JP2006159412A - Composite film forming method and composite film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite film forming method for forming a composite film which enables the reinforcement of a base material, has high followability with respect to the displacement of the base material and can ensure a sufficient peeling-off preventing function even under a low and high temperature environment, and the composite film. <P>SOLUTION: In the composite film forming method including a process (1) for forming an uncured resin film by coating the base material with a curable resin composition, a process (2) for pasting a high tensile force cloth on the uncured resin film and a process (3) for embedding the pasted high tensile force cloth in the uncured resin film, both of the cohesive force of the cured resin film obtained by coating the curable resin composition on the base material with the curable resin composition to cure the coated base material and the adhesive force of the base material and the cured resin film at the interface of them at 23°C are 0.1 kg/mm or above, the tensile strength of the high tensile force cloth at 23°C is 10 N/mm or above and the cutting elongation thereof is 3% or above. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for forming a composite film including a curable resin composition and cloth, and a composite film.

  Concrete may deteriorate due to salt damage, neutralization, alkali-aggregate reaction, frost damage, etc., and peel off. When concrete is used in structures such as roads, railway elevateds, tunnels, etc., if this deterioration has progressed, the stress and repeated vibration caused by the passage of automobiles and railways will trigger the stripped concrete pieces. The danger of falling is pointed out. In order to prevent such peeling of the concrete piece and to find a place where the concrete piece is peeled off, a coating layer for preventing the peeling may be formed on the concrete surface in some cases.

  As a method for forming this coating layer, there is a method in which one or more coating layers including a resin coating film having specified tensile strength and tensile elongation are formed on the surface of a concrete structure (for example, see Patent Document 1). ). However, since the coating layer is made only of a resin, it may be difficult to deal with a wide range of temperature environments.

  In addition, since the coating layer obtained by this method is made of resin, it has sufficient followability to concrete displacement such as cracks and cracks in the concrete, but is insufficient from the viewpoint of reinforcing the concrete frame.

  On the other hand, as a method for forming a reinforcing layer for protecting a concrete surface, there is a method of forming a reinforcing layer composed of a glass fiber sheet and a thermosetting resin for impregnation (see, for example, Patent Document 2).

However, although the coating layer obtained by this method is sufficient from the viewpoint of reinforcing the concrete frame, followability to the displacement of the concrete is insufficient.
JP 2004-60197 A JP 2003-213624 A

  The present invention provides a composite film forming method and a composite film that can reinforce a base material, have high followability to displacement of the base material, and can ensure a sufficient peeling prevention function even in a low temperature and high temperature environment. For the purpose.

  The present invention includes a step (1) of forming a non-cured resin film by applying a curable resin composition on a substrate, and a high tensile strength cloth is affixed on the uncured resin film obtained in the step (1). This is a method of forming a composite film including the step (2) and the step (3) in which the high tensile strength cloth adhered in the step (2) is adhered to the uncured resin film formed in the step (1). Then, at 23 ° C., the cohesive force of the cured resin film obtained by applying and curing the curable resin composition on the substrate, and the adhesive force at the interface between the substrate and the cured resin film Are both 0.1 kg / mm or more, the tensile strength of the high tensile strength cloth at 23 ° C. is 10 N / mm or more, and the elongation at break is 3% or more. It is a forming method. Here, after the step (3), it is preferable to further include a step (4) of applying a curable resin composition to form an uncured resin film. Here, for example, the high tensile strength cloth is made of resin fibers, and the base material is, for example, a concrete base material.

  The present invention also provides a composite film obtained by the above-described composite film forming method.

  Furthermore, a cured resin film in which a high tensile strength cloth is embedded on a base material, the cohesive force of the cured resin film at 23 ° C., and the base material and the cured resin film The adhesive strength at the interface is 0.1 kg / mm or more, the tensile strength of the high tensile strength cloth at 23 ° C. is 10 N / mm or more, and the cut elongation is 3% or more. It is a composite film characterized by this.

  Furthermore, this invention is a multilayer film formation method which includes the process (5) of apply | coating topcoat further and forming a topcoat film after said composite film formation method.

  Furthermore, the present invention is a multilayer film obtained by the above multilayer film forming method.

  Since the composite film forming method of the present invention uses the above-described constituent components, the obtained composite film has high followability to the displacement of the substrate. Here, when the base material is concrete, the film is hardly broken even against cracks in the concrete, and the concrete can be sufficiently protected. Furthermore, even if the concrete piece peels due to deterioration, the composite film can prevent the concrete piece from falling.

  Moreover, since the obtained composite film is tough and has excellent adhesion to the base material, it can be used as a reinforcing material for concrete itself.

  In particular, when the high tensile strength cloth is embedded in an uncured resin film, the high tensile strength cloth and the cured resin film are integrated in the resulting composite film, and the followability is further improved and the toughness is enhanced. A complex film.

  In addition, since the composite film formation method of this invention uses the said cured resin film and the said high tensile strength cloth, these functions can be hold | maintained also in a low temperature and high temperature environment. In particular, when a cloth processed at a temperature equal to or higher than the environmental temperature is used, since the change in physical properties is small when the temperature changes below the processing temperature, the function of the obtained composite film is considered to be independent of the environmental temperature.

  The composite film forming method of the present invention includes a step (1) of forming a non-cured resin film by applying a curable resin composition on a substrate, and a high amount on the uncured resin film obtained in the above step (1). A composite comprising the step (2) of applying a tensile strength cloth and the step (3) of embedding the high tensile strength cloth applied in the step (2) in the uncured resin film formed in the step (1). This is a method of forming a film.

  In the composite film forming method of the present invention, first, the above-described step (1), that is, the step of forming an uncured resin film by applying a curable resin composition on a substrate is performed. Examples of the base material include concrete base materials such as cements, limes, and plaster.

  As said curable resin composition, the cohesive force of the cured resin film obtained by apply | coating and curing the said curable resin composition on the said base material at 23 degreeC, and the said base material and the said cured resin film Adhesive strength at the interface with the above becomes 0.1 kg / mm or more. That is, the cohesive force and adhesive force defined when a single film obtained from the cured resin is formed on the substrate. When the cohesive force and the adhesive force are less than 0.1 kg / mm, the strength of the resulting composite membrane is low, and breakage or peeling tends to occur. Preferably it is 0.3 kg / mm or more. Here, the adhesive force at 23 ° C. is preferably equal to or greater than the cohesive force. If the adhesive force is weaker than the cohesive force, when the composite film is formed on the concrete base material, the composite film may be peeled off at the interface with the base material due to the peeling of the concrete piece. In addition, when moisture enters the peeled portion due to condensation or the like, the deterioration rate of the composite film may be increased.

  The adhesive force may vary greatly depending on the surface state of the substrate. When the adhesive strength is less than 0.1 kg / mm, before carrying out the step (1), physical irregularities are formed on the surface of the base material by performing keren to obtain an anchor effect. The adhesive force can be increased to 0.1 kg / mm or more by removing the fragile layer on the surface layer, or by applying a primer such as a primer or an undercoat. As the above-mentioned keren method, the above-mentioned base conditioning material, undercoat paint and coating method thereof, those well known by those skilled in the art can be used.

  Specifically, the cohesive force and the adhesive force are referred to as a peeling test for a sample in which a cured resin film obtained by applying the curable resin composition on the substrate and then curing it is formed. For example, it can be measured by a tensile tester such as Autograph AG-100KNE (manufactured by Shimadzu Corporation) or Tensilon (manufactured by Toyo Baldwin). Here, let the obtained peeling strength be the said cohesion force or the said adhesive force. Specifically, when peeling occurs due to breakage inside the cured resin film, it is assumed that the obtained peeling strength is cohesive force and the adhesive force exceeds the cohesive force. On the other hand, when peeling occurs at the interface between the substrate and the cured resin film, it is assumed that the obtained peeling strength is an adhesive force and the cohesive force exceeds the adhesive force.

  Here, the cohesive force of the cured resin film is related to the tensile strength and elongation, which are physical properties of the film, and the content of the filler. The cohesive force of the resin film can be controlled.

  On the other hand, the adhesive force of the cured resin film is generally the intermolecular force between the base material and the cured resin film, in particular, the polar functional group on the surface of the base material and the polar functional group on the surface of the cured resin film. Since the hydrogen bonding force is considered to be related, the adhesive force at the interface between the substrate and the cured resin film can be controlled by adjusting the hydrogen bonding force. Specifically, it is controlled by changing the amount of polar functional groups on the surface of the cured resin film. As said polar functional group, a hydroxyl group, an amino group, an isocyanate group, an epoxy group, a carboxyl group etc. can be mentioned, for example.

  The curable resin composition that can obtain such a cured resin film includes a resin having a curable functional group and a curing agent having a curable functional group capable of undergoing a curing reaction with the curable functional group, or polar. Examples thereof include those containing an unsaturated group-containing resin having a functional group and an oxidative polymerization accelerator.

  The curable resin composition is not particularly limited, and the above adhesive strength and agglomeration such as those that can be cured at room temperature where curing proceeds by drying, curing that proceeds by moisture, and those that cure by heating, etc. Adhesives and paints that are well known by those skilled in the art can be used as long as they have strength, but it is preferable that they can be cured at room temperature from the situation of application. From the viewpoint of chemical resistance of the resulting composite film, for example, a urethane resin system including a hydroxyl group-containing resin and an isocyanate group-containing curing agent, a urea resin system including an amino group-containing resin and an isocyanate group-containing curing agent, and an epoxy Examples thereof include an epoxy resin system containing a group-containing resin and an amino group-containing curing agent, or an unsaturated resin system containing an unsaturated group-containing resin and an oxidative polymerization accelerator. The curable resin composition can take various forms such as an aqueous type, an organic solvent type, and a solventless type.

  Examples of the hydroxyl group-containing resin include acrylic resins having a hydroxyl group as a curable functional group, polyester resins, polyether resins, and polybutadiene resins. Examples of the amino group-containing resin include aliphatic polyamines having an amino group as a curable functional group, aromatic polyamines, alicyclic polyamines, and modified products thereof. Examples of the epoxy resin include, for example, glycidyl ether type having an epoxy group as a curable functional group, glycidyl ester type, and other glycidyl type epoxy resins, and alicyclic epoxy resins, and these may be oil-modified, Examples thereof include those obtained by urethane modification. Examples of the unsaturated group-containing resin include acrylic resins, polyester resins, and polyether resins having an unsaturated group as a curable functional group.

  Examples of the isocyanate group-containing curing agent include monomers such as aromatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates, dimers and trimers, and polypropylene glycols and the like. Examples thereof include those obtained by chain extension modification with diol. Examples of the amino group-containing curing agent include those having a relatively small molecular weight among the amino group-containing resins described above.

  Examples of the oxidative polymerization accelerator include transition metal compounds such as cobalt compounds.

  These resins and curing agents may each have a curable functional group as the polar functional group, or may have a polar functional group not involved in curing. In particular, in the case of an unsaturated group-containing resin system, since the action is weak as a polar functional group of a cured functional group, the unsaturated group-containing resin needs to have the polar functional group.

  The curable resin composition may further contain a pigment. The pigment is not particularly limited, and examples thereof include inorganic pigments such as yellow lead, yellow iron oxide, iron oxide, carbon black, and titanium dioxide, azo chelate pigments, insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, and indigo. Pigments, perinone pigments, perylene pigments, dioxane pigments, quinacridone pigments, isoindolinone pigments, colored pigments such as organic pigments such as metal complex pigments, calcium carbonate, precipitated barium sulfate, clay, talc, etc. Examples include extender pigments.

  Selection of the said curable resin composition used for the composite film formation method of this invention can be performed with the following procedures. That is, if the cured resin film satisfies the cohesive force and the adhesive force, the resin composition may be selected. When the resin composition does not satisfy the conditions of the cohesive force and the adhesive force, the configuration of the resin composition may be changed so as to satisfy the above conditions.

  It is considered that the tensile strength and the elongation rate related to the cohesive force of the cured resin film are closely related to each other. In general, when the tensile strength is large, the elongation rate is small, and the film is hard and brittle. On the contrary, if the elongation is large, the tensile strength becomes small, and the film becomes soft and weak. The tensile strength and elongation can be adjusted by the glass transition temperature (Tg) of the film, the molecular weight between crosslinks, and the pigment volume concentration and the like when a pigment is included. That is, when the Tg of the film is increased, the tensile strength is generally increased and the elongation is decreased. Increasing the molecular weight between the crosslinks generally increases the elongation and decreases the tensile strength. Further, when the pigment volume concentration is increased, the tensile strength is decreased and the elongation is decreased. Based on this idea, the configuration of the curable resin composition can be changed.

  The Tg of the cured resin film can be controlled by the Tg of the resin and the curing agent, the amount of curable functional group, and the like. On the other hand, the molecular weight between crosslinks can be controlled by the molecular weight of the resin and the curing agent, the concentration of the cured functional group, and the like. For example, the Tg of the resin can be selected depending on the type. In general, Tg of polyether resin and polybutadiene resin tends to be low, and Tg of acrylic resin and polyester resin is easily controlled by Tg of raw material. As for the Tg of the curing agent, for example, when the curing agent has an isocyanate group, a Tg having a high Tg such as an aromatic group or an aggregate such as an isocyanurate body is selected. On the other hand, a low Tg can be obtained by using a soft diol for chain extension of the diisocyanate. The amount and concentration of the curable functional group and the molecular weight can be adjusted by methods well known to those skilled in the art. However, since the Tg and curable functional group amount of the resin and the curing agent and the tensile strength and elongation of the film are not necessarily uniquely correlated, the target curable resin can be obtained through trial and error. It is preferred to select a composition.

  On the other hand, the adhesive force is closely related to the polar functional group concentration of the cured resin film. In general, when the polar functional group concentration is high, the adhesive strength is increased. As a method for increasing the concentration, for example, when the curable functional group is used as a polar functional group, as described above, the resin / curing agent ratio is adjusted and obtained after curing. Examples thereof include a method in which the curable functional group is designed to remain in the cured resin film, or a resin having a polar functional group different from the curable functional group and the curable functional group is used. However, when the polar functional group is the same as the curable functional group, the Tg of the obtained film is increased at the same time as the concentration of the polar functional group is increased, and as a result, the tensile strength and elongation rate may be affected. Therefore, it is preferable to select a target curable resin composition by repeated trial and error.

  In changing the configuration of the curable resin composition, each component may be produced by itself or selected from commercially available materials.

  Furthermore, the curable resin composition contains other resins, organic solvents, antifoaming agents, thickeners, surface conditioners, plasticizers, ultraviolet absorbers, light stabilizers and the like used in the general paint field. Can be included.

  The method for applying the curable resin composition in the step (1) is not particularly limited, and examples thereof include methods well known by those skilled in the art, such as brush coating, spray coating, roller coating, iron coating, and spatula coating. Specifically, it can be appropriately selected according to the type of the curable resin composition. The coating film thickness is not particularly limited, and the dry film thickness is, for example, greater than or equal to the film thickness that enables the application of the high tensile strength cloth used in the step (2) described later.

  In the composite film forming method of the present invention, next, the step (2) of applying a high tensile strength cloth on the uncured resin film obtained in the step (1) is performed. The high tensile strength cloth has a tensile strength of 10 N / mm at 23 ° C. and a cut elongation of 3% or more. If the tensile strength is less than 10 N / mm, the effect of reinforcing the substrate is insufficient. Although it does not specifically limit as an upper limit, It is 100 N / mm substantially. When it exceeds 100 N / mm, there is a possibility that the above-mentioned condition of cutting elongation is not satisfied. Preferably it is 13-90 N / mm. Moreover, the followability with respect to the displacement of a base material will fall that the said cutting elongation is less than 3%. The upper limit is not particularly limited, but is substantially 100% or less. If the cut elongation exceeds 100%, the tensile strength may be insufficient. Preferably it is 4 to 70%.

  The tensile strength and the cut elongation can be measured in the same manner as the measurement method of tensile strength and elongation described for the cured resin film.

  The form of such a high tensile strength cloth is not particularly limited, and examples thereof include plain weave, triaxial mesh, and non-woven fabric. The material of the high tensile strength cloth is not particularly limited, and examples thereof include carbon fiber-containing materials, metal fibers-containing materials, glass fibers-containing materials, and resin fibers-containing materials. It is preferably made of resin fibers capable of achieving both a high level of cutting elongation and a high elongation. It does not specifically limit as said resin fiber, Nylon fiber, an aramid fiber, an acrylic fiber, a polyester fiber, a vinylon fiber, etc. can be mentioned, It is preferable that it was processed at the temperature of 100 degreeC or more. Moreover, in order to improve adhesiveness with the said curable resin composition, it is preferable that the said resin fiber has a hydroxyl group. Examples of commercially available high tensile strength cloths include vinylon cloth UV # 130, UV # 200, Trineo TSS-1810-Y (all manufactured by Unitika Ltd.), and the like.

  In the step (2), the method for applying the high tensile strength cloth is not particularly limited, and specifically, the high tensile strength cloth cut in accordance with the shape of the base material is attached on the uncured resin film. When a bonded portion is generated, it is preferable to provide an overlapping allowance so that no gap is generated in the bonded portion.

  In addition, it does not specifically limit as a process space | interval with the said process (1) in the composite film formation method of this invention, and the said process (2), The kind of the said curable resin composition, the temperature at the time of application | coating, humidity, etc. Although it can be set as appropriate depending on the surrounding environment, coating film thickness, etc., it is necessary that the uncured resin film obtained in the above step (1) has adhesiveness, and it is continuous without leaving a time interval. Can be done.

  In the composite film forming method of the present invention, subsequently, the step (3) is performed in which the high tensile strength cloth pasted in the step (2) is closely attached to the uncured resin film formed in the step (1). By adhering to each other, the curable resin composition is sufficiently adapted between the eyes of the high tensile strength cloth, and the resulting composite film is further improved in the integration of the cured resin film and the high tensile strength cloth, and thus has a tougher composite film. Obtainable. The method for the close contact is not particularly limited, and examples thereof include a method of pushing with a spatula or the like. It does not specifically limit as a process space | interval of the said process (2) and the said process (3), It can carry out continuously similarly to the process space | interval of the said process (1) and the said process (2).

  In the composite film formation method of this invention, after the said process (3), the said curable resin composition may be apply | coated and the process (4) which forms an uncured resin film may be performed further. By carrying out this step (4), the high tensile strength cloth can be sufficiently embedded in the uncured resin film. As a result, the composite film obtained can be integrated to enhance the adhesion between the cured resin film and the high tensile strength cloth, and as a result, the composite film can be made tougher. In addition, by implementing the step (3), the high tensile strength cloth is sufficiently embedded in the uncured resin film obtained in the step (1), and the high tensile strength cloth becomes the uncured resin film. If it is completely covered, this step (4) is not necessary.

  It does not specifically limit as a process space | interval of the said process (3) and the said process (4), It can carry out continuously similarly to the process space | interval between the said process (1) and the said process (2). The coating method is not particularly limited, and specific examples include those described in the step (1). Moreover, it does not specifically limit as said coating film thickness, The said high tensile cloth is completely covered by the uncured resin film obtained at the said process (1), and the uncured resin film obtained at this process (4). It is preferable that the film thickness be able to.

  In the composite film forming method of the present invention, when the step (4) is not carried out, the step (3) is finished, and when the step (4) is carried out, the step (4) is finished or left at room temperature or forced. By drying, a composite film in which the curable resin composition and the high tensile strength cloth are integrated can be obtained.

  In addition, the position of the high tensile strength cloth in the obtained composite membrane is not particularly limited, and the obtained composite membrane is obtained by integrating the curable resin composition and the high tensile strength cloth. It is possible to obtain the base material reinforcement and peeling prevention functions which are the effects of the invention.

  Here, the composite film formation method of this invention can be used for concrete peeling prevention, when a base material is a concrete-type base material. The composite film preferably has a maximum displacement of 10 mm or more and a maximum load of 0.3 kN or more in the concrete punching test. In the case of a film that breaks with a displacement of less than 10 mm, it is difficult to withstand the displacement of the substrate. In particular, when the composite film is used for preventing concrete from peeling off, the film cannot withstand peeling due to deterioration of the concrete, and the film may be easily broken and the concrete may be peeled off.

Further, if the maximum load is less than 0.3 kN, the composite film cannot withstand peeling due to deterioration of the concrete, and the film may be easily broken and the concrete may be peeled off. Preferably it is 1.5 kN or more, and although the upper limit is not particularly limited, it is preferably substantially 5 kN. The concrete push-out test is performed as follows.
(I) U-shaped lid defined in JIS A 5372: 2000 (precast reinforced concrete product) cured under an environment of a temperature of 20 ° C. and a relative humidity of 65%, designated type 1 300 (length 400 mm × width 600 mm × thickness 60 mm) A central portion of the concrete plate is drilled vertically with a shape of 100 mm in diameter, with a bottom portion left by a core cutter for concrete. In addition, drilling is performed from the back side of the construction surface. Furthermore, surface treatment is performed on the construction surface with Thunder Keren or the like.
(Ii) Next, based on the construction specifications, a composite film is formed to prepare a specimen. The area to be formed is a U-shaped lid center part 400 mm × 400 mm.
(Iii) Using the obtained test plate in an environment of a temperature of 20 ° C. and a relative humidity of 65%, using a tensile tester of grade 1 or higher specified in 6 of JIS B 7733 as a punching tester, Measured by loading from above with the steel plate facing down and fixed on H steel. The loading speed is 1 mm / min until the initial peak, and 5 mm / min after the initial peak value appears.

  The tensile tester is not particularly limited, and examples thereof include Autograph AG (manufactured by Shimadzu Corporation).

  Since the composite film of the present invention is obtained by the above-described composite film forming method, the base material can be reinforced, the followability to the displacement of the base material is high, and it is sufficient even in a low temperature and high temperature environment. Can be secured.

  Further, the composite film of the present invention includes a cured resin film in which a high tensile strength cloth is embedded on a substrate, and the cohesive force of the cured resin film at 23 ° C. and the substrate And the cured resin film have an interfacial adhesive strength of 0.1 kg / mm or more, a tensile strength of the high tensile strength cloth at 23 ° C. of 10 N / mm or more, and a cutting elongation. It is characterized by being 3% or more.

  Since the high tensile strength cloth is embedded in the cured resin film, the obtained composite film is more rigid because the cured resin film and the high tensile strength cloth are integrated.

  In the multilayer film forming method of the present invention, after the above-described composite film forming method, a top coating film is formed by further applying a top coating material for the purpose of improving corrosion resistance, imparting fire resistance, preventing UV deterioration, improving landscape, and the like. Step (5) is included. The top coating is not particularly limited, and examples thereof include those well known by those skilled in the art, such as acrylic resin-based paints, urethane resin-based paints, and fluororesin-based paints. In addition, when the said base material is a concrete-type base material, it is preferable to use what has the elasticity called a flexible type so that the displacement of a base material can be tracked.

  In addition, when the composite film formation method or the multilayer film formation method of the present invention is used for the concrete peeling prevention method, displacement of the composite film or the multilayer film may occur due to peeling of the concrete piece. In that case, concrete can be repaired as follows.

  The occurrence of the displacement is confirmed by visually inspecting the surface of the composite film or the multilayer film. Here, the displacement refers to the amount of change in the vertical direction with respect to the composite film or multilayer film surface. For example, if the amount of change is 10 mm, it is determined that a displacement of 10 mm has occurred. In the concrete repair performed on the portion where the displacement is generated, the composite film or the multilayer film in the portion where the displacement is confirmed is excised, and then the concrete is repaired by a method well known by those skilled in the art, for example, repair mortar.

  It is preferable that the repaired concrete is subjected to the above-described composite film formation method or the above-described multilayer film formation method again after performing necessary treatment on the surface thereof.

  EXAMPLES Hereinafter, although a specific Example is given and this invention is demonstrated in detail, this invention is not limited by a following example. In the following description, “part” means “part by mass”.

Production Example 1 Preparation of Substrate 1 After the concrete-based substrate surface is cleansed with a sander, a tough guard E-VM primer (manufactured by Nippon Paint Co., Ltd., epoxy resin-based paint) is applied in an amount of 0.2 kg / m ^2. And applied for 16 hours. Then, tough guard E putty N-2 (manufactured by Nippon Paint Co., Ltd., epoxy resin-based paint) was applied with a spatula so that the coating amount was 0.5 kg / m ^2, and the surface was adjusted and left for one day. The base material 1 was produced.

Production Example 2 U-shaped lid defined in JIS A 5372: 2000 (precast reinforced concrete product) cured under an environment of substrate 2 at a production temperature of 20 ° C. and a relative humidity of 65%, nominal type 1 300 (length 400 mm × width 600 mm × A central portion of a concrete plate having a thickness of 60 mm was drilled vertically with a shape having a diameter of 100 mm and a bottom portion left by a core cutter for concrete.

The surface that was not drilled was cleaned with a sander. Using this surface as a construction surface, the tough guard E-VM primer was applied by brush so that the coating amount was 0.2 kg / m ² and left for 4 hours. Thereafter, tough guard E putty N-2 was applied with a spatula so that the coating amount was 0.5 kg / m ² , the surface was adjusted, and the substrate 2 was produced by leaving it for one day.

Example 1
Polyhardener UD-503 (Daiichi Kogyo Seiyaku Co., Ltd., polyether resin having a hydroxyl group) 30 parts, Taipei R-820 (Ishihara Sangyo Co., Ltd., titanium dioxide) 15 parts, Talc PK50 (Fuji Talc Co., Ltd., talc) 47 And 10 parts of xylene were mixed and kneaded, and then 100 parts of Polyflex FL-83 (Daiichi Kogyo Seiyaku Co., Ltd., isocyanate group-containing curing agent) was mixed to obtain a urethane-based curable resin composition. At this time, the hydroxyl group / isocyanate group functional group ratio was 1 / 1.2, and the volume pigment concentration of the curable resin composition was 15%.

<Evaluation of tensile strength and elongation of cured resin film>
In addition, according to JIS K7113-1981, using the free film of the cured resin film obtained from this curable resin composition, Autograph AG-100KNE (manufactured by Shimadzu Corporation, tensile tester, tensile condition 10 mm / Minutes), the film physical properties were measured, and the tensile strength was 9.3 MPa and the elongation was 350%.

<Measurement of adhesive strength and peel strength of cured resin film>
By applying the obtained curable resin composition to the base material 1 obtained in Production Example 1 by brushing at a coating amount of 0.45 kg / m ² , and leaving it at 23 ° C. for 7 days, A cured resin film was produced on the substrate 1 to obtain a test substrate 1. 45 degree peel test between the base material 1 and the cured resin film with the autograph AG-100KNE (tensile condition 10 mm / min) in an environment of a temperature of 23 ° C. and a humidity of 65% with respect to the obtained test base material 1 As a result, peeling occurred due to breakage inside the cured resin film, and the peeling strength at that time was 0.8 kg / mm.

<Evaluation of maximum load and maximum displacement of membrane by concrete punching test>
On the base material 2 obtained in Production Example 2, the obtained curable composition was applied with a spatula at a coating amount of 0.45 kg / m ² so that the coating area was 400 mm × 400 mm, and an uncured resin film was formed. Formed. Immediately thereafter, vinylon cloth # UV200 (manufactured by Unitika Ltd., vinylon cloth) having a tensile strength of 70 N / mm and a cutting elongation of 14% was applied to the entire uncured resin film surface. After pasting, the vinylon cloth was pressed with a spatula to infiltrate the uncured resin film into the vinylon cloth. Further, from this, the obtained curable resin composition was applied with a spatula at an application amount of 0.45 kg / m ² so that the application area was 400 mm × 400 mm to form an uncured resin film. Thereafter, the composite film was produced on the base material 2 by leaving it at 23 ° C. for 7 days to obtain a test base material 2.

  In an environment of a temperature of 20 ° C. and a relative humidity of 65%, the obtained test substrate 2 was fixed on the H steel with a span of 400 mm so that the composite film faced downward. Using Autograph AG (manufactured by Shimadzu Corporation), load the ball seat on the center of the drilled cylindrical part so that the load is applied vertically and evenly, and measure the maximum load and maximum displacement. did. The loading speed was 1 mm / min until the initial peak, and 5 mm / min after the initial peak value appeared. Further, when the maximum load and maximum displacement of the film at this time were measured, the maximum load was 6 kN and the maximum displacement was 50 mm or more.

  Further, after leaving the test substrate 2 in a constant temperature room at a temperature of 50 ° C. for 48 hours, the maximum load and the maximum displacement of the film were measured in the same manner. In addition, as a test apparatus, the hydraulic press made from Oxjack company which attached the pressure sensor and the displacement sensor was used. The measurement was performed while adjusting the hydraulic press so that the loading speed was the same as 20 ° C. Further, in the same manner, measurement was performed in a thermostatic chamber at a temperature of −30 ° C. The results obtained are shown in Table 1.

<Top coatability and repairability>
Moreover, when a tough guard UD topcoat (manufactured by Nippon Paint Co., Ltd., flexible urethane resin-based paint) is applied by brush so that the coating amount becomes 0.12 kg / m ² , a good multilayer film can be obtained. I was able to.

  Further, a part of the multilayer film was peeled off with a disk sander to expose the concrete, and then a tough guard E-VM primer was applied in the same manner as in Production Example 2. Next, after leaving for 16 hours, tough guard E putty N-2 was applied to the obtained primer surface in the same manner as in Production Example 2 to adjust the surface. Further, after 7 days, when the above-described curable resin composition was applied to the entire top coat and putty surface obtained in the same manner, it was found that the construction could be performed without any problems.

Example 2
Instead of urethane-based curable resin composition, 100 parts of Adeka Resin EPU-86 (Asahi Denka Co., urethane-modified epoxy resin), 15 parts of Tyco R-820, 40 parts of talc PK50 and 10 parts of xylene are mixed. After kneading, a test substrate was prepared in the same manner as in Example 1 except that 14 parts of Adeka Hardener EH-220 (Asahi Denka Co., Ltd., amino group-containing curing agent) was mixed and an epoxy-based curable resin composition was used. Materials 1 and 2 were prepared and the above measurements were performed. The results obtained are shown in Table 1. The functional group ratio of epoxy group / amino group at this time was 1 / 1.2, and the PVC of the paint was 15%.

Example 3
Test substrate 1 in the same manner as in Example 1 except that vinylon cloth # UV130 (manufactured by Unitika Ltd., vinylon cloth, tensile strength 50 N / mm, cutting elongation 14%) was used instead of vinylon cloth # UV200. And 2 were prepared and the above measurements were performed. The results obtained are shown in Table 1. In the same manner as in Example 1, a good multilayer film could be obtained.

Example 4
A test substrate was prepared in the same manner as in Example 1 except that Trineo TSS-1810-Y (manufactured by Unitika Ltd., Vinylon cloth, tensile strength 27 N / mm, cutting elongation 7%) was used instead of Vinylon cloth # UV200. Materials 1 and 2 were prepared and the above measurements were performed. The results obtained are shown in Table 1. In the same manner as in Example 1, a good multilayer coating film could be obtained.

Comparative Example 1
Test substrates 1 and 2 were prepared and measured in the same manner as in Example 2 except that 100 parts of talc PK50 and 8 parts of Adeka Hardener EH-220 were used. The results obtained are shown in Table 1. At this time, the functional group ratio of epoxy group / amino group was 1 / 0.7, and the PVC of the paint was 29%. Further, in the same manner as in Example 1, each measurement was performed in an environment of 20 ° C., 50 ° C., and −30 ° C. In addition, a multilayer film could be obtained in the same manner as in Example 1.

  As is clear from the results in Table 1, the composite film obtained by the composite film forming method of the present invention has sufficient cohesive force and adhesion to the substrate. The displacement was large. Similarly, as is clear from the results in Table 2, it was found that high maximum load and maximum displacement were exhibited even in a low temperature environment and a high temperature environment.

  Furthermore, it was found that the multilayer film obtained by applying a top coating on the obtained composite film had no problem and no problem with repairability.

  However, when a curable resin composition that does not have a predetermined cohesive force or adhesive force is used, or when a cloth that does not have a predetermined tensile strength or cut elongation is used, the maximum load or maximum It was found that the displacement was low.

  The composite film forming method of the present invention and the composite film of the present invention can be suitably used as a concrete peeling prevention method for concrete structures such as bridges and viaducts and a composite film for preventing concrete peeling.

Claims (8)

Step (1) of applying a curable resin composition on a substrate to form an uncured resin film, and step (2) of applying a high tensile strength cloth on the uncured resin film obtained in the step (1). And a method of forming a composite film including the step (3) of adhering the high tensile strength cloth pasted in the step (2) to the uncured resin film formed in the step (1),
At 23 ° C., the cohesive force of the cured resin film obtained by applying and curing the curable resin composition on the substrate, and the adhesive force at the interface between the substrate and the cured resin film, Both are 0.1 kg / mm or more,
A method for forming a composite film, wherein the high tensile strength cloth has a tensile strength of 10 N / mm or more at 23 ° C. and a cut elongation of 3% or more.   The method for forming a composite film according to claim 1, further comprising a step (4) of applying an curable resin composition to form an uncured resin film after the step (3).   The composite film forming method according to claim 1, wherein the high tensile strength cloth is made of resin fibers.   The composite film forming method according to claim 1, wherein the base material is a concrete base material.   A composite film obtained by the composite film forming method according to claim 1. On the base material, it is equipped with a cured resin film embedded with a high tensile strength cloth,
The cohesive force of the cured resin film at 23 ° C. and the adhesive force at the interface between the substrate and the cured resin film are both 0.1 kg / mm or more,
And,
A composite film, wherein the high tensile strength cloth has a tensile strength of 10 N / mm or more at 23 ° C. and a cut elongation of 3% or more.   5. A multilayer film forming method comprising a step (5) of applying a top coating material to form a top coating film after the composite film forming method according to any one of claims 1 to 4.   A multilayer film obtained by the multilayer film formation method according to claim 7.