WO2018116780A1 - 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

Resist substrate pretreatment composition and method for producing resist substrate

The present invention relates to a resist substrate pretreatment composition and a method for producing a resist substrate. Specifically, the present invention 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 producing a resist substrate using the resist substrate pretreatment composition.

In recent years, pattern formation using an inkjet method has been proposed for a solder resist that protects a conductor circuit formed on a wiring board (see Patent Document 1 and Patent Document 2). In the conventional screen printing method, an insulating film is applied to form a pattern, and then preliminary drying, development of a coating film, post-cure, and uncured resist removal are required. On the other hand, when the ink jet method is used, a pattern can be formed by ejecting insulating film ink and exposing and curing after patterning. Therefore, the operation becomes simpler than the conventional screen printing method, and the manufacturing cost can be greatly reduced.

However, in order to use the inkjet method, it is necessary to use a resin composition having a lower viscosity than the photocurable resin composition used in the conventional screen printing method, and there is a problem that bleeding occurs during the curing process. .

To address these issues, countermeasures such as improving the reactivity and adhesion of resist inks used in the ink jet method have been taken, but they all have a large wetting spread on the substrate and are insufficient for fine patterning. (See Patent Document 3 and Patent Document 4). In addition, a method of treating the copper surface described in Patent Document 5 with an organic substance such as a fatty acid or a resin acid before printing has been studied, but is insufficient.

JP-A-7-263845 Japanese Patent Laid-Open No. 9-18115 JP 2007-227715 A JP 2012-64640 A Japanese Patent No. 4850282

When a resist ink is applied on a substrate by an ink jet method, the resist ink wets and spreads until the ink is cured, and it is difficult to form a fine resist pattern with high definition.

The purpose of the present invention is to perform pretreatment on the substrate before resist ink coating, so that wetting and spreading after applying the resist ink by the ink jet method can be suppressed, and a fine resist pattern can be formed with high accuracy. It is to provide a resist substrate pretreatment composition that can be made.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have reached the present invention.
That is, the present invention is a resist substrate pretreatment composition containing an amphoteric surfactant (A1), an anionic surfactant (A2), and water, such as the amphoteric surfactant (A1). The numerical value obtained by subtracting the numerical value of the pH of the resist substrate pretreatment composition from the numerical value of the resist substrate (the numerical value of the isoelectric point of the amphoteric surfactant (A1))-[the numerical value of the pH of the resist substrate pretreatment composition] ) Is from -3 to 4, and the number of moles of the amphoteric surfactant (A1) relative to the total number of moles of the amphoteric surfactant (A1) and moles of the anionic surfactant (A2) The ratio of the number ([molar number of amphoteric surfactant (A1)] / ([molar number of amphoteric surfactant (A1)] + [molar number of anionic surfactant (A2)])) is 0. Resist substrate pretreatment composition characterized by being 1 to 0.9; A substrate preparation step for preparing the formed substrate, a pretreatment step for pretreating the substrate using the resist substrate pretreatment composition of the present invention, and a resist on the substrate after the pretreatment step. And a resist placement step for placing a resist substrate.

The resist substrate pretreatment composition of the present invention has an effect of suppressing the wetting and spreading of the inkjet resist in the manufacturing process of the resist substrate. Therefore, a fine resist pattern can be created with high accuracy, and the wiring density can be increased.

The resist substrate pretreatment composition of the present invention will be used for a substrate.
As a substrate, a single base material such as phenol resin, epoxy resin, polyimide resin, polyethylene terephthalate, Teflon (registered trademark), ceramic, or a composite base material combining them with glass or paper on an insulating base material , And a metal such as copper or aluminum arranged as a circuit material.

The resist substrate pretreatment composition of the present invention is a resist substrate pretreatment composition containing an amphoteric surfactant (A1), an anionic surfactant (A2), and water, the amphoteric surfactant described above. A value obtained by subtracting the value of the pH of the resist substrate pretreatment composition from the value of the isoelectric point of (A1) ([value of isoelectric point of amphoteric surfactant (A1)]-[resist substrate pretreatment composition] The pH value of the amphoteric surfactant] is from -3 to 4, and the amphoteric surfactant with respect to the total number of moles of the amphoteric surfactant (A1) and the number of moles of the anionic surfactant (A2) Proportion of the number of moles of (A1) ([number of moles of amphoteric surfactant (A1)] / ([number of moles of amphoteric surfactant (A1)] + [number of moles of anionic surfactant (A2)]) ) Is 0.1 to 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) ([amphoteric surfactant (A1) The numerical value of the isoelectric point]-[the numerical value of the pH of the resist substrate pretreatment composition]) is from -3 to 4. That is, the isoelectric point of the amphoteric surfactant (A1) is at least 3 smaller than the pH value of the resist substrate pretreatment composition, and less than or equal to 4 greater than the pH value of the resist substrate pretreatment composition. It is. That is, it is preferable that the amphoteric surfactant is not excessively negatively charged in the resist substrate pretreatment composition of the present invention, and is preferably not excessively positively charged.
The 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) is preferably −2.5 to 3.8, more preferably −2 to 3.6.
If the value obtained by subtracting the value of the pH of the resist substrate pretreatment composition from the value of the isoelectric point of the amphoteric surfactant (A1) is outside the range of -3 to 4, the amphoteric surfactant (A1) Since it is charged too positively or negatively, the resist ink wetting and spreading suppression performance deteriorates.

In this specification, “isoelectric point of amphoteric surfactant (A1)” means a value measured by the following method.
That is, first, 4 wt% or more amphoteric surfactant (A1) 1 wt% aqueous solutions having different pHs are prepared.
Next, these electrical conductivities are measured, and a correlation graph between pH and electrical conductance is created.
In this correlation graph, when a minimum value appears in electrical conductivity, the numerical value of pH at which the minimum value appears is the “isoelectric point of amphoteric surfactant (A1)”.
In this correlation graph, when a minimum value does not appear in the electrical conductivity, an amphoteric surfactant (A1) 1% by weight aqueous solution having a different pH is prepared until the minimum value appears in the correlation graph. Measure.

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

In the resist substrate pretreatment composition of the present invention, the amount of the amphoteric surfactant (A1) relative to the total number of moles of the amphoteric surfactant (A1) and the number of moles of the anionic surfactant (A2). The ratio of the number ([molar number of amphoteric surfactant (A1)] / ([molar number of amphoteric surfactant (A1)] + [molar number of anionic surfactant (A2)])) is 0. It is 1 to 0.9, preferably 0.15 to 0.85, and more preferably 0.2 to 0.8.
If the above numerical value is less than 0.1, the resist ink wetting and spreading suppression performance deteriorates, and if it exceeds 0.9, the resist ink wetting and spreading suppression performance deteriorates.

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.
As the organic solvent (S), ethylene glycol (boiling point: 198 ° C., SP value: 17.8), diethylene glycol (boiling point: 244 ° C., SP value: 15.0), propylene glycol (boiling point: 188 ° C., SP value: 15.9), alcohols such as propylene glycol monomethyl ether (boiling point: 120 ° C., SP value: 11.3), glycerin (boiling point: 290 ° C., SP value: 20.0), diethylene glycol dimethyl ether (boiling point: 162 ° C., SP Value: 8.1) ether, monoethanolamine (boiling point: 171 ° C., SP value: 14.3), isopropanolamine (boiling point: 160 ° C., SP value: 13.1), 2- (2-aminoethyl) Amino) ethanol (boiling point: 244 ° C., SP value: 13.1), ethylenediamine-N, N, N ′, N′-tetraethano Le (boiling point: 280 ° C., SP value: 15.2) include alkanolamines such like.
The organic solvent (S) is ethylene glycol, diethylene glycol, propylene glycol, glycerin, 2- (2-aminoethylamino) ethanol, ethylenediamine-N, N, from the viewpoint of suppressing increase in viscosity when using the resist substrate pretreatment composition. N ′, N′-tetraethanol is preferred, and diethylene glycol, propylene glycol, ethylenediamine-N, N, N ′, N′-tetraethanol is more preferred.
When the resist substrate pretreatment composition of the present invention contains an organic solvent (S), the viscosity of the resist substrate pretreatment composition increases with time when the resist substrate pretreatment composition is used in an open environment. Can be suppressed.
As a result, the stability of the resist substrate pretreatment composition in an open environment is improved and handling is improved.
In the resist substrate pretreatment composition of the present invention, the content of the organic solvent (S) is preferably from the viewpoint of suppressing an increase in viscosity when the resist substrate pretreatment composition is used, with respect to the weight of the resist substrate pretreatment composition. It is 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 the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, FEBRUARY, 1974, Vol. 14, No. 2, ROBERT F. FEDORS. (Pp. 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 group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, nonyl group, decyl group, undecyl group, Examples include lauryl group, stearyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group and tetracosyl group.
Examples of the monovalent unsaturated hydrocarbon group having 2 to 25 carbon atoms include an octadecenyl group and an octadecadienyl group.
R ¹ is preferably an octyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group and a stearyl group, more preferably an octyl group and a lauryl group, and even more preferably a lauryl group from the viewpoint of suppressing wetting and spreading of the resist ink.

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 group, propylene group, butylene group, isobutylene group, pentylene group, isopentylene group, and neopentylene group. Group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene group, 2-methylpentylene group, 3- Methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2 -Trimethylpropylene group, 1-ethyl-2-methylpropylene group, 1-ethyl-1-methylpropylene group and the like.
R ² is preferably a divalent saturated hydrocarbon group having 1 to 25 carbon atoms from the viewpoint of solubility in water, more preferably an ethylene group, a propylene group and a butylene group, still more preferably an ethylene group and a propylene group, and an ethylene group. Particularly preferred.

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 group, ethylene group, propylene group, butylene group, isobutylene group, pentylene group, and isopentylene. Group, neopentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2-dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohesylene group, 1-methylpentylene group, 2-methylpentylene group 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1, 2,2-trimethylpropylene group, 1-ethyl-2-methylpropylene group, 1-ethyl-1-methylpropylene group, etc. .
R ³ is preferably a methylene group, an ethylene group, a propylene group or a butylene group, more preferably a methylene group or an ethylene group, and even more preferably a methylene group from the viewpoint of solubility in water.

X in the general formula (1) is an integer of 1 to 20. From the viewpoint of suppressing wetting and spreading of the resist ink, it is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 5.
Each hydrocarbon group represented by R ² when x is 2 or more may be the same hydrocarbon group or different hydrocarbon groups.

In the general formula (1), M ⁺ is a counter ion. Any anion can be used as long as it can neutralize the anion electrically and form a water-soluble salt with the anion, such as a cation, proton, protonated amine, and ammonium ion formed from an alkali metal or alkaline earth metal. Is mentioned.
Specifically, sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine); secondary amines (dialkylamines such as dimethylamine, diethylamine and dibutylamine and diethanolamine) ); Tertiary amines {trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine, N-methyldiethanolamine and 1,4-diazabicyclo [2.2.2] octane etc.}; amidine {1,8-diazabicyclo [5.4.0] -7-undecene (hereinafter abbreviated as DBU), 1,5-diazabicyclo [4.3.0] -5-nonene, 1H-imidazole, 2-methyl-1H-imidazole, 2 -Ethyl-1H- Midazole, 4,5-dihydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4,5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine, etc.}, Counterions such as ammonium and quaternary ammonium (such as tetraalkylammonium), methylammonium, isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium can be mentioned.

Specific examples of the compound represented by the general formula (1) include octylamine ethyleneimine 2-mol adduct sodium acetate, nonylamine ethyleneimine 2-mol adduct sodium acetate, decylamine ethyleneimine 2-mol adduct acetic acid. Sodium, undecylamine ethyleneimine 2 mol adduct sodium acetate, sodium laurylamine ethyleneimine 2 mol adduct sodium acetate, stearylamine ethyleneimine 2 mol adduct sodium acetate, laurylamine ethyleneimine 1 mol adduct sodium acetate, laurylamine ethylene Imine 3 mol adduct sodium acetate, laurylamine ethyleneimine 4 mol adduct sodium acetate, laurylamine ethyleneimine 5 mol adduct sodium acetate, laurylamine propyleneimine 2 mol adduct sodium acetate Laurylamine butyleneimine 2 mol adduct sodium acetate, potassium laurylamine ethyleneimine 2 mol adduct potassium acetate, laurylamine ethyleneimine 2 mol adduct acetic acid monoethanolamine salt, laurylamine ethyleneimine 2 mol adduct acetic acid DBU salt, Laurylamine ethyleneimine 2 mol adduct tetramethylammonium acetate, laurylamine ethyleneimine 1 mol adduct sodium propionate, laurylamine ethyleneimine 2 mol adduct sodium propionate, laurylamine ethyleneimine 2 mol adduct sodium butyrate, etc. Can be mentioned.
From the viewpoint of suppressing wetting and spreading of resist ink, sodium octylamine ethyleneimine 2 mol adduct sodium acetate, sodium laurylamine ethyleneimine 2 mol adduct sodium acetate, sodium laurylamine ethyleneimine 3 mol adduct sodium acetate, 2 mol laurylamine ethyleneimine adduct Potassium acetate and laurylamine ethyleneimine 2-mole adduct sodium propionate are preferred, sodium laurylamine ethyleneimine 2-mole adduct sodium acetate and laurylamine ethyleneimine 2-mole adduct potassium acetate are more preferred, and laurylamine ethyleneimine 2-mole adduct Sodium acetate is more preferable.

In the resist substrate pretreatment composition of the present invention, the isoelectric point of the amphoteric surfactant (A1) is preferably 8.0 to 11.0, more preferably 8 from the viewpoint of the effect of suppressing wetting and spreading of the resist ink. .5 to 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 group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, Nonyl group, decyl group, undecyl group, lauryl group, stearyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, Examples include a tetracosyl group, an octadecenyl group, and an octadecadienyl group.
R ⁴ is preferably a saturated hydrocarbon group having 1 to 25 carbon atoms from the viewpoint of suppressing the wetting and spreading of the resist ink, more preferably an octyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, and a stearyl group. A lauryl group is further preferred, and a lauryl group is particularly preferred.

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 ethylene group, propylene group, butylene group, isobutylene group, pentylene group, isopentylene group, neopentylene group, 1-methylbutylene group, 2-methylbutylene group, 1,2 -Dimethylpropylene group, 1-ethylpropylene group, hexylene group, isohexylene group, 1-methylpentylene group, 2-methylpentylene group, 3-methylpentylene group, 1,1-dimethylbutylene group, 1,2- Dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2-trimethylpropylene group, 1-ethyl-2-methylpropylene group and 1- Examples thereof include an ethyl-1-methylpropylene group.
A ¹ is preferably an ethylene group, a propylene group, or a butylene group from the viewpoint of solubility in water, more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.

In the general formula (2), y is an integer of 1 to 20. From the viewpoint of suppressing wetting and spreading of the resist ink, it is preferably 1 to 15, more preferably 1 to 10, and still 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.

In the general formula (2), M ⁺ is a counter ion. Any anion can be used as long as it can neutralize the anion electrically and form a water-soluble salt with the anion, such as a cation, proton, protonated amine and ammonium ion formed from an alkali metal or alkaline earth metal. Is mentioned.
M ⁺ includes sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine); secondary amines (dialkylamines such as dimethylamine, diethylamine and dibutylamine and diethanolamine) ); Tertiary amines {trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine, N-methyldiethanolamine and 1,4-diazabicyclo [2.2.2] octane etc.}; amidine {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-Di Hydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4,5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine etc.}, ammonium and quaternary ammonium Counter ions such as (tetraalkylammonium etc.), methylammonium, isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium.

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 group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, Nonyl group, decyl group, undecyl group, lauryl group, stearyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, Examples include a tetracosyl group, an octadecenyl group, and an octadecadienyl group.
R ⁴ is preferably a saturated hydrocarbon group having 1 to 25 carbon atoms from the viewpoint of suppressing the wetting and spreading of the resist ink, more preferably an octyl group, a nonyl group, a decyl group, an undecyl group, a lauryl group, and a stearyl group. A lauryl group is further preferred, and a lauryl group is particularly preferred.

M ⁺ in the general formula (3) is a counter ion. Any anion can be used as long as it can neutralize the anion electrically and form a water-soluble salt with the anion, such as a cation, proton, protonated amine and ammonium ion formed from an alkali metal or alkaline earth metal. Is mentioned.
M ⁺ includes sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine); secondary amines (dialkylamines such as dimethylamine, diethylamine and dibutylamine and diethanolamine) ); Tertiary amines {trialkylamines such as trimethylamine, triethylamine and tributylamine, triethanolamine, N-methyldiethanolamine and 1,4-diazabicyclo [2.2.2] octane etc.}; amidine {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-Di Hydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4,5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine etc.}, ammonium and quaternary ammonium Counter ions such as (tetraalkylammonium etc.), methylammonium, isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium.

In the resist substrate pretreatment composition of the present invention, the anionic surfactant (A2) is an alkyl sulfate ester (salt) having a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms (salt) ( A2-1) and polyoxyalkylene alkyl ether sulfate (salt) (A2-2) in which the alkyl group is a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms.

Alkyl sulfate ester (salt) (A2-1) having a saturated or unsaturated hydrocarbon group having 1 to 25 carbon atoms includes mono- and diesters such as propanol, capryl alcohol, lauryl alcohol and oleyl alcohol; The salt etc. are mentioned.

Examples of the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) include mono- and diesterified products 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 linear, branched or cyclic, and may have a saturated or unsaturated bond. Specific examples of primary alcohols include hexane-1-ol, heptane-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol, dodecan-1-ol, and tetradecan-1-ol. Hexadecan-1-ol, octadecan-1-ol, icosan-1-ol linear amine, branched alcohols such as isodecyl alcohol, cyclic alcohols such as cyclohexanol, beef tallow alcohol, hardened tallow alcohol and palm which are mixtures thereof Examples include primary alcohols derived from animal and vegetable oils such as oil alcohol.

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. Secondary alcohols include propan-2-ol, butan-2-ol, cyclohexanol, decan-2-ol and the like. As the secondary alcohol, one kind or a mixture of two or more kinds may be used.

The alkylene oxide in the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) is an alkylene oxide having 2 to 12 carbon atoms, such as ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,2 -Hexylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran and the like. When the number of alkylene oxides to be added 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 sulfate sodium (salt), lauryl alcohol ethylene oxide 5 mol propylene oxide 3 mol adduct sulfuric acid. Sodium ester (salt), myristyl alcohol ethylene oxide 8 mol adduct sulfate sodium salt (salt), tetradecyl alcohol ethylene oxide 3 mol adduct sodium sulfate ester (salt), octyl alcohol ethylene oxide 2 mol adduct sodium sulfate ester (salt) ) And lauryl alcohol ethylene oxide 2-mol adduct sulfate sodium (salt).

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

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

In the resist substrate pretreatment composition of the present invention, the ratio of the total weight of the amphoteric surfactant (A1) and the anionic surfactant (A2) to the weight of the resist substrate pretreatment composition ({[amphoteric surfactant (Total weight of (A1) and anionic surfactant (A2)] / [weight of resist substrate pretreatment composition]} × 100) is preferably 0.01 to 20 from the viewpoint of suppressing wetting and spreading of the resist ink. % By weight, more preferably 0.1 to 15% by weight, 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 spreading of the resist, it is preferably 7.5 to 11.5, more preferably 8.0 to 11.0, and still more preferably 8.5 to 11.0.

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

Examples of the pH adjuster (B) include acids (inorganic acids and organic acids) and alkalis (inorganic alkalis 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 producing a resist substrate in the present invention is a method for producing a resist substrate including a step of performing substrate pretreatment before resist application using the resist substrate pretreatment composition of the present invention.
That is, the method for producing a resist substrate of the present invention includes a substrate preparation step of preparing a substrate on which a circuit material is formed, and a pretreatment step of pretreating the substrate using the resist substrate pretreatment composition of the present invention. And a resist placement step of placing a resist on the substrate after the pretreatment step.

In the method for producing a resist substrate of the present invention, the circuit material formed on the substrate may be at least one selected from the group consisting of copper, aluminum, iron, tin, silver, nickel, titanium, chromium, and zinc. preferable.

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

Hereinafter, although an example and a comparative example explain the present invention still in detail, the present invention is not limited to these. Unless otherwise specified, “parts” means “parts by weight” and “%” means “% by weight”. The water used in the examples and comparative examples has a specific resistance value of 18 MΩ or more.

<Production Example 1>
205 parts of lauryl chloride and 103 parts of diethylenetriamine were charged into a stainless steel autoclave equipped with stirring and temperature control functions, and the reaction was carried out at 80 to 120 ° C. for about 1 hour after the inside of the mixed system was replaced with nitrogen. After the reaction, the reaction mixture was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand for liquid separation. After removing the lower layer (aqueous layer), the gas layer was replaced with nitrogen and distilled under reduced pressure (distillation conditions for the main product: 185 to 240 ° C., 5 to 20 mmHg). Water and 271 parts of the main product were put into a glass reaction vessel, and an aqueous solution of monochloroacetic acid (95 parts) was added at 50 to 100 ° C. while nitrogen was passed through the gas phase part. The pH was adjusted with an aqueous sodium oxide solution to obtain sodium laurylamine ethyleneimine 2-mol adduct sodium acetate (A1-1).

<Production Example 2>
205 parts of lauryl chloride and 60 parts of ethylenediamine were charged into a stainless steel autoclave having a stirring and temperature control function, and the reaction was carried out at 80 to 120 ° C. for about 1 hour after substituting nitrogen in the mixed system. After the reaction, the reaction mixture was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand for liquid separation. After removing the lower layer (aqueous layer), the gas layer was replaced with nitrogen and distilled under reduced pressure (distillation conditions for the main product: 185 to 240 ° C., 5 to 20 mmHg). Water and 271 parts of the main product were put into a glass reaction vessel, and an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100 ° C. while reacting nitrogen at the gas layer, and reacted at 90 to 110 ° C. The pH was adjusted with an aqueous sodium hydroxide solution to obtain sodium laurylamine ethyleneimine 1-mol adduct sodium propionate (A1-2).

<Production Example 3>
205 parts of lauryl chloride and 103 parts of diethylenetriamine were charged into a stainless steel autoclave equipped with stirring and temperature control functions, and the reaction was carried out at 80 to 120 ° C. for about 1 hour after the inside of the mixed system was replaced with nitrogen. After the reaction, the reaction mixture was cooled, an aqueous sodium hydroxide solution was added, and the mixture was stirred and then allowed to stand for liquid separation. After removing the lower layer (aqueous layer), the gas layer was replaced with nitrogen and distilled under reduced pressure (distillation conditions for the main product: 185 to 240 ° C., 5 to 20 mmHg). Water and 271 parts of the main product were put into a glass reaction vessel, and an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100 ° C. while reacting nitrogen at the gas layer, and reacted at 90 to 110 ° C. The pH was adjusted with an aqueous sodium hydroxide solution to obtain sodium laurylamine ethyleneimine 2-mol adduct sodium propionate (A1-3).

<Production Example 4>
In a container similar to Production Example 1, 186 parts of lauryl alcohol, 0.32 part of magnesium perchlorate, and 0.03 part of magnesium hydroxide were charged, and the inside of the mixed system was replaced with nitrogen, and then under reduced pressure (20 mmHg) And dehydration at 120 ° C. for 1 hour. Next, 88 parts of ethylene oxide (hereinafter also referred to as “EO”) was introduced at 150 ° C. so that the gauge pressure was 1 to 3 kgf / cm ² . The reaction product was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was gradually added dropwise over 4 hours while maintaining the temperature at 20 ° C. After dehydrochlorination for 2 hours while blowing nitrogen gas at the same temperature, the sulfuric acid ester was neutralized with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, and lauryl alcohol ethylene oxide 3 mol adduct sulfate An aqueous solution of sodium salt (A2-2-1) was obtained.

<Production Example 5>
In a container similar to Production Example 1, 186 parts of lauryl alcohol, 0.32 part of magnesium perchlorate, and 0.03 part of magnesium hydroxide were charged, and the inside of the mixed system was replaced with nitrogen, and then under reduced pressure (20 mmHg) And dehydration at 120 ° C. for 1 hour. Next, 220 parts of EO and 174 parts of propylene oxide (hereinafter also referred to as “PO”) were introduced at 150 ° C. so that the gauge pressure was 1 to 3 kgf / cm ² . The reaction product was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was gradually added dropwise over 4 hours while maintaining the temperature at 20 ° C. After dehydrochlorination for 2 hours while blowing nitrogen gas at the same temperature, the sulfuric ester was neutralized with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, and 5 moles of lauryl alcohol ethylene oxide and 3 moles of propylene oxide. An aqueous solution of adduct sulfate sodium salt (A2-2-2) was obtained.

<Production Example 6>
In a container similar to Production Example 1, 214 parts of myristyl alcohol, 0.32 part of magnesium perchlorate, and 0.03 part of magnesium hydroxide were charged, and the inside of the mixed system was replaced with nitrogen, and then under reduced pressure (20 mmHg) And dehydration at 120 ° C. for 1 hour. Next, 235 parts of EO was introduced at 150 ° C. so that the gauge pressure was 1 to 3 kgf / cm ² . The reaction product was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was gradually added dropwise over 4 hours while maintaining the temperature at 20 ° C. After dehydrochlorination for 2 hours while blowing nitrogen gas at the same temperature, the sulfuric acid ester was neutralized with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, and the myristyl alcohol ethylene oxide 8-mole adduct sulfate. An aqueous solution of sodium salt (A2-2-3) was obtained.

<Examples 1 to 22> and <Comparative Examples 1 to 3>
Each component was blended so as to have the composition shown in Tables 1 to 3, and stirred at 25 ° C. with a magnetic stirrer at 40 rpm for 20 minutes to prepare resist substrate pretreatment compositions (E1) to (E22) and comparative examples. Resist substrate pretreatment compositions (H1) to (H3) were obtained. The weight part of each component is a numerical value converted into a pure component, and water in each component was included in the pure water.

<Measurement of pH>
The pH of the resist substrate pretreatment 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 contact angle between resist and 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) One substrate is immersed in 100 ml of 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, and then rinsed with pure water having an electrical resistivity of 18 MΩ · cm or more for 10 seconds and then in 300 ml of pure water for 30 seconds. It was immersed for cleaning and dried with nitrogen.
(2) Next, the substrate is immersed in a resist substrate pretreatment composition at 25 ° C. for 1 minute, and then rinsed with pure water having an electrical resistivity of 18 MΩ · cm or more for 10 seconds and immersed in 300 ml of pure water for 30 seconds for cleaning. Then, the substrate was dried with nitrogen to obtain a substrate after surface treatment.
(3) Using triethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.) as a model resist, the contact angle between the model resist and the substrate after surface treatment is fully automatic contact angle meter ( Kyowa Interface Science Co., Ltd., “Fully Automatic Contact Angle Meter DM700”). The results are shown in Tables 1 to 3. A contact angle of 40 ° or more is good and indicates that wetting spread is suppressed.

<Measurement of contact angle between resist and substrate after surface treatment-2 (surface treatment of copper substrate on which 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) One substrate is immersed in 100 ml of 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, and then rinsed with pure water having an electrical resistivity of 18 MΩ · cm or more for 10 seconds and then in 300 ml of pure water for 30 seconds. It was immersed for cleaning and dried with nitrogen.
(2) Next, after immersing the substrate in 5% hydrogen peroxide solution for 1 minute, the substrate was rinsed with pure water having an electrical resistivity of 18 MΩ · cm or more for 10 seconds, and immersed in 300 ml of pure water for 30 seconds for cleaning. Then, it was dried with nitrogen. By this operation, a copper oxide film was formed on the surface of the copper substrate.
(3) A copper substrate on which a copper oxide film is formed is dipped in a resist substrate pretreatment composition at 25 ° C. for 1 minute, and then rinsed with pure water having an electrical resistivity of 18 MΩ · cm or more for 10 seconds to obtain 300 ml of pure water. After being immersed in the substrate for 30 seconds and washed, the substrate was dried with nitrogen to obtain a substrate after surface treatment.
(4) Using triethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.) as a model resist, the contact angle between the model resist and the substrate after the surface treatment is fully automatic contact angle meter ( Kyowa Interface Science Co., Ltd., “Fully Automatic Contact Angle Meter DM700”). The results are shown in Tables 1 to 3. A contact angle of 35 ° or more is good and indicates that wetting spread is suppressed.

<Measurement of viscosity of resist substrate pretreatment composition>
(1) Immediately after compounding the resist substrate pretreatment composition, 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.
(2) 300 g of the resist substrate pretreatment composition was put in a resin container, and the temperature was adjusted to 50 ° C. in an open system, and left for 10 hours. Thereafter, using an E-type viscometer (manufactured by Brookfield), the temperature was adjusted to 25 ° C. and the viscosity was measured. The results are shown in Tables 1 to 3.
(3) The viscosity increase rate of the resist substrate pretreatment composition in an open heating environment was calculated by the following equation. The results are shown in Tables 1 to 3.
Viscosity increase rate in open heating environment of resist substrate pretreatment composition (%)
= {([Viscosity (mPa · s) after temperature adjustment to 50 ° C. in an open system and standing for 10 hours]] − [Viscosity immediately after compounding (mPa · s)]) / [Viscosity immediately after compounding (mPa · s) s)]} × 100

As is apparent from the results shown in Tables 1 to 3, the copper substrate subjected to the surface treatment with the resist substrate pretreatment compositions of Examples 1 to 22 has a large resist contact angle regardless of the surface oxidation state. As a result, wetting and spreading were suppressed. On the other hand, it was confirmed that the copper substrate subjected to the surface treatment with the resist substrate pretreatment compositions of Comparative Examples 1 to 3 had a small contact angle regardless of the surface oxidation state, and the wetting spread was not sufficiently suppressed.
Further, it was confirmed that the resist substrate pretreatment compositions of Examples 12 to 22 had a small viscosity increase rate in the open heating environment, and the stability of the resist substrate pretreatment composition in the open heating environment was improved. .

The resist substrate manufactured by using the resist substrate pretreatment composition of the present invention can suppress the spread of the resist and perform fine patterning on 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 resist substrate pretreatment composition containing an amphoteric surfactant (A1), an anionic surfactant (A2), and water,
The value obtained by subtracting the value of the pH of the resist substrate pretreatment composition from the value of the isoelectric point of the amphoteric surfactant (A1) (the value of the isoelectric point of the amphoteric surfactant (A1))-[resist The numerical value of the pH of the substrate pretreatment composition]) is -3 to 4,
Ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the amphoteric surfactant (A1) and the number of moles of the anionic surfactant (A2) ([amphoteric surfactant (Number of moles of (A1)] / ([number of moles of amphoteric surfactant (A1)] + [number of moles of anionic surfactant (A2)]) is 0.1 to 0.9. A resist substrate pretreatment composition. The resist substrate pretreatment composition according to claim 1, further comprising an organic solvent (S) having a boiling point of 100 ° C or higher and an SP value of 8 to 20. The resist substrate pretreatment composition according to claim 1 or 2, 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 are independent of each other. Represents a divalent saturated hydrocarbon group having 1 to 25 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms, wherein x is an integer of 1 to 20 and x is 2 or more. Each hydrocarbon group represented by ² may be the same hydrocarbon group or a different hydrocarbon group, and M ⁺ represents a counter ion. ] The resist substrate pretreatment composition according to any one of claims 1 to 3, wherein the anionic surfactant (A2) is a compound represented by the following general formula (2) and / or general formula (3).

[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, y is an integer of 1 to 20, each alkylene group represented by A ¹ when y is 2 or more may be the same alkylene group or different alkylene groups, and M ⁺ represents a counter ion . ]

[In 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 counter ion. ] The resist substrate pretreatment composition according to any one of claims 1 to 4, wherein an isoelectric point of the amphoteric surfactant (A1) is 8.0 to 11.0. The weight ratio of the amphoteric surfactant (A1) to the anionic surfactant (A2) ([weight of amphoteric surfactant (A1)] / [weight of anionic surfactant (A2)]) The resist substrate pretreatment composition according to any one of claims 1 to 5, which is 0.1 to 5.0. Ratio of the total weight of the amphoteric surfactant (A1) and the anionic surfactant (A2) and the weight of the resist substrate pretreatment composition ({[amphoteric surfactant (A1) and the anionic interface 7. The resist substrate pretreatment composition according to claim 1, wherein the total weight of the activator (A2) / [weight of the resist substrate pretreatment composition]} × 100) is 0.01 to 20% by weight. object. The resist substrate pretreatment composition according to any one of claims 1 to 7, which has a pH of 7.0 to 12.0. A substrate preparation step of preparing a substrate on which circuit material is formed;
A pretreatment step of pretreating the substrate using the resist substrate pretreatment composition according to any one of claims 1 to 8;
A resist placement step of placing a resist on the substrate after the pretreatment step. The method for manufacturing a resist substrate according to claim 9, wherein the circuit material is at least one selected from the group consisting of copper, aluminum, iron, tin, silver, nickel, titanium, chromium, and zinc.