minute, and then the resistivity was 18MΩ. The pure water of cm or more was washed for 10 seconds, immersed in 300 ml of pure water for 30 seconds, washed, and then dried with nitrogen. With this operation, a copper oxide film is formed on the surface of the copper substrate.

(3) The copper substrate on which the copper oxide film was formed was immersed in a resist substrate pretreatment composition at 25 ° C for 1 minute, and the resistivity of the erosion was 18MΩ. Pure water of cm or more was washed for 10 seconds, immersed in 300 ml of pure water for 30 seconds, washed, and then dried with nitrogen to prepare a substrate after surface treatment.

(4) Using triethylene glycol diacrylate (manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.) as model resists, using a fully automatic contact angle meter (Kyowa Interface Science) Manufactured by the company, "Automatic Contact Angle Meter DM700") measures the contact angle between the model resist and the substrate after surface treatment. The results are shown in Tables 1 to 3. If the contact angle is 35 ° or more, it means that the contact angle is good and the wetting and diffusion are suppressed.

<Measurement of the viscosity of a resist substrate pretreatment composition>

(1) An E-type viscometer (manufactured by Brookfield) was used immediately after the resist substrate pretreatment composition was blended, and the viscosity was measured by adjusting the temperature to 25 ° C. The results are shown in Tables 1 to 3.

(2) Put 300 g of the resist substrate pre-treatment composition into a resin container, adjust the temperature to 50 ° C. in an open system, and leave it to stand for 10 hours. After that, the viscosity was measured by adjusting the temperature to 25 ° C using an E-type viscometer (manufactured by Brookfield). The results are shown in Tables 1 to 3.

(3) The viscosity increase rate of the resist substrate pre-treatment composition under an open heating environment is calculated by the following formula. The results are shown in Tables 1 to 3.

Viscosity increase rate (%) of the pretreatment composition of the resist substrate in an open heating environment = {([viscosity (mPa · s) after temperature adjustment to 50 ° C in an open system and standing for 10 hours]]-[just doped Viscosity after mixing (mPa.s)]) / [Viscosity after mixing (mPa.s)]} × 100

As can be seen from the results shown in Tables 1 to 3, regarding the copper substrates that have been surface-treated with the resist substrate pre-treatment composition of Examples 1 to 22, it is confirmed that the contact angle of the resist is relatively high regardless of the oxidation state of the surface. Large, wetting diffusion is suppressed. On the other hand, regarding the copper substrate surface-treated with the resist substrate pre-treatment composition of Comparative Examples 1 to 3, it was confirmed that the contact angle was small regardless of the oxidation state of the surface, and wetting and diffusion were not sufficiently suppressed.

Furthermore, regarding the resist substrate pretreatment composition of Examples 12 to 22, it was confirmed that the viscosity increase rate in the open heating environment was small, and the stability of the resist substrate pretreatment composition in the open heating environment was improved.

    [Industrial availability]    

A resist substrate manufactured using the resist substrate pretreatment composition of the present invention can suppress the wetting and diffusion of the resist and finely pattern the substrate. Therefore, the resist substrate pretreatment composition of the present invention is useful for applications such as a resist substrate, particularly a printed wiring board substrate.

Claims (10)

    A pretreatment composition for a resist substrate, which contains an amphoteric surfactant (A1), an anionic surfactant (A2), and water, and is characterized in that the value of the isoelectric point of the amphoteric surfactant (A1) is reduced. The value obtained by removing the value of the pH value of the above-mentioned resist substrate pre-treatment composition ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the value of the pH value of the pre-treatment composition of the resist substrate]) is -3 ~ 4, and the molar number of the amphoteric surfactant (A1) is relative to the total molar number of the amphoteric surfactant (A1) and the molar number of the anionic surfactant (A2) The ratio of the number ([Mole number of the amphoteric surfactant (A1)] / ([Mole number of the amphoteric surfactant (A1)] + [Mole number of the anionic surfactant (A2)]) is 0.1 ~ 0.9.         For example, the pretreatment composition for a resist substrate according to item 1 of the patent application scope further contains an organic solvent (S) having a boiling point of 100 ° C. or higher and an SP value of 8 to 20.     For example, the pretreatment composition for a resist substrate according to item 1 or 2 of the application scope, wherein the amphoteric surfactant (A1) is a compound represented by the following general formula (1), [In the general formula (1), R ¹ represents a monovalent saturated hydrocarbon group having 1 to 25 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 25 carbon atoms, and R ² and R ³ each independently represent a carbon number of 1 to 25 bis Valence saturated hydrocarbon group or divalent unsaturated hydrocarbon group with 2 to 25 carbon atoms, x is an integer of 1 to 20, and each hydrocarbon group represented by R ² when x is 2 or more may be the same hydrocarbon group or different hydrocarbon groups, M ⁺ represents counter ion]. For example, the anti-substrate pretreatment composition according to any one of the claims 1 to 3, wherein the anionic surfactant (A2) is represented by the following general formula (2) and / or general formula (3) Represented compounds, [In the general formula (2), R ⁴ represents a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms, A ¹ represents an alkylene group having 2 to 12 carbon atoms, and y is an integer of 1 to 20 , When y is 2 or more, each of the alkylene groups represented by A ¹ may be the same alkylene group or different alkylene groups, and M ⁺ represents a relative ion], R ⁵ O-SO ₃ ^- M ⁺ ( 3) [In the general formula (3), R ⁵ represents a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms, and M ⁺ represents a relative ion].     For example, the resist substrate pretreatment composition according to any one of claims 1 to 4, wherein the isoelectric point of the amphoteric surfactant (A1) is 8.0 to 11.0.         For example, a resist substrate pretreatment composition according to any one of claims 1 to 5, wherein the weight ratio of the amphoteric surfactant (A1) to the anionic surfactant (A2) ([amphoteric interface activity The weight of the agent (A1)] / [the weight of the anionic surfactant (A2)]) is 0.1 to 5.0.         For example, a resist substrate pretreatment composition according to any one of the claims 1 to 6, wherein the total weight of the amphoteric surfactant (A1) and the anionic surfactant (A2) is the same as that of the resist substrate The ratio of the weight of the pre-treatment composition ([[Total weight of the amphoteric surfactant (A1) and the above-mentioned anionic surfactant (A2)] / [weight of the resist substrate pre-treatment composition]} × 100) is 0.01 ~ 20% by weight.         For example, the resist substrate pretreatment composition according to any one of claims 1 to 7 has a pH value of 7.0 to 12.0.         A method for manufacturing a resist substrate includes the following steps: a substrate preparation step for preparing a substrate on which a circuit material is formed; and a pre-processing step for using a resist substrate pre-treatment in any one of claims 1 to 8 The composition pre-processes the substrate; and a resist placement step is a step in which a resist is disposed on the substrate after the pre-treatment step.         For example, the method for manufacturing a resist substrate according to item 9 of the application, wherein the circuit material is composed of at least one selected from the group consisting of copper, aluminum, iron, tin, silver, and nickel. , Titanium, chromium and zinc.