JPH02308875A - Polishing agent composition - Google Patents

Abstract

PURPOSE:To provide the title composition capable of giving polish with both depth and transparency unique to silicone, good in polish retentivity and resistant to soiling, comprising a silicone emulsion prepared by emulsifying a specific organopolysiloxane oil. CONSTITUTION:The objective-composition comprising a silicone emulsion prepared by emulsifying an organopolysiloxane oil 50-100000cS in viscosity at 25 deg.C with the contents of respective low-molecular weight siloxanes <=12 in siloxane unit number being <=50ppm [e.g. a compound of the formula (R1 is alkyl, alkenyl or aryl; R2 and R3 are each monovalent organic group: R4 is H or monovalent organic group; l is positive integer)].

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention reduces troubles in electrical contacts caused by polishing agent compositions, particularly low-molecular siloxanes, and also prevents poisoning of platinum catalysts for exhaust gas combustion in deodorizing equipment. The present invention relates to a silicone emulsion-based polishing agent composition that provides a deep and transparent polishing effect unique to silicone, which can reduce

[Prior art] Silicone oil, which is mainly composed of organopolysiloxane, gives a beautiful luster and smooth texture to various solid surfaces, so it can be soaked in cloth as it is, or dispersed in water, or treated with organic solvents. It is also used as a polishing agent when added to conventional wax-based polishing agents, which improves gloss retention and makes stains less likely to stick. has been done.

[Problems to be Solved by the Invention] However, since silicone oil mainly composed of organopolysiloxane always contains a small amount of low-molecular-weight siloxane during its manufacture, For example, when a polishing agent is applied to the surface of offset printed matter or the surface of a painted object,
This small amount of low-molecular-weight siloxane will volatilize into the atmosphere, and over a long period of time, this accumulation will poison the platinum catalyst and mouthpiece catalyst installed in the deodorizing device for exhaust gas combustion, reducing their lifespan. There is a problem of damaging the

Therefore, when using a conventionally known wax-based polishing agent mainly composed of hydrocarbons, there is no such poisoning and the catalyst life of this deodorizing device can be maintained for at least 3 years. If a silicone-based polish is used, it will need to be renewed every two years or so, which costs a considerable amount of money. There is also the problem that contact trouble occurs due to volatilization of this low-molecular-weight siloxane when it is close to light electrical parts that use voltage and current of less than 500 mA.

Therefore, in order to avoid such disadvantages, it is sufficient to use a polishing agent that uses hydrocarbon-based fatty acid wax, etc., but this type of polishing agent does not have the depth of polishing agent that uses silicone oil. However, it is not possible to obtain a unique gloss with transparency, and this has the disadvantage that it does not have the advantages of good gloss retention and resistance to staining, which are the advantages of silicone polishing agents.

[Means for Solving the Problems] The present invention relates to a silicone emulsion-based polishing agent composition that solves the above disadvantages and disadvantages, and is characterized in that the content of each low-molecular-weight siloxane having 12 or less siloxane units is is 50 ppm or less, and the silicone emulsion is formed by emulsifying an organopolysiloxane oil having a viscosity of 50 to 100,000 cS at 25°C.

In other words, the present inventors conducted various studies to develop a silicone emulsion-based polishing agent that reduces the poisoning of platinum catalysts for exhaust gas combustion in deodorizing devices and other devices, and reduces contact troubles in electrical equipment. Since this is based on the presence of low-molecular-weight siloxane contained in organopolysiloxane, there is a permissible amount of low-molecular-weight siloxane in order to avoid such disadvantages.
This is 50 ppm or less for each siloxane having 12 or less siloxane units, and the total amount is 50 ppm or less.
In addition to discovering that it is sufficient as long as it is 0 ppm or less,
The present invention was completed by conducting research on a method for reducing the amount of low-molecular-weight siloxane to below this permissible range.

[Function] The polishing agent composition of the present invention is said to be a silicone emulsion type because it gives a unique luster with depth and transparency, but this silicone emulsion emulsifies organopolysiloxane oil. It is assumed that

This organopolysiloxane oil is represented by the general formula, R1
From monovalent hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, butyl, amyl, and octyl groups, alkenyl groups such as vinyl and allyl groups, and aryl groups such as phenyl and tolyl groups. selected groups, R2,
R3 is the same or different organic group, a group selected from the same monovalent hydrocarbon group as R1, an amino group-containing organic group, a polyether group-containing organic group, and an epoxy group-containing organic group, R4 is a hydrogen atom , the same one organic group as R2 or R3, and a group selected from a hydroxyl group, and C is a positive integer such that the polysiloxane oil has a viscosity of 50 to 100,000 cS. It is preferable that the molecular chain terminal of this product is blocked with a trimethylsilyl group, and 95 mol% of the above R1-R3 is considered from the viewpoint of ease of synthesis and stability of the resulting glossy film.
More preferably, all of the above are methyl groups, and the above R4 is most preferably a methyl group because it is easy to synthesize and the intermediate raw materials are easily available. However, if the viscosity of this dimethylpolysiloxane oil at 25°C is lower than 50cS, the polishing agent made from it will not have the deep gloss unique to silicone oil, and its gloss retention will be poor. It becomes difficult to reduce the total amount of low-molecular-weight siloxane to 500 ppm or less;
If it is larger than .000 cs, the polishing agent to be made will not spread well and will feel sticky after application, so it is necessary to have a viscosity of 50 to 10Q., 000 cs at 25°C. There is.

Such an organopolysiloxane oil can be manufactured by a conventionally known method. For example, dimethylpolysiloxane oil can be manufactured by converting a low molecular weight cyclic siloxane such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane into sulfuric acid. , chlorosulfonic acid, nitric acid,
Acidic catalysts such as phosphoric acid, activated clay, acid clay, trifluoroacetic acid, or potassium hydroxide, sodium hydroxide, rubidium hydroxide, cesium hydroxide, potassium oxide,
This can be carried out by carrying out a ring-opening reaction in the presence of an alkaline catalyst such as potassium acetate or potassium syralate, followed by polymerization, or by controlling the degree of polymerization of the resulting dimethylpolysiloxane to achieve the desired viscosity. In order to obtain dimethylpolysiloxane having the following properties, a low molecular weight siloxane having an end-capping group such as hexamethyldisiloxane, octamethyltrisiloxane or decamethyltetrasiloxane may be appropriately added during the polymerization.

Note that organopolysiloxanes containing carbon functional groups, such as organopolysiloxanes containing amino groups, are synthesized by dealcoholization condensation reaction of organopolysiloxanes containing one or more silanol groups and alkoxysilanes containing amino groups. Organopolysiloxane containing an epoxy group or a polyether group is a compound containing an epoxy group or a polyether group and an unsaturated group such as a vinyl group in the same molecule, and an organohydrocarbon containing a hydrogen atom bonded to a silicon atom. It can be synthesized by addition reaction using diene polysiloxane and a platinum catalyst.

However, since the organopolysiloxane oil obtained by these methods becomes an equilibrium mixture of polysiloxanes with various degrees of polymerization during the synthesis process, it usually contains nearly 10% of low-molecular-weight siloxanes with 12 or less siloxane units. This low molecular weight siloxane is represented by the general formula, where R5 is a hydrogen atom, a methyl group or an ethyl group,
R6 is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a vinyl group, or a hydroxyl group, and m is an integer of O to 10, such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexadecamethylheptasiloxane Low molecular chain siloxanes such as
Further, it is represented by the general formula, R7 is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, or a vinyl group, and n is an integer of 3 to 12, for example, hexamethylcyclotrisiloxane,
Octamethylcyclotetrasiloxane, 1.1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1.1-diphenylhexamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 1.1-diphenyloctamethyl Examples include low molecular weight cyclic siloxanes such as cyclotetrasiloxane and dodecamethylcyclohexasiloxane.

Therefore, the organopolysiloxane oil produced by the above method is usually stripped after synthesis at a temperature of 120 to 250°C under reduced pressure to remove these low-molecular-weight siloxanes. Siloxane is still 500-20. OOOppm also remains, and these have particularly strong adsorption properties and impede the catalytic reaction with other non-polar combustible gases, reducing the performance of catalysts such as platinum catalysts.
The silicone adsorbed here is gradually catalytically oxidized to 5i
n2・nH2O→α5in2, which accumulates on the catalyst surface and reduces the oxidation performance of the catalyst.
It is said that this phenomenon tends to occur in honeycomb catalysts.

The present invention relates to a silicone emulsion polishing agent that solves these disadvantages, and as described above, the content of each low molecular weight siloxane having 12 or less siloxane units is 50 ppm or less. , is made by emulsifying the organopolysiloxane described above, and the present inventor believes that the low molecular weight siloxane that causes the disadvantages described above will not cause such disadvantages if it is contained in a small amount of 50 ppm or less. This is based on the new knowledge discovered by et al., but the removal of this low-molecular-weight siloxane can be done by stripping the organopolysiloxane oil under a reduced pressure of 50 mmHg or less and at a high temperature of 150 to 300 °C in a dry nitrogen gas atmosphere. This may be carried out by extracting the low-molecular-weight siloxane contained in this organopolysiloxane oil with an alcohol-based or ketone-based solvent. The organopolysiloxane oil from which low-molecular-weight siloxanes have been removed in this way can have a content of each low-molecular-weight siloxane contained therein at 50 ppm or less, and can contain all low-molecular-weight siloxanes containing 2 to 12 siloxane units. The total amount of siloxane must be kept at 500 ppm or less, so if a silicone emulsion obtained by emulsifying this is used as a polishing agent, since it is a silicone-based polishing agent, it will produce a deep and transparent luster unique to silicone. This product has the advantage of retaining its luster well, being resistant to stains, and not poisoning catalysts such as platinum in deodorizing equipment or causing contact problems in electrical equipment. It will be done.

This organopolysiloxane oil is emulsified and used as a silicone emulsion as a polishing agent, but the emulsifier used to emulsify this organopolysiloxane oil does not need to be specified; Those used in emulsification, such as long-chain alkyl sulfates, alkyl sulfonates, anionic surfactants such as polyoxyethylene alkylphenyl ether sodium sulfate; polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, sorbitan monoester, etc. Nonionic surfactants such as: or cationic surfactants such as tetraalkylammonium salts may be selected as appropriate. However, if the amount of this emulsifier is less than 1 part by weight per 100 parts by weight of organopolysiloxane oil, the stability of the emulsion will deteriorate, and if it is more than 30 parts by weight, the transparent gloss of this composition will deteriorate. Therefore, the amount added is preferably in the range of 1 to 30 parts by weight, preferably 5 to 15 parts by weight, based on the organopolysiloxane oil. Also,
When emulsifying this organopolysiloxane, water is added to the system, but if the amount added is less than 15 parts by weight, emulsification will be difficult, whereas if it is more than s, ooo parts by weight, water can be obtained. After applying the composition, the amount of siloxane deposited on the treated surface will be too small and the effect as a polishing agent will be reduced. It is preferable to do so.

The silicone emulsion compositions made by the method described above are particularly useful as polishes;
Depending on the purpose, various additives such as fragrances, colorants, preservatives, etc. may be added as appropriate.

[Example] Next, examples of synthesis, examples, and comparative examples of organopolysiloxane oil for producing the polishing agent of the present invention will be given.
The parts in the examples are parts by weight, the viscosity is the value measured at 25°C, and the physical property values of the silicone emulsion in the examples are the values measured by the following method.

(Gloss) The 60 degree specular gloss was measured according to the gloss measurement method of JIS 28741.

(Spread) Measured by the presence or absence of resistance when applying gauze to the vinyl chloride leather surface.

No resistance/feeling...○, resistance...×(stickiness) Judging by feeling the treated surface with your fingers.

No sticky feeling...○, Sticky feeling...X.

Medium stickiness...△.

Synthesis Example A mixture of 990.5 parts of octamethylcyclotetrasiloxane and 9.5 parts of hexamethyldisiloxane was subjected to ring-opening polymerization using a sulfuric acid catalyst, neutralized with sodium carbonate, filtered, and dried with nitrogen gas. When stripped for 4 hours at 180°C under reduced pressure of Ig (50 mm) in ashes, the molecular chain terminals were blocked with trimethylsilyl groups and the viscosity was 500 cS.
dimethylpolysiloxane oil (hereinafter abbreviated as A-1)
was gotten.

Next, this dimethylpolysiloxane oil A-1 was stripped in a dry nitrogen gas atmosphere to a thickness of 10 mm) at 280°C for 8 hours under a reduced pressure of 1g) to obtain a dimethylpolysiloxane oil (hereinafter referred to as A-2) with a further reduced amount of low molecular weight siloxane. This dimethylpolysiloxane oil (hereinafter abbreviated as A-3) was prepared, and the dimethylpolysiloxane oil-1 was extracted and washed twice with ethanol, and then stripped under the same conditions as above. ) was created.

Next, this dimethylpolysiloxane oil-1 to 8-31
g was extracted by immersion in 10 mA ethanol for 24 hours, and the low-molecular-weight siloxane was quantified using temperature-programmed gas chromatography using decamethylcyclopentasiloxane (purity 99.5% or more) as a standard substance. The results shown in Table 1 were obtained.

Table 1 Dimethylpolysiloxane oils A-1 to A produced in Synthesis Examples
- To 3250 parts, 20 parts of polyoxyethylene nonylphenyl ether with an HLB of 13.8 and 730 parts of water were added, and these were emulsified with a homomixer to produce a 316 kg/c
The silicone emulsion E-
1 to E-3 were prepared.

Next, this emulsion was applied to a commercially available black vinyl chloride leather using gauze, and this surface was lightly wiped <10 times. When the physical properties of this treated surface were examined, the results were obtained as shown in Table 2 below. It was done.

Table 2 Next, this emulsion E-I NF-3 was separately coated on the printed paper surface which was offset printed with an offset rotary press, Isopia [Mitsubishi Heavy Industries ■Tearing product name], and was placed in the exhaust gas deodorizing device and the combustion device. The content of silicon atoms (p
When we investigated the change in pm) over time, we obtained the results shown in Table 3. The catalyst in this combustion device was platinum in alumina at 1.8 g/j! Emulsion E-1 was supported at a concentration of 150 J2, but the catalyst activity of the equipment using Emulsion E-1 as a polishing agent decreased significantly in the second year, so the operation of the equipment was stopped. Although it was necessary to interrupt the process and replace the platinum catalyst, the apparatuses using emulsions E-2 and E-3 as polishing agents were able to continue operating because the decrease in catalyst activity was relatively small.

Table 3 [Effects of the Invention] As described above, the polishing agent of the present invention has a viscosity of 50 to 100.000, in which the content of low molecular weight siloxane having 12 or less siloxane units is 50 ppm or less, respectively.
This product is characterized by being made of a silicone emulsion formed by emulsifying cS organopolysiloxane oil, and this product contains various low-molecular-weight siloxanes containing 2 to 12 siloxane units in this organopolysiloxane oil. All of these products contain only 50 ppm or less of this low-molecular-weight siloxane, so 500 to 20,000 ppm of this low-molecular-weight siloxane
Conventional silico-emulsion polishing agents made from organopolysiloxane oils that contain PM amounts can poison platinum catalysts for exhaust gas combustion installed in deodorizing equipment. It has the industrial advantage of being able to avoid this kind of trouble, whereas it used to cause contact troubles in electrical equipment, and since it is a silicone emulsion type, it is carbonized. Compared to polishes using hydrogen-based waxes, etc., silicone has the advantage of providing a deep, transparent gloss unique to silicone, retaining the gloss well, and being resistant to stains.

Claims (1)

[Claims] 1. At 25°C, the content of each low molecular weight siloxane having 12 or less siloxane units is 50 ppm or less.
1. A polish composition comprising a silicone emulsion obtained by emulsifying an organopolysiloxane oil having a viscosity of 50 to 100,000 cS.