JP2006306968A - Detergent for electronic part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a detergent for an electronic part, excellent in non-corrosive properties to aluminum, etc. <P>SOLUTION: This detergent for the electronic part contains an alkylene oxide adduct (A) of an amino compound, wherein a content of alkali metal atoms (B) in the adduct (A) is not more than 1 ppm in weight. The adduct (A) especially preferably comprises an alkylene oxide adduct expressed by general formula (1) (R is a 1-24C hydrocarbon group, a 2-4C hydroxy-terminated alkyl or H; A is a 2-12C alkylene; and m and n are each 0 or an integer of 1 to 10, provided that m+n is an integer of 1 to 20). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  INDUSTRIAL APPLICABILITY The present invention is used for cleaning electronic components such as removing resists used to remove oils and fats, resins, particles, etc. adhering to the surface of liquid crystal panels and semiconductors and creating wiring patterns, and cleaning resist residues. It relates to cleaning agents.

Conventionally, alkali metal compounds, quaternary ammonium hydroxides, nonionic surfactants, and the like have been proposed as main components of electronic component cleaning agents.
However, alkali metal compounds are excellent in cleaning properties, but may corrode aluminum wiring in electronic components and easily cause poor conduction and malfunction. Quaternary ammonium hydroxide also corrodes aluminum wiring. was there.
On the other hand, as nonionic surfactants, combined use of alkylene oxide adducts such as alcohols or fatty acid polyoxyalkylene alkyl ethers (Patent Documents 1 to 3) and alkylamine alkylene oxide adducts (Patent Document 4) However, there was a problem of poor conduction and poor conduction due to corrosion of aluminum wiring.
JP-A-5-148499 Japanese Patent Laid-Open No. 5-179289 JP-A-5-302096 Japanese Patent Laid-Open No. 7-216394

  The subject of this invention is providing the cleaning agent for electronic components which has the outstanding detergency and does not raise | generate conduction | electrical_connection defects, such as aluminum wiring.

  As a result of intensive studies to achieve the above object, the present inventor has reached the present invention. That is, the present invention is a cleaning agent for electronic parts containing an alkylene oxide adduct (A) of an amino compound, and the content of alkali metal atoms (B) based on the weight of (A) is 1 ppm or less. It is a cleaning agent for electronic parts.

Since the cleaning agent of the present invention is excellent in non-corrosiveness to aluminum wiring or the like, it can be cleaned without damaging the aluminum wiring or color filter member of the glass substrate for a liquid crystal panel, for example, with poor conduction.
The cleaning agent of the present invention is also excellent in the ability to remove oil, fingerprints, resin and particles.

The electronic component cleaning agent of the present invention contains an alkylene oxide adduct (A) of an amino compound, and the content of alkali metal atoms (B) based on the weight of (A) is 1 ppm or less, preferably 0.3 ppm. The gist of the invention is as follows (in the following, ppm represents ppm by weight).
When the alkali metal atom (B) exceeds 1 ppm, conduction failure or malfunction is likely to occur.

Examples of the alkali metal atom (B) in the present invention include lithium, sodium and potassium. The alkali metal atom is usually contained in (A) in the form of the compound. Specific examples of the alkali metal atom compounds include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkali metal carbonate phosphates such as sodium carbonate and potassium carbonate, sodium pyrophosphate, Alkali metal silicates such as potassium pyrophosphate, sodium tripolyphosphate and potassium tripolyphosphate, sodium silicate and potassium silicate, organic acid alkali metal salts such as potassium acetate, sodium acetate, potassium lactate and sodium lactate and These mixtures may be mentioned, and may be contained in the form of an alkali metal alcoholate of alkylene oxide (A).
The content of the alkali metal atom (B) in the alkylene oxide adduct (A) can be measured by an atomic absorption analyzer.

The amino compound constituting the alkylene oxide adduct (A) of the amino compound in the present invention is an amino compound having an active hydrogen atom in the amino group, and includes compounds having a primary and secondary amino group.
Examples of the compound having a primary amino group include aliphatic monoalkylamines having 1 to 24 carbon atoms, hydroxyalkyl monoamines having 2 to 24 carbon atoms, and aromatic monoamines having 6 to 24 carbon atoms.
Examples of the compound having a secondary amino group include an aliphatic dialkylamine having 1 to 24 carbon atoms in an alkyl group, a di (hydroxyalkyl) amine having 4 to 24 carbon atoms, and an alkylarylamine having 7 to 24 carbon atoms. It is done.
Of the amino compounds, amino compounds having a primary amino group (hereinafter abbreviated as primary amino compounds) are preferred from the viewpoint of detergency.

Examples of the alkylene oxide constituting (A) include 2 to 12 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), butylene oxide, and 1,2-dodecene oxide. And a combination of two or more of these.
Among the alkylene oxides, those having 2 to 8 carbon atoms, particularly EO and PO, are preferred, and EO alone and random or block addition of EO and PO are more preferred.
The number of added moles of alkylene oxide is preferably 1 to 50 moles, more preferably 2 to 40 moles from the viewpoint of detergency.

  Of the alkylene oxide adducts of the primary amino compound, the adduct represented by the general formula (1) is preferable from the viewpoint of detergency.

  In the formula, R is a hydrocarbon group having 1 to 24 carbon atoms, a terminal hydroxylalkyl group having 2 to 4 carbon atoms or a hydrogen atom, A is an alkylene group having 2 to 12 carbon atoms, and m and n are 0 or 1 to 1 It is an integer of 10 and m + n is an integer of 1-20.

Of R in the general formula (1), the hydrocarbon group having 1 to 24 carbon atoms includes a linear or branched saturated or unsaturated hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic ring-containing hydrocarbon group. Can be mentioned.
Examples of the linear or branched saturated hydrocarbon group include alkyl groups (such as methyl group, ethyl group, n-, i-, sec- and t-butyl group, octyl group, 2-ethylhexyl group, and octadecyl group); Linear or branched unsaturated hydrocarbon groups include alkenyl groups (such as vinyl, propenyl, allyl, and butenyl groups); alicyclic hydrocarbon groups include cycloalkyl groups (such as cyclohexyl groups); aromatic rings Containing hydrocarbon groups include aryl groups (such as phenyl and naphthyl groups), aralkyl groups (such as benzyl and phenethyl groups), alkylaryl groups (such as methylphenyl, ethylphenyl, nonylphenyl, methylnaphthyl and ethyl). Naphthyl group, etc.).
Among these hydrocarbon groups, alkyl groups, alkenyl groups and cycloalkyl groups are preferable from the viewpoint of detergency, and more preferable are those having 2 to 8 carbon atoms from the viewpoint of appearance stability of the detergent. It is.
If the carbon number of R is 24 or less, the detergency is excellent.

  Among R in the general formula (1), examples of the terminal hydroxylalkyl group having 2 to 4 carbon atoms include hydroxyethyl, hydroxypropyl, and hydroxybutyl, and hydroxyethyl is preferable.

A in the general formula (1) includes an alkylene group having 2 to 12 carbon atoms, such as an ethylene group, a 1,2-propylene group, a butylene group, and a 1,2-dodecylene group.
If the carbon number of A is 2-8, the detergency can be further improved.
m and n are 0 or an integer of 1 to 10, m + n is an integer of 1 to 20, and if m + n is 20 or less, the detergency is good.

The method for producing an alkylene oxide adduct (A) of an amino compound in the present invention is a method in which an alkylene oxide is subjected to a ring-opening reaction in the presence or absence of a catalyst. Examples of the catalyst include potassium hydroxide and sodium hydroxide. The reaction temperature is 80 ° C. to 180 ° C., and the pressure is 0 to 5 atm.
In order to make the content of the alkali metal atom (B) based on the weight of the alkylene oxide adduct (A) of the present invention 1 ppm or less, the reaction is preferably carried out in the absence of a catalyst.
Moreover, when an alkali metal compound is used as a catalyst, it is preferable to remove the alkali metal compound with an adsorbent or the like after the reaction to make it 1 ppm or less.
Examples of the adsorbent include KYOWARD (manufactured by Kyowa Chemical Co., Ltd.).

  The content ratio of (A) based on the weight of the cleaning agent of the present invention is 10% by weight or more, preferably 20% or more (in the following, unless otherwise specified,% represents% by weight), more preferably 30% or more. It is.

In addition to (A) and (B), the detergent of the present invention may further contain other surfactant (C), amide group-containing hydrophilic solvent (D), other additives (E) and / or if necessary. It can contain water.
Other surfactants (C) include nonionic surfactant (C1), anionic surfactant (C2), cationic surfactant (C3), amphoteric surfactant (C4) and mixtures thereof. .

  Examples of (C1) include alkylene oxide addition type nonionic surfactants [higher alcohol (8 to 18 carbon atoms), alkylphenol (10 to 24 carbon atoms), higher fatty acid (12 to 24 carbon atoms) directly alkylene oxide. [C2-C4, such as EO, propylene oxide, butylene oxide, the same shall apply hereinafter] (Mn158-200,000); polyoxyalkylene glycol (Mn150-6,000) and higher fatty acids (C12 To 24); an alkylene oxide is added to an esterified product obtained by reacting a higher fatty acid (12 to 24 carbon atoms) with a hydroxyl group-containing compound such as a diol or a tri- to 8-valent polyhydric alcohol. (Mn 250-30,000), higher fatty acid (carbon number 8-24) amide and alkyl An oxide added (Mn 200 to 30,000), a polyhydric alcohol (the above) an alkyl (carbon number 8 to 60) ether added with an alkylene oxide (Mn 120 to 30,000), and the like], and Polyhydric alcohol (carbon number 3-20) type nonionic surfactant [polyhydric alcohol fatty acid (carbon number 8-60) ester, polyhydric alcohol alkyl (carbon number 8-60) ether, fatty acid (carbon number 8-60) ) Alkanolamide etc.].

Examples of (C2) include carboxylic acid (saturated or unsaturated fatty acid having 8 to 22 carbon atoms) salt, carboxymethylated salt [aliphatic alcohol having 8 to 16 carbon atoms and / or EO thereof (1 to 10 mol). ) Salts of carboxymethylated products such as adducts], sulfate esters [higher alcohol sulfate esters (sulfate esters of aliphatic alcohols having 8 to 18 carbon atoms, etc.)], higher alkyl ether sulfate esters [carbon number Sulfuric acid ester salt of EO (1 to 10 mol) adduct of 8-18 aliphatic alcohol], sulfated oil (salt obtained by sulfating and neutralizing natural unsaturated fat or unsaturated wax as it is), sulfated Fatty acid ester (salt obtained by sulfating and neutralizing lower alcohol ester of unsaturated fatty acid), sulfated olefin (sulfating olefin having 12 to 18 carbon atoms) Hydrated salts), sulfonates [alkylbenzene sulfonates, alkylnaphthalene sulfonates, sulfosuccinic acid diester types, α-olefins (12 to 18 carbon atoms) sulfonates, Igepon T type, etc.] and phosphate ester salts [ Higher alcohol (carbon number 8 to 60) phosphoric acid ester salt, higher alcohol (carbon number 8 to 60) EO adduct phosphoric acid ester salt, alkyl (carbon number 4 to 60) phenol EO adduct phosphoric acid ester salt, etc.] Can be mentioned.
Examples of the salt include alkali metal (sodium, potassium, etc.) salt, alkaline earth metal (calcium, magnesium, etc.) salt, ammonium salt, alkylamine (C1-20) salt and alkanolamine (C2-12). For example, mono-, di- and triethanolamine) salts.

  (C3) includes quaternary ammonium salt type [tetraalkyl (4 to 100 carbon atoms) ammonium salt such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide; 3-80) benzylammonium salts, such as lauryldimethylbenzylammonium chloride (benzalkonium chloride); alkyl (2-60 carbons) pyridinium salts, such as cetylpyridinium chloride; polyoxyalkylene (2-4 carbons) tri Alkyl ammonium salts such as polyoxyethylene trimethyl ammonium chloride; sapamine type quaternary ammonium salts such as stearamide ethyl diethyl methyl Ammonium methosulphate], amine salt type [aliphatic higher amines (12 to 60 carbon atoms, such as laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine, etc.) Salt or organic acid (C2-C22, for example, acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid, azelaic acid) salt; higher fatty acid (lower C1-C11) fatty acid ( C12-24, e.g., stearic acid, oleic acid) salts; inorganic acid (above) salts or organic acid (above) salts such as EO adducts of aliphatic amines (C1-30); 3 Inorganic acids (such as triethanolamine monostearate, stearamide ethyl diethylmethylethanolamine, etc.) ) Salts or organic acids (above one) salts], and others.

  Examples of (C4) include amino acid type amphoteric surfactants [higher alkylamine (carbon number 12 to 18) sodium propionate and the like], betaine type amphoteric surfactants [alkyl (carbon number 12 to 18) dimethyl betaine, alkyl ( Carbon number 12-18) dihydroxyethyl betaine, coconut oil fatty acid amide propyl betaine, etc.], sulfate ester type amphoteric surfactant [higher alkyl (carbon number 8-18) amine sulfate ester sodium salt, hydroxyethyl imidazoline sulfate sodium salt Salt], sulfonate-type amphoteric surfactant (pentadecylsulfotaurine, imidazoline sulfonic acid, etc.), phosphate ester-type amphoteric surfactant [glycerin higher fatty acid (carbon number 8-22) esterified phosphoric acid Ester amine salts] and the like.

  Among (C1) to (C4), (C1) and (C2) are preferable from the viewpoint of detergency and non-corrosiveness, and (C1) is more preferable. The content of (C) is 30% or less, preferably 1 to 20%, based on the total weight of the cleaning agent.

The amide group-containing hydrophilic solvent (D) is a water-soluble amide having a water solubility at 20 ° C. (g / 100 g H 2 O) of 3 or more and containing one or more amide groups in the molecule, and 2-pyrrolidone And N-alkyl (C1-C3) -2-pyrrolidone and the like. Of these, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, Nn-propyl-2-pyrrolidone and N-isopropyl-2-pyrrolidone are preferable from the viewpoints of detergency and rinsing properties. The content of (D), which is preferably N-methyl-2-pyrrolidone, is preferably 30% or less, more preferably from the viewpoints of detergency, rinse and corrosion resistance, based on the total weight of the detergent. Is 1-20%.

Other additives (E) include rust inhibitor [chromate, nitrite, higher fatty acid (carbon number 8-30) salt of amine (carbon number 6-30), dicarboxylic acid (carbon number 12-24) Alkali metal (sodium, potassium, etc.) salts, alkanolamides (e.g., dodecenyl succinic acid diethanolamide) of dicarboxylic acids (e.g., 12-24 carbon atoms), alkanolamide alkali metal salts of dicarboxylic acids (e.g., 12-24 carbon atoms) (e.g., Dodecenyl succinic acid diethanolamide sodium salt)], antioxidant [phenol compound (2,6-di-t-butyl-4-methylphenol etc.), sulfur-containing compound (dilauryl thiodipropionate etc.), amine compound ( Octylated diphenylamine), phosphorus compounds (such as triphenyl phosphite)], metals On sequestering agent (sodium ethylenediamine tetraacetate, sodium citrate), and the like.
The content of (E) is usually 20% or less, preferably 0.5 to 10% for the rust inhibitor, and usually 5% or less, preferably 0.1 to 10% for the antioxidant based on the total weight of the detergent. 1%, sequestering agent is usually 20% or less, preferably 0.5 to 10%.

  The water content is preferably 90% or less, more preferably 1 to 80%, particularly preferably 2 to 70% from the viewpoints of detergency, rinsing properties and non-corrosive properties based on the total weight of the cleaning agent. is there.

  Based on the weight of the cleaning agent of the present invention, the total content of (C), (D) and (E) is 40% or less, preferably 30% or less, and more preferably 20% or less.

Viscosity at 25 ° C. of the cleaning agent of the present invention is usually 2~300mm ² / s, from the viewpoint of detergency and rinsing properties, preferably 3~100mm ² / s, more preferably 4~50mm ² / s. The viscosity can be measured with a viscometer such as Ostwald or Ubbelohde.
The pH (10% aqueous solution) of the cleaning agent of the present invention is usually 8 to 14, and preferably 9 to 13 from the viewpoints of cleaning properties and non-corrosive properties.

  The cleaning agent of the present invention is usually used for cleaning electronic parts, and can be widely used for cleaning electronic parts in which aluminum is used for some or all of the parts. Examples thereof include glass substrates for liquid crystal panels (cleaning before alignment film patterning, peeling cleaning of defective alignment films), printed boards, plasma display glass substrates, semiconductor integrated circuits, electronic components such as thermal heads, and the like. Examples of the object to be cleaned (dirt) include organic substances such as oil, fingerprints, resist resins, and organic particles, and inorganic substances such as inorganic particles (for example, glass powder, ceramic powder, and metal powder).

As a method for cleaning a glass substrate for a liquid crystal panel using the cleaning agent of the present invention, for example, a cleaning method using ultrasonic cleaning, shower cleaning, spray cleaning, immersion, immersion rocking, or a combination thereof can be applied.
The cleaning agent of the present invention at the time of washing may be further diluted with water if necessary, but is preferably within the above-mentioned water content range.

  The washing temperature is usually about 10 to 70 ° C, preferably about 15 to 60 ° C. The washing time is usually 0.2 to 120 minutes, preferably 0.5 to 30 minutes. The rinsing temperature with water is usually 5 to 90 ° C., preferably 10 to 70 ° C. As the rinsing method, the same method as the above washing method can be applied. After rinsing, a clean glass substrate for a liquid crystal panel can be obtained by heating and drying at 50 to 150 ° C., preferably 60 to 100 ° C. for 1 to 120 minutes, preferably 3 to 60 minutes.

<Example>
EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this. In addition, a part shows a weight part below.

Example 1
Into a 1 L stainless steel autoclave, 297 g (3 mol) of cyclohexylamine was charged, and 264 g of EO was added dropwise at a temperature in the range of 80 to 180 ° C. to react to obtain a 2 mol adduct of cyclohexylamine EO. As a result of measuring the alkali metal atom content by atomic absorption analysis, it contained 0.002 ppm of sodium. This product was designated as the cleaning agent (A-1) of Example 1.

Example 2
It was 1.25 ppm as a result of measuring alkali metal atom content of commercial diethanolamine (made by Wako Pure Chemical Industries).
As a result of adding 2% of Kyoward 600 as a treating agent to the diethanolamine, treating it under conditions of nitrogen aeration at 70 to 120, and filtering, a purified product having an alkali metal atom content of 0.04 ppm as potassium was obtained. Obtained. This purified product was used as the cleaning agent (A-2) of Example 2.

Example 3
A crude cyclohexylamine EO 2 mol adduct was obtained in the same manner as in Example 1 except that 160 ppm of potassium hydroxide was used as a catalyst. As a result of adding 3% of Kyoward 600 as a treating agent to this crude cyclohexylamine EO 2 mol adduct, treating it under conditions of 70 to 120 under aeration of nitrogen, and performing filtration three times, an alkali metal atom was obtained. A purified product having a potassium content of 0.15 ppm was obtained. This purified product was used as the cleaning agent (A-3) of Example 3.

Comparative Example 1
Commercially available diethanolamine (the result of measuring the alkali metal atom content was 1.25 ppm) was used as the cleaning agent (B-1) of the comparative example.

Comparative Example 2
Commercially available tetramethylammonium hydroxide pentahydrate (which was 0.01 ppm as a result of measuring the alkali metal atom content) was used as the cleaning agent (B-2) of the comparative example.

  The evaluation test methods for the cleaning agents obtained in Examples and Comparative Examples are shown below, and the evaluation results are shown in Table 1.

1. Glass substrate washability A glass substrate (25 × 25 mm, thickness 0.75 mm) was used as a test piece. The test piece was immersed for 3 minutes in a detergent diluent (25 ° C.) adjusted to a solid content concentration (solid content means a component other than water; the same applies hereinafter) of 40%, and then the test piece was stainless steel mesh. It was placed on a basket and rinsed with ion-exchanged water for 1 minute, and the back side surface was rinsed in the same manner. Next, the test piece was dried for 10 minutes in an air circulation dryer at 70 ° C., and then observed with a microscope to confirm the number of particles per 1 cm ^2, and the removability was evaluated in the following five stages. The number of particles before washing was 100 to 120.
<Evaluation criteria>
5: No particles at all on the glass substrate surface.
4: About 1 to 5 particles remain on the glass substrate surface.

2. Conductivity Cleaning with a glass substrate test piece (25 × 25 mm, thickness 0.75 mm, number of lines 10) deposited with aluminum wiring (film thickness 0.1 μm, line width 10 μm) adjusted to a solid content concentration of 40% The specimen was immersed in an agent diluent (40 ° C.) for 3 minutes, placed on a stainless steel basket, rinsed with ion-exchanged water for 1 minute, and the back side was rinsed in the same manner. Next, after the test piece was dried for 10 minutes in a circulating air dryer at 70 ° C., conduction was confirmed for the aluminum wiring, and (number of wiring with conduction / total number of wiring) was described in the table.

  As shown in Comparative Example 1 of Table 1, when the alkali metal atom content exceeded 1 ppm, and when quaternary ammonium was used as the alkali component, wiring that caused poor conduction was observed, the cleaning agent of the present invention In Examples 1 to 3, no conduction failure was observed in all the aluminum wirings.

  Since the cleaning agent of the present invention does not cause poor conduction and has an excellent ability to remove oil, fingerprints, resin and particles, it can be applied to cleaning electronic parts such as glass substrates for liquid crystal panels. Very useful.

Claims (3)

  A cleaning agent for electronic parts containing an alkylene oxide adduct (A) of an amino compound, wherein the content of alkali metal atoms (B) based on the weight of (A) is 1 ppm or less. The cleaning agent for electronic parts according to claim 1, wherein (A) is an alkylene oxide adduct represented by the following general formula (1).

[In the formula, R is a hydrocarbon group having 1 to 24 carbon atoms, a terminal hydroxylalkyl group having 2 to 4 carbon atoms or a hydrogen atom, A is an alkylene group having 2 to 12 carbon atoms, and m and n are 0 or 1 Where m + n is an integer of 1-20. ]   The electronic component cleaning agent according to any one of claims 1 to 3, wherein the electronic component cleaning agent is a liquid crystal panel cleaning agent, a semiconductor cleaning agent, or a resist stripping cleaning agent.