JP2009242505A - Coating material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating material forming a cured layer having hardness corresponding to hardness of an object to be coated with the coating material by selecting a blending ratio of a silane compound to an organosiloxane oligomer according to the hardness of the object. <P>SOLUTION: In the coating material for forming the cured layer to protect the object by mixing the organosiloxane oligomer and the silane compound and applying the resultant mixture on the object, upon addition of the silane compound, an addition rate of the silane compound to 100 pts.wt. organosiloxane oligomer is selected so that the cured layer having pencil hardness equal to or harder than the pencil hardness of the object is formed based on the fact that the pencil hardness of the cured layer is changed in a range of 9H to F by adding 1 to 28 pts.wt. silane compound to 100 pts.wt. organosiloxane oligomer. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention provides a coating material that can form a hardened layer having a hardness corresponding to the hardness of the object by selecting a blending ratio of the silane compound to the organosiloxane oligomer according to the hardness of the object to which the coating material is applied. About.

  Conventionally, a method of providing a coating layer (cured layer) made of silicon resin or polymer on a painted surface of a vehicle body has been proposed. For example, a two-component mixed paint containing an organic solvent and silicone resin is applied to the body of an automobile and wiped, and another two-component mixed paint having different components is applied and wiped off, thereby forming a silicone resin on the vehicle body. A method of providing a coating layer has been proposed, but this method uses two types of two-component mixed paints, which requires time and effort for mixing work, and is suitable for continuous work because the composition differs from process to process. There was no problem. In addition, since the mixed paint contains an organic solvent, there is a problem that the viscosity of the paint and the resin concentration change with time, and the ease of applying the paint and the thickness of the paint change. In addition, the coating layer produced by the above method may have fingerprints or interference fringes after drying.

In recent years, a one-pack type coating material that solves such problems has been proposed (see, for example, Patent Documents 1 and 2).
JP 05-68942 A JP 2006-77071 A

  Patent Document 1 describes a coating material for protecting a reflecting mirror obtained by mixing a silica-dispersed oligomer solution of organosilane, a silanol group-containing polyorganosiloxane, and a catalyst. Patent Document 2 describes an organolane oligomer. And a coating material for protecting automobile paint, which contains a catalyst, a silane compound, and a titanium compound and has a viscosity at 25 ° C. of 50 mPa · s or less.

  However, Patent Documents 1 and 2 do not describe any technique that enables the formation of a hardened layer having a suitable hardness corresponding to the material of the object to which the coating material is applied, particularly the hardness of the object surface, Therefore, since there has conventionally not been an index for forming a hardened layer having a hardness corresponding to the hardness of various objects, a hardened layer having a predetermined hardness is obtained by trial and error for each of various objects. The blending ratio of each component was adjusted so that the process was formed, and this had the problem that the work became very complicated.

  That is, in order to protect the object over a long period of time by applying a coating material to the object to form a cured layer, a cured layer having a hardness corresponding to the hardness of the object is formed, and It is desirable that cracks such as cracks do not occur.

  For example, moving bodies such as automobiles, trains, airplanes, etc., and guardrails, iron bridges, and other metal structures such as iron, aluminum-based metals, and stainless steel that are installed outdoors are severely affected by the impact of flying objects and wind and rain. In order to protect the substrate over a long period of time by preventing problems such as erosion and wear due to rust and the like. In the case of a substrate provided with such a coating, the cured layer formed by applying the coating material needs to be set to a hardness that can stably protect the coated surface over a long period of time.

  On the other hand, in the case of a base material made of unpainted metal, tile, concrete, stone, hardness plastic, etc., the coating material is applied directly to the object that is the surface of the base material. The hardness of the hardened layer is desired to be equal to or higher than the hardness of the substrate surface, and it is desired to set the hardness as high as possible within a range not causing the problem of cracking of the hardened layer.

  In addition, in the case of a deformable base material such as a thin and deformable metal, soft plastic, wood, etc., the problem is that the hardened layer is cracked or peeled off, so the hardened layer may be cracked even if the base material is deformed. It is desirable to set the hardness as high as possible within the range where peeling does not occur.

  In the past, there was no coating material that could cope with the hardness of the object despite the above-mentioned requirements. Therefore, when manufacturing the coating material, trials were made for each object hardness. A complicated work of adjusting the hardness of the cured layer by adjusting the blending ratio of each component while making mistakes was required.

  The present invention has been made in view of the above problems, and by selecting the blending ratio of the silane compound to the organosiloxane oligomer according to the hardness of the object to which the coating material is applied, the hardness corresponding to the hardness of the object is obtained. An object of the present invention is to provide a coating material capable of forming a cured layer.

  The present invention is a coating material for protecting a target object by forming a cured layer by mixing an organosiloxane oligomer and a silane compound and applying the mixture to the target object. Based on the fact that the pencil hardness of the cured layer changes in the range of 9H to F by adding 1 to 28 parts by weight, a cured layer having a pencil hardness equal to or higher than the pencil hardness of the object is formed. The present invention relates to a coating material characterized by selecting and adding an addition ratio of a silane compound with respect to 100 parts by weight of the organosiloxane oligomer.

  In the above coating material, the addition ratio of the silane compound with respect to 100 parts by weight of the organosiloxane oligomer in the case of applying to an object consisting of coating on the substrate is 1 to 20 parts by weight, preferably 3 to 16 parts by weight. The pencil hardness of the hardened layer at this time is 9H to 4H, preferably 8.5H to 5H.

  In addition, in the coating material, when the silane compound is added to 100 parts by weight of the organosiloxane oligomer when directly applied to an object on the substrate surface, the pencil hardness of the cured layer is equal to or higher than the pencil hardness of the substrate surface, and It is preferable that it is the addition ratio which shows the pencil hardness below which a crack occurs in a hardened layer.

  In addition, in the above coating material, when the silane compound is added to 100 parts by weight of the organosiloxane oligomer when applied to an object that is the surface of the base material to be deformed, the pencil hardness of the cured layer is 20 parts by weight or more indicating 4H or less. The addition ratio is preferable.

  In the coating material, it is preferable to add a catalyst for adjusting the curing rate.

  According to the coating material of the present invention, by determining the relationship between the addition ratio of the silane compound and the pencil hardness of the cured layer when the addition ratio of the silane compound to the organosiloxane oligomer is changed, the pencil hardness of the object is obtained. The coating material can be manufactured by selecting the addition ratio of the silane compound with respect to the organosiloxane oligomer so that a cured layer having a pencil hardness equal to or higher than that can be formed. Therefore, by applying this coating material to an object It is possible to form a hardened layer with a suitable pencil hardness according to the pencil hardness of the object, and also prevent problems such as erosion due to rust, wear, etc. by preventing the problem of cracking of the hardened layer An excellent effect that the object can be stably protected over a long period of time can be achieved.

  The coating material of the present invention is produced by mixing (a) an organosiloxane oligomer, (b) a silane compound, and (c) a catalyst for adjusting the curing rate as necessary.

The reaction of the coating material comprising the above (a) organosiloxane oligomer and (b) silane compound is represented by the following formula (1)
[Chemical 1]
2 3 Si-OR + 2H ₂ O → 2 3 Si—OH + 2 ROH ↑ → 3 Si—O—Si 3 + H ₂ O
Three Si-OR + three Si-OH → three Si-O-Si- + ROH ↑ (1)
And the reaction is initiated by moisture in the air. The three-dimensionally crosslinked siloxane skeleton exhibits a high hardness by having a large binding energy.

  While the organosiloxane oligomer is an oligomer (low polymer) polymerized to some extent, the silane compound is a monomer having a functional group that reacts with an organic material and a functional group that reacts with an inorganic material at the same time in the molecule ( (Monomers) as the main component. Silane compounds are effective in improving the adhesion at the interface between organic and inorganic materials, and have the effect of imparting weather resistance, antistatic properties, antibacterial resistance, abrasion resistance, etc. to the substrate. It has permeability to.

  And by mixing the said silane compound with an organosiloxane oligomer, in addition to the characteristic which the said silane compound has, it can have high weather resistance with respect to the film increase property, water repellency, and the alkali by a rain or cement.

  Next, each component constituting the coating material will be described.

(A) Organosiloxane oligomer The organosiloxane oligomer has the following formula (2):
[Chemical 2]
R ¹ ₃ SiO (R ¹ ₂ SiO) lSiR ¹ ₃ (2)
(Wherein R ¹ represents a hydrogen atom, a hydroxyl group, a halogen atom, or a monovalent organic group having 1 to 8 carbon atoms, which may be the same or different from each other. An organosiloxane oligomer represented by the following formula: Examples of the derivatives include hydrolysates of organosiloxane oligomers and condensates of organosiloxane oligomers. In addition, such (a) organosiloxane oligomer may be used individually by 1 type, or may be used in mixture of 2 or more types.

Examples of the halogen atom constituting R ¹ include fluorine and chlorine.

Examples of the organic group having 1 to 8 carbon atoms constituting R ¹ include alkyl groups such as methyl group, ethyl group and propyl group, alkoxyl groups such as methoxy group and ethoxy group, and phenyl group.

R ¹ may be partially substituted by a substituent such as a halogen atom, an amino group, an epoxy group, a carboxyl group, a hydroxyl group, a methacryl group, a mercapto group, a phenyl group, or a vinyl group. A part of the group may be further substituted with the above substituent.

  Among these, an organosiloxane oligomer containing a structure in which a silicon atom is bonded to a hydrolyzable group and / or a hydroxyl group, for example, a condensate of alkoxysilane or a condensate of chlorosilane is preferable. Such an organosiloxane oligomer can provide a stable cured layer by co-condensing with a silane compound and fixing when the coating material according to the present invention is cured.

  In addition, as an organosiloxane oligomer, you may prepare and use said compound, and may use what is marketed. Examples of commercially available organosiloxane oligomers include KC89S and KR400 manufactured by Shin-Etsu Chemical Co., Ltd., XC96-B0446 and XR31-B2230 manufactured by GE Toshiba Silicone Co., Ltd. These organosiloxane oligomers may be used as they are or after hydrolysis.

  Since the organosiloxane oligomer is a base resin, the amount is 100 parts by weight and is used as a reference for comparison.

(B) Silane compound The silane compound is represented by the following formula (3):
[Chemical formula 3]
R ² _m SiR ³ _4-m (3)
(In the formula, R ² represents a hydrogen atom or a monovalent organic group having 1 to 8 carbon atoms, and R ³ represents a halogen atom, a hydroxyl group or a monovalent alkoxyl group having 1 to 8 carbon atoms. In the case where there are a plurality of them, they may be the same or different from each other, where m is an integer of 0 to 3.) Examples of the derivatives include hydrolysates of silane compounds and condensates of silane compounds. In addition, such (b) silane compound may be used individually by 1 type, or 2 or more types may be mixed and used for it.

Examples of the organic group having 1 to 8 carbon atoms constituting R ² include an alkyl group such as a methyl group, an ethyl group, and a propyl group, a vinyl group, and a phenyl group.

Further, a part of R ² is substituted with a substituent such as a vinyl group, an epoxy group, a styryl group, a methacryloxy group, an acryloxy group, an amino group, a ureido group, a halogen atom, a mercapto group, a sulfide group, an isocyanate group, or a carboxyl group. May be.

Examples of the halogen atom constituting R ³ include fluorine and chlorine. The monovalent alkoxyl group having 1 to 8 carbon atoms constituting the R ^3, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy group, and the like.

  Specific examples of such silane compounds include tetraalkoxysilanes such as tetramethoxysilane, trialkoxysilanes such as methyltrimethoxysilane, dialkoxysilanes such as dimethyldimethoxysilane, and monoalkoxysilanes such as trimethylmethoxysilane. Examples include chlorosilanes such as alkoxysilanes and trichlorosilane.

  Among these, trialkoxysilanes and trichlorosilanes are preferable, and among them, a silane coupling agent having both a reactive group that chemically bonds with an organic substance and a reactive group that chemically reacts with an inorganic substance is preferable. This is because the silane coupling agent accelerates curing and imparts the effect of improving crosslinkability and adhesiveness.

  As such a silane coupling agent, specifically, vinyltrichlorosilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, Examples include 3-acryloxypropyl trimethoxysilane, 3-aminopropyltrimethoxysilane, and p-styryltrimethoxysilane.

  As the silane compound, the above compound may be prepared and used, or a commercially available one may be used. Examples of commercially available silane compounds include KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd. The silane compound may be used as it is or after hydrolysis.

  Here, a catalyst (c) for adjusting the curing rate can be further added to the mixture of the above (a) organosiloxane oligomer and (b) silane compound.

(C) Catalyst As the catalyst, an acidic compound, an alkaline compound, a salt compound, an amine compound, an organometallic compound and / or a partial hydrolyzate thereof (hereinafter referred to as an organometallic compound and / or a partial hydrolyzate thereof, Organic metal compounds ”). In addition, such (c) catalyst may be used individually by 1 type, or 2 or more types may be mixed and used for it.

  Examples of the acidic compound include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid and the like.

  Examples of the alkaline compound include sodium hydroxide and potassium hydroxide.

  Examples of the salt compound include alkali metal salts such as naphthenic acid and octylic acid.

  Examples of the amine compound include aminosilane, ethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, alkylamine salts, and quaternary ammonium salts. In addition, various modified amines that can be used as curing agents for epoxy resins are also included.

Examples of the organometallic compounds include organic zirconium compounds such as di-n-butoxy bis (ethyl acetoacetate) zirconium and n-butoxy tris (ethyl acetoacetate) zirconium, and di-i-propoxy bis (ethyl acetoacetate). Organic titanium compounds such as acetate) titanium, di-i-propoxy bis (acetylacetate) titanium, organoaluminum compounds such as di-i-propoxy acetylacetonato aluminum, i-propoxy bis (ethylacetoacetate) aluminum, (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H _{17) 2} organotin compounds such as and their Partial hydrolysis products thereof.

  The catalyst may be blended in the step of preparing the coating material according to the present invention, or may be blended in the coating material in the step of forming the coating film. You may mix | blend with both a formation process.

  As the catalyst, the above compound may be prepared and used, or a commercially available one may be used. As a commercially available catalyst, Shin-Etsu Chemical Co., Ltd. D-20 which is a polymer (partial hydrolyzate) of tetraalkoxy titanium is mentioned.

  The amount of the catalyst is 0.1 to 40 parts by weight, preferably 0.5 to 35 parts by weight, and more preferably 1 to 30 parts by weight with respect to 100 parts by weight of the (a) organosiloxane oligomer. When the amount of the catalyst exceeds the above upper limit, the storage stability is deteriorated and the curing rate becomes extremely fast, so that it is difficult to apply the coating material. On the other hand, when the amount of the catalyst exceeds the above lower limit, the curing rate is extremely lowered, and the coating time and the curing time are prolonged. In extreme cases, the original expression may not be possible due to poor curing.

  The present inventors prepared coating material samples in which the ratio of addition of the silane compound (b) added to 100 parts by weight of the above (a) organosiloxane oligomer was varied, and the samples of each coating material were applied to the substrate surface. After applying and curing, a test was conducted in which the hardness of the cured layer was measured by the pencil method. The pencil hardness represents a scratch hardness performed using a pencil method by a coating film measuring / inspecting instrument, and this pencil hardness is a method generally used for representing the hardness of a painted surface. The pencil hardness is determined in 17 levels of 9H to H, F, HB, and B to 6B from the higher hardness side.

  FIG. 1 shows the pencil hardness of a hardened layer formed by applying to a substrate surface using a sample prepared by changing the addition ratio of the silane compound to 100 parts by weight of the organosiloxane oligomer in the range of 1 to 30 parts by weight. And the hardness curve X which connected and showed the measured value is represented. Here, the coating material was applied to the surface of the substrate uniformly and then wiped to adjust the coating thickness to 5 μm or less.

  As shown in FIG. 1, in the range where the addition ratio of the silane compound with respect to 100 parts by weight of the organosiloxane oligomer is increased to approximately 1 to 20 parts by weight, the pencil hardness of the cured layer linearly decreases to approximately 9H to 4H, When the addition ratio of the silane compound is further increased from 20 parts by weight, the pencil hardness of the cured layer suddenly decreases, and when the addition ratio of the silane compound is approximately 25 parts by weight, the pencil hardness of the cured layer becomes approximately 2H. When the addition ratio of the silane compound is approximately 28 parts by weight, the pencil hardness of the cured layer is approximately F. When the addition ratio of the silane compound is further increased from 28 parts by weight, the pencil hardness of the cured layer is lower than F (softer). Turned out to be.

  From the above test, the inventors added the silane compound in an amount of 1 to 28 parts by weight with respect to 100 parts by weight of the organosiloxane oligomer, and the pencil hardness of the cured layer is as shown in the hardness curve X of FIG. Since it has been found that it varies in the range of 9H to F, when applying the coating material to various objects, the hardness curve X is set so that a hardened layer having a suitable hardness corresponding to the hardness of the object is formed. As an index, the addition ratio of the silane compound relative to 100 parts by weight of the organosiloxane oligomer can be determined.

  Furthermore, using the hardness curve X in FIG. 1 as an index, a test was conducted to select the addition ratio of the silane compound so that a good cured layer corresponding to the hardness of various objects was formed.

  As shown in FIG. 2, on the surface of the base material 1 made of a metal structure such as a moving body such as an automobile, a train, an airplane, and the like, a guard rail, an iron bridge, and other iron, aluminum-based metal, stainless steel, etc. In general, a coating 2 is applied to prevent corrosion and the like of the base material 1 and to prevent wear.

  The coating material applied to the coating 2 in order to protect such an object made of the coating 2 adjusts the addition ratio of the silane compound so that a cured layer 3 having a hardness equal to or higher than the hardness of the coating 2 is formed. . Here, since the white paint has the highest hardness (pencil hardness of about 4H) among various paints usually used in automobiles, the coating material for protecting the paint 2 is the pencil of the white paint. What can form the hardened layer 3 having a pencil hardness of 4H or higher is preferable. Incidentally, the pencil hardness of painting in the case of black paint is usually around 2H.

  Moreover, when the pencil hardness of the hardened layer 3 is increased, there is a problem that cracks such as cracks are likely to occur in the hardened layer 3. According to this test, it was found that cracks are likely to occur when the pencil hardness of the hardened layer 3 is 9H or higher.

  Therefore, for the object made of coating 2, when the addition ratio of the silane compound is 1 to 20 parts by weight with respect to 100 parts by weight of the organosiloxane oligomer, the pencil hardness of the hardened layer 3 is 9H to 4H and effective. Furthermore, when the addition ratio of the silane compound is 3 to 16 parts by weight, the pencil hardness of the hardened layer 3 is 8.5H to 5H, so that the surface of the coating 2 is harder than the pencil hardness of the coating 2 and cracked. Therefore, the coating layer 2 can be effectively protected over a long period of time.

  FIG. 3 shows the case of the base material 1 made of uncoated metal, tile, concrete, stone, hard plastic, etc. In this case, the coating material is directly applied to the surface of the base material 1 and cured. In this case, it is preferable to form the hardened layer 3 having a higher pencil hardness within a range in which the hardened layer 3 is not cracked.

  Specifically, the addition ratio of the silane compound is 1 weight so that the pencil hardness of the hardened layer 3 is equal to or higher than the pencil hardness of the base material 1 and the pencil hardness of 9H or less is maintained so as not to cause cracking. More preferably, the addition ratio of the silane compound, which can obtain a pencil hardness of about 8H, is preferably about 5 parts by weight.

  FIG. 4 shows the case of an object composed of a flexible material such as a thin metal or soft plastic, or a base material 1a that is softly deformed like wood, and the surface of the base material 1a deformed in this way. As the coating material to be applied to the object, it is preferable to form the hardened layer 3 having a higher hardness within a range in which the hardened layer 3 is not cracked or peeled by deformation of the base material 1a, specifically, It is preferable to add 20 parts by weight or more of the silane compound so that the pencil hardness of the cured layer 3 is 4H or less with respect to 100 parts by weight of the organosiloxane oligomer. Moreover, it is preferable to adjust so that the coating thickness of the coating material at this time may be 5 micrometers or less.

  Thus, according to the coating material in which the addition ratio of the silane compound is adjusted so that the pencil hardness of the hardened layer 3 is 4H or less, even if the base material 1a is deformed, the hardened layer 3 is cracked or peeled off. It is possible to protect the substrate 1a over a long period of time without doing so.

  According to the coating material of the present invention, the hardness that can adjust the pencil hardness of the cured layer in the range of 9H to F by adding the silane compound in the range of 0.1 to 28 parts by weight with respect to 100 parts by weight of the organosiloxane oligomer. Since the curve X is obtained, the hardened layer 3 having a pencil hardness corresponding to the pencil hardness of the coating 2 applied to the base material 1 or corresponding to the pencil hardness of the surface of the base material 1 or 1a is formed. Without causing cracks in the hardened layer 3, the surface of the object can be suitably protected over a long period of time without causing problems such as erosion such as rust and wear.

  In addition, this invention is not limited only to the said form, Of course, a various change can be added in the range which does not deviate from the summary of this invention.

It is explanatory drawing of the hardness curve X which shows the result of having measured the pencil hardness of the hardened layer by the sample which changed the addition ratio of the silane compound with respect to the organosiloxane oligomer. It is sectional drawing which shows the example which formed the hardened layer in the target object consisting of the coating formed in the base material. It is sectional drawing which shows the example which formed the hardened layer in the target object in the target object consisting of a base material. It is sectional drawing which shows the example which formed the hardened layer in the target object which consists of a base material to deform | transform.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Base material 1a Deformable base material 2 Coating 3 Hardened layer

Claims (5)

  A coating material that forms a cured layer to protect an object by mixing an organosiloxane oligomer and a silane compound and applying the mixture to the object, and the silane compound is added in an amount of 1 to 28 with respect to 100 parts by weight of the organosiloxane oligomer. The organosiloxane oligomer is formed so that a hardened layer having a pencil hardness equal to or higher than the pencil hardness of the object is formed on the basis that the pencil hardness of the hardened layer is changed in the range of 9H to F when added in the range of parts by weight. A coating material characterized by selecting and adding an addition ratio of a silane compound with respect to 100 parts by weight.   The ratio of the silane compound added to 100 parts by weight of the organosiloxane oligomer in the case of applying to an object consisting of a coating on the substrate is 1 to 20 parts by weight, preferably 3 to 16 parts by weight. The coating material according to claim 1, wherein the layer has a pencil hardness of 9H to 4H, preferably 8.5H to 5H.   When the silane compound is added to 100 parts by weight of the organosiloxane oligomer when directly applied to an object on the surface of the substrate, the pencil hardness of the cured layer is equal to or higher than the pencil hardness of the substrate surface and the cured layer is cracked. The coating material according to claim 1, which has an addition ratio indicating a hardness of less.   The addition ratio of the silane compound to 100 parts by weight of the organosiloxane oligomer in the case of applying to an object which is the surface of the base material to be deformed is an addition ratio of 20 parts by weight or more indicating that the pencil hardness of the cured layer is 4H or less. The coating material as described in.   The coating material as described in any one of Claims 1-4 to which the catalyst for adjusting a cure rate was added.

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