JP5829503B2 - Surface treatment agent - Google Patents

Description

  The present invention relates to a surface treatment agent for treating the surface of a vehicle, a building, etc., and relates to a surface treatment agent for reducing the frictional property of the surface.

As described in Patent Document 1, an organic solvent-based rust-proof / stain-resistant composition containing a silicone resin and dimethyl silicone oil is known.
Further, it is known to apply a rust-proof / stain-resistant composition to a car, particularly a metal part, to protect a predetermined part of the car.

  Further, as described in Patent Document 2, a cleaning polish that is a W / O emulsion containing a wax, an emulsifier, a silicone oil, a silicone resin, an organic solvent, and water is known.

  As described in Patent Document 3, it is also known that an O / W emulsion composition containing polyorganosiloxane and polyorganosilsesquioxane powder is used as a polish.

  As described in Patent Document 4, a cleaning and water-repellent polishing agent for automobiles containing a silicone resin, a surfactant, and dimethyl silicone oil is also known.

  As described in Patent Document 5, a composition containing polyorganosiloxane, a nonionic surfactant, a specific ester or an ester compound for improving luster and polishing for automobiles is known. .

Each of the compositions described in the above Patent Documents 1 to 5 has an effect of polishing and the like of an automobile, and for that purpose is a treatment composition containing dimethyl silicone oil or silicone resin. However, these compositions have the effect of improving the gloss of the surface to be treated and increasing the water repellent effect.
However, it is not an invention that exhibits the effect of improving the touch when the treated surface is touched with the hand, but rather the water repellency is improved. There is no surface treatment agent that requires the property that it is smooth or has an improved gloss.

JP 2000-095999 A JP 2010-144025 A JP 09-291215 A Japanese Patent Laid-Open No. 11-106708 JP 2011-006500 A

As described above, the conventional surface treatment agent merely improves the slipperiness when touched by hand while improving the storage stability, and merely making the surface water-repellent or improving the gloss. It was not a surface treatment agent that improves workability by making the surface low friction. Therefore, for example, when the gloss of the surface of an automobile is improved, the appearance of the automobile can be made to have a higher-grade appearance due to light reflection, but such is extremely difficult.
That is, even if a surface having improved slip properties and gloss is desired, a treatment agent necessary to obtain such a surface is not known.
Accordingly, an object of the present invention is to realize a surface that exhibits gloss and good slip properties with excellent workability while improving water repellency using a surface treatment agent having excellent storage stability.

1. An aqueous surface treating agent comprising 0.05 to 0.5% by weight of a silicone resin and a silicone oil containing hydroxyl groups at both terminals.
2. 2. The aqueous surface treating agent according to 1, further comprising dimethyl silicone oil.
3. The aqueous surface treating agent according to 2, wherein the dimethyl silicone oil has a viscosity of 50 to 10,000 cSt at 25 ° C.
4). The aqueous surface treating agent according to any one of 1 to 3 containing ethanol.
5. The aqueous surface treating agent according to any one of 1 to 4, wherein the content ratio of the both-end hydroxyl group-containing silicone oil is 0.1 to 3.0% by weight.
6). The aqueous surface treating agent according to any one of 1 to 5, wherein the viscosity of the both-end hydroxyl group-containing silicone oil is 10,000 to 300,000 cSt at 25 ° C.
7). The aqueous surface treating agent according to any one of 2 to 6, wherein the content ratio of the dimethyl silicone oil is 0.01 to 2.0% by weight.
8). The aqueous surface treating agent according to any one of 4 to 7, wherein the ethanol content is 1.0 to 15.0% by weight.

According to the present invention, on any surface, a surface treatment agent excellent in storage stability is used to improve the water repellency and achieve a glossy and slippery surface with excellent workability. be able to.
When the surface is treated with the surface treatment agent of the present invention, when the surface is rubbed to clean the surface, the surface can be rubbed smoothly with less force, and even a surface having water repellency can be cleaned more easily. It can be carried out.
In addition, the touch and the touch when touching the skin become smooth due to the improvement of the smooth feeling, and the brightness of the light reflected from the surface is improved, so that the appearance becomes more gorgeous.

The aqueous surface treating agent of the present invention is used for treating a surface made of each material such as a coating film, resin, metal, ceramic, paper, wood, fabric, etc., and is also used for automobiles, machines, furniture, and architecture. It can be used for various purposes such as objects and joinery.
Furthermore, the aqueous surface treating agent of the present invention can be used on the surface of the object by known means such as spray, dipping, roller, brush, etc., and by polishing with a cloth or the like as necessary after spraying, Or after making it adhere to cloth etc. by a spray etc., the surface of a subject is wiped using the cloth, and a stronger slipperiness and low friction nature can be given to the subject surface.
When processing with the aqueous surface treating agent of the present invention, the surface of the object may be a dry surface or a wet surface to which water droplets adhere. It is also possible to adhere the aqueous surface treating agent of the present invention to a cloth or the like by spraying or the like, and to wipe up the surface of the object with water droplets attached thereto.
Thereafter, when the coating with the surface treatment agent on the surface has been lost as it is used, it is possible to improve the gloss and slipperiness (low friction) of the surface again by performing the surface treatment again. .

  The silicone resin used in the present invention has a three-dimensional network structure or can be formed, specifically, straight silicone resins such as methyl silicone resin and phenyl silicone resin, alkyd modified silicone resins, polyester modified silicone resins. Modified silicone resins such as acrylic-modified silicone resins, epoxy-modified silicone resins, phenol-modified silicone resins, urethane-modified silicone resins, and melamine-modified silicone resins can be used.

  The concentration of the silicone resin contained in the aqueous surface treatment agent of the present invention is 0.05 to 0.5% by weight, preferably 0.08 to 0.3% by weight, and more preferably 0.10 to 0.0. 2% by weight. If it is less than 0.05% by weight, it becomes difficult to give the surface slipperiness, sufficient gloss, and water repellency.

The viscosity at 25 ° C. of the both-end hydroxyl group-containing silicone oil used in the present invention is preferably 10,000 to 300,000 cSt, more preferably 30,000 to 200,000 cSt, still more preferably 50,000 to 150,000 cSt.
Further, the both-end hydroxyl group-containing silicone oil to be used may be one kind, but for example, two or more both-end hydroxyl group-containing silicone oils having different viscosities and structures may be used in combination.

The dimethyl silicone oil used in the present invention can be used for the purpose of improving workability. Further, the viscosity at 25 ° C. is preferably 50 to 10,000 cSt, more preferably 150 to 5000 cSt.
One kind of dimethyl silicone oil may be used. For example, two or more kinds of dimethyl silicone oils having different viscosities may be used in combination.
In the present invention, when dimethyl silicone oil is not used, the treated surface has very good slipperiness, gloss and water repellency due to a smooth feel, and has excellent workability and storage stability. It has the property of not causing problems. On the other hand, when a dimethyl silicone oil having a viscosity at 25 ° C. of less than 50 cSt is used, workability can be further improved and the wiped treated surface is not uneven.
When a dimethyl silicone oil having a viscosity at 25 ° C. of 50 cSt or more is used, the treated surface has extremely good gloss and water repellency, and the wiped treated surface has no unevenness and the workability is extremely good. In addition, it can be a very smooth feel.
Thus, workability | operativity can be improved by using a dimethyl silicone oil.
In addition, the slip property can be further improved by setting the viscosity of the dimethyl silicone oil at 25 ° C. in the range of 50 to 10,000 cSt.

  The solvent for the aqueous surface treating agent of the present invention may be water or water containing ethanol. In the case of containing ethanol, the concentration of ethanol is 1% by weight or more and 15% by weight or less, preferably 10% by weight or less, more preferably 7% by weight or less. Inclusion of ethanol improves storage stability. be able to. In addition, when it exceeds 15% by weight, the storage stability may be deteriorated.

In the present invention, a surfactant can also be added.
The surfactant may be any surfactant that can disperse a water-insoluble silicone resin, a hydroxyl group-containing silicone oil, and dimethyl silicone oil in an aqueous solvent. As such a surfactant, any of a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant may be used.

  Nonionic surfactants include glyceryl fatty acid esters such as glyceryl monolaurate, glyceryl monomyristate, glyceryl monostearate, glyceryl monooleate; polyglycerin fatty acid esters having similar fatty acid residues, sorbitan fatty acid esters, poly Oxyethylene glycerin fatty acid esters, polyoxyethylene sorbitan fatty acid esters and polyoxyethylene fatty acid esters; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether Polyoxyethylene such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether Alkyl phenyl ethers; polyoxyethylene-oxypropylene block copolymer; as well as polyether-modified polydimethylsiloxane is illustrated.

  Anionic surfactants include sodium hexylbenzenesulfonate, sodium octylbenzenesulfonate, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium cetylbenzenesulfonate, sodium alkylbenzenesulfonate such as sodium myristylbenzenesulfonate. A sodium alkyl naphthyl sulfonate such as sodium butyl naphthyl sulfonate; a polyoxyethylene monoalkyl ether such as sodium polyoxyethylene octyl ether sulfate, sodium polyoxyethylene decyl ether sulfate, sodium polyoxyethylene icosyl ether sulfate Sodium sulfate ester; polyoxyethylene decyl phenyl ether sulfate Polyoxyethylene mono (alkylphenyl) ether sulfate sodium salt such as Le sodium are exemplified.

  Cationic surfactants include octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tallow trimethylammonium chloride, coconut oil trimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethylbenzylammonium chloride, dioctadecyldimethyl Examples include quaternary ammonium salts such as ammonium chloride.

  The amphoteric surfactant is not particularly limited, and various amphoteric surfactants can be mentioned. Specifically, for example, betaine surfactants such as alkylbetaines, alkyldimethylaminoacetic acid betaines, alkylamidopropylbetaines, alkylsulfobetaines, for example, imidazoline-based amphoteric surfactants that are alkylimidazoline-derived amphoteric surfactants. Agents, for example, amino acid-type amphoteric surfactants composed of N-alkylamino acids or salts thereof, for example, amphoteric surfactants that are sodium salts or hydrochlorides of alkyldiaminoethylglycine and alkylpolyaminoethylglycine.

  These surfactants are usually used in combination of two or more of the same system or different systems, and a good emulsion can be easily obtained, or in combination with other emulsions or in other emulsions. Nonionic surfactants are preferred because they can be used.

  The concentration of the surfactant contained in the aqueous surface treating agent of the present invention varies depending on the type and amount of the silicone resin, the hydroxyl group-containing silicone oil, and further the dimethyl silicone oil, but the concentration is up to 5% by weight. It can be made to contain.

Furthermore, in the present invention, the solvent for the aqueous surface treatment agent is a water-based solvent, and further, by adding an alcohol, it is possible to improve storage stability at low temperatures.
As such alcohol, ethanol is preferable from the viewpoint of availability, but propanol or methanol may be used.
Further, in the solvent, the concentration of other organic solvents is within a range of up to 5% by weight, preferably up to 3% by weight, and more preferably within a range of up to 1% by weight, as long as low temperature stability is not affected. Can be mixed. As such an organic solvent, for example, alcohols other than ethyl acetate, dimethyl ether, ethanol, and the like can be used. By using these alcohols together, the storage stability of the aqueous surface treatment agent can be improved.

In addition, a wax may or may not be added to the aqueous surface treating agent of the present invention.
When the wax is blended, the gloss of the surface is improved, but if the amount added is too large, the slipperiness may be deteriorated.
Usable waxes include, for example, carnauba wax, candelilla wax, montan wax, ceresin, paraffin, microcrystalline wax, ozokerite, natural wax, α-olefin wax, Fischer-Tropsch wax and derivatives thereof, Polyolefin waxes (for example, polyethylene waxes) and derivatives thereof, oxidized paraffin, oxidized microcrystalline wax, caster wax, acid wax and ester wax and derivatives thereof based on montan wax, lanolin derivatives, petroleum-based olefin-based olefins and Wax, metal soap, fats and oils, higher fatty acids, higher alcohols, hardened oils, fats made of maleic anhydride or acrylic acid or vinyl acetate Examples thereof include wax-like substances typified by acid amides and polyethers, and various modified waxes such as fluorine-modified wax, silicone-modified wax, and resin-modified wax. It can be added up to% by weight.
In addition, the water-based surface treatment agent of the present invention may be added with known additives used for ordinary surface treatment agents such as fragrances, colorants, pigments, fungicides, antioxidants, and ultraviolet absorbers. Good.

  As the method for producing the aqueous surface treating agent of the present invention, water containing a water-soluble organic solvent such as ethanol is optionally added to a silicone resin, a silicone oil containing hydroxyl groups at both ends, and optionally dimethyl silicone oil. And a stirring method using a known stirring device such as a blade-type stirrer or a homomixer.

(Hereinafter examples and comparative examples)
An aqueous surface treating agent was produced using the raw materials shown in Table 1 below.
(Slidability measurement method and its judgment condition)
An aqueous surface treatment agent was dropped onto an acrylic resin coating test piece, and after wiping up, the smooth feeling when sliding on the surface was evaluated.
◎ ・ ・ ・ Smooth feel ○ ・ ・ ・ Smooth feel △ ・ ・ ・ Slightly slippery feeling × ・ ・ ・ Same as before construction

(Gloss measurement method and its judgment condition)
The aqueous surface treatment agent was dropped onto an acrylic resin coating test piece, and after wiping, the gloss was visually evaluated.
○ ・ ・ ・ There is gloss △ ・ ・ ・ Slightly gloss × ・ ・ ・ No change from before construction

(Water repellency measuring method and its judgment condition)
The aqueous surface treatment agent was dropped onto an acrylic resin coating test piece, and after wiping, the state of water droplets after spraying water using a trigger spray was evaluated.
○ ・ ・ ・ Water drops are round △ ・ ・ ・ Parts of water drops are crushed × ・ ・ ・ Water drops are crushed

(Workability measurement method and its judgment conditions)
The aqueous surface treatment agent was sprayed on the outer surface of the automobile and then wiped up to confirm the presence or absence of unevenness after the construction.
○ ・ ・ ・ Finished evenly △ ・ ・ ・ Slightly uneven but can be wiped up × ・ ・ ・ Uneven and cannot be wiped up

(Storage stability measurement method and judgment conditions)
An aqueous surface treatment agent was filled in a sealed container. This was stored for one month under each temperature condition of 100 ° C., 70 ° C., room temperature and −20 ° C., and then the appearance was confirmed.
If all of the above four temperature conditions were not good, the overall evaluation was not good. If there is even one Δ, the overall evaluation is Δ, and if there is one ×, the overall evaluation is ×.
○ ・ ・ ・ Appearance just after adjusting the aqueous surface treatment agent Δ ・ ・ ・ Separation is observed in the appearance of the aqueous surface treatment agent × ・ ・ ・ Aqueous surface treatment agent is separated and does not have predetermined properties

Note (1) KM9717 Shin-Etsu Chemical MQ resin Note (2) X-52-8005 Shin-Etsu Chemical MQ resin
Note (3) YMR7212 Momentive Performance Material Japan Note (4) Polon MF-17 Shin-Etsu Chemical Note (5) X-51-1330 Shin-Etsu Chemical Note (6) TSM630 Momentive Performance Material Japan Note (7) TSM632 Momentive Performance Material Japan Note (8) TSM6343 Momentive Performance Material Japan

The surface slipperiness, gloss, and water repellency obtained with the aqueous surface treating agents of Examples 1 to 4 were all very good, and the workability and storage stability were good.
As in the example of Example 5, when dimethyl silicone oil having a viscosity at 25 ° C. of 10 cSt was further added to the aqueous surface treating agent of Example 1, it was possible to finish evenly and workability was improved.
The aqueous surface treatment agents of Examples 6 to 9 obtained by replacing the dimethyl silicone oil of the aqueous surface treatment agent of Example 5 with a dimethyl silicone oil having a higher viscosity of 200 to 10000 cSt have a very smooth feel. Improved slipperiness. In addition, the workability was extremely good.
The aqueous surface treating agent of Example 10 obtained by further blending ethanol with the aqueous surface treating agent of Example 6 so as to be 5% by weight can maintain the appearance immediately after adjustment at any temperature. The storage stability was extremely good.

On the other hand, according to the aqueous surface treating agent of Comparative Example 1 containing no both-end hydroxyl group-containing silicone oil, although the gloss and water repellency of the surface are extremely good, the slipperiness, workability, and storage stability are poor. The result was.
In addition, when the content of the silicone resin was 0.03% by weight and less than the content of the present invention, the workability and storage stability were very good, but the slipperiness, gloss and water repellency were poor. Met.
As can be understood from these examples and comparative examples, the present invention is excellent in all properties of slipperiness, gloss, water repellency, workability, and storage stability by adopting a specific configuration. .

Claims (7)

For coating film, metal, ceramic, paper, wood part or fabric surface containing 0.05 to 0.5% by weight of silicone resin , dimethyl silicone oil and silicone oil containing hydroxyl groups at both ends and no amino-modified silicone Aqueous surface treatment agent. Aqueous surface treatment agent according to claim 1, wherein those having a viscosity of 50~10000cSt in dimethyl silicone oil 25 ° C.. The aqueous surface treating agent according to claim 1 or 2 containing ethanol. The aqueous surface treating agent according to any one of claims 1 to 3 , wherein the content ratio of the both-end hydroxyl group-containing silicone oil is 0.1 to 3.0% by weight. The aqueous surface treating agent according to any one of claims 1 to 4 , wherein the viscosity of the both-end hydroxyl group-containing silicone oil is 10,000 to 300,000 cSt at 25 ° C. The aqueous surface treating agent according to any one of claims 1 to 5 , wherein a content ratio of the dimethyl silicone oil is 0.01 to 2.0% by weight. The aqueous surface treating agent according to any one of claims 3 to 6 , wherein the ethanol content is 1.0 to 10.0% by weight .