JP3398541B2 - Cleaning composition for resin stain and cleaning method - 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 resin stains and a cleaning method, and more particularly, it is attached to an optical component such as a plastic lens or a mother die / tool used in the manufacturing process thereof. Plastic lens resins, adhesives, resins such as adhesives, semiconductors and lead frames, liquid crystal color filters, ceramic electronic parts such as magnetic heads, printed wiring boards, resists when manufacturing metal stamping products, aluminum sashes and buildings Coating film of structures such as
Adhesion to hard surfaces such as bodies when changing colors during automobile manufacturing, coating jigs, coatings for automobile bumpers during recovery and recycling, cured products of ink attached to printing machines during printing such as gravure printing TECHNICAL FIELD The present invention relates to a detergent composition and a cleaning method that are excellent in the cleaning property of difficult-to-clean resin stains.

[0002]

2. Description of the Related Art Plastic lens resin attached to optical parts such as plastic lenses or mother dies / jigs used in the manufacturing process thereof, resins such as adhesives and adhesives, semiconductors, lead frames, liquid crystal color filters, Ceramic electronic parts such as magnetic heads, printed wiring boards, resists when manufacturing stamped metal products, coating films for structures such as aluminum sashes and buildings, bodies when changing colors during automobile manufacturing, coating curing Resin stains such as paints on automobiles and bumpers for automobiles during recovery and recovery adhere firmly to hard surfaces (adhesion)
In addition, since the resin stain itself has a high molecular weight, it is very difficult to wash with a chemical agent that utilizes dissolution, swelling, softening, disintegration, peeling action and the like. Among them, the plastic lens resin stain adhered to the glass matrix during the production of the plastic lens has a very high molecular weight and is one of the most difficult resin stains to wash.

Resins for plastic lenses include resins obtained by radical polymerization of diethylene glycol bisallyl carbonate, methacrylic resins, fumaric acid ester / allyl monomer copolymer resins, triazine ring acrylic resins, polycarbonate resins, and bromine compounds. Resins, urethane resins, sulfur-containing urethane resins, thioether / ester resins, etc. are used.

As a general method of manufacturing a plastic lens, an annular packing (gasket) or tape made of synthetic resin attached to one and two glass mother dies having a predetermined curvature on the inner surface and the outer peripheral side thereof is used. It is carried out by a method of injecting a monomer of a forming material into a constituted mold and then performing heat polymerization. After this polymerization step, the annular packing is removed from the mold, and the glass matrix and the plastic lens are released from the mold. Since the finished plastic lens has a non-uniform outer peripheral portion, the outer peripheral portion is shaped, the edge portion is chamfered, and the plastic lens is sent to the cleaning step. After cleaning the oligomer and polymer stains adhering to the lens surface during mold release, polymer powder adhering during peripheral shaping and chamfering, unreacted monomer remaining on the lens surface, and other dust in the atmosphere, dyeing, hard coating,
Surface-treated with anti-reflection coating, aqua coating, etc. to obtain a product.

The glass mold used in the production of plastic lenses is very expensive.
Used repeatedly thousands of times. Therefore, similar to the plastic lens itself, it is necessary to clean the oligomers and polymer-like stains derived from the raw materials that are spilled during the monomer injection. If the glass mold is not clean, a good quality plastic lens with a smooth surface cannot be obtained, and the glass mold must be discarded. As a result, it is also very uneconomical.

Conventionally, alkali cleaning agents based on sodium hydroxide or potassium hydroxide, methylene chloride and the like have been used for cleaning oligomers and polymeric stains of glass matrix used in the production of plastic lenses.
Of these, the alkaline cleaners have insufficient cleaning power and require a long time to completely remove stains or need to be manually removed. In addition, methylene chloride is insufficient in detergency by itself, so it may be used in combination with an alkaline detergent. Further, since methylene chloride may be a carcinogenic substance, strict regulations are imposed on the discharge of wastewater and leakage into the atmosphere, and the reduction / prohibition of its use is being called for.

Regarding the cleaning of oligomers and polymer-like stains on plastic lenses and glass mother molds involved in the production of plastic lenses, see, for example, JP-A-5-26944.
Japanese Unexamined Patent Publication No. 8 discloses a method of cleaning a plastic lens and a glass mother die having dirt attached thereto by dispersing a monomer in a solvent and performing ultrasonic cleaning, liquid / air shower cleaning, and stirring cleaning. However, with this cleaning method,
The larger the molecular weight of the resin stain, the longer it took to dissolve and disperse, and the cleaning property was insufficient.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems that have not been solved thus far. That is, by improving the drawbacks of conventional cleaning agents,
It is an object of the present invention to provide a cleaning composition and a cleaning method which are excellent in cleaning properties and safety against resin stains.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a cleaning in which a specific organic compound, a glycol ether compound, and an ethylene glycol compound are combined in a specific ratio. Achieves excellent safety and achieves high detergency by using a cleaning agent and a specific aromatic compound, a metal sealant, a cleaning agent that combines alkali metal hydroxide and water in a specific ratio, alone, in combination, or in combination. They have found that they can do so and have completed the present invention.

That is, the gist of the present invention is as follows. [1] The following components (a) to (c): (A) General formula (1)       Ph-XY (1) (However, Ph represents a phenyl group, and X represents

[0011]

[Chemical 3]

And Y is --C _k H _{2k + 1} , --OCH ₃ ,
-OH (where k is an integer of 1 to 11)), an aromatic monocyclic compound, 1,4-butanediol, dimethyl adipate, propylene carbonate, triethylene glycol dimethyl ether, and diacetone alcohol. One or more compounds selected from the group consisting of 65
To 94% by weight; (b) General formula (2) R ¹ O (CH ₂ CH ₂ O) _j —H (2) (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and j is 1 to 8).
Is an integer. 5 to 20% by weight of one or more glycol ether compounds represented by the formula;), and (c) general formula (3) HO- (CH ₂ CH ₂ O) _m —H (3) (where m is 1 to 1 to 15% by weight of one or more ethylene glycol-based compounds represented by the formula (1), or a plastic lens or the like.
Cleaning agent composition for resin stains attached to mother dies / tools used in the manufacturing process of [2] The following components (d) to (g): (d) General formula (4)

[0013]

[Chemical 4]

(Wherein R ² is a hydrocarbon group having 6 to 18 carbon atoms, and M is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom). 0.25 to 10% by weight; (e) 0.2 parts by weight of metal sealant, 2.0 parts by weight of sodium hydroxide, 1.0 part by weight of iron stearate, and 9
A mixture of 6.8 parts by weight of water was shaken at 80 ° C. for 10 minutes, cooled to room temperature, and then filtered with a filter paper of 5C to give a metal sealant having a filtration residue of 100 ppm or more. 25 to 10% by weight; (f) 0.5 to 20% by weight of alkali metal hydroxide; and (g) 60 to 99% by weight of water, in a plastic lens or a manufacturing process thereof. used
Cleaning composition for resin stain adhered to mother dies / jigs , [3] Resin stain adhered to hard surface is first cleaned with the detergent composition described in [1], and then washed according to [2]. A method for cleaning resin stains, which comprises washing with an agent composition and then rinsing with rinsing water, [4] removing resin stains adhered to a hard surface from the above [1]
[A] / [B] = 20/80 to 9 by weight ratio of the cleaning composition [A] described above and the cleaning composition [B] described in [2] above.
The present invention relates to a method for washing resin stains, which comprises washing with a liquid mixed at 5/5 and then rinsing with rinsing water.

[0015]

DETAILED DESCRIPTION OF THE INVENTION

1. Detergent Composition [A] Of the components used in the detergent composition [A] of the present invention,
As the component (a), an aromatic monocyclic compound is first mentioned and represented by the general formula (1). Ph-XY (1) (wherein Ph represents a phenyl group and X represents

[0016]

[Chemical 5]

And Y is --C _k H _{2k + 1} , --OCH ₃ ,
It is -OH (however, k is an integer of 1-11). X is

[0018]

[Chemical 6]

More preferably, Y is —OCH ₃ or —OH.
Further, it is more preferable that either or both X and Y contain polar oxygen. )

Specific examples of such aromatic monocyclic compounds include ethylbenzene, propylbenzene, butylbenzene, pentylbenzene, hexylbenzene, cyclohexylbenzene, heptylbenzene, octylbenzene,
Nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene, tridecylbenzene, acetophenone, ethylphenylketone, propylphenylketone, butylphenylketone, pentylphenylketone,
Hexyl phenyl ketone, cyclohexyl phenyl ketone, heptyl phenyl ketone, octyl phenyl ketone, nonyl phenyl ketone, decyl phenyl ketone, undecyl phenyl ketone, propyl phenyl ether,
Butyl phenyl ether, pentyl phenyl ether,
Hexyl phenyl ether, cyclohexyl phenyl ether, heptyl phenyl ether, octyl phenyl ether, nonyl phenyl ether, decyl phenyl ether, undecyl phenyl ether, dodecyl phenyl ether, tridecyl phenyl ether, benzyl methyl ether, methoxyethyl benzene, methyl benzoate, mono Ethylene glycol phenyl methyl ether,
Benzyl alcohol, 2-phenylethyl alcohol,
Examples thereof include benzoic acid and monoethylene glycol monophenyl ether.

Examples of the component (a) further include 1,4-butanediol, dimethyl adipate, propylene carbonate, triethylene glycol dimethyl ether and diacetone alcohol. The above compounds may be used alone or in combination of two or more.

Of the above compounds, ethylbenzene, propylbenzene, butylbenzene, nonylbenzene, decylbenzene, undecylbenzene, dodecylbenzene,
Tridecylbenzene, acetophenone, ethyl phenyl ketone, propyl phenyl ketone, butyl phenyl ketone, benzyl methyl ether, methyl benzoate, monoethylene glycol phenyl methyl ether, benzyl alcohol, 2-phenylethyl alcohol, monoethylene glycol monophenyl ether, 1 , 4-butanediol, dimethyl adipate, propylene carbonate, triethylene glycol dimethyl ether, and diacetone alcohol can be preferably used from the viewpoint of cleaning performance and easy availability.

Component (a) is contained in the cleaning composition [A] of the present invention in an amount of 65 to 94% by weight, preferably 70 to 9% by weight.
0% by weight, particularly preferably 75 to 85% by weight. If the content is less than 65% by weight, the cleaning property for resin stains may be poor, and if the content exceeds 94% by weight, the rinsing property may be poor.

Among the components used in the detergent composition [A] of the present invention, the glycol ether compound as the component (b) is represented by the general formula (2). R ¹ O (CH ₂ CH ₂ O) _j —H (2) (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, j is 1 to 8).
Is an integer. In the general formula (2), R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, and particularly preferably a hydrocarbon group having 3 to 6 carbon atoms. When the carbon number of R ¹ exceeds 8, the solubility in water becomes worse and the viscosity also rises, which may result in poor workability. Specific examples of the hydrocarbon group of R ¹ include methyl group, ethyl group, propyl group, isopropyl group, allyl group, butyl group, isobutyl group, hexyl group,
Examples thereof include 2-ethylhexyl group, octyl group, phenyl group and benzyl group. j is an integer of 1 to 8, preferably 1 to 4. When j exceeds 8, the viscosity may increase and the workability may deteriorate.

Specific examples of such glycol ether compounds include the compounds shown below. Monoethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, pentaethylene glycol monomethyl ether, hexaethylene glycol monomethyl ether, heptaethylene glycol monomethyl ether, octaethylene glycol monomethyl ether [the above compounds (POE) ₁ monomethyl ether, (POE)
₂ monomethyl ether, (POE) ₃ monomethyl ether, (POE) ₄ monomethyl ether, (POE) ₅ monomethyl ether, (POE) ₆ monomethyl ether,
It may be abbreviated as (POE) ₇ monomethyl ether and (POE) ₈ monomethyl ether. Also, sometimes referred to as collectively these compounds and (POE) ₁ ~ ₈ monomethyl ether. In addition, similar compounds and the like may be abbreviated in the same manner as above with corresponding expressions. ],
(POE) ₁ ~ ₈ monoethyl ether, (POE) ₁ ~
₈ monopropyl ether, (POE) ₁ ~ ₈ monoisopropyl ether, (POE) ₁ ~ ₈ monoallyl ether, (POE) ₁ ~ ₈ monobutyl ether, (POE)
_1-8 monoisobutyl ether, (POE) _1-8 monohexyl ether, (POE) _1-8 mono-2-ethylhexyl ether, (POE) _1-8 monooctyl ether, (POE) _1-8 monophenyl ether, ( PO
E) ethylene glycol monomethyl ethers such as _1-8 monobenzyl ether.

[0026] Among the above compounds, (POE) ₁ ~ ₄ monomethyl ether, (POE) ₁ ~ ₄ monoethyl ether, (POE) ₁ ~ ₄ monoisopropyl ether, (P
OE) ₁ ~ ₄ monoallyl ether, (POE) ₁ ~ ₄ monobutyl ether, (POE) ₁ ~ ₄ monoisobutyl ether, (POE) ₁ ~ ₄ monohexyl ether, (P
OE) ₁ ~ ₄ mono-2-ethylhexyl ether, (PO
E) ₁ to ₄ monophenyl ether and (POE) ₁ to ₄ monobenzyl ether can be preferably used from the viewpoints of performance and availability. The glycol ether compounds may be used alone or in combination.

The glycol ether compound as the component (b) is contained in the detergent composition in an amount of 5 to 20% by weight, more preferably 7 to 15% by weight, and particularly preferably 8 to 13% by weight. If the content is less than 5% by weight, the rinsing property may be inferior, and if it exceeds 20% by weight, the cleaning property for resin stains may be inferior. These glycol ether compounds can be obtained, for example, by adding ethylene oxide in a gaseous state to an alcohol having 1 to 8 carbon atoms in the presence of a catalyst such as caustic soda and heating the mixture to react.

Among the components used in the detergent composition [A] of the present invention, the ethylene glycol compound as the component (c) is represented by the general formula (3). _{HO- (CH 2 CH 2 O)} m -H (3) ( where, m is an integer of from 1 to 10.) In the general formula (3), m is an integer of from 1 to 10, preferably 1 to 5 is there. If m exceeds 10, the viscosity may increase and workability may deteriorate.

Specific examples of such ethylene glycol compounds include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, octaethylene glycol, nonaethylene glycol and decaethylene glycol. Is mentioned. Among the above compounds, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, and pentaethylene glycol can be preferably used from the viewpoints of cleaning property, rinsing property, and safety. These ethylene glycol compounds may be used alone or in combination without any problem.
The ethylene glycol compound as the component (c) is contained in the detergent composition [A] in an amount of 1 to 15% by weight, more preferably 2-1.
0% by weight, particularly preferably 4 to 8% by weight. If the content is less than 1% by weight, the rinsing property may be poor,
On the other hand, if it exceeds 15% by weight, the cleaning property for resin stains may be poor.

The cleaning composition [A] of the present invention may be used in a non-aqueous system or may be diluted with water to an appropriate concentration. When diluted with water, the amount of water added is not particularly limited, but from the viewpoint of safety and detergency, it is preferably 3 per 100 parts by weight of the detergent composition.
-15 parts by weight, more preferably 5-12 parts by weight. The water used for dilution is not particularly limited as long as it does not impair the effects of the cleaning composition [A] of the present invention, and ultrapure water, pure water, ion-exchanged water, distilled water,
Normal tap water or the like is used.

In the cleaning composition [A] of the present invention,
A compound having a chelating power such as aminocarboxylic acid salts, such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, and ethylenediaminetetraacetic acid, which are usually used in detergents, as long as the effects of the present invention are not impaired, Antiseptic agent, anticorrosive agent, antifoaming agent such as silicone, antioxidant, nitrogen atom number 1 to 5 and molecular weight 50 to 300
-Based amine compounds; alkanolamines, morpholines, cyclic amines, polyamines, amine compounds such as linear and branched alkylamines, esters of coconut fatty acid methyl, benzyl acetate, etc., hydrocarbon solvents Alternatively, alcohols or the like can be appropriately used in combination.

The detergent composition [A] of the present invention can be produced by mixing the components (a) to (c) and optional components by a conventional method. The cleaning composition [A] of the present invention is applied to resin stains. Such resin stains include resin adhered to optical parts or mother dies and jigs used in the manufacturing process, semiconductors and lead frames, liquid crystal color filters, ceramic electronic parts of magnetic heads, printed wiring boards, metal stamping products. , A coating film for the structure of aluminum sashes and buildings, a coating for the body when changing colors during automobile manufacturing or a jig for coating the same, a coating film for a car bumper during recovery and recycling, and One or more resin stains selected from the group consisting of a cured product of the ink adhered to the printing machine at the time of printing such as gravure printing. Especially, it is particularly preferably applied to a lens resin at the time of manufacturing a plastic lens.

2. Detergent Composition [B] Of the components used in the detergent composition [B] of the present invention,
The aromatic compound as the component (d) is represented by the general formula (4).

[0034]

[Chemical 7]

(However, R ² is a hydrocarbon group having 6 to 18 carbon atoms, M is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom.) In the general formula (4), R ² is It is a hydrocarbon group having 6 to 18 carbon atoms. Outside these ranges, sufficient detergency may not be obtained, and it may be difficult to obtain. R
Specific examples of ² , hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group,
Linear alkyl groups such as heptadecyl group and octadecyl group,
1,3-dimethylbutyl group, 3,3-dimethylbutyl group, 1-methylheptyl group, 2-ethylhexyl group,
Branched chain alkyl groups such as a 1,5-dimethylhexyl group, a t-octyl group, and a t-tridecyl group are exemplified. M is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. The M's may be the same or different.

These aromatic compounds are purified, for example, by reacting a linear or branched olefin having 6 to 18 carbon atoms with diphenyl ether while heating in the presence of a catalyst such as aluminum chloride. Then, it is obtained by reacting sulfur trioxide in a solvent such as 1,2-dichloroethane to form a sulfonate, and distilling off the solvent. The carbon number of the hydrocarbon group of the aromatic compound thus obtained is
It depends on the carbon number distribution of a linear or branched olefin having 6 to 18 carbon atoms as a raw material. 8 to 16 as the average carbon number
Those falling within the range are particularly preferable.

The aromatic compound as the component (d) is contained in the cleaning composition [B] in an amount of 0.25 to 10% by weight, more preferably 0.
5 to 8% by weight, particularly preferably 1.0 to 5.0% by weight. If the content is less than 0.25% by weight, the detergency may be poor, and if it exceeds 10% by weight, the viscosity may increase and the workability may deteriorate. It should be noted that these aromatic compounds may be used alone or in combination.

Of the components used in the cleaning composition [B] of the present invention, the metal sealant as the component (e) is not particularly limited, but those having the following properties are preferably used. That is, 0.2 parts by weight metal sealant, 2.0 parts by weight sodium hydroxide, 1.0 parts by weight iron stearate, and 9 parts by weight.
A mixture of 6.8 parts by weight of water was shaken at 80 ° C. for 10 minutes, cooled to room temperature, and then cooled to 5 C (φ110 m).
m is a metal sealant having a filtration residue of 100 ppm or more when filtered with a filter paper of Toyo Roshi Kaisha, Ltd. As the filtration residue, 200 to 1000 ppm is more preferable, and 30
0 to 700 ppm is particularly preferred. 100 pp of filtration residue
If the metal sealant is less than m, sufficient cleaning properties may not be obtained.

Specific examples of such a metal sealant include gluconic acid, tannic acid, 2,3-dihydroxybenzoic acid,
3,4-dihydroxybenzoic acid (protocatechuic acid),
Carboxylic acids such as 2,3,4-trihydroxybenzoic acid (gallic acid), poly-α-hydroxyacrylic acid, and glucuronic acid, and salts of these with alkali metals, heptonic acid, 2,3-dihydroxyphenol ( Pyrogallol), 2-hydroxyphenol, D-sorbit, D
- mannitol, dulcite, D- arabitol, xylitol, gluconolactone, D- mannose, D- galactose, threitol, salts with amino naphthol, aminonaphthol SO ₃ H, and the alkali metal or the like thereof,
Examples include triethanolamine.

Among the above compounds, carboxylic acids such as gluconic acid, tannic acid, 3,4-dihydroxybenzoic acid (protocatechuic acid), and 2,3,4-trihydroxybenzoic acid (gallic acid), and alkali metals and the like. And salts of 2,3-dihydroxyphenol (pyrogallol), D-sorbitol, D-mannitol, gluconolactone, D-galactose, aminonaphthol, aminonaphthol SO ₃ H, and salts of these with alkali metals, Triethanolamine can be preferably used from the viewpoint of detergency and rinsing property. In addition, these metal sealants may be used alone or in combination.

The metal sealant as the component (e) is contained in the cleaning composition [B] in an amount of 0.25 to 10% by weight, more preferably 0.
The content is 5 to 8.5% by weight, particularly preferably 1.0 to 5.0% by weight. If the content is less than 0.25% by weight, the detergency may be inferior, and if it exceeds 10% by weight, undissolved substances may remain or the viscosity may increase, resulting in poor workability.

Among the components used in the detergent composition [B] of the present invention, examples of the alkali metal hydroxide as the component (f) include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like, Particularly, sodium hydroxide and potassium hydroxide are preferably used. These alkali metal hydroxides may be used alone or in combination of two or more. The alkali metal hydroxide as the component (f) is contained in the detergent composition [B] in an amount of 0.5 to 20% by weight, more preferably 1 to 18% by weight, and particularly preferably 3 to 15% by weight.
Contained. If the content is less than 0.5% by weight, the detergency may be inferior, while if it exceeds 20% by weight, the uniformity of the product may be impaired or the risk of alkali may increase.

Among the components used in the detergent composition [B] of the present invention, the water as the component (g) is used as a solvent for uniformly dissolving the components (d), (e) and (f). 60 to 99% by weight in the agent composition [B], more preferably 75
.About.95% by weight, particularly preferably 85 to 92% by weight. The water used here is not particularly limited as long as it does not impair the effects of the cleaning composition [B] of the present invention, and ultrapure water, pure water, ion-exchanged water, distilled water,
Normal tap water or the like is used.

In the cleaning composition [B] of the present invention,
A compound having a chelating power such as aminocarboxylic acid salts, such as hydroxyethylaminoacetic acid, hydroxyethyliminodiacetic acid, and ethylenediaminetetraacetic acid, which are usually used in detergents, as long as the effects of the present invention are not impaired, Antiseptic, rust preventive, antifoaming agent such as silicon, antioxidant, nitrogen atom number is 1 to 5 and molecular weight is 50 to 300
-Based amine compounds; alkanolamines, morpholines, cyclic amines, polyamines, amine compounds such as linear and branched alkylamines, esters of coconut fatty acid methyl, benzyl acetate, etc., hydrocarbon solvents Alternatively, alcohols or the like can be appropriately used in combination. The detergent composition [B] of the present invention can be produced by mixing the components (d) to (g) and optional components by a conventional method. The cleaning composition [B] of the present invention is applied to resin stains. Here, the resin stain is the same as the detergent composition [A], and the detergent composition [B] of the present invention is particularly preferably applied to the lens resin at the time of manufacturing the plastic lens.

3. Cleaning Method The cleaning method of the present invention is carried out using the above-mentioned cleaning composition [A] and [B], and the following two modes are exemplified. 1) The resin stain adhered to the hard surface is first washed with the cleaning composition [A] and then with the cleaning composition [B], and then rinsed with rinsing water. 2) For the resin stain attached to the hard surface, the weight ratio of the cleaning composition [A] and the cleaning composition [B] is [A] / [B].
= 20/80 to 95/5, using a mixed solution, and then rinsed with rinse water.

In the embodiment 1), first, the cleaning composition [A].
And then using the detergent composition [B]. In the order of using this cleaning composition [A] → [B], [A]
After the resin stain is disintegrated and dissolved in step (B), the resin stain is peeled off in step (B), so that a higher cleaning effect is exhibited.

Further, in the embodiment 2), the cleaning composition [A] and the cleaning composition [B] are mixed for cleaning. The mixing ratio is [A] / [B] = 20/80 to 9 by weight.
It is 5/5, preferably 50/50 to 90/10, particularly preferably 60/40 to 80/20. Outside the above range, the increase in cleaning effect may not be achieved.
That is, since the mixed solution in the above mixing ratio range tends to be suspended and separated, as described above, the resin stain is disintegrated and dissolved in [A] and then the resin stain is removed in [B]. It is considered to be expressed in the tank. The optimum range varies depending on the type of resin stain and the difference in polymerization / adhesion state. However, for most resin stains, [A] component is in continuous phase and [B] component is in emulsified state. Is preferred. In the case of completely cured plastic lens resin stains, the cleaning power may be increased by strengthening the peeling force. As described above, it goes without saying that the above ratio is controlled depending on the type of resin stain and the difference in the state of polymerization and adhesion.

In order to clean resin stains adhered to a hard surface by using the cleaning composition and the cleaning method of the present invention, for example, a dipping method, an ultrasonic cleaning method, and a dipping method using the cleaning composition of the present invention are used. Various cleaning methods such as rocking method and spraying method can be adopted, and finally, a method of continuously rinsing with solvent or warm water is cited as an efficient cleaning method, and a preferable result is obtained. You can The rinse water is not particularly limited as long as it can remove contaminants on the surface, but, for example, ultrapure water, pure water, ion-exchanged water, distilled water, ordinary tap water, etc. are preferable from the viewpoint of rinsing property. .

The cleaning composition and the cleaning method of the present invention are excellent in the cleaning property of the difficult-to-clean resin stain adhering to the hard surface. Resin stains attached to hard surfaces are optical parts such as plastic lenses, or the mold used in the manufacturing process.
Plastic lens resin attached to jigs, adhesives,
Resins such as adhesives, semiconductors and lead frames, liquid crystal color filters, ceramic electronic parts such as magnetic heads, printed wiring boards, resists when manufacturing metal stamping products, coating films for structures such as aluminum sashes and buildings Cleaning of resin stains such as cured bodies of ink adhered to printing bodies during printing, such as bodies for color changing during automobile manufacturing, coating jigs, coatings for automobile bumpers during recovery and recycling, and gravure printing. Applied to. Above all, it is also suitably used for washing plastic lens resin stains adhered to the glass matrix during the production of a plastic lens which has a very high molecular weight and is most difficult to wash.

[0050]

EXAMPLES The present invention will be described in detail below with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. Production Example 1 Into a 1-liter four-necked flask, 204.3 g (1.2 mol) of diphenyl ether and 8.0 g (0.06 mol) of anhydrous aluminum chloride powder were charged, and the temperature was raised to 90 ° C. while stirring well. Warmed. Then 1-dodecene 1
68.3 g (1 mol) was dropped in a nitrogen atmosphere for 1 hour, and further reacted at 60 ° C. for 1 hour. After the reaction,
After washing 4 times by adding the same amount of water,
Excessive low boiling point components such as diphenyl ether were distilled off.

3 of the obtained dodecyl diphenyl ether
3.9 g (0.1 mol) was placed in another 1-liter four-necked flask, and 678 g (2 mol) of 1,2-dichloroethane was added.
(0 times amount) was charged and the temperature was lowered to 5 ° C. with stirring. Then 18.4 g (0.23 mol) of liquid SO ₃
Was added dropwise under a nitrogen atmosphere for 1 hour to cause reaction little by little. From the reaction product on the rotary evaporator,
1,2-Dichloroethane was distilled off to obtain dodecyl diphenyl ether sulfonic acid. The obtained dodecyl diphenyl ether sulfonic acid is a dialkyl body: 20 mol%,
Monoalkyl compound: 80 mol%, sulfonation degree is 1.9
It was 8.

Production Example 2 204.3 g (1.2 mol) of diphenyl ether and 8.0 g (0.06 mol) of anhydrous aluminum chloride powder were charged into a 1-liter four-necked flask, and the mixture was heated to 90 ° C. with good stirring. The temperature was raised until. Then 1-octene 1
12.2 g (1 mol) was added dropwise under a nitrogen atmosphere for 1 hour and further reacted at 60 ° C. for 1 hour. After the reaction,
After washing 4 times by adding the same amount of water,
Excessive low boiling point components such as diphenyl ether were distilled off.

2 of the obtained octyl diphenyl ether
8.2 g (0.1 mol) was placed in another one-liter four-necked flask, and 565 g (2 mol) of 1,2-dichloroethane was added.
(0 times amount) was charged and the temperature was lowered to 5 ° C. with stirring. Then 16.8 g (0.21 mol) of liquid SO ₃
Was added dropwise under a nitrogen atmosphere for 1 hour to cause reaction little by little. From the reaction product on the rotary evaporator,
1,2-Dichloroethane was distilled off to obtain octyl diphenyl ether sulfonic acid. The obtained octyl diphenyl ether sulfonic acid is a dialkyl compound: 25 mol%,
Monoalkyl compound: 75 mol%, sulfonation degree is 1.9
It was 0.

Examples 1 to 20 and Comparative Examples 1 to 18 (Glass matrix cleaning test) Various detergent compositions having the compositions shown in Tables 1 to 4 (composition ratio unit: wt%) were prepared, and these compositions were prepared. With the cleaning composition,
Detergency was evaluated by the combinations shown in Table 5 and Table 6.

[Residual filtration value of metal sealant] The residual filtration value (ppm) of the metal sealant used in this example and the like was measured as follows. 0.2 parts by weight of metal sealant used, 2.0
1 part by weight of sodium hydroxide, 1.0 part by weight of iron stearate, and 96.8 parts by weight of water were mixed. This was shaken at 80 ° C. for 10 minutes, cooled to room temperature, and then 5
It was filtered with a filter paper of C (φ110 mm, manufactured by Toyo Roshi Kaisha, Ltd.). Then, the obtained filtration residue is blown with a constant temperature dryer (FV-6
30, manufactured by Toyo Seisakusho Co., Ltd., dried at 80 ° C. for 1 hour, and then weighed.

[Test Piece] On the outer peripheral side of the glass mother die having a diameter of 8.0 cm and an outer peripheral side of 0.5 cm, a thickness of 0.1 c
A silicon rubber sheet of m (manufactured by Inouchi Seieidou Co., Ltd.) was cut into a piece having a width of 0.5 cm and a length of 30.0 cm, which was wound, and the end was fixed with cellophane tape. 100 parts by weight of diethylene glycol bisallyl carbonate: CR-39 monomer (manufactured by PPG) as a monomer and diisopropyl peroxydicarbonate: perloyl IPP-27 (as a polymerization catalyst) in a gap between the outer peripheral edge of the glass matrix and the wound silicon rubber sheet. CR) (NOF CORPORATION)
(Manufactured by Mitsui Chemicals Co., Ltd.), and 0.3 mL of a monomer mixture was added which was stirred at a low temperature so as to be uniform. Place this glass mold in a 500 mL glass beaker with a stopper,
Sealed with nitrogen. After heating and polymerization at 40 ° C. for 2 hours, 60 ° C. for 2 hours, and 80 ° C. for 18 hours, the silicone rubber sheet was removed to obtain a test piece for a cleaning test.

[Washing Test] The test piece of the above-mentioned glass mold was immersed in the detergent composition shown in Table 5 and Table 6 kept at 60 ° C., and was ultrasonically washed at 39 kHz and 200 W (SILENTSONIC UT-204). , Sharp Co., Ltd.) for 60 seconds. Here, Examples 1 to 12 and Comparative Examples 1 to 11
As described above, in the example in which the cleaning was performed with one type of component alone, the cleaning was performed for 60 seconds in one tank (one tank). Examples 13-1
6. As in Comparative Examples 12 to 14, the examples in which the cleaning is performed by the two-stage cleaning system of [A] → [B] or [B] → [A] are 1 tank = 30 seconds × 2 tanks, that is, The total cleaning time was 60 seconds (two tanks). Further, Examples 17 to 20 and Comparative Example 15
In the examples in which the cleaning was performed with the [A] / [B] mixed system as in Nos. 17 to 17, the cleaning was performed for 60 seconds using only one tank (mixing).

Then, it is immersed in ion-exchanged water at 30 ° C.,
A rinse (first rinse) was performed for 60 seconds using the same ultrasonic cleaning device as used for cleaning. Furthermore, similarly, it was immersed in ion-exchanged water at 30 ° C. and a final rinse (second rinse) was performed for 60 seconds with an ultrasonic cleaner. After this, air blow for 1 minute, and 80 with a constant temperature blower (FV-630, manufactured by Toyo Seisakusho Co., Ltd.)
C., dried for 10 minutes. In Comparative Example 18, methylene chloride was used as a cleaning agent in one tank at a cleaning temperature of 35 ° C. (boiling point: 40.2 ° C.) for 60 seconds. Then, it was immersed in methylene chloride (at room temperature), rinsed twice for 60 seconds (first rinse, second rinse) using the above ultrasonic cleaning device, and then air-dried indoors. For each detergent composition, five glass mother die test pieces were washed under the same conditions, and the degree of washing (washability) was visually evaluated. The evaluation criteria are as follows. ⊚: 100% (completely) cleaned of resin stains. ◯: At least about 90% of resin stains were washed off. B: At least about 70% of resin stains were washed off. X: 50% or more of resin stain remained. The above results are shown in Tables 5 and 6.

[0059]

[Table 1]

[0060]

[Table 2]

[0061]

[Table 3]

[0062]

[Table 4]

[0063]

[Table 5]

[0064]

[Table 6]

From the above results, it can be seen that the detergent composition of the present invention is excellent in detergency (Examples 1 to 1).
2). Furthermore, by using the two detergent compositions of the present invention in combination, the cleaning property can be further improved (Examples 13 to 16) and the apparatus and process can be simplified (Example 17). ~ 20). Further, if the composition is out of the range of the present invention, all of them have poor detergency (Comparative Examples 1 to 18).

Examples 21 to 32 and Comparative Examples 19 to 26
(Peeling / Cleaning Test of Painted Film) Various cleaning compositions having the compositions shown in Tables 1 to 4 (composition ratio unit: wt%) were prepared, and using these cleaning compositions,
Detergency was evaluated by the combinations shown in Table 7. [Test piece] Acrylic melamine electrostatically coated product (primer is epoxy-melamine, coating thickness: total 40 µm), polyester powder electrostatically coated product (coating thickness: 8 cm x 4 cm x 0.5 mm). max 4400 μm)
Were obtained and used as test pieces.

[Peeling / Cleaning Test] 500 mL of each cleaning solution
Collect 500 mL in a glass beaker and keep in a constant temperature bath (hot water bath)
Then, the test piece was immersed in the test piece for a set time after the temperature was raised to the set temperature. Then, after rinsing with running tap water for 1 minute and air blowing for 1 minute, the degree of peeling / cleaning of the coating film (cleanability) was visually evaluated. The evaluation criteria are as follows. A: 100% (completely) resin was peeled off and washed. ◯: At least about 70% of the resin was peeled off and washed. Δ: Less than 70% (part) the resin was peeled off and washed. X: The resin was not peeled or washed at all. The results are shown in Table 7.

[0068]

[Table 7]

From the above results, it can be seen that the detergent composition of the present invention has excellent releasability and detergency with respect to acrylic melamine-based and polyester-based coatings (Example 2).
1-24, Examples 27-30). Further, by using the two detergent compositions of the present invention in combination, the releasability / cleanability can be further improved (Examples 25, 26, 3).
1, 32). Further, if the composition is out of the range of the present invention, all of them have poor detergency (Comparative Examples 19 to 26).

[0070]

The detergent composition of the present invention is excellent in resin stains which are difficult to wash. Moreover, it is excellent in safety because it does not use methylene chloride. Further, the cleaning method of the present invention provides a method for effectively cleaning resin stains that are difficult to clean in a simple process, and further, by combining the cleaning composition in a specific ratio, Since it can be carried out only by providing a cleaning tank, it also provides a cleaning method with simple equipment.

Continuation of front page (56) Reference JP-A-7-173492 (JP, A) JP-A-6-248206 (JP, A) JP-A-7-179892 (JP, A) JP-A-8-81698 (JP , A) Present state and problems of coating film peeling technology from the viewpoint of solvent-based release agent, industrial coating, 1996, No. 138, p. 21-27 Paint Stripping with Nontoxic Chemi cals, METAL FINISH NG, 1995, APRIL, p. 34-38 (58) Fields investigated (Int.Cl. ⁷ , DB name) C11D 7/24 C11D 7/26 C11D 7/50 C11D 17/08 Patent file (PATOLIS)

Claims (4)

(57) [Claims] 1. The following components (a) to (c): (a) General formula (1) Ph-XY (1) (wherein Ph represents a phenyl group and X represents In it, Y is _{-C k H 2k + 1, -OCH} 3, -OH ( provided that, k is an integer of 1 to 11.)) Aromatic monocyclic compounds represented by 1,4-butanediol 65 to 94% by weight of one or more compounds selected from the group consisting of dimethyl adipate, propylene carbonate, triethylene glycol dimethyl ether, and diacetone alcohol; (b) General formula (2) R ¹ O (CH ₂ CH _{2 2} O) _j —H (2) (wherein R ¹ is a hydrocarbon group having 1 to 8 carbon atoms, j is 1 to 8)
Is an integer. 5 to 20% by weight of one or more glycol ether compounds represented by the formula;), and (c) general formula (3) HO- (CH ₂ CH ₂ O) _m —H (3) (where m is 1 to 1 to 15% by weight of one or more ethylene glycol-based compounds represented by the formula (1), or a plastic lens or the like.
Cleaning agent composition for resin stains attached to mother dies and jigs used in the manufacturing process of. 2. The following components (d) to (g): (d) General formula (4) (However, R ² is a hydrocarbon group having 6 to 18 carbon atoms, and M 2
Is a hydrogen atom, an alkali metal atom, or an alkaline earth metal atom. 0.25 to 10% by weight of one or more aromatic compounds represented by the formula; (e) 0.2 part by weight of metal sealant, 2.0 parts by weight of sodium hydroxide, 1.0 part by weight. Iron stearate, and 9
A mixture of 6.8 parts by weight of water was shaken at 80 ° C. for 10 minutes, cooled to room temperature, and then filtered with a filter paper of 5C to give a metal sealant having a filtration residue of 100 ppm or more. 25-10% by weight; (f) an alkali metal hydroxide and 0.5 to 20 wt%; and (g) water 60 to 99 wt%; plastic lens or its characterized by containing the
Cleaning agent composition for resin stains attached to mother dies and jigs used in the manufacturing process of. 3. A resin stain adhered to a hard surface is first washed with the cleaning composition according to claim 1 and then with the cleaning composition according to claim 2, and then rinsed with rinsing water. The characteristic method for cleaning resin stains. 4. The cleaning agent composition [A] according to claim 1 and the cleaning agent composition [B] according to claim 2 in the resin stain adhering to the hard surface in a weight ratio [A] / [B]. = 20 / 80-9
A method for cleaning resin stains, which comprises cleaning using a liquid mixed at 5/5 and then rinsing with rinsing water.