JPH01135899A - Nonadsorbing penetration treating agent - Google Patents

Abstract

PURPOSE:To obtain the above efficient treating agent, containing a specific six-membered ring boric acid ester as an active component, capable of acting and activating the surface and interior of a metal, glass, ceramic, plastic, etc., and nonabsorptive itself without causing residual bad effects. CONSTITUTION:The aimed treating agent containing one or more six-membered ring boric acid esters expressed by the formula (A is 1-8C alkoxy, phenoxy, cresyloxy, terpenyloxy, furfuryloxy or tetrahydrofurfuryloxy; R1 and R2 are H or methyl; R3 and R4 are H, methyl, methoxymethyl or ethoxymethyl; R5 is H, methyl or propyl; m and n are 0<=m<=4; 0<=n<=4 and 1<=m+n<=4). Furthermore, [{2-(2-methoxypropyloxy)propyl)}-butylene-1,3-]borate, etc., a cited as preferred examples of the above-mentioned esters.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention relates to a penetrant treatment agent. More specifically, when acting on and activating the surfaces and interiors of metals, glass, ceramics, plastics, etc., it is itself non-adsorptive, and therefore efficient and free from residual harmful effects. This article relates to a useful treatment agent that does not cause this.

``Conventional technology'' Traditionally, it has been necessary to clean the material in the plating pretreatment process and the glass lens cleaning process, and various infiltration treatments have been used to do so. In today's highly information-oriented society that uses computers, cleaning the substrates used in the production of ICs has become an important task, and strong penetration treatment agents are being sought after. On the other hand, in light of the reality of an aging society, a great deal of attention is paid to maintaining health in daily life, and from that point of view, taking a bath in a clean bathroom or bathtub is a necessary condition. Bathroom cleaners and mold removal agents have been devised for this purpose. In addition, the main components or auxiliary components of the above drugs are glycol ether-based water-soluble organic solvents, or conversely, water-insoluble halogen-based solvents and various surfactants, etc. Some of the materials used are inorganic substances such as acids and alkalis.

However, these conventional raw materials have drawbacks such as their permeation treatment effect is weak, they are harmful substances that have a negative impact on the surroundings, or they themselves are adsorbed to and remain on the treated object. , improvements were desired.

In addition, in particular, in the case of grease, which is a complex type of dirt, there are many cases in which metallic soap-like substances such as lime soap get into the oil and accumulate while forming reverse micelles. Since the particles could not be removed by dissolving them with agents, or by floating or dispersing them, they had to be scraped off using systems containing inorganic substances. For example, similar common stains include bathroom scale and limescale on walls, floors, washroom sinks, etc., but there is no chemical agent yet that can smoothly remove these stains.

[Non-adsorptive penetrant treatment agent of the present invention and its mechanism of action] As a result of various studies, the present inventors have discovered that the unique ring vibration exhibited by the six-membered ring boric ester structure and the free rotation of the ether bond can be combined simultaneously. The boric acid ester has a very good permeation treatment effect, and since both ends of the molecule are made of inert hydrocarbon groups, it has the same adsorption properties as surfactants even though it has a good permeation ratio. The present inventors have achieved an invention in which the penetration treatment agent is not strong and therefore does not remain on the surface or inside of the object to be treated.

That is, the present invention is based on the following general formula 1 (where A is an alkoxy group having 1 to 8 carbon atoms, or a phenoxy group, a cresyloxy group, a terpenyloxy group,
It is a furfuryloxy group or a tetrahydrofurfuryloxy group, R1 and R2 are hydrogen or a methyl group, and R8 and R4 are both hydrogen, a methyl group, a methoxymethyl group, or an ethoxymethyl group, or one of them is a methoxymethyl group. or when one is a methyl group, the other is hydrogen, or when one is a methyl group, the other is a methoxymethyl or ethoxymethyl group, or when one is an ethyl group, the other is hydrogen. hydrogen or a methoxymethyl group or an ethoxymethyl group, R6 is hydrogen, a methyl group or a propyl group,
0≦m≦4.0≦n≦4, and 1≦m + n≦4
It is. ), a six-membered ring boric acid ester (hereinafter referred to as a predetermined boric acid ester) is used as a penetration treatment agent.

In a given boric acid ester, the B-0 bond part has a planar structure as shown below, and the 10-c-c-
The c-o-bond part exhibits a gauche-type bond structure, but within the six-membered ring, only the part to which carbon is attached has a unique ring vibration that vibrates up and down, and this movement and We speculate that the combination of free rotational motion in the ether oxygen part on the opposite side of the ring provides strong penetrating and dissolving power.

Next, to describe the method for producing a prescribed boric acid ester that can be used as a non-adsorptive penetrating treatment agent of the present invention, the prescribed boric acid ester has a total number of carbon atoms each having an OH group connected to one carbon. A monool having a total of 3 to 22 carbon atoms (hereinafter referred to as a "predetermined monool") linking a 3 to 9 diol (hereinafter referred to as a "predetermined diol") and at least one oxypropylene group and/or oxyethylene group. ) and boric acid or a boric acid triester of a lower alcohol in a ratio of 1:1:l (molar ratio) or very close to that, and under normal pressure or reduced pressure,
It is produced by carrying out a boric acid esterification reaction at 0 to 300°C, preferably 150 to 250°C. In this case, injecting an inert gas such as N gas facilitates completion of the reaction. Furthermore, in the case of a dehydration esterification reaction using boric acid, it is also effective to carry out azeotropic dehydration in the coexistence of toluene, xylene, etc., and then remove the azeotropic solvent afterwards.

Here, as the predetermined diol, for example, 1゜3-propanediol, 1,3-butanesil, 2-methyl-
2,4-pentanediol, 2,2,4-trimethyl-
1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methoxyglycerin, 2-ethoxyglycerin, monomethoxytrimethylolethane, monoethoxytrimethylolethane, monomethoxytrimethylolpropane, monoethoxytrimethylol Propane, dimethoxypentaerythritol, jetoxypentaerythritol, etc. may be mentioned, and the predetermined monools include, for example, methyl alcohol, ethyl alcohol,
n = propyl alcohol, isopropyl alcohol, n
- 1 to 4 mole ethylene oxide adducts of butyl alcohol, isobutyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, benzine alcohol, methylbenzyl alcohol, phenol, cresol, terpenol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc.; Examples include a 4 mol propylene oxide adduct and a 1 to 4 mol (ethylene oxide/propylene oxide) coadduct. In addition, the boric acid triesters of lower alcohols to be reacted with these include trimethyl bollard, triethyl bollard, tripropyl bollard, triisopropyl bollard, tri(n-
butyl) bollard, etc. Table 1 shows representative examples of certain boric acid esters.

Here, in relation to general formula (■), if we consider a six-membered ring boric acid ester that is outside the scope of the predetermined boric acid esters, including the above-mentioned representative examples, for example, when the number of carbon atoms in the alkoxy group of A is larger than 8 , and when m+n is larger than 4, the proportion of the six-membered ring boric acid ester becomes small in terms of the entire molecular structure, and the penetrating power is extremely reduced.
Undesirable. In addition, if m+n=o, that is, neither oxypropylene groups nor oxyethylene groups are connected, the structure will not cause free rotational movement of multiple ether oxygens, and the penetrating power will similarly decrease. I don't like it because it stows away.

[Example] The present invention will be explained below with reference to Examples.

Example 1 In an ultrasonic multi-tank cleaning system consisting of the flow sheet shown below, a solvent and a detergent or the penetration treatment agent of the present invention consisting of a prescribed boric acid ester were used only on one side, and the cleaning basket had a diameter of 50 m. After accommodating 20 m optical lenses each,
The processing time for each type was 30 seconds, and cleaning was performed for each type. In addition, as comparative tests, examples using known glycol ether-based hydrophilic solvents, chlorinated solvents, and anionic and nonionic surfactants were also conducted. The results are shown in Table 2.

Note: All injection chemicals in the (water + detergent) tank were made to be 5% aqueous solutions.・※※The test method for penetrating cleanability is to use a cotton swab soaked in a standard solution for measuring wettability index made by mixing formamide and ethylene glycol monoethyl ether in an arbitrary volume ratio. A line was quickly drawn on the surface of the optical lens of 1 set), and changes in the liquid film were observed to see if it broke or contracted within 2 seconds.

The standard values for penetrating and cleaning properties are as follows.

A: The film of the standard solution of formamide:ethylene glycol monoethyl ether = 99:1 (V/V%) does not change on all 20 optical lenses for 2 seconds.

A゛...The film of the standard solution of formamide:ethylene glycol monoethyl ether = 99:1 (V/V%) does not change for 2 seconds on 20 optical lenses 915-19.

B...Formamide 22thylene glycol monoethyl alcohol) 90.7: The film of the standard solution of 9.3 (V/V%) does not change on all 20 optical lenses for 2 seconds.

C... Formamide 22thylene glycol monoethyl ether = 80.3: 19.7 (V/V%) The film of the standard solution does not change on all 20 optical lenses for 2 seconds.

D...Formamide: Ethylene glycol monoethyl ether = 80.3719.7 (V/V%) The film of the standard solution changes on the surface of the optical lens under test within 2 seconds.

Example 2 A polished cold-rolled steel plate (50 x 10 x 1 mrnI) was immersed in an oil bath consisting of 96 parts of kerosene, 4 parts of #60 spirton oil, and 0.1 part of calcium stearate for 5 seconds, and then taken out. It was allowed to stand at room temperature for 10 hours.

Next, the surface was strongly pressed with a finger to leave a fingerprint, which was used as a test piece.

Thereafter, 100 g of the penetration treatment agent of the present invention in the form of an aqueous solution or emulsion was prepared as a test liquid, and one of the above test pieces was suspended therein, and the test piece was heated at 50°C for 10 minutes.
Stirring was performed at 800 rpm.

In addition, as a comparative test, examples using known glycol ether solvents, hydrocarbon solvents, and nonionic surfactants were also conducted.

Table 3 shows the results of investigating the surface cleanliness.

Note) *The quality of penetrating cleaning performance was determined by observing the surface of the test steel plate with an optical microscope. The target price criteria are as follows.

A: Fingerprints on the test steel plate are completely removed, and the surface has good gloss.

A': Fingerprints on the test steel plate have been removed, but the surface gloss of that area has become somewhat dull.

B: Fingerprints on the test steel plate remain indistinct, but the surface gloss of other parts is good.

C: Fingerprints on the test steel plate remain clear,
Moreover, the surface gloss of other parts has also become dull.

Example 3 An aluminum wafer coated with a phenol-novolac positive resist was used as a test piece, and the above test piece was placed in the penetration treatment agent of the present invention heated to 80°C in a peeling system consisting of the following flow sheet. The wafer was immersed in the wafer, and the peeling rate of the resist and the presence or absence of corrosion of the wafer were examined.

In addition, as a comparative test, examples using known glycol ether-based stripping agents and chlorine-based stripping agents were also conducted.

The results are shown in Table 4.

Note) *The presence or absence of corrosivity of aluminum/nium wafers can be determined by immersing an aluminum test piece with a purity of 99.9% or higher in a test solution kept at a constant temperature of 50°C for 24 hours, and measuring the amount of dissolved aluminum ions by atomic absorption spectrometry. After the investigation, it was converted, and the case where the solute was 0.1 person/min or less was judged as absent, and the case where the solute was 0.1 person/min or more was judged as present.
゛Example 4 One with a volume of 360cm x 180cm x 120cm and one
80 cm x 1'80 cm x 70 cm capacity connected bathtub with 500 z of warm water per day.
Washing area of a public bath that meets the specified time (however, the area is 10
In the center of the floor of the floor of
After arranging the square plate (m x 5 cm), it took one week.
A total of 1,500 people were bathed and washed.

Next, take out the white tile and 20°0150%R)(
The sample was left to stand for 72 hours under constant temperature and humidity conditions, and was then adjusted. "Next, 5 g of the penetration treatment agent of the present invention heated to 30° C. was weighed into Petri dishes each having a diameter of 8 cm, and the test specimen was immersed therein for 15 minutes.

Next, take out the test specimen and soak it with 20°C water at 15I/
After washing for 5 minutes at a flow rate of min.
%RH The surface reflectance of the product was left standing for 72 hours under constant temperature and humidity conditions to determine its scale removal properties.

Additionally, residual odor was observed.

As a comparative test, examples using known glycol ether solvents and surfactants were also conducted.
The results are shown in Table 5.

Note) *However, the amount of 50% aqueous solution of sodium dodecyl sulfate used in the comparative test was twice that of other penetration treatment agents.
It was set to 0g.

※※Evaluation of scale removability is as follows: First, cleanliness value = 100 - (reflectance of unused white tile -
After determining the reflectance of the white tile after the penetration treatment test, the following criteria were established.

A: Those with a cleanliness value of 98 to 100.

B... 95 to less than 98 C... //90 to less than 95 D... // Less than 90 // Example 5 FRP with a volume of 78 cm x 68 cm x 58 cm
A bathtub (material composition: 40% styrene-grafted unsaturated polyester resin, 30% glass fiber, 30% calcium carbonate) is filled with 2501 warm water at 5% per day.
5cm below the water surface, place an FRP resin plate made of the same material as the bathtub (5cm x 5cm)
m square board) is fixed vertically, and 5 adults (however,
The average weight was 60 kg. ) was repeatedly bathed for 30 minutes each for 20 days.

Next, the FRP resin plate was taken out and allowed to stand for 72 hours under constant temperature and humidity conditions of 20° C. and 50% RH, and the resulting condition was used as a test specimen.

Next, 5 g of each of the penetration treatment agents of the present invention, whose temperature was adjusted to 20'C, was weighed into Petri dishes with a diameter of 8 cm.
The test specimen was immersed in it for 10 minutes.

Next, the test specimen was taken out and its surface was rubbed with cotton gauze 20 times with a force of 20kg/crrr.
Rinse for 10 seconds in water at 20°C, 150% RH.
After being allowed to stand for 72 hours under constant temperature and humidity conditions, the surface reflectance was measured to examine scale removal performance.

Additionally, residual odor was observed.

As a comparative test, examples using known glycol ether solvents and surfactants were also conducted. The results are shown in Table 6.

Note) *Evaluation of descaling ability is performed by first determining the cleanliness value = 100 - (reflectance of unused FRP resin board - reflectance of FRP resin board after penetration treatment test), and then using the following criteria: I set it up and went.

A... Those with a cleanliness value of 98 to 100 B...
95 to less than 98 Nol C...//90 to less than 95? / D, 1. /No Less than 90 No/Example 6 An ethylene-vinyl acetate copolymer resin film consisting of 9:l (mole ratio) (However, a rectangular shape of 21 cm x 30 cm,
A specimen with a thickness of 200μ) was used as a test specimen, and 50μ
1 g of the penetration treatment agent of the present invention heated to 0.degree. C. was added and spread throughout using cotton gauze.

Next, 100% emulsion paint of styrene-ethyl acrylate copolymer consisting of 1:3 (mole ratio) was applied.
It was applied to a thickness of μ in a -like manner, left to stand at 50°C for 2 hours,
After drying, it was kept under constant temperature and humidity conditions of 20° C. and 50% RH for 24 hours.

Thereafter, a peel test was conducted using a base grain test to examine the adhesion. Further, examples using known glycol ether solvents and surfactants were also conducted. The results are shown in Table 7.

Note) *Adhesion was evaluated by making cuts of 1 mm vertically and 1 mm horizontally in the coating film, and making a total of 100 1 mm pieces (after cutting,
A commercially available cellophane adhesive tape was applied and forcefully peeled off, and the number of frames detached from the surface of the ethylene-vinyl acetate copolymer resin film was determined. The evaluation criteria are as follows.

A...The number of pieces of the paint film that are adhered without detaching is 98/
100-1007100 B...
〃94/100-97/
100 "C.../l 〃 90/loo~93/1001/D.../I // Less than 90/100/1 As is clear from the examples shown above, the non-adsorptive penetration treatment agent of the present invention The effects brought about by emphasizing the inherent ring vibration and multiple free rotation properties of a certain boric acid ester, which is an active ingredient, solve various problems that were insufficient in conventional systems that apply solvents and surfactants. I found that it helped me solve the problem.

Furthermore, by applying the non-adsorptive penetrating treatment agent of the present invention, it becomes possible to completely remove processing aids from powder-molded products such as aluminum die-casting, and perform precision cutting of metals, etc. Water soluble 1 can also be used as a grease cleaner for automobiles, aircraft, etc.

It can also be applied in the field of daily necessities, such as as an oil film remover for automobiles, a stain remover for clothing, a ventilation fan, a sink cleaner, and a nail polish remover.

On the other hand, when polymer moldings made by copolymerization or polymer blending are properly processed and contacted with the non-adsorptive penetrants of the present invention, very small continuous pores can be created and, in some cases, selective It is also possible to create a target gas permeate.

Claims (6)

[Claims] (1) General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼...I (However, A is an alkoxy group having 1 to 8 carbon atoms, or a phenoxy group, cresyloxy group, terpenyloxy group,
It is a furfuryloxy group or a tetrahydrofurfuryloxy group, R_1 and R_2 are hydrogen or a methyl group, and R_3 and R_4 are both hydrogen, a methyl group, a methoxymethyl group, or an ethoxymethyl group, or one of them is a methoxymethyl group. or when one is a methyl group, the other is hydrogen, or when one is a methyl group, the other is a methoxymethyl or ethoxymethyl group, or when one is an ethyl group, the other is hydrogen. hydrogen, methoxymethyl group or ethoxymethyl group, R_5 is hydrogen, methyl group or propyl group, 0≦m≦4, 0≦n≦4, and 1
≦m+n≦4. 1. A non-adsorptive penetration treatment agent characterized by containing as an active ingredient one or more kinds of six-membered ring boric acid esters (hereinafter referred to as predetermined boric acid esters) represented by: (2) A given boric acid ester is [{2-(2-methoxypropyloxy)propyl}=butylene-1,3-]=
The non-adsorptive penetrant treatment agent according to claim 1, which is a borate. (3) If a given boric acid ester is (2-butoxyethyl=
2-Methylpentylene, -2,4-) = borate, non-adsorptive infiltration treated according to claim 1. (4) The non-adsorptive penetrant treatment agent according to claim 1, wherein the predetermined boric acid ester is [{2-(2-methoxyethyloxy)ethyl}=butylene-1,3-]=borate. (5) The non-alcoholic acid ester according to claim 1, wherein the predetermined boric acid ester has a residue of a 1 molar propylene oxide adduct of terpeol and a residue of 2-methyl-2,4 pentanediol. Adsorbent penetration treatment agent. (6) A predetermined boric acid ester is a residue of a 2 mole ethylene oxide adduct of tetrahydrofurfuryl alcohol and 1
, 3-butanediol. 3-Butanediol.