JP3326041B2 - Detergent composition for hybrid IC substrate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning composition for a hybrid IC substrate, and more particularly to a cleaning composition for a hybrid IC substrate overcoated with a low melting point solder glass containing metal ions such as lead and zinc. The present invention relates to a cleaning composition for a hybrid IC substrate, which is excellent in removing dirt such as rosin-based flux, prevents erosion of solder glass, and has no influence on metal members.

[0002]

2. Description of the Related Art As a hybrid IC substrate, for example, a hybrid IC for a vehicle is used.
The C substrate is a hybrid IC substrate designed so that it can be used in a severe environment, such as an automobile, as compared with general home electric appliances and the like. The production is a thick film printing process of printing / drying / firing conductor printing / drying / firing, resistor printing / drying / firing on an alumina-based ceramic substrate, and then printing / drying / firing a low melting point solder glass as overcoat glass.
It is performed through a component assembly process such as various component assembly / soldering / flux cleaning / drying / wire bonding, a package process, an inspection process, and the like.

Here, the overcoat layer made of low melting point solder glass is generally called a passivation function. However, in a severe vehicle environment such as high temperature and high humidity and exhaust gas, moisture, sulfur content in the exhaust gas, It has a function of preventing corrosion of thick film conductors such as silver and copper due to intrusion of corrosive ions and the like, migration, deterioration of thick film resistance and fluctuation of characteristic values. In order to sufficiently exhibit this function and to ensure the reliability of the substrate, it is important to sufficiently wash the flux and the like after soldering and not to erode the overcoat layer.

Conventionally, to remove dirt such as rosin-based flux present on the surface of electronic components such as hybrid IC substrates, alcohol-based solvents such as ethanol and isopropanol; hydrocarbon-based solvents such as kerosene, benzene, and xylene; trichloroethylene Solvent-based cleaning agents such as chlorine-based solvents such as chlorobenzene and tetrachloroethylene; and chlorofluorocarbon-based solvents such as trichlorotrifluoroethane.

However, alcohol solvents have safety problems, and hydrocarbon solvents, especially benzene,
Xylene and the like are highly toxic and are designated as hazardous substances in terms of occupational safety and health. Considering the danger and complexity of handling such substances, it is not preferable to use them as cleaning agents. On the other hand, it has been clarified that cleaning agents using chlorine-based and chlorofluorocarbon-based solvents have serious problems in safety, toxicity, environmental pollution, and the like, and are being abolished on an international level.

Recently, the use of an improved water-based cleaning agent or a water-rinsable cleaning agent for removing stains such as rosin-based flux present on the surface of electronic components has been studied. These detergents have a detergency equal to or higher than that of a solvent-based detergent by appropriately selecting and blending a surfactant and a builder used in the detergent, or there is no danger of fire or explosion because there is no flammability. And so on.

However, when cleaning a hybrid IC substrate using these water-based cleaning agents, the ability to remove dirt such as flux is poor, or the overcoat layer made of solder glass is eroded, and the passivation function is accordingly reduced. Significantly inhibits As a result, there is a disadvantage that the electrical reliability of the substrate is also reduced.

[0008] There have been many attempts to use water-based detergents for general glass materials.
For example, Japanese Patent Application Laid-Open No. Hei 5-271699 discloses that
The use of an organic alkali aqueous solution obtained by adding a non-ionic surfactant and an alkanolamine to a quaternary ammonium base as an alkali base material is disclosed as a detergent. However, these do not have sufficient cleaning properties for stains such as rosin flux. Further, not only does the solder glass used for the hybrid IC substrate have the effect of preventing erosion, but also the electrode members and components such as aluminum and copper are eroded, and the electrical reliability is reduced.

Further, Japanese Patent Application Laid-Open No. 5-302099 discloses that a composition containing ethylene glycol monohexyl ether, a surfactant, an auxiliary solvent and water is used as a detergent. However, these are hardly expected to have the effect of preventing erosion of the solder glass.

[0010] On the other hand, regarding "burn" of glass material,
For example, the Ceramic Industry Association, Vol. 87, No. 1 (1979) states that erosion of a surface layer by an alkali solution of alkali glass, so-called "latent scratch", is caused by Ca ²⁺ , tetramethylammonium ion (N (CH ₃ ) ₄ ⁺ ) Is disclosed that can be delayed. However, in the solder glass used for the hybrid IC substrate targeted in the present invention,
Due to the high content of modified oxides, more intense elution occurs. In addition, some components contained in dirt such as rosin flux easily bind to metal ions of these modified oxides, and significantly promote erosion. It is.

An object of the present invention is to solve a problem which has not been solved thus far. That is,
To provide a cleaning composition for a hybrid IC substrate which improves the disadvantages of conventional cleaning agents, has excellent safety, cleaning properties, and rinsing properties, prevents solder glass erosion, and does not affect metal members. is there.

[0012]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that a glycol ether compound, an ethylene oxide adduct of a monocyclic aromatic diamine, and an alkyl phosphate have a branched chain. Alkyl first
A cleaning composition comprising a compound neutralized with a secondary amine, a non-ionic surfactant, and water is used as a hybrid IC.
Excellent safety, cleaning and rinsing properties when cleaning the substrate,
The present invention was found to be excellent in preventing erosion of the solder glass and not affecting metal members, and completed the present invention.

That is, the gist of the present invention is as follows: (1) The following components (A) to (E) (A) The following general formula (I) R ¹ -O- (CH ₂ CH ₂ O) _i -H ( I) (wherein R ¹ represents a hydrocarbon group having 1 to 4 carbon atoms, and i represents an integer of 2 to 3) 70 to 95% by weight of a glycol ether compound represented by the following formula: Of the general formula (II)

[0014]

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(Where j and k are integers of 0 to 2).
a, b, c and d are integers satisfying 2 ≦ a + b + c + d ≦ 10. (C) 0.3 to 5% by weight of an ethylene oxide adduct of a monocyclic aromatic diamine represented by the following formula (III):

[0016]

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(Wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
0.2 to 5% by weight of a compound obtained by neutralizing 0% equivalent with a branched alkyl primary amine having 4 to 22 carbon atoms; (D) the following general formula (IV): R ³ —O— (CH ₂ CH) ₂ O) _p- H (IV) (wherein, R ³ represents a linear or branched alkyl, alkenyl, phenyl or phenyl group having 12 to 18 carbon atoms)
Represents a phenyl group substituted with a straight-chain or branched-chain alkyl group of 1 to 9, and p represents an integer of 4 to 13. A hybrid IC containing 1 to 15% by weight of a nonionic surfactant represented by the following formula: (E) 3 to 15% by weight of water
The present invention relates to a cleaning composition for a substrate.

Among the components used in the cleaning composition of the present invention, the glycol ether compound as the component (A) is represented by the general formula (I). In the general formula (I), R ¹ is a hydrocarbon group having 1 to 4 carbon atoms, and i is an integer of 2 to 3. When R ¹ is not a hydrocarbon group, the affinity for organic stains such as flux tends to decrease. Further, from the viewpoint of solubility in water, R ¹ is a saturated or unsaturated hydrocarbon group, and more preferably has 2 to 4 carbon atoms. This is because if the solubility of the glycol ether compound in water deteriorates, the viscosity of the cleaning solution itself also increases, which is inappropriate for cleaning a hybrid IC substrate or the like. Further, when i is 2 or more, the flash point exceeds 90 ° C. and there is no danger of ignition, while when i exceeds 3, the viscosity of the cleaning liquid itself tends to increase. That is, the glycol ether compound used in the present invention preferably has a flash point of 90 ° C. or higher and is soluble in water by 50% or higher.

Specific examples of such glycol ether compounds include diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether and diethylene glycol monoallyl ether; Triethylene glycol monoalkyl ethers such as triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monoisopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monoisobutyl ether, and triethylene glycol monoallyl ether Kind, and the like. The above compound can be obtained from a general trader.

Among the above compounds, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,
Diethylene glycol monoisobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether can be preferably used from the viewpoint of performance and availability.

These glycol ether compounds are
For example, it can be obtained by adding ethylene oxide in a gaseous state to an alcohol having a hydrocarbon group having 1 to 4 carbon atoms while heating in the presence of a catalyst such as caustic soda to cause a reaction.

These glycol ether compounds are
From the viewpoints of detergency, its durability and cost-by-performance, it is preferable to add 70 to 95% by weight, especially 80 to 90% by weight in the detergent composition. These glycol ether compounds may be used alone or in combination of two or more.

Among the components used in the cleaning composition of the present invention, the ethylene oxide adduct of the monocyclic aromatic diamine of the component (B) is represented by the above general formula (II). In the general formula (II), j and k are integers of 0 to 2, and a, b,
c and d are integers satisfying 2 ≦ a + b + c + d ≦ 10. Monocyclic aromatic diamines in which j and k exceed 2 are difficult to obtain and very expensive. From the viewpoint of the alkalinity of the monocyclic aromatic diamine and the effect of preventing erosion of the solder glass, a + b + c + d is more preferably 3 to 8. This is because if the alkalinity of the monocyclic aromatic diamine is high, the electrical characteristics of the hybrid IC substrate are degraded when the cleaning agent remains, and the metal member is rusted. Here, the combination of a, b, c, and d is not particularly limited as long as it satisfies the above numerical range.

Specific examples of the ethylene oxide adduct of a monocyclic aromatic diamine include m-xylylenediamine, p-xylylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, and 1,4. -Ethylene oxide added to phenylenediamine, 2-aminobenzylamine, 4-aminobenzylamine, 2- (4-aminophenyl) ethylamine, etc., that is, 1 mole of m-xylylenediamine contains 2 moles of ethylene oxide. A compound to which 10 to 10 mol has been added (abbreviated as (POE) _2-10 adduct of m-xylylenediamine; similar compounds are also abbreviated by corresponding expressions), p
-(POE) _2-10 adduct of xylylenediamine, 1,2
-(POE) _2-10 adduct of phenylenediamine, 1,3
-(POE) _2-10 adduct of phenylenediamine, 1,4
- (POE) _2-10 adducts of phenylenediamine, 2-amino-benzyl (POE) _2-10 adducts of amines, 4-amino-benzylamine (POE) _2-10 adduct, 2- (4-
And (POE) _2-10 adduct of (aminophenyl) ethylamine.

[0025] Among these, from the viewpoints of performance and availability, m- xylylene amine (POE) _2-10 adduct, p- xylylene amine (POE) _2-10 adduct,
(POE) _2-10 adduct of 1,2-phenylenediamine,
(POE) _2-10 adducts of 1,3-phenylenediamine are more preferred. The monocyclic aromatic diamine can be obtained from a general handling company.

The ethylene oxide adduct of these monocyclic aromatic diamines is obtained by reacting the above monocyclic aromatic diamine by adding ethylene oxide in a gaseous state while heating in the presence of a catalyst such as caustic soda. can get.

These monocyclic aromatic diamine ethylene oxide adducts are used in an amount of 0.3 to 5 parts by weight in the detergent composition from the viewpoints of the effect of preventing erosion of the solder glass, its durability and cost-by-performance. %, Especially 0.5
It is preferable to mix ３3% by weight. These ethylene oxide adducts of monocyclic aromatic diamines may be used alone or in combination of two or more.

Of the components used in the cleaning composition of the present invention, 50 to 10 of the alkyl phosphate of component (C) are used.
In a compound in which 0% equivalent is neutralized with a branched-chain alkyl primary amine, the alkyl phosphate is represented by the general formula (II)
I). In the general formula (III), R ² has 1 carbon atom
X is a hydrogen atom or a C1 to C4 alkyl group.
4 alkyl group. When R ² is not an alkyl group,
And when X is not a hydrogen atom or an alkyl group, the effect of preventing erosion of the solder glass and its sustainability tend to be insufficient. When R ² or X is an alkyl group having more than 4 carbon atoms, the viscosity of the neutralized product with the branched-chain alkyl primary amine increases, and the rinsing properties tend to decrease.

Specific examples of such alkyl phosphates include monoalkyl phosphates such as monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate and monobutyl phosphate; dialkyl phosphates such as dimethyl phosphate, diethyl phosphate, diisopropyl phosphate and dibutyl phosphate; A mixture of these monoalkyl phosphates and dialkyl phosphates (hereinafter, this mixture is referred to as sesquialkyl phosphate. The alkyl chains of the dialkyl phosphates may be the same or different). Specific examples of sesquialkyl phosphate include sesquimethyl phosphate, sesquiethyl phosphate, sesquiisopropyl phosphate,
Sesquibutyl phosphate and the like can be mentioned.

Of the above compounds, monomethyl phosphate, monoethyl phosphate, monoisopropyl phosphate, monobutyl phosphate, sesquimethyl phosphate, sesquiethyl phosphate, sesquiisopropyl phosphate, and sesquibutyl phosphate are particularly preferably used from the viewpoint of performance and availability. be able to.

The above-mentioned monoalkyl phosphate, dialkyl phosphate and sesquialkyl phosphate are, for example, alcohols having 1 to 4 carbon atoms, such as diphosphorus pentoxide, phosphorus oxychloride, phosphorus trichloride, etc., active phosphorus derivatives, orthophosphoric acid, condensate, etc. It is obtained by a method of reacting phosphoric acids such as phosphoric acid (polyphosphoric acid).

In the present invention, in order to use a monoalkyl phosphate, the alkyl phosphate obtained as described above is neutralized with an inorganic alkali such as sodium hydroxide or an organic amine such as sodium hydroxide, for example, in water. After forming a salt and dissolving it in an organic solvent such as acetone or ethanol to precipitate a monoalkyl phosphate, or after dissolving a sesquialkyl phosphate in a heated organic solvent such as n-hexane. It may be isolated by a usual separation method such as cooling and precipitation of a monoalkyl phosphate. In order to use the dialkyl phosphate, the dialkyl phosphate may be isolated by a usual separation method such as concentration and drying from an organic solvent solution from which the precipitate of the monoalkyl phosphate has been removed.
The above alkyl phosphates may be used alone or in combination of two or more.

The above-mentioned alkyl phosphates are
It is used by neutralizing 100% equivalent with a branched alkyl primary amine having 4 to 22 carbon atoms. When the alkyl group is not a branched chain, the effect of preventing erosion of the solder glass and its persistence tend to be insufficient. The number of carbon atoms is more preferably 5 to 19 from the viewpoint of the odor of the obtained detergent composition and the viscosity of the neutralized product with the alkyl phosphate.

Specific examples of such branched alkyl primary amines include isobutylamine, t-butylamine,
-Methylbutylamine, 1-ethylpropylamine, 2
-Methylbutylamine, isoamylamine, dimethylpropylamine, t-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-aminoheptane, 1-methylheptylamine, 2-ethylhexylamine, Examples thereof include 1,5-dimerhexylamine, t-octylamine, t-tridecylamine, and t-nonadecylamine. The above compound can be obtained from a general trader.

Of the above compounds, t-butylamine,
T-amylamine, t-octylamine, t-tridecylamine and t-nonadecylamine can be preferably used from the viewpoint of performance and availability. These branched alkyl primary amines may be used alone or in combination of two or more.

The neutralized product of such an alkyl phosphate with a branched alkyl primary amine is, for example, the above alkyl phosphate and the branched alkyl primary amine in a solution of water and / or a solvent, or a detergent composition. It can be obtained by mixing by conventional methods. The degree of neutralization at this time is from 50 to 100% equivalent, preferably from 60 to 95% equivalent of the alkyl phosphate from the viewpoint of preventing rusting of the metal member due to a decrease in the pH of the detergent.

The compound obtained by neutralizing the above-mentioned alkyl phosphate with a branched-chain alkyl primary amine is effective in preventing the erosion of solder glass and its persistence, as well as the cost-performance and the viscosity of the detergent. It is preferable to add 0.2 to 5% by weight, particularly 0.3 to 3% by weight therein.

[0038] Among the components used in the cleaning composition of the present invention, the nonionic surfactant of component (D) is represented by the general formula (IV). In the general formula (IV), R ³ represents a linear or branched alkyl group having 12 to 18 carbon atoms, an alkenyl group, a phenyl group, or a phenyl group substituted with a linear or branched alkyl group having 8 to 9 carbon atoms. And p is an integer of 4 to 13.

R ³ is a straight-chain or branched-chain alkyl group having 12 to 18 carbon atoms, preferably 12 to 15 carbon atoms, a phenyl group, or a carbon atom having 8 to 18 carbon atoms, from the viewpoint of the detergent effect and its durability.
A phenyl group substituted with 9 linear or branched alkyl groups; Further, p is an integer of 4 to 13, preferably 6 to 1 from the viewpoints of the washing effect, lipophilicity and hydrophilicity.
It is an integer of 1. This is because when the lipophilicity is increased, the rinsing property is reduced, while when the hydrophilicity is increased, the cleaning property of the oily stain is reduced.

Examples of such nonionic surfactants include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol,
Straight or branched chain alkyl, alkenyl, or phenyl group-containing alcohols such as synthetic alcohols having 12 to 14 carbon atoms (abbreviated as _C12-14 synthetic alcohol); and ethylene oxide adducts; Examples include an ethylene oxide adduct of a phenol substituted with a chain or branched alkyl group.

Specifically, a compound in which 4 to 13 moles of ethylene oxide is added to 1 mole of a C _12-14 synthetic alcohol ((POE) _4-13 C _12-14 synthetic alcohol ether). Is abbreviated similarly in the corresponding expression.), (POE) _4-13 lauryl ether,
(POE) _4-13 myristyl ether, (POE) _4-13 cetyl ether, (POE) _4-13 stearyl ether,
Polyoxyethylene alkyl ethers such as (POE) _4-13 oleyl ether, (POE) _4-13 octyl phenyl ether, (POE) _4-13 nonyl phenyl ether, polyoxyethylene alkenyl ether, polyoxyethylene alkyl phenyl ether, etc. No. These compounds can be obtained from general suppliers.

Of the above compounds, (POE) _5-9 C
_12-14 Synthetic alcohol ether, (POE) _4-10 lauryl ether, (POE) _5-8 cetyl ether, (POE
E) _11-14 Stearyl ether, (POE) _6-13 oleyl ether, (POE) _7-10 octylphenyl ether, (POE) _5-12 nonylphenyl ether can be preferably used from the viewpoint of performance and availability. .

These nonionic surfactants can be obtained by reacting the above-mentioned alcohols and alkylphenols by adding ethylene oxide in a gaseous state while heating in the presence of a catalyst such as caustic soda.

These nonionic surfactants are preferably incorporated in the detergent composition in an amount of 1 to 15% by weight, particularly 3 to 10% by weight, from the viewpoint of exhibiting the effect and cost-performance. These nonionic surfactants may be used alone or in combination of two or more.

[0045] Among the components used in the cleaning composition of the present invention, water as the component (E) is selected from the viewpoints of safety and detergency.
3 to 15% by weight, preferably 5 to 10% by weight in the detergent composition
% By weight. The water used here is not particularly limited as long as it does not impair the effect of the cleaning composition of the present invention, and ultrapure water, pure water, ion-exchanged water, distilled water, ordinary tap water, and the like. Is used.

In the cleaning composition of the present invention, hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminetetraacetic acid, etc., which are usually used in cleaning agents, as far as the effects of the present invention are not impaired. Compounds with chelating power such as aminocarboxylates, preservatives, rust inhibitors, defoamers such as silicon, antioxidants, esters such as coconut fatty acid methyl and benzyl acetate, hydrocarbon solvents or alcohols, etc. They can be used as appropriate.

The cleaning composition of the present invention comprises the above (A) to
It can be produced by mixing the component (E) and optional components in a conventional manner.

To clean a hybrid IC substrate using the cleaning composition of the present invention, for example, using the cleaning composition of the present invention, immersion, ultrasonic cleaning, immersion rocking, spraying, Various cleaning methods such as a hand wiping method can be adopted, and a method of continuously performing a method such as rinsing with a solvent or hot water at the end can be cited as an efficient cleaning method, and preferable results can be obtained.

[0049]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Production Comparative Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[Production of Ethylene Oxide Adduct of Monocyclic Aromatic Diamine] Production Example 1 In a 1-liter autoclave purged with nitrogen, 1,2-
Phenylenediamine (reagent, ALDRICH CHEMICAL COMPAN
108.2 g (1 mol) and 100% KO
0.56 g (0.01 mol) of H was charged, and the temperature was raised to 110 ° C. with good stirring. Next, 440.0 g (10 mol) of ethylene oxide was added at a temperature of 110 to 120.
C. and a pressure of 1 to 4 kg / cm ² (gauge) little by little, and then reacted for 5 hours. After completion of the reaction, the temperature was cooled to room temperature, and the compound (1,1) in which 10 mol of ethylene oxide was added per 1 mol of 1,2-phenylenediamine.
Abbreviated as (POE) ₁₀ adduct of 2-phenylenediamine. Further, similar compounds are similarly abbreviated by corresponding expressions. ) Got. The yield of the reaction product was 98.2%. The number of moles added was determined by hydroxyl value and NMR analysis.

Production Example 2 In a 1-liter autoclave purged with nitrogen, 1,3-
Phenylenediamine (reagent, ALDRICH CHEMICAL COMPAN
108.2 g (1 mol) and 100% KO
0.56 g (0.01 mol) of H was charged, and the temperature was raised to 100 ° C. with good stirring. Then, 264.0 g (6 mol) of ethylene oxide was added at a temperature of 100 to 110.
C., under a pressure of 1 to 4 kg / cm ² (gauge), and the mixture was reacted for 4 hours. After completion of the reaction, the temperature was cooled to room temperature, and (PO) of 1,3-phenylenediamine was
E) A _6- adduct was obtained. The yield of the reaction product was 97.6%.

Production Example 3 In a 1-liter autoclave purged with nitrogen, 1,3-
Phenylenediamine (reagent, ALDRICH CHEMICAL COMPAN
Y., INC.) (108.2 g, 1 mol) and heated to 100 ° C. with good stirring. Then, 88.0 g (2 moles) of ethylene oxide was added at a temperature of 100 to 12%.
It was added little by little at 0 ° C. under a pressure of 1 to 4 kg / cm ² (gauge), and then reacted for 2 hours. After completion of the reaction, the temperature was cooled to room temperature, and (PO) of 1,3-phenylenediamine was
E) _Two adducts were obtained. The yield of the reaction product was 98.1%.

Production Example 4 In a 1 liter autoclave, 13 parts of m-xylylenediamine (reagent, manufactured by ALDRICH CHEMICAL COMPANY, INC.) Were added.
6.0 g (1 mol) was charged, and 120 ° C. with good stirring
The temperature was raised until. Then ethylene oxide 17
6.0 g (4 moles) at a temperature of 120 to 130 ° C. and a pressure of 1 to 1
It was added little by little under 4 kg / cm ² (gauge) and then reacted for 3 hours. After the completion of the reaction, the temperature was cooled to room temperature to obtain a (POE) ₄ adduct of m-xylylenediamine. The yield of the reaction product was 97.8%.

Production Example 5 In a 1-liter autoclave, 13 parts of p-xylylenediamine (reagent, manufactured by ALDRICH CHEMICAL COMPANY, INC.) Were added.
6.0 g (1 mol) charged, 100 ° C. with good stirring
The temperature was raised until. Next, ethylene oxide 88.
0 g (2 mol) at a temperature of 100 to 110 ° C and a pressure of 1 to 4 k
It was added little by little under g / cm ² (gauge) and then reacted for 3 hours. After completion of the reaction, the temperature is cooled to room temperature, and p
-(POE) ₂ adduct of xylylenediamine was obtained. The yield of the reaction product was 97.5%.

Production Example 6 2-aminobenzylamine (reagent, manufactured by ALDRICH CHEMICAL COMPANY, INC.) Was placed in a 1-liter autoclave.
22.0 g (1 mol) and 0.56 g of 100% KOH
(0.01 mol), and the temperature was raised to 120 ° C. with good stirring. Next, ethylene oxide 352.
0 g (8 mol) at a temperature of 120-130 ° C and a pressure of 1-4 k
It was added little by little under g / cm ² (gauge), and then reacted for 4 hours. After completion of the reaction, the temperature is cooled to room temperature, and 2
(POE) ₈ adduct of -aminobenzylamine was obtained.
The yield of the reaction product was 98.7%.

Production Example 7 4-aminobenzylamine (reagent, manufactured by ALDRICH CHEMICAL COMPANY, INC.) Was placed in a 1-liter autoclave.
22.0 g (1 mol) and 0.56 g of 100% KOH
(0.01 mol), and the temperature was raised to 100 ° C. with good stirring. Next, ethylene oxide 220.
0 g (5 mol) at a temperature of 100 to 110 ° C and a pressure of 1 to 4 k
It was added little by little under g / cm ² (gauge) and then reacted for 3 hours. After completion of the reaction, the temperature is cooled to room temperature, and 4
A (POE) ₅ adduct of -aminobenzylamine was obtained.
The yield of the reaction product was 98.9%.

Production Example 8 In a 1-liter autoclave, 2- (4-aminophenyl) ethylamine (reagent, ALDRICH CHEMICAL COMPAN
Y. INC.) (136.0 g, 1 mol) was charged, and the temperature was raised to 110 ° C. with good stirring. Then, 132.0 g (3 mol) of ethylene oxide was added at a temperature of 110 to 1
It was added little by little at 20 ° C. under a pressure of 1 to 4 kg / cm ² (gauge), and then reacted for 3 hours. After completion of the reaction, the temperature was cooled to room temperature to obtain a (POE) ₃ adduct of 2- (4-aminophenyl) ethylamine. The yield of the reaction product was 97.6%.

Comparative Production Example 1 In a 1-liter autoclave purged with nitrogen, 1,3-
108.2 g (1 mol) of phenylenediamine and 100
% KOH was charged to 0.56 g (0.01 mol), and the temperature was raised to 100 ° C. with good stirring. Then, 528.0 g (12 mol) of ethylene oxide was added at a temperature of 100 to
It was added little by little at 110 ° C. under a pressure of 1 to 4 kg / cm ² (gauge), and then reacted for 5 hours. After the completion of the reaction, the temperature was cooled to room temperature to obtain a (POE) ₁₂ adduct of 1,3-phenylenediamine. The yield of the reaction product was 97.
9%.

Production Comparative Example 2 In a 1 liter autoclave, 136.0 g (1 mol) of m-xylylenediamine and 0.5% of 100% KOH were added.
6g (0.01mol), 120
The temperature was raised to ° C. Then ethylene oxide 66
0.0 g (15 mol) at a temperature of 120 to 130 ° C. and a pressure of 1
It was added little by little under ４4 kg / cm ² (gauge), and then reacted for 6 hours. After completion of the reaction, the temperature was cooled to room temperature to obtain a (POE) ₁₅ adduct of m-xylylenediamine. The yield of the reaction product was 98.1%.

[Production of Alkyl Phosphate] Production Example 9 64.0 g (2 mol) of methanol, 18.0 g (1 mol) of deionized water, and 141.9 g of diphosphorus pentoxide were placed in a reaction vessel.
(1 mol), immerse in an oil bath with good stirring,
The temperature was raised to ° C. Thereafter, the reaction was carried out for 25 hours to obtain a reaction product having a monomethyl phosphate content of 90 mol%.

Production Example 10 96.0 g (3 mol) of methanol and 141.9 g (1 mol) of diphosphorus pentoxide were placed in a reaction vessel, immersed in an oil bath with good stirring, and heated to 70.degree. Thereafter, the reaction was carried out for 18 hours to obtain sesquimethyl phosphate of 61 mol% of monomethyl phosphate and 39 mol% of dimethyl phosphate.

Production Example 11 92.2 g (2 mol) of ethanol, 18.0 g (1 mol) of ion-exchanged water and 141.9 g of diphosphorus pentoxide were placed in a reaction vessel.
(1 mol), immerse it in an oil bath with good stirring,
The temperature was raised to ° C. Thereafter, the reaction was carried out for 20 hours to obtain a reactant having a monoethyl phosphate content of 86 mol%.

Production Example 12 138.3 g (3 mol) of ethanol and 141.9 g (1 mol) of diphosphorus pentoxide were put in a reaction vessel, immersed in an oil bath with good stirring, and heated to 75 ° C. Thereafter, the reaction was carried out for 20 hours to obtain sesquiethyl phosphate having 63 mol% of monoethyl phosphate and 37 mol% of diethyl phosphate.

Production Example 13 120.2 g (2 mol) of isopropanol was added to a reaction vessel.
18.0 g (1 mol) of ion-exchanged water, 14 phosphorus pentoxide
1.9 g (1 mol) was added, immersed in an oil bath with good stirring, and the temperature was raised to 70 ° C. Thereafter, the reaction was carried out for 18 hours so that the content of monoisopropyl phosphate was 89 mol%.
Reaction product was obtained.

Production Example 14 74.1 g (1 mol) of butanol, 9.0 g (0.5 mol) of ion-exchanged water, and 71.0 g of diphosphorus pentoxide were placed in a reaction vessel.
(0.5 mol), immerse it in an oil bath with good stirring,
The temperature was raised to 85 ° C. Thereafter, the reaction was carried out for 12 hours to obtain a reaction product having a monobutyl phosphate content of 86 mol%.

Production Example 15 222.3 g (3 mol) of butanol and 141.9 g (1 mol) of diphosphorus pentoxide were placed in a reaction vessel, immersed in an oil bath with good stirring, and heated to 85 ° C. Thereafter, the reaction was carried out for 20 hours to obtain sesquibutyl phosphate having 62 mol% of monobutyl phosphate and 38 mol% of dibutyl phosphate.

Comparative Production Example 3 310.0 g (3 mol) of 1-hexanol and 141.9 g (1 mol) of diphosphorus pentoxide were placed in a reaction vessel, immersed in an oil bath with good stirring, and heated to 90 ° C. . Then 1
The reaction was carried out for 8 hours to obtain sesquihexyl phosphate having 57 mol% of monohexyl phosphate and 43 mol% of dihexyl phosphate.

Production Comparative Example 4 In a reaction vessel, 129.6 g (1 mol) of octanol, 9.0 g (0.5 mol) of ion-exchanged water, and 71.0 g of phosphorus pentoxide.
After adding 0 g (0.5 mol), the mixture was immersed in an oil bath with good stirring, and the temperature was raised to 90 ° C. Thereafter, the reaction was carried out for 20 hours. Further, this reaction product was dissolved in hexane at 50 ° C.
After cooling to 20 ° C., monooctyl phosphate was precipitated. This was filtered to obtain a reaction product having a monooctyl phosphate content of 93 mol%.

Examples 1 to 10 and Comparative Examples 1 to 9 The cleaning compositions (a to
A cleaning test was performed by cleaning using s). The results are shown in Tables 1 to 4. Tables 5 and 6 show the origin of the compounds shown in Tables 1 to 4. The test conditions are as follows.

[0070]

[Table 1]

[0071]

[Table 2]

[0072]

[Table 3]

[0073]

[Table 4]

[0074]

[Table 5]

[0075]

[Table 6]

(Preparation of Test Piece) Lead (Pb) was placed on an alumina substrate having a length of 36 mm × a width of 21 mm × a thickness of 1 mm.
The PbO-SiO ₂ containing 50 wt% -B ₂ O ₃ -A
The l ₂ O ₃ solder glass was printed and fired at a thickness of about 15 μm. Add flux (Solbond R500)
2.5 g / m ^{2 of} Japan Alpha Metals Co., Ltd.)
, And reflowed at 250 ° C. for 2 minutes, and cooled to room temperature to obtain a test piece.

(Cleaning test) The above test piece was heated at 60 ° C.
Immersed in the cleaning composition described in Tables 1-4 maintained at 39 k
Hz, 200W ultrasonic cleaning equipment (SILENTSONIC UT-20
4, Sharp Corporation) for 20 minutes. Then
It was immersed in ion-exchanged water at 30 ° C., and rinsed (the first rinse) for 20 minutes with the same ultrasonic cleaner as in the cleaning. Further, similarly, it is immersed in ion-exchanged water at 30 ° C., and
Finish rinse (second rinse) for 0 minutes. After repeating this washing / first rinsing / second rinsing four times, air was blown for one minute and dried at 80 ° C. for 10 minutes by a blast constant temperature dryer (FV-630, manufactured by Toyo Seisakusho).

(Evaluation Method and Evaluation Criteria) The evaluation of the detergency of the flux was carried out visually at a magnification of 50 times with an optical microscope according to the following criteria. ◎: Extremely clean with no residual flux on the surface, very good ○: Few residual flux on the surface, good Δ: Slight residual flux on the surface, slightly poor ×: Flux on the surface Evaluation of the erosion of the solder glass after cleaning was visually made at a magnification of 50 times with an optical microscope and visually evaluated according to the following criteria. ：: No discoloration or etching was observed on the glass surface, and there was no change from before cleaning. ：: Slightly brownish discoloration is observed on the glass surface. Δ: Discoloration from brown to blue is observed on the entire glass surface. ×: Not only discoloration of the glass surface but also loss of gloss due to etching is observed.

As can be seen from Tables 1 and 2, the cleaning composition of the present invention was excellent in flux cleaning properties and had excellent properties of not eroding the solder glass (Examples 1 to 1).
0). Further, since the cleaning composition of the present invention does not essentially contain an alcohol-based solvent, a hydrocarbon-based solvent, a chlorine-based solvent, or a chlorofluorocarbon-based solvent, it is environmentally friendly and highly safe. On the other hand, from Tables 3 and 4, examples in which the component (C) is not blended (Comparative Example 1), examples in which the component (B) is not blended (Comparative Example 2), and examples in which the component (D) is not blended (Comparative Example 3), an example in which the component (C) is not neutralized (Comparative Example 4), an example in which the alkyl phosphate of the component (C) has a large number of carbon atoms (Comparative Examples 5 and 6), and ethylene as the component (B) In an example in which the number of added oxides is large (Comparative Examples 7 and 8) and an example in which the amine in the component (C) is not a branched primary amine (Comparative Example 9), there is an example in which the detergency of the flux is slightly better. All were found to erode the solder glass.

[0080]

By using the cleaning composition of the present invention, the hybrid IC substrate can be cleaned safely, with good cleaning and rinsing properties, without eroding the solder glass, and without affecting metal members. can do.

Continuing from the front page (72) Inventor Shinkichi Obayashi 1-1-1, Showa-cho, Kariya-shi, Aichi, Japan Inside Denso Corporation (72) Inventor Yasuhiko Suzuki 1-1-1, Showa-cho, Kariya-shi, Aichi Japan Inside Denso Corporation (72 ) Inventor Yasuhide Sonoda 1-1-1, Showa-cho, Kariya-shi, Aichi Japan Inside Denso Co., Ltd. (56) References JP-A-3-161310 (JP, A) JP-A-4-327519 (JP, A) 62-197345 (JP, A) JP-A-8-127798 (JP, A) West German Patent Application Publication 1227178 (DE, A1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 1 / 72 C11D 3/20 C11D 3/30 C11D 3/36 H01L 21/304 Patent file (PATOLIS) JICST file (JOIS) CAPLUS (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. The following components (A) to (E): (A) the following general formula (I): R ¹ —O— (CH ₂ CH ₂ O) _i —H (I) wherein R ¹ is A hydrocarbon group having 1 to 4 carbon atoms, i represents an integer of 2 to 3), 70 to 95% by weight of a glycol ether compound represented by the following general formula (II): ] (In the formula, j and k represent integers of 0 to 2. a, b, c, and d are integers satisfying 2 ≦ a + b + c + d ≦ 10.)
0.3 to 5% by weight of an ethylene oxide adduct of a monocyclic aromatic diamine represented by the following formula: (C) the following general formula (III): (Wherein, R ² represents an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
0.2 to 5% by weight of a compound neutralized with a branched alkyl primary amine having 4 to 22 carbon atoms, (D) the following general formula (IV): R ³ —O— (CH ₂ CH ₂ O) _p − H (IV) (wherein, R ³ is a linear or branched alkyl group having 12 to 18 carbon atoms, an alkenyl group, a phenyl group, or a carbon atom having 8 carbon atoms)
Represents a phenyl group substituted with a straight-chain or branched-chain alkyl group of 1 to 9, and p represents an integer of 4 to 13. A hybrid IC containing 1 to 15% by weight of a nonionic surfactant represented by the following formula: (E) 3 to 15% by weight of water
A cleaning composition for a substrate.