JPH09302387A - Cleansing agent for two-part curing resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject halogen-free cleansing agent, composed of γ- butyrolactone, a hydrocarbon and a specific component, excellent in detergency, low in a danger of catching fire, having little effect on the environment and useful especially as a cleansing agent for a resin extrusion apparatus. SOLUTION: This cleansing agent is composed of (A) γ-butyrolactone, (B) a >=10C hydrocarbon (e.g. decane or dipentene) and (C) at least one kind selected from a >=5C fatty acid ester (preferably, a >=6 fatty acid alkyl ester such as hexyl acetate), a glycol ether of the formula (R<1> is a 1-8C alkyl, a phenyl, etc.; R<2> is H or methyl; R<3> is H, 1-6C alkyl, etc.; (n) is 1-3) (e.g. ethylene glycol monomethyl ether) and an acetic acid ester of the glycol ether. The contents of the components A, B and C are preferably 10-85wt.%, 10-70wt.% and 5-50wt.%, respectively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cleaning agent suitable for cleaning a two-part curable resin, particularly for cleaning a mixing section and a nozzle section of a resin discharging device.

[0002]

2. Description of the Related Art In recent years, various electric / electronic parts, medical equipment parts, automobile parts, etc. have been treated with epoxy, urethane, silicone,
A resin ejection device is widely used for the purpose of joining, filling, or sealing with a resin such as polyester. The resin used for this purpose is often a two-pack type that crosslinks and cures at around room temperature.
It is possible to mix and stir and continuously discharge. However, when using a two-liquid type resin, it is necessary to clean the mixing section and nozzle section in order to prevent the resin from hardening in the discharge device before interrupting the work such as lunch break or the end of the work day. There is.

These cleanings are nonflammable and have low toxicity,
Since it has many characteristics, such as excellent solubility,
1,1,1-Trichloroethane has been widely used. However, it was revealed that it destroys the ozone layer in the stratosphere, though it is an extremely excellent cleaning agent, and it has been internationally agreed to abolish it. Also,
There are some halogen-based solvents such as methylene chloride that have not been completely abolished, but they are also shunned by carcinogenicity and other environmental pollution problems.

Under such circumstances, expectations are high for a non-halogen alternative cleaning agent which is safe and has little influence on the environment, but it is the current situation that one satisfying all the required performances has not yet been obtained. . For example, acetone has an excellent detergency, but has a low flash point, and it is dangerous to use it for cleaning a resin discharge device having many ignition sources such as a heater. In addition, adimethic acid, succinic acid and / or glutaric acid dimethimester and γ-butyrolactone are also used in some parts, but these have a high flash point of around 100 ° C, but silicone resins and some urethanes. The detergency of the system resin is decisively insufficient.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a non-halogen type two-component curable resin cleaning agent having excellent cleaning power, low risk of ignition, and low environmental impact. is there.

[0006]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, selected from the group consisting of γ-butyrolactone an appropriate amount of a hydrocarbon and a fatty acid ester or glycol ether or an acetic acid ester thereof. The inventors have found that the addition of at least one selected can significantly improve the detergency of the urethane resin without impairing the detergency of the epoxy resin, and completed the present invention.

That is, the present invention provides the following (a):
(B) and (c) The present invention relates to a cleaning agent for a two-part curable resin containing three components. (A) γ-butyrolactone. (B) A hydrocarbon having 10 or more carbon atoms. (C) At least one selected from fatty acid esters having 5 or more carbon atoms, glycol ether represented by the following formula (1), or acetic acid ester thereof.

[0008]

Embedded image

(Wherein R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or a phenyl group, R ² is hydrogen or a methyl group, R ³ is hydrogen, or an alkyl group having 1 to 6 carbon atoms or an acetyl group. Group, n represents an integer of 1 to 3.) In a preferred embodiment of the present invention, the content of (a) is 10
~ 85 wt%, the content of (b) is 10-70 wt%,
The content of (c) is 5 to 50% by weight.

Hereinafter, the present invention will be described in detail. In the present invention, the content of the component (a) is preferably 10 to 85% by weight from the viewpoint of solubility in a wide variety of resins. In the present invention, as the hydrocarbon used as the component (b), a linear or branched saturated aliphatic hydrocarbon having 10 or more carbon atoms, an alicyclic hydrocarbon, an olefinic hydrocarbon,
It can be selected from terpene-based hydrocarbons, aromatic hydrocarbons and the like, but it is preferable to select from the former three, which have less problems of unique odor and toxicity. Even if the one having less than 10 carbon atoms is used, there is no problem in the cleaning performance, but the flash point is lowered, which is not preferable. Specific examples of hydrocarbons include, for example, decane, undecane, tridecane, tetradecane,
Pentadecane, menthane, bicyclohexyl, cyclododecane, decalin, 2,2,4,4,6,8,8-heptamethylnonane, 2,6,10,14-tetramethylpentadecane, α-pinene, dipentene, 1- Decene, 1
-Undecene, 1-dodecene, 1-tridecene, 1-tetradecene and the like can be mentioned, and these can be used alone or in a mixture of two or more kinds. The hydrocarbon content is preferably 10% by weight or more in order to improve the dissolving power of the urethane resin to a practically significant degree, but when it exceeds 70% by weight, the dissolving power of the epoxy resin decreases. Tend to come.

The cleaning agent of the present invention comprises the main component (a) γ
Component (c) is necessary in order to keep the mixture of butyrolactone and hydrocarbon (b) uniform over a wide temperature range. The component (c) is at least one selected from fatty acid esters having 5 or more carbon atoms, glycol ethers represented by the above formula (1), or acetic acid esters thereof.

Alkyl esters are preferred as the fatty acid ester, and those having 6 or more carbon atoms are preferred in view of the safety of the resulting composition against ignition. Specific examples include butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, -3 acetate.
-Methoxybutyl, acetic acid-3-methoxy-3-methylbutyl, butyl propionate, isopentyl propionate, ethyl butyrate, isopropyl butyrate, butyl butyrate, isopentyl butyrate, methyl isovalerate, isopropyl isovalerate, methyl caproate, caprylic acid Examples thereof include methyl, methyl caprate, methyl undecylate, methyl laurate, and methyl benzoate.

Specific examples of glycol ethers or acetic acid esters thereof include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether. Isopropyl ether, diethylene glycol monoisopropyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, ethylene glycol Rumonoisobutyl ether, diethylene glycol monoisobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, ethylene glycol mono-2 ethylhexyl ether, diethylene glycol mono-2 ethylhexyl ether, ethylene glycol monophenyl ether, propylene glycol monophenyl ether, propylene glycol monocyclohexyl ether Etc. and acetic acid esters thereof, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether Ether, and propylene glycol cyclohexylmethyl ether.

These fatty acid esters or glycol ethers or acetic acid esters thereof can be added alone or in combination, but if the addition amount is less than 5% by weight, the effect is insufficient, but usually 50% by weight or less. A sufficient effect can be obtained. Further, the cleaning agent of the present invention, if necessary, stabilizers such as known antioxidants, for example, benzotriazoles, amines, alkanolamines,
Nitrite, phosphite, phenol and the like can be added.

The cleaning agent of the present invention is useful for cleaning a two-part curable resin, and is particularly suitable as a cleaning agent for a resin discharge device.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[0017]

[Example 1] 50% by weight of γ-butyrolactone, normal undecane (trade name: N11, manufactured by Nikko Petrochemical Co., Ltd.)
30% by weight, diethylene glycol diethyl ether 2
2% as shown in Table 1 using 0% by weight of detergent
A solubility test of the liquid resin compound was conducted.

The main component of each resin and the curing agent were mixed well at a predetermined ratio (weight ratio), 0.2 g was taken and left for 10 minutes, 10 ml of the above-mentioned cleaning agent was added, and shaken (180 times /
Then, all the resins were completely dissolved or dispersed within 5 minutes.

[0019]

[Example 2] The same operation as in Example 1 was carried out except that normal undecane was used as a paraffin / naphthene mixture (trade name: Fukko High Solvent 200, manufactured by Fuji Kosan Co., Ltd.), and all the resins were completely removed within 5 minutes. Dissolved or dispersed in.

[0020]

[Example 3] The same operation as in Example 1 was carried out except that normal undecane was changed to 1-dodecene (trade name: Dialene 12, manufactured by Mitsubishi Chemical), and all the resins were not completely dissolved within 5 minutes. Dispersed.

[0021]

Example 4 The same operation as in Example 1 was carried out except that diethylene glycol diethyl ether was replaced with 3-methoxybutyl acetate, and all the resins were completely dissolved or dispersed within 5 minutes.

[0022]

Example 5 The same operation as in Example 1 was carried out except that 2-ethylenehexyl acetate was used as the diethylene glycol diethyl ether, whereby all the resins were completely dissolved or dispersed within 5 minutes.

[0023]

Example 6 The same operation as in Example 1 was carried out except that diethylene glycol diethyl ether was changed to diethylene glycol monobutyl ether. As a result, all the resins were completely dissolved or dispersed within 5 minutes.

[0024]

Example 7 The same operation as in Example 1 was carried out except that diethylene glycol diethyl ether was changed to methyl laurate, whereby all the resins were completely dissolved or dispersed within 5 minutes.

[0025]

Comparative Example 1 The cleaning composition was changed to 75% by weight of γ-butyrolactone, 5% by weight of normal undecane, and 20% by weight of diethylene glycol diethyl ether, and the same operation as in Example 1 was carried out. It was completely dissolved or dispersed within, but almost no urethane resin was dissolved or dispersed.

[0026]

Comparative Example 2 The same operation as in Example 1 was carried out except that the detergent composition was changed to 5% by weight of γ-butyrolactone, 75% by weight of normal undecane, and 20% by weight of diethylene glycol diethyl ether. It was completely dissolved or dispersed within minutes, but almost no epoxy resin was dissolved or dispersed.

[0027]

[Comparative Example 3] The same operation as in Example 1 was carried out except that γ-butyrolactone was used as the cleaning agent. As a result, the three epoxy resins were completely dissolved or dispersed within 5 minutes, but almost no urethane-based resin was used. It did not dissolve or disperse.

[0028]

[Comparative Example 4] The same operation as in Example 1 was carried out except that γ-butyrolactone was used as the cleaning agent. As a result, three kinds of epoxy resins were completely dissolved or dispersed within 5 minutes. It did not dissolve or disperse.

[0029]

[Comparative Example 5] As a cleaning agent, a mixture of dimethyl esters of adipic acid, succinic acid and glutaric acid (trade name: DBE,
When the same operation as in Example 1 was carried out in place of DuPont), three epoxy resins were completely dissolved or dispersed within 5 minutes, but almost no urethane-based resin was dissolved or dispersed.

[0030]

Comparative Example 6 A uniform liquid was not obtained when 4% by weight of diethylene glycol diethyl ether was used without changing the ratio of γ-butyrolactone and normal undecane in Example 1.

[0031]

[Table 1]

[0032]

The cleaning agent of the present invention is a two-part curing resin used for joining, filling, or sealing various electric / electronic parts, medical device parts, automobile parts, etc., such as epoxy and urethane. It is capable of cleaning a wide range of resins such as silicone, polyester, etc., and is particularly epoch-making as a cleaning agent for resin ejection devices. Moreover, since it does not contain halogen atoms, there is no danger of depleting the ozone layer, it has little impact on the environment, and it has a high flash point, so it is extremely useful as a substitute cleaning agent for 1,1,1-trichloroethane and methylene chloride.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C11D 7:24)

Claims (2)

[Claims] 1. A cleaning agent for a two-part curable resin, which contains the following three components (a), (b) and (c). (A) γ-butyrolactone. (B) A hydrocarbon having 10 or more carbon atoms. (C) At least one selected from fatty acid esters having 5 or more carbon atoms, glycol ether represented by the following formula (1), or acetic acid ester thereof. Embedded image (In the formula, R ¹ is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group or a phenyl group, R ² is hydrogen or a methyl group,
R ³ represents hydrogen, an alkyl group having 1 to 6 carbon atoms or an acetyl group, and n represents an integer of 1 to 3. ) 2. The content of (a) is 10 to 85% by weight,
The cleaning agent according to claim 1, wherein the content of (b) is 10 to 70% by weight and the content of (c) is 5 to 50% by weight.