Exterior wall tile delamination prevention structure and exterior wall tile delamination prevention method

Abstract

To provide an exterior wall tile detachment prevention structure and an exterior wall tile detachment prevention construction method that prevent detachment without impairing the design of tiles attached to a building.SOLUTION: Provided is an exterior wall tile detachment prevention structure 20 in which an anchor pin 4 is driven into an exterior wall tile 3 or a joint 7 to fix the anchor pin 4 to a concrete frame 1, a transparent primer layer 8 is formed by applying silicone acrylic resin primer to a head 4b of the anchor pin 4, the exterior wall tile 3 surface and the joint 7, a transparent reinforcing layer 9 is formed by applying a transparent polyurea resin coating material containing a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, a hydrophilic finely divided silica, a rheology control agent, a light stabilizer, an ultraviolet absorber and silane compounds having two or more alkoxy groups bonded to silicon atoms in one molecule, and a transparent protective layer 10 is formed by applying an acrylic silicon resin coating material.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an exterior wall tile delamination prevention structure and an exterior wall tile delamination prevention method that prevent exterior wall tiles installed on existing buildings from peeling off from the building structure and falling to the ground due to vibrations such as earthquakes or deterioration of the adhesive layer over time, without impairing the aesthetic appearance of the exterior wall tiles. [Background technology]

[0002] Traditionally, concrete buildings have had tiles attached to their concrete surfaces to effectively prevent concrete carbonation and to enhance their aesthetic appeal. However, since cement mortar is often used to attach tiles to concrete surfaces, the tiles may detach from the concrete and fall to the ground due to vibrations from vehicle traffic, earthquakes, wind, repeated heating and cooling of the mortar, and deterioration over time due to moisture.

[0003] To prevent this, a construction method for building exterior walls and the exterior wall itself have been proposed (Patent Document 1). The construction method for building exterior walls is characterized in that, in a building exterior wall in which tiles are arranged on the surface of the foundation exterior wall, a thin layer of latex mortar as a base material is applied to the surface of the area where the tiles are peeling due to loosening, a net is then placed on the surface, then a pin is driven into the foundation exterior wall from above the net, the net is held down with a flange that extends around the head of the pin, and the surface of the net and the head of the pin are made substantially flush, and then latex mortar is applied again to the upper surface of the pin and the net so that the net and the pin are covered. Furthermore, the exterior wall described in Patent Document 1 is an exterior wall for a building in which tiles are arranged on the surface of the foundation exterior wall, wherein a thin layer of latex mortar is formed on the surface of the tiles, a net is arranged on the upper surface of the latex mortar, and multiple points of the arranged net are pressed down by pins having a single flange that spreads out around the head, the pins are fixed to the foundation exterior wall, the heads of the pins and the surface of the net are arranged to be substantially flush, and a layer of latex mortar is formed on the net. However, the construction method of this exterior wall for a building and the exterior wall itself have the problem that, because at least two layers of latex mortar are applied to the surface of the tiles, the decorative tiles are covered with latex mortar, thus impairing the decorative properties provided by the tiles, and also the problem that the construction is difficult because the net needs to be arranged over the entire surface without twisting or sagging.

[0004] Furthermore, a method for repairing existing exterior tile walls has been proposed (Patent Document 2) that effectively prevents tile peeling while preserving the color tone and appearance of the existing exterior tile wall, thereby restoring its aesthetic appeal, providing stain resistance, and enhancing its waterproofing. This method for repairing existing exterior tile walls involves applying a transparent primer to the existing exterior tile wall to form a primer layer, applying a main material paint mainly composed of a transparent acrylic resin emulsion multiple times to the primer layer to form a main material layer, and applying a transparent topcoat paint to the main material layer to form a topcoat layer, wherein the main material paint is characterized by containing reinforcing fibers, having a viscosity of 20,000 to 70,000 mPa·s, and a thixotropy index of 4.0 to 10.0. However, the existing exterior tile wall repair method involves applying a main coating, primarily composed of a transparent acrylic resin emulsion, multiple times to form the main coating layer, resulting in a complex construction process. Furthermore, because it uses a one-component acrylic resin emulsion that requires film formation at the application temperature, the glass transition temperature (Tg) of the acrylic resin is low. Therefore, if the repair surface reaches temperatures above 50°C in areas exposed to direct sunlight, such as the south-facing side of a building, the tensile strength at that temperature will be low. If there are areas with thin coating thickness, these areas may lack sufficient rigidity to adequately hold loose tiles. Additionally, even without a temperature rise on the repair surface, the main coating layer is formed by the drying of multiple coats of acrylic resin emulsion, making it difficult to achieve high initial tensile strength. Consequently, over time, the effects of ultraviolet radiation may lead to insufficient rigidity to adequately hold loose tiles.

[0005] In order to solve these problems, the present applicant has proposed new outer wall tile peeling prevention structures (Patent Documents 3 to 6). For example, the outer wall tile peeling prevention structure disclosed in Patent Document 6 is structured such that anchor pins are driven into the outer wall tile surface or joints to fix the anchor pins to a concrete frame; a silicon acrylic resin primer containing an amino group-containing acrylic resin and epoxy silane is applied to the heads of the anchor pins, the outer wall tile surface and the joints to form a transparent primer layer; a transparent polyurea resin coating material containing a non-yellowing isocyanate prepolymer having an NCO weight percentage of 5 to 10 wt%, an alicyclic polyamine, transparent reinforcing short fibers, hydrophilic fine powder silica, a rheology control agent, a light stabilizer and an ultraviolet absorber is applied onto the transparent primer layer to form a transparent reinforcing layer; and an acrylic silicone resin coating material containing a light stabilizer and an ultraviolet absorber is applied onto the transparent reinforcing layer to form a transparent protective layer. [Prior Art Document] [Patent Documents]

[0006] [Patent Document 1] Japanese Examined Patent Publication No. 8-14182 [Patent Document 2] Japanese Unexamined Patent Publication No. 2007-247279 [Patent Document 3] Japanese Unexamined Patent Publication No. 2014-141817 [Patent Document 4] Japanese Unexamined Patent Publication No. 2015-227541 [Patent Document 5] Japanese Unexamined Patent Publication No. 2016-011529 [Patent Document 6] Japanese Unexamined Patent Publication No. 2016-030974 [Summary of the Invention] [Problem to be Solved by the Invention]

[0007] However, although the outer wall tile peeling prevention structures according to Patent Documents 3 to 6 all have excellent effects of solving the problems according to Patent Documents 1 and 2, when the surface condition of the base tile surface or joints is not smooth and has severe unevenness, the thickness of the transparent reinforcing layer locally exceeds a certain value, and depending on construction conditions, the transparent reinforcing layer may locally become white and cloudy, which as a result may impair the design properties of the tiles.

[0008] Therefore, the problem to be solved by the present invention is to provide an outer wall tile peeling prevention structure and an outer wall tile peeling prevention construction method that can prevent the tiles from peeling off without impairing the design properties of the tiles attached to the concrete outer skin of a building without causing clouding in the transparent reinforcing layer even when the thickness of the transparent reinforcing layer is locally thickened due to the influence of the surface condition of the base tile surface or joints, requires fewer construction steps than conventional methods, and can sufficiently prevent tile peeling even when the temperature of the outer wall surface of the building rises or the transparent reinforcing layer is deteriorated by ultraviolet rays by increasing the initial strength of the transparent reinforcing layer. [Means for Solving the Problems]

[0009] In order to solve the above problems, the invention according to claim 1 is characterized in that an anchor pin is driven into an outer wall tile surface or a joint to fix the anchor pin to a concrete skeleton, a silicone acrylic resin primer containing an amino group-containing acrylic resin having an amine value of 10 to 50 mgKOH / g and a glass transition temperature of 10°C or higher and lower than 50°C, and epoxysilane is applied to the head of the anchor pin, the outer wall tile surface, and the joints to form a transparent primer layer, a transparent polyurea resin coating material containing a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, hydrophilic finely divided silica, a rheology control agent, a light stabilizer, an ultraviolet absorber, and a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule is applied onto the transparent primer layer to form a transparent reinforcing layer, A transparent protective layer is formed by applying an acrylic silicone resin coating material containing a light stabilizer and an ultraviolet absorber onto the transparent reinforcing layer. The amount of silane compound in the aforementioned polyurea resin coating material is more than 0.5 parts by weight and less than 5 parts by weight per 100 parts by weight of the entire polyurea resin coating material. the law of nature, The silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule is vinyltrimethoxysilane. The present invention provides an exterior wall tile peeling prevention structure characterized by the following:

[0011] Claim 2 The invention described provides an exterior wall tile peeling prevention structure according to claim 1, characterized in that the light stabilizer is a hindered amine-based light stabilizer and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber.

[0012] Claim 3 The invention described is an alicyclic polyamine of formula I: [ka] The characteristic feature is that the formula is one or more polyamines represented by (wherein X is an m-valence group obtained by removing primary amino groups from an organic polyamine with a number average molecular weight of 88 to 400 that is inert to an isocyanate group and contains m primary amino groups bonded to an alicyclic hydrocarbon, R1 and R2 are the same or different, and are organic groups having 1 to 18 carbon atoms, and m is at least an integer of 2) or claim 2 The present invention provides a structure to prevent the peeling of exterior wall tiles.

[0013] Claim 4 The invention involves driving anchor pins into the exterior wall tile surface or joints to fix the anchor pins to the concrete structure, A silicone acrylic resin primer containing an amino group-containing acrylic resin and epoxy silane, with an amine value of 10 to 50 mg KOH / g and a glass transition temperature of 10°C or higher and less than 50°C, is applied to the head of the anchor pin, the exterior wall tile surface, and the joints to form a transparent primer layer. A transparent reinforcing layer is formed by applying a transparent polyurea resin coating material containing a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, hydrophilic fine silica powder, a rheology control agent, a light stabilizer, an ultraviolet absorber, and a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule, on the transparent primer layer; a transparent protective layer is formed by applying an acrylic silicone resin coating material containing a light stabilizer and an ultraviolet absorber on the transparent reinforcing layer; and the amount of silane compound in the polyurea resin coating material is more than 0.5 parts by weight and less than 5 parts by weight per 100 parts by weight of the total polyurea resin coating material. The silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule is vinyltrimethoxysilane. The present invention provides a method for preventing the peeling of exterior wall tiles, characterized by the following features.

[0015] Claim 5 The described invention is characterized in that the light stabilizer is a hindered amine-based light stabilizer, and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber. 4 This invention provides a method for preventing the peeling of exterior wall tiles.

[0016] Claim 6 The invention described is an alicyclic polyamine of formula I: [ka] The polyamine is characterized by being one or more polyamines represented by the formula (wherein X is an m-valence group obtained by removing primary amino groups from an organic polyamine with a number-average molecular weight of 88 to 400 that is inert to an isocyanate group and contains m primary amino groups bonded to an alicyclic hydrocarbon, R1 and R2 are the same or different, and are organic groups having 1 to 18 carbon atoms, and m is at least an integer of 2). 4 or claim 5 This invention provides a method for preventing the peeling of exterior wall tiles. [Effects of the Invention]

[0017] The exterior wall tile delamination prevention structure according to claims 1 to 4 of the present invention has the effect of fixing the exterior wall tiles to the concrete structure either directly with the anchor pins or through the joints, by driving anchor pins into the exterior wall tile surface or joints and fixing the anchor pins to the concrete structure. Furthermore, a transparent primer layer is formed by applying an amino group-containing acrylic resin and a silicone acrylic resin primer containing epoxysilane to the heads of the anchor pins, the exterior wall tile surface, and the joints, and a transparent polyurea resin coating material is applied on top of the transparent primer layer to form a transparent reinforcing layer. As a result, the transparent reinforcing layer has the effect of integrating with the concrete structure via the transparent primer layer, the heads of the anchor pins, and the anchor pins. In particular, the polyurea resin coating material forming the transparent reinforcing layer has higher strength compared to conventional acrylic resin emulsions, so even if the temperature of the wall surface rises and the temperature of the transparent reinforcing layer rises, it maintains high rigidity and effectively prevents the delamination of exterior wall tiles.

[0018] Furthermore, since the transparent reinforcing layer contains a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule, even if a minute amount of moisture is present in the transparent reinforcing layer, this moisture is stably removed by the silane compound. As a result, even if the transparent reinforcing layer is applied thickly in areas with significant unevenness in the substrate's exterior wall tile surface and joints, micro-foaming due to trace amounts of moisture in the coating film does not occur, preventing clouding of the coating film. This has the effect of ensuring that the aesthetic appearance of the tiles attached to the concrete skin of the building is not impaired even after the exterior wall tile surface and joints are covered with the transparent reinforcing layer. In addition, there is no reduction in coating film strength due to the occurrence of micro-foaming.

[0019] Furthermore, the polyurea resin coating material that forms the transparent reinforcing layer is formed by the reaction of a non-yellowing isocyanate with an alicyclic polyamine having only secondary amino groups. The alicyclic polyamine used in this invention has the advantage of being able to be applied with a trowel, roller, or brush because its reaction is slower compared to aliphatic amines, which are ultrafast curing. In addition, compared to aromatic amines, which have a slow curing reaction and are generally used to ensure a longer pot life, the cured coating film is less prone to yellowing.

[0020] Furthermore, the transparent reinforcing layer has a transparent protective layer formed by applying an acrylic silicone resin coating material. Since both the transparent reinforcing layer and the transparent protective layer contain light stabilizers and UV absorbers, the transparent reinforcing layer and the transparent protective layer are less susceptible to deterioration from ultraviolet rays and other elements, resulting in less reduction in strength over the long term and effectively preventing the peeling of exterior wall tiles over the long term.

[0021] Furthermore, since the transparent primer layer, transparent reinforcing layer, and transparent protective layer applied on top of the tiles are all transparent, they have the effect of preventing the exterior wall tiles from peeling off while maintaining the aesthetic appeal of the exterior wall tiles.

[0022] Furthermore, the exterior wall tile peeling prevention method described in claims 5 to 8 of the present invention has the effect of being able to be applied with a trowel or roller brush, in addition to the effects of the exterior wall tile peeling prevention structure described in claim 1, because the coating material that forms the transparent reinforcing layer on the transparent primer layer is a polyurea resin coating material consisting of a non-yellowing isocyanate prepolymer and an alicyclic polyamine having only secondary amino groups, and the cured coating film is less prone to yellowing.

[0023] Furthermore, the exterior wall tile peeling prevention structure described in claim 2 of the present invention is particularly effective in removing minute amounts of moisture from the transparent reinforcing layer because the silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule of the exterior wall tile peeling prevention structure described in claim 1 is a compound having one silicon atom in one molecule and two or more alkoxy groups bonded to that silicon atom. As a result, the aesthetic appearance of the tiles is less likely to be impaired.

[0024] Furthermore, the exterior wall tile delamination prevention method described in claim 6 of the present invention is particularly effective in removing minute amounts of moisture from the transparent reinforcing layer because the silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule of the exterior wall tile delamination prevention method described in claim 5 is a compound having one silicon atom in one molecule and two or more alkoxy groups bonded to that silicon atom. As a result, the aesthetic appearance of the tiles is less likely to be impaired.

[0025] Furthermore, the exterior wall tile peeling prevention structure described in claim 3 of the present invention has the effect of preventing yellowing and deterioration of strength of the transparent reinforcing layer and the transparent protective layer over a long period of time, particularly because the light stabilizer of the exterior wall tile peeling prevention structure described in claim 1 or claim 2 is a hindered amine-based light stabilizer, and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber.

[0026] Furthermore, the exterior wall tile delamination prevention method described in claim 7 of the present invention is particularly effective in preventing yellowing and strength reduction of the transparent reinforcing layer and the transparent protective layer over a long period of time, as the light stabilizer in the exterior wall tile delamination prevention method described in claim 5 or claim 6 is a hindered amine-based light stabilizer, and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber. [Brief explanation of the drawing]

[0027] [Figure 1] This is a cross-sectional view of the exterior wall tile peeling prevention structure according to the present invention. [Modes for carrying out the invention]

[0028] The present invention will be described in detail below.

[0029] Figure 1 is a cross-sectional view of the exterior wall tile peeling prevention structure 20 described in claims 1 to 4. 1 is the concrete structure, which is the outer skin of a concrete building to which the exterior wall tiles are attached, and the exterior wall tiles 3 are attached to the concrete structure 1 with adhesive mortar 2. An anchor pin 4 is driven into approximately the center of the tile surface of the exterior wall tile 3.

[0030] The anchor pin 4 is press-fitted into an anchor hole 5 that is continuously drilled in the exterior wall tile 3, the adhesive mortar 2, and the concrete structure 1. The threaded foot 4a of the anchor pin 4 is positioned in the anchor hole 5 located in the adhesive mortar 2 and the concrete structure 1. The area around the foot 4a is filled with epoxy resin adhesive 6, which hardens to fix the anchor pin 4 to the concrete structure 1.

[0031] The anchor pin 4 has a thin, flange-shaped head 4b, and the back side of the flange portion of the head 4b abuts against the tile surface of the exterior wall tile 3, fixing and holding the exterior wall tile 3 in place so as to press it toward the concrete structure 1.

[0032] A tile-pressing portion 4c is formed in the intermediate part between the head 4b and the foot 4a of the anchor pin 4, with a diameter thicker than the shaft diameter of the foot 4a and thinner than the flange diameter of the head 4b. Multiple small flanges 4d are provided on the tile-pressing portion 4c, and when the anchor pin 4 is pressed into the anchor hole 5, the flanges 4d are deformed and crushed, thereby fixing the anchor pin 4 to the exterior wall tile 3.

[0033] A silicone acrylic resin primer is applied to the head 4b of the anchor pin 4 and the tile surface and joint 7 of the exterior wall tile 3 to form a transparent primer layer 8, and a polyurea resin coating is applied on top of the transparent primer layer 8 to form a transparent reinforcing layer 9.

[0034] An acrylic silicone resin coating is applied on top of the transparent reinforcing layer 9 to form a transparent protective layer 10.

[0035] The exterior wall tile peeling prevention structure 20 described in claims 1 to 4 is formed as described above, but the exterior wall tile peeling prevention method described in claims 5 to 8 is a construction method for forming the exterior wall tile peeling prevention structure 20.

[0036] Next, the silicone acrylic resin primer, polyurea resin coating material, and acrylic silicone resin coating material used in the exterior wall tile peeling prevention structure described in claims 1 to 4 and the exterior wall tile peeling prevention method described in claims 5 to 8 will be described in detail.

[0037] <Silicone acrylic resin primer> For the silicone acrylic resin primer used to form the transparent primer layer in the present invention, it is preferable to use an acrylic resin in which part of the main chain or side chain is amine-modified as the amino group-containing acrylic resin. The acid value of the amine-modified acrylic resin is preferably 1.0 to 10.0 mgKOH / g, and the amine value is preferably 10 to 50 mgKOH / g. If the amine value is less than 10 mgKOH / g, the adhesion to the polyurea resin coating material that will be applied to the upper layer will be insufficient, and if the amine value is greater than 50 mgKOH / g, the amount of epoxysilane used as a curing agent will increase, resulting in higher costs. Note that the acid value refers to the measured value of the number of milligrams of potassium hydroxide equivalent to the molar equivalent of carboxyl groups in 1 g of polymer (solids), and the amine value refers to the measured value of the number of milligrams of potassium hydroxide equivalent to the molar equivalent of amino groups in 1 g of polymer (solids).

[0038] The glass transition temperature of the above-mentioned amino group-containing acrylic resin is preferably 10°C or higher and less than 50°C. If the glass transition temperature is below 10°C, the heat resistance will be insufficient, and when the temperature of the transparent reinforcing layer or the base tile becomes high in summer, the adhesion will decrease, and if it exceeds 50°C, the adhesion to the tile will decrease. The glass transition temperature referred to here means the value measured using a differential scanning calorimetry (DSC) in accordance with JIS K 7121-1987. An example of such a commercially available resin is ACRYDIC A-9521 (acid value: 3 mg KOH / g or less, amine value: 20 mg KOH / g, glass transition temperature: 15°C, manufactured by DIC Corporation, trade name).

[0039] Furthermore, the epoxysilane used in combination with the amino group-containing acrylic resin of the silicone acrylic resin primer that forms the transparent primer layer used in the present invention functions as a curing agent. The epoxy equivalent of such an epoxysilane curing agent is preferably in the range of 210 to 740 g / eq in terms of solid content. Note that epoxy equivalent is the theoretical value of the molecular weight of epoxysilane per functional group (epoxy group). If the epoxy equivalent is less than 210, the curing reaction is accelerated and workability is reduced, and if it exceeds 740, the heat resistance is insufficient, and adhesion decreases when the temperature of the transparent reinforcing layer or the base tile becomes high in the summer. Examples of commercially available epoxysilanes include ACRYDICA-9585 (epoxy equivalent: 560 g / eq, manufactured by DIC Corporation, product name), ACRYDIC A-9585-BA (a product with only the solvent changed from A-9585, manufactured by DIC Corporation, product name), ACRYDICFZ-521 (epoxy equivalent: 590 g / eq, manufactured by DIC Corporation, product name), and ACRYDIC FZ-523 (epoxy equivalent: 680-740 g / eq, manufactured by DIC Corporation, product name).

[0040] The blending ratio of epoxysilane to amino group-containing acrylic resin is determined as follows. First, the number of amino groups in 1 g of amino group-containing acrylic resin is determined by dividing the sum of the amine value (mg) and acid value (mg) by the molecular weight of KOH (mg). Next, the number of epoxy groups in 1 g of epoxysilane is determined by dividing 1 g by the epoxy equivalent. The approximate blending amounts of each are then determined so that the ratio of amino groups to epoxy groups is 1:1. After that, the optimal amount of epoxysilane by weight is determined after experimentally confirming the adhesion to the base tile or anchor pins and the adhesion between the silicone acrylic resin primer and the transparent reinforcing layer described later. In this invention, 50% to 100% of the determined amount of epoxysilane by weight is preferred as the blending amount per 100 parts by weight of amino group-containing acrylic resin.

[0041] <Polyurea resin coating material> The polyurea resin coating material used to form the transparent reinforcing layer in the present invention is characterized by comprising a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, hydrophilic fine silica powder, a rheology control agent, a light stabilizer, an ultraviolet absorber, and a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule.

[0042] Non-yellowing isocyanate prepolymers can be made from aliphatic bifunctional isocyanates such as hexamethylene diisocyanate (HDI), alicyclic bifunctional isocyanates such as isophorone diisocyanate (IPDI), or 4,4'-diphenylmethane diisocyanate (MDI) or 4,4'-methylenebis(cyclohexyl isocyanate) (hydrogenated MDI) prepolymerized with polyhydric alcohols (adducts) or as cyclized trimers (isocyanurates).

[0043] The NCO weight percentage of the non-yellowing isocyanate prepolymer is preferably 5 to 20% by weight, and more preferably 10 to 15% by weight. Below 5% by weight, the coating strength is insufficient, and above 20% by weight, the elongation of the coating decreases. Below 10% by weight, the coating strength tends to be insufficient, and above 15% by weight, the elongation of the coating tends to decrease, and the pot life tends to be shorter when using this material in summer. When using a non-yellowing isocyanate prepolymer alone, the NCO weight percentage of that non-yellowing isocyanate prepolymer should be within the above range, and when using a mixture of two or more, the NCO weight percentage of the mixture should be within the above range. A non-yellowing isocyanate prepolymer with an NCO weight percentage outside the above range can also be used. Commercially available non-yellowing isocyanate prepolymers that can be used include Duranate TSE-100 (HDI-based isocyanurate prepolymer, viscosity: 1650 mPa·s / 25℃, NCO wt%: 12.0%, weight-average molecular weight (Mw): 7890, manufactured by Asahi Kasei Corporation, trade name), Duranate E402-100 (HDI-based adduct prepolymer, viscosity: 6000 mPa·s / 25℃, NCO wt%: 8.5%, weight-average molecular weight (Mw): 3970, manufactured by Asahi Kasei Corporation, trade name), Duranate TSA-100 (HDI-based isocyanurate prepolymer, viscosity: 500 mPa·s / 25℃, NCO wt%: 20.6%, weight-average molecular weight (Mw): 1360, manufactured by Asahi Kasei Corporation, trade name), etc.

[0044] Alicyclic polyamines are polyamines in which at least one amino group, such as isophorone diamine, is directly bonded to a cyclohexane ring, etc., and amines having only secondary amino groups and no primary amino groups are used. The weight-average molecular weight (Mw, theoretical value) is preferably 300 to 1000. If it is less than 300, the pot life is shortened and workability is poor, and if it is greater than 1000, the reaction rate decreases, delaying the time to touch-dry and the rise of coating strength. Only by using alicyclic polyamines having only secondary amino groups can a sufficient pot life be ensured for applying the polyurea resin coating material with a trowel or roller brush, and furthermore, when used in combination with a non-yellowing isocyanate prepolymer, the cured coating film will not yellow under ultraviolet light.

[0045] The alicyclic polyamine is represented by the above formula I, where X, R1, R2, and m are one or more polyamines as described above. This alicyclic polyamine is a polyaspartate ester or polyaspartate, and m is preferably 2. Polyaspartate esters in which X represents a divalent hydrocarbon group having 6 to 30 carbon atoms, such as 4,4'-diaminodicyclohexylmethane (4,4'-methylenebis(cyclohexylamine)), 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (4,4'-methylenebis(2-methylcyclohexylamine)), 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, hexahydro- (containing at least 2,4-diaminotoluene or 2,6-diaminotoluene), isomeric C-monomethyldiaminodicyclohexylmethane, and a group obtained by removing a primary amino group from 3(4)-aminomethyl-1-methylcyclohexylamine, can be suitably used. In particular, compounds of formula I in which X represents a divalent hydrocarbon group that can be obtained by removing a primary amino group from 4,4'-diaminodicyclohexylmethane (4,4'-methylenebis(cyclohexylamine)) or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (4,4'-methylenebis(2-methylcyclohexylamine)) are more preferred.

[0046] The alicyclic polyamine represented by formula I preferably has R1 and R2 as methyl, ethyl, n-butyl, or 2-ethylhexyl, and is produced by reacting a primary polyamine represented by formula X-(-NH2)m with a maleic acid ester or fumaric acid ester represented by formula R1OOC-CH=CH-COOR2.

[0047] The alicyclic polyamine obtained by reacting 1 mole of 4,4'-methylenebiscyclohexylamine with 2 moles of diethyl maleate is supplied to the market as 4,4'-methylenebiscyclohexylamine-diethyl maleate adduct, with a weight-average molecular weight (Mw) of 548 (theoretical value) and a viscosity of 2000 mPa·s / 23℃. Similarly, the alicyclic polyamine obtained by reacting 1 mole of 4,4'-methylenebis(2-methylcyclohexylamine) with 2 moles of diethyl maleate is supplied to the market as 4,4'-methylenebis(2-methylcyclohexylamine)-diethyl maleate adduct, with a weight-average molecular weight (Mw) of 578 (theoretical value) and a viscosity of 2000 mPa·s / 23℃.

[0048] The equivalent ratio (NCO group / active hydrogen group) of the non-yellowing isocyanate prepolymer to the active hydrogen group of the alicyclic polyamine is preferably 0.8 to 1.2. If it is less than 0.8, the viscosity may increase rapidly after mixing the main agent and the curing agent, resulting in a shorter pot life. If it is greater than 1.2, the time to touch-dry and the onset of coating strength may be delayed.

[0049] The non-yellowing isocyanate prepolymer and the alicyclic polyamine are thoroughly mixed and used immediately before applying the polyurea resin coating material onto an already formed transparent primer layer.

[0050] Hydrophilic fine silica is a non-crystalline fine powder of hydrophilic fumed silica, with a specific surface area of ​​150-500 m² as measured by the BET method. 2 It can be used if it has a specific surface area of ​​150 m². 2 For amounts less than / g, sufficient thixotropy is not imparted, 500m 2At concentrations exceeding 2SiOH / nm, the workability of applying the transparent reinforcing layer with a roller brush decreases. Furthermore, the silanol group density of hydrophilic fine silica is 2SiOH / nm. 2 The above is desirable. A hydrophilic fine silica that satisfies these conditions is HDK-N20 (specific surface area (BET method): 170~230 g / m²). 2 , silanol group density: 2SiOH / nm 2 It is manufactured by Asahi Kasei Wacker Silicone Co., Ltd. (product name).

[0051] Furthermore, the rheology control agent is a thixotropic enhancer having free OH groups that form hydrogen bonds with the silanol groups on the particle surface of hydrophilic fine silica, thereby forming a three-dimensional structure with the silica particles. Polyhydroxycarboxylic acid amides are particularly suitable for use. A commercially available rheology control agent is BYK-405 (polyhydroxycarboxylic acid amide content: 51%, manufactured by Big Chemie Co., Ltd., trade name).

[0052] The polyurea resin coating material according to the present invention further contains a light stabilizer and an ultraviolet absorber, so that the strength of the transparent reinforcing layer does not decrease even when exposed to ultraviolet light for a long period of time. A hindered amine-based light stabilizer can be used as the light stabilizer, and a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber can be used as the ultraviolet absorber. A commercially available hindered amine-based light stabilizer is TINUVIN 292 (chemical name: bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by BASF, trade name). A commercially available hydroxyphenyltriazine-based UV absorber is TINUVIN 400 (chemical name: reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl and oxirane, manufactured by BASF, trade name). A commercially available benzotriazole-based UV absorber is TINUVIN 928 (chemical name: 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, manufactured by BASF, trade name).

[0053] Furthermore, the polyurea resin coating material contains a silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule.

[0054] A silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule may be either a compound having one silicon atom in one molecule with two or more alkoxy groups bonded to that silicon atom, or an organopolysiloxane compound having two or more silicon atoms in one molecule, with a polysiloxane skeleton, and two or more alkoxy groups bonded to the silicon atom. However, the former type of silane compound is preferred.

[0055] Examples of silane compounds having one silicon atom in a molecule with two or more alkoxy groups bonded to the silicon atom include dialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane; trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltriethoxysilane, and vinyltrimethoxysilane; tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetraisopropyloxysilane; hydrolysates of trialkoxysilanes and tetraalkoxysilanes; and (meth)acryloxyalkyltrialkoxysilanes such as γ-(meth)acryloxypropyltrimethoxysilane and γ-(meth)acryloxypropyltriethoxysilane. Among these, vinyltrimethoxysilane is preferred due to its ease of availability and hydrolysis resistance. When vinyltrimethoxysilane is used, the amount to be blended is preferably more than 0.5 parts by weight and less than 5 parts by weight per 100 parts by weight of the total polyurea resin coating material. However, when using other silane compounds, the amount to be blended can be determined based on the aesthetic appearance of the underlying tile surface and the ease of application of the transparent reinforcing layer when the polyurea resin coating material is applied to the underlying tile surface, joints, and anchor pin heads and hardened.

[0056] Furthermore, in the polyurea resin coating material of the present invention, the absence of a silanol condensation catalyst further prevents damage to the aesthetic appearance of the base tile. Examples of the silanol condensation catalyst include organotin compounds such as tin octoate, tin neodecanoate, tin naphthenate, tin stearate, dibutyltin dioctoate, dibutyltin dilaurate, dioctyltin diversate, dibutyltin bistriethoxysilicate, dibutyltin dioleylmalate, dibutyltin diacetate, 1,1,3,3-tetrabutyl-1,3-dilauryloxycarbonyl-distanoxane, dibutyltin oxybisethoxysilicate, dibutyltin oxide, reaction products of dioctyltin salt and orasilicate ethyl, reaction products of dibutyltin salt and orasilicate ethyl, reaction products of dibutyltin oxide and phthalate ester, reaction products of dibutyltin oxide and maleate diester, and dibutyltin diacetylacetonate.

[0057] If a silanol condensation catalyst is included, the silane compound will decompose due to moisture, and the resulting silanol groups will condense to produce water again. The presence of this water may cause the transparent reinforcing layer to become partially cloudy, potentially impairing the aesthetic appearance of the underlying tiles.

[0058] Furthermore, in the polyurea resin coating material of the present invention, the absence of reinforcing short fibers further prevents damage to the aesthetic appearance of the base tile. Examples of such reinforcing short fibers include vinylon, nylon, and glass short fibers with an average fiber length of 25 to 20,000 μm and a fiber diameter of 1 to 150 μm. Commercially available products include, for example, Milled Fiber EFDE-50-31 (glass short fiber, average fiber length: 50 μm, fiber diameter: 6 μm, surface treatment: silane-based, manufactured by Central Glass Fiber Co., Ltd., product name) and Tough Binder (nylon fiber, average fiber length: 3 mm, average fiber diameter: 28 μm, manufactured by Toray Amtec Co., Ltd., product name).

[0059] When reinforcing short fibers are included, the mixing and stirring of the main component and hardener of the polyurea resin coating material at the construction site varies depending on the worker. If a large amount of trapped foam is generated, the reinforcing short fibers will trap this foam, causing it to remain in the coating film. As a result, the transparent reinforcing layer may become cloudy white, impairing the aesthetic appearance of the underlying tiles. In addition, compared to cases without reinforcing short fibers, the coating strength may be lower due to the large amount of foam remaining in the coating film. Furthermore, the inclusion of reinforcing short fibers may lead to a greater reduction in pot life during the summer months.

[0060] <Acrylic silicone resin coating material> The acrylic silicone resin coating material used to form the transparent protective layer according to the present invention comprises an acrylic silicone oligomer having alkoxysilyl groups as the main component, and a tin-based curing catalyst can be used as the curing agent. The main component and curing agent are uniformly mixed immediately before applying the acrylic silicone resin coating material onto the already formed transparent reinforcing layer, and then applied using a roller brush or the like. The alkoxysilyl groups of the main component are crosslinked by the tin-based curing catalyst of the curing agent to form stable siloxane bonds, resulting in excellent durability.

[0061] The alkoxysilyl group content is preferably 2% to 30% by weight. Below 2% by weight, weather resistance decreases, and above 30% by weight, viscosity increases, reducing workability. A commercially available acrylic silicone oligomer containing alkoxysilyl groups is Kaneka Zemlac YC4383 (siloxane crosslinked reactive polymer, viscosity: 4000 mP·s / 23℃, alkoxysilyl group content: 15% by weight, manufactured by Kaneka Corporation, trade name). A commercially available tin-based curing catalyst is Kaneka Zemlac BT405Z (organotin compound, effective tin content: 1-2% by weight, manufactured by Kaneka Corporation, trade name) and Kaneka Zemlac ZT406Z (organotin compound, effective tin content: 1-2% by weight, manufactured by Kaneka Corporation, trade name).

[0062] The acrylic silicone resin coating material of the present invention contains a light stabilizer and an ultraviolet absorber, and the strength of the transparent reinforcing layer does not decrease even when exposed to ultraviolet light for a long period of time. Hindered amine-based light stabilizers can be used as light stabilizers, and a commercially available hindered amine-based light stabilizer is TINUVIN 292 (bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by BASF, trade name). Hydroxyphenyl triazine-based UV absorbers or benzotriazole-based UV absorbers can be used as UV absorbers, and a commercially available hydroxyphenyl triazine-based UV absorber is TINUVIN 400 (2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl and oxirane reaction product, manufactured by BASF, trade name). A commercially available benzotriazole-based UV absorber is TINUVIN 928 (chemical name; 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, manufactured by BASF, trade name).

[0063] The following will provide a detailed explanation using examples and comparative examples. [Examples]

[0064] <Examples and Comparative Examples 1 to 5> ACRYDIC A-9521 was used as the amino group-containing acrylic resin and ACRYDIC A-9585 as the epoxy silane for the silicone acrylic resin primer forming the transparent primer layer. The main component and curing agent were prepared in the formulations shown in Table 1. The weight ratio of the main component to the curing agent was 13:1. These main components and curing agents were uniformly mixed to obtain the silicone acrylic resin primers of Example and Comparative Examples 1 to 5.

[0065] The polyurea resin coating material forming the transparent reinforcing layer uses the above-mentioned 4,4'-methylenebiscyclohexylamine diethyl maleate adduct (weight-average molecular weight (Mw): 548 (theoretical value), viscosity: 2000 mP·s / 23℃) as alicyclic polyamine A, the above-mentioned 4,4'-methylenebis(2-methylcyclohexylamine) diethyl maleate adduct (weight-average molecular weight (Mw): 578 (theoretical value), viscosity: 2000 mP·s / 23℃) as alicyclic polyamine B, HDK-N20 as hydrophilic fine silica powder, BYK-405 as rheology control agent, and TIN as light stabilizer. UBIN292 is used, TINUVIN400 as an ultraviolet absorber, GENIOSILXL-10 (vinyltrimethoxysilane, manufactured by Asahi Kasei Wacker Silicone Co., Ltd., trade name) as a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule, Duranate TSE-100 as non-yellowing isocyanate prepolymer A, Duranate TSA-100 as non-yellowing isocyanate prepolymer B, and in addition, milled fiber EFDE-50-31 as reinforcing short fibers, and molecular sieve 5A powder (average particle size D) as a dehydrating agent. 50 Using a 6μm (manufactured by Union Showa Co., Ltd., product name) as an antifoaming agent, an acrylic antifoaming agent was used, and the main component and hardener were prepared in the formulations shown in Table 1. The weight ratio of the main component to the hardener was 1:1, and these main components and hardeners were used to obtain the polyurea resin coating materials of Example and Comparative Example 1 to Comparative Example 5.

[0066] Kaneka Zemurac YC4383 was used as the acrylic silicone oligomer having an alkoxysilyl group for the acrylic silicone resin coating material that forms the transparent protective layer, TINUBIN292 as the light stabilizer, TINUVIN928 as the ultraviolet absorber, a silicone-based defoamer as the defoamer, Kaneka Zemurac ZT406Z as the curing catalyst, and turpentine thinner #50 as the petroleum-based diluent as the diluent. The main component and curing agent were prepared in the formulations shown in Table 1. The weight ratio of the main component to the curing agent was 2:1. Acrylic silicone resin coating materials of Examples and Comparative Examples 1 to 5 were obtained using these main components and curing agents.

[0067] <Comparative Example 6> The silicone acrylic resin primer of the above example was used as the coating material for forming the transparent primer layer, the acrylic silicone resin coating material of the above example was used as the coating material for forming the transparent reinforcing layer, and a transparent acrylic emulsion with a resin solid content of 50% (butyl acrylate / methyl methacrylate copolymer, viscosity 50 Pa·s / 20°C, T.I value (JIS A 6024 thixotropic index: 5.7), containing 2% by weight of short nylon fibers (fiber length 5 mm)) was used as the coating material for forming the transparent reinforcing layer.

[0068]

Table 1

[0069] <Evaluation Method> The following evaluations were carried out for the above-mentioned Examples and Comparative Examples. Unless otherwise specified, preparation of test specimens, curing and evaluation tests were carried out under an environment of 23°C and 50% RH.

[0070] <Tensile Strength> The polyurea resin coating materials of the Examples and Comparative Examples for forming the transparent reinforcing layer were spread into a sheet shape with a thickness of 2 mm, cured for 7 days, and then molded into the shape of No. 2 dumbbell specimens specified in the tensile test method for vulcanized rubber of JIS K 6251. Thereafter, in accordance with the test method, the specimen was pulled at a tensile speed of 500 mm / min, and the strength at break was taken as the tensile strength (MPa). The tests were carried out under the conditions of 23°C and 60°C.

[0071] <Adhesion Strength to Mortar> The surface of a mortar test plate (70×70 mm, thickness 20 mm) specified in Clause 10.4 of JIS R 5201 was sanded, and the silicone acrylic resin primers of the Examples and Comparative Examples were applied to the treated surface at an application amount of 0.12 kg / m 2 , followed by drying. Thereafter, for the Examples and Comparative Examples 1 to 5, a polyurea resin coating material was applied at an application amount of 0.4 kg / m 2 , cured for 24 hours, and then the same polyurea resin coating material was further applied at an application amount of 0.3 kg / m 2 , cured for 24 hours, and then an acrylic silicone resin coating material was further applied at an application amount of 0.08 kg / m2 The sample was coated twice, cured for 7 days, and then prepared as a test specimen. For Comparative Example 6, a transparent acrylic emulsion was applied at a rate of 0.5 kg / m² over a dried silicone acrylic resin primer. 2 Apply the material, and after drying, apply the same material at a rate of 0.8 kg / m². 2 Apply the material, and after drying, apply the same material again at a rate of 0.8 kg / m². 2 After applying and drying, apply acrylic silicone resin coating material at a rate of 0.08 kg / m². 2 The mortar was applied twice and cured for 7 days to create the test specimens. The adhesion strength of each test specimen was measured according to JIS A 6909 7.9 Adhesion Strength Test. Since the mortar test boards broke in all test specimens, the adhesion strength at that point was defined as the mortar adhesion strength (MPa).

[0072] <UV resistance> For the examples and comparative examples 1 to 5, the polyurea resin coating was spread in a sheet to a thickness of 2 mm and cured for 24 hours, after which the acrylic silicone resin coating was applied at a rate of 0.08 kg / m². 2 The sample was coated twice, cured for 7 days, and then prepared as a test specimen. For Comparative Example 6, a transparent acrylic emulsion was first applied at a rate of 0.5 kg / m² to form a 2 mm thick sheet. 2 Apply the material, and after drying, apply the same material at a rate of 0.8 kg / m². 2 Apply the material, and after drying, apply the same material again at a rate of 0.8 kg / m². 2 After applying and drying, apply acrylic silicone resin coating material at a rate of 0.08 kg / m². 2 The test specimens were coated twice, cured for 7 days, and then prepared as test specimens. Each test specimen was tested using a Super UV Tester (Model: SUV-W151, manufactured by Iwasaki Electric Co., Ltd., irradiation conditions: water-cooled metal halide lamp used, temperature 63℃, humidity 50%, illuminance 100mW / cm²). 2 After continuous irradiation for 180 hours, the sample was molded into the shape of a No. 2 dumbbell as specified in JIS K 6251, the tensile test method for vulcanized rubber. Subsequently, the appearance was visually inspected, and at the same time, the sample was pulled at a tensile speed of 500 mm / min according to the same test method, and the strength at the break was defined as the tensile strength (MPa).

[0073] <Bending strength> A mortar board (100 x 200 mm, 30 mm thick) as specified in JIS R 5201 10.4 is split in two by applying a load to the center of its longitudinal direction. The fractured surfaces are butted together and fixed, and the surface is sanded. The silicone acrylic resin primer of the example and comparative example is then applied to the treated surface at a rate of 0.12 kg / m². 2 The material was applied and dried. Subsequently, for the examples and comparative examples 1 to 5, the polyurea resin coating material was applied at a rate of 0.4 kg / m². 2 After applying the coating and allowing it to cure for 24 hours, another layer of the same polyurea resin coating material is applied at a rate of 0.3 kg / m². 2 After applying the coating and allowing it to cure for 24 hours, an acrylic silicone resin coating material was applied at a rate of 0.08 kg / m². 2 The sample was coated twice, cured for 7 days, and then prepared as a test specimen. For Comparative Example 6, a transparent acrylic emulsion was applied at a rate of 0.5 kg / m² over a dried silicone acrylic resin primer. 2 Apply the material, and after drying, apply the same material at a rate of 0.8 kg / m². 2 Apply the material, and after drying, apply the same material again at a rate of 0.8 kg / m². 2 After applying and drying, apply acrylic silicone resin coating material at a rate of 0.08 kg / m². 2 The specimens were coated twice, cured for 7 days, and then prepared as test specimens. Each specimen was subjected to a bending test using a 4-point bending method at a loading rate of 1.67 mm / min, and its bending strength (N) was measured. The upper load span was 50 mm, and the lower load span was 150 mm.

[0074] <Maximum push-out load> A concrete core cutter was used to cut the back surface of the central part of a U-shaped side ditch (lid) of type 300 (400 x 600 x 60 mm) (hereinafter referred to as "U-shaped lid"), a type lid specified in Annex 5 of JIS A 5372 (Precast Reinforced Concrete Products), with a diameter of φ100 mm and a depth of 55 mm ± 3 mm. The surface was sanded, and the silicone acrylic resin primer of the example and comparative example was applied to this treated surface at a rate of 0.12 kg / m². 2 The material was applied and dried. Subsequently, for the examples and comparative examples 1 to 5, the polyurea resin coating material was applied at a rate of 0.4 kg / m². 2After applying the coating and allowing it to cure for 24 hours, another layer of the same polyurea resin coating material is applied at a rate of 0.3 kg / m². 2 After applying the coating and allowing it to cure for 24 hours, an acrylic silicone resin coating material was applied at a rate of 0.08 kg / m². 2 The sample was coated twice, cured for 7 days, and then prepared as a test specimen. For Comparative Example 6, a transparent acrylic emulsion was applied at a rate of 0.5 kg / m² over a dried silicone acrylic resin primer. 2 Apply the material, and after drying, apply the same material at a rate of 0.8 kg / m². 2 Apply the material, and after drying, apply the same material again at a rate of 0.8 kg / m². 2 After applying and drying, apply acrylic silicone resin coating material at a rate of 0.08 kg / m². 2 The specimens were coated twice, cured for 7 days, and then prepared as test specimens. The test was conducted in accordance with JHS424-2004, the method for puncture testing to prevent delamination, and the maximum load was defined as the maximum puncture load (kN).

[0075] <Pot life> For the polyurea resin coatings of the Examples and Comparative Examples 1 to 5, the main agent and curing agent were each prepared at 23°C. Immediately after mixing the main agent and curing agent, the viscosity was measured using a Type B rotational viscometer No. 5 rotor at 20 rpm to determine the initial viscosity. Thereafter, the viscosity was measured every 5 minutes, and the time until the viscosity reached twice the initial viscosity was calculated as the pot life.

[0076] <Anchor pin adhesion> For the examples and Comparative Examples 1 to 5, a silicone acrylic resin primer was applied at a rate of 0.08 kg / m² to the flat surface (acrylic silicone resin coating) of the head cap that is fixed to the tile fixing anchor pin JB-TA (made of SUS304, manufactured by Aica Kogyo Co., Ltd., product name). 2 After applying the primer and allowing it to cure for 7 days, the tip of a utility knife blade was inserted along the interface between the head flange and the hardened silicone acrylic resin primer layer, and the degree of peeling of the silicone acrylic resin primer layer was evaluated. The evaluation was performed as follows. ○: No peeling occurs around the tip of the cutter knife blade that has been inserted. △: There is a slight peeling around the tip of the cutter knife blade that was inserted. ×: Peeling has occurred all around the tip of the cutter knife blade that was inserted.

[0077] <Adhesion of tiles / transparent reinforcing layer> For the examples and comparative examples 1 to 5, a silicone acrylic resin primer was applied at a rate of 0.12 kg / m² to commercially available porcelain tiles Aurora Pale 50·2T PL-100 (95 x 45 mm, 7 mm thick, Class I (porcelain), manufactured by Danto Co., Ltd., product name). 2 After applying and drying, apply a polyurea resin coating at a rate of 0.4 kg / m². 2 The coating was applied, and after curing for 7 days, a scraper was inserted between the porcelain tile and the polyurea resin coating to forcibly separate and peel off the polyurea resin coating. By visually observing the peeled polyurea resin coating and the surface of the porcelain tile, the adhesion between the tile and the silicone acrylic resin primer (primer layer), and the adhesion between the silicone acrylic resin primer (primer layer) and the polyurea resin coating (transparent reinforcing layer) were determined. Good adhesion was evaluated as ○, and all other cases as ×.

[0078] <Drip-stopping properties> Commercially available porcelain tiles, Aurora Pale 50-2T PL-100 (95 x 45 mm, 7 mm thick, Class I (porcelain), manufactured by Danto Co., Ltd., product name), are pre-attached to the surface of a dried concrete slab (300 x 300 mm, 60 mm thick) conforming to JISA 5371 using commercially available epoxy resin adhesive, and the concrete slab is held vertically. The silicone acrylic resin primers of Examples and Comparative Examples 1 to 5 are applied at a rate of 0.12 kg / m². 2 After applying and drying, apply a polyurea resin coating at a rate of 0.5 kg / m². 2 The coating was applied to the surface of porcelain tiles, and the degree of dripping was visually evaluated. The evaluation was as follows: no dripping occurred (○), slight dripping occurred (△), and dripping occurred throughout (×).

[0079] <Transparency> A glass plate (150 x 150 mm, 2 mm thick) was coated with the polyurea resin coating material of Example and Comparative Examples 1 to 5 at a rate of 0.5 kg / m². 2 Or 1.0 kg / m 2 The coating was applied, and the transparency of the cured coating was visually evaluated. A ○ was used to indicate high transparency, a △ to indicate slight cloudiness, and a × to indicate opacity.

[0080] <Application workability> Commercially available porcelain tiles, Aurora Pale 50-2T PL-100 (95 x 45 mm, 7 mm thick, Class I (porcelain), manufactured by Danto Co., Ltd., product name), are pre-applied to the surface of a dried concrete slab (300 x 300 mm, 60 mm thick) conforming to JISA 5371 using commercially available epoxy resin adhesive. Silicone acrylic resin primers of Examples and Comparative Examples 1 to 5 are applied to the surface of the porcelain tiles at a rate of 0.12 kg / m². 2 After applying and drying the coating, apply the polyurea resin coating material using a trowel and roller brush at a rate of 0.5 kg / m². 2 The product was applied, and the ease of application was evaluated. The evaluation was as follows: ○ indicates that it could be easily applied using a trowel and roller brush; △ indicates that it could be applied with a trowel but not with a roller brush; and × indicates that it could not be applied with either a trowel or a roller brush.

[0081] <Evaluation Results> The evaluation results are shown in Table 2.

[0082] [Table 2] [Explanation of symbols]

[0083] 1. Concrete structure 2. Adhesive mortar 3. Exterior wall tiles 4 Anchor pins 4a Foot 4b head 4c Press-fit section 4D flange 5 Anchor holes 6. Epoxy resin adhesive 7 Joint 8. Transparent primer layer 9. Transparent reinforcing layer 10 Transparent protective layer 20. Exterior wall tile peeling prevention structure

Claims

1. Anchor pins are driven into the exterior wall tile surface or joints and fixed to the concrete structure. A transparent primer layer is formed by applying a silicone acrylic resin primer containing an amino group-containing acrylic resin with an amine value of 10 to 50 mg KOH / g and a glass transition temperature of 10°C or higher and less than 50°C, and epoxy silane, to the head of the anchor pin, the exterior wall tile surface, and the joints. A transparent polyurea resin coating material is applied onto the transparent primer layer to form a transparent reinforcing layer, the coating material containing a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, hydrophilic fine silica powder, a rheology control agent, a light stabilizer, an ultraviolet absorber, and a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule. A transparent protective layer is formed by applying an acrylic silicone resin coating material containing a light stabilizer and an ultraviolet absorber onto the transparent reinforcing layer. The amount of silane compound in the aforementioned polyurea resin coating material is more than 0.5 parts by weight and less than 5 parts by weight of the total 100 parts by weight of the polyurea resin coating material. An exterior wall tile peeling prevention structure characterized in that the silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule is vinyltrimethoxysilane.

2. The exterior wall tile peeling prevention structure according to Claim 1, characterized in that the light stabilizer is a hindered amine-based light stabilizer and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber.

3. The alicyclic polyamine is of formula I: 【Chemistry 1】 The exterior wall tile peeling prevention structure according to claim 1 or 2, characterized by being one or more polyamines represented by the formula (wherein X is an m-valence group obtained by removing primary amino groups from an organic polyamine with a number average molecular weight of 88 to 400 that is inert to an isocyanate group and contains m primary amino groups bonded to an alicyclic hydrocarbon, R1 and R2 are the same or different, and are organic groups having 1 to 18 carbon atoms, and m is at least an integer of 2).

4. Anchor pins are driven into the exterior wall tile surface or joints and fixed to the concrete structure, A silicone acrylic resin primer containing an amino group-containing acrylic resin with an amine value of 10 to 50 mg KOH / g and a glass transition temperature of 10°C or higher and less than 50°C, along with epoxy silane, is applied to the head of the anchor pin, the exterior wall tile surface, and the joints to form a transparent primer layer. A transparent polyurea resin coating material is applied onto the transparent primer layer to form a transparent reinforcing layer, the coating material containing a non-yellowing isocyanate prepolymer, an alicyclic polyamine having only secondary amino groups, hydrophilic fine silica powder, a rheology control agent, a light stabilizer, an ultraviolet absorber, and a silane compound having two or more alkoxy groups bonded to silicon atoms in one molecule. A transparent protective layer is formed by applying an acrylic silicone resin coating material containing a light stabilizer and an ultraviolet absorber onto the transparent reinforcing layer. The amount of silane compound in the aforementioned polyurea resin coating material is more than 0.5 parts by weight and less than 5 parts by weight of the total 100 parts by weight of the polyurea resin coating material. A method for preventing exterior wall tile peeling, characterized in that the silane compound having two or more alkoxy groups bonded to a silicon atom in one molecule is vinyltrimethoxysilane.

5. The exterior wall tile peeling prevention method according to Claim 4, characterized in that the light stabilizer is a hindered amine-based light stabilizer and the ultraviolet absorber is a hydroxyphenyltriazine-based ultraviolet absorber or a benzotriazole-based ultraviolet absorber.

6. The alicyclic polyamine is of formula I: 【Chemistry 1】 The exterior wall tile peeling prevention method according to claim 4 or 5, characterized by being one or more polyamines represented by the formula (wherein X is an m-valence group obtained by removing primary amino groups from an organic polyamine with a number average molecular weight of 88 to 400 that is inert to an isocyanate group and contains m primary amino groups bonded to an alicyclic hydrocarbon, R1 and R2 are the same or different, and are organic groups having 1 to 18 carbon atoms, and m is at least an integer of 2).

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