JP2017199448A - Surface preparation agent for electronic material and method for manufacturing electronic material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface preparation agent for an electronic material which can prevent strong adherence of such particles as abrasive grains or polished dusts and of foreign substances generated from a packing container on a long-term basis and which can significantly reduce foreign substances remaining on a base plate in a later cleaning step.SOLUTION: The surface preparation agent (B) for an electronic material includes at least one type of chemical compound (A) selected from the group of a chemical compound (a1) expressed by the following general formula (1), a chemical compound (a2) expressed by the general formula (2), and a chemical compound (a3) expressed by the following general formula (3), and further includes water as an essential component.SELECTED DRAWING: None

Description

  The present invention relates to a surface treatment agent for an electronic material and a method for producing the electronic material. More specifically, in the method of manufacturing an electronic material having a polishing step for polishing an electronic material intermediate, a surface treatment that can prevent foreign matters such as abrasive grains and polishing dust particles from firmly adhering to the surface of the electronic material The present invention relates to an agent and a method for producing an electronic material using the surface treatment agent. In addition, in a method for producing an electronic material having a drying step for drying an electronic material intermediate, a surface treatment agent capable of preventing foreign matter such as particles in the atmosphere from firmly adhering to the surface of the electronic material, and the surface treatment The present invention relates to a method for producing an electronic material using an agent.

Electronic materials, especially magnetic disks, are becoming smaller and higher capacity year by year, and the distance between the magnetic head and the magnetic disk substrate is becoming smaller.
Therefore, there is a demand for a substrate in which particles such as abrasive grains used for polishing and generated polishing scraps do not remain as much as possible in a cleaning process immediately after the polishing process in manufacturing a magnetic disk substrate. There is also a demand for reduction of surface roughness, minute waviness, and surface defects such as scratches and pits.

The magnetic disk manufacturing process includes (1) a substrate process, which is a process for producing a flattened substrate, and (2) a media process, which is a process for forming a magnetic layer on the substrate.
Among these, in the substrate process, polishing with a slurry containing abrasive grains such as alumina, cerium oxide, colloidal silica is performed for planarization of the substrate, and particles such as abrasive grains and polishing debris on the substrate surface are cleaned in the cleaning process. After removal, the product is packed in a predetermined container and transported through a drying process.

  Here, the polishing process and the cleaning process in the substrate process are completely separate from each other, and the substrate after the polishing process cannot be immediately transferred to the cleaning process depending on the operating conditions of the cleaning equipment and the apparatus. There are cases where it is necessary to wait for about 10 to 10 hours. If the substrate after the polishing process is left to dry in the air, particles remaining on the substrate adhere firmly to the substrate and cannot be easily removed by the cleaning process, so it is necessary to wait in this way. If not obtained, the substrate is stored in a pure water so that the substrate is not dried. However, even when immersed in pure water, there is a problem that particles adhere firmly to the substrate surface over time.

In addition, when transporting the substrate from the substrate process to the media process, there is a period in which the substrate must be stored in a dry state. During this storage period, dust, dust and substrate processes in the air could not be removed. There is a problem that foreign substances such as particles adhere strongly to the substrate. Foreign substances such as particles are also more difficult to remove by washing, as described above.
In this way, a substrate with a foreign object firmly adhered to the substrate cannot obtain a sufficiently satisfactory cleanliness by one cleaning, and the cleaning process is performed again, but the target cleanliness cannot be satisfied yet Is a problem because it significantly reduces production efficiency.
For this reason, in order to improve the removability of these foreign substances that are likely to adhere, improvement in the performance of the cleaning agent used in each cleaning step and the increase in the cleaning time have been studied (Patent Document 1).
In addition, by using a surface protective agent that adheres to the surface of the substrate before foreign matter such as particles, dust, or dust adheres firmly to the surface of the substrate, the substrate in the subsequent cleaning process can be prevented Investigations have been made to reduce the residual foreign matter (Patent Document 2).

JP 2009-280802 A JP 2012-252772 A

However, in Patent Document 1, repeated cleaning of a substrate and long-time cleaning not only reduce productivity, but also cause new defects such as surface roughness of the substrate and generation of pits. In addition, improvement of the performance of the cleaning agent has problems such as surface roughness of the substrate and generation of pits as described above.
Further, in Patent Document 2, the use of a surface protective agent suppresses adhesion of foreign matters such as particles to the substrate surface, but there is room for further substrate quality improvement by adsorbing the surface protective agent more closely to the substrate surface. . When the surface protective agent is not densely adsorbed on the substrate surface, there is a problem that the effect of suppressing the adhesion of foreign matters when the substrate is stored for a long period of time is reduced, and the capacity of the magnetic disk is reduced.
Therefore, in particular, before the foreign matter firmly adheres to the substrate surface, it is adsorbed densely on the substrate surface, preventing the strong adherence of foreign matters such as these particles for a long period of time. An object of the present invention is to provide a surface treatment agent for electronic materials and a method for producing the electronic material that can significantly reduce the amount of the material.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention relates to a compound (a1) represented by the following general formula (1), a compound (a2) represented by the following general formula (2), and a compound (a3) represented by the following general formula (3). A surface treatment agent for electronic materials containing at least one compound (A) selected from the group consisting of: a surface treatment agent for electronic materials further containing water as an essential component; and the surface treatment agent. It is a manufacturing method of an electronic material.

  The surface treatment agent for electronic materials of the present invention prevents particles such as abrasive grains and polishing debris and foreign matter generated from a packing container from firmly sticking to the electronic material substrate, and provides a high recording density of the electronic material. It is possible to provide an electronic material with a high degree of cleanliness that is required in the process.

The electronic material in the present invention is not particularly limited as long as it is an electronic material including a polishing step and a subsequent cleaning step during the manufacturing process.
For example, (1) a magnetic disk substrate such as a magnetic disk glass substrate and a magnetic disk aluminum substrate whose surface is nickel-phosphorus (Ni-P) plated, (2) a semiconductor substrate such as a semiconductor element and a silicon wafer, (3) Compound semiconductor substrates such as SiC substrates, GaAs substrates, GaN substrates, AlGaAs substrates, and (4) sapphire substrates for LEDs and the like.

  Among these, from the viewpoint of improving production efficiency, a magnetic disk substrate is preferable, and specifically, a magnetic disk glass substrate and a magnetic disk aluminum substrate whose surface is plated with nickel-phosphorus (Ni-P).

  The electronic material intermediate in the present invention represents an electronic material during the manufacturing process, specifically, a polished glass substrate, a polished Ni-P plated aluminum substrate, or the like, or dried It refers to the front glass substrate substrate and the aluminum substrate substrate before drying.

［式中、Ｒ^１は、炭素数６〜２４の直鎖又は分岐鎖のアルキル基を表し、Ａ^１は炭素数２〜８のアルキレン基を表し、Ｒ^２は炭素数１〜５の直鎖又は分岐鎖のアルキレン基を表し、Ｍ^＋は水素イオン、アルカリ金属イオン又は有機カチオンを表す。ｍはＡ^１Ｏの付加モル数を表し、１〜１００の整数であり、ｍが２以上の場合のＡ^１は同一でも異なっていてもよい。］

［式中、Ｒ^３は、炭素数６〜２４の直鎖又は分岐鎖のアルキル基を表し、Ａ^２は炭素数２〜８のアルキレン基を表し、Ｘ^＋は水素イオン、アルカリ金属イオン又は有機カチオンを表し、ｔは１又は２の整数を表す。ｔが１の場合、［Ｒ^３Ｏ（Ａ^２Ｏ）_ｋ］は同一でも異なっていてもよい。ｋはＡ^２Ｏの付加モル数を表し、１〜１００の整数であり、ｋが２以上の場合のＡ^２は同一でも異なっていてもよい。］

［式中、Ｒ^４は、炭素数６〜２４の直鎖又は分岐鎖のアルキル基を表し、Ｑは、−（ＣＨ_２）_ｐ−ＣＯＯ⁻Ｚ^＋又は水素原子を表す。Ｙ^＋は、水素イオン、アルカリ金属イオン又は有機カチオンを表す。Ｚ^＋は、水素イオン、アルカリ金属イオン又は有機カチオンを表す。ｒは１〜８の整数であり、ｐは１〜８の整数であり、ｕは０〜８の整数である。］ The surface treating agent for electronic materials (B) of the present invention includes a compound (a1) represented by the following general formula (1), a compound (a2) represented by the following general formula (2), and the following general formula (3). The surface treatment agent for electronic materials containing 1 or more types of compounds chosen from the group which consists of a compound (a3) represented by these, Comprising: Water is further contained as an essential component.

[Wherein, R ¹ represents a linear or branched alkyl group having 6 to 24 carbon atoms, A ¹ represents an alkylene group having 2 to 8 carbon atoms, and R ² represents a linear chain having 1 to 5 carbon atoms. Alternatively, it represents a branched alkylene group, and M ⁺ represents a hydrogen ion, an alkali metal ion or an organic cation. m represents the number of added moles of A ¹ O, is an integer of 1 to 100, and A ¹ when m is 2 or more may be the same or different. ]

[Wherein R ³ represents a linear or branched alkyl group having 6 to 24 carbon atoms, A ² represents an alkylene group having 2 to 8 carbon atoms, and X ⁺ represents a hydrogen ion, an alkali metal ion or an organic group. Represents a cation, and t represents an integer of 1 or 2. When t is 1, [R ³ O (A ² O) _k ] may be the same or different. k represents the number of added moles of A ² O, is an integer of 1 to 100, and A ² when k is 2 or more may be the same or different. ]

[Wherein, R ⁴ represents a linear or branched alkyl group having 6 to 24 carbon atoms, and Q represents — (CH ₂ ) _p —COO ⁻ Z ⁺ or a hydrogen atom. Y ⁺ represents a hydrogen ion, an alkali metal ion, or an organic cation. Z ⁺ represents a hydrogen ion, an alkali metal ion, or an organic cation. r is an integer of 1 to 8, p is an integer of 1 to 8, and u is an integer of 0 to 8. ]

R ¹ in the general formula (1) represents a linear or branched alkyl group having 6 to 24 carbon atoms. From the viewpoint of preventing sticking of foreign matter, the number of carbon atoms is preferably 8-20, and more preferably 10-18. When it is not in the range of 6 to 24 carbon atoms, the anti-sticking property of foreign matters such as particles deteriorates.

  Specific examples of the linear or branched alkyl group having 6 to 24 carbon atoms include lauryl group, hexyl group, cyclohexyl group, octyl group, decyl group, undecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, oleyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, octadecenyl group and octadecadienyl group.

Examples of the alkylene group having 2 to 8 carbon atoms represented by A ¹ in the general formula (1) include an ethylene group, a 1,2-propylene group, a 1,2-butylene group, a 1,4-butylene group, and 1-phenyl. Examples include -1,2-ethylene group.
Of these, ethylene and 1,2-propylene are preferred from the viewpoint of solubility in a solvent.

M in the general formula (1) represents the number of added moles of A ¹ O, and is a number of 1 to 100, preferably a number of 1 to 50, and more preferably a number of 1 to 30. If m exceeds 100, the viscosity increases and handling may be difficult. A ¹ when m is 2 or more may be the same or different, and the (A ¹ O) _m portion may be a random bond or a block bond.

R ² in the general formula (1) represents a linear or branched alkylene group having 1 to 5 carbon atoms.
Specific examples of the linear or branched alkylene group having 1 to 5 carbon atoms include methylene group, ethylene group, propylene group, 2-methylpropylene group, 2,2-dimethylpropylene group, butylene group and 2-methylbutylene. Groups and the like.
Among these, a methylene group, an ethylene group, and a 1,2-propylene group are preferable from the viewpoint of solubility in a solvent.

M ⁺ is a hydrogen ion, an alkali metal ion or an organic cation. Moreover, each cation may use together 1 type, or 2 or more types.

Examples of the alkali metal ion include sodium ion and potassium ion.
Organic cations include 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}; 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 Examples include methylammonium, isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium, dimethylethylammonium, and the like, which include quaternary ammonium (such as tetraalkylammonium).
Among these, M ⁺ is preferably sodium ion, potassium ion, primary amine, secondary amine, tertiary amine, ammonium or quaternary ammonium from the viewpoint of solubility.

  Specific examples of the compound (a1) include (2-lauryloxyethoxy) acetic acid, [2- (2-lauryloxyethoxy) ethoxy] acetic acid, [2- (2- (2-lauryloxyethoxy) -ethoxy)- Ethoxy] acetic acid, [2- (2- (2- (2-lauryloxyethoxy) -ethoxy) -ethoxy) -ethoxy] acetic acid, (2-tetradecyloxyethoxy) acetic acid, (2-octadecyloxyethoxy) acetic acid, (2-Icosyloxyethoxy) acetic acid and [2- (2-lauryloxyethoxy) ethoxy] propionic acid, [2- (2- (2- (2-hexyloxypropoxy) -ethoxy) -ethoxy) -ethoxy] Acetic acid, [2- (2- (2- (2-oleyloxyethoxy) -ethoxy) -ethoxy) -ethoxy] acetic acid, [(2-lauryloxy) 2 triacontanyl ethoxy] acetic acid, [2- (2- (2- (2-lauryl-oxy ethoxy) - ethoxy) - ethoxy) - ethoxy] propionic acid; and salts thereof. Two or more of these may be combined.

  Among these, as the compound (a1), [2- (2-lauryloxyethoxy) ethoxy] acetic acid, [2- (2- (2-lauryl) from the viewpoints of solubility in a solvent and prevention of foreign matter sticking. Oxyethoxy) -ethoxy) -ethoxy] acetic acid, [(2-lauryloxy) -2-tricontataethoxy] acetic acid, [2- (2- (2- (2-lauryloxyethoxy) -ethoxy) -ethoxy)- Ethoxy] propionic acid and [2- (2- (2- (2-lauryloxyethoxy) -ethoxy) -ethoxy) -ethoxy] acetic acid are preferred.

  The content of the compound (a1) is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, particularly preferably from the viewpoint of handling properties, based on the weight of the surface treatment agent for electronic materials. 0.5 to 20% by weight.

  Compound (a1) is produced by subjecting a monohydroxyl compound and a monohalogen lower carboxylate to a condensation reaction in the presence of a catalyst. Examples of the catalyst include alkali catalysts such as sodium hydroxide and potassium hydroxide, and Lewis acid catalysts such as boron trifluoride and tin tetrachloride. Among these, an alkali catalyst is preferable, and sodium hydroxide and potassium hydroxide are more preferable.

  The production method of compound (a1) may be any production method. For example, the reaction system is dried at 30 ° C. to 200 ° C., a catalyst is added, and the system is dehydrated (preferably moisture of 500 ppm or less), and then the monohydroxyl compound and the monohalogen lower carboxylate are preferably 30-100. The reaction can be carried out at ° C, more preferably at 40 to 70 ° C. The reaction time is preferably 4 to 48 hours, more preferably 6 to 40 hours. The end point of the reaction can be managed by liquid chromatography.

A ² in the general formula (2) represents an alkylene group having 2 to 8 carbon atoms. Specific examples of the alkylene group having 2 to 8 carbon atoms include ethylene group, 1,2-propylene group, 1,2-butylene group, 1,4-butylene group and 1-phenyl-1,2-ethylene group. It is done.
Of these, ethylene and 1,2-propylene are preferred from the viewpoint of solubility in a solvent.

K in the general formula (2) represents the number of added moles of A ² O and is a number of 1 to 100, preferably a number of 1 to 50, more preferably a number of 1 to 30. When k exceeds 100, the viscosity increases and handling may be difficult. A ² when k is 2 or more may be the same or different, and the (A ² O) _k moiety may be a random bond or a block bond.

T in the general formula (2) is an integer of 1 or 2. When t is 1, the [R ³ O (A ² O) _k ] moiety may be the same or different.

R ³ in the general formula (2) represents a linear or branched alkyl group having 6 to 24 carbon atoms. From the viewpoint of preventing sticking of foreign matter, the number of carbon atoms is preferably 8-20, and more preferably 10-18. When it is not in the range of 6 to 24 carbon atoms, the anti-sticking property of foreign matters such as particles deteriorates.

  Specific examples of the linear or branched alkyl group having 6 to 24 carbon atoms include lauryl group, hexyl group, cyclohexyl group, octyl group, decyl group, undecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, oleyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, octadecenyl group and octadecadienyl group.

X ⁺ is a hydrogen ion, an alkali metal ion or an organic cation. Moreover, each cation may use together 1 type, or 2 or more types.

Examples of the alkali metal ion include sodium ion and potassium ion.
Organic cations include 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}; 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 Examples include methylammonium, isopropylammonium, butylammonium, dipropylammonium, diisopropylammonium, trimethylammonium, triethylammonium, dimethylethylammonium, and the like, such as quaternary ammonium.
Among these, as X ⁺ , sodium ion, potassium ion, primary amine, secondary amine, tertiary amine, ammonium and quaternary ammonium are preferable from the viewpoint of solubility.

  Specific examples of the compound (a2) include EO2 mol adduct phosphate ester potassium salt of octyl alcohol, EO 2.5 mol adduct phosphate sodium salt of decyl alcohol, and EO3 mol adduct phosphate ester of lauryl alcohol. Potassium salt, phosphate ester potassium salt of tridecyl alcohol EO 5 mol adduct, phosphate ester potassium salt of EO 3 mol adduct of isotridecyl alcohol, phosphate ester of lauryl alcohol EO 3 mol adduct, lauryl alcohol EO 2 mol addition And phosphoric acid ester potassium salt of pentadecyl lauryl alcohol EO 5 mol adduct. Two or more of these may be combined.

  Among these, from the viewpoint of solubility in a solvent and prevention of foreign matter sticking, phosphate sodium salt of EO 2.5 mol adduct of decyl alcohol, phosphate ester of lauryl alcohol EO 3 mol adduct, lauryl alcohol EO 2 mol The adduct phosphate triethylammonium salt and the EO3 molar adduct phosphate potassium salt of lauryl alcohol are preferred.

  The content of the compound (a2) is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, particularly preferably from the viewpoint of handling properties, based on the weight of the surface treatment agent for electronic materials. 0.5 to 20% by weight.

The production method of compound (a2) may be any production method. For example, the compound (a2) can be obtained by reacting an alcohol with inorganic phosphoric acid (for example, phosphorus pentoxide).
In this reaction, by adjusting the synthesis conditions (reaction temperature, molar ratio of raw materials, etc.), the molar ratio of the mono-form in which t is 2 and the di-form in which t is 1 in the general formula (2) is arbitrary. Although an organic phosphate compound can be obtained, generally, a mixture of a mono-form and a di-form is obtained.

<Method for measuring molar ratio of di-form / mono-form>
0.5 g of compound (a2) is precisely weighed into a 100 ml beaker, and 50 ml of a mixed solution of denatured alcohol / xylene (2/1 by volume) is added and dissolved. While stirring this solution, it is applied to a potentiometric titration apparatus and titrated with a 0.1N potassium hydroxide / methyl alcohol titration solution, and the molar ratio of a mono-form and a di-form is calculated by the following formula.
Ratio of di-form / mono-form = (X−Y) / Y
Where X is the number of titrations of 0.1N potassium hydroxide / methyl alcohol titration solution required up to the first inflection point, and Y is 0.1N water required from the first inflection point to the second inflection point. This represents the titration ml number of potassium oxide / methyl alcohol titration solution.

R ⁴ in the general formula (3) represents a linear or branched alkyl group having 6 to 24 carbon atoms. When it is not in the range of 6 to 24 carbon atoms, the anti-sticking property of foreign matters such as particles deteriorates.

  Specific examples of the linear or branched alkyl group having 6 to 24 carbon atoms include lauryl group, hexyl group, cyclohexyl group, octyl group, decyl group, undecyl group, n-tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group. Group, heptadecyl group, octadecyl group, oleyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group, tricosyl group, tetracosyl group, octadecenyl group and octadecadienyl group.

Q is _- represents a Z ⁺ or a hydrogen atom ^- _(CH 2) p -COO.

Y ⁺ is a hydrogen ion, an alkali metal ion or an organic cation. Moreover, each cation may use together 1 type, or 2 or more types. Examples of the alkali metal ion or organic cation include the same compounds as M ^{+ in the} general formula (1).
Among these, sodium ion, potassium ion, primary amine, secondary amine, tertiary amine, ammonium and quaternary ammonium are preferable from the viewpoint of solubility.

Z ⁺ is a hydrogen ion, an alkali metal ion or an organic cation. Moreover, each cation may use together 1 type, or 2 or more types. Examples of the alkali metal ion or organic cation include the same compounds as M ^{+ in the} general formula (1).
Among these, sodium ion, potassium ion, primary amine, secondary amine, tertiary amine, ammonium and quaternary ammonium are preferable from the viewpoint of solubility.

  R in the general formula (3) is an integer of 1 to 8, and is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, from the viewpoint of solubility.

  P in the general formula (3) is an integer of 1 to 8, and is preferably an integer of 1 to 5, more preferably an integer of 1 to 3, from the viewpoint of solubility.

  U in the general formula (3) is an integer of 0 to 8, and is preferably an integer of 0 to 5 and more preferably an integer of 0 to 3 from the viewpoints of solubility and handling properties.

  Specific examples of the compound (a3) include 1- (hexylamino) acetic acid, 1- (octylamino) dipropionic acid dipotassium salt, 1- (laurylamino) propionic acid sodium salt, 1- (myristylamino) propionic acid. Sodium salt, 1- (oleylamino) propionic acid sodium salt, laurylaminoethylaminoethylglycine sodium salt and tetradecylaminoethylaminoethylglycine sodium salt, 1- (hexylamino) propionic acid potassium salt, 1- (laurylamino) Examples thereof include dipropionic acid dipotassium salt, 1- (laurylamino) propionic acid tetraethylammonium salt, [laurylaminoethyl-di (aminoethyl)] glycine sodium salt, and the like. Two or more of these may be combined.

  Of these, as the compound (a3), 1- (laurylamino) propionic acid sodium salt, 1- (oleylamino) propionic acid sodium salt, 1- (laurylamino) propionic acid sodium salt, (Laurylamino) propionic acid tetraethylammonium salt and dodecylaminoethylaminoethylglycine sodium salt are preferred.

  The content of the compound (a3) is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, particularly preferably from the viewpoint of handling properties, based on the weight of the surface treatment agent for electronic materials. 0.5 to 20% by weight.

  The compound (a3) represented by the general formula (3) is composed of a monocarboxylic acid compound and a dicarboxylic acid compound, and the weight ratio of the monocarboxylic acid compound to the dicarboxylic acid compound is preferably from the viewpoint of preventing sticking of foreign matters such as particles. Is 100/0 to 10/90, more preferably 100/0 to 20/80.

  The production method of compound (a3) may be any production method. For example, in the compound (a3) represented by the general formula (3), Michael addition reaction of alkylamine or alkenylamine with acrylic acid or a salt thereof or an acrylate ester, and the resulting reaction product is hydrolyzed as necessary. Can be manufactured. The Michael addition reaction temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C. If it is 0 ° C. or less, the cooling is costly, and if it exceeds 100 ° C., coloring may be remarkable. As the acrylic ester used in the Michael addition reaction, methyl ester or ethyl ester is preferable from the viewpoint of cost. The amount of acrylic acid or a salt thereof or an acrylic ester used in the Michael addition reaction is preferably 1.0 to 5.0 times mol, more preferably 1.05 to 2 with respect to the alkylamine or alkenylamine. .1 mole. When the ratio is less than 1.0, unreacted alkylamine or alkenylamine remains. Unreacted acrylic acid or acrylic acid ester can be removed under reduced pressure. The degree of vacuum is preferably 0 to 400 mmHg, and the temperature is preferably 40 to 150 ° C. In the hydrolysis, acid hydrolysis using hydrochloric acid, sulfuric acid, etc .; alkaline hydrolysis using metal sodium, liquid methylate, NaOH, KOH, etc .; hydrolysis with water alone can be used. The hydrolysis temperature is preferably 50 to 150 ° C, more preferably 70 to 110 ° C. If it is 50 ° C. or lower, it takes time, and if it exceeds 150 ° C., coloring may be remarkable.

  The surface treatment agent for electronic materials (B) of the present invention is not limited to one or more compounds (A) selected from the group consisting of the compound (a1), the compound (a2) and the compound (a3), and water, and the following general formula You may contain the compound (a4) represented by (4). By using together the compound (a4) and one or more compounds (A) selected from the group consisting of the compounds (a1), (a2) and (a3), the amino group contained in the compound (a4) and the compound It is estimated that long-term foreign matter adhesion suppression effect can be enhanced because the carboxyl group contained in (A) promotes dense adsorption of the surface treatment agent to the electronic material intermediate surface by electrostatic interaction. The

［式中、Ｌ^１はｓ個の活性水素を持つアミンから活性水素を除いた残基を表し、Ａ^３は炭素数２〜８のアルキレン基を表す。ｎはＡ^３Ｏの付加モル数を表し、１〜１００の整数であり、ｎが２以上の場合のＡ^３は同一でも異なっていてもよい。ｓは１〜４０の整数である。ｓが２以上の場合、［（Ａ^３Ｏ）_ｎＨ］は同一でも異なっていてもよい。］

[Wherein L ¹ represents a residue obtained by removing active hydrogen from an amine having s active hydrogens, and A ³ represents an alkylene group having 2 to 8 carbon atoms. n represents the number of added moles of A ³ O, is an integer of 1 to 100, and A ³ when n is 2 or more may be the same or different. s is an integer of 1-40. When s is 2 or more, [(A ³ O) _n H] may be the same or different. ]

The alkylene group having 2 to 8 carbon atoms represented by ^{A 3} in the general formula (4), an ethylene group, a 1,2-propylene group, 1,2-butylene group, 1,4-butylene and 1-phenyl Examples include -1,2-ethylene group.
Of these, ethylene and 1,2-propylene are preferred from the viewpoint of solubility in a solvent.

N in the general formula (4) represents the number of added moles of A ³ O, preferably 1 to 100, more preferably 1 to 50, and particularly preferably 1 to 30. . When n exceeds 100, the viscosity becomes high and handling may be difficult. A ¹ when n is 2 or more may be the same or different, and the (A ³ O) _n portion may be a random bond or a block bond.

s is an integer of 1-40. Preferably it is 1-6, More preferably, it is 1-2. When s exceeds 40, the viscosity increases and handling may be difficult. When s is 2 or more, [(A ³ O) _n H] may be the same or different.

In the general formula (4), L ¹ can represent a residue obtained by removing active hydrogen from an amine having s active hydrogens. The amine is not particularly limited as long as it is a compound having an active hydrogen derived from an amino group in the molecule, but is preferably a compound having 1 to 6 active hydrogens derived from an amino group in the molecule, more preferably 1 It is a compound having ˜2.

Specific examples of the amine include the following (1) to (4).
(1) Aliphatic amine compound (i) Aliphatic monoamine (preferably having 6 to 48 carbon atoms and 1 functional group);
Laurylamine, hexylamine, cyclohexylamine, octylamine, decylamine, undecylamine, n-tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, icosylamine, hencicos Derived from animal and vegetable oils such as luamine, docosylamine, tricosylamine, tetracosylamine, octadecenylamine and octadecadienylamine, and their mixtures beef tallow amine, hardened tallow amine, coconut oil amine, palm oil amine and soybean oil amine Dioctylamine, dibutylamine, dihexylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipen Decylamine, dihexadecylamine, secondary amines such as di-heptadecyl amine and di octadecyl amine;
(Ii) aliphatic polyamines (preferably having 2 to 18 carbon atoms and 2 to 7 functional groups);
C2-C6 alkylenediamine such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine; diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, Polyalkylene (2 to 6 carbon atoms) polyamine such as pentaethylenehexamine;
(Iii) an alkyl (carbon number 1-4) or hydroxyalkyl (carbon number 2-4) substitution product of (ii);
Dialkyl (1 to 3 carbon atoms) aminopropylamine, trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine and the like;
(Iv) an alicyclic or heterocyclic ring-containing aliphatic polyamine;
3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like;
(V) Aromatic ring-containing aliphatic amine compound (C8-15)
Xylylenediamine, etc .;

(2) alicyclic amine compound (i) alicyclic monoamine (preferably having 6 to 48 carbon atoms and 1 functional group);
Cyclohexylamine, etc .;
(Ii) alicyclic polyamines (6 to 15 carbon atoms, 2 to 3 functional groups);
1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedianiline), etc .;
(3) a heterocyclic amine compound (preferably having 4 to 15 carbon atoms and 1 to 3 functional groups);
Piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4bis (2-amino-2-methylpropyl) piperazine and the like;
(4) an aromatic amine compound (preferably having 6 to 20 carbon atoms and 1 to 3 functional groups);
(I) Monoamines such as unsubstituted aromatic amine aniline; 1,2-, 1,3- or 1,4-phenylenediamine, 2,4′- and 4,4′-diphenylmethanediamine, crude diphenylmethanediamine (polyphenyl) Polymethylene polyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m-aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine Polyamines such as naphthylenediamine;

(Ii) an aromatic amine having a nuclear substituent [C1-C4 alkyl group such as methyl, ethyl, n- or i-propyl or butyl; alkoxy group such as methoxy or ethoxy; nitro group or the like];
2,4- and 2,6-tolylenediamine, diethyltolylenediamine, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4,4'-bis (o-toluidine), dianisidine, 1,3 -Dimethyl-2,4-diaminobenzene, 1,4-dibutyl-2,5-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 3,3'-diethyl-2,2'-diaminodiphenylmethane 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 5-nitro-1,3-phenylenediamine, bis (4-amino-3-methoxyphenyl) disulfide, and isomers thereof A mixture of various proportions of the body, etc .;

(Iii) an aromatic polyamine having a secondary amino group [a part or all of —NH 2 of the aromatic amine of the above (i) to (ii) is —NH—R ′ (R ′ is an alkyl group such as methyl, ethyl, etc.] A lower alkyl group of
4,4'-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and the like;
And mixtures of two or more of these. Among these, the aliphatic amine compound and the alicyclic amine compound (1) are preferable, and the aliphatic monoamine and the alicyclic monoamine are more preferable. Particularly preferred are aliphatic monoamines having 6 to 36 carbon atoms. When the number of carbon atoms is 6 to 36, the adsorptivity to the substrate is excellent. Further, the hydrocarbon group portion may be linear or branched and may have a saturated or unsaturated bond.

  Compound (a4) is an amine oxide [ethylene oxide (hereinafter, abbreviated as EO), 1,2-propylene oxide (hereinafter, 1,2-propylene oxide is abbreviated as PO) in the absence of a catalyst or in the presence of a catalyst. 1,2-butylene oxide (hereinafter 1,2-butylene oxide is abbreviated as BO), 1,4-butylene oxide, 1-phenyl-1,2-ethylene oxide, or a mixture thereof]. Produced by addition reaction. In the case of using a catalyst, alkali catalysts such as sodium hydroxide, potassium hydroxide, metallic sodium and metallic potassium, and Lewis acid catalysts such as boron trifluoride and tin tetrachloride are exemplified. Among these, an alkali catalyst is preferable, and potassium hydroxide is more preferable.

  The reaction system is dried at 60 ° C. to 200 ° C., a catalyst is added, the system is dehydrated (preferably water content is 500 ppm or less), and then the alkylene oxide is preferably 80 to 200 ° C., more preferably 100 to 180 ° C. Can be reacted. The reaction time is preferably 4 to 48 hours. The end point of the reaction can be controlled by the total amine value.

(Total amine value measurement method)
The total amine value is the number of mg of potassium hydroxide equivalent to perchloric acid required to neutralize amine in 1 g, and represents the content of amine contained in the sample. The measuring method is as follows.
Weigh sample accurately into a glass bottle. The amount of sampling is 7 g when the expected total amine number is less than 0.5, 4.5 g when it is 0.5 or more and less than 2, and 2 g or less when it is 2 or more. After sampling, 50 mL of acetic acid is added to dissolve the sample. Potentiometric titration is performed with N / 100 perchloric acid standard solution. At the same time, a blank test is performed.
Total amine number = (K′−B ′) × Y ′ × 0.56111 / Z
K ′: titration ml number of N / 100 perchloric acid standard solution required for this test B ′: titration ml number of NN / 100 perchloric acid standard solution required for blank test Y ′: N / 100 perchloric acid standard Solution titer Z: Sampling amount (g)

  The average addition mole number n of the alkylene oxide in General formula (4) can be calculated | required by measuring the total amine number of the compound (a4) represented by General formula (4).

Specific examples of the compound (a4) include laurylamine EO8 mol adduct, hexylamine EO8 mol adduct, cyclohexylamine EO8 mol adduct, octylamine EO8 mol adduct, decylamine EO8 mol adduct, undecylamine EO8 mol adduct. N-tridecylamine EO8 mol adduct, tetradecylamine EO8 mol adduct, pentadecylamine EO8 mol adduct, hexadecylamine EO8 mol adduct, heptadecylamine EO8 mol adduct, octadecylamine EO8 mol adduct , Nonadecylamine EO8 mol adduct, icosylamine EO8 mol adduct, heicosylamine EO8 mol adduct, docosylamine EO8 mol adduct, tricosylamine EO8 mol adduct, tetracosylamine EO8 mol adduct, octadecenyl Mine EO 8 mol adduct, octadecadienylamine EO 8 mol adduct, beef tallow amine EO 8 mol adduct, hardened beef tallow amine EO 8 mol adduct, coconut oil amine EO 1 mol adduct, coconut oil amine EO8 mol adduct, palm oil amine EO8 mol adduct, soybean oil amine EO8 mol adduct, hexadecylamine EO25 mol PO5 mol random adduct, cocoamine EO8 mol adduct, cocoamine EO30 mol adduct, etc. Dioctylamine EO12 mol adduct, dibutylamine EO12 mol adduct, dihexylamine EO12 mol adduct, didecylamine EO12 mol adduct, diundecylamine EO12 mol adduct, didodecylamine EO12 mol adduct, ditridecylamine EO12 mol adduct , Jite Radeshiruamin EO12 mol adduct, dipentaerythritol decylamine EO12 mol adduct, dihexadecylamine EO12 mol adduct, di heptadecyl amine EO12 mole adduct and dioctadecylamine EO12 mole adducts.
Two or more of these may be combined. Further, it may be an alkylene oxide adduct of a mixture of amines such as PO and EO, BO and EO, BO and PO, or PO, EO and BO.

  Of these, the compound (a4) is preferably tetradecylamine EO8 mol adduct, coconut oil amine EO8 mol adduct, octylamine EO8 mol adduct from the viewpoints of solubility in a solvent and prevention of foreign matter sticking. Coconut oil amine EO 1 mol adduct, cocoamine EO 8 mol adduct and coconut oil amine EO 8 mol adduct.

  The content of the compound (a4) is preferably 0.1 to 30% by weight, more preferably 0.5 to 25% by weight, particularly preferably 0.5 to 25% by weight, based on the weight of the surface treatment agent for electronic materials, from the viewpoint of handling properties. Preferably it is 0.5 to 20% by weight.

  The cloud point in a 2% by weight aqueous solution of compound (a4) is preferably 10 ° C. or higher, more preferably 30 ° C. or higher, from the viewpoint of handling properties.

  The total concentration of the compound (A) and the compound (a4) contained in the surface treatment agent (B) during actual use is 0.001 to 10% by weight.

  Examples of the water for the surface treatment agent (B) for electronic materials include pure water, ion exchange water, reverse osmosis water (RO water), and distilled water having an electrical resistivity of 18 MΩ · cm or more from the viewpoint of cleanliness. Of these, pure water having an electrical resistivity of 18 MΩ · cm or more is preferable.

In addition to the compound (A) and water, the surface treatment agent for electronic materials (B) may further contain an additive (C) as a constituent component from the viewpoint of preventing adhesion of foreign matters such as particles.
Examples of the additive (C) include surfactants other than the chelating agent (D), the compound (A) and the compound (a4), pH adjusters (inorganic alkalis such as potassium hydroxide, isopropanolamine, monoethanolamine, 2 -Organic alkalis such as aminoethylaminoethanol and ethylenediaminetetraethanol), hydrotropes (such as p-toluenesulfonate and benzoate), and preservatives.

As the chelating agent (D), a phosphonic acid chelating agent (a chelating agent containing a phosphonic acid (salt) group or a phosphoric acid (salt) group in the molecule) (D1), a carboxylic acid chelating agent (carboxyl group and / or Or the chelating agent (D2) which contains a carboxylate group in a molecule | numerator, and another chelating agent (D3) are mentioned. Phosphonic acid (salt) refers to phosphonic acid and / or phosphonate. The same applies to other acids.
As the phosphonic acid chelating agent (D1), methyldiphosphonic acid (salt), aminotri (methylenephosphonic acid) (salt), 1-hydroxyethylidene-1, 1-diphosphonic acid (salt) (HEDP), nitrilotrismethylene Phosphonic acid (salt) (NTMP), ethylenediaminetetra (methylenephosphonic acid) (salt), hexamethylenediaminetetra (methylenephosphonic acid) (salt), propylenediaminetetra (methylenephosphonic acid) (salt), diethylenetriaminepenta (methylenephosphone) Acid) (salt), triethylenetetramine hexa (methylenephosphonic acid) (salt), triaminotriethylamine hexa (methylenephosphonic acid) (salt), trans-1,2-cyclohexanediaminetetra (methylenephosphonic acid) (salt), Glycol ether diamine Examples include tiger (methylene phosphonic acid) (salt) and tetraethylenepentamine hepta (methylene phosphonic acid) (salt), metaphosphoric acid (salt), pyrophosphoric acid (salt), tripolyphosphoric acid (salt) and hexametaphosphoric acid (salt). It is done.

  Examples of the carboxylic acid chelating agent (D2) include a hydroxycarboxylic acid having a hydroxyl group and / or a salt thereof (D21) and a carboxylic acid not having a hydroxyl group and / or a salt thereof (D22). Examples of the hydroxycarboxylic acid and / or its salt (D21) include citric acid (salt), lactic acid (salt), gallic acid (salt) and the like. Carboxylic acids having no hydroxyl group and / or salts thereof (D22) include ethylenediaminetetraacetic acid (EDTA) (salt), diethylenetriaminepentaacetic acid (DTPA) (salt), hydroxyethyl-iminodiacetic acid (HIDA) (salt), 1,2-diaminocyclohexanetetraacetic acid (DCTA) (salt), triethylenetetraminehexaacetic acid (TTHA) (salt), nitrilotriacetic acid (NTA) (salt), β-alanine diacetate (salt), aspartate diacetate (salt) Salt), methylglycine diacetic acid (salt), iminodisuccinic acid (salt), serine diacetic acid (salt), aspartic acid (salt) and glutamic acid (salt), pyromellitic acid (salt), benzopolycarboxylic acid (salt), cyclo Pentanetetracarboxylic acid (salt), carboxymethyloxysuccinate, oxydisuccinate , Maleic acid derivatives, oxalic acid (salt), malonic acid (salt), succinic acid (salt), or the like glutaric acid (salt) and adipic acid (salts).

  Other chelating agents (D3) include N, N′-bis (salicylidene) -1,2-ethanediamine, N, N′-bis (salicylidene) -1,2-propanediamine, and N, N′-bis. Examples include (salicylidene) -1,3-propanediamine and N, N′-bis (salicylidene) -1,4-butanediamine.

The concentration of the chelating agent (D) during actual use is preferably 0.001 to 2% by weight based on the weight of the processing agent for electronic materials.
The weight ratio (D) / {(A) + (a4)} of (D) to the total weight of compound (A) and compound (a4) is preferably 0.01 to 10.

  The processing agent for electronic materials of the present invention is preferably a magnetic disk substrate from the viewpoint of preventing foreign matters from sticking.

The method for producing an electronic material according to the present invention includes a step of using a surface treatment agent for electronic material (B) so that the contact angle of water with respect to the surface of the electronic material intermediate is 35 ° or more at 25 ° C., and the electronic material after the step A cleaning step may be included in which the contact angle of water with respect to the intermediate surface is 30 ° or less at 25 ° C.
An electronic material intermediate having a contact angle of water with respect to the surface of the electronic material intermediate of 35 ° C or more at 25 ° C. is surface-treated to prevent strong adhesion of foreign matters such as particles directly on the surface of the electronic material intermediate. It can be estimated that the cleanliness of the electronic material finally obtained can be improved by removing the protective layer by the cleaning process.
In the electronic material intermediate before the cleaning step, the contact angle of water with respect to the surface of the electronic material intermediate is preferably 35 ° or more at 25 ° C., more preferably 35 ° It is 180 °, more preferably 50 ° to 180 °, particularly preferably 60 ° to 180 °.
In the cleaning step, the electronic material intermediate has a contact angle of water with respect to the surface of the electronic material intermediate of preferably 30 ° or less at 25 ° C., more preferably 0 ° to 30 °, from the viewpoint of improving the cleanliness of the electronic material. More preferably, it is 0 ° to 20 °, and particularly preferably 0 ° to 10 °.
The contact angle of water with respect to the surface of the electronic material intermediate is a value measured at 25 ° C. with a fully automatic contact angle meter (manufactured by Kyowa Interface Science, “Fully Automatic Contact Angle Meter DM700”).

  An electronic material intermediate in which the contact angle of water with respect to the surface of the electronic material intermediate is 35 ° or more at 25 ° C., and the electronic material intermediate subjected to surface treatment using a cleaning agent (E) is washed to obtain an intermediate between the electronic materials An electronic material with a higher degree of cleanliness of the electronic material can be produced by the cleaning step in which the contact angle of water with the body surface is 30 ° or less at 25 ° C.

  The cleaning agent (E) is preferably a cleaning agent containing water and an additive (F) as constituent components. In the cleaning process, it is possible to significantly reduce the residue of the chemical used for performing the surface treatment by containing the additive (F) as compared with the case of cleaning with water alone.

  Examples of the additive (F) include a chelating agent (F1), a surfactant (F2), an organic alkali (F3), a stabilizer (F4), a pH adjuster (F5), a preservative (F6), and the like. . Two or more of these may be combined.

  Examples of the chelating agent (F1) include the same chelating agents as the chelating agent (D). From the viewpoint of improving detergency, the chelating agent (F11) and phosphone containing a carboxyl group and / or a carboxylate group in the molecule are preferable. A chelating agent (F12) containing an acid (salt) group or a phosphoric acid (salt) group in the molecule, more preferably citric acid (salt), EDTA (salt), DTPA (salt), HIDA (salt) , NTA (salt), NTMP (salt), HEDP (salt), ethylenediaminetetramethylenephosphonic acid (salt), pyrophosphoric acid (salt), and the like. Particularly preferred are HEDP (salt), NTMP (salt), ethylenediaminetetramethylenephosphonic acid (salt), citric acid (salt), DTPA (salt), and HIDA (salt).

  Examples of the surfactant (F2) include nonionic surfactants and anionic surfactants other than the compound (A).

Examples of nonionic surfactants include alkylene oxide addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants.
As an alkylene oxide addition type nonionic surfactant, a C1-C18 alcohol alkylene oxide 1-30 mol addition product, a C1-C12 alkylphenol ethylene oxide 1-30 mol addition product, a C8-C18 addition product. Examples include fatty acid ethylene oxide 1-30 mol adducts and polypropylene glycol (molecular weight 200-4000) ethylene oxide adducts.
As the polyhydric alcohol type nonionic surfactant, fatty acid (carbon number) of polyhydric (2 to 8 or more) alcohols (2 to 30 or more carbon atoms) such as glycerin fatty acid ester, sorbitan monolaurate, sorbitan monooleate, etc. 8-24) Fatty acid alkanolamides such as esters, lauric acid monoethanolamide and lauric acid diethanolamide. Specific examples include adducts of 9 moles of alcohol ethylene oxide having 12 carbon atoms, adducts of 30 moles of glycerol monooleate and polypropylene glycol ethylene oxide.

Examples of anionic surfactants include sulfonic acid surfactants (sulfosuccinic acid diesters (salts), dodecylbenzenesulfonic acid (salts), etc. of alcohols having 8 carbon atoms), sulfate ester surfactants (alcohols having 14 carbon atoms). Ethylene oxide 3 mol adduct sulfate (salt), C8 alcohol ethylene oxide 2 mol adduct sulfate (salt), C12-13 alcohol sulfate (salt), fatty acid surfactant (C10 fatty acids (salts), etc.), phosphate ester surfactants (e.g., phosphate monoesters (salts) of C8 alcohols), polymeric anionic surfactants (polystyrene sulfonic acid, styrene) / Styrenesulfonic acid copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) a Rylic acid copolymer, 2- (meth) acryloylamino-2,2-dimethylethanesulfonic acid / (meth) acrylic acid / acrylamide copolymer, naphthalenesulfonic acid formaldehyde condensate, methylnaphthalenesulfonic acid formaldehyde condensate, dimethyl Naphthalenesulfonic acid formaldehyde condensates and the like and salts thereof, poly {2-hydroxyethyl (meth) acrylate sulfate}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate sulfate copolymer, poly {2-hydroxyethyl (meth) acrylate} sulfates and the like and salts thereof, poly {(meth) acryloyloxyethylphosphonic acid}, 2-hydroxyethyl (meth) acrylate / (meth) acryloyloxye Ruphosphonic acid copolymer, naphthalenephosphonic acid formaldehyde condensate, etc. and their salts, poly {2-hydroxyethyl (meth) acrylate phosphate}, 2-hydroxyethyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate Phosphoric acid ester copolymer, phosphoric acid ester of poly {2-hydroxyethyl (meth) acrylate} and salts thereof, poly (meth) acrylic acid, (meth) acrylic acid-maleic acid copolymer, (meth) Acrylic acid-itaconic acid copolymer, (meth) acrylic acid-fumaric acid copolymer, (meth) acrylic acid / vinyl acetate copolymer and 2-hydroxyethyl methacrylate / (meth) acrylic acid copolymer, poly { Carboxymethylated product of 2-hydroxyethyl (meth) acrylate}, carbo Xymethyl cellulose, carboxymethyl methyl cellulose, carboxymethyl ethyl cellulose, benzoic acid formaldehyde condensate, benzoic acid-phenol-formaldehyde condensate, and salts thereof).
Among the anionic surfactants, a polymer type anionic surfactant is preferable from the viewpoint of preventing reattachment of particles. When using a polymer type anionic surfactant, if necessary, one or more selected from sulfonic acid surfactants, sulfate ester surfactants, fatty acid surfactants and phosphate ester surfactants May be used in combination.

  Other examples of the surfactant (F2) include cationic surfactants.

Examples of the organic alkali (F3) include primary amines (alkylamines such as methylamine, ethylamine and butylamine, monoethanolamine and guanidine); secondary amines (dialkylamines such as dimethylamine, diethylamine and dibutylamine and diethanolamine). Etc.); 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-1 -Imidazole, 4,5-dihydro-1H-imidazole, 2-methyl-4,5-dihydro-1H-imidazole, 1,4,5,6-tetrahydro-pyrimidine, 1,6 (4) -dihydropyrimidine, etc.} , Polyamines (2-aminoethylaminoethanol, ethylenediaminetetraethanol and the like), ammonium and quaternary ammonium (tetraalkylammonium and the like).
The salt in the case where the chelating agent (F1) or the anionic surfactant forms a salt is preferably a primary amine, a secondary amine, a tertiary amine, or a salt from the viewpoint of preventing metal contamination to the substrate. And particularly preferably a primary amine, secondary amine, polyvalent amine, amidine and ammonium, most preferably diethanolamine, isopropanolamine, monoethanolamine, 2-aminoethylaminoethanol, Ethylenediaminetetraethanol, 1,8-diazabicyclo [5.4.0] undecene-7 and 1,5-diazabicyclo [4.3.0] nonene-5.

  Examples of the stabilizer (F4) include p-toluenesulfonate and benzoate.

  Examples of the pH adjuster (F5) include sodium hydroxide and potassium hydroxide.

  As the preservative (F6), a commercially available preservative can be used.

  Based on the weight of the cleaning agent (E) during actual use, the concentration of the additive (F) is 0.001 to 2% by weight.

The electronic material intermediate whose water contact angle with respect to the surface of the electronic material intermediate is 35 ° or more at 25 ° C. is an electronic material intermediate that is surface-treated with the surface treatment agent (B). It is preferable from the viewpoint of adhesion prevention. As a method for setting the contact angle to the surface of the electronic material intermediate to 35 ° or more at 25 ° C., a method of immersing the electronic material intermediate in the surface treatment agent (B) and a spraying of the surface treatment agent (B) on the electronic material intermediate And the like. Alternatively, a method of cleaning the electronic material intermediate using the surface treatment agent (B) (immersion (dip cleaning), scrub cleaning using a sponge mainly composed of polyvinyl alcohol or the like) may be used. The electronic material intermediate may be washed with water after the surface treatment agent (B) is used for the electronic material intermediate, and the electronic material intermediate may be dried after washing with water. . Further, the electronic material intermediate may be dried after the surface treatment agent (B) is used to treat the electronic material intermediate by the above method.
Preferably, after the electronic material intermediate is immersed in the surface treatment agent (B) or the surface treatment agent (B) is sprayed on the electronic material intermediate, the electronic material intermediate is further washed with water.

In the cleaning step, as a method for cleaning the electronic material intermediate in which the contact angle of water with respect to the surface of the electronic material intermediate is 35 ° or less at 25 ° C., the electronic material intermediate was immersed (dip) cleaned and used with ultrasonic waves. Examples thereof include dip cleaning, tape cleaning using a cleaning tape, and scrub cleaning using a sponge mainly composed of polyvinyl alcohol.
From the viewpoint of prevention of sticking of foreign matters such as particles, the electronic material intermediate is preferably immersed in the surface treatment agent (B) or the surface treatment agent (B) is sprayed on the electronic material intermediate, and then the electronic material intermediate is further added with water. It is a method of washing the body. From the viewpoint of removability of the drug used for the surface treatment, dipping cleaning and dip cleaning using ultrasonic waves are preferable.

Another embodiment of the present invention is a method for producing an electronic material having a polishing step for polishing an electronic material intermediate, and the surface treatment is performed on the surface of the electronic material intermediate using the surface treatment agent (B). It is a manufacturing method of an electronic material including the process which makes the contact angle of water 35 degrees or more at 25 degreeC. Immediately after the polishing step, for example, by immersing the electronic material intermediate in the surface treatment agent (B) or spraying the surface treatment agent (B) on the electronic material intermediate, adhesion of foreign substances such as abrasive particles can be prevented. Therefore, it is possible to manufacture an electronic material in which surface defects such as scratches and pits generated in the subsequent process are reduced.
Furthermore, the electronic material intermediate subjected to the surface treatment is cleaned to make the contact angle of water with respect to the surface of the electronic material intermediate at 30 ° C. or less at 25 ° C. The material can be manufactured.

An example of a manufacturing process (part) of an aluminum substrate for a magnetic disk whose surface is plated with nickel-phosphorus (Ni-P) using the manufacturing method of the present invention is shown below.
(1) In the substrate process, the aluminum substrate is polished using colloidal silica as abrasive grains.
(2) After lightly rinsing the polished aluminum substrate with pure water, the aluminum substrate is immersed in the surface treatment agent (B).
(3) After pulling up the aluminum substrate and rinsing lightly with pure water, it is set in a cleaning machine charged with the cleaning agent (E) and scrub cleaning or dip cleaning using ultrasonic waves is performed.
(4) After washing, rinse with pure water and dry by spin drying.
(5) Pack the aluminum substrate in a container and transport it to the media process.

  The immersion temperature in the production step (2) is preferably 5 to 100 ° C, more preferably 10 to 90 ° C, and particularly preferably 20 to 80 ° C.

  The immersion time in the production step (2) is preferably 3 seconds to 20 hours, more preferably 5 minutes to 15 hours, and particularly preferably 10 minutes to 10 hours.

  The washing temperature in the production step (3) is preferably 5 to 100 ° C, more preferably 10 to 90 ° C, and particularly preferably 20 to 80 ° C.

  The washing time in the production step (3) is preferably 1 minute to 20 hours, more preferably 5 minutes to 15 hours, and particularly preferably 10 minutes to 10 hours.

Another embodiment of the present invention is a production method having a drying step of drying an electronic material intermediate, wherein surface treatment is performed using the surface treatment agent (B), and water on the surface of the electronic material intermediate is treated. It is a manufacturing method of an electronic material including the process which makes a contact angle 35 degrees or more at 25 degreeC. Before the drying step, for example, the electronic material intermediate is immersed in the surface treatment agent (B), the surface treatment agent (B) is sprayed on the electronic material intermediate, or the electronic material intermediate is used with the surface treatment agent (B). Since it is possible to prevent adhesion of foreign matters after drying, it is possible to manufacture an electronic material with a high cleanliness.
Furthermore, the electronic material intermediate that has been subjected to surface treatment is cleaned to produce an electronic material with a further improved substrate cleanliness through a cleaning process in which the contact angle of water with the surface of the electronic material intermediate is 30 ° or less at 25 ° C. It becomes possible to do.

An example of a manufacturing process (part) of an aluminum substrate for a magnetic disk whose surface is plated with nickel-phosphorus (Ni-P) using the manufacturing method of the present invention is shown below.
(A) In the substrate process, the aluminum substrate is polished using colloidal silica as abrasive grains.
(B) The polished aluminum substrate is pulled up, rinsed lightly with pure water, and then set in a cleaning machine to perform scrub cleaning or dip cleaning using ultrasonic waves.
(C) After washing and rinsing with pure water, the aluminum substrate is immersed in the surface treatment agent (B).
(D) The soaked aluminum substrate is pulled up, rinsed purely, and then dried by spin drying.
(E) Pack the aluminum substrate in a container and transport it to the media process.
(F) After transporting, receiving cleaning is performed by dip cleaning using ultrasonic waves using the cleaning agent (E).

  The immersion temperature in the above (c) is preferably 5 to 100 ° C, more preferably 10 to 90 ° C, and particularly preferably 20 to 80 ° C.

  The immersion time in the above (c) is preferably 3 seconds to 20 hours, more preferably 5 minutes to 15 hours, and particularly preferably 10 minutes to 10 hours.

  The number of rotations in the above (d) is preferably 1000 to 6000 rpm, and more preferably 2000 to 5000 rpm. The spin drying time in the above (d) is preferably 1 to 10 minutes.

  The washing temperature in the above (f) is preferably 5 to 100 ° C, more preferably 10 to 90 ° C, and particularly preferably 20 to 80 ° C.

  The washing time in the above (f) is preferably 1 minute to 20 hours, more preferably 5 minutes to 15 hours, and particularly preferably 10 minutes to 10 hours.

The electronic material manufactured by the method for manufacturing an electronic material of the present invention is not particularly limited as long as it is an electronic material including a polishing step and a subsequent cleaning step in the manufacturing process, as described above. Examples include a substrate, a silicon semiconductor substrate, a compound semiconductor substrate, and a sapphire substrate.
Among these, from the viewpoint of improving production efficiency, a magnetic disk substrate is preferable, and specifically, a magnetic disk glass substrate and a magnetic disk aluminum substrate whose surface is plated with nickel-phosphorus (Ni-P). .

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these.

Examples 1-28 and Comparative Examples 1-7
Each component is mix | blended so that it may become a composition of Tables 1-3, and it stirs at 25 rpm and 40 rpm and a magnetic stirrer for 20 minutes, Surface treatment agent (B-1)-(B-28) of this invention. ), Comparative surface treatment agents (B-29) to (B-34), pure water, and a cleaning agent (E) used in the cleaning step were obtained.
As a blank, pure water having an electrical resistivity of 18 MΩ · cm was used as Comparative Example 5.

The performance evaluation test was performed by the following method.
This evaluation was conducted in a clean room of class 1,000 (FED-STD-209D, US Federal Standard, 1988) to prevent contamination from the atmosphere.
A 2.5-inch glass substrate for a magnetic disk or an Ni-P plated aluminum substrate for a magnetic disk was used as an electronic material intermediate, and the contact angle of water on the substrate surface after the surface treatment of the test substrate was measured. The prevention of adhesion of foreign matters such as particles was performed by counting the number of foreign matters on the test substrate. Further, the contact angle of water with the substrate surface after the test substrate was cleaned was measured. The cleanliness of the substrate after the cleaning step was evaluated by confirming the presence or absence of a peak derived from C—H stretching vibration appearing in the range of 2800 to 3200 cm ⁻¹ on the substrate after cleaning.

<Measurement of contact angle after surface treatment>
(1) The aqueous solutions (B-29) to (B-34) of Examples 1 to 28 (B-1) to (B-28) and Comparative Examples 1 to 6 were diluted 50 times to evaluate the surface treatment power. A test solution was obtained. In Comparative Example 7, pure water was used as it was as a test solution.
(2) A 2.5-inch glass substrate for magnetic disk or an Ni-P plated aluminum substrate for magnetic disk was immersed in a beaker containing 1000 mL of the above test solution in the vertical direction and allowed to stand for 10 minutes.
(3) After 10 minutes, the glass substrate and the aluminum substrate were pulled up, rinsed gently with flowing pure water for 10 seconds, and dried with nitrogen to prepare a test substrate.
(4) The contact angle of ion-exchanged water with respect to each substrate was measured with a fully automatic contact angle meter (manufactured by Kyowa Interface Science, “Fully Automatic Contact Angle Meter DM700”). The results are shown in Tables 4-6.

<Evaluation 1 of adhesion prevention (when immersed and temporarily stored)>
(1) Commercially available colloidal silica slurry (Fujimi Incorporated “COMPOL80” particle size of about 80 nm) (about 30% by weight) 100 mL was diluted 10 times with pure water to prepare 1000 mL of a test slurry solution.
(2) Immediately after the above test substrate was prepared in a beaker containing 1000 mL of the test slurry, the test substrate was immersed in the vertical direction and allowed to stand for 6 hours.
(3) After 6 hours, the test substrate was pulled up, rinsed lightly with flowing pure water for 10 seconds, and then dried with nitrogen to prepare a surface protection performance evaluation substrate.
(4) The surface of the substrate was observed with a surface inspection device (MicroMax VMX-6100SK, manufactured by Vision Cytec Co., Ltd.), and the number of particles on the substrate was counted.
The number of particles on the glass substrate of the blank comparative example 7 was 500, and the number of particles on the aluminum substrate of the blank comparative example 5 was 300.

The number of particles on each substrate was compared with the number of particles on the substrate of the blank (Comparative Example 7), and the anti-adhesion effect for suppressing the particles from adhering to the substrate was evaluated and determined according to the following criteria.
The results are shown in Tables 4-6.
5: Less than 10% of blank 4: 10% to less than 40% of blank 3: 40% to less than 60% of blank 2: 60% to less than 80% of blank 1: 80% or more of blank

<Evaluation of adhesion prevention 2 (in dry state)>
(1) 1 g of a commercially available powdered silica (particle size of about 3 μm) was sprayed on a test substrate immediately after it was prepared, and allowed to stand for 1 week.
(2) After 1 week, the test substrate was rinsed lightly with running pure water for 10 seconds and then dried with nitrogen to prepare a substrate for surface protection performance evaluation.
(3) The substrate surface was observed with a surface inspection device (MicroMax VMX-6100SK, manufactured by Vision Cytec Co., Ltd.), and the number of particles on the substrate was counted.
In the case of the glass substrate, the number of particles on the substrate of Comparative Example 5 of the blank was 100, and in the case of the aluminum substrate, the number of particles on the substrate of Comparative Example 5 of the blank was 70.

Compare the number of foreign substances such as particles on each substrate with the number of foreign substances on the blank (Comparative Example 7), and in accordance with the following criteria, the anti-adhesion effect that suppresses the adhesion of foreign substances such as particles to the substrate Evaluated and judged.
The results are shown in Tables 4-6.
5: Less than 10% of blank 4: 10% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Evaluation 1 of long-term adhesion prevention (when immersed and temporarily stored)>
(1) Commercially available colloidal silica slurry (Fujimi Incorporated “COMPOL80” particle size of about 80 nm) (about 30% by weight) (about 30% by weight) was diluted 10 times with pure water to prepare a test slurry solution of 1000 mL.
(2) The test substrate was left in a clean room for 1 week in a beaker containing 1000 mL of the test slurry, and then immersed in the vertical direction and allowed to stand for 6 hours.
(3) After 6 hours, the test substrate was pulled up, rinsed lightly with flowing pure water for 10 seconds, and then dried with nitrogen to prepare a surface protection performance evaluation substrate.
(4) The surface of the substrate was observed with a surface inspection device (MicroMax VMX-6100SK, manufactured by Vision Cytec Co., Ltd.), and the number of particles on the substrate was counted.
In addition, the number of particles on the glass substrate of the blank comparative example 5 was 500, and the number of particles on the aluminum substrate of the blank comparative example 5 was 300.

The number of particles on each substrate was compared with the number of particles on the substrate of the blank (Comparative Example 7), and the anti-adhesion effect for suppressing the particles from adhering to the substrate was evaluated and determined according to the following criteria.
The results are shown in Tables 4-6.
5: Less than 10% of blank 4: 10% to less than 40% of blank 3: 40% to less than 60% of blank 2: 60% to less than 80% of blank 1: 80% or more of blank

<Evaluation 2 of long-term adhesion prevention (when dry)>
(1) 1 g of commercially available silica powder (particle size: about 3 μm) was sprayed on a test substrate after being left in a clean room for 1 week, and allowed to stand for 1 week.
(2) After 1 week, the test substrate was rinsed lightly with running pure water for 10 seconds and then dried with nitrogen to prepare a substrate for surface protection performance evaluation.
(3) The substrate surface was observed with a surface inspection device (MicroMax VMX-6100SK, manufactured by Vision Cytec Co., Ltd.), and the number of particles on the substrate was counted.
In the case of the glass substrate, the number of particles on the substrate of Comparative Example 5 of the blank was 100, and in the case of the aluminum substrate, the number of particles on the substrate of Comparative Example 5 of the blank was 70.

Compare the number of foreign substances such as particles on each substrate with the number of foreign substances on the blank (Comparative Example 7), and in accordance with the following criteria, the anti-adhesion effect that suppresses the adhesion of foreign substances such as particles to the substrate Evaluated and judged.
The results are shown in Tables 4-6.
5: Less than 10% of blank 4: 10% to less than 40% 3: 40% to less than 60% 2: 60% to less than 80% 1: 80% or more

<Measurement of contact angle after cleaning>
(1) Detergents (C-29) to (C-30) of Examples 1 to 28 (C-1) to (C-28) and Comparative Examples 5 to 6 were diluted 50 times and used for surface treatment. A test solution for evaluation of drug removability was obtained. In Comparative Examples 1-4 and 7, pure water was used as it was as a test solution.
(2) The test substrate was immersed in a beaker containing 1000 mL of the above test solution in the vertical direction and allowed to stand for 10 minutes.
(3) After 10 minutes, the test substrate was pulled up, rinsed lightly with flowing pure water for 10 seconds, and dried with nitrogen to prepare a substrate for evaluation of removability.
(4) The contact angle of ion-exchanged water with respect to each substrate was measured with a fully automatic contact angle meter (manufactured by Kyowa Interface Science, “Fully Automatic Contact Angle Meter DM700”). The results are shown in Tables 4-6.

<Evaluation of cleanliness of substrate after cleaning>
Using a Fourier transform infrared spectrophotometer (manufactured by Thermo Electron Ltd., Nicolet 6700), a peak derived from C—H stretching vibration appearing in a range of 2800 to 3200 cm ⁻¹ is measured on the substrate for evaluation of removability. did.
○: No peak is observed.
X: A peak was observed.

  From Tables 4 to 6, the glass substrates and aluminum substrates of Examples 1 to 28 can prevent adhesion of foreign substances such as particles for a long period of time as compared with those of Comparative Examples 1 to 7, and after cleaning. It can be seen that the cleanliness of the substrate is high.

The surface treatment agent and the method for producing an electronic material of the present invention suppress the adhesion of foreign matters such as abrasive grains and particles of polishing scraps to the substrate surface, and further improve the cleanliness of the substrate surface with the conventional surface treatment agent and Compared with the manufacturing method, it can be greatly improved. Therefore, it can be used as a surface treatment agent and a manufacturing method for a substrate in a manufacturing process of an electronic material that requires polishing during the manufacturing process, particularly a magnetic disk substrate such as a hard disk.

Claims (6)

It is selected from the group consisting of the compound (a1) represented by the following general formula (1), the compound (a2) represented by the following general formula (2) and the compound (a3) represented by the following general formula (3). A surface treatment agent for electronic materials containing at least one compound (A), further comprising water as an essential component (B).

[Wherein, R ¹ represents a linear or branched alkyl group having 6 to 24 carbon atoms, A ¹ represents an alkylene group having 2 to 8 carbon atoms, and R ² represents a linear chain having 1 to 5 carbon atoms. Alternatively, it represents a branched alkylene group, and M ⁺ represents a hydrogen ion, an alkali metal ion or an organic cation. m represents the number of added moles of A ¹ O, is an integer of 1 to 100, and A ¹ when m is 2 or more may be the same or different. ]

[Wherein R ³ represents a linear or branched alkyl group having 6 to 24 carbon atoms, A ² represents an alkylene group having 2 to 8 carbon atoms, and X ⁺ represents a hydrogen ion, an alkali metal ion or an organic group. Represents a cation, and t represents an integer of 1 or 2. When t is 1, [R ³ O (A ² O) _k ] may be the same or different. k represents the number of added moles of A ² O, is an integer of 1 to 100, and A ² when k is 2 or more may be the same or different. ]

[Wherein, R ⁴ represents a linear or branched alkyl group having 6 to 24 carbon atoms, and Q represents — (CH ₂ ) _p —COO ⁻ Z ⁺ or a hydrogen atom. Y ⁺ represents a hydrogen ion, an alkali metal ion, or an organic cation. Z ⁺ represents a hydrogen ion, an alkali metal ion, or an organic cation. r is an integer of 1 to 8, p is an integer of 1 to 8, and u is an integer of 0 to 8. ] The surface treating agent for electronic materials according to claim 1, wherein the surface treating agent for electronic materials (B) further contains a compound (a4) represented by the following general formula (4).

[Wherein L ¹ represents a residue obtained by removing s active hydrogens from an amine having s active hydrogens, and A ³ represents an alkylene group having 2 to 8 carbon atoms. n represents the number of added moles of A ³ O, is an integer of 1 to 100, and A ³ when n is 2 or more may be the same or different. s is an integer of 1-40. When s is 2 or more, [(A ³ O) _n H] may be the same or different. ]   The surface treatment agent for electronic materials (B) is a surface treatment agent containing the additive (C) as a constituent component, and the additive (C) is a surfactant other than the chelating agent (D) and the compound (A). The surface treatment agent for electronic materials according to claim 1, which is one or more additives selected from the group consisting of a pH adjusting agent, a hydrotrope agent and a preservative.   The surface treatment agent for an electronic material according to claim 1, wherein the electronic material is a magnetic disk substrate.   A method for producing an electronic material, comprising the step of using the surface treatment agent for electronic material (B) according to any one of claims 1 to 4 so that the contact angle of water with respect to the surface of the electronic material intermediate is 35 ° or more at 25 ° C. .   6. The manufacturing method according to claim 5, wherein a cleaning agent (E) is used after the step of using (B) to make the contact angle of water with respect to the surface of the electronic material intermediate 35 ° or more at 25 ° C. The manufacturing method of the electronic material which has the washing process which makes the contact angle of water with respect to the intermediate body surface 30 degrees or less at 25 degreeC.