CN110730811A - Surface treatment method and composition for surface treatment - Google Patents

Surface treatment method and composition for surface treatment Download PDF

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Publication number
CN110730811A
CN110730811A CN201880038688.9A CN201880038688A CN110730811A CN 110730811 A CN110730811 A CN 110730811A CN 201880038688 A CN201880038688 A CN 201880038688A CN 110730811 A CN110730811 A CN 110730811A
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surface treatment
treatment method
polishing
coated
mass
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桐野学
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ThreeBond Co Ltd
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ThreeBond Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Paints Or Removers (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)

Abstract

The invention provides a surface treatment method and a surface treatment composition suitable for the method, wherein the surface treatment method can realize film formation with improved appearance and excellent durability on a coating surface at one time through simple construction independent of the strength of an operator. The present invention is a surface treatment method using a composition for surface treatment, which is applied by a polishing machine, the composition for surface treatment comprising: (A) a high-molecular organic silane having a reactive group, (B) a reaction catalyst, and (C) abrasive particles containing an inorganic compound having an average primary particle diameter of 0.1 to 10000 nm.

Description

Surface treatment method and composition for surface treatment
Technical Field
The present invention relates to a surface treatment method using a composition containing a reactive high-molecular organic silane. More particularly, the present invention relates to a surface treatment technique for forming a coating film having excellent durability and improved appearance by applying a finishing agent to a substrate such as a metal steel material, a synthetic resin material, glass, or ceramics, for example, a vehicle body or a window of an automobile such as an automobile or a train, a structural member of a building such as a rear view mirror, a road, or a bridge pier, a wall or a window of a building such as a house or a building, a roof, or a building member, or particularly a substrate coated on the surface thereof, thereby protecting the substrate from stains or damages.
Background
Conventionally, coating and application of a solid, semisolid, or liquid curable composition have been performed for the purpose of improving the appearance and protecting the coated steel sheet of an automobile body or the like. As such a curable composition, for example, a composition obtained by adding a volatile organopolysiloxane oil and a volatile dimethylpolysiloxane to a moisture-curable organopolysiloxane, an organic solvent and a curing catalyst (Japanese patent application laid-open No. 2006-45507) and a composition obtained by adding a high-viscosity silicone rubber (Japanese patent application laid-open No. 2013-194058) are known. However, the coating film using these compositions is difficult to develop water repellency for a long period of time because the non-reactive organopolysiloxane oil component volatilizes and dissipates over time or flows out due to the influence of rain or the like.
In order to solve the above problems, various compositions comprising a moisture-curable organopolysiloxane, an organic solvent, a curing catalyst, and a silicone oil having a reactive functional group in the molecule have been proposed. Jp 2008-75021 discloses a composition using a reactive silicone oil having reactive groups selected from a carbinol group, a carboxyl group, an amino group, a hydroxyl group (silanol group) and the like at both ends of a molecular chain, and jp 2006-45507 a, jp 2007-161989 a and the like disclose a composition obtained by diluting a low-viscosity reactive organopolysiloxane having an alkoxysilyl group at an end of a molecular chain in an alcohol-based solvent or a paraffin-based solvent, an aromatic-based solvent, an ester-based solvent, a glycol-based solvent and the like. In addition, jp 2010-31074 a proposes a composition using a reactive silicone oil having a carbinol group or an amino group in a side chain of the molecule, and international publication No. 96/000758 (corresponding to U.S. Pat. No. 6000339) proposes a composition containing a fluorine-containing alkoxysilane. Japanese patent laid-open Nos. 2009-138063, 2009-138062, 2013-166957, and 2010-202717 disclose compositions obtained by diluting a reactive organopolysiloxane having an alkoxysilyl group at a molecular chain end with a large amount of an isoparaffin solvent or a solvent such as kerosene. Jp 2012-241093 a (corresponding to the specification of U.S. patent application publication No. 2014/065396) discloses a composition prepared by diluting a reactive organopolysiloxane with a high-boiling isoparaffin solvent.
On the other hand, jp 2010-163553 a and jp 2015-059187 a disclose polishing compositions suitable for application by a polishing machine, which are obtained by dispersing or mixing a resin component such as a silicone resin or a silicone elastomer in water. Japanese patent application laid-open No. 2002-47455 discloses a composition comprising a silicone having a condensation reactive group and the like, and a method for treating a surface of a vehicle body using a mechanical continuous construction device such as a polisher. The surface treatment by the polishing machine is basically to level the surface smoothly by grinding the surface of the vehicle body, thereby improving the beauty thereof.
Disclosure of Invention
The compositions disclosed in jp-a-10-36771, jp-a-2013-194058, jp-a-2008-75021, jp-a-2006-45507, jp-a-2007-161989, jp-a-2010-31074, international publication No. 96/000758, jp-a-2009-138063, jp-a-2009-138062, jp-a-2013-166957, jp-a-2010-202717 and jp-a-2012-241093 can protect the surface of a substrate made of metal or the like, but cannot improve the beauty of the surface of a substrate deteriorated by sunlight, wind, rain and other various factors, and finally give gloss to and maintain the state of a coating film at the time of construction. In addition, in order to uniformly apply these compositions, a liquid agent for wiping with water or other means is required, and if the application is performed only by dry wiping, the application cannot be smoothly performed, which causes problems such as spots on the coating film and the like, and thus, the application property is difficult. On the other hand, in the polishing treatment using the techniques described in japanese patent laid-open nos. 2010-163553, 2015-059187 and 2002-47455, attention is mainly paid to the effect of improving the appearance by polishing the surface of the vehicle body, and for example, the compositions described in japanese patent laid-open nos. 2010-163553 and 2015-059187 do not contain a reactive silicon oligomer that can contribute to the formation of a strong coating film after the application. The composition described in jp 2002-47455 a contains a silicone having a condensation-reactive group, but does not contain a curing catalyst, and therefore crosslinking between silicones hardly proceeds under a catalyst-free condition, and it is difficult to form a coating film having sufficient durability. Therefore, in the polishing treatment using the techniques described in japanese patent laid-open nos. 2010-163553, 2015-059187, and 2002-47455, the durable coating film needs to be applied through another route in order to form a coating film that functions for a long period of time.
As described above, it is difficult to form a coating film that can achieve both aesthetic appearance and durability by a simple application method using a conventional film-forming curable composition, but intensive studies have been made to achieve these by the present invention, and as a result, the following methods have been achieved. That is, a surface treatment method according to an embodiment of the present invention is a surface treatment method using a surface treatment composition including:
(A) a high-molecular organic silane having a reactive group,
(B) A reaction catalyst,
(C) Abrasive particles having an average primary particle diameter of 0.1 to 10000 nm.
The present invention also includes the following embodiments.
A second embodiment is the surface treatment method, wherein the content of (B) is 0.001 to 0.5 part by mass and the content of (C) is 0.01 to 1.0 part by mass relative to 1 part by mass of (A).
A third embodiment is the surface treatment method, wherein the component (a) is an organopolysiloxane having a reactive group.
A fourth embodiment is the surface treatment method described above, wherein the organic solvent (D) containing substantially no water is contained in an amount of 0.1 to 100 parts by mass based on 1 part by mass of the component (a).
A fifth embodiment is the surface treatment method, wherein the content of (D) is in a range of 1.0 to 10 parts by mass relative to 1 part by mass of (a).
A sixth embodiment is the surface treatment method described above, wherein the reactive group in the above (a) is a hydrolytic-polymerizable reactive group.
A seventh embodiment is the surface treatment method, wherein the average primary particle diameter of the (C) is in the range of 0.1 to 200 nm.
An eighth embodiment is the surface treatment method, wherein the average primary particle diameter of the (C) is in a range of 1 to 150 nm.
A ninth embodiment is the surface treatment method, wherein the component (C) is abrasive particles containing an inorganic compound.
A tenth embodiment is the surface treatment method, wherein the component (C) is abrasive particles including silica particles having a surface subjected to hydrophobic treatment.
An eleventh embodiment is the surface treatment method described above, wherein the surface to be treated by the polishing machine is a coated surface which is previously coated.
A twelfth aspect is the surface treatment method described above, wherein the previously coated surface to be coated is a surface of a steel sheet to be coated and/or a surface of a resin member to be coated for use in exterior body trim of an automobile.
A thirteenth embodiment is the surface treatment method described above, wherein the polishing machine is a rotary polishing machine.
A fourteenth embodiment is the surface treatment method, wherein the polishing machine is a single-action rotary polishing machine or a double-action rotary polishing machine.
A fifteenth embodiment is the surface treatment method described above, wherein the application uses a polishing machine provided with an abutment member made of ultrafine fibers.
A sixteenth embodiment is a surface treatment composition for use in construction of a polishing machine, comprising:
(A) a high-molecular organic silane having a reactive group,
(B) A reaction catalyst, and
(C) abrasive particles having an average primary particle diameter of 0.1 to 10000 nm.
Drawings
FIG. 1 is a photograph comparing a state (a) before a test of an automobile body surface coated part evaluated in examples with a state (b) after the test in example 14.
Detailed Description
The surface treatment method of the present invention is a method for polishing and coating a surface of a substrate, wherein a surface treatment composition comprising (A) a high-molecular organic silane having a reactive group, (B) a reaction catalyst, and (C) abrasive particles having an average primary particle diameter of 0.1 to 10000nm is used and applied by a polisher. The surface treatment composition for use in buffing machine application of the present invention comprises the components (a) to (C). The surface treatment method of the present invention having the above-described configuration and the surface treatment composition used in the method can form a coating film excellent in both appearance and durability by a simple and easy method with little skill dependence of an operator, in which the surface of a substrate used in a vehicle body of an automobile or the like, particularly the surface of a substrate after coating, is subjected to a finishing work.
The details of the present invention will be described further below.
[ A ] A high-molecular organic silane having a reactive group >
The component (A) contained in the surface treatment composition used in the present invention is a polymer organic compound having a reactive groupA silane. This component is a main component of the cured coating film formed by the surface treatment of the present invention, and has durability. Here, the high-molecular organic silane means: having a structure of-SiR like polysilazane1R2-NR3The compound having an organic group and Si in the main chain skeleton of the polymer, such as a polymer compound having a main skeleton composed of units, a polymer compound having a main skeleton composed of siloxane bonds, such as organopolysiloxane, means a compound having a molecular weight of generally 500 or more. Among them, from the viewpoint of easy control of curing properties and easy application to a polishing machine, an organopolysiloxane having a reactive group is preferable.
The reactive group is not particularly limited as long as it is a functional group that can contribute to curing by crosslinking between the compounds of the component (a) or a functional group that can contribute to forming a durable coating film by reacting with a reaction point on the surface of a substrate. Examples of the reactive group include a hydrolytic polymerizable group, an addition polymerizable group such as a hydrosilyl group and an alkenyl group, a radical polymerizable group such as an acryloyl group, and a functional group such as an epoxy group. In the present invention, since a coating film having excellent durability and gloss can be formed on the surface of the base material by applying treatment in an ambient temperature environment, a hydrolytic polymerizable reactive group is particularly preferable. As the reactive group, for example, the following functional groups bonded to a silicon atom may be selected: the amino group, the epoxy group, the mercapto group, the methacryl group, the acryl group, the carbinol group, the carboxyl group, the alkoxy group, the aminoxy group, the ketoxime group, the alkenyloxy group, the amide group, and the acetoxy group are preferably alkoxy groups selected from methoxy group, ethoxy group, propoxy group, and phenoxy group, and more preferably alkoxy groups selected from methoxy group and phenoxy group, from the viewpoint of easiness of forming a cured coating film under a working environment. The compound of the component (a) may have an unreactive functional group selected from methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and phenyl, and more preferably an organic group selected from methyl, ethyl and phenyl, from the viewpoint of easily forming a coating film having high hardness and high water resistance. The polymer having 2 or more of the above-mentioned hydrolytic polymerizable reactive groups in total at the terminal or side chain of the molecular chain and having the above-mentioned organic group having no reactivity as another functional group is subjected to condensation reaction by the action of a reaction catalyst of the component (B) described later present in the system, and a coating film is formed by intermolecular crosslinking or reaction with the reaction site on the surface of the substrate, whereby coating excellent in durability can be performed on the surface of the substrate.
The high-molecular organic silane as the component (a) in the present invention is typically polysilazane or organopolysiloxane. The polysilazane that can be used in the present invention is not particularly limited, and is a polysilazane having — (SiR) in the molecule1R2-NR3) The compound having the repeating structure of (E-O-X) may be a compound having a chain, ring or intermolecular cross-linked structure, and the like. In the above formula, R1、R2And R3Each independently represents a hydrogen atom or an organic group selected from optionally substituted hydrocarbon groups, preferably a hydrogen atom or an organic group selected from optionally substituted hydrocarbon groups having 1 to 6 carbon atoms, more preferably a hydrogen atom or an organic group selected from optionally substituted aliphatic hydrocarbon groups having 1 to 4 carbon atoms. Herein, R in the above formula1、R2And R3Compounds which are all hydrogen atoms are generally referred to as inorganic polysilazanes or perhydropolysilazanes, R1、R2And R3The compound containing an organic group in any of (1) is generally called an organopolysiloxane (organopolysiloxane). In the present invention, both organic polysilazane and inorganic polysilazane can be used, and these can be used in combination, and can be appropriately selected depending on the properties required for the cured product. A wide range of compositions can be prepared, for example, a composition containing a large amount of inorganic polysilazane when a certain degree of high hardness is required for a cured product, a composition containing a large amount of organic polysilazane when flexibility is required, and the like. In addition, R which is a modified product of polysilazane may be used1And R2Polymetal of compounds in which a part of the compound is substituted with a metal atomSilazanes.
Polysilazanes are known to form polysiloxanes by causing a sol-gel reaction by contact with moisture in the air. The polysiloxane layer is formed on an adherend and becomes a main component of a coating film excellent in water resistance, oil resistance, impact resistance, and the like. At this time, nitrogen in the molecule is removed to generate ammonia, which serves as a catalyst to further promote the reaction. This reaction is a reaction in which the Si-N bond is changed to the Si-O bond, and there is an advantage that curing shrinkage due to generation of a leaving group such as crosslinking between alkoxysilane molecules and reduction in the distance between atoms hardly occurs. This can reduce the occurrence of cracks, which are a drawback of the formation of a polysiloxane film due to a sol-gel reaction, and thus can form a film having excellent conformability to a substrate having irregularities.
As the commercially available products of polysilazanes, a variety of commercially available Materials such as AQUAMICA (registered trademark) NN110, NN120-10, NN120-20, NN310, NN320, NL110A, NL120A, NL120-20, NL150A, NP110, NP140-01, NP140-02, NP140-03, SP140, KiON (registered trademark) HTT1880, KiON (registered trademark) HTA1500 ramp Cure, KiON (registered trademark) HTA1500 ramp, tuToProm (registered trademark) HD, tuToProm (registered trademark) bright G, CAG 37, tuToProm (registered trademark) bright, Duke's trademark) blend, and a variety of Materials such as Raza 120, NAza 120, and NAza 120, and NAza 2, which are respectively known to be used alone or in the trade of AZ Electronic Materials.
The organopolysiloxane that can be used in the present invention is not particularly limited, and any material can be appropriately selected depending on the required properties as long as it is a compound having a structure having a reactive group in a polymer as a skeleton structure of Si — O, preferably a compound having a structure having 2 or more reactive groups in total. The compound corresponds to, for example: a so-called reactive silicone oil which is a chain polymer having 2 or more reactive groups in total at the terminal or side chain of the molecular chain; a so-called reactive silicon oligomer which is a polymer having a three-dimensional network structure in a molecule and has a plurality of reactive groups; further, a so-called reactive silicone resin or the like, which is a polymer having a large polymerization degree and a complicated network structure, may be used in combination according to the required characteristics.
Typical examples of the use of the reactive silicone oil alone as a component for forming a cured film include polymers having a structure in which the reactive groups are present in a total of 2 or more at the end of a linear molecule or in a side chain of a siloxane skeleton, and the non-reactive organic group is bonded as a functional group on another silicon atom. When the reactive silicone oil is used as a component for forming a cured coating film in combination with a silicon oligomer or a silicon resin, the structure is not limited to the above, and may be, for example, a structure in which the number of reactive groups present in the molecule is 1. As the commercial products of the compound, X-22-161A, X-22-161B, X-22-162C, X-22-163A, X-22-163B, X-164A, X-22-164B, X-22-167B, X-167C, X-22-169B, KF-8012, KF-8008, KF-6000, KF-6001 and X-21-5841 available from shin-Etsu chemical Co., Ltd, KF-9701, BY16-750, BY16-201, BY16-853U, BY16-873, SF8427, FZ-3736, FZ-3704, etc., available from Toray Corning corporation, YF3800, XF3905, YF3057, YF3807, YF3802, YF3897, XC96-723, etc., available from Momentive Performance Materials.
The reactive silicone oligomer and the reactive silicone resin are typically polymers having a structure in which 1 or more of the reactive groups are present on Si in a polymer having a siloxane skeleton with a three-dimensional network structure, and the non-reactive organic group is bonded as a functional group on other Si. Examples of commercially available products of the compound include: KR-500, KC-89S, X-40-9225, X-40-9250, X-40-9227, KR-510, KR-511, X-41-1805, X-41-1810, X-24-9590, KR-251, KR-255 and KR-112 manufactured by shin-Etsu chemical Co., Ltd, KR-400, KR-401, X-40-2327, XC96-B0446, XR31-B1410, XR31-B2733, XR31-B2230, TSR165, XR31-B6667, XR31-B1763, SILRES MSE, SILRES H44, SH550, available from Toureto Corning K.K., containing a curing catalyst, available from shin-Etsu chemical Co., Ltd., and many of these can be used alone or in combination.
The high molecular weight organic silane of the component (a) particularly preferred in the present invention is an organopolysiloxane, more preferably a high molecular weight organic silane selected from a reactive silicon oligomer and a reactive silicon resin, and most preferably a reactive silicon oligomer. By using the reactive silicon oligomer, the surface treatment by the method of the present invention can maintain workability based on an appropriate pot life and liquid viscosity, and also has appropriate toughness and flexibility for the cured film to be formed and excellent durability.
The high molecular weight organic silane as the component (a) in the present invention is particularly preferably a reactive silicon oligomer, typically a partial hydrolysis condensate of an alkoxysilane compound represented by the following structural formula (1).
[ solution 1]
R4 x-Si(OR5)4-x… type (1)
Herein, R is4、R5Preferably, each of the substituents is independently a substituent selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, and phenyl, more preferably a substituent selected from the group consisting of methyl and phenyl, and particularly preferably each of methyl. In addition, x is an integer of 0 to 3, preferably 0 or 1, and particularly preferably 1. The polymer organosilane as the component (a) can be obtained by adding a known hydrolysis catalyst to the compound represented by the above structural formula, and heating the mixture while stirring the mixture in the presence of moisture to cause partial hydrolytic condensation. In the above structural formula, when x is 0 OR 1, the side chain of the polymer of the compound has a structure represented by (OR)5) Alkoxy groups are shown. In the case where the polymer does not form a linear structure and forms a three-dimensional crosslinked structure, the structure may partially contain an alkoxy group. The compound may include those in which x is 2 or 3, but in order to effectively add an alkoxy group to the structure of the polymer organosilane of the component (a), a compound in which x is 0 or 1 is particularly preferable. In addition, the compound is prepared fromFrom the viewpoint of workability of (a), it is preferable to use a component based on JIS Z8803: 2011 and has a dynamic viscosity measurement at 25 ℃ of about 0.1 to 1000mm2s-1More preferably 0.5 to 500mm in the range of2s-1(ii) in the range of (a). When the dynamic viscosity of the polymeric organosilane as the component (a) is within the above range, the cured film of the surface treatment composition has particularly good properties such as water repellency, lubricity and abrasion resistance, and the workability during the construction is also suitable.
< reaction catalyst (B) >
The component (B) contained in the surface treatment composition used in the present invention is a reaction catalyst and is a component for reacting a reactive group contained in the polymer organic silane of the component (a). The compound as a reaction catalyst of the component (B) is typically a compound in which the reactive group is a hydrolytic-polymerizable reactive group (Si-OR)5) In the case of (3), a hydrolysis reaction catalyst for causing condensation reaction of the hydrolytic polymerizable group by reaction with moisture in the air or the like. The hydrolysis catalyst may be selected from organic metal compounds such as organic tin compounds, organic titanium compounds, organic nickel compounds and organic aluminum compounds, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as p-toluenesulfonic acid and various aliphatic or aromatic carboxylic acids, inorganic bases such as ammonia and sodium hydroxide, tributylamine and 1, 5-diazabicyclo [4.3.0 ]]Nonene-5 (DBN), 1, 8-diazabicyclo [5.4.0]Organic bases such as undecene-7 (DBU) and the like are appropriately selected and used.
The reaction catalyst of the component (B) in the present invention is preferably an organometallic compound, and specifically, the following may be exemplified: organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctoate, dioctyltin diacetate, dibutyltin bisacetoacetate, dioctyltin bisaceturate, organic titanium compounds such as tetrabutyl titanate, tetranonyl titanate, tetraethylene glycol methyl ether titanate, tetraethylene glycol ethyl ether titanate, bis (acetylacetonitrile) dipropyl titanate, aluminum salt compounds such as aluminum octoate, aluminum triacetate and aluminum tristearate, aluminum alkoxide compounds such as aluminum trimetholate, aluminum triethoxide, aluminum triallyl oxide and aluminum trisphenoxide, aluminum methoxybis (ethylacetoacetate), aluminum methoxybis (acetylacetonate), aluminum ethoxybis (ethylacetoacetate), aluminum ethoxybis (acetylacetonate), aluminum isopropoxybis (ethylacetoacetate), An organonickel compound such as aluminum isopropoxide bis (methylacetoacetate) aluminum, aluminum isopropoxide bis (t-butylacetoacetate), aluminum butoxybis (ethylacetoacetate), aluminum dimethoxy (acetylacetonate), aluminum diethoxy (ethylacetoacetate), aluminum diethoxy (acetylacetonate), aluminum diisopropoxide (ethylacetoacetate), aluminum diisopropoxide (methylacetoacetate), aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum octylaluminum diisopropylacetoacetate, or nickel (II) acetylacetonate or nickel (II) hexafluoroacetylacetonate hydrate, and these may be used alone or in combination of plural kinds. Among these compounds, particularly preferred are organoaluminum compounds, and more preferred are organoaluminum compounds selected from aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum diisopropoxide (ethylacetoacetate), octylaluminum diisopropylacetoacetate, and aluminum monoacetylacetonate bis (ethylacetoacetate).
As the reaction catalyst for the component (B), known commercially available products can be used. For example, as the organoaluminum compound, DX-9740 (mixture of aluminum alkoxide compounds), CAT-AC (mixture of aluminum alkoxide compounds, 50% by mass of diluted toluene), aluminum chelate A (W) (aluminum tris (acetylacetonate)), aluminum chelate D (aluminum monoacetylacetonate bis (ethylacetoacetate), 76% by mass of the active ingredient), AIPD (aluminum isopropylate), ALCH (aluminum diisopropoxide (ethylacetoacetate), ALCH-TR (aluminum tris (ethylacetoacetate)), A0246 (aluminum isopropoxide) manufactured by Tokyo Chemical Co., Ltd., Orgaitix TA-10 (titanium tetraisopropoxide), ORGATIX TA-25 (titanium tetra-n-butoxide) manufactured by Matsumofilto Chemical Co., Ltd., can be used, as the organic zirconium compound, ORGATIX ZA-40 (zirconium tetra-n-propoxide), ORGATIX ZA-65 (zirconium tetra-n-butoxide), manufactured by Matsumoto Fine Chemical Co., Ltd., or the like can be used. These may be used alone or in combination.
The content of the reaction catalyst of the component (B) in the present invention is not particularly limited, but is preferably in the range of 0.001 to 0.5 parts by mass, more preferably 0.003 to 0.3 parts by mass, and still more preferably 0.005 to 0.2 parts by mass, based on 1 part by mass of the component (a). When the content is not less than the lower limit of the content, the surface treatment composition of the present invention does not cause a defect in curing and can form a cured coating film having sufficient strength. On the other hand, when the content is not more than the upper limit of the content, the possibility of the problem of the storage property of the surface treatment composition of the present invention at normal temperature can be reduced. When the reactive group contained in the high-molecular organic silane of the component (a) is not a hydrolytic polymerizable reactive group, a catalyst necessary for the crosslinking reaction using various reactive groups can be appropriately selected and used. For example, as the reactive group, in the case of (i) an addition polymerizable reactive group having a combination of a hydrosilyl group and an alkenyl group, an addition polymerization catalyst composed of a platinum compound or the like may be selected, in the case of (ii) a radical polymerizable reactive group such as an acryloyl group, an azo compound, an organic peroxide, an acyloin compound, a benzophenone or the like may be selected, in the case of (iii) an epoxy group, an amine compound, an arylonium salt compound or the like may be selected, and a compound which is incorporated into the system and deactivated after the reaction may be used.
(C) abrasive particles having an average primary particle diameter of 0.1 to 10000nm
The component (C) contained in the surface treatment composition used in the present invention is abrasive particles having an average primary particle diameter of 0.1 to 10000nm, and is a component which smoothens and uniformizes the surface of a substrate in a polishing treatment by polishing and exhibits a function of contributing to the formation of a cured film having excellent durability after a curing reaction. The abrasive particles of the component (C) are particles selected from inorganic compounds and organic compounds. Among them, examples of the particles of the inorganic compound include: calcined or unfired kaolin, alumina, silica, talc, glass, mica, diamond, bentonite, montmorillonite, celite, volcanic ash particles (シラスバルー ン), ceramics, silica, diatomaceous earth, pearlite, calcium carbonate, zeolite, hydrous silicic acid, chromium oxide, titanium oxide, zinc oxide, iron oxide, zirconium oxide, cerium oxide, magnesium oxide, calcium fluoride, aluminum silicate, calcium silicate, zirconium silicate, aluminum hydroxide, barium sulfate, various metal colloids, montmorillonite, silicon carbide, aluminum phosphate, colloidal silica, spherical powder such as fumed silica, flaky powder or amorphous powder, and hollow spherical powder such as colloidal silica, fumed silica, alumina, silica gel, and fine powder obtained by surface-treating or coating these with an organic compound, but not limited thereto. Examples of the particles of the organic compound include: fine particles of poly (meth) acrylate, polystyrene, polyolefin, phenol resin, epoxy resin, polyacrylonitrile, polybutadiene, styrene resin, high-density polyethylene resin, urea resin, polyester resin, polyvinyl chloride, nylon (registered trademark), polyamide, cellulose, polycarbonate, fluorine-containing resin, crosslinked polymers thereof, and the like, and substances obtained by surface-coating these particles with an inorganic compound, a metal, or the like, or substances obtained by treatment such as introduction of a functional group, and the like, but the present invention is not limited thereto. The abrasive particles of the component (C) in the present invention may be used in combination of 2 or more of these in the surface treatment composition, depending on the required properties. The shape of the particles of these inorganic compounds and organic compounds is not particularly limited, and various shapes such as spherical, scaly, amorphous, needle-like, and fibrous shapes can be used. In addition, so-called hollow particles having a void inside the particle may be used. In the present invention, the abrasive particles of the component (C) are preferably abrasive particles containing the inorganic compound, more preferably abrasive particles selected from the inorganic compounds, still more preferably abrasive particles containing 1 or more selected from kaolin, talc, silica, mica, alumina, celite, calcium carbonate, titanium oxide, zinc oxide and iron oxide, particularly preferably abrasive particles containing 1 or more selected from kaolin, alumina, silica, celite, calcium carbonate, titanium oxide and zinc oxide, particularly preferably abrasive particles containing 1 or more selected from kaolin, alumina, silica and celite, and most preferably abrasive particles containing 1 or more selected from kaolin and silica.
As the kaolin particles, hydrous kaolin particles and calcined kaolin particles are known, and they can be used in the present invention, but calcined kaolin particles are preferably used. As commercially available kaolin particles, for example, there are known hydrous kaolin particles such as ASP-G92, ASP-200, ASP-170, ASP-600, ASP-900, Hydrite (registered trademark) PXN-LCS, Hydrite (registered trademark) RS, Hydrite (registered trademark) Flat-DS, Barrisurf HX Eckalite 1 and Eckalite ED, all of which are available from BASF corporation. Known examples of the untreated calcined kaolin particles include Satintone (registered trademark) W, Satintone (registered trademark) SP-33, Satintone (registered trademark) 5HB, Satintone (registered trademark) specal, No.5, Satintone (registered trademark) PLUS, Neogen (registered trademark) 2000, Polestar (registered trademark) 400, Glomax (registered trademark) LL, and Polestar (registered trademark) 200R, manufactured by BASF corporation. Known examples of the surface-hydrophobicized calcined kaolin particles include Translink (registered trademark) 37, Translink (registered trademark) 77, Translink (registered trademark) 445, Translink (registered trademark) 555, and Polarite (registered trademark) 103A, Polarite (registered trademark) 503S, Polarite (registered trademark) 102A manufactured by BASF corporation. These known materials can be used in appropriate combinations as the kaolin particles.
As the silica particles, silica particles having surfaces subjected to hydrophobic treatment (also referred to as hydrophobic silica particles) and non-treated hydrophilic silica particles are known, and can be used in the present invention. In the component (C), abrasive particles containing the hydrophobic silica particles are more preferably used, and abrasive particles composed of the hydrophobic silica particles are further preferably used, from the viewpoint of the water repellency of the cured coating film. The silica particles having surfaces subjected to hydrophobic treatment are silica particles having surfaces of crude silica particles subjected to modification treatment with a hydrophobic treatment agent. As the hydrophobizing agent, fatty acids, resin acids, fatty acid esters, fatty acid metal salts, alkoxysilyl compounds such as silane coupling agents, silazane compounds, silicone oils, and the like are known. Particularly preferred hydrophobizing treatment agents are alkoxysilyl compounds or silazane compounds. As the alkoxysilyl compound, there are known: alkoxysilanes such as methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, butyltrimethoxysilane, octyltriethoxysilane, hexyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, vinyltriethoxysilane, methacryloxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, mercaptopropyltrimethoxysilane, chloropropyltrimethoxysilane, aminopropyltrimethoxysilane, (2-aminoethyl) aminopropylmethyldimethoxysilane, and the like. As the silazane compound, hexamethyldisilazane and the like are known. In these hydrophobizing agents or diluted solutions thereof, the surface of the crude silica particles is modified by stirring the crude silica particles under appropriate conditions.
As commercially available products of the silica particles, for example, AEROSIL (registered trademark) 90, AEROSIL (registered trademark) 130, AEROSIL (registered trademark) 150, AEROSIL (registered trademark) 200, AEROSIL (registered trademark) 255, AEROSIL (registered trademark) 300, AEROSIL (registered trademark) 380, AEROSIL (registered trademark) OX50, AEROSIL (registered trademark) TT600, AEROSIL (registered trademark) 200F, Aerosil (registered trademark) 380, HDK (registered trademark) S13, HDK (registered trademark) V15, HDK (registered trademark) N20, HDK (registered trademark) N20P, HDK (registered trademark) T30, HDK (registered trademark) T40, and the like, which are manufactured by AEROSIL co. Further, as the hydrophobic silica, there are known AEROSIL (registered trademark) R972, AEROSIL (registered trademark) R974, AEROSIL (registered trademark) R104, AEROSIL (registered trademark) R106, AEROSIL (registered trademark) R202, AEROSIL (registered trademark) R208, AEROSIL (registered trademark) R805, AEROSIL (registered trademark) R812, AEROSIL (registered trademark) R7200, AEROSIL (registered trademark) RY50, AEROSIL (registered trademark) RY200, AEROSIL (registered trademark) R, Aerosil (registered trademark) RX200, AEROSIL (registered trademark) RX300, AEROSIL (registered trademark) RX380S, AEROSIL (registered trademark) R976, Wacker HDK (registered trademark) H3932, hdh 38764, hdh 387h 3875, hdh 387h 3, HDK 3, and HDK 3, manufactured by AEROSIL co. These known materials can be used in appropriate combinations as the silica particles.
Further, as the abrasive particles, in addition to 1 or more kinds of abrasive particles selected from the above-mentioned most preferable kaolin and silica, commercially available abrasive particles used in examples may be used. Specifically, as examples of abrasive particles selected from inorganic compounds, commercially available alumina particles are known: AL1600SG3 and AL43M available from showa electric corporation. As a commercially available titanium oxide particle having a surface subjected to water repellent treatment, AEROXIDE TiO manufactured by AEROSIL CORPORATION, Japan, is known2T805, and the like. As a commercially available product of the zinc oxide particles subjected to the surface recombination treatment, FINEX-33W-LP2 made by Sakai chemical industry Co., Ltd is known. As a commercial product of the C salt particles, Celite (registered trademark) 209 manufactured by IMERYS corporation and the like are known. As a commercially available product of heavy calcium carbonate particles, SOFTON 1800 manufactured by Kaolinitum Kaisha and the like are known. As a commercially available product of the light calcium carbonate particles, Brilliant-1500F manufactured by Kaolinitum Kaisha, and the like are known. As an example of the abrasive particles selected from the organic compound, KLT-500F manufactured by XTOKIWA K.K. is known as a commercially available product of tetrafluoroethylene tetrafluoride resin powder.
The abrasive particles of the component (C) have an average primary particle diameter in the range of 0.1 to 10000 nm. In the present invention, the average primary particle diameter of the abrasive particles of the component (C) is more preferably in the range of 0.1 to 2000nm, still more preferably in the range of 0.1 to 500nm, particularly preferably in the range of 0.1 to 200nm, and most preferably in the range of 1 to 150 nm. Within this range, a plurality of species having different average primary particle diameters may be mixed. When the average primary particle size of the abrasive particles is not less than the lower limit of the above range, the surface of the base material can be appropriately smoothed in the polishing treatment. On the other hand, when the average primary particle size of the abrasive particles is not larger than the upper limit of the above range, the coating film after the treatment is free from unevenness, and can be formed to be smooth and have excellent appearance. Here, the average primary particle diameter is an average value when the diameters (sphere equivalent diameters) of 10 or more primary particles are measured at random by an electron microscope. When 2 or more different raw materials are mixed and used as the abrasive particles of the component (C), the average primary particle diameter is defined as an average primary particle diameter of diameters (sphere equivalent diameters) measured by randomly selecting 10 or more primary particles from the mixed powder. Here, the primary particles are particles in a state where a plurality of particles are not aggregated. In particular, it is preferable that the average primary particle diameter of the abrasive particles of the component (C) is in the range of 0.1 to 200nm, in order to obtain the above-mentioned effects more remarkably. Among them, the abrasive particles of the component (C) are particularly excellent in that the above-mentioned effects are most remarkably obtained if the average primary particle diameter is in the range of 1 to 150 nm.
The content of the abrasive particles of the component (C) in the present invention is not particularly limited, but is preferably in the range of 0.01 to 1.0 part by mass, more preferably 0.02 to 0.8 part by mass, and still more preferably 0.025 to 0.75 part by mass, relative to 1 part by mass of the component (a). When the content is not less than the lower limit of the content, the surface treatment composition of the present invention can impart sufficient strength and durability to a cured coating film. On the other hand, when the content is not more than the upper limit of the content, the surface of the substrate after the surface treatment with the surface treatment composition of the present invention is smooth and glossy, and a coating film having excellent appearance can be formed.
In the present invention, the hardness of the abrasive particles of the component (C) is not limited, but is preferably equal to or less than the hardness of the surface of the base material. The action of the abrasive particles of the above (C) in the present invention is, as described above, to cause friction between the particles and the surface of the base material during the polishing treatment, and as a result, the surface of the base material can be polished to an insufficient extent only by the polishing work, and a smooth surface can be formed. The polymer organic silane of the component (a) is cured to form a coating film, and then stays in the coating film to enhance the coating film, thereby contributing to the formation of a coating film having excellent durability.
In addition, in order to improve workability during construction, etc., an organic solvent substantially free of water may be further added as the component (D) to the surface treatment composition used in the present invention. The component (D) is a liquid at room temperature which can dissolve and dilute the components (a) and (B) uniformly, and is not particularly limited as long as it volatilizes for several minutes to several days in a state after film coating at room temperature and normal pressure. In order to maintain the stability of the surface treatment composition during storage, an organic solvent substantially free of water is used as the component (D) in order to avoid reaction between the high-molecular organic silane of the component (a) and the component (D). Examples of the component (D) include: solvent naphtha, n-hexane, isohexane, cyclohexane, petroleum hydrocarbon compounds (mixture of C9 alkylcyclohexane), ethylcyclohexane, methylcyclohexane, n-heptane, 2,4,6, 6-pentamethylheptane, isooctane, n-decane, n-pentane, propylcyclohexane, 1,3, 5-trimethylcyclohexane, 1,2, 3-trimethylcyclohexane, 1,2, 4-trimethylcyclohexane, cyclooctane, 1,3, 5-tetramethylcyclohexane, cyclooctane, isododecane, isononane (isomer mixture of C9 alkane), hydrocarbon compounds such as toluene, xylene, styrene, isoparaffin, hydrogenated light naphtha hydrocarbon compounds, halogenated hydrocarbon compounds such as dichloromethane, trichloromethane, dichloroethane, trichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene, tetrachloroethylene, bromopropane, etc., alcohol compounds such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, cyclohexanol, butane diol, 2-ethyl-1-hexanol, and benzyl alcohol, ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and diacetone alcohol, ethyl acetate, methyl acetate, and butyl acetate, ester compounds such as sec-butyl acetate, methoxybutyl acetate, amyl acetate, n-propyl acetate, isopropyl acetate, ethyl lactate, methyl lactate, and butyl lactate, ether compounds such as diethyl ether, propyl ether, methyl ethyl ether, isopropyl ether, tetrahydrofuran, tetrahydropyran, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 1, 4-dioxane, and propylene glycol monomethyl ether acetate, fluorine-based solvents, and the like, and these may be used alone or in a mixture of a plurality of them.
The content of the component (D) in the case of containing the component (D) in the present invention is preferably in the range of 0.1 to 100 parts by mass, more preferably 0.2 to 75 parts by mass, further preferably 0.5 to 50 parts by mass, and most preferably 1.0 to 10 parts by mass, relative to 1 part by mass of the component (a). When the amount of the surface treatment composition is within this range, appropriate workability is provided when the surface treatment composition of the present invention is used for surface treatment, so that coating is easy and the thickness of the cured coating film is appropriate. In particular, when the component (D) is contained, the content of the component is preferably in the range of 1.0 to 10 parts by mass relative to 1 part by mass of the component (a), from the viewpoint of more remarkably obtaining the above-mentioned effects.
In the surface treatment composition of the present invention, any additive component not contained in the constituent components (a) to (D) of the present invention may be added as appropriate within a range not impairing the properties thereof. For example, a reactive or non-reactive silicone oil, a water repellency-imparting agent such as an alkoxysilane compound, a long-chain alkyl hydrocarbon compound, or a fluorinated alkyl compound, an adhesion-imparting agent such as a silane coupling agent, an anti-aging agent, an anti-rust agent, a coloring agent, a surfactant, a rheology-adjusting agent, an ultraviolet absorber, an infrared absorber, a fluorescent agent, a perfume, a filler, and the like can be selected.
The surface of the substrate to be treated by the polishing machine of the surface treatment method of the present invention may be applied to the body of a vehicle such as an automobile, a two-wheeled automobile, a train, an agricultural vehicle, a ship, and an aircraft, the body of a window, an exterior member such as a rear view mirror, a headlamp, a turn signal lamp, a car width lamp, other lighting equipment, a wheel, a road, a bridge pier, a bridge, a tunnel, a protective wall, a surface of a substrate of a structural member such as a traffic light, a wall of a building such as a house or a building, a power plant, a solar cell panel, an antenna, a gas tank, a vending machine, or a vinyl house, a building such as a roof or a window, or a building member, the surface of the substrate being made of any member such as metal, glass, ceramic, or resin, and a surface of the substrate being made of a member to be coated (also referred to as a coating film) which is obtained by coating the surface of any member. The surface of the substrate to be treated by the polishing machine of the surface treatment method of the present invention is particularly preferably the surface of the substrate made of a pre-coated member to be coated (coated), and most preferably the surface of the substrate made of a member to be coated (coated) which has been coated in advance. The material of the specific member on the surface of the base material to be worked by the surface treatment method of the present invention using the polishing machine is a metal steel plate or a resin. The surface is preferably a surface in which a member to be coated (coated) is coated on a surface of a member made of such a material as a substrate, and particularly preferably a surface in which a steel sheet to be coated used for exterior coating of a vehicle body such as an automobile body and a bumper is coated as a substrate (also referred to as a surface of a steel sheet to be coated) and/or a surface in which a resin member to be coated is coated as a substrate (also referred to as a surface of a resin member to be coated).
The surface treatment method of the present invention is not limited to the method of use thereof, but can be used for a vehicle in a state immediately after coating with a normal paint, that is, in a state of a new vehicle, when applied to the surface of a coated steel sheet and/or the surface of a coated resin member for exterior coating of the vehicle body of the automobile. In addition, the present invention can be used for a vehicle in which the coating is deteriorated by ultraviolet rays, wind and rain, dust, heat, or other external air with the vehicle outside, that is, a used vehicle or a vehicle used for long-term display. In the case of a vehicle used for a new vehicle, a painted surface, for example, a vehicle body or a bumper, painted with a normal paint is treated to maintain its gloss, color, and the like for a long period of time, thereby being able to delay fading degradation. When used in a vehicle such as a second-hand vehicle, the faded coated surface of the vehicle body, bumper, or the like can be restored to a state close to the state immediately after coating by only the treatment by the surface treatment method of the present invention without recoating the coated surface, and the state of the coating film can be protected for a long period of time, thereby exhibiting useful effects in a simple operation.
The polishing machine of the present invention can be used for the construction by a conventionally known method. In general, a polishing machine is an instrument having a driving unit that performs a periodic operation such as a rotation operation, a reciprocating slide, and vibration in any other direction within a certain range using air pressure and electric power as a driving source, and is mainly used for polishing. Among the tools having the same function, the tool mainly used for grinding is called a grinder, but the tools having these functions are not particularly distinguished in the present invention and are collectively called a polisher. An abutting member that directly contacts the surface of the object is disposed in a driving section of the polishing machine. As the contact member, a member called a polished material (バ フ) obtained by processing a fibrous material such as natural fibers or synthetic resin fibers into a sponge shape, a brush shape, a belt shape having a constant thickness, or the like can be used. In addition, a fiber material such as a ready-made nonwoven fabric or a microfiber cloth may be used with or without the above-mentioned polished material. The present invention is directed to a polishing machine, a polishing method, a polishing program, a recording medium, and a recording medium. In this polishing treatment, a liquid material called a polishing agent is impregnated into the abutment member to perform the treatment. However, conventionally known polishing agents generally achieve improvement in workability such as improvement in polishing characteristics and adjustment of frictional resistance by flattening the surface of an object to be polished, and formation of a coating film having excellent durability has not been mainly focused on. In the surface treatment method of the present invention, by using the surface treatment composition of the present invention in place of a conventional polishing agent, it is possible to improve workability of polishing and to form a coating film which can maintain the gloss and color of the coated surface after the treatment over a long period of time and has excellent durability.
The polishing machine usable in the present invention is not particularly limited, and a known commercially available product can be used. The periodic operation of the polishing machine may be any of a rotational operation, a reciprocating slide, and other vibrations in any direction, and the rotational operation is particularly preferable from the viewpoint of ease of work and the appearance of the finished product. In the present invention, the polishing machine that performs the rotation operation is also referred to as a rotary polishing machine, and the rotary polishing machine may be selected from products having different rotation orbits, specifically, a single-action polishing machine, a double-action polishing machine, a gear-action polishing machine, and the like, according to purposes. The single action polisher is a polisher that rotates periodically on a single orbit, and can increase the rotational torque, so that the polishing efficiency of the coated surface is high, and stains such as attachments can be removed in a relatively short time. However, the following features are provided: a certain level of skill is required for the operation in which friction heat generated by the rotation of the polishing machine is large. The double-action polisher is a polisher that periodically rotates while rotating on its own axis on a revolution orbit, and it is generally difficult to increase the rotation torque, so the polishing efficiency as a coated surface is inferior to that of a single-action polisher. However, the following features are provided: the polishing machine is less in heat generation, less in cross-impact and straight-strike of the abutment member during polishing, and the like, and does not require a relative skill in handling. The gear action polisher is a polisher that periodically rotates while performing vibration/eccentric rotation on a revolution orbit, and has a characteristic in the middle of a single-action polisher and a double-action polisher. In the present invention, it is particularly preferable to use each of the polishing machines as appropriate according to the skill of the worker. Among them, from the viewpoint of ease of control of the polishing force, a single-action rotary polisher or a double-action rotary polisher is preferable. The rotation speed of the rotary polisher may be any rotation speed according to the purpose, but in the case of large-area processing, a rotation speed of 100 to 20000 revolutions per minute (1.67 to 333.33s-1) is usually used. In addition, in the case of small area processing or small part processing, a smaller polisher may be used, or processing may be performed with a lower speed rotation. Here, as the drive source of the polisher, any drive source may be used depending on the ease of equipment or work at a work site such as an AC power supply, a battery, and compressed air. The size of the polisher may be any size depending on the area and shape of the surface to be treated and the ease of handling by the operator.
As commercially available products of single action polishers, PE-1400, PE-2010, PE-2100, etc., SI-2400, SI-2009H, SI-2224, etc., C-150N, C-201, etc., manufactured by Centraalbo corporation, PED series, such as PED-130KT, etc., manufactured by Ryobi corporation, P-150N, P-185N, etc., are known, as commercially available products of double action polishers, PEG series, such as PEG-130, manufactured by Ryobi corporation, SI-2415, manufactured by Centraalbo corporation, G-150N, etc., are known, and these known devices can be appropriately selected according to the purpose.
The contact member that can be used in the present invention is not particularly limited, and a known commercially available product can be used in combination with the polishing machine. The contact member is preferably a member obtained by processing a fibrous material such as natural fiber or synthetic resin fiber into a sponge shape, a brush shape, a band shape having a thickness (these are collectively referred to as a ground material), a nonwoven fabric, or a microfiber cloth. The material for these materials may be selected from cotton, silk, hemp, wool, polyurethane, polyester (preferably polyethylene terephthalate), polyethylene, polypropylene, nylon, polystyrene, and the like. The contact member in the present invention is preferably in the form of a sponge or a microfiber cloth, and the material is preferably selected from polyester (preferably polyethylene terephthalate) and nylon. Particularly preferred is a microfiber cloth, which is a cloth-like material obtained by interlacing split composite spun fibers having a fiber diameter of 10 μm or less, and particularly a nanofiber cloth when the split composite spun fibers have a diameter of 0.1 μm or less. By providing such a very fine fiber diameter and having a large surface area, the surface can be made extremely smooth in the surface polishing at the time of polishing treatment, and the liquid agent can be uniformly permeated, so that the work can be performed without unevenness. Further, the microfiber has a characteristic that the fiber fineness is close to the size of the stain film as a characteristic of the microfiber itself, and thus the scraping effect of the oil-film stain is high.
The contact member may be disposed on the drive portion of the polishing machine by any method, and is preferably bonded to the drive portion of the polishing machine through a flat member, which is usually called a pad, and the flat member is preferably used. The thickness of the contact member in the present invention is not limited, and is preferably in the range of 1 to 70 mm. In the case where the thickness of the contact member is small, an arbitrary material (hereinafter, also referred to as a spacer) having an appropriate thickness may be combined with the contact member to compensate for the thickness in order to improve workability, and in this case, the total thickness of the contact member and the spacer is preferably within the above range. Here, the spacer may be replaced with a member made of the same material as the polished object. In addition, in the case of using the spacer, a method of bonding the abutment member to the polisher or the pad, and a method of bonding the abutment member-spacer combination to the polisher or the pad may be selected from suitable methods such as adhesion with an adhesive, thermal fusion, sewing, surface fastener, fixation with rubber or string, and coating with a cover. Here, when the ultra-fine fiber cloth is used as the contact member, the pad or the spacer is made of a soft material, and the surface of the pad or the spacer is bonded with an adhesive to the back side of the hook-shaped raised part of the surface fastener. The hook-shaped raised portion is preferably bonded to the microfiber cloth by directly contacting the raised portion with the microfiber cloth and by interweaving the raised portion with the fibers forming a loop of the microfiber cloth. In this case, it is more preferable to use a material in which the surface of the ultrafine fiber cloth is raised to a length that is so long as to be entangled with the hook-shaped raised portions of the surface fastener. The length of the fuzz is preferably about 0.5 to 10mm from the surface of the surface fastener fuzz and the surface of the ultra-fine fiber cloth. As commercially available products of the ultrafine fiber cloth, a Belima (registered trademark) series of split composite spun fibers made of nylon and polyester manufactured by KB SEIREN corporation, a Toraysee (registered trademark) series of sea-island composite fibers made of polyester manufactured by dongli corporation, and the like are known, and these can be appropriately selected from these according to the purpose. The size of the abutment member, pad, spacer, etc. may be any size depending on the area and shape of the surface to be treated and the ease of handling by the operator.
In the surface treatment method of the present invention, the surface treatment composition is dropped on the abutment member or on the surface of the substrate as the surface to be treated in an appropriate amount, and the surface of the substrate as the coating surface to be treated is polished, thereby simultaneously polishing the surface of the substrate and applying the surface treatment composition. The amount of the coating is about 0.01 to 25ml, preferably about 0.1 to 10ml, per one time of polishing of the abutment member, and the surface of the substrate to be treated is polished. If the surface treatment composition is removed from the abutment member to a certain extent, the surface treatment composition is dropped again onto the abutment member to make it uniform, and the surface treatment is performed again, preferably by the above-described steps. By setting the amount of impregnation in the abutment member within an appropriate range at a stroke, a homogeneous and flat cured coating film can be relatively easily obtained. By the polishing treatment, stains such as grease and solid components are removed by the polishing action of the abrasive particles in the surface treatment composition, and the stains and the detached abrasive particles are adsorbed to the abutment member as the treatment progresses. As a result, the following states were obtained: the surface treatment composition, which is a component for forming a coating film in the present invention, adheres to the surface of the substrate, which is the coating surface, without leaving any stain on the surface of the substrate, which is the coating surface after the treatment. As a technique for forming a coating film having good appearance and excellent durability, conventionally known methods require two-stage operations of polishing by a polishing treatment and then applying a surface treatment agent containing other reactive silicone or the like. However, in the present invention, after the polishing treatment, the other steps of applying the surface treatment agent can be eliminated, and the productivity can be greatly improved.
After the application by the buffing treatment, the surface treatment composition is allowed to stand at normal temperature or under a heated environment, and when a volatile component is contained, the volatile component is volatilized and a crosslinking curing reaction proceeds, thereby forming a cured coating film on the surface of the substrate as a coated surface. Thereafter, if necessary, a post-treatment of wiping the surface of the cured coating film with a cloth or the like is performed, whereby the surface of the cured coating film having excellent appearance can be formed. The surface of the cured coating film may be subjected to a conventionally known post-treatment method of wiping with a cloth or the like containing a liquid such as water or a silicon emulsion and then performing dry wiping, or may be subjected to a post-treatment by a suitable method.
The present invention also relates to a surface treatment composition used in the above surface treatment method. The composition for surface treatment of the present invention is a composition for use in the above-mentioned construction by a polishing machine, and comprises the following components:
(A) a high-molecular organic silane having a reactive group,
(B) A reaction catalyst,
(C) Abrasive particles having an average primary particle diameter of 0.1 to 10000 nm.
The components described above are the same as those of the surface treatment composition included in the present invention relating to the surface treatment method, and other optional components are also based on the same.
Examples
Hereinafter, the effects of the present invention will be described in detail by examples, but these examples are not intended to limit the embodiments of the present invention.
The properties of the surface treatment composition used in the present invention were evaluated by the following methods, examples and comparative examples. Here, as a composition suitable for use in forming a film, it is preferable that all the properties are acceptable. The surface treatment compositions (hereinafter, also simply referred to as "compositions") or the treatment agents evaluated in the examples and comparative examples of the present invention were prepared by mixing the raw materials shown in table 1 at the mass ratios shown in the table and stirring at 25 ℃ for 20 minutes. The blank column in table 1 indicates that the raw material was not used.
[ preparation of test piece ]
Scratch resistance evaluation test piece
In order to evaluate scratch resistance, a test piece was prepared by the following method, which was a material obtained by reproducing flaws on the coated surface. For the standard based on JIS G3141: 2017, a black coated plate (material: SPCC-SD (cold rolled steel plate), size: 0.8 mm. times.70 mm. times.150 mm, coated plate which was subjected to a black amino alkyd coating on one side after chemical electrodeposition and top clear coating, manufactured by Asahi beer Techno (アサヒビーテク ノ)), was coated with a coating solution containing a liquid composition (scratch-resistant 3000) manufactured by Soft 99Corporation, a fine-meshed polyurethane sponge as an abutting member, and a double-action polisher PED-130 manufactured by Ryobi Corporation at 8000rpm (1335s polishing) to form a coating film-1) The rotation speed of (3) was subjected to polishing treatment for 20 seconds and sufficiently ground, thereby forming a smooth surface in advance. The surface to be treated was treated with a composition containing 5 mass% of a surfactant according to JIS Z8901: in 2006, the flannel cloths of the water suspensions of 7 types (kanto mud powder) of the test powder 1 were vigorously rubbed with hands 10 times to generate scratches due to the mud powder. Then, the surface was sufficiently cleaned with running water, and then degreased and cleaned with isopropyl alcohol, and the resultant was used as a scratch resistance evaluation test piece.
Preparation of test piece for evaluation of rain-stain removability
In order to evaluate the rain stain removability, a test piece was prepared by the following method, which reproduced a material having rain stains on the coated surface. This test piece was obtained by dropping 1 drop (0.05ml) of tap water to the side of the scratch resistance evaluation test piece using a dropper, and then placing the test piece in a constant temperature drying oven set at 50 ℃ for 1 hour to evaporate water. The surface was left with residues of bleaching powder components derived from tap water, and the stains were spotted to form virtual rainstains observed, thereby obtaining a test piece for evaluating rainstain removability.
[ evaluation tests for scratch resistance and rain-stain removability ]
As the contact member used for the polishing treatment, a polyurethane sponge polishing product (product of SOVEREIGN, product of "polyurethane sponge polishing product for polisher (for fine eyes)", hereinafter also referred to as "sponge polishing product") having a diameter of 180mm and a thickness of 30mm or a sponge polishing product as a spacer was used, and a microfiber cloth (hereinafter also referred to as "fiber polishing product") was bonded thereto. The latter is prepared by the following sequence.
Preparation of the fiber polishing material: a fiber-polished product was produced by cutting a cloth-like ultrafine fiber cloth (ThreeBond 6649G manufactured by Kagaku Kogyo Co., Ltd.) of 75% by mass of polyethylene terephthalate and 25% by mass of polyamide and having a thickness of 0.5mm into a circular shape having a diameter of 185mm, and bonding the cut cloth to the polyurethane-made sponge-polished product. The surface fastener is bonded to the surface of the sponge-like ground material by adhering the back surface of the hook-like raised portion side of the surface fastener with an elastic adhesive, and the surface of the raised portion of the surface fastener is directly brought into contact with the microfiber cloth.
The surface treatment composition described in examples 1 to 12 and comparative example 1, which will be described later, was dropped on the surface of each of these abutment members with a 3g (about 2.5ml) dropper, and gently impregnated. The contact member was disposed at a drive portion of a double action polisher PED-130 manufactured by Ryobi corporation, and the coating surfaces of the scratch resistance evaluation test piece and the rain stain removal evaluation test piece were set at 8000rpm (1335 s)-1) Is subjected to a polishing treatment for 20 seconds. Within 5 minutes after the treatment, the treated surface was uniformly wiped with a dry and clean ultrafine fiber cloth (ThreeBond 6649G), and each evaluation was performed. On the other hand, the test pieces of comparative examples 2 and 3 were constructed as follows. Each test piece was impregnated with the surface treatment composition or treatment composition without using a polishing machine on the coated surfaceThe above sponge polishing of the treatment agent was rubbed with a hand for 20 seconds in a whirling manner, and then the surface was uniformly wiped with a dry and clean ultra-fine fiber cloth (ThreeBond 6649G) within 5 minutes, thereby treating.
[ evaluation criteria for scratch resistance and rain-stain removability ]
Evaluation of scratch resistance
The coated surface of the scratch resistance evaluation test piece after the above scratch resistance and rain stain removal evaluation test was evaluated by comparing and observing the state before and after the evaluation test. The observation means is performed by visual confirmation of the state of remaining scratches and color difference comparison using a spectrophotometer. The above spectrophotometer was used to measure the color difference Δ L before and after the evaluation test using CM-2600D manufactured by Konika Mingta, measurement mode SCE, field of view 10 °, and "CIE standard illuminant D65" as measurement conditions. The results are also shown in Table 1 based on the following evaluation criteria. Here, the color difference Δ L value is an index of whiteness, and since the scratch mark on the coating surface is removed by the surface treatment method of the present invention, the diffuse reflection from the scratch mark is reduced, and therefore, it is judged that the scratch resistance is increased as the value becomes smaller, that is, the whiteness is reduced. In the evaluation based on any of the surface treatment compositions, the state after the above test was that large and deep scratches were significantly reduced and the gloss was increased by visual observation:
the evaluation results are in the range of-3.0 < DeltaL ≦ -2.0, labeled ○
The evaluation results are in the range of 4.0< DeltaL ≦ -3.0, labeled ◎
The result of the evaluation is a range of preferably-6.0 < DeltaL ≦ -4.0, labeled ◎◎.
Evaluation of rain-stain removability
The state of the virtual rain stain present on the coating surface of the rain stain removability evaluation test piece after the above-described evaluation tests for scratch resistance and rain stain removability was evaluated by comparing with the state before the evaluation test by visual observation. The results are based on the following evaluation criteria and are also shown in table 1. If the area of the virtual raindrop is reduced to be within a range of 30% to 100%, the virtual raindrop is determined to be acceptable and acceptable, and if the area of the virtual raindrop is reduced to be less than 30% and does not change from before application, the virtual raindrop is determined to be difficult to be practical and unacceptable.
The evaluation results showed no significant change compared to the pre-coating results and were marked as
The area of the non-defective rain spot was evaluated to decrease by less than 30%, and was designated △
The evaluation results showed that the area of good (pass) · virtual rain stain was reduced to 30% or more and less than 100%, or 100% disappeared, but only the trace of the virtual rain stain was confirmed when viewed from each angle, which was marked ○
As a result of the evaluation, the area of the excellent (acceptable) · virtual rainstain disappeared 100%, and no trace was observed even from each angle, which was marked ◎.
[ Water repellency evaluation test and evaluation criteria ]
Each scratch resistance evaluation test piece polished by the above scratch resistance and rain stain removal evaluation tests was left to stand at 25 ℃ for 1 day, and thereafter, the contact angle of pure water (1 μ L) to the surface to be treated of the test piece was measured using a contact angle meter "MSA" manufactured by KRUSS corporation which can measure the contact angle fully automatically. The results are shown in table 1 as initial contact angles (°). The characteristic value of the coating film having excellent water repellency (stain resistance) is about 95 or more.
[ evaluation test for durable Water repellency and evaluation Standard thereof ]
Each of the scratch resistance evaluation test pieces after polishing treatment in the above scratch resistance and rain stain removal evaluation tests was allowed to stand at 25 ℃ for 7 days. Thereafter, the surface of the test piece to be treated was subjected to abrasion by setting a friction material at a speed of 30 times/min, a moving distance of 100mm and a load of 500g using a simple friction tester (manufactured by yohimoto corporation) and 100 strokes, and the water contact angle of the coating surface after the abrasion treatment was measured as a contact angle (degree) after the durability test to evaluate the durable water repellency. Here, the friction material used in this test was: a dry clean fabric (water-absorbent fabric made of cellulose/cotton composite fiber, ThreeBond 6644E manufactured by triple bond Co., Ltd.) having a width of 40mm was sufficiently impregnated with distilled water, and was wound around a stainless steel cylinder having a diameter of 20 mm. The friction material is set so that the axis of the cylinder faces in a direction perpendicular to the sliding direction, and the friction material is slid. After the sliding treatment, the steel sheet was left to stand at room temperature for 30 minutes to be dried, and the contact angle after the durability test measured by the same method as the above-mentioned water repellency evaluation test is shown in table 1. The characteristic value of the coating film having excellent durable water repellency (durable stain resistance) is about 90 or more.
The following raw materials were used in the surface treatment compositions and the treatment agents of the examples and comparative examples.
[ composition for surface treatment ]
< ingredient (a): commercially available product of high-molecular organic silane having reactive group >
KR-500: in the above formula (1), R4、R5A partial hydrolysis condensate of an alkoxysilane compound each having a methyl group, a compound having a weight average molecular weight of about 1000, and a dynamic viscosity of 25mm at 25 ℃2s-1The reactive silicon oligomer of (1), manufactured by shin-Etsu chemical Co., Ltd
X-40-9250: in the above formula (1), R4、R5A partially hydrolyzed condensate of an alkoxysilane compound which is methyl in all, has a weight average molecular weight of about 2100 and a dynamic viscosity of 160mm at 25 ℃2s-1The reactive silicon oligomer of (1), a product of shin-Etsu chemical Co., Ltd
X-40-2327: in the above formula (1), R4、R5A partial hydrolytic condensate of an alkoxysilane compound which is methyl and has a dynamic viscosity of 0.9mm at 25 DEG C2s-1Contains 30 mass% of a reaction catalyst as component (B): X-40-2309A, available from shin-Etsu chemical Co., Ltd
X-22-170 DX: single terminal methanol modified dimethylSilicone oil (polydimethylsiloxane) having a dynamic viscosity of 40mm at 25 DEG C2S-1, manufactured by shin-Etsu chemical industries, Ltd
A-1: a dimethylsilicone oil having silanol groups at both ends and having a viscosity of 5100 mPas at 25 ℃.
< ingredient (B): commercial product of reaction catalyst >
DX 9740: alkoxyaluminum compound, product of shin-Etsu chemical Co., Ltd
D25: organic titanium Compound, product of shin-Etsu chemical Co., Ltd
X-40-2309A: phosphate, manufactured by shin Etsu chemical industries Co.
< ingredient (C): commercially available abrasive particles having an average primary particle diameter of 0.1 to 10000nm >
Satytone (サテント ン) (registered trademark) 5 HB: particles of unfired kaolin manufactured by BASF Corp, having an average primary particle diameter of 0.8 μm
Translink (トランスリン ク) (registered trademark) 77: kaolin clay prepared by BASF Corp having a surface-treated calcined clay particle with an average primary particle diameter of 0.8 μm
AL1600SG 3: amorphous alumina particles having an average primary particle diameter of 0.5 μm manufactured by Showa Denko K.K
AL 43M: amorphous alumina particles having an average primary particle diameter of 1.5 μm, available from Showa Denko K.K
Aerosil (registered trademark) R972: fumed silica particles having an average primary particle diameter of 16nm and having a surface treated with dimethyldichlorosilane and having been made by AEROSIL CORPORATION, Japan
Aerosil (registered trademark) R976: fumed silica particles having an average primary particle diameter of 7nm and having a surface treated with dimethyldichlorosilane and having been made by AEROSIL CORPORATION, Japan
Aerosil (registered trademark) R805: fumed silica particles having an average primary particle diameter of 12nm and having a surface treated to have water repellency with octylsilane, manufactured by AEROSIL CORPORATION, Japan
Aerosil (registered trademark) 200: fumed silica particles having an average primary particle diameter of 12nm and having no surface treatment, manufactured by AEROSIL CORPORATION, Japan
Aerosil (registered trademark) RX 380S: fumed silica particles having an average primary particle diameter of 7nm and having a surface treated with a hydrophobic agent by hexamethyldisilazane, manufactured by AEROSIL CORPORATION
AEROXIDE TiO 2T 805: titanium oxide particles having an average primary particle diameter of 40nm and subjected to hydrophobic treatment on the surface with octylsilane, manufactured by AEROSIL CORPORATION, Japan
FINEX-33W-LP 2: surface-treated Zinc oxide particles having an average Primary particle diameter of 35nm made by Sakai chemical industry Co., Ltd
KLT-500F: polytetrafluoroethylene resin powder manufactured by Xylomura corporation having an average primary particle diameter of 1 μm
Celite (registered trademark) 209: average primary particle size of C salt particles manufactured by IMERYS corporation of 8 μm
SOFTON 1800: ground calcium carbonate particles having an average primary particle diameter of 1.25 μm, manufactured by Baishi calcium Co., Ltd
Brilliant-1500F: the average primary particle diameter of the light calcium carbonate particles was 150nm, manufactured by Baishi calcium Co.
< ingredient (D): commercially available product of organic solvent substantially free of water >
Swaclean 150: mixture of C9 alkylcyclohexane, initial boiling point 145 deg.C, dry point 170 deg.C, pill-good petrochemical Co., Ltd
Marukazole R: 2,2,4,6, 6-pentamethylheptane, boiling point 177 ℃, Takayasu petrochemical Co
Kyowazol C-900: isononane (isomer mixture of C9 alkane), initial boiling point 131 deg.C, dry point 141 deg.C, KH Neochem
Exxsol (registered trademark) D40: an organic solvent containing a hydrogenated light naphtha hydrocarbon compound, having an initial boiling point of 166 ℃, a dry point of 191 ℃ and a product of ExxonMobil
Isopar (registered trademark) E: an organic solvent containing isoparaffin, having an initial boiling point of 114 deg.C, a dry point of 139 deg.C, manufactured by ExxonMobil
N-propanol: fuji film and reagent manufactured by Wako pure chemical industries, Ltd
Solve 55: fluorine-containing solvent, product of Solvex corporation
PMA: propylene glycol monomethyl ether acetate, manufactured by Sanshika chemical Co., Ltd.
[ treating agent: comparative example 2 Material used ]
Commercial semi-solid wax with abrasive: a composite wax-dark and metallic color vehicle manufactured by Rinrey corporation.
[ tables 1-1]
[ tables 1-1]
Figure BDA0002312628910000281
[ tables 1-2]
[ tables 1-2]
Figure BDA0002312628910000291
[ tables 1 to 3]
[ tables 1 to 3]
Figure BDA0002312628910000301
[ tables 1 to 4]
[ tables 1 to 4]
Figure BDA0002312628910000302
Note that 1) all units of numerical values indicating the contents of raw materials of the components of the compositions of examples in tables 1 to 1 and tables 1 to 2 and comparative example 1 are "mass%".
Note 2) the blank column of the raw materials for the components of the compositions of tables 1-1 and 1-2 for each example and comparative example 1 indicates that the raw materials are not included. That is, the content of the raw material in the blank part was 0 mass%.
Note that 3) the component (D) of the compositions of examples 1 to 4 in tables 1 to 1 and 1 to 2 and the components (C) and (D) of the composition of comparative example 1 do not contain the respective raw materials. Therefore, the total content of the components (C) and (D) is indicated as "0" (mass%).
Note 4) in comparative examples 2 and 3 of tables 1 to 2, a treating agent (comparative example 2) or a composition and a method of applying the same (comparative example 3) are described instead of the contents of raw materials representing the components of the composition.
Note 5) preparation of "X-40-2327" of ingredient (A) of example 8 of Table 1-1: 30 parts by mass of a reaction catalyst "X-40-2309A" containing the component (B) 9 parts by mass.
[ conditions of polishing machine and types of polished materials ]
The test pieces were polished under various conditions shown in examples 13 to 20 and comparative example 4 in table 2 using the surface treatment composition described in example 5. As the test body, the entire body surface coating portion of an automobile (AiRWave (black, continuous riding for 2007 to 2016, travel distance 106000km)) used as a passenger car was used. The automobile is characterized in that the whole body of the coating part on the surface of the automobile body is uniform, and a large number of fine scratches and rain stains are observed. The coated portions of the vehicle body surface were divided into 30cm × 30cm sections, and the polishing treatment with the surface treatment composition was applied to each section under the conditions shown in table 2. After the surface was uniformly wiped with a dry and clean ultrafine fiber cloth (ThreeBond 6649G) until 5 minutes passed after the treatment, the following items were evaluated for each part after the treatment, and the results are shown in table 2. The types and product names of the polishing machines used for the evaluation are as follows.
Ryobi PED-130: electric double-action polishing machine manufactured by Ryobi corporation
Makita PV 7001C: electric single-action polishing machine manufactured by Makita corporation
Ryobi PEG-130: electric gear action polisher manufactured by Ryobi corporation
Compact Tool P-150N: electric double-action polishing machine manufactured by Compact Tool corporation
Compact Tool MODEL 942: air-driven mini double-action sander manufactured by Compact Tool corporation
Compact Tool MODEL 813: air-driven orbital sander manufactured by Compact Tool corporation.
The "electric drive" and the "air drive" respectively indicate that the drive source is electric power or air pressure, and the "single action", "double action", and "gear action" respectively indicate the drive methods. "mini" indicates that the size of the driving unit is smaller than a normal diameter, and "orbital sander" indicates a device of a driving method that performs eccentric motion while vibrating.
[ polishing efficiency ]
The polishing efficiency was evaluated for a time required until scratches were scratched in the treated portion of the test piece and were hardly visible by visual observation. The results are based on the following evaluation criteria and are also set forth in table 2:
the evaluation result is that the time is not more than 5 minutes, and the mark is a substantial one
The evaluation result is within the range of 1-5 minutes, and is marked as ○
The result of the evaluation was a good · · less than 1 minute, labeled ◎.
The evaluation was performed by the following steps, and the total of the time for actually performing the polishing treatment was evaluated: the surface state was carefully observed by wiping with a dry cloth at a timing when the flaw was hardly visible in the visual processing portion, and if it was confirmed that a minute flaw remained, the polishing process was performed again.
[ easiness of work ]
An actual operator evaluates whether it is easy to perform control for holding the polisher at a position suitable for coating without generating scratches on the vehicle body. The results are shown in table 2 based on the following evaluation criteria:
the evaluation result was that the labor required for the good · · control was small and fatigue was hard to feel, and it is marked ◎
As a result of the evaluation, the labor required for the control was large, and the control was easy to feel fatigue, but the evaluation was carried out, and the result is marked ○
The evaluation results were that the control was impossible or that the labor required for the control was significantly large and fatigue was great, and the results were marked as "x".
[ Water repellency ]
On the coated surface after the treatment under each of the above conditions, 10ml of tap water was sprayed by hand after 1 hour from the treatment, and the water-repellent state was visually observed and evaluated. The results are set forth in table 2 based on the following evaluation criteria:
the evaluation results showed that the shape of the water droplet at the portion after ejection was circular, and if the water droplet was rapidly dropped, it was judged that the water repellency was excellent, and the mark was ◎
As a result of the evaluation, the shape of the water droplet at the sprayed portion was not rounded, and the water repellency was judged to be deteriorated without rapid dropping, and the mark was X.
[ Table 2]
Figure BDA0002312628910000331
In table 2, the same polishes as those in table 1 were used for the sponge polishes and the fiber polishes of the contact member. In the fiber polishing product, the thickness of the base polyurethane sponge was set to 10mm instead of 30 mm.
From the results shown in table 1, it is understood that the scratch resistance and the rain stain removal property were good and the contact angles at the initial stage and after the durability test were sufficient in the case of applying the surface treatment composition by the polishing treatment in the surface treatment methods of examples 1 to 4, that is, in the case of applying the surface treatment composition by the polishing treatment. This confirmed that the antifouling property and the durable antifouling property were both excellent. On the other hand, as shown in comparative examples 1 to 2, it was found that the performance of sufficiently removing stains was insufficient because the rain stain removing property was insufficient without the surface treatment method using the surface treatment composition of the present invention. In addition, in comparative example 2, the contact angle after the durability test was insufficient, and thus the required characteristics were not satisfied in the durable stain-proofing property. As shown in comparative example 3, it was found that the ability to remove stains sufficiently was insufficient because the rain stain removing ability was insufficient without using the surface treatment method of the present invention. From examples 5 to 12, it was confirmed that the surface treatment composition used in the present invention can be used also by further including (D), and that the respective properties exhibit high performance and a well-balanced and excellent function by combining the respective components (a), (B), (C), and (D) in various kinds and composition ratios within the range of the present invention.
Further, from the results shown in table 2, it was confirmed that according to examples 13 to 20, when the surface treatment method of the present invention was used, various kinds and conditions of a polishing machine or an abutment member such as a polished material can be applied to equipment and structures represented by an automobile surface-coated surface. Thus, the usefulness of the surface treatment method of the present invention is demonstrated. On the other hand, as shown in comparative example 4, it was confirmed that when the surface treatment method of the present invention was not used, although there was no problem in water repellency, the polishing efficiency and the ease of work were not sufficient, and it was not a method for improving the work efficiency.
Fig. 1 shows photographs of the automobile surface coated part before and after the treatment in example 14, wherein a represents a state before the treatment and b represents a state after the treatment. The white point in the photograph is a reflection of the LED lamp for appearance inspection. As a state before the treatment, a was found to be a state in which a small scratch was large as a whole and a cloudiness was caused by a spot-like stain on the surface or diffuse reflection of light due to a small scratch, and the contour of the reflection of the LED lamp was unclear and the visibility was poor. B, which is the state after the treatment, is a surface state of a blacker and deep glossy surface with the above-mentioned small scratches and diffuse reflection suppressed. Further, the LED lamp was found to have a clear outline and improved visibility.
Industrial applicability
The surface treatment method of the present invention is extremely useful for forming a coating film having improved appearance and excellent durability at one time by simple construction with little force dependency of an operator on the surface of a base material used for a vehicle body of an automobile or various building structural members, equipment members, and the like.
The present application is based on the japanese patent application No. 2017-117664 filed on 6/15/2017, the disclosure of which is incorporated by reference in its entirety.

Claims (16)

1. A surface treatment method for polishing and coating film formation treatment of a surface of a base material, wherein a surface treatment composition is used and applied by a polishing machine, the surface treatment composition comprising:
(A) a high-molecular organic silane having a reactive group,
(B) A reaction catalyst, and
(C) abrasive particles having an average primary particle diameter of 0.1 to 10000 nm.
2. The surface treatment method according to claim 1, wherein the content of (B) is 0.001 to 0.5 part by mass and the content of (C) is 0.01 to 1.0 part by mass with respect to 1 part by mass of the (A).
3. The surface treatment method according to claim 1 or 2, wherein the (a) is an organopolysiloxane having a reactive group.
4. A surface treatment method according to any one of claims 1 to 3, further comprising (D) an organic solvent substantially free of water in a range of 0.1 to 100 parts by mass relative to 1 part by mass of the (A).
5. The surface treatment method according to claim 4, wherein the content of (D) is in the range of 1.0 to 10 parts by mass relative to 1 part by mass of (A).
6. The surface treatment method according to any one of claims 1 to 5, wherein the reactive group of (A) is a hydrolytic-polymerizable reactive group.
7. The surface treatment method according to any one of claims 1 to 6, wherein the average primary particle diameter of the (C) is in the range of 0.1 to 200 nm.
8. The surface treatment method according to any one of claims 1 to 7, wherein the average primary particle diameter of the (C) is in the range of 1 to 150 nm.
9. The surface treatment method according to any one of claims 1 to 8, wherein the (C) is an abrasive particle containing an inorganic compound.
10. The surface treatment method according to any one of claims 1 to 9, wherein the (C) is an abrasive particle comprising a silica particle having a surface subjected to hydrophobic treatment.
11. The surface treatment method according to any one of claims 1 to 10, wherein the surface to be finished by polishing is a coated surface which is previously coated.
12. The surface treatment method according to claim 11, wherein the surface to be coated that is coated in advance is a surface of a steel sheet to be coated and/or a surface of a resin member to be coated for use in exterior body trim of an automobile.
13. The surface treatment method according to any one of claims 1 to 12, wherein the polishing machine is a rotary polishing machine.
14. The surface treatment method according to claim 13, wherein the rotary polisher is a single-action rotary polisher or a double-action rotary polisher.
15. The surface treatment method according to any one of claims 1 to 14, wherein a polishing machine provided with an abutment member made of ultrafine fibers is used for the application.
16. A surface treatment composition for use in construction of polishing machines, comprising:
(A) a high-molecular organic silane having a reactive group,
(B) A reaction catalyst, and
(C) abrasive particles containing an inorganic compound having an average primary particle diameter of 0.1 to 10000 nm.
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Application publication date: 20200124