JPS6124425B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a polishing agent, and particularly to a polishing agent that forms a strong glossy film on a painted metal surface and has excellent wash resistance. Moreover, the present invention
The present invention relates to a method for producing such a polishing agent. Conventionally, polishing agents have mainly been wax-based, which can be dissolved in a solvent or emulsified in water using a surfactant, and if necessary, a polishing agent or spray agent can be added. It is used as a spray or in various shapes, and silicone oils such as dimethyl silicone oil or methylphenyl silicone oil are added to improve the gloss effect and workability. Ta. The polishing effect obtained by adding such silicone oil is inferior in durability and wash resistance. On the other hand, it is known that a polishing agent with excellent durability and wash resistance can be obtained by adding an amino group-containing polyorganosiloxane, but this reacts with wax, which is the main component of the polishing agent. It has the disadvantage of making wax fluid. Another drawback is that the amino group-containing polyorganosiloxane crosslinks and forms a film, which peels off and becomes scum when a polishing agent is next applied, and the scum cannot be easily removed. Furthermore, in order to suppress the reaction between amino group-containing polyorganosiloxane and wax, there is a proposal to use a reaction product of the siloxane and a dibasic acid (Japanese Patent Application Laid-open No. 103388/1983). As a result, one of the disadvantages of polishing agents using amino group-containing polyorganosiloxane mentioned above, in that they fluidize the wax, has been solved, but the disadvantage is that scum accumulates during repeated applications and cannot be easily removed. is left behind. As a result of continuing research aimed at creating a silicone-containing polish that provides a film with excellent gloss durability and wash resistance and does not leave any residue, the inventor discovered that silicone oil and a polyorganosiloxane resin with a specific structure have been developed. The present inventors have discovered that a polishing agent that satisfies the objective can be obtained by combining the following, and have thus completed the present invention. That is, the present invention provides a polishing agent containing a polyorganosiloxane, in which (A) the terminal consists of HOR ¹ ₂ SiO _1/2 units or R ¹ ₃ SiO _1/2 units, and Siloxane units are 90~
Linear or branched, consisting of 100% R ² ₂ SiO units and the remaining R ² _a SiO〓〓〓 units (where a is 0 or 1) and having a viscosity of 30 to 1000 cSt at 25°C liquid polyorganosiloxane (wherein R ¹ and R ² each represent the same or different monovalent hydrocarbon group,
and (B) consists of ^R33SiO _1/2 units and _SiO2 units, _and is 50 to 97% by weight of the total polyorganosiloxane,
A benzene-soluble polyorganosiloxane resin having ⁴ OR groups bonded to atoms (where R ³ is the same or different monovalent hydrocarbon group, R ⁴
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 3 in the total polyorganosiloxane
50% by weight), and a polishing agent containing a polyorganosiloxane, wherein the polyorganosiloxane has (A) terminals of HOR ¹ ₂ SiO _1/ Consists of ₂ units or R ¹ ₃ SiO _1/2 units, with 90 to 90 siloxane units other than the terminals.
A linear or branched liquid consisting of 100% R ² ₂ SiO units and the remaining R ² _a SiO〓〓〓 units (where a is 0 or 1) and has a viscosity of 30 to 1000 cSt at 25°C. Polyorganosiloxane (wherein R ¹ and R ² each represent the same or different monovalent hydrocarbon group, and are 50 to 97% by weight of the total polyorganosiloxane), and (B) R ³ ₃ Consists of SiO _1/2 unit and SiO ₂ unit, Si
A benzene-soluble polyorganosiloxane resin having ⁴ OR groups bonded to atoms (where R ³ is the same or different monovalent hydrocarbon group, R ⁴
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 3 in the total polyorganosiloxane
~50% by weight) of the total polyorganosiloxane.
This is a method for producing a polishing agent, which includes a step of mixing (A) and (B) in an amount of 20 to 50% by weight based on the total polyorganosiloxane and heating the mixture. (A) used in the present invention is a polishing agent that imparts gloss and workability unique to silicone, and is a liquid polyorganic polyorganic resin having a linear or slightly branched structure and having R ² ₂ SiO units as the main structural unit. It is a siloxane and is generally called silicone oil. The terminal group may be a triorganosiloxy group, or some or all of the terminal groups may be a diorganohydroxysiloxy group. A substantially triorganosiloxy group is preferable because it can be easily obtained, it does not prevent (A) from being wrapped in the network structure of (B), and it is stable in the heating process. . R ¹ may be the same or different,
Alkyl groups such as methyl group, ethyl group, propyl group, butyl group, amyl group, hexyl group, octyl group, decyl group, dodecyl group, alkenyl group such as vinyl group, aryl group such as phenyl group,
Examples include aralkyl groups such as β-phenylethyl group and β-phenylpropyl group, but methyl group is most preferred since intermediate raw materials are easily obtained and synthesis is easy. R ² may be the same or different, and monovalent hydrocarbon groups similar to those exemplified as R ¹ are exemplified, but they are easy to synthesize and have good spreadability during coating. From the viewpoint of good workability and good gloss, it is preferable that methyl groups or a portion thereof be phenyl groups, and it is particularly preferable that substantially all of them are methyl groups. Among the structural units of (A), 90 to 100% of the units excluding the terminal group are such R ² ₂ SiO units,
The remaining units include R ² SiO _3/2 and SiO ₂ units. In order to easily obtain a controlled viscosity, linear polydiorganosiloxanes having substantially 100% R ² ₂ SiO units are preferred, but
Even if R ² SiO _3/2 units or SiO ₂ units are present in amounts up to 10%, there is no particular effect on gloss or elongation. R2SiO3 _/ ²
If the amount of units or SiO ₂ units exceeds 10%, it becomes difficult to synthesize. The viscosity is not particularly restricted, but 25
Select a range of 30 to 1000 cSt at °C. 30cSt
If it is less than that, the gloss will be poor and the durability will be poor. In particular, if it is less than 10 cSt, the volatility becomes large, which is not preferable. On the other hand, if it exceeds 1000 cSt, the viscosity of the entire system increases and workability deteriorates. In addition, especially those of 200 cSt or less have good affinity with the polyorganosiloxane resin (B), and after mixing with (B) and heating, (B)
When adopting the manufacturing method of the present invention,
It has a great effect of increasing the durability and wash resistance of the polishing agent. (B) used in the present invention has a
By forming a film that envelops (A), it imparts gloss durability and wash resistance to the polishing agent. R ³ may be the same or different, and examples thereof include methyl group, vinyl group, and phenyl group, but they should be easy to synthesize and do not interfere with wrapping (A) into a network structure. In particular, a methyl group is preferred because it facilitates film formation. In addition, as the ^OR4 group bonded to the Si atom, in addition to the hydroxyl group, an alkoxy group that can be easily hydrolyzed such as a methoxy group, an ethoxy group, and a propoxy group is selected, and they may be the same or different. . The number of carbon atoms in R ⁴ is 4
The above is not preferable because the reactivity decreases.
The amount of R ³ ₃ SiO _1/2 units per mole of SiO ₂ units is:
The range is preferably from 0.4 to 1.0 mol, and more preferably from 0.5 to 0.8 mol. If it is less than 0.4 mol, it is difficult to stably obtain a benzene-soluble low-molecular compound, and it tends to gel during synthesis or storage, resulting in an insoluble and infusible polymer. Moreover, if it exceeds 1.0 mol, the durability of the gloss and the wash resistance of the surface coated with the polishing agent cannot be obtained. Such polyorganosiloxane resin (B) is
A tetrafunctional silicon compound selected from alkyl silicates such as ethyl silicate and propyl silicate, their partial hydrolysates, silicon tetrachloride, and water glass is mixed with trimethylchlorosilane, dimethylvinylchlorosilane, and dimethylphenyl in the presence of a solvent. It is obtained in the form of a solution by cohydrolysis with a triorganochlorosilane such as chlorosilane and removal of the by-products by conventional means. Hydrocarbons such as benzene, toluene, xylene, gasoline, n-hexane, and n-heptane are generally used as the solvent. The polishing agent of the present invention contains (A) in an amount of 50 to 97% by weight, preferably 50 to 80% by weight as a polyorganosiloxane.
A mixture containing (B) in a range of 3 to 50% by weight, preferably 20 to 50% by weight is used. If (A) is less than 50% by weight, the viscosity of the entire product increases, resulting in poor workability, and also tends to produce scum during repeated use. If (A) exceeds 97% by weight, the durability of gloss and wash resistance will deteriorate. To produce the polishing agent of the present invention, polyorganosiloxanes (A) and (B) may be mixed separately with components other than polyorganosiloxane, or
A mixture of (A) and (B) may be mixed with other components. Furthermore, during this mixing step, add a step of heating after mixing part or all of (A) so that (A) is 50 to 80% by weight and (B) is 20 to 50% by weight. As a result, (A) and (B) blend well together, and the chain-like or slightly branched molecules of (A), which are effective for the polishing effect, are wrapped in the network molecular structure of (B), which increases the durability of the gloss of the polishing agent. It has been found that the effect of improving wash resistance is particularly remarkable. If the proportion of (B) in the polyorganosiloxane to be mixed and heated is less than 20% by weight, it will be insufficient to form a film that envelops (A), and the durability of gloss and wash resistance will not improve. It is lower than when it is more than % by weight. In addition, since (B) is usually obtained as a solution of a hydrocarbon solvent, it is more efficient to add a predetermined amount of (A) to it and heat it under normal pressure or reduced pressure to remove the solvent. However, it is preferable to heat the solvent under reflux and then remove the solvent by heating under reduced pressure. The heating temperature is
A range of 100 to 200°C is preferred. Heating temperature is 100℃
This is because if it is less than 200°C, the effect of heating the mixture is low, and even if it exceeds 200°C, no significant increase in the effect is expected. If the solvent is xylene, for example 30Torr
If heated at 130°C, (A) and (B) can be blended together and the solvent can be removed, and a temperature range of 120 to 150°C is suitable. The polish of the present invention is prepared by mixing (A) and (B), preferably premixed and heated (A) and (B), with other ingredients. That is, solid or pasty polishing agents include waxes such as carnauba wax, beeswax, solid paraffin, and montan wax, solvents such as mineral turpentine, gasoline, mineral spirits, and kerosene, and fragrances and colors as necessary. The polyorganosiloxane mixture is added to the materials and other additives, heated and dissolved, and then gradually cooled to room temperature. Emulsion-type polishing agents are made by emulsifying and dispersing a polyorganosiloxane mixture in water together with waxes and, if necessary, solvents in the presence of a surfactant. Alternatively, an aerosol type polish can be obtained by sealing it in an aerosol can together with waxes, solvents, and propellants such as fluorocarbons and lower hydrocarbons. Furthermore, these polishing agents may be used in combination with abrasives, preservatives, antifungal agents, etc., if necessary. The content of polyorganosiloxane in polishing agents is usually 0.1
-20% by weight, preferably 0.5-10% by weight.
If it is less than 0.1% by weight, there is no effect of blending the polyorganosiloxane, and if it is blended in excess of 20% by weight, there is no significant effect and it is economically disadvantageous. The polishing agent of the present invention, and especially the polishing agent produced by the manufacturing method of the present invention, provides excellent gloss unique to silicone to various substrates, especially metal surfaces and painted surfaces, and is superior to conventional silicone-based polishing agents. Excellent gloss durability and wash resistance, and no residue or adhesion occurs when repeatedly applied. Therefore, the polishing agent of the present invention is useful as a polishing agent for automobiles and other applications. Hereinafter, the present invention will be explained with reference to Examples. In the examples, all parts are by weight. Further, polyorganosiloxanes mixed and heated according to the production method of the present invention are referred to as polyorganosiloxane composites. Reference example 1 The terminal is blocked with a trimethylsiloxy group, and the temperature at 25℃
Polydimethylsiloxane with a viscosity of 100 cSt
70 parts, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, the ratio of the former to 1 mol of the latter being 0.75 mol,
50 parts of a 60% xylene solution of polymethylsiloxane resin having a hydroxyl group bonded to a Si atom was charged into a container equipped with a stirrer, a thermometer, and a reflux condenser that could be switched to a desolvation device. to about
Heated to 140°C for 1 hour. Next, xylene is distilled off while gradually reducing the pressure, and finally
It was kept at 30 Torr and 140° C. for 1 hour to completely remove xylene. After slowly cooling this, 97 parts of colorless and transparent
A viscous polymethylsiloxane composite S-1 was obtained. Reference example 2 The terminal is blocked with a trimethylsiloxy group, and the temperature at 25℃
Polydimethylsiloxane with a viscosity of 50 cSt
65 parts, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, the ratio of the former to 1 mol of the latter being 0.65 mol,
50% xylene solution of polymethylsiloxane resin with hydroxyl and isopropoxy groups bonded to Si atoms
70 parts were charged into a container similar to that used in Reference Example 1, and xylene was distilled off while heating under reduced pressure.
It was kept at 30 Torr and 130° C. for 1 hour to completely remove xylene. After slowly cooling this, 94 parts of colorless and transparent
A viscous polymethylsiloxane composite S-2 was obtained. Reference example 3 The end is blocked with a trimethylsiloxy group, and the temperature at 25℃
Polydimethylsiloxane with a viscosity of 50 cSt
65 parts, (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, the ratio of the former to 1 mol of the latter is 0.70 mol,
58 parts of a 60% toluene solution of polymethylsiloxane resin having a hydroxyl group bonded to a Si atom was heated at 50 Torr and 130°C under reduced pressure in the same manner as in Reference Example 2.
The mixture was kept for 1 hour to completely remove toluene. This was slowly cooled to obtain 95 parts of a colorless, transparent, and viscous polymethylsiloxane composite S-3. Reference example 4 Instead of linear polydimethylsiloxane, the terminal was blocked with trimethylsiloxy group and 5 mol%
In the same manner as in Reference Example 1, except that 70 parts of branched polymethylphenylsiloxane having a viscosity of 120 cSt at 25°C, which is composed of C ₆ H ₅ SiO _3/2 units and the remaining dimethylsiloxy units, was used, 92 parts of colorless A transparent, viscous polyorganosiloxane composite S-4 was obtained. Example 1 Using the polyorganosiloxane composites S-1 to S-4 obtained in Reference Examples 1 to 4, they were charged into a container equipped with a reflux condenser according to the compounding ratio shown in Table 1, and heated to 100°C. The mixture was uniformly mixed by heating for 10 minutes, and then slowly cooled to prepare polishing agents 10 to 16.
However, polishing agent 10 is a comparative sample. After polishing the surface of an iron plate coated with melamine resin with each of these polishing agents 10 to 16, the gloss, water repellency, and wash resistance thereof were measured in the following trials. The results of these tests were as shown in Table 1. Test A: The gloss of the specimen after applying the polishing agent was observed with the naked eye. Test B: A small amount of water was sprinkled on the same sample as above, and water repellency was observed. Test C: After washing the specimen with a 2% neutral detergent solution, the gloss was observed in the same manner as in Test A, and the number of washings until the gloss was lost was recorded. Note that the observation was performed in units of 5 washes, and was discontinued after 25 washes. Test D: After performing the same washing as in Test C, water repellency was observed in the same manner as in Test B, and the number of washings until water repellency was lost was recorded. Note that the observation was performed in units of 5 washes, and was discontinued after 25 washes. Test E: The coupons were rubbed vigorously for 2 minutes with a cotton cloth moistened with a 2% neutral detergent solution, and then the surface was washed with tap water. After repeating this 5 times,
After drying, the surface gloss was observed.

【table】

[Table] Example 2 Using the polyorganosiloxane composites S-1 to S-3 obtained in Reference Examples 1 to 3, polishing agents were prepared according to the compounding ratios shown in Table 2. That is, polyorganosiloxane and mineral turpentine were charged into a container equipped with a reflux condenser, and after uniformly dissolving, waxes and sorbitan monostearate were added and heated and stirred at 80° C. for 1 hour. Separately, the above polysiloxane-containing solution was added to an aqueous solution obtained by adding POE sorbitan monostearate to water and heating and stirring at 60°C, and the mixture was passed through an emulsifying machine to obtain emulsion-type polishing agents 20 to 23.
However, polishing agent 20 is a comparative sample. Using these polishing agents, specimens were prepared in the same manner as in Example 1, and the gloss, water repellency, and wash resistance thereof were measured by Tests A to D described in Example 1, respectively. These results were as shown in Table 2.

【table】

【table】

Claims (1)

[Scope of Claims] 1. A polishing agent containing a polyorganosiloxane, wherein the polyorganosiloxane (A) has terminals consisting of HOR ¹ ₂ SiO _1/2 units or R ¹ ₃ SiO _1/2 units, and The siloxane unit of is 90~
A linear chain consisting of 100% R ² ₂ SiO units and the remainder R ² _a SiO _(4-a)/2 units (where a is 0 or 1) and has a viscosity of 30 to 1000 cSt at 25°C. or branched liquid polyorganosiloxane (wherein R ¹ and R ² each represent the same or different monovalent hydrocarbon group, and
97% by weight), and (B) consisting of R ³ ₃ SiO _1/2 units and SiO ₂ units, Si
A benzene-soluble polyorganosiloxane resin having ⁴ OR groups bonded to atoms (where R ³ is the same or different monovalent hydrocarbon group, R ⁴
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 3 in the total polyorganosiloxane
~50% by weight). 2. The polishing agent according to claim 1, wherein the terminal group of (A) is substantially a trimethylsiloxy group. 3. Claim 1, in which R ² is a methyl group
Polishing agent as described in section. 4. The polishing agent according to claim 1, wherein (A) is a linear polydiorganosiloxane. 5 Claim 1, in which R ³ is a methyl group
Polishing agent as described in section. Claim 1, wherein the amount of R ³ ₃ SiO _1/2 units per 1 mol of SiO ₂ units of 6 (B) is 0.4 to 1.0 mol.
Polishing agent as described in section. 7 Polyorganosiloxane content is 0.1 to 20
% by weight, the polishing agent according to claim 1. 8 A polishing agent containing a polyorganosiloxane, wherein the polyorganosiloxane (A) has terminals consisting of HOR ¹ ₂ SiO _1/2 units or R ¹ ₃ SiO _1/2 units, and siloxane units other than the terminals 90～
A linear chain consisting of 100% R ² ₂ SiO units and the remainder R ² _a SiO _(4-a)/2 units (where a is 0 or 1) and has a viscosity of 30 to 1000 cSt at 25°C. or branched liquid polyorganosiloxane (wherein R ¹ , R ² and R ² each represent the same or different monovalent hydrocarbon group, and 50 to 97% by weight of the total polyorganosiloxane) ), and (B) consists of R ³ ₃ SiO _1/2 units and SiO ₂ units, and Si
A benzene-soluble polyorganosiloxane resin having ⁴ OR groups bonded to atoms (where R ³ is the same or different monovalent hydrocarbon group, R ⁴
represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and 3 in the total polyorganosiloxane
~50% by weight) of the total polyorganosiloxane.
A method for producing a polishing agent, comprising the step of mixing and heating (A) and 20 to 50% by weight of (B) based on the total polyorganosiloxane. 9. The method for producing a polish according to claim 8, wherein the terminal group of (A) is substantially a trimethylsiloxy group. 10. The method for producing a polishing agent according to claim 8, wherein the heating temperature is 100 to 200°C. 11 25℃ of (A) used for mixing with (B) and heating
9. The method for producing a polishing agent according to claim 8, wherein the polishing agent has a viscosity of 30 to 200 cSt.