JP6425432B2 - Outer wall tile peeling prevention structure and outer wall tile peeling prevention method - Google Patents

Description

  The present invention is an outer wall tile peeling prevention structure and outer wall tile peeling that prevents outer wall tiles installed in an existing building from peeling off from the casing and falling to the ground due to vibration such as earthquake or aging deterioration of the adhesive layer. The present invention relates to a preventive method and an alicyclic polyamine used for the same.

  Conventionally, in concrete buildings, tiles may be pasted on the outer surface of a concrete for the purpose of effectively preventing neutralization of concrete and providing design properties. However, since affixing tiles to the concrete shell often uses affixing mortar mainly composed of cement mortar, it is due to passage of vehicles, earthquake, vibration due to wind, cold heat repetition of affixing mortar, aging deterioration due to moisture, etc. The tiles may come off from the concrete shell and fall on the ground.

  In order to prevent this, the construction method of the outer wall for buildings and its outer wall are proposed (patent document 1). The construction method of the outer wall for building is to thinly apply a latex mortar as a ground material to the surface of the part where there is peeling due to the floating of the tile in the outer wall for building where tiles are arranged on the surface of base outer wall Then, place a net on the surface, then drive a pin from the top of the net to the base outer wall and press the net with a single flange that spreads around the head of the net and the pin It is characterized in that the head and the upper surface of the pin and the net are coated with latex mortar again so that the net and the pin may be worn. Moreover, the outer wall of Patent Document 1 is a building outer wall in which a tile is disposed on the surface of a base outer wall, a thin layer of latex mortar is formed on the surface of the tile, and a net is disposed on the upper surface of the latex mortar. And holding a plurality of locations of the arranged net on the head by a pin with a single flange extending around the periphery, fixing the pin to the base outer wall, the head of the pin and the net And a layer of latex mortar formed on the net.

  On the other hand, while leaving the appearance of the color tone and color tone of the existing exterior tile wall surface, the tile flakes are effectively prevented from peeling off, the design is restored, the stain preventing function is imparted, and the waterproofness is enhanced. The repair method of the existing exterior tile wall surface which can be done is proposed (patent document 2). The method of repairing the existing exterior tile wall surface applies a transparency primer to the existing exterior tile wall surface to form a primer layer, and applies a main material paint mainly composed of a transparent acrylic resin emulsion to the primer layer multiple times A main material layer, and applying a transparent topcoat paint to the main material layer to form a topcoat layer, wherein the reinforcing material is added to the main material paint. It is mix | blended, viscosity is 20000-70000 mPa * s, and thixotropy index is 4.0-10.0. It is a repair method of the existing exterior tile wall surface characterized by the above-mentioned.

Japanese Examined Patent Publication 8-14182 JP 2007-247279 A

  However, since the method of applying the outer wall for a building and the outer wall shown in Patent Document 1 apply at least two layers of latex mortar to the tile surface, the tile having designability is covered with the latex mortar and the tile is covered by the tile There is a problem that the applied design is lost, and it is necessary to arrange the net on the entire surface so that there is no twist or slack, so there is a problem that the construction is difficult.

  Moreover, since the repair method of the existing exterior tile wall surface shown by patent document 2 applies the main material paint which has a transparent acrylic resin emulsion as a main component several times, and forms a main material layer, there is a problem that there are many construction processes. In order to apply a one-component acrylic resin emulsion that needs to be formed at the construction temperature, the glass transition temperature Tg of the acrylic resin is low, and in areas exposed to direct sunlight in the south face of a building etc. If the surface to be repaired becomes 50 ° C or higher, the tensile strength at that temperature will be low, and if there is a portion with a small applied thickness, the rigidity may not be sufficient to hold the tile to be peeled off at that portion. There is a problem that there is. In addition, even if there is no temperature rise on the repair surface, it is difficult to increase the initial tensile strength because the main material layer is a layer formed by dry film formation of the acrylic resin emulsion applied a plurality of times. There is a problem that the rigidity for sufficiently holding the tile in the peeled state may be insufficient due to the influence of ultraviolet rays for a long time.

  The problem to be solved by the present invention is to prevent the peeling of the tile without impairing the design of the tile applied to the concrete shell of the building, the number of construction steps is smaller than before, and the initial stage of the transparent reinforcing layer Even if the temperature of the outer wall of the building rises or the ultraviolet ray causes deterioration of the transparent reinforcing layer, the outer wall tile can be sufficiently prevented from peeling off by increasing the strength of the wall. It is an object of the present invention to provide a prevention structure and an outer wall tile peeling prevention method and an alicyclic polyamine used for these.

In the invention according to claim 1, the anchor pin is driven into the outer wall tile surface or joint to fix the anchor pin to the concrete casing, and the head and outer wall tile surface of the anchor pin and the joint have an amine value of 10 to 50 mg KOH / g And applying a silicon acrylic resin primer containing an amino group-containing acrylic resin having a glass transition temperature of 10 ° C. or more and less than 50 ° C. and an epoxy silane to form a transparent primer layer, and NCO weight on the transparent primer layer Apply a clear polyurea resin coating material containing 5 to 10% by weight of non-yellowing isocyanate prepolymer, alicyclic polyamine having only secondary amino group , reinforcing fiber, reinforcing fiber, light stabilizer and UV absorber Form a transparent reinforcing layer, and apply an acrylic silicone resin coating material containing a light stabilizer and a UV absorber on the transparent reinforcing layer to protect it To the formation of the providing an outer wall tile spalling prevention structure according to claim.

In the invention according to claim 2, the anchor pin is driven into the outer wall tile surface or joint to fix the anchor pin to the concrete casing, and the head and outer wall tile surface and joint of the anchor pin have an amine value of 10 to 50 mg KOH / g And applying a silicon acrylic resin primer containing an amino group-containing acrylic resin having a glass transition temperature of 10 ° C. or more and less than 50 ° C. and an epoxy silane to form a transparent primer layer, and NCO weight on the transparent primer layer Apply a clear polyurea resin coating material containing 5 to 10% by weight of non-yellowing isocyanate prepolymer, alicyclic polyamine having only secondary amino group , reinforcing fiber, reinforcing fiber, light stabilizer and UV absorber Form a transparent reinforcing layer, and apply an acrylic silicone resin coating material containing a light stabilizer and a UV absorber on the transparent reinforcing layer to protect it Forming a provides an outer wall tile spalling prevention method according to claim.

  In the invention according to claim 3, the light stabilizer of the outer wall tile peeling prevention structure according to claim 1 is a hindered amine light stabilizer, and the ultraviolet absorber is a hydroxyphenyltriazine ultraviolet absorber or a benzotriazole ultraviolet absorber. The outer wall tile peeling prevention structure according to claim 1 is provided.

  In the invention according to claim 4, the light stabilizer of the outer wall tile peeling prevention method according to claim 2 is a hindered amine light stabilizer, and the ultraviolet absorber is a hydroxyphenyltriazine ultraviolet absorber or a benzotriazole ultraviolet absorber. The outer wall tile peeling prevention method according to claim 2, characterized in that

In the invention according to claim 5, the alicyclic polyamine is a compound of formula I:

(In the formula, X is inert to an isocyanate group and removes a primary amino group from an organic polyamine having a number average molecular weight of 88 to 400 containing m primary amino groups bonded to an alicyclic hydrocarbon And R ₁ and R ₂ are the same or different and each is an organic group having 1 to 18 carbon atoms, and m is an integer of at least 2) The outer wall tile peeling prevention structure according to claim 1 or claim 3, which is the above polyamine.

  The invention according to claim 6 provides the outer wall tile peeling prevention method according to claim 2 or 4, wherein the alicyclic polyamine is one or more polyamines represented by the formula I above.

  In the outer wall tile peeling prevention structure according to claim 1, 3 and 5 of the present invention, the outer wall tile is a direct anchor pin because the anchor pin is driven into the outer wall tile surface or joint to fix the anchor pin to the concrete casing. The effect of being fixed to the concrete frame is to be fixed to the concrete frame through the joint. In addition, a silicone acrylic resin primer containing amino group-containing acrylic resin and epoxysilane is applied to the head and outer wall tile surface of the anchor pin and the joint to form a transparent primer layer, and a transparent polyurea is formed on the transparent primer layer. Since the resin coating material is applied to form a transparent reinforcing layer, the transparent reinforcing layer has an effect of being integrated with the concrete casing through the transparent primer layer, the anchor pin head and the anchor pin. In particular, since the polyurea resin coating material forming the transparent reinforcing layer has higher strength compared to the conventional acrylic resin emulsion, the rigidity is high even if the temperature of the wall surface rises and the temperature of the transparent reinforcing layer rises. It has the effect of holding the wall and surely preventing the exfoliation of the outer wall tile.

  In addition, since the transparent reinforcing layer contains reinforcing fibers, the reinforcing fibers have the effect of further reinforcing the coating film formed by the reaction of the non-yellowing isocyanate and the alicyclic polyamine, and in particular, the transparent reinforcing layer is on the south sidewall surface In this case, even if the temperature of the transparent reinforcing layer rises due to solar radiation, the decrease in strength is small, and there is an effect of reliably preventing exfoliation of the outer wall tile, and the reinforcing fiber to be blended in the present invention has a fiber length of 0.5 to 20 mm Since the transparent reinforcing layer is thixotropic, it has the effect of making it difficult to cause sag even if it is applied to an upright surface.

  Moreover, the polyurea resin coating material which forms a transparent reinforcement layer is formed into a film by reaction of non-yellowing isocyanate and cycloaliphatic polyamine whose NCO weight% is 5 to 10 weight%, and the cycloaliphatic polyamine used by this invention is The reaction is slower compared to aliphatic amines that are ultra-rapid curing, and since non-yellowing isocyanate has a low NCO weight% of 5 to 10 weight%, it has the effect of being able to be applied with scissors even under high temperatures in summer is there. In addition, as compared with aromatic amines which are generally used to secure a pot life and have a slow curing reaction, the cured coating film has an effect of causing less yellowing.

  Further, a transparent protective layer formed by applying an acrylic silicone resin coating material is formed on the transparent reinforcing layer, and the transparent reinforcing layer and the transparent protective layer contain a light stabilizer and an ultraviolet light absorber, so that the transparent protective layer And the transparent reinforcement layer of the lower layer is hard to receive degradation by ultraviolet rays etc., and has the effect that a reduction in strength is small over a long period, and it is effective in preventing exfoliation of an outer wall tile certainly over a long period.

  In addition, since all of the transparent primer layer, the transparent reinforcing layer, and the transparent protective layer applied on the tile are transparent, the peeling of the outer wall tile is prevented while maintaining the design of the outer wall tile having the designability. Has the effect of

  In the outer wall tile peeling prevention method according to claim 2, 4 and 6 of the present invention, in addition to the effect of the outer wall tile peeling prevention structure according to claim 1, a transparent reinforcing layer on a transparent primer layer. The coating material to form is a polyurea resin coating material consisting of a non-yellowing isocyanate prepolymer and cycloaliphatic polyamine having a NCO weight% of 5 to 10 weight%. It has the effect of having a possible pot life.

  In the outer wall tile peeling prevention structure according to claim 3 of the present invention, in particular, the light stabilizer of the outer wall tile peeling prevention structure according to claim 1 is a hindered amine light stabilizer, and the ultraviolet absorber is a hydroxyphenyl triazine type The UV absorber or the benzotriazole-based UV absorber has an effect of preventing yellowing and strength reduction of the transparent reinforcing layer and the transparent protective layer over a long period of time.

  In the outer wall tile peeling prevention method according to claim 4 of the present invention, in particular, the light stabilizer of the outer wall tile peeling prevention method according to claim 2 is a hindered amine light stabilizer, and the ultraviolet absorber is a hydroxyphenyl triazine type The UV absorber or the benzotriazole-based UV absorber has an effect of preventing yellowing and strength reduction of the transparent reinforcing layer and the transparent protective layer over a long period of time.

  Moreover, since the alicyclic polyamine according to claim 7 of the present invention is used for the outer wall tile peeling prevention structure according to claim 1 or claim 3, the alicyclic polyamine is compared to the case where an aliphatic amine is used. There is an effect that it is possible to secure the pot life at the time of coating by using a carbon black etc., and there is an effect that yellowing of the cured coating is less as compared with the aromatic amine.

  In addition, since the alicyclic polyamine according to claim 8 of the present invention is used for the method for preventing the exfoliation of the outer wall tile according to claim 2 or claim 4, compared with the case where an aliphatic amine is used There is an effect that it is possible to secure the pot life at the time of coating by using a carbon black etc., and there is an effect that yellowing of the cured coating is less as compared with the aromatic amine.

It is a cross-sectional state figure of the outer wall tile peeling prevention structure which concerns on this invention.

  The present invention will be described in detail below.

  FIG. 1 is a cross-sectional view of an outer wall tile peeling prevention structure 20 according to claim 1, claim 3 or claim 5. Reference numeral 1 denotes a concrete housing which is an outer shell of a concrete building to which outer wall tiles are attached, and the outer wall tiles 3 are attached to the concrete housing 1 by a bonding mortar 2. An anchor pin 4 is driven into a substantially central portion of the tile surface of the outer wall tile 3.

  The anchor pin 4 is pressed into the anchor hole 5 continuously drilled in the outer wall tile 3, the pasting mortar 2 and the concrete casing 1, and the screw-like foot 4 a of the anchor pin 4 is in the pasting mortar 2 and the concrete casing 1 part. It is disposed in a certain anchor hole 5. The anchor pin 4 is fixed to the concrete housing 1 by filling the epoxy resin adhesive 6 around the foot 4 a and solidifying it.

  The anchor pin 4 is formed with a thin flange-like head 4b, and the back side of the flange portion of the head 4b is held in contact with the tile surface of the outer wall tile 3 to hold the outer wall tile 3 to the concrete housing 1 side doing.

  A tile press-in portion 4c larger in diameter than the shaft diameter of the foot 4a and smaller in diameter than the flange diameter of the head 4b is formed at an intermediate portion between the head 4b and the foot 4a of the anchor pin 4 A plurality of small flanges 4d are provided, and the anchor pins 4 are fixed to the outer wall tile 3 by pressing the anchor pins 4 into the anchor holes 5 so that the flanges 4d are deformed and crushed. There is.

  A silicone acrylic resin primer containing an amino group-containing acrylic resin and an epoxysilane is applied to the tile surface and joints 7 of the head 4 b of the anchor pin 4 and the outer wall tile 4 to form a transparent primer layer 8. A transparent reinforcing layer 9 is formed on the layer 8 by applying a transparent polyurea resin coating material containing non-yellowing isocyanate prepolymer, alicyclic polyamine, reinforcing fiber, light stabilizer and UV absorber. There is.

  On the transparent reinforcing layer 9, an acrylic silicone resin coating material containing a light stabilizer and a UV absorber is applied to form a transparent protective layer 10.

  Although the outer wall tile peeling prevention structure 20 according to claim 1, claim 3 or claim 5 is formed as described above, the outer wall tile peeling prevention method according to claim 2, claim 4 or claim 6 is This is a construction method according to a construction method for forming the outer wall tile peeling prevention structure 20.

  Next, the outer wall tile peeling prevention structure according to claim 1, claim 3 or claim 5 and the silicon acrylic resin primer used in the outer wall tile peeling prevention method according to claim 2, claim 4 or claim 6, polyurea The resin coating material and the acrylic silicone resin coating material will be described in detail.

Silicon Acrylic Resin Primer As the amino group-containing acrylic resin of the silicone acrylic resin primer forming the transparent primer layer used in the present invention, an acrylic resin in which a part of the main chain or side chain is amine-modified may be used preferable. The acid value of the amine-modified acrylic resin is preferably 1.0 to 10.0 mg KOH / g, and the amine value is preferably 10 to 50 mg KOH / g. If the amine value is less than 10 mg, the adhesion to the upper layer of the polyurea resin coating material is insufficient, and if the amine value is more than 50 mg, the amount of the epoxysilane to be a curing agent increases and the cost increases. In addition, an acid value means the actual value of the milligram number of potassium hydroxide which becomes a molar equivalent with the carboxyl group in 1 g of polymers (solid content), and an amine value means in 1 g of polymers (solid content). It means the measured value of the number of milligrams of potassium hydroxide that is equivalent to the amino group.

  The glass transition temperature of the amino group-containing acrylic resin described above is preferably 10 ° C. or more and less than 50 ° C. The glass transition temperature as referred to herein means a value measured according to JIS K 7121-1987 using a differential scanning calorimeter (DSC). As such commercial resin, there is ACRYDIC A-9521 (acid value = 3 mg KOH / g or less, amine value = 20 mg KOH / g, Tg = 15 ° C) of DIC Corporation. If the glass transition temperature is less than 10 ° C., the heat resistance is insufficient, and if the temperature of the transparent reinforcing layer or the base tile becomes high in summer, the adhesiveness decreases, and if it exceeds 50 ° C., the adhesiveness to the tile decreases.

  The epoxysilane used in combination with the amino group-containing acrylic resin of the silicone acrylic resin primer forming the transparent primer layer used in the present invention functions as a resin curing agent. The epoxy equivalent of such an epoxy silane curing agent is preferably in the range of 210 to 740 g / eq in terms of solid content. In addition, an epoxy equivalent is a theoretical value of the molecular weight of the epoxy silane per one functional group (epoxy group). When the epoxy equivalent is less than 210, the curing reaction is accelerated and the workability is reduced. When it is more than 740, the heat resistance is insufficient and the adhesiveness is reduced when the temperature of the transparent reinforcing layer and the base tile becomes high in summer. As such commercially available epoxy silanes, ACRYDIC A-9585 (epoxy equivalent 560 g / eq) of DIC Corporation, A-9585-BA (product in which only the solvent of A-9585 is changed), FZ-521 (epoxy equivalent) 590 g / eq), FZ-523 (epoxy equivalent 680-740 g / eq) and the like.

  The compounding ratio of epoxysilane to amino group-containing acrylic resin is determined as follows. First, the number of amino groups contained in 1 g of amino group-containing acrylic resin is determined by dividing the total number (mg) of the amine value (mg) and the acid value (mg) by the molecular weight (mg) of KOH. The number of epoxy groups contained in 1 g of epoxysilane is determined by dividing the 1 g by the epoxy equivalent, and the approximate number of compounding parts is determined so that the ratio of the number of amino groups to the number of epoxy groups is 1: 1. Then, the adhesion to the base tile or anchor pin and the adhesion between the silicone acrylic resin primer and the transparent reinforcing layer to be described below are experimentally confirmed, and the optimum blending weight part of epoxysilane is determined. In the present invention, 50% to 100% of the blending weight part of the epoxysilane determined is preferable as the blending number with respect to 100 parts by weight of the amino group-containing acrylic resin.

Polyurea resin coating material The polyurea resin coating material forming the transparent reinforcing layer used in the present invention is a non-yellowing isocyanate prepolymer having 5 to 10% by weight of NCO, an alicyclic polyamine, a reinforcing fiber and a light stabilizer. Non-yellowing isocyanate prepolymers containing 5 to 10% by weight of NCO and containing aliphatic UV absorbers and alicyclic difunctional isocyanates such as hexamethylene diisocyanate (HDI) and alicyclic ones such as isophorone diisocyanate (IPDA) It is possible to use one obtained by prepolymerizing bifunctional isocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-methylene bis (cyclohexyl isocyanate) (hydrogenated MDI) or the like with a polyhydric alcohol.

  Alicyclic polyamines are polyamines in which at least one amino group such as isophorone diamine is directly bonded to a cyclohexane ring or the like, and an amine having only a secondary amino group not containing a primary amino group is used . The weight average molecular weight (theoretical value) is preferably 300 to 1000. If it is less than 300, the working life becomes short and the workability becomes poor, and if it exceeds 1000, the reaction speed decreases, and the time to dry to the touch and the rising of the coating strength are delayed. Only by using an alicyclic polyamine having only a secondary amino group, it is possible to sufficiently secure a pot life capable of applying a polyurea resin coating material with a brush or the like, and further to prevent yellowing. By using in combination with the isocyanate-modified prepolymer, the cured coating does not yellow with ultraviolet light.

Alicyclic polyamines are represented by formula I above, wherein X, R ₁ , R ₂ , m are one or more polyamines as described above. The cycloaliphatic polyamine is a polyaspartic acid ester or polyaspartate, and m is preferably 2. And X is 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- (at least 2,4-diaminotoluene or 2,6-diaminotoluene Use of polyaspartic acid ester representing a group obtained by removing a primary amino group from isomeric C-monomethyldiaminodicyclohexylmethane and 3 (4) -aminomethyl-1-methylcyclohexylamine. it can. In particular, X is 4,4'-diaminodicyclohexylmethane (4,4 'methylenebis (cyclohexylamine)) or 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (4,4' methylenebis (2-methylcyclohexylamine) More preferred are compounds of the formula I which represent divalent hydrocarbon radicals which can be obtained by removing a primary amino group from)).

The alicyclic polyamine represented by the formula I is preferably a primary polyamine represented by the formula X-(-NH ₂ ) m, in which R ₁ and R ₂ are methyl, ethyl, n-butyl or 2-ethylhexyl. is prepared by reacting a ₁ OOC-CH = CH-COOR maleic or fumaric acid esters represented by _2.

  An alicyclic polyamine having only a secondary amino group, which is obtained by reacting 1 mol of 4,4 'methylene biscyclohexylamine with 2 mol of diethyl maleate, is 4,4'-methylene biscyclohexylamine maleic acid It is commercially supplied as a diethyl adduct, and its weight average molecular weight (Mw) is 548 (theoretical value), and its viscosity is 2000 mP · s / 23 ° C. In addition, as an alicyclic polyamine having only a secondary amino group, which is obtained by reacting 1 mol of 4,4 'methylene bis (2-methylcyclohexylamine) with 2 mol of diethyl maleate, 4,4'- It is supplied to the market as methylene bis (2-methylcyclohexylamine) -maleic acid diethyl adduct, and its weight average molecular weight (Mw) is 578 (theoretical value), viscosity: 2000 mP · s / 23 ° C.

  The non-yellowing isocyanate prepolymer having 5 to 10% by weight of NCO includes, as described above, an aliphatic bifunctional isocyanate such as hexamethylene diisocyanate (HDI) or an alicyclic bifunctional such as isophorone diisocyanate (IPDA) It is possible to use isocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 4,4′-methylenebis (cyclohexyl isocyanate) (hydrogenated MDI) or the like, which is prepolymerized with polyhydric alcohol. In particular, a non-yellowing isocyanate prepolymer obtained by reacting a polycaplactone modified polyol with 1,6-hexamethylene diisocyanate is suitable, and Duranate E402-100 (trade name, manufactured by Asahi Kasei Chemicals Corporation) is suitable as the prepolymer. NCO weight%: 8.5%, number average molecular weight 1580, viscosity 6000 mPa · s / 25 ° C., number average functional group number 3.2, solid content 90%). If the NCO weight% is less than 5 weight%, the coating strength becomes insufficient, and if it exceeds 10 weight%, the usable life time when using this material in the summer season becomes short.

The equivalent ratio of active hydrogen groups of non-yellowing NCO groups of the isocyanate prepolymer and alicyclic polyamine (NCO groups / active hydrogen group) is 0.8 to 1.2 is preferred. If it is less than 0.8, the viscosity increase after mixing the main agent and the curing agent becomes fast and the pot life becomes short. If it exceeds 1.2, the time to touch dry and the rise of the coating strength are delayed.

  The non-yellowing isocyanate prepolymer and the cycloaliphatic polyamine are thoroughly mixed and used immediately before applying the polyurea resin coating material on the already formed transparent primer layer.

  Reinforcement fibers included in the polyurea resin coating material according to the present invention may be vinylon, nylon, glass, polyethylene fibers having an average fiber length of 0.5 to 20 mm and a fiber diameter of 10 to 150 μm, and no yellowing By blending 1 part by weight or more and 20 parts by weight or less with respect to a total of 100 parts by weight of the isocyanate prepolymer and the alicyclic polyamine, the strength of the transparent reinforcing layer is improved while maintaining the transparency of the transparent reinforcing layer. The transparent reinforcing layer can be thixotropic. If it is less than 1 part by weight, the strength improvement of the transparent reinforcing layer is insufficient, and if it is more than 20 parts by weight, the transparency of the transparent reinforcing layer is lowered. As a commercially available reinforcing fiber, a tough binder 5 mm (trade name, average fiber length 5 mm, fiber diameter 28 μm, manufactured by Toray Amtec Co., Ltd.) as nylon fiber, Chemibest FD 380 (trade name, average fiber length 0.7 mm) as polyethylene fiber And fiber diameter 20 to 70 μm, manufactured by Mitsui Chemicals, Inc.).

  The polyurea resin coating material according to the present invention further contains a light stabilizer and an ultraviolet light absorber, so that the strength of the transparent reinforcing layer does not decrease even when exposed to ultraviolet light for a long time. As the light stabilizer, a hindered amine light stabilizer can be used, and as the ultraviolet light absorber, a hydroxyphenyltriazine-based ultraviolet light absorber or a benzotriazole-based ultraviolet light absorber can be used. Commercially available hindered amine light stabilizers include TINUVIN 292 (trade name, chemical name; bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate), manufactured by Ciba Japan Co., Ltd. As a hydroxyphenyl triazine type ultraviolet absorber, TINUVIN 400 (trade name, chemical name; 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-) The reaction product of hydroxyphenyl and oxirane, manufactured by Ciba Japan Ltd., is a commercially available benzotriazole-based UV absorber, and includes TINUVIN 928 (trade name, chemical name; 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, thiocyanate Japan KK) there is.

Acrylic silicone resin coating material The acrylic silicone resin coating material used when forming the transparent protective layer according to the present invention mainly comprises an acrylic silicone oligomer having an alkoxysilyl group and uses a tin-based curing catalyst as a curing agent. Immediately before applying the acrylic silicone resin coating material onto the transparent reinforcing layer which has already been formed, the main agent and the curing agent are uniformly mixed and applied by roller brush or the like. The alkoxysilyl group of the main agent is cross-linked by a tin-based curing catalyst as a curing agent to form a stable siloxane bond, and exhibits excellent durability.

  The content of the alkoxysilyl group is preferably 2% by weight to 30% by weight. If the amount is less than 2% by weight, the weatherability is lowered, and if the amount is more than 30% by weight, the workability is lowered due to the increase in viscosity. As an acrylic silicon oligomer having a commercially available alkoxysilyl group, Kanekazem Lac YC 4383 (trade name, siloxane cross-linked reactive polymer, viscosity 4000 mP · s / 23 ° C., alkoxylyl group content; 15% by weight, Kaneka Co., Ltd. ). A commercially available tin-based curing catalyst is BT405Z (trade name, chemical name; organic tin compound, effective tin component: 1.3%, Kaneka Co., Ltd.).

  The acrylic silicone resin coating material of the present invention contains a light stabilizer and an ultraviolet light absorber, and the strength of the transparent reinforcing layer does not decrease even when exposed to ultraviolet light for a long time. As a light stabilizer, a hindered amine light stabilizer can be used, and as a commercially available hindered amine light stabilizer, TINUVIN 292 (trade name, chemical name; bis (1,2,2,6,6-pentamethyl-4) (Piperidyl) (sebacate), manufactured by Ciba Japan Ltd.), and as the UV absorber, a hydroxyphenyltriazine-based UV absorber or a benzotriazole-based UV absorber can be used, and a commercially available hydroxyphenyltriazine-based UV absorber As the agent, TINUVIN 400 (trade name, chemical name; 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hydroxyphenyl and oxirane The reaction product, manufactured by Ciba Japan Co., Ltd., as a commercially available benzotriazole ultraviolet absorber TINUVIN 928 (trade name, chemical name; 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) Phenol, manufactured by Ciba Japan Ltd.).

  Hereinafter, the present invention will be specifically described in Examples and Comparative Examples.

EXAMPLES ACRYDIC A-9521 was used as an amino group-containing acrylic resin of a silicone acrylic resin primer forming a transparent primer layer, and ACRYDIC A-9585 was used as an epoxysilane, to obtain a main agent and a curing agent in the formulations shown in Table 1. The weight ratio of the main agent to the curing agent was 13: 1, and the main agent and the curing agent were uniformly mixed to obtain a silicone acrylic resin primer.

  As a polyurea resin coating material to form a transparent reinforcing layer, Duranate E402-100 is used as the main component without using yellowing isocyanate prepolymer, and the above 4,4'-methylenebiscyclohexylamine diethyl maleate as an alicyclic polyamine A An adduct (weight average molecular weight (Mw): 548 (theoretical value), viscosity 2000 mP · s / 23 ° C.) as the alicyclic polyamine B is the above 4,4′-methylenebis (2-methylcyclohexylamine) · diethyl maleate Additive (weight-average molecular weight (Mw): 578 (theoretical value), viscosity: 2000 mP · s / 23 ° C.), reinforcing fiber using nylon fiber tough binder 5 mm and polyethylene fiber Chemibest FD 380 at a weight ratio of 1: 1 , Light stabilizer TINUBIN 292, UV absorber TINUVIN4 In addition, as an antifoaming agent, Floren AC-303 (trade name, an acrylic antifoaming agent, manufactured by Kyoeisha Chemical Co., Ltd.), and as a wetting agent, SH6020 (trade name, aminosilane, Toray Dow Corning Co., Ltd.) was blended in a predetermined amount by weight shown in Table 1 as a curing agent. The composition of the SH6020 has the effect of maintaining the coating film strength even when the temperature of the transparent reinforcing layer becomes high due to solar radiation. The weight ratio of the main agent to the curing agent was 3: 2, and a polyurea resin coating material of Example was obtained with these main agents and the curing agent.

  Kanekazem rack YC4383 is used as an acrylic silicon oligomer having an alkoxysilyl group as an acrylic silicone resin coating material to form a transparent protective layer, TINUBIN 292 as a light stabilizer, TINUVIN 928 as an ultraviolet absorber, and other petroleum based dilutions As a main agent, turpen thinner # 50 was blended, and as an antifoamer, BYK-066N (trade name, silicone antifoamer, manufactured by BIC-Chemie Co., Ltd.) was compounded as shown in Table 1 as a main component. The curing catalyst BT405Z was used as a curing agent. The weight ratio of the main agent to the curing agent was 19: 1, and an acrylic silicone resin coating material of Example was obtained with these main agents and the curing agent.

Comparative example
A transparent acrylic emulsion (butyl acrylate) having a resin solid content of 50% is used as the coating material for forming the transparent reinforcing layer of the comparative example, using the silicone acrylic resin primer of the above example as the coating material for forming the transparent primer layer of the comparative example. / Methyl methacrylate copolymer, viscosity 50 Pa · s / 20 ° C., T.I value (JIS A 6024 thixotropic index: 5.7), containing 2% by weight of nylon staple fiber (fiber length 5 mm) was used.

Evaluation method

The coated materials of Examples and Comparative Examples for forming a transparent reinforcing layer are applied in a sheet shape with a thickness of 2 mm under conditions of tensile strength 23 ° C., RH 50%, and tensile test method of JIS K 6251 vulcanized rubber after 7 days curing. It was molded into a prescribed No. 2 dumbbell piece shape. Thereafter, it was pulled at a tensile speed of 500 mm / min according to the same test method, and the strength at break was taken as the tensile strength (MPa). The test was performed at 23 ° C and 60 ° C.

The surface of a 70 mm × 70 mm × 20 mm mortar test plate (JIS R 5201 10.4 standard) is sanded at a mortar adhesion strength of 23 ° C. and 50% RH, and the treated surface is silicon in the case of the embodiment. the acrylic resin primer 0.08 kg / ^{m 2} was applied after drying polyurea resin coating material 0.7 kg / ^{m 2} and coating twice, further Shi painted twice the acrylic silicone resin coating material with 0.08 kg / ^{m 2} after drying After curing for 7 days, the adhesion strength was measured in accordance with the JIS A 6909 7.9 adhesion strength test. For the comparative example, after coating and drying the silicone acrylic resin primer 0.08 kg / ^{m 2,} spread the transparent acrylic emulsion at 0.5 kg / ^{m 2,} dried, the same material 0.8 kg / ^{m 2} After spreading, further drying, the same material is spread at 0.8 kg / m ² and dried, then an acrylic silicone resin coating material is applied twice (layer) at 0.1 kg / m ² and aged for 7 days After that, the adhesion strength was measured according to JIS A 6909 7.9 adhesion strength test. Since the mortar board broke in all the test bodies, the adhesion strength was made into mortar adhesion strength (MPa). The test was performed at 23 ° C.

Under the conditions of UV resistance 23 ° C. and RH 50%, in the case of the example, a polyurea resin coating material is applied in a sheet shape with a thickness of 2 mm, and after drying, an acrylic silicone resin coating material is further added at 0.08 kg / m ² . Apply for 7 days and cure. In the case of the comparative example, the transparent acrylic emulsion is spread, dried with a thickness of 2 mm, 0.5 kg / m ² , dried, then spread with the same material at 0.8 kg / m ² , and further dried, with the same material. Is applied at 0.8 kg / m ² and dried, and then an acrylic silicone resin coating material is applied twice (layer) at 0.1 kg / m ² and aged for 7 days. These sheet-like cured products are continuously used for 180 hours with a super UV tester (model: SUV-W151, made by Iwasaki Electric, irradiation conditions: using a water-cooled metal halide lamp, temperature 63 ° C, humidity 50%, illuminance 100mW / cm ² ) After irradiation, it was molded into a dumbbell No. 2 piece shape prescribed in JIS K 6251 vulcanized rubber tensile test method. Thereafter, the appearance was visually confirmed, and at the same time, the film was pulled at a tensile rate of 500 mm / min according to the same test method, and the strength at break was taken as the tensile strength (MPa). The test was performed at 23 ° C.

Bending strength A mortar board (100 mm × 200 mm × 30 mm) specified in JIS R 5201 10.4 is loaded at the longitudinal center and divided into two. The fractured surface is put together and the surface fixed is fixed by sanding, and in the case of the embodiment, the coated surface is coated with a silicone acrylic resin primer 0.08 kg / m ² and dried, and the polyurea resin coated material 0.7 kg / m after the drying. After two coats of m ² and drying, two coats of acrylic silicone resin coating material are further applied at 0.08 kg / m ² , and after curing for 7 days, 4-point bending at a loading speed of 1.67 mm / min. The bending test was performed by the method and the bending strength (N) was measured. The upper load span was 50 mm and the lower load span was 150 mm. For the comparative example, after coating and drying the silicone acrylic resin primer 0.08 kg / ^{m 2,} spread the transparent acrylic emulsion at 0.5 kg / ^{m 2,} dried, the same material 0.8 kg / ^{m 2} After spreading, further drying, the same material is spread at 0.8 kg / m ² and dried, then an acrylic silicone resin coating material is applied twice (layer) at 0.1 kg / m ² and aged for 7 days After that, the same test was performed to measure the bending strength (N).

Punching maximum load
The central part of the concrete of the type name 300 (400 x 600 x 60 mm) (hereinafter referred to as "U-shaped lid") of the upper lid type U-shaped gutter (lid) specified in JIS A 5372 (precast reinforced concrete product) Annex 5 The back surface was incised with a core cutter for concrete with a shape of φ100 mm and a depth of 55 mm ± 3 mm. The surface is sanded, and to this treated surface, the silicone acrylic resin primer described in the above-mentioned example is applied and dried with a roller brush at 0.08 kg / m ^{2 for the} examples. Next, the polyurea resin coating material described in the above example is evenly coated with a gold crucible at 0.7 kg / m ² , and the polyurea resin coating material described in the above example is uniformly coated by a gold crucible at 0.7 kg / m ² Apply to Next subjected 0.08 kg / ^{m 2} coating an acrylic silicone resin coating material of the above Examples according to ² with coating 0.08 kg / ^m and the acrylic silicone resin coating material further above embodiment described later dry to the touch. It was aged for 7 days under conditions of 23 ° C. and 50% RH to obtain a specimen for push-out maximum load measurement. After that, the test was carried out according to the JHS 424-2004 anti-dropout push-out test method, and the maximum load was taken as the maximum load (KN).
For comparative example, after coating and drying the silicone acrylic resin primers at roller brush at 0.08 kg / ^{m 2,} it spreads the transparent acrylic emulsion at 0.5 kg / ^{m 2,} dried, and the same material 0.8kg / ^m spreadability at ^2, further dried, dried spread the same material with 0.8 kg / ^{m 2,} then twice with 0.1 kg / ^{m 2} and the acrylic silicone resin coating material (layer) coated After aging for 7 days under conditions of 23 ° C. and 50% RH, the same test was performed.

Working time For the polyurea resin coating material of the working example, the main agent and the curing agent are respectively prepared at 23 ° C., and the viscosity is measured with a B-type rotational viscometer 7 rotor 20 rpm immediately after mixing the main agent and the curing agent to obtain an initial viscosity Then, the viscosity was measured every 5 minutes, and the time to reach a viscosity twice as high as the initial viscosity was calculated as the usable time.

Anchor pin adhesion Tile anchor anchor JB-TA (trade name, made of SUS304, made by Aika Kogyo Co., Ltd.) 0.08 kg of silicone acrylic resin primer on the flat part (acrylic silicone resin coating film) of the head cap after curing at coating and drying after 7 days 23 ° C. with / m ^2, the tip of the blade of the cutter knife intruded along the interface of the silicon acrylic resin primer layer cured with a head flange, silicone acrylic resin at that time The peeling state of the primer layer was evaluated. Evaluation was performed by the following.
○: Peeling does not occur around the tip of the inserted cutter knife.
Fair: There is a slight exfoliation around the tip of the blade of the incorporated cutter knife.
X: Peeling has occurred entirely around the tip of the blade of the incorporated cutter knife.

Adhesive commercial tile of tile / transparent reinforcement layer Porcelain tile of Aurora Pale 50 · 2 T PL-100 (trade name, 95 x 45 mm, thickness 7 mm, class I (porcelain), manufactured by Danto Corporation) above silicone acrylic resin primer Apply 0.08 kg / m ² , apply one coat of 0.7 kg / m ² of polyurea resin coating after drying, and dry at 23 ° C for 7 days, then peel peel between porcelain tile and polyurea resin coating. It was inserted to forcibly separate and peel the polyurea resin coating material. The adhesion between the tile and the silicone acrylic resin primer (primer layer) and the silicone acrylic resin primer (primer layer) and the polyurea resin coated material (transparent reinforcing layer) by visually observing the peeled polyurea resin coated material and the surface of the porcelain tile The adhesion with) was determined. Those with good adhesion were judged to be ○, and the others were judged to be x.

Evaluation Results Evaluation results are shown in Table 2.

Reference Signs List 1 concrete frame 2 paste mortar 3 outer wall tile 4 anchor pin 4 a foot 4 b head 4 c press-fit portion 4 d flange 5 anchor hole 6 epoxy resin adhesive 7 joint 8 transparent primer layer 9 transparent reinforcing layer 10 transparent protective layer 20 outer wall tile peel-off prevention Construction

Claims (6)

An anchor pin is driven into the outer wall tile surface or joint to fix the anchor pin to the concrete casing, and an amine value is 10 to 50 mg KOH / g and a glass transition temperature is 10 on the head and outer wall tile surface and joint of the anchor pin. Apply a silicone acrylic resin primer containing an amino group-containing acrylic resin and an epoxysilane at a temperature of 50 ° C to less than 50 ° C to form a transparent primer layer, and 5 to 10% by weight of NCO on the 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 a secondary amino group, a reinforcing fiber, a light stabilizer, and an ultraviolet light absorber, An acrylic silicone resin coating material containing a light stabilizer and a UV absorber is applied on the transparent reinforcing layer to form a transparent protective layer. Outer wall tile flaking prevention structure. An anchor pin is driven into the outer wall tile surface or joint to fix the anchor pin to the concrete casing, and an amine value is 10 to 50 mg KOH / g and a glass transition temperature is 10 on the head and outer wall tile surface and joint of the anchor pin. Apply a silicone acrylic resin primer containing an amino group-containing acrylic resin and an epoxysilane at a temperature of 50 ° C to less than 50 ° C to form a transparent primer layer, and 5 to 10% by weight of NCO on the 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 a secondary amino group, a reinforcing fiber, a light stabilizer, and an ultraviolet light absorber, A transparent protective layer is formed by applying an acrylic silicone resin coating material containing a light stabilizer and a UV absorber on the transparent reinforcing layer. Outer wall tile flaking prevention method to be.   The light stabilizer of the outer wall tile peeling prevention structure according to claim 1 is a hindered amine light stabilizer, and the ultraviolet light absorber is a hydroxyphenyltriazine ultraviolet light absorber or a benzotriazole ultraviolet light absorber. The outer wall tile peeling prevention structure of 1 statement.   The light stabilizer of the outer wall tile peeling prevention method according to claim 2 is a hindered amine light stabilizer, and the ultraviolet light absorber is a hydroxyphenyl triazine based ultraviolet light absorber or a benzotriazole based ultraviolet light absorber. The outer wall tile peeling prevention method as described in 2. Alicyclic polyamines have the formula I:

(In the formula, X is inert to an isocyanate group and removes a primary amino group from an organic polyamine having a number average molecular weight of 88 to 400 containing m primary amino groups bonded to an alicyclic hydrocarbon And R ₁ and R ₂ are the same or different and each is an organic group having 1 to 18 carbon atoms, and m is an integer of at least 2) It is the above polyamine, The outer wall tile peeling prevention structure of Claim 1 or 3 characterized by the above-mentioned. Alicyclic polyamines have the formula I:

(In the formula, X is inert to an isocyanate group and removes a primary amino group from an organic polyamine having a number average molecular weight of 88 to 400 containing m primary amino groups bonded to an alicyclic hydrocarbon And R ₁ and R ₂ are the same or different and each is an organic group having 1 to 18 carbon atoms, and m is an integer of at least 2) The outer wall tile peeling prevention method according to claim 2 or 4, which is the above-mentioned polyamine.