JP3425889B2 - Cleaning composition for epoxy resin stains - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition for resin stains, and more particularly to a detergent composition excellent in cleanability of epoxy resin stains attached to a hard surface.

[0002]

2. Description of the Related Art Resin for plastic lenses of optical parts,
Coatings, cured products of ink, resin-based adhesives, adhesives, sealants, pressure-sensitive adhesives, binders, protective films, etc. used in the fields of electronics and electronics are firmly attached or adhered to hard surfaces. Therefore, it is very difficult to clean with chemicals. Especially in the electronic and electrical industry, semiconductor / crystal materials such as silicon, gallium / arsenic, and gallium / phosphorus, electronic component-related materials such as crystal, quartz, and glass, magnetic materials such as ferrite, samarium / cobalt, and magnetic heads. In the processing steps of magnetic materials, metals such as piezoelectric materials, ceramics materials, etc., the processing accuracy has been rapidly improved, and therefore the requirements for the adhesive force and the removal / cleanability of the resin materials have become strict. Above all, in the epoxy resin adhesives widely used in these fields, the amount of the epoxy resin adhesives used is increasing, and the demand for stronger adhesive strength is becoming stricter.

As a cleaning agent that meets these requirements, a cleaning agent composition for an epoxy resin, which contains an organic solvent having a cyclic structure in its molecular structure and having a nitrogen atom, an oxygen atom, a sulfur atom, etc. as an essential component, is known. Although proposed (JP-A-1
No. 0-110193), this cleaning composition is neutral, so it may take a long time to peel it off unless the corresponding temperature is raised. In addition, a stripping solution composition containing an organic acid, benzyl alcohols and water as essential components has been proposed (JP-A-4-361265), but the strippability is insufficient. In addition to these, aromatic compounds,
A detergent composition for resin stains containing an alkylene oxide compound and / or an alkali metal hydroxide and water as essential components has been proposed (JP-A-10-195492), but this detergent composition is alkaline. Therefore, when the hard surface is glass or aluminum, the surface is adversely affected, or the cleaning property is poor depending on the type of resin.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a detergent composition which is excellent in detergency against resin stains firmly adhered and adhered to a hard surface.

[0005]

The present invention provides (a) formula (I):

[0006]

[Chemical 2]

[Wherein R ¹ is a hydrogen atom or a carbon number of 1 to 4]
Hydrocarbon group, X is O, CH ₂ O, C═O or (CH ₂ ).
_k (k represents 1 or 2), Y is OH, a hydrocarbon group having 1 to 7 carbon atoms or (R ² O) _j H (R ² is an alkylene group having 2 to 3 carbon atoms, j is 1 to 8). And an oxygen atom is contained in at least one of X and Y], (b) Formula (II): R ³ —O— (R ⁴ —O) _m -R ⁵ (II) wherein, R ³ is an alkyl group or an allyl group having 1 to 8 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, R ⁵ is a hydrogen atom, 1 to 4 carbon atoms alkyl group, an acyl group or an allyl group having 1 to 4 carbon atoms, m is an alkylene oxide compound represented by an integer of 1-8], and also contains the (c) acid, and (d) water, pH 1 It relates to an epoxy resin soiled detergent composition which have a 6.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION R ¹ of the aromatic compound represented by the formula (I) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and the hydrocarbon group may be straight-chain or branched. A chain or cyclic saturated hydrocarbon group is preferred. Further, the hydrocarbon group having 1 to 7 carbon atoms in Y is preferably a linear or branched saturated hydrocarbon group and a cyclic saturated or unsaturated hydrocarbon group.

Specific examples of the aromatic compound represented by the formula (I) include JP-A-10-195492, page 5, column 8, 3
The compounds described in lines 2 to 6, column 9, line 4 can be mentioned. Among them, benzyl alcohol, 4-ethylbenzyl alcohol, β-phenylethyl alcohol, anisole, phenetole, isopropyl phenyl ether, butyl phenyl ether, benzyl methyl ether, benzyl ethyl ether, benzyl from the viewpoint of cleaning performance and easy availability. Isopropyl ether, benzyl butyl ether, diphenyl ether, acetophenone, p-methyl acetophenone, ethyl phenyl ketone, isopropyl phenyl ketone, benzyl methyl ketone, benzyl ethyl ketone, benzyl isopropyl ketone, benzyl butyl ketone, butyl phenyl ketone, (POE (polyoxyethylene, hereinafter the same)) _1-3 monophenyl ether, (POE) _1-3 monobenzyl ether, (PO
P (polypropylene, hereinafter the same)) _1-3 monophenyl ether, and (POP) _1-3 monobenzyl ether. Further, from the viewpoint of uniformity of the detergent composition, alcohols such as benzyl alcohol, 4-ethylbenzyl alcohol, β-phenylethyl alcohol; glycol ether compounds (POE) ₁ to ₃ monophenyl ether and (POE). ) _1-3 monobenzyl ether is more preferable. These aromatic compounds may be used alone or in combination of two or more.

The content of the aromatic compound in the detergent composition is preferably 10% by weight or more from the viewpoint of cleaning performance of resin stains, and preferably 93% by weight or less from the viewpoint of water rinsing property after cleaning. The content of the aromatic compound is preferably 10 to 93% by weight, more preferably 20 to 80% by weight, and particularly preferably 30 to 66% by weight.

Alkylene oxide represented by the formula (II)
Specific examples of the compound are described in JP-A-10-195492.
The compounds described on page 9, column 40 line to page 7, column 11, line 20 are mentioned.
To be Among them, from the viewpoint of cleaning performance and availability.
Et al (POE)₁ ~_FiveMonomethyl ether, (POE)
₁ ~_FiveMonoethyl ether, (POE)₁ ~_FiveMono professional
Pill ether, (POE)₁ ~_FiveMonobutyl ether,
(POE)₁ ~_FiveMonoisobutyl ether, (POE)
₁ ~_FiveMonoallyl ether, (POE)₁~_FiveMonoheki
Silether, (POE)₁ ~_FiveMonooctyl ete
Le, (POE)₁~_FiveMono 2-ethylhexyl ete
Le; (POE)₁ ~_FiveDimethyl ether, (POE)₁ 
~_FiveDiethyl ether, (POE)₁ ~_FiveDipropyle
Ether, (POE)₁ ~_FiveDibutyl ether, (PO
E)₁ ~_FiveEthyl methyl ether, (POE)₁ ~_FiveBu
Cylmethyl ether, (POE)₁ ~_FiveHexylmethyl
Ether; (POP)₁ ~₃Monomethyl ether, (P
OP)₁ ~₃Monoethyl ether, (POP)₁ ~₃Mo
Nopropyl ether, (POP)₁ ~₃Monobutyl A
Tell, (POP)₁ ~₃Monohexyl ether; (PO
P)₁ ~₃Dimethyl ether, (POP)₁ ~₃Jiechi
Ruther, (POP)₁ ~₃Dipropyl ether,
(POP)₁ ~₃Dibutyl ether, (POP)₁ ~₃
Isopropyl methyl ether and (POP)₁ ~₃Iso
Propyl ethyl ether is preferred. Furthermore, no acid
Uniformity of detergent composition when using organic acid, when rinsing with water
In the formula (I), R³Is carbon
Number 1 to 6 alkyl group or allyl group, R ^FourHas 2 carbon atoms
Alkylene group, R³And R^FiveThe total number of carbons in 1 to 8
And are preferred. Specifically, (POE)₁ ~_FiveMonomethy
Ruether, (POE)₁ ~_FiveMonoethyl ether,
(POE)₁ ~_FiveMonopropyl ether, (POE)₁ 
~_FiveMonobutyl ether, (POE)₁ ~_FiveMonoisobu
Chill ether, (POE)₁~_FiveMonoallyl ether,
(POE)₁ ~_FiveMonohexyl ether; (POE) ₁ 
~_FiveDimethyl ether, (POE)₁ ~_FiveDiethyl a
Tell, (POE)₁ ~ _FiveDipropyl ether, (PO
E)₁ ~_FiveDibutyl ether, (POE)₁ ~_Fiveethyl
Methyl ether, (POE)₁ ~_FiveButyl methyl ether
And (POE) ₁ ~_FiveHexyl methyl ether is better
Detergent composition using an organic acid as an acid
From the viewpoint of the uniformity of R in the formula (II), R³Has 1 carbon
~ 6 alkyl group or allyl group, R^FourIs a C3 al
Xylene group, R³And R^FiveHas a total carbon number of 1 to 8
preferable. Specifically, (POP)₁ ~₃Monomethyl et
Ether, (POP)₁ ~₃Monoethyl ether, (PO
P)₁ ~₃Monopropyl ether, (POP)₁ ~₃Mo
Nobutyl ether, (POP)₁ ~₃Monohexyl A
Tell; (POP)₁ ~₃Dimethyl ether, (POP)
₁ ~₃Diethyl ether, (POP)₁ ~₃Dipropyl
Ether, (POP)₁ ~₃Dibutyl ether, (PO
P)₁ ~₃Isopropyl methyl ether and (POP)
₁ ~₃Isopropyl ethyl ether is more preferred. This
These alkylene oxide compounds may be used alone or in combination of two or more.
You may mix and use the above.

The content of the alkylene oxide compound in the detergent composition is preferably 1% by weight or more from the viewpoint of uniformity and rinsing property of the detergent composition, and is preferably 47% by weight or less from the viewpoint of detergency. The content of the alkylene oxide compound is preferably 1 to 47% by weight, more preferably 4 to 33% by weight, and particularly preferably 6 to 2%.
It is 2% by weight.

As the acid, inorganic acids such as oxo acid, hydrogen acid and peroxo acid; carboxylic acid, thiocarboxylic acid, peracid,
Examples thereof include organic acids such as mercaptan, sulfonic acid, phosphatidic acid, dithiocarboxylic acid, sulfinic acid, phosphonic acid, and phosphinic acid.

Specific examples of the inorganic acid include boric acid, iodic acid, nitric acid, phosphoric acid, diphosphoric acid, tripolyphosphoric acid, sulfuric acid,
Oxo acids such as hypobromic acid, hypochlorous acid, chlorous acid, perchloric acid, nitrous acid, hypophosphorous acid, phosphorous acid, and sulfurous acid; hydrobromic acid, hydrochloric acid, hydrofluoric acid, iodide Hydrogen acids such as hydrogen acid and hydrosulfuric acid; and peroxo acids such as peroxo nitric acid, peroxophosphoric acid, peroxodiphosphoric acid, peroxosulfuric acid and peroxodisulfuric acid.

Specific examples of the organic acid include linear saturated monocarboxylic acids having 1 to 18 carbon atoms such as formic acid, acetic acid and propionic acid; linear unsaturated monocarboxylic acids such as acrylic acid, crotonic acid and vinylacetic acid. Isobutyric acid, isovaleric acid,
Branched saturated monocarboxylic acids such as pivalic acid; branched unsaturated monocarboxylic acids such as methacrylic acid, tiglic acid, citronellic acid; saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid and sebacic acid Acids; unsaturated polycarboxylic acids such as maleic acid, fumaric acid and citraconic acid; hydroxycarboxylic acids such as lactic acid, gluconic acid, tartaric acid, malic acid and citric acid; alicyclic carboxylic acids such as cyclohexanecarboxylic acid; alkoxycarboxylic Acids; carboxylic acids having a heterocyclic ring such as nicotinic acid; carboxylic acids of saturated polycarboxylic acids such as polyacrylic acid and polymaleic acid; thiocarboxylic acids such as o-thioacetic acid; and performic acid, peracetic acid, perbenzoic acid and the like. Peracid; mercaptans such as ethyl mercaptan and thiophenol; benzene sulfonic acid, toluene sulphate Acid, naphthalene sulfonic acid, etc .; naphthol sulfonic acid; taurine, sulfanilic acid, naphthylamine sulfonic acid; sulfonic acid such as sulfobenzoic acid; phosphatidic acid such as diacyl-L-3-glycerophosphate; other, dithiocarboxylic acid, sulfin Examples of the acid include phosphonic acid and phosphinic acid. These acids may be used alone or in combination of two or more.

Among the acids, inorganic acids are preferred from the viewpoints of having a strong acidity to lower the molecular weight of resin stains and enhance the detergency, and impart excellent detergency. Among them,
From the viewpoints of improvement of cleaning property, sustainability, easy availability and economical efficiency, oxo acids such as nitric acid, phosphoric acid and sulfuric acid; and hydrous acids such as hydrochloric acid and hydrofluoric acid are more preferable.

On the other hand, metals such as aluminum, nickel, copper, zinc and tin, alloys such as brass, brass and solder, and metal components related to cleaning equipment such as plated parts are suppressed,
Organic acids are preferred from the viewpoint of exhibiting even more excellent detergency due to the effect of penetrating and swelling inside the resin stain due to its high compatibility with the resin stain. Among them, from the viewpoints of improvement of detergency, durability, easy availability and economy, carboxylic acids such as formic acid, acetic acid, propionic acid, acrylic acid,
Methacrylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, citraconic acid, lactic acid, gluconic acid, tartaric acid, malic acid, citric acid, nicotinic acid, polyacrylic acid and More preferred is polymaleic acid.

From the viewpoint of detergency, the content of the acid in the detergent composition is preferably 0.5% by weight or more, and from the viewpoint of the uniformity of the detergent composition and the risk of acid, 5
It is preferably 0% by weight or less. The content of acid is 0.5 to 50
Weight% is preferable, 1 to 20 weight% is more preferable, and 3 to 15 weight% is particularly preferable.

PH of the detergent composition The present invention, in view of the cleaning resin stains, 1-6, preferably 2-5 der
It

Water is used as a solvent for uniformly dissolving the aromatic compound, the alkylene oxide compound and the acid, and as a solvent for promoting the action of the acid. Water is not particularly limited as long as it does not impair the effects of the cleaning composition of the present invention, and includes ultrapure water, pure water, ion-exchanged water, distilled water, ordinary tap water and the like.

The content of water in the detergent composition is preferably 5% by weight or more from the viewpoints of detergency and uniformity of the detergent composition, and preferably 88% by weight or less from the viewpoint of detergency. The water content is preferably 5 to 88% by weight, more preferably 15 to 60% by weight, and particularly preferably 25.
-40% by weight.

The cleaning composition further contains a water-soluble polyhydric alcohol to improve the cleaning property, the rinsing property in water rinsing after cleaning, and the compatibility when other components such as water are mixed. Can be improved.

Specific examples of the water-soluble polyhydric alcohol are described in JP-A-10-195492, page 7, column 12, line 37 to page 8, 13
The compounds described in column 16 line are mentioned. Among them, from the viewpoint of improving detergency, rinseability and compatibility of various components, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol,
Heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, propylene glycol, dipropylene glycol,
Tripropylene glycol, 1,2-propanediol, 1,3-propanediol, 2-methyl-1,3-
Propanediol, 1,3-butanediol, 1,4-
Butanediol, 1,4-butenediol, 1,4-pentanediol, 1,5-pentanediol, 1,5-
A divalent water-soluble polyhydric alcohol having a linear molecular structure such as hexanediol and 1,6-hexanediol and having one hydroxyl group near both ends of the molecule is preferable. Further, from the viewpoint of avoiding danger such as flammability and easy availability, ethylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol; dipropylene glycol such as propylene glycols; Of the diols, 1,3-butanediol, 1,4-butanediol, 1,4-pentanediol, 1,5-pentanediol, 1,5-hexanediol and 1,6-hexanediol are more preferred. These water-soluble polyhydric alcohols may be used alone or in combination of two or more.

The amount of the water-soluble polyhydric alcohol is not particularly limited, but from the viewpoint of exhibiting the effect of improving the performance by addition to 100 parts by weight of the total amount of the aromatic compound and the alkylene oxide compound, The amount is preferably 1 part by weight or more, and is preferably 81 parts by weight or less from the viewpoint of cleanability. The amount of the water-soluble polyhydric alcohol is preferably 1 to 81 parts by weight, more preferably 5 to 25 parts by weight.

In the detergent composition, if necessary, a surfactant, a sequestering agent, a preservative, a rust preventive, which are commonly used in detergents, are used as long as the object of the present invention is not impaired. A defoaming agent, an antioxidant and the like can be contained as appropriate.

The cleaning composition of the present invention comprises an aromatic compound,
It can be produced by mixing an alkylene oxide compound, an acid and water, a water-soluble polyhydric alcohol, optional components and the like by a conventional method. The detergent composition can also be obtained by mixing a mixture of an aromatic compound and an alkylene oxide compound in a predetermined mixing ratio and an acid-based detergent containing acid and water in a predetermined ratio.

The detergent composition of the present invention is used in the prime apply with respect to dirt firmly adhering and bonding epoxy resins into hard quality surface.

The resin stain can be removed from the object to be cleaned by cleaning the object to be cleaned to which the resin stain is attached by using the cleaning composition of the present invention. Specific examples of the cleaning method include a method in which an object to be cleaned with resin stains is cleaned with the cleaning composition of the present invention and then rinsed with a rinse liquid.

The method for cleaning the object to be cleaned with resin stains using the cleaning composition of the present invention is not particularly limited, and a commonly used known method can be used. . Examples of the cleaning method include an immersion method, an ultrasonic cleaning method, an immersion rocking method, and a spray method. In addition, the cleaning conditions such as the temperature of the cleaning composition and the cleaning time are not particularly limited, and the type of resin stain, the mode of adhesion, the constituents, the polymerization state, the adhesion amount, the adhesion place, the adhesion state, and the object to be cleaned. It may be appropriately selected depending on the material, the required degree of cleanliness, the capacity of the washing machine, the permissible washing time, and the like.

The rinse liquid used for rinsing the washed object with the rinse liquid is not particularly limited as long as it can remove contaminants remaining on the surface of the object to be cleaned. Examples thereof include organic solvents such as isopropyl alcohol, ultrapure water, pure water, ion-exchanged water, distilled water,
Water such as ordinary tap water can be used. From the viewpoint of avoiding dangers such as flammability, it is preferable to use water. The rinsing method is also not particularly limited, and the same method as the method of cleaning using the cleaning composition can be adopted.

[0031]

Examples Examples 1 to 10 and Comparative Examples 1 to 6 As shown in Tables 1 and 2, respective components were mixed to prepare a detergent composition having a predetermined composition, and the obtained detergent composition was obtained. Was used to evaluate the detergency according to the following method. The results are shown in Tables 1-2.

[Cleanability] (1) Preparation of test piece 1 mm × 76 mm × 26 mm slide glass (manufactured by Matsunami Glass Industry Co., Ltd., trade name: MICRO SLIDE GLASS S-111)
Apply 0.2 g of epoxy resin adhesive evenly to the center of 2) to form a circle with a diameter of 20 mm.
After curing for 1 hour in an atmosphere of ° C, it was left for 3 hours at room temperature.

The following epoxy resin adhesives were used. W-Bond NC-15K (manufactured by Nika Seiko Co., Ltd., trade name) Main agent: Hardener = 2: 1 (weight ratio) Araldite Standard (Nagase Ciba Co., Ltd.,
Trade name: Main agent: Hardener = 1: 1 (weight ratio) Bond Quick 5 (Konishi Co., Ltd., trade name) Agent A: Agent B: 1: 1 (weight ratio)

(2) Cleaning test The time required for the epoxy resin adhesive to be completely peeled off and dropped at a liquid temperature of 75 ° C. by immersing the test piece in a standing state in the cleaning composition. Was measured. This operation was repeated 5 times, and the average value was taken as the peeling time (minute).
The short peeling time means that the epoxy resin is peeled off in a short time, that is, the cleaning performance is good.

[0035]

[Table 1]

[0036]

[Table 2]

From the results shown in Tables 1 and 2, the use of the detergent compositions obtained in the examples makes it possible to efficiently wash the resin stains firmly adhered to and adhered to the hard surface of the epoxy resin. I know that I can do it.

[0038]

EFFECT OF THE INVENTION The cleaning composition of the present invention has the effect of efficiently cleaning resin stains firmly adhered to and adhered to a hard surface.

Claims (4)

(57) [Claims] 1. (a) Formula (I): [In the formula, R ¹ is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, X is O, CH ₂ O, C═O or (CH ₂ ) _k (k is 1
Or 2), Y is OH, a hydrocarbon group having 1 to 7 carbon atoms or (R ² O) _j H (R ² is an alkylene group having 2 to 3 carbon atoms, j is an integer of 1 to 8). And an oxygen atom is contained in at least one of X and Y], (b) Formula (II): R ³ —O— (R ⁴ —O) _m —R ⁵ ( II) wherein, R ³ is an alkyl group or an allyl group having 1 to 8 carbon atoms, R ⁴ is an alkylene group having 2 to 4 carbon atoms, R ⁵ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, carbon atoms 1-4 acyl group or an allyl group, m is an alkylene oxide compound represented by an integer of 1-8], and also contains the (c) acid, and (d) water, to have a pH1~6 Detergent composition for epoxy resin stains. 2. (a) 10 to 93% by weight of an aromatic compound,
(B) 1 to 47% by weight of an alkylene oxide compound,
The cleaning composition according to claim 1, which comprises (c) 0.5 to 50% by weight of acid and (d) 5 to 88% by weight of water. 3. The cleaning composition according to claim 1, further comprising a water-soluble polyhydric alcohol. 4. The (c) acid is derived from oxo acid, hydrogen acid, peroxo acid, carboxylic acid, thiocarboxylic acid, peracid, mercaptan, sulfonic acid, phosphatidic acid, dithiocarboxylic acid, sulfinic acid, phosphonic acid and phosphinic acid. The cleaning composition according to claim 1, which is one or more selected from the group consisting of: