JPH07768B2 - Polish composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention reduces troubles of electrical contacts caused by a polish composition, particularly low-molecular siloxane, and poisons a platinum catalyst for exhaust gas combustion in a deodorizing device. The present invention relates to a silicone emulsion-based polish composition that can reduce the amount of water and impart a unique clearing effect to silicone with deep transparency.

[Prior Art] Silicone oils, which are mainly composed of organopolysiloxane, give various solid surfaces a clean luster and a smooth texture. Therefore, they can be soaked in cloth as they are, or emulsified and dispersed in water, or What is dissolved in a solvent is used as a polish, and when it is added to a conventional polish with wax as the main ingredient, it retains good gloss and does not easily get dirty, so it is also used as a raw material for polish. It is used.

[Problems to be Solved by the Invention] However, since the silicone oil mainly composed of this organopolysiloxane contains a small amount of low-molecular-weight siloxane at the time of its production, this silicone oil is always used. For example, when applying a matte polish to the surface of printed matter that has been offset printed or the surface of a coated article,
This small amount of low-molecular-weight siloxane volatilizes into the atmosphere, and after a long time, this accumulated substance poisons the platinum catalyst and rhodium catalyst for exhaust gas combustion installed in the deodorizing device, and its life is extended. There is a problem of damaging it.

Therefore, when a conventionally known wax type wax containing mainly hydrocarbon is used as the polishing agent, the catalyst life of the deodorizing device can be maintained for at least 3 years because the poisoning is small. On the other hand, when a silicone-based polish is used, it needs to be renewed in about two years, which causes a problem that it costs a considerable amount. In addition, like a small relay of a small motor, 50V
There is also a problem that contact problems may occur due to volatilization of the low-molecular siloxane when it is close to a weak electrical component that uses the following voltage and a current of 500 mA or less.

Therefore, in order to avoid such disadvantages, it is only necessary to use a polish with a hydrocarbon-based fatty acid wax, but this type of polish has the same depth as a polish with silicone oil. , I can't get a transparent and unique luster. This also has the disadvantage that it does not provide the benefits of silicone polishes such as better luster retention and less dirt.

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

That is, the present inventors have variously studied to develop a silicone emulsion-based polish which reduces poisoning of a platinum catalyst for exhaust gas combustion such as a deodorizing device and reduces contact troubles of electric devices, and as a result, these disadvantages are found. Since it is based on the presence of the low-molecular siloxane contained in the organopolysiloxane, there is an allowable amount of this low-molecular siloxane in order to avoid such a disadvantage.
It was found that this was 50 ppm or less for each siloxane having 12 or less siloxane units, and that the total amount of these should be 500 ppm or less, and a study on a method for keeping the amount of this low-molecular siloxane present within this allowable range To complete the present invention.

[Working] The polish composition of the present invention is considered to be a silicone emulsion type because it gives a unique gloss with depth and transparency. This silicone emulsion emulsifies an organopolysiloxane oil. It is supposed to be.

This organopolysiloxane oil has the general formula R ¹ represents a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, an alkyl group such as an octyl group, a vinyl group, an alkenyl group such as an allyl group, a phenyl group, an aryl group such as a tolyl group, and the like. A group selected from monovalent hydrocarbon groups, R ² and R ³ are the same or different monovalent organic groups, respectively, and are the same monovalent hydrocarbon groups, amino group-containing organic groups, and polyether group-containing organic groups as R ^1. , A group selected from an epoxy group-containing organic group, R ⁴ is a hydrogen atom, the same monovalent organic group as R ² or R ³ , a group selected from a hydroxyl group, and 1 is a polysiloxane oil having a viscosity of 50 to 100,000 cS. Shall be a positive integer. It is preferable that the end of the molecular chain of this is blocked with a trimethylsilyl group, and the above R ^{1 to} R ³ can be easily synthesized and the stability of the resulting glossy coating is 95%. It is preferred that up to mol%, more preferably all are methyl groups, said R ⁴
The compound (3) is most preferably a methyl group because it is easy to synthesize and the intermediate raw material is easily available. However, with respect to this dimethylpolysiloxane oil, if the viscosity at 25 ° C is less than 50 cS, the polish made from this will not give the deep gloss unique to silicone oil, and the gloss retention will also deteriorate, and further, it will not be contained. It will be difficult to keep the total amount of low-molecular-weight siloxane to be 500 ppm or less, and if it is more than 100,000 cS, the polish produced from this will become inferior,
This is 25 as it becomes sticky after application.
Viscosity at 50 ° C must be 50-100,000 cS.

Such organopolysiloxane oil may be produced by a conventionally known method. For example, dimethylpolysiloxane oil may be produced by adding a low molecular cyclic siloxane such as octamethylcyclotetrasiloxane or decamethylcyclopentasiloxane to sulfuric acid. , Chlorosulfonic acid, nitric acid,
Acidic catalysts such as phosphoric acid, activated clay, acid clay, trifluoroacetic acid, potassium hydroxide, sodium hydroxide,
The ring-opening reaction may be carried out in the presence of an alkaline catalyst such as rubidium hydroxide, cesium hydroxide, potassium oxide, potassium acetate, calcium silanolate and the like, followed by polymerization. In order to obtain a dimethylpolysiloxane having a desired viscosity by controlling the degree of polymerization, a low molecular weight siloxane having a terminal blocking group such as hexamethyldisiloxane, octamethyltrisiloxane and decamethyltetrasiloxane should be appropriately added during this polymerization. Good.

The organopolysiloxane containing a carbon functional group, for example, an amino group-containing organopolysiloxane is synthesized by a dealcoholization condensation reaction between an organopolysiloxane containing one or more silanol groups and an amino group-containing alkoxysilane. The organopolysiloxane containing an epoxy group or a polyether group is an organohydrogen group containing a hydrogen atom in which a compound containing an epoxy group or a polyether group and an unsaturated group such as a vinyl group in the same molecule is bonded to a silicon atom. It may be synthesized by an addition reaction using a diene polysiloxane and a platinum catalyst.

However, since the organopolysiloxane oil obtained by these methods becomes an equilibrium mixture of polysiloxanes having various degrees of polymerization in its synthesis process, it usually contains as much as 10% of low-molecular siloxanes having 12 or less siloxane units. The general formula for this low-molecular-weight siloxane is R ⁵ is a hydrogen atom, a same or different group selected from a methyl group or an ethyl group, R ⁶ is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a vinyl group or a hydroxyl group, m
Is an integer of 0 to 10, for example, low molecular chain siloxanes such as hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, hexadecamethylheptasiloxane, and the general formula And R ⁷ is a hydrogen atom, a methyl group, an ethyl group, a phenyl group, a same or different group selected from a vinyl group, and n is an integer of 3 to 12, for example, hexamethylcyclotrisiloxane, Octamethylcyclotetrasiloxane, 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,
1-diphenylhexamethylcyclotetrasiloxane,
Examples are low molecular cyclic siloxanes such as decamethylcyclopentasiloxane, 1,1-diphenyloctamethylcyclotetrasiloxane, dodecamethylcyclohexasiloxane.

Therefore, organopolysiloxane oils made by the above method are usually stripped under reduced pressure after synthesis at temperatures of 120-250 ° C. to remove these low molecular siloxanes. However, in such a treatment, low-molecular-weight siloxane is still 500 to 2
Remaining 0,000 ppm, these have particularly strong adsorptivity compared to other non-polar combustible gases, and impede the contact between non-polar combustible gas and catalysts such as platinum to reduce the catalytic performance of platinum catalysts. Then, the low-molecular-weight siloxane adsorbed here gradually undergoes catalytic oxidation to become SiO ₂ · nH ₂ O → αSiO ₂ , which is deposited on the catalyst surface and deteriorates the performance of the catalyst. This tendency is due to alumina, silica, titania, which has a strong bond with silicone,
It is also said that pellets using zirconia or the like as a carrier material and honeycomb type catalysts are likely to occur.

The present invention relates to a silicone emulsion-based polish which has solved such disadvantages, and as described above, the content of each low-molecular siloxane having 12 or less siloxane units is 50 ppm or less. It is obtained by emulsifying the above-mentioned organopolysiloxane,
This is based on the new finding found by the present inventors that the above-mentioned disadvantageous low-molecular-weight siloxane does not cause such a disadvantage if it is a small amount of 50 ppm or less. This low-molecular-weight siloxane can be removed by stripping the organopolysiloxane oil produced by the above method under a reduced pressure of 50 mmHg or less at a high temperature of 150 to 300 ° C. in a dry nitrogen gas atmosphere, or by adding it to the organopolysiloxane oil. The low molecular weight siloxane may be extracted with an alcohol or ketone solvent. The organopolysiloxane oil thus produced can contain each low-molecular siloxane contained therein in an amount of 50 ppm or less.
The total amount of all low molecular weight siloxanes that are 2 can also be 500 ppm or less. When a silicone emulsion obtained by emulsifying this is used as a glossing agent, it gives a unique silicone gloss with depth and transparency because it is a silicone type, and it has good gloss retention and stains. It becomes difficult to stick. Further, there is an advantage that a catalyst such as platinum in the deodorizing device is not poisoned and contact trouble of electric equipment is not caused.

The organopolysiloxane oil is emulsified and used as a silicone emulsion to give a polish, but the emulsifier used for emulsifying the organopolysiloxane oil does not need to be specified. These include those conventionally used for emulsifying silicone compounds, such as long-chain alkyl sulphates, alkyl sulphonates, anionic surfactants such as sodium polyoxyethylene alkyl-phenyl ether sulfate; polyoxyethylene alkyl phenyl ethers, polyoxy It may be appropriately selected from nonionic surfactants such as ethylene alkyl ether and sorbitan monoester; and cationic surfactants such as etolaalkylammonium salt. However, if the amount of this emulsifier is less than 1 part by weight per 100 parts by weight of the organopolysiloxane oil, the stability of the emulsion becomes poor, and if it is more than 30 parts by weight, the transparent luster of this composition is obtained. Since it is impaired, the addition amount should be in the range of 1 to 30 parts by weight, preferably 5 to 15 parts by weight with respect to the organopolysiloxane oil. Further, in the emulsification of this organopolysiloxane oil, water is added to this system, but if the amount added is 15 parts by weight or less, it becomes difficult to emulsify, while if it is 5,000 parts by weight or more, When the resulting composition is applied, the amount of siloxane attached to the treated surface is too small, and the effect as a polish is reduced, so this is 15 to 5,000 parts by weight,
It is preferably in the range of 150 to 600 parts by weight.

The silicone emulsion composition made by the above method is particularly useful as a polish, which has the purpose of:
Various additives such as flavors, colorants, and preservatives may be appropriately added depending on the application.

[Examples] Next, synthesis examples, examples, and comparative examples of the organopolysiloxane oil for producing the polish of the present invention will be described.
The parts in the examples are parts by weight, the viscosity is the value measured at 25 ° C., and the physical properties of the silicone emulsion in the examples are the values measured by the following methods.

(Gloss) The 60-degree specular gloss was measured according to the JIS Z8741 gloss measurement method.

(Noby) Measured with or without resistance when applying vinyl chloride leather surface with gauze.

No resistance… ○, resistance… × (sticky) Judgment based on the feel of the processed surface.

No stickiness… ○, Sticky feeling… ×, Middle stickiness… △.

Synthetic 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, passed, and depressurized to 50 mmHg in a dry nitrogen gas atmosphere. When stripped down at 180 ° C. for 4 hours, a dimethylpolysiloxane oil (hereinafter abbreviated as A-1) having a viscosity of 500 cS in which a molecular chain end was blocked with a trimethylsilyl group was obtained.

Then, this dimethylpolysiloxane oil A-1 was stripped in a dry nitrogen gas atmosphere at a reduced pressure of 10 mmHg at 280 ° C. for 8 hours, and the amount of low-molecular siloxane was further reduced (hereinafter abbreviated as A-2). ) Is prepared, and this dimethylpolysiloxane oil A-1 is extracted and washed twice with ethanol, and then stripped under the same conditions as above to obtain dimethylpolysiloxane oil (hereinafter abbreviated as A-3). Had made.

Next, add 1 g of this dimethylpolysiloxane oil A-1 to A-3 to 10 m.
It was soaked and extracted in l of ethanol for 24 hours, and the low-molecular siloxane was quantified using a temperature-increasing gas chromatogram with decamethylcyclopentasiloxane (purity 99.5% or more) as a standard substance. The results were as shown.

Example Dimethyl polysiloxane oil A-1 to A-3 2 produced in the synthesis example
To 50 parts, add 20 parts of polyoxyethylene) nylphenyl ether with HLB of 13.8 and 730 parts of water, emulsify them with a homomixer, and pass through a Gaurin homogenizer at a pressure of 316 kg / cm ² (4,500 psi). And homogenized to prepare silicone emulsions E-1 to E-3.

Then, this emulsion was coated on a commercially available black vinyl chloride leather with gauze and the surface was lightly wiped 10 times. The physical properties of this treated surface were examined. The results shown in Table 2 below were obtained. It was

Next, each of these emulsions E-1 to E-3 was separately applied to a printing paper surface that was offset-printed continuously with an offset rotary press / Isovia [trade name of Mitsubishi Heavy Industries, Ltd.] The change over time in the content (ppm) of silicon atoms contained in the combustor catalyst gave the results shown in Table 3. The catalyst in this combustor contained platinum on alumina of 1.8%. It was loaded at a concentration of g / and had a volume of 150. Emulsion E
In the equipment that used -1 as a polish, the activity of the catalyst decreased significantly in the second year, so it was necessary to suspend the operation of the equipment to renew the platinum catalyst, but emulsion E-2, E-3 The device using the slag as a polish has a relatively small decrease in catalytic activity, and thus could be continuously operated.

[Effects of the Invention] As described above, the polish of the present invention has a low-molecular siloxane content of 12 or less siloxane units.
It is characterized by comprising a silicone emulsion obtained by emulsifying an organopolysiloxane oil having a viscosity of 50 to 100,000 cS, which is 50 ppm or less, but this one has the number of siloxane units contained in this organopolysiloxane oil. Since each low molecular siloxane of 2 to 12 contains only 50 ppm or less, it is made from the conventional organopolysiloxane oil containing 500 to 20,000 ppm of this low molecular siloxane. The silicone emulsion type polishing agent poisoned the exhaust gas combustion platinum catalyst etc. installed in the deodorization device and caused contact troubles of electrical equipment, but avoid this kind of trouble. It has the industrial advantage of being capable of producing hydrocarbons, and since it is also of the silicone emulsion type, it is a hydrocarbon type wax. Depth than like polishes with box, giving a silicone unique luster sense of transparency may be retention of gloss, those having the advantage that dirt less likely month.

Claims (1)

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