KR102120022B1 - Resist substrate pretreatment composition and method for manufacturing resist substrate - Google Patents

Abstract

Provided is a resist substrate pretreatment composition capable of suppressing the wet spreading property after coating a resist ink by an inkjet method and capable of forming a fine resist pattern with high definition.
The resist substrate pretreatment composition of the present invention is a resist substrate pretreatment composition containing an amphoteric surfactant (A1), anionic surfactant (A2), and water, from the numerical value of the isoelectric point of the amphoteric surfactant (A1). , The value obtained by subtracting the value of the pH of the resist substrate pretreatment composition ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the value of the pH of the resist substrate pretreatment composition]) is -3 to 4, the amphoteric interface Ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the mole number of the active agent (A1) and the anionic surfactant (A2) ([mole number of the amphoteric surfactant (A1)] / ([ The number of moles of amphoteric surfactant (A1)] + [the number of moles of anionic surfactant (A2)])) is characterized in that it is 0.1 to 0.9.

Description

Resist substrate pretreatment composition and method for manufacturing resist substrate

The present 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 copper alloy using a solder resist, and a method for manufacturing a resist substrate using the resist substrate pretreatment composition.

In the solder resist that protects the conductor circuit formed on the wiring board, pattern formation using an inkjet method has been recently proposed (see Patent Documents 1 and 2). In the conventional screen printing method, after forming an insulating film to form a pattern, pre-drying, development of the coating film, post-cure, and uncured resist removal process work are required. On the other hand, if the inkjet method is used, the pattern can be formed by discharging and patterning the insulating film ink, followed by photosensitive and curing, so that the operation is simplified compared to the conventional screen printing method, and manufacturing cost can be significantly reduced.

However, in order to use the inkjet method, it is necessary to use a resin composition having a low viscosity as compared with the photocurable resin composition used in the conventional screen printing method, and there is a problem that smearing occurs during the curing process.

Responsiveness or improvement in adhesion of the resist ink used in the inkjet method has been addressed to these problems, but all of them have large wet spreadability on the substrate and are insufficient to perform fine patterning (see Patent Documents 3 and 4). ). In addition, a method of 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 been studied, but is insufficient.

Japanese Patent Application Publication No. Hei 7-263845 Japanese Patent Application Publication No. 9-18115 Japanese Patent Application Publication No. 2007-227715 Japanese Patent Application Publication 2012-64640 Japanese Patent No. 4850282

When a resist ink is coated on the substrate by an inkjet method, there is a problem that it is difficult to form a fine resist pattern with high definition while the resist ink spreads wet while the ink is cured.

An object of the present invention is to provide a resist substrate pretreatment composition capable of suppressing the wet spread property after coating the resist ink by an inkjet method by pre-treating the substrate before the resist ink is coated, thereby forming a fine resist pattern with high definition. Is to do.

The inventors of the present invention have reached the present invention as a result of earnestly examining to solve the above problems.

That is, the present invention is a resist substrate pretreatment composition containing an amphoteric surfactant (A1), an anionic surfactant (A2), and water, from the numerical value of the isoelectric point of the amphoteric surfactant (A1), the resist The value obtained by subtracting the value of the pH of the substrate pretreatment composition ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the value of the pH of the resist substrate pretreatment composition]) is -3 to 4, and the amphoteric surfactant (A1 Ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the mole number of) and the number of moles of the anionic surfactant (A2) ([molar number of the amphiphilic surfactant (A1)] / ([amphoteric interface Molar number of activator (A1)] + [molar number of anionic surfactant (A2)])) is 0.1 to 0.9, characterized in that the resist substrate pretreatment composition; A substrate preparation process for preparing a substrate on which a circuit material is formed, a pretreatment process for pretreating the substrate using the resist substrate pretreatment composition of the present invention, and a resist for disposing a resist on the substrate after the pretreatment process It is a manufacturing method of the resist substrate characterized by including a batch process.

The resist substrate pretreatment composition of the present invention exerts an effect of suppressing the wettability of the inkjet resist in the manufacturing process of the resist substrate. Therefore, a fine resist pattern can be created with high definition, and the wiring can be made high in density.

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

As the substrate, a single base material such as phenol resin, epoxy resin, polyimide resin, polyethylene terephthalate, Teflon (registered trademark), ceramic, or a composite base material obtained by combining glass or paper with them on an insulating base material is copper or aluminum. Metals, such as those arrange|positioned as a circuit material, are mentioned.

The resist substrate pretreatment composition of the present invention is a resist substrate pretreatment composition containing an amphoteric surfactant (A1), anionic surfactant (A2), and water, from the numerical value of the isoelectric point of the amphoteric surfactant (A1). , The value obtained by subtracting the value of the pH of the resist substrate pretreatment composition ([the value of the isoelectric point of the amphoteric surfactant (A1)]-[the value of the pH of the resist substrate pretreatment composition]) is -3 to 4, the amphoteric interface Ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the mole number of the active agent (A1) and the anionic surfactant (A2) ([mole number of the amphoteric surfactant (A1)] / ([ The number of moles of amphoteric surfactant (A1)] + [the number of moles of anionic surfactant (A2)])) is characterized in that it is 0.1 to 0.9.

In the resist substrate pretreatment composition of the present invention, the value of the pH of the resist substrate pretreatment composition is subtracted 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 pH of the substrate pretreatment composition]) is -3 to 4. That is, the isoelectric point of the amphoteric surfactant (A1) is at least a value as small as 3 from the pH value of the resist substrate pretreatment composition, and is at most a value as large as 4 from the pH value of the resist substrate pretreatment composition. In short, in the resist substrate pretreatment composition of the present invention, it is preferable that the amphoteric surfactant is not overcharged negatively, and it is preferable that it is not overcharged positively.

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 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) is positively or negatively charged. The performance of suppressing the wet spread property of the resist ink deteriorates.

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

That is, first, an aqueous solution of 1% by weight of an amphoteric surfactant (A1) having 4 or more samples each having a different pH is prepared.

Next, these electrical conductivity is measured, and a correlation graph of pH and electrical conductivity is generated.

In this correlation graph, when a minimum value appears in the electrical conductivity, the pH value when the minimum value appears is the "isoelectric point of the amphoteric surfactant (A1)".

In this correlation graph, when a minimum value does not appear in the electrical conductivity, an electrical conductivity is measured by preparing a 1% by weight aqueous solution of an amphoteric surfactant (A1) having a different pH until a minimum value appears in the correlation graph.

In the present 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 ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the mole number of the amphoteric surfactant (A1) and the number of moles of the anionic surfactant (A2) ([Amphotericity] The number of moles of surfactant (A1)] / ([the number of moles of amphoteric surfactant (A1)] + [the number of moles of anionic surfactant (A2)])) is 0.1 to 0.9, preferably 0.15 to 0.85, More preferably, it is 0.2 to 0.8.

When the above value is less than 0.1, the suppression performance of the wet spreadability of the resist ink deteriorates, and when it exceeds 0.9, the suppression performance of the resist spreadability is similarly deteriorated.

It is preferable that the resist substrate pretreatment composition of this invention also contains the organic solvent (S) whose boiling point is 100 degreeC or more, and SP value is 8-20.

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), etc. Ether, 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), and alkanolamines such as ethylenediamine-N,N,N',N'-tetraethanol (boiling point: 280 DEG C, SP value: 15.2).

The organic solvent (S) is ethylene glycol, diethylene glycol, propylene glycol, glycerin, 2-(2-aminoethylamino)ethanol, ethylenediamine-N, from the viewpoint of suppressing the increase in viscosity when using the resist substrate pretreatment composition. N,N',N'-tetraethanol is preferable, and diethylene glycol, propylene glycol, and ethylenediamine-N,N,N',N'-tetraethanol are more preferable.

When the resist substrate pretreatment composition of the present invention contains the organic solvent (S), when the resist substrate pretreatment composition is used in an open environment, the increase in viscosity of the resist substrate pretreatment composition over time can be suppressed.

As a result, stability under the open environment of the resist substrate pretreatment composition is improved and handling property is improved.

In the resist substrate pretreatment composition of the present invention, the content of the organic solvent (S) is preferably 1 to 40% by weight from the viewpoint of suppressing the increase in viscosity when the resist substrate pretreatment composition is used relative to the weight of the resist substrate pretreatment composition. , More preferably, it is 3 to 30% by weight, and most preferably 5 to 20% by weight.

In addition, SP value in this specification is calculated by the method described in the following literature proposed by Fedors et al.

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

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

[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.

As a monovalent saturated hydrocarbon group having 1 to 25 carbon atoms, methyl group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, nonyl group, decyl group, undecyl group, lauryl group, ste Aryl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, isocosyl group, henicosyl group, docosyl group, tricosyl group and tetracosyl group, etc. Can be heard.

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 more preferably a lauryl group from the viewpoint of suppressing the wettability of the resist ink. Do.

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.

As a C2-C25 divalent saturated hydrocarbon group and a C2-C25 divalent unsaturated hydrocarbon group, an ethylene group, a propylene group, a butylene group, an isobutylene group, a pentylene group, an isopentylene group, a neopentylene group, 1-methyl Butylene 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, And 1-ethyl-2-methylpropylene group and 1-ethyl-1-methylpropylene group.

R ² is preferably a C 1 to C 25 divalent saturated hydrocarbon group from the viewpoint of solubility in water, more preferably an ethylene group, a propylene group and a butylene group, more preferably an ethylene group and a propylene group, and particularly preferably an ethylene group. .

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.

The divalent saturated hydrocarbon group having 1 to 25 carbon atoms and the divalent unsaturated hydrocarbon group having 2 to 25 carbon atoms are methylene group, 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-methyl Pentylene group, 1,1-dimethylbutylene group, 1,2-dimethylbutylene group, 2,2-dimethylbutylene group, 1-ethylbutylene group, 1,1,2-trimethylpropylene group, 1,2,2-trimethyl And propylene groups, 1-ethyl-2-methylpropylene groups, and 1-ethyl-1-methylpropylene groups.

R ³ is preferably a methylene group, an ethylene group, a propylene group, and a butylene group from the viewpoint of solubility in water, more preferably a methylene group and an ethylene group, and more preferably a methylene group.

X in general formula (1) is an integer of 1-20. 1-15 are preferable, 1-10 are more preferable, and 1-5 are still more preferable from a viewpoint of suppressing the wet spread property of a resist ink.

Each hydrocarbon group represented by R ² when x is 2 or more may be the same hydrocarbon group or a different hydrocarbon group.

M ⁺ in General Formula (1) is a counter ion. As long as the anion is neutralized electrically, a water-soluble salt can be formed together with the anion, for example, cations, protons, protonated amines and ammonium ions formed from alkali metals or alkaline earth metals can be mentioned. have.

Specifically, sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine, etc.); 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-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 (such as tetraalkylammonium), methylammonium, isopropylammonium, butylammonium, dipropyl And counter ions such as ammonium, diisopropylammonium, trimethylammonium, triethylammonium and dimethylethylammonium.

As the compound represented by the general formula (1), specifically, octylamineethyleneimine 2 mol adduct sodium acetate, nonylamineethyleneimine 2 mol adduct sodium acetate, decylamineethyleneimine 2 mol adduct sodium acetate, undecyl Amine ethyleneimine 2 mol adduct sodium acetate, 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, laurylamine ethyleneimine 2 mol adduct potassium acetate, laurylamine ethyleneimine 2 mol adduct monoacetic 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. have.

From the viewpoint of suppressing the wet-spreading property of the resist ink, 2 moles of octylamineethyleneimine adduct, sodium acetate, laurylamineethyleneimine 2mol adduct, sodium acetate, laurylamineethyleneimine, 3mol adduct, sodium acetate, laurylamineethyleneimine 2 mol adduct potassium acetate and laurylamine ethyleneimine 2 mol adduct sodium propionate are preferred, laurylamine ethyleneimine 2 mol adduct sodium acetate and laurylamine ethyleneimine 2 mol adduct potassium acetate are more preferred, The laurylamine ethyleneimine 2 mol adduct sodium acetate is more preferred.

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, and more preferably 8.5 to 11.0 from the viewpoint of the effect of suppressing the wettability of the resist ink.

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

[Formula 2]

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.

As a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms, a methyl group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, nonyl group, decyl group, and unde Real group, lauryl group, stearyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, And tricosilyl groups, tetracosilyl groups, octadecenyl groups, and octadecadienyl groups.

R ⁴ is preferably a saturated hydrocarbon group having 1 to 25 carbon atoms from the viewpoint of suppressing the wettability 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, and an octyl group and A lauryl group is more preferable, and a lauryl group is particularly preferable.

A ¹ in General Formula (2) is an alkylene group having 2 to 12 carbons.

Specifically as an alkylene group having 2 to 12 carbon atoms, 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 -Ethyl-1-methylpropylene group and the like.

A ¹ is preferably an ethylene group, a propylene group, and a butylene group from the viewpoint of solubility in water, more preferably an ethylene group and a propylene group, and more preferably an ethylene group.

Y in general formula (2) is an integer of 1-20. 1-15 are preferable, 1-10 are more preferable, and 1-5 are still more preferable from a viewpoint of suppressing the wet spread property of a resist ink. Each alkylene group represented by A ¹ when y is 2 or more may be the same alkylene group or a different alkylene group.

M ⁺ in General Formula (2) is a counter ion. As long as the anion is neutralized electrically, a water-soluble salt can be formed together with the anion, for example, cations, protons, protonated amines and ammonium ions formed from alkali metals or alkaline earth metals can be mentioned. have.

As M ⁺ , sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine, etc.); 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-imi Dazole, 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, trimethyl And counter ions such as ammonium, triethylammonium and dimethylethylammonium.

[Formula 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.

As a saturated hydrocarbon group having 1 to 25 carbon atoms or an unsaturated hydrocarbon group having 2 to 25 carbon atoms, a methyl group, ethyl group, n-propyl group, hexyl group, cyclohexyl group, n-butyl group, octyl group, nonyl group, decyl group, and unde Real group, lauryl group, stearyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, And tricosilyl groups, tetracosilyl groups, octadecenyl groups, and octadecadienyl groups.

R ⁴ is preferably a saturated hydrocarbon group having 1 to 25 carbon atoms from the viewpoint of suppressing the wettability 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, and an octyl group and A lauryl group is more preferable, and a lauryl group is particularly preferable.

M ⁺ in General Formula (3) is a counter ion. As long as the anion is neutralized electrically, a water-soluble salt can be formed together with the anion, for example, cations, protons, protonated amines and ammonium ions formed from alkali metals or alkaline earth metals can be mentioned. have.

As M ⁺ , sodium, potassium, primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine, etc.); 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-imi Dazole, 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, trimethyl And counter ions such as ammonium, triethylammonium and dimethylethylammonium.

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

The alkyl sulfuric acid ester (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 is mono and diesters such as propanol, capryl alcohol, lauryl alcohol or oleyl alcohol, and the like. And salts.

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

The primary alcohol serving as a raw material for the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) may be a straight chain, branched chain or cyclic, or may have a saturated or unsaturated bond. Specific examples of the primary alcohol include hexane-1-ol, heptan-1-ol, octan-1-ol, nonan-1-ol, decan-1-ol, dodecan-1-ol, tetradecane-1 -Ol, hexadecan-1-ol, octadecane-1-ol, dicarboxylic acid-1-ol straight chain amine, branched alcohol such as isodecyl alcohol, cyclic alcohol such as cyclohexanol, Uji alcohol as a mixture thereof , Primary alcohols derived from animal and vegetable oils such as hydrogenated tallow alcohol and palm oil alcohol.

The secondary alcohol serving as a raw material for the polyoxyalkylene alkyl ether sulfate (salt) (A2-2) may be a straight chain, branched chain or cyclic, or may have a saturated or unsaturated bond. Examples of the secondary alcohol include propan-2-ol, butan-2-ol, cyclohexanol, and decan-2-ol. As the secondary alcohol, one kind or a mixture of two or more kinds may be used.

As the alkylene oxide in the polyoxyalkylene alkyl ether sulfate ester (salt) (A2-2), an alkylene oxide having 2 to 12 carbon atoms, for example, ethylene oxide, 1,2-propylene oxide, 1,2- And butylene oxide, 1,2-hexylene oxide, tetrahydrofuran, and 3-methyltetrahydrofuran. 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 random bonds or block bonds.

As a specific polyoxyalkylene alkyl ether sulfate ester (salt) (A2-2), lauryl alcohol ethylene oxide 3 mol adduct sulfate sodium (salt), lauryl alcohol ethylene oxide 5 mol propylene oxide 3 mol adduct sulfate ester Sodium (salt), myristyl alcohol ethylene oxide 8 mol adduct sodium sulfate (salt), tetradecyl alcohol ethylene oxide 3 mol adduct sodium sulfate (salt), octyl alcohol ethylene oxide 2 mol adduct sodium sulfate (salt) ) And lauryl alcohol ethylene oxide 2 mol adduct sodium sulfate (salt) and the like.

In the resist substrate pretreatment composition of the present invention, water includes ultrapure water, ion-exchanged water, reverse osmosis (RO) water, and distilled water, and ultrapure water is preferred from the viewpoint of cleanliness.

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

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) and the weight of the resist substrate pretreatment composition ({[[Amphoteric Surfactant (A1) and Anionic) The total weight of the surfactant (A2)] / [weight of the resist substrate pretreatment composition]} × 100) is preferably from 0.01 to 20% by weight, more preferably from 0.1 to 15, from the viewpoint of suppressing the wettability of the resist ink. It is weight%, More preferably, it is 1-10 weight%.

It is preferable that the pH of the resist substrate pretreatment composition of this invention is 7.0-12.0. From the viewpoint of suppressing the wet spreading property of the resist, it is preferably 7.5 to 11.5, more preferably 8.0 to 11.0, further preferably 8.5 to 11.0.

The resist substrate pretreatment composition of the present invention may contain a pH adjusting agent (B), a preservative (C), or the like as other constituent materials.

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

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

The manufacturing method of the resist substrate in this invention is a manufacturing method of the resist substrate including the process of performing the substrate pre-treatment before apply|coating resist using the resist substrate pre-treatment composition of this invention.

That is, the method for manufacturing a resist substrate of the present invention includes a substrate preparation process for preparing a substrate on which a circuit material is formed, a pretreatment process for pretreating the substrate using the resist substrate pretreatment composition of the present invention, and the pretreatment process. And a resist disposing step of disposing the resist on the substrate.

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

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

Example

Hereinafter, the present invention will be described in more detail by examples and comparative examples, but the present invention is not limited to these. In the following, unless otherwise specified, parts by weight represent% by weight and% by weight. In addition, those used in Examples and Comparative Examples were those having a specific resistance of 18 MΩ or more.

<Production Example 1>

205 parts of lauryl chloride and 103 parts of diethylenetriamine were added to a stainless steel autoclave equipped with a stirring and temperature control function, and then the reaction was carried out at 80 to 120° C. for about 1 hour after nitrogen was replaced in the mixed system. After the reaction, the mixture was cooled, an aqueous sodium hydroxide solution was added, stirred, and then allowed to stand. After removing the lower layer (water layer), the base layer was replaced with nitrogen and distilled under reduced pressure (distillation conditions of the main product: 185 to 240°C, 5 to 20 mmHg). Water and 271 parts of the main product were added to a glass reaction vessel, and nitrogen was passed through the base layer, while an aqueous monochloroacetic acid (95 parts) solution was added at 50 to 100°C, reacted at 90 to 110°C, and then pH with an aqueous sodium hydroxide solution. By adjustment, laurylamine ethyleneimine 2 mol adduct sodium acetate (A1-1) was obtained.

<Production Example 2>

205 parts of lauryl chloride and 60 parts of ethylenediamine were added to an autoclave made of stainless steel with a stirring and temperature control function, and the reaction was carried out at 80 to 120° C. for about 1 hour after nitrogen was replaced in the mixed system. After the reaction, the mixture was cooled, and an aqueous sodium hydroxide solution was added, followed by stirring, followed by static separation. After removing the lower layer (water layer), the base layer 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 introduced into a glass reaction vessel, and nitrogen was passed through the base layer, while an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100°C, reacted at 90 to 110°C, and then pH with an aqueous sodium hydroxide solution. By adjustment, laurylamine ethyleneimine 1 mol adduct sodium propionate (A1-2) was obtained.

<Production Example 3>

205 parts of lauryl chloride and 103 parts of diethylenetriamine were added to a stainless steel autoclave equipped with a stirring and temperature control function, and then the reaction was carried out at 80 to 120° C. for about 1 hour after nitrogen was replaced in the mixed system. After the reaction, the mixture was cooled, and an aqueous sodium hydroxide solution was added, followed by stirring, followed by static separation. After removing the lower layer (water layer), the base layer 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 introduced into a glass reaction vessel, and nitrogen was passed through the base layer, while an aqueous solution of monochloropropionic acid (109 parts) was added at 50 to 100°C, reacted at 90 to 110°C, and then pH with an aqueous sodium hydroxide solution. By adjustment, laurylamine ethyleneimine 2 mol adduct sodium propionate (A1-3) was obtained.

<Production Example 4>

To the same container as in Production Example 1, 186 parts of lauryl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were added, and the mixture was replaced with nitrogen, and then dehydrated at 20°C under reduced pressure (20 mmHg) for 1 hour. Was conducted. Next, 88 parts of ethylene oxide (hereinafter also referred to as "EO") were introduced at 150°C so that the gauge pressure was 1 to 3 kgf/cm 2. The reaction was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20°C. After performing hydrochloric acid for 2 hours while blowing nitrogen gas at the same temperature, neutralizing the sulfuric acid ester with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, sodium lauryl alcohol ethylene oxide 3 mol adduct sulfate salt (A2- An aqueous solution of 2-1) was obtained.

<Production Example 5>

To the same container as in Production Example 1, 186 parts of lauryl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were added, and the mixture was replaced with nitrogen, and then dehydrated at 20°C under reduced pressure (20 mmHg) for 1 hour. Was conducted. Subsequently, 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 was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20°C. After performing hydrochloric acid for 2 hours while blowing nitrogen gas at the same temperature, neutralizing the sulfuric acid ester with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, sodium lauryl alcohol ethylene oxide 5 mol propylene oxide 3 mol adduct sodium sulfate An aqueous solution of salt (A2-2-2) was obtained.

<Production Example 6>

In the same container as in Production Example 1, 214 parts of myristyl alcohol, 0.32 parts of magnesium perchlorate, and 0.03 parts of magnesium hydroxide were added, and the inside of the mixed system was replaced with nitrogen, and then dehydrated under reduced pressure (20 mmHg) at 120° C. for 1 hour. Was conducted. Subsequently, 235 parts of EO were introduced at 150° C. so that the gauge pressure was 1 to 3 kgf/cm 2. The reaction was transferred to a glass reaction vessel, and 120 parts of chlorosulfonic acid was slowly added dropwise over 4 hours while maintaining the temperature at 20°C. After performing hydrochloric acid for 2 hours while blowing nitrogen gas at the same temperature, neutralizing the sulfuric acid ester with an aqueous solution in which 41.2 parts of sodium hydroxide was dissolved in 102 parts of water, sodium myristyl alcohol ethylene oxide 8 mol adduct sulfate 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 the mixture was stirred at 25°C and a magnetic stirrer for 40 rpm for 20 minutes to prepare resist substrate pretreatment compositions (E1) to (E22) and comparative resist substrate pretreatment compositions ( H1) to (H3) were obtained. The weight part of each component is a numerical value in terms of pure, and water in each component is included in 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 1-3.

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

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

(1) A substrate is immersed in 100 ml of 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, followed by rinsing with pure water having an electrical resistivity of 18 MΩ·cm or more for 10 seconds and immersing in 300 ml of pure water for 30 seconds. Washing was performed and dried with nitrogen.

(2) Next, after immersing the substrate in a resist substrate pretreatment composition at 25° C. for 1 minute, rinsing with pure water having an electrical resistivity of 18 MΩ·cm or more for 10 seconds, immersing in 300 ml of pure water for 30 seconds, and then washing, It was dried with nitrogen to obtain a substrate after surface treatment.

(3) As a model resist, triethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.) are used to measure the contact angle between the model resist and the substrate after surface treatment. (Measured by Kyowa Interface Science Co., Ltd., "Full Automatic Contact Angle Meter DM700"). The results are shown in Tables 1-3. If the contact angle is 40° or more, it is satisfactory, indicating that wet spreadability is suppressed.

<Measurement of contact angle of substrate after surface treatment with resist-2 (surface treatment of copper substrate with copper oxide film formed)>

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

(1) A substrate is immersed in 100 ml of 1% citric acid aqueous solution for 1 minute to remove copper oxide on the surface, followed by rinsing with pure water having an electrical resistivity of 18 MΩ·cm or more for 10 seconds and immersing in 300 ml of pure water for 30 seconds. Washing was performed and dried with nitrogen.

(2) Next, after immersing the substrate in 5% hydrogen peroxide for 1 minute, rinsing with pure water having an electrical resistivity of 18 MΩ·cm or more for 10 seconds, immersing in 300 ml of pure water for 30 seconds, and then washing with nitrogen. Ordered. A copper oxide film was formed on the surface of the copper substrate by this operation.

(3) After immersing the copper substrate on which the copper oxide film was formed in a resist substrate pretreatment composition at 25° C. for 1 minute, rinse with pure water having an electrical resistivity of 18 MΩ·cm or more for 10 seconds, and rinsing for 30 seconds in 300 ml of pure water. After drying, it was dried with nitrogen to obtain a substrate after surface treatment.

(4) As a model resist, using triethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) and glycidyl methacrylate (manufactured by Dow Chemical Co., Ltd.), the contact angle of the substrate after surface treatment with the model resist is fully automatic contact angle meter ( It measured by Kyowa Interface Science Co., Ltd., "Full automatic contact angle meter DM700"). The results are shown in Tables 1-3. If the contact angle is 35° or more, it is satisfactory, indicating that wet spreadability is suppressed.

<Measurement of viscosity of resist substrate pretreatment composition>

(1) Immediately after compounding the resist substrate pretreatment composition, an E-type viscometer (manufactured by Brookfield) was used to warm the mixture to 25°C to measure viscosity. The results are shown in Tables 1-3.

(2) 300 g of the resist substrate pretreatment composition was placed in a resin container, warmed to 50°C in an open system, and left to stand for 10 hours. Thereafter, using an E-type viscometer (manufactured by Brookfield), the temperature was adjusted to 25°C to measure viscosity. The results are shown in Tables 1-3.

(3) The rate of increase in viscosity of the resist substrate pretreatment composition under an open heating environment was calculated by the following equation. The results are shown in Tables 1-3.

Rate of increase in viscosity of the resist substrate pretreatment composition in an open heating environment (%)

={([Viscosity after warming to 50°C in an open system and standing for 10 hours (mPa·s)]-[Viscosity immediately after compounding (mPa·s)]) / [Viscosity immediately after compounding (mPa·s)]} × 100

As is evident from the results shown in Tables 1 to 3, it was confirmed that the copper substrates subjected to the surface treatment with the resist substrate pretreatment compositions of Examples 1 to 22 had a large contact angle of the resist regardless of the oxidation state of the surface, and the wet spreadability Suppressed. On the other hand, it was confirmed that the copper substrates 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 oxidation state of the surfaces, and the wet spreadability was not sufficiently suppressed.

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

Industrial availability

The resist substrate prepared using the resist substrate pretreatment composition of the present invention can be subjected to fine patterning on the substrate by suppressing the wettability of the resist. Therefore, the resist substrate pretreatment composition of the present invention is useful for applications such as resist substrates, particularly printed wiring board substrates.

Claims (10)

A resist substrate pretreatment composition containing an amphoteric surfactant (A1), 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)]-[the value of the pH of the resist substrate pretreatment composition] ]) is -3 to 4,
The ratio of the number of moles of the amphoteric surfactant (A1) to the total number of moles of the mole number of the amphoteric surfactant (A1) and the anionic surfactant (A2) ((the number of moles of the amphoteric surfactant (A1) ] / ([Molarity of amphiphilic surfactant (A1)] + [Molarity of anionic surfactant (A2)])) is 0.1 to 0.9, characterized in that the resist substrate pretreatment composition. According to claim 1,
Moreover, the resist substrate pretreatment composition containing the organic solvent (S) whose boiling point is 100 degreeC or more, and SP value is 8-20. According to claim 1,
A resist substrate pretreatment composition, 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 monovalent unsaturated hydrocarbon group having 2 to 25 carbon atoms, and R ² and R ³ are each independently a divalent carbon atom having 1 to 25 carbon atoms. It represents a saturated hydrocarbon group or a divalent unsaturated hydrocarbon group having 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 a different hydrocarbon group, or M ^+. Represents a counter ion.] According to claim 1,
The said anionic surfactant (A2) is a compound represented by the following general formula (2) and/or general formula (3), The resist substrate pretreatment composition.

[In the general formula (2), R ⁴ represents a saturated hydrocarbon group having 1 to 25 carbon atoms or 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 carbon atoms. , Each alkylene group represented by A ¹ when y is 2 or more may be the same alkylene group or a different alkylene group, and M ⁺ represents a counter ion.]

[In the general formula (3), R ⁵ represents a saturated hydrocarbon group having 1 to 25 carbon atoms or unsaturated hydrocarbon group having 2 to 25 carbon atoms, and M ⁺ represents a counter ion.] According to claim 1,
The resist substrate pretreatment composition having an isoelectric point of 8.0 to 11.0 in the amphoteric surfactant (A1). According to claim 1,
The weight ratio of the amphoteric surfactant (A1) and the anionic surfactant (A2) ([weight of the amphoteric surfactant (A1)] / [weight of the anionic surfactant (A2)]) is 0.1 to 5.0, Resist substrate pretreatment composition. According to claim 1,
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 surfactant (A2) The total weight of / / [weight of resist substrate pretreatment composition]} × 100) is 0.01 to 20% by weight, a resist substrate pretreatment composition. According to claim 1,
A resist substrate pretreatment composition having a pH of 7.0 to 12.0. A substrate preparation process for preparing a substrate on which circuit materials are formed,
A pre-treatment step of pre-treating the substrate using the resist substrate pre-treatment composition according to any one of claims 1 to 8,
And a resist disposing step of disposing a resist on the substrate after the pre-treatment step. The method of claim 9,
The said circuit material is a manufacturing method of the resist substrate which consists of at least 1 sort(s) selected from the group which consists of copper, aluminum, iron, tin, silver, nickel, titanium, chromium, and zinc.