JP6668196B2 - Waterproof laminated structure and manufacturing method thereof - Google Patents

Description

  The present invention relates to a waterproof laminated structure and a method for manufacturing the same.

  In structures such as buildings and roads made of concrete or asphalt (hereinafter, these buildings and structures are referred to as "bases"), various functions such as waterproofing are imparted to the surface thereof. Is provided with a covering material. As a resin used for the coating material, a synthetic resin such as an epoxy resin, a urethane resin, and an acrylic resin is known.

  When applying a coating material containing these synthetic resins to concrete, apply a primer in advance to improve the adhesion to concrete and suppress the influence of the groundwork, and then apply a synthetic resin coating floor material on top. The stacking method is generally adopted.

  For example, Patent Literature 1 discloses a waterproofing construction method in which a primer layer, a waterproof layer made of a methacrylic resin, and an adhesive layer made of a methacrylic resin are formed on a concrete floor slab. It is also described that an aggregate is sprinkled on the upper surface of the adhesive layer before the curing of the adhesive layer is completed, an asphalt emulsion is sprinkled after waterproofing, and an asphalt mixture (asphalt pavement material) is further laid.

  Patent Literature 2 discloses that in a waterproofing method in which a post-cast material is cast on a synthetic resin waterproof material, two or more layers of the synthetic resin waterproof material are applied, and the last applied synthetic resin waterproof material is in a semi-cured state. A waterproofing method is disclosed in which an aggregate is sprayed to form a waterproof layer, a binder coating material is applied thereon to form a coating layer, and then a post-implant material is cast to form a post-implant material layer. .

JP 2011-157772 A JP 2002-348896 A

  In the waterproofing laminate including the base material to the asphalt mixture (paving material), cracks may occur in the base material, and the interval between the cracks may change due to a change in temperature.

  At this time, since the waterproof layer and the asphalt mixture laid on the waterproof layer do not have sufficient adhesive strength, a layer for bonding the waterproof layer and the asphalt mixture is required.

  As a layer for bonding the waterproof layer and the asphalt mixture, an aggregate is sprayed on the waterproof material when the waterproof layer is formed, or a thermoplastic resin and granular asphalt are sprayed.

  Even if a sprinkling material such as aggregate is sprayed when the waterproofing layer is formed, the sprinkling material sinks and the sprinkling material does not come out on the surface of the waterproofing layer, so that a sufficient spraying effect cannot be obtained. In some cases, the sprinkling material accumulates, the elongation of the waterproof layer is suppressed, and the substrate does not follow the change in the crack interval of the base. In addition, when the asphalt mixture was cast, the waterproof layer was damaged by the aggregate of the asphalt mixture.

  In addition, after coating a synthetic resin-based material as an adhesive layer on the waterproof layer, a sprinkling material such as an aggregate, a thermoplastic resin, and granular asphalt is sprinkled and integrally cured, and then, the sprinkling material is coated on the sprinkling material. In a method in which a pavement adhesive such as asphalt emulsion is applied and an asphalt mixture (pavement material) is cast thereon, the synthetic resin material used as the adhesive layer is too hard, and the waterproof layer changes in cracks. When the adhesive layer was stretched to follow, the adhesive layer could not sufficiently follow, and cracks and the like sometimes occurred between the waterproof layer and the adhesive layer. Furthermore, in order to suppress the breakage of the waterproof layer due to the aggregate of the asphalt mixture when the asphalt mixture is cast, increase the application thickness of the adhesive layer and increase the amount of the scattered material such as the aggregate. Such a response was necessary.

  For this reason, in the waterproof laminated body, in order to maintain waterproofness and functionality, the waterproof layer can follow the change in the interval between cracks in the base, prevent the waterproof layer from being damaged, and do not increase the manufacturing cost too much. Is required.

  However, the resin compositions and the waterproofing methods disclosed in Patent Literatures 1 and 2 may not be able to sufficiently follow the cracks of the base material at low temperatures, particularly when the temperature becomes lower than −10 ° C.

  Therefore, an object of the present invention is to provide a waterproof laminated structure excellent in the ability of a substrate to follow a crack even at a low temperature.

According to one aspect of the present invention, a waterproof laminated structure provided between a base and a pavement material,
The waterproof laminated structure includes a waterproof layer and an adhesive protective layer in order from the base side,
The waterproof layer is a coating film of a resin composition for a waterproof layer,
The resin composition for a waterproof layer has a cured product having a tensile elongation at break of 80% or more measured at −10 ° C. according to a measurement method defined in JIS K6251: 2010,
The adhesive protective layer is a coating film in which the coating amount of the resin composition for an adhesive protective layer is 0.2 to 0.5 kg / m ² (excluding aggregate), and is 0.5 to 2.0 kg / m ² . Including aggregate,
The cured resin has a tensile elongation at break of 10% or more measured at −10 ° C. according to a measurement method specified in JIS K6251: 2010 and a tensile strength measured at 23 ° C. A waterproof laminated structure having a breaking elongation of 100% or more is provided.

According to another aspect of the present invention, there is provided a method for manufacturing the above waterproof laminated structure,
A step of applying the resin composition for a waterproof layer on the surface of a substrate or a surface of a primer layer provided on the surface of the substrate, and curing to form a waterproof layer,
A method for producing a waterproof laminated structure, comprising a step of applying the resin composition for an adhesive protective layer on the surface of the waterproof layer, spraying an aggregate before curing, and then curing to form an adhesive protective layer. Is provided.

  According to another aspect of the present invention, there is provided a waterproof pavement laminate having a base, a pavement, and the above-described waterproof laminate structure between the base and the pavement.

  ADVANTAGE OF THE INVENTION According to this invention, the waterproof laminated structure excellent in the crack following of the base | substrate even at low temperature can be provided.

FIG. 4 is a schematic diagram for explaining a state of an aggregate of an adhesive protective layer in an example of a waterproof laminated structure according to an embodiment of the present invention.

The waterproof laminated structure according to the embodiment of the present invention is provided between a base and a pavement material. The waterproof laminated structure includes a waterproof layer and an adhesive protective layer in order from the base.
In addition, a waterproof pavement laminate according to another embodiment of the present invention has a base, a pavement material (for example, asphalt mixture), and the waterproof laminate structure between them.
Such a waterproof laminate structure and a waterproof pavement laminate are suitable for waterproof coating of structures such as concrete and asphalt.

  This waterproof pavement laminate can have a primer layer between the substrate and the waterproof layer. This waterproof pavement laminate can have a paving adhesive between the adhesive protective layer and the paving material.

  The substrate is preferably a structure formed of concrete or asphalt.

  The waterproof layer is a coating film of the resin composition for a waterproof layer. The cured product of the resin composition for a waterproof layer (resin used for the waterproof layer) has a tensile elongation at break of 80% or more measured at -10 ° C in accordance with the measurement method specified in JIS K6251: 2010. Is preferred. Further, the resin composition for a waterproof layer is preferably a radical polymerization type acrylic resin composition.

  The adhesive protective layer preferably includes a cured product of the resin composition for an adhesive protective layer and an aggregate, and is preferably a layer in which the aggregate and the cured product are integrated. This adhesive protective layer can be formed on the waterproof layer as follows. A resin composition for an adhesive protective layer is applied on the waterproof layer, and an aggregate is sprayed before curing, and then cured to form an adhesive protective layer containing the aggregate.

The adhesive protective layer is a coating film in which the coating amount of the resin composition for an adhesive protective layer is 0.2 to 0.5 kg / m ² (excluding aggregate), and is 0.5 to 2.0 kg / m ² in bone. Preferably, a material is included.
A cured product of the resin composition for an adhesive protective layer (resin used for the adhesive protective layer) has a tensile elongation at break of 10% at −10 ° C. according to a measurement method specified in JIS K6251: 2010. As described above, the tensile elongation at break measured at 23 ° C. is preferably 100% or more. The glass transition temperature of the cured product (the resin used for the adhesive protective layer) is preferably from -25 to 15C. Further, the resin composition for an adhesive protective layer is preferably a radical polymerization type acrylic resin composition.

  The aggregate preferably has a specific gravity of 2.2 to 3.5, and the aggregate having a particle size of 0.5 to 2.0 mm preferably accounts for 90% by mass or more of the aggregate.

  The aggregate preferably has a minimum particle size of 0.5 mm and a maximum particle size of 3.0 mm. The particle size and particle size distribution of the aggregate were measured by dry sieving according to JIS-Z8815 sieving test method.

The amount of aggregate contained in the adhesive protective layer is preferably 0.5~2.0kg / ^{m 2.} When the amount of the aggregate is less than 0.5 kg / m ² , the distribution becomes difficult over the entirety of the adhesive protective layer. Therefore, the amount of the aggregate distributed on the surface of the adhesive protective layer is reduced. However, the pavement adhesive and the adhesion protective layer are hardly adhered to each other, and the adhesion is low. On the other hand, when the amount of the aggregate exceeds ² kg / m ² , even if the resin composition for the adhesive protective layer is cured, a large amount of the aggregate that cannot be integrated with the adhesive protective layer remains and the surplus aggregate is present. The labor for collecting aggregates increases. FIG. 1 schematically shows the state of the aggregate of the adhesive protective layer in an example of the waterproof laminated structure according to the embodiment of the present invention. It is preferable that the aggregate is also distributed on the surface of the adhesive protective layer and distributed over the entire adhesive protective layer so as to be exposed.

  The resin composition for an adhesive protective layer preferably has a solution viscosity of 300 to 1,500 mPa · s measured at 23 ° C. with a Brookfield viscometer specified in JIS-Z8803. In addition, the resin composition for an adhesion protective layer preferably has a TI value (thixotropic index) of 1.5 or more determined by a measurement method specified in JIS-K6833.

  The resin composition for an adhesion protective layer comprises a monomer (A) having one (meth) acryloyl group, a monomer (B) having two or more (meth) acryloyl groups, and a monomer (A). It is preferable that the resin composition contains A) and a resin (C) soluble in the monomer (B).

  The resin composition for an adhesive protective layer is preferably a radical polymerization type acrylic syrup composition.

This radical polymerization type acrylic syrup composition,
A monomer (A) having one (meth) acryloyl group,
A monomer (B) having two or more (meth) acryloyl groups, and a resin (C) that is soluble in the monomers (A) and (B) and has a glass transition temperature of 110 ° C. or lower. It is preferable to include

  It is preferable that the total of the monomer (A), the monomer (B), and the resin (C) is 80% by mass or more based on 100% by mass of the radical polymerization type acrylic syrup composition.

  With respect to the total of the monomer (A), the monomer (B) and the resin (C), the monomer (A) is 60 to 80% by mass, the monomer (B) is 20% by mass or less, and the resin is (C) is preferably 5 to 30% by mass,

  Hereinafter, the laminate according to the embodiment of the present invention will be described in more detail.

  A laminate according to an embodiment of the present invention is a laminate having a waterproof layer and an adhesive protective layer and formed on the surface of a base. The waterproof layer is formed on the surface of the base, and the adhesive protective layer is formed on the surface of the waterproof layer. The waterproof layer may be formed on the surface of the substrate coated with the primer.

  The substrate to which the present invention is applied is preferably a structure formed of concrete or asphalt, and includes, for example, floor slabs (road slabs, bridge slabs, viaduct slabs, etc.), and building floors. Can be In addition, the base body may be a structure in which a pavement layer is formed on a floor slab, or a structure after an existing pavement layer or an existing waterproof layer is peeled off.

  The shape of the substrate is not particularly limited, and examples thereof include a flat surface, a curved surface, an inclined surface, and an upright surface.

  Examples of concrete include cement concrete, asphalt concrete, mortar concrete, resin concrete, permeable concrete, ALC (Autoclaved Lightweight aerated Concrete) plate, PC (prestressed concrete) plate and the like. These may be used alone or in combination of two or more. When the base is concrete, it may or may not include a reinforcing bar.

  The surface of the adhesive protective layer of the laminate according to the embodiment of the present invention can be paved or covered with a resin top coat.

(Adhesive protective layer)
The adhesive protective layer can be formed by applying the resin composition for an adhesive protective layer on the surface of the waterproof layer, spraying the aggregate before curing, and then curing the aggregate. Since the aggregate is sprayed on the applied adhesive protective layer resin composition while maintaining the liquid state, when the aggregate is cured, the sprayed aggregate is taken in and the aggregate is fixed ( (Aggregate scattering layer) is formed. At this time, the aggregate and the cured product can be chemically bonded by a coupling agent or the like. It is preferable that the state of the adhesive protective layer after curing is such that the aggregate is distributed throughout, and a part of the aggregate is exposed on the adhesive protective layer.

  As a method of applying the resin composition for the adhesive protective layer, a normal application method using a roller, a gold trowel, a brush, a universal bokeh, a coating machine (spray coating machine, two-component airless coating machine, etc.) or the like may be applied. Can be. In the case of using a two-component airless coating machine, it is preferable to divide the two components into a main component and a curing agent, to add a curing accelerator to the main component, and to add a peroxide such as benzoyl peroxide to the curing agent.

  After forming the adhesive protective layer, it is preferable to provide a pavement adhesive and then provide a pavement material.

  By providing the pavement adhesive on the adhesive protective layer, the adhesiveness can be improved as compared to the adhesive provided on the waterproof layer without the adhesive protective layer.

  The adhesive protective layer resin (cured product of the adhesive protective layer resin composition) has a tensile elongation at break of 10% or more measured at −10 ° C. according to a measurement method specified in JIS K6251: 2010, and There is no particular limitation as long as the tensile elongation at break measured at 23 ° C. is 100% or more. When the tensile elongation at break of the resin of the adhesive protective layer is equal to or more than the lower limit value, it is possible to maintain the crack followability of the laminate at a low temperature. The tensile elongation at break measured at −10 ° C. is more preferably 20% or more. The tensile elongation at break measured at 23 ° C. is preferably 120% or more.

  The resin composition for an adhesive protective layer has a viscosity of 300 to 1,500 mPa · s measured at 23 ° C. using a Brookfield viscometer specified in JIS-Z8803, and a measurement specified in JIS-K6833. The TI value obtained by the method is preferably 1.5 or more. When the viscosity is within the above range, workability on an inclined place such as a slope or a slope can be improved.

  When the solution viscosity and the TI value of the resin composition for the adhesive protective layer are below the above ranges, the dispersed aggregate or the like sinks into the adhesive protective layer (as a result, the aggregate cannot be distributed throughout) or is dispersed. Adhesion is reduced due to being sucked up by aggregates and the like due to capillary action.

  Further, when the viscosity of the resin composition for an adhesive protective layer exceeds the above range, the workability is reduced during coating, or the dispersed aggregate or the like does not sink into the resin (as a result, the aggregate is Adhesion is low).

  However, when the resin composition for an adhesive protective layer is applied to a standing surface such as a wall surface, if the viscosity is too low, the resin composition will hang after the application, and thus a thixotropic agent (eg, hydrophilic silica, hydrophobic Additives such as aerosil such as silica, montmorillonite, synthetic mica, inorganic layered compounds such as organic bentonite, fibrous minerals such as sepiolite, etc.), thixotropic agents, thickeners, and extender pigments such as calcium carbonate. You may make it sticky. In consideration of thickening, the total content of the additives such as the thixotropic agent, the thixotropic agent, the thickener, and the extender is 0.1% in 100% by mass of the resin composition for the adhesive protective layer. It is preferably 5 to 10% by mass. The viscosity of the resin composition at that time is preferably from 300 to 3,000 mPa · s, and more preferably from 300 to 2,000 mPa · s.

The coating amount of the resin composition for an adhesive protective layer is preferably 0.2 to 0.5 kg / m ² . When the application amount of the resin composition for an adhesive protective layer is less than 0.2 kg / m ^2, it becomes easy to be sucked up by a sprinkled aggregate or the like by a capillary phenomenon, and as a result, the aggregate gets on the adhesive protective layer. It is likely to be in a state (point bonding state). In such a state, when the pavement adhesive is applied to the upper layer of the scattered aggregate, the pavement adhesive and the aggregate are sufficiently bonded, but the aggregate and the adhesive protective layer are point-bonded and sufficiently bonded. Since the property cannot be obtained, it is easy to break at the portion of the aggregate and the adhesive protective layer.

Further, when the application amount of the resin composition for an adhesive protective layer exceeds 0.5 kg / m ² , it is necessary to disperse an excessive amount of aggregate in order to bring out the aggregate on the surface of the adhesive protective layer. Because the aggregates scatter and sink into the adhesive protective layer, making it difficult for the aggregates to come out to the surface, even if the paving adhesive is applied, the adhesive and the adhesive protective layer will not adhere well. , Adhesion is low.

  Specific examples of the resin constituting the adhesive protective layer (adhesive protective layer resin) include a solvent-based resin or an emulsion-based resin, or an epoxy resin, a polyurethane resin, an unsaturated polyester resin, an acrylic resin (methacrylic resin), or the like. A synthetic resin that can be cured is used, and a synthetic resin-based paint is used as the resin composition for the adhesive protective layer. As this resin, an acrylic resin is preferable.

  As the resin composition for the adhesive protective layer, a radical polymerizable resin composition is preferable because it can be cured in a short time at normal temperature and low temperature and has excellent coating workability. This resin composition is applied, and before the coating film is hardened, a sprinkling material containing aggregate is sprinkled, and then hardened to form an adhesive protective layer in which the hardened resin and the sprinkling material are integrated. preferable.

  As the radical polymerizable resin composition forming the adhesion protective layer, a resin composition containing a monomer (A), a monomer (B), and a resin (C) is preferable. This resin composition can further include a urethane acrylate oligomer (D).

<Monomer (A)>
The monomer (A) is a monomer having one (meth) acryloyl group. The monomer (A) is a component capable of adjusting the viscosity of the resin composition and adjusting the mechanical strength and the like of the adhesive protective layer formed from the resin composition.

  Examples of the monomer (A) include the following (a-1) to (a-11). Among these, (a-3) and (a-6) are selected in that the viscosity of the resin composition can be easily adjusted and the mechanical strength of the adhesive protective layer formed from the resin composition can be easily adjusted. Is preferred.

(A-1): A monomer having one (meth) acryloyl group and at least one carboxy group.
(A-2): A monomer having one (meth) acryloyl group and at least one hydroxyl group (excluding the above (a-1)).
(A-3): a monomer having a molecular weight of less than 130 and having one (meth) acryloyl group (excluding the above (a-1) and (a-2)).
(A-4): A monomer having a molecular weight of 130 to 300 and having one (meth) acryloyl group and a hetero ring (excluding the above (a-1) and (a-2)).
(A-5): Oligoethylene glycol monoalkyl ether (meth) acrylate having a molecular weight of 130 to 300 and having one (meth) acryloyl group (provided that (a-1), (a-2) except for).
(A-6): an alkyl (meth) acrylate having a molecular weight of 130 to 300, having a long-chain alkyl group of 4 to 15 carbon atoms, and having one (meth) acryloyl group (provided that the (a) -1) and (a-2)).
(A-7): a polyalkylene glycol mono (meth) acrylate having a molecular weight of 130 to 300 (excluding (a-1) and (a-2)).
(A-8): a fluorine atom-containing (meth) acrylate having a molecular weight of 130 to 300 (excluding (a-1) and (a-2)).
(A-9): a hydrocarbon ring-containing (meth) acrylate having a molecular weight of 130 to 300 (except for (a-1) and (a-2)).
(A-10): a silane coupling agent having a molecular weight of 130 to 300 and having one (meth) acryloyl group (excluding the above (a-1) and (a-2)).
(A-11): a monomer having a molecular weight of more than 300 and having one (meth) acryloyl group (excluding the above (a-1) and (a-2)).

  As the monomer (A), one type may be used alone, or two or more types may be used in combination.

  As the monomer (a-1) (monomer having one (meth) acryloyl group and at least one carboxy group), an acid anhydride and a hydroxyl group-containing (meth) acrylate are prepared by a known method. What is obtained by making it react is mentioned.

  Examples of the acid anhydride include aliphatic acid anhydrides such as succinic anhydride, maleic anhydride, tetrapropenyl succinic anhydride, and octenyl succinic acid; phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic acid And alicyclic acid anhydrides.

  Examples of the hydroxyl group-containing (meth) acrylate include a monoester of a polyhydric alcohol such as a dihydric alcohol and a trihydric alcohol and (meth) acrylic acid. Specific examples of the hydroxyl group-containing (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, and hydroxyoctyl (meth). ) Acrylate, glycerin (meth) acrylate and the like.

  Specific examples of the monomer (a-1) include 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate, and hexahydrofuran. 2- (meth) acryloyloxyethyl phthalate and the like can be mentioned.

  Examples of the monomer (a-2) (a monomer having one (meth) acryloyl group and at least one hydroxyl group) include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate And hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate and glycerin (meth) acrylate.

  Among these, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 4-hydroxybutyl (meth) acrylate are particularly preferred.

  Examples of the monomer (a-3) (a monomer having a molecular weight of less than 130 and having one (meth) acryloyl group) include methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic. Examples include acid, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, allyl (meth) acrylate, and the like.

  Among them, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, i-butyl acrylate, and t-butyl acrylate are particularly preferable.

  The lower limit of the molecular weight of the monomer (a-3) is not particularly limited, but is preferably 86 or more.

  Examples of the monomer (a-4) (a monomer having a molecular weight of 130 to 300 and having one (meth) acryloyl group and a hetero ring) include a furan ring, a hydrofuran ring, a pyran ring, and a hydropyran ring. A (meth) acrylate having a heterocycle selected from the group consisting of:

  Examples of the (meth) acrylate having a furan ring include furyl (meth) acrylate and furfuryl (meth) acrylate.

  Examples of the (meth) acrylate having a hydrofuran ring include tetrahydrofuryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and caprolactone-modified tetrahydrofurfuryl (meth) acrylate.

  Examples of the (meth) acrylate having a pyran ring include pyranyl (meth) acrylate.

  Examples of the (meth) acrylate having a hydropyran ring include dihydropyranyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, dimethyldihydropyranyl (meth) acrylate, and dimethyltetrahydropyranyl (meth) acrylate.

  Among these, tetrahydrofurfuryl methacrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate, dimethyldihydropyranyl methacrylate, and dimethyltetrahydropyranyl methacrylate are preferred.

  Examples of the monomer (a-5) (oligoethylene glycol monoalkyl ether (meth) acrylate having a molecular weight of 130 to 300 and having one (meth) acryloyl group) include ethylene glycol monomethyl ether methacrylate and ethylene glycol. Glycol monoethyl ether methacrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, 2-ethoxylated 2-ethylhexyl (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (Meth) acrylate and the like.

  As the monomer (a-6) (alkyl (meth) acrylate having a molecular weight of 130 to 300, having a long-chain alkyl group of 4 to 15 carbon atoms, and having one (meth) acryloyl group) Is n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate , Dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, and the like.

  Among these, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) ) Acrylates are particularly preferred.

  Examples of the monomer (a-7) (polyalkylene glycol mono (meth) acrylate having a molecular weight of 130 to 300) include polyethylene glycol mono (meth) acrylate (the number of repeating ethylene glycol is 4 or less) and polypropylene glycol mono ( Meth) acrylates (the number of repetitions of polypropylene glycol is 2 or less).

  Examples of the monomer (a-8) (fluorine atom-containing (meth) acrylate having a molecular weight of 130 to 300) include trifluoroethyl (meth) acrylate and tetrafluoroethyl (meth) acrylate.

  Examples of the monomer (a-9) (hydrocarbon ring-containing (meth) acrylate having a molecular weight of 130 to 300) include di- or trialkylcyclohexyl groups such as dimethylcyclohexyl (meth) acrylate and trimethylcyclohexyl (meth) acrylate. (Meth) acrylates; di- or trialkylphenyl group-containing (meth) acrylates such as dimethylphenyl (meth) acrylate and trimethylphenyl (meth) acrylate; benzyl methacrylate, isobornyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate; Phenoxyethyl methacrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, and the like.

  Examples of the monomer (a-10) (a silane coupling agent having a molecular weight of 130 to 300 and having one (meth) acryloyl group) include 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyl. Examples include trimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

  Examples of the monomer (a-11) (a monomer having a molecular weight of more than 300 and having one (meth) acryloyl group) include stearyl (meth) acrylate, cetyl methacrylate, and 2- (meth) acryloyloxyethyl -2-hydroxypropyl phthalate, octafluoropentyl methacrylate, heptadecafluorodecyl (meth) acrylate, polyethylene glycol mono (meth) acrylate (the number of repeating ethylene glycol is 5 or more), polypropylene glycol mono (meth) acrylate (of polypropylene glycol Such as hydroxyl-terminated polyalkylene glycol mono (meth) acrylate (such as having a repeating number of 3 or more); Like real sharp glycol monoalkyl ether (meth) acrylate.

  The upper limit of the molecular weight of the monomer (a-11) is not particularly limited, but is preferably 1,000 or less.

  The above-mentioned monomers (A) may be used alone or in combination of two or more.

  The content of the monomer (A) is preferably 60 to 80 parts by mass when the total of the components (A), (B) and (C) is 100 parts by mass. When the component (D) is contained, the content of the monomer (A) is set to 100 parts by mass in total of the components (A), (B), (C) and (D). In this case, the amount is preferably 55 to 85 parts by mass, more preferably 60 to 85 parts by mass. When the content of the monomer (A) is at least the lower limit, the surface curability of the resin composition and the strength of the cured coating film can be improved, and the coating workability can be improved. On the other hand, if the content of the monomer (A) is equal to or less than the upper limit, the cured coating film can be prevented from being hard and brittle.

In the monomer (A), the glass transition temperature (Tg _S ) of the cured product obtained from the Fox equation shown in the following equation (3) may satisfy the range of −25 ° C. to 15 ° C. preferable.
1 / (273 + Tg _S ) = Σ (W _Ax / (273 + Tg _Ax )) (3)

In the formula (3), “Tg _S ” is a glass transition temperature (° C.) of a cured product of a monomer mixture of a radical polymerization type acrylic resin composition. The monomer (A) is composed of x kinds (x ≧ 1) of monomers (A1), (A2)... (Ax), and “W _Ax ” is each unit in the monomer (A). It is the mass fraction of the monomer (however, these mass fractions are values when the total of the monomer (A) is converted into 100% by mass). “Tg _Ax ” is a glass transition temperature (° C.) of a homopolymer of each monomer in the monomer (A).

Tg _S of the cured product of the monomer (A) is equal to or -25 ° C. or higher, the mechanical strength is improved and the surface curability of the adhesive protective layer can be maintained. On the other hand, if Tg _S of the cured product of the monomer (A) is at 15 ℃ or less, it can maintain the flexibility of the adhesive protective layer.

  In order to further improve the crack followability, the monomer (A) preferably contains an alkyl (meth) acrylate and a silane coupling agent having one (meth) acryloyl group. As the alkyl (meth) acrylate, those exemplified for the monomer (a-3) and the monomer (a-6) can be used. According to these monomers, the mechanical strength can be easily adjusted. As the silane coupling agent having one (meth) acryloyl group, those exemplified for the monomer (a-10) can be used. According to these monomers, the adhesion to the scattered aggregate can be improved, and as a result, the crack followability can be improved.

  Examples of the acrylic resin satisfying the condition of the tensile elongation at break include cured products of the following resin compositions (i) to (iii).

(I) Resin containing polybutylene glycol di (meth) acrylate (b-1) as monomer (B), monomer (A) having one (meth) acryloyl group, and resin (C) Composition.
(Ii) Monomer (b-2) having two or more (meth) acryloyl groups other than polybutylene glycol di (meth) acrylate (b-1) as monomer (B), and (meth) acryloyl A resin composition comprising a monomer (A) having one group and a resin (C).
(Iii) A resin composition containing a monomer (A) having one (meth) acryloyl group, a urethane acrylate oligomer (D), a monomer (B), and a resin (C).

In this specification, “(meth) acryl” is a general term for acryl and methacryl. “(Meth) acrylate” is a general term for acrylate and methacrylate. “(Meth) acryloyl group” is a general term for an acryloyl group and a methacryloyl group, and the general formula CH ₂ ＣC (R) —C (＝ O) — [R represents a hydrogen atom or a methyl group. ].

<Monomer (B)>
The monomer (B) is a monomer having two or more (meth) acryloyl groups. The monomer (B) is a component that can impart toughness to the cured coating film, and can improve the mechanical strength of the cured product.

  Examples of the monomer (B) include the following (b-1) and (b-2).

<Polybutylene glycol di (meth) acrylate (b-1)>
Polybutylene glycol di (meth) acrylate (b-1) is a bifunctional monomer represented by the following general formula, and the repeating unit (C ₄ H ₈ O) _{n in} the following general formula has a mass average molecular weight of 1, 000 or more. The weight average molecular weight of the repeating unit (C ₄ H ₈ O) _n of polybutylene glycol di (meth) acrylate (b-1) is preferably 1,400 or more, and 3,000 or less. preferable.

(In the formula, each R independently represents a hydrogen atom or CH _3. N is an integer of 1 or more.)

  When the resin composition for an adhesive protective layer contains polybutylene glycol di (meth) acrylate (b-1), the tensile elongation at break and the maximum tensile strength in a wide range can be easily improved.

  When the mass average molecular weight of the repeating unit is not less than the lower limit, the tensile elongation at break and flexibility of the cured product of the resin composition can be sufficiently increased, particularly, the tensile elongation at break under low temperature and flexibility. The property can be sufficiently increased.

  When the mass average molecular weight of the repeating unit is equal to or less than the upper limit, the viscosity becomes appropriate and the coating workability can be improved. When the weight average molecular weight of the repeating unit is less than the upper limit, it becomes difficult to dissolve in water, and the water resistance of the waterproof layer can be improved.

  In the resin composition (i) for an adhesive protective layer, the content of the component (b-1) is 0 when the total of the components (A), (B), and (C) is 100 parts by mass. It is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 15 parts by mass. If the content of the component (b-1) is equal to or more than the lower limit, the tensile elongation at break at low temperature is higher. If the content is equal to or less than the upper limit, the tensile elongation at break is increased and the maximum tensile strength is also increased. Get higher.

<Monomer (b-2)>
The monomer (b-2) is a monomer having two or more (meth) acryloyl groups other than the polybutylene glycol di (meth) acrylate (A).

  The monomer (b-2) is a component that can impart toughness to the cured coating film, and can improve the mechanical strength of the cured product.

  Also in the case of the monomer (b-2), similarly to the polybutylene glycol di (meth) acrylate (A), the flexibility and tensile elongation at break of the cured product of the resin composition can be increased.

  As the monomer (b-2), ethylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol Di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, bisphenol A propylene oxide adduct di (meth) acrylate, bisphenol A diglycidyl ether (meth) Crylic acid adduct, neopentyl glycol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tricyclodecanedimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are listed. Among these, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, and bisphenol A propylene oxide adduct di (meth) acrylate are preferred.

  As the monomer (b-2), one type may be used alone, or two or more types may be used in combination.

  The monomer (b-2) may or may not be used together with the polybutylene glycol di (meth) acrylate (b-1) to such an extent that the elongation at break and the flexibility are not impaired.

  In the resin composition (ii) for the adhesion protective layer, the content of the monomer (b-2) is 20 when the total of the components (A), (B), and (C) is 100 mass. It is preferably at most 15 parts by mass, more preferably at most 15 parts by mass, further preferably at most 10 parts by mass, particularly preferably at most 7 parts by mass. When the content of the monomer (b-2) is equal to or less than the upper limit, the time required for curing is not too short, the coating workability is improved, and the flexibility of the cured product is not impaired. The lower limit of the content of the monomer (b-2) is not particularly limited, but is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of obtaining a sufficient effect of addition.

<Resin (C)>
The resin (C) is soluble in the components (A) and (B), and has a glass transition temperature (Tg _C ) of 110 ° C. or less. The glass transition temperature (Tg _C ) of the resin (C) is preferably 20 ° C. or higher. Resin (C) is a component that can improve the viscosity and curability of the resin composition for an adhesive protective layer.

The glass transition temperature (Tg _C ) of the resin (C) is determined by the following equation (4) based on the Fox equation.
1 / (273 + Tg _C ) = Σ (W _n / (273 + Tg _n )) (4)

In the formula (4), “Tg _C ” is a glass transition temperature (° C.) of the resin (C). The resin (C) is a polymer of n kinds (n ≧ 1) of the monomers (1), (2),... (N), and “W _n ” represents each monomer constituting the resin (C). the mass fraction of the body, "Tg _n" is the resin glass transition temperature of the homopolymer of each monomer constituting the (C) (℃).

Here, when the resin (C) is a copolymer composed of, for example, two or more types of monomers (1), (2),..., The glass transition temperature (Tg _C ) of the resin ( _C ) is expressed by the Fox equation. It is obtained from the equation shown in the following equation (4 ′) based on
1 / (273 + Tg _C ) = W ₁ / (273 + Tg ₁ ) + W ₂ / (273 + Tg ₂ ) + (4 ′)

In the formula (4 ′), “W1”, “W2”,... Are the mass fractions of the monomers (1), (2), respectively, and are “Tg ₁ ”, “Tg ₂ ”. ... are the glass transition temperatures (° C.) of the homopolymers of the monomers (1), (2)..., Respectively. These glass transition temperatures are defined as “Polymer Handbook 3rd Edition” (A WILEY-INTERSCIENCE). PUBLICATION, 1989).

Tg _C of the resin (C) is preferably from 20 to 110 ° C., more preferably from 20 to 90 ° C.. When the Tg _{C of the} resin (C) is at least 20 ° _C , the surface curability of the resin composition will be good. On the other hand, if Tg _C of the resin (C) is 110 ° C. or lower, the coating film can be prevented from being hard and brittle. In addition, when the resin composition is produced, the solubility in the monomer (A) and the monomer (B) is improved.

The type of the resin (C) is not particularly limited as long as it is soluble in the components (A) and (B) and the Tg _C is within the above range. For example, the following (c-1) and (c-2) ) And (c-3).

(C-1): A homopolymer or copolymer of an alkyl (meth) acrylate, a cellulose acetate butyrate resin, a diallyl phthalate resin, and a saturated polyester resin.
(C-2): A polymer having a unit having an alkyl group having 2 or more carbon atoms or a methyl methacrylate or alkyl (meth) acrylate unit and having a double bond.
(C-3): thermoplastic elastomers such as olefin-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, styrene-butadiene thermoplastic elastomers, and styrene-isoprene thermoplastic elastomers.

<Resin (c-1)>
Monomers constituting the homopolymer or copolymer of alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i- Butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl ( (Meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) Acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxy Ethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, and the like. .

  As the resin (c-1), a homopolymer or copolymer of an alkyl (meth) acrylate and a cellulose acetate butyrate resin are preferable.

  As the resin (c-1), one type may be used alone, or two or more types may be used in combination.

  The mass average molecular weight (hereinafter, referred to as “Mw”) of the resin (c-1) is preferably from 5,000 to 200,000, more preferably from 10,000 to 180,000, and from 30,000 to 160,000. Is particularly preferred. When Mw is equal to or more than the lower limit, the strength of the cured coating film of the resin composition can be improved. When Mw is equal to or less than the above upper limit, the solubility in the component (A) and the component (B) becomes good when the resin composition is produced.

  The Mw of the resin (c-1) is a value obtained by dissolving the resin in a solvent (tetrahydrofuran) and converting the molecular weight measured by gel permeation chromatography (GPC) into polystyrene.

  The content of the resin (c-1) is preferably 5 to 30 parts by mass, and more preferably 15 to 30 parts by mass, when the total of the components (A), (B) and (C) is 100 parts by mass. More preferred. When the content of the resin (c-1) is equal to or less than the upper limit, the pot life of the resin composition (the time when the composition has fluidity and the coating operation can be performed) can be sufficiently obtained, and the coating workability can be improved. Can be improved. On the other hand, when the content of the resin (c-1) is equal to or more than the lower limit, the viscosity of the resin composition can be balanced, the curability thereof can be improved, and the curing time can be appropriately shortened.

  The content of the resin (c-1) is within the above range (5 to 30 parts by mass) when the total of the components (A), (B) and (C) is 100 parts by mass, and It is more preferable that the ratio satisfies the following expression (5). If the following formula (5) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained well.

  200,000 <Mw of resin (c-1) × content of resin (c-1) <1,800,000 (5)

  In the formula (5), the “content of the resin (c-1)” refers to the content of the resin (c-1) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  When the resin (c-1) is a mixture of the resins (c-1-1), (c-1-2),..., The following formula (5 ′) is used.

  200,000 <{Mw of resin (c-1-1) × content of resin (c-1-1)} + {Mw of resin (c-1-2) × of resin (c-1-2) Content｝ + ... <1,800,000 (5 ')

<Resin (c-2)>
The resin (c-2) is a polymer having a unit having an alkyl group having 2 or more carbon atoms or a methyl methacrylate or alkyl (meth) acrylate unit and having a double bond.

  The double bond in the resin (c-2) is a double bond involved in a radical polymerization reaction, and examples of the functional group having such a double bond include a vinyl group, an allyl group, and a (meth) acryloyl group. Can be The resin (c-2) can contribute to the mechanical strength of a cured coating film of the resin composition.

  The resin (c-2) is preferably a copolymer of methyl methacrylate (cm1) and another acrylic monomer (cm2). Examples of other acrylic monomers (cm2) include other monofunctional acrylic monomers, polyfunctional acrylic monomers, (meth) acrylic acid, and the like.

  Specific monomers (cm2) include ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate; cycloalkyl (meth) acrylates such as isobornyl (meth) acrylate and cyclohexyl (meth) acrylate; alkyl (meth) having an alkyl group having two or more carbon atoms as described above Glycidyl (meth) acrylate or (meth) acrylic acid is mentioned as an acrylic unit not included in any of the acrylate unit and the cycloalkyl (meth) acrylate unit. One of these may be used alone, or two or more may be used in combination.

  As a monomer constituting the resin (c-2), methyl methacrylate (cm1), and as another acrylic monomer (cm2), an alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms, isobornyl (meth) It is preferable to use a monomer selected from acrylate, glycidyl (meth) acrylate, and (meth) acrylic acid. Methyl methacrylate (cm1), glycidyl (meth) acrylate, and other acrylic monomers (cm2) It is more preferable to use (meth) acrylic acid.

  As the alkyl methacrylate having an alkyl group having 2 to 4 carbon atoms, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, and sec-butyl methacrylate are preferable, and n-butyl methacrylate is particularly preferable.

  The method for producing the resin (c-2) is not particularly limited, but the following production method is preferred.

  That is, first, as a first-stage reaction, two or more kinds of methyl methacrylate (cm1) and another acrylic monomer (cm2) and a monomer having a first functional group involved in the esterification reaction Is copolymerized to obtain a first copolymer having the first functional group. Next, as a reaction of the second step, the first copolymer is esterified with the second monomer having a second functional group and a double bond that undergoes an esterification reaction with the first functional group. By reacting, a resin (c-2) having a double bond is obtained.

  As the combination of the first functional group and the second functional group, a carboxy group and a glycidyl group, a hydroxy group and an isocyanate group are preferable.

  A more specific method for producing the resin (c-2) includes the following method.

  First, in a first-stage reaction, (meth) acrylic acid and one or more of methyl methacrylate (cm1) and another acrylic monomer (cm2) are subjected to suspension polymerization to form a first copolymer having a carboxyl group. In the second stage reaction, the obtained first copolymer is added to methyl methacrylate (cm1), and glycidyl (meth) acrylate is esterified with the first copolymer in the solution by the esterification reaction. A method of obtaining the resin (c-2) by addition is preferred.

  The polymerization temperature during suspension polymerization in the first-stage reaction is preferably in the range of 70 to 98 ° C., and the polymerization time is preferably about 2 to 5 hours.

  The reaction temperature in the second stage reaction is preferably 90 to 95 ° C, and the reaction time is preferably about 1 to 4 hours.

  The preferred composition ratio of the monomers used in the first-stage reaction is as follows: 20 to 95% by mass of methyl methacrylate (cm1), 80 to 5% by mass of another acrylic monomer (cm2), and (meth) acrylic acid. Is preferably 0.3 to 4% by mass. Further, the content of (meth) acrylic acid is more preferably 0.3 to 2% by mass.

  In the second stage reaction, 100 parts by mass of the first stage copolymer was added to 70 to 150 parts by mass of the methyl methacrylate monomer (b-3), and the mixture was used in the first stage reaction (meth). It is preferable to react 0.9 to 1.2 moles of glycidyl (meth) acrylate with respect to 1 mole of acrylic acid, more preferably 1.0 to 1.1 moles.

  The suspension in which the suspension polymerization is carried out in the first stage reaction is preferably an aqueous suspension.

  It is preferable to add a dispersant to the aqueous suspension.

  The dispersant is not particularly limited. For example, poorly water-soluble inorganic compounds such as calcium phosphate, aluminum hydroxide, and starch powder silica; nonionic polymer compounds such as polyvinyl alcohol, polyethylene oxide, and cellulose derivatives; alkali poly (meth) acrylate Examples thereof include metal salts and anionic polymer compounds such as alkali metal salts of (meth) acrylic acid and methyl (meth) acrylate copolymer.

  The amount of the dispersant added is preferably in the range of 0.005 to 5% by mass, more preferably 0.01 to 1% by mass, based on the suspension.

  Further, it is preferable that the suspension at the time of the suspension polymerization contains an electrolyte such as sodium carbonate, sodium sulfate, and manganese sulfate. When an electrolyte is contained, the dispersion stability can be improved.

  The addition amount of the electrolyte may be set as appropriate, and is not particularly limited.

  In the suspension polymerization, a polymerization initiator is used.

  The polymerization initiator is not particularly limited. For example, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-tert) -Butylcyclohexyl) organic peroxides such as peroxydicarbonate; and azo compounds such as 2,2'-azobisisobutyronitrile and 2,2'-azobis-2-methylbutyronitrile. These may be used alone or in combination of two or more.

  The amount and method of addition of the polymerization initiator may be appropriately set and are not particularly limited.

  It is preferable to use a chain transfer agent in the suspension polymerization. When a chain transfer agent is used, the polymerization reaction of the monofunctional acrylic monomer can be easily controlled.

  A thiol compound is suitably used as a chain transfer agent.

  The thiol compound is not particularly limited. For example, alkyl mercaptans such as t-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan; aromatic mercaptans such as thiophenol thionaphthol: thioglycolic acid and octyl thioglycolate And alkyl glycolate.

  The amount and method of addition of the chain transfer agent may be appropriately set and are not particularly limited.

  In the second stage reaction, an esterification catalyst can be used to promote the reaction between the first functional group and the second functional group.

  Examples of the esterification catalyst include amines such as triethylamine; quaternary ammonium salts such as tetraethylammonium chloride and tetrabutylammonium bromide; and phosphorus compounds such as triphenylphosphine. These may be used alone or in combination of two or more.

  The amount of the esterification catalyst to be added may be appropriately set and is not particularly limited.

  In the second stage reaction, a polymerization inhibitor may be added. When the polymerization inhibitor is added, the second-stage reaction can be performed more stably.

  Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-t-butyl 4-methylphenol, and the like. These may be used alone or in combination of two or more.

  The addition amount of the polymerization inhibitor may be appropriately set and is not particularly limited.

  The weight average molecular weight of the first copolymer obtained in the first stage reaction is preferably in the range of 5,000 to 200,000, and more preferably in the range of 10,000 to 180,000. , 30,000 to 180,000.

  When the weight average molecular weight is at least the lower limit, the strength of the cured product tends to be sufficiently high. When the weight average molecular weight is equal to or less than the upper limit, workability when handling the resin composition is improved.

  The mass average molecular weight in the present specification is a value obtained by dissolving a resin in a solvent (tetrahydrofuran) and measuring the molecular weight by gel permeation chromatography (hereinafter, referred to as “GPC”) in terms of polystyrene.

  The resin (c-2) obtained in the second-stage reaction has a double bond, that is, the carboxyl group contained in the first copolymer is changed to the glycidyl group of glycidyl (meth) acrylate by the second-stage reaction. The reaction can be confirmed by the fact that the acid value of the resin (c-2) is smaller than the value estimated from the (meth) acrylic acid used in the first-stage reaction.

  The acid value (unit: mgKOH / g) is preferably 1 or less, more preferably 0.5 or less.

  The value of the acid value in this specification is a value obtained by dissolving a polymer in toluene and titrating with phenolphthalein as an indicator using a 0.1 N KOH ethanol solution.

  As for the compounding amount of the resin (c-2) in the resin composition, the number of parts by mass when the total of the components (A), (B), and (C) is 100 parts by mass is 5 to 30 parts by mass. More preferably, it is more preferably within the above range (5 to 30 parts by mass) and within the range satisfying the following formula (6). When the following formula (6) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be favorably maintained.

  200,000 <Mw of resin (c-2) × content of resin (c-2) <1,800,000 (6)

  In the formula (6), the “content of the resin (c-2)” refers to the content of the resin (c-2) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  When the resin (c-2) is a mixture of the resins (c-2-1), (c-2-2),..., The following formula (6 ′) is used.

  200,000 <{Mw of resin (c-2-1) × content of resin (c-2-1)} + {Mw of resin (c-2-2) × of resin (c-2-2) Content｝ + ... <1,800,000 (6 ′)

  Also, in the case of a mixture of the resin (c-1) and the resin (c-2)..., It is also preferably within the range satisfying the following formula (7). When the following formula (7) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <{Mw of resin (c-1) × content of resin (c-1)} + {Mw of resin (c-2) × content of resin (c-2)} +... < 1,800,000 ・ ・ ・ (7)

<Resin (c-3)>
The resin (c-3) is a thermoplastic elastomer such as an olefin thermoplastic elastomer, a polybutadiene thermoplastic elastomer, a styrene / butadiene thermoplastic elastomer, and a styrene / isoprene thermoplastic elastomer. The structure may be linear, branched, grafted, or core / shell.

  The mixing amount of the resin (c-3) in the resin composition is 3 to 30 parts by mass assuming that the total of the components (A), (B), and (C) is 100 parts by mass. More preferably, it is within the above range (3 to 30 parts by mass), and more preferably within the range satisfying the following formula (8). When the following formula (8) is satisfied, the viscosity of the resin composition does not become too high, and good coating workability can be maintained.

  200,000 <Mw of resin (c-3) × content of resin (c-3) <1,800,000 (8)

  In the formula (8), the “content of the resin (c-3)” refers to the content of the resin (c-3) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  Similarly, when the mixture is a mixture of the resin (c-1), the resin (c-2), and the resin (c-3), it is preferable that the mixture satisfy the following formula (8 '). When the following formula (8 ') is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <{Mw of resin (c-1) × content of resin (c-1)} + {Mw of resin (c-2) × content of resin (c-2)} + {resin (c −3) Mw × content of resin (c-3)｝ <1,800,000 (8 ′)

<Urethane acrylate oligomer (D)>
As the urethane acrylate oligomer (D), for example, a resin obtained mainly from a polyvalent isocyanate component (ua), a polyol component (ub) and a hydroxyl group-containing (meth) acrylate component (uc), etc. No.

  As the polyvalent isocyanate component (ua), a compound having two or more isocyanate groups in a molecule which is usually used can be used. Specific examples of such isocyanate compounds include aromatic isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and naphthalene diisocyanate (NDI); and isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI). Aliphatic isocyanates; and the like. In addition, a mixture of triisocyanate compounds such as a buret-modified product and a nurate-modified product of isophorone diisocyanate and hexamethylene diisocyanate; and a mixture of trivalent or higher polyvalent isocyanate compounds such as polymethylene polyphenyl polyisocyanate are also included. These may be used alone or in combination of two or more.

  Among them, tolylene diisocyanate (TDI) is particularly preferable from the viewpoint of intentional molecular design at the time of synthesizing urethane (meth) acrylate.

  As the polyol component (ub), a commonly used compound having a divalent or higher alcoholic hydroxyl group can be used. Specific examples thereof include polyether polyols such as polytetramethylene ether glycol; polyester polyols such as a reaction product of adipic acid and propylene glycol; polyacryl polyol; and the like. These may be used alone or in combination of two or more.

  As the polyol component (ub), a polyester polyol is particularly preferred from the viewpoint of exhibiting flexibility.

  The mass average molecular weight of the polyol component (ub) is preferably 400 or more from the viewpoint of exhibiting intended flexibility. In addition, it is preferably 10,000 or less from the viewpoint that the balance between flexibility and curability is easily obtained. Further, the mass average molecular weight is more preferably 1,000 or more, and more preferably 3,000 or less.

  In the related art, a chain extender may be generally blended as a part of the polyol forming the polyurethane. However, many chain extenders generally have a low molecular weight, and the difference in reactivity between the polyol and the chain extender may cause a bias in the molecular weight of the oligomer formed or may impair the properties of the polyol to be expressed. Therefore, in the present invention, it is not preferable to add a chain extender.

  Specific examples of the hydroxyl group-containing (meth) acrylate component (uc) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl ( (Meth) acrylates having a hydroxyalkyl group such as meth) acrylate; γ-butyrolactone ring-opened adduct or ε-caprolactone ring-opened adduct to 2-hydroxyethyl (meth) acrylate; ethylene to (meth) acrylic acid Ring-opening adduct of oxide or ring-opening adduct of propylene oxide, 2-hydroxyethyl (meth) acrylate or dimer or trimer of 2-hydroxypropyl (meth) acrylate having a hydroxyl group at the terminal (meth) Acrylates; polyethylene glycol mono ( (Meth) acrylate, polypropylene glycol mono (meth) acrylate; and the like. These may be used alone or in combination of two or more.

  The hydroxyl group-containing (meth) acrylate component (uc) is 2-hydroxyethyl (meth) acrylate or 4-hydroxybutyl (meth) acrylate from the viewpoint of compatibility with other components in the resin composition and various physical properties. Is preferred.

  The mass average molecular weight of the urethane acrylate oligomer (D) is preferably 1,000 or more, more preferably 5,000 or more, from the viewpoint of imparting good flexibility to an appropriate distance between crosslinking points. From the viewpoint of improving the coating workability, the weight average molecular weight is preferably 50,000 or less, more preferably 20,000 or less.

  When synthesizing the urethane acrylate oligomer (D), the usage ratio of the polyvalent isocyanate component (ua) / polyol component (ub) and the hydroxyl group-containing (meth) acrylate component (uc) [(ua)] / ((Ub) + (uc))] is preferably set to 1/1 in terms of a functional group molar ratio (NCO / OH). However, even if it fluctuates within the range of 1 / 0.95 to 0.95 / 1, there is no particular problem.

  The specific operation in the synthesis of the urethane acrylate oligomer (D) is not particularly limited. For example, an inert solvent is added to the polyvalent isocyanate component (ua), and a catalyst (such as di-n-butyltin dilaurate) is further added. There is a method in which a (meth) acrylate component (uc) and a polyol component (ub) are sequentially dropped. Further, a method may be used in which an inert solvent and a catalyst are added to the hydroxyl group-containing (meth) acrylate component (uc) and the polyol component (ub), and the polyvalent isocyanate component (ua) is gradually added. .

  As the inert solvent, for example, a (meth) acrylic acid alkyl ester having no hydroxyl group or the like can be used.

  In the resin composition (iii) for an adhesive protective layer, the content of the component (D) is defined assuming that the total of the components (A), (B), (C), and (D) is 100 parts by mass. The amount is preferably 0 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, still more preferably 1 to 15 parts by mass, and particularly preferably 2 to 15 parts by mass. If the content of the component (D) is at least the lower limit (0.1 parts by mass), the tensile elongation at break at low temperatures tends to be higher. And the maximum tensile strength tends to increase.

<Wax (E)>
The resin composition for an adhesive protective layer preferably contains a wax (E) in order to shut off air on the surface of the coating film during the curing reaction and improve the surface curability. As the wax (E), those that do not dissolve in the components (A) and (B) can be used.

  Examples of the wax (E) include various known waxes such as paraffin wax and microcrystalline wax.

  The melting point of the wax (E) is preferably 40 ° C. or higher, and the upper limit of the melting point of the wax is preferably 120 ° C. Two or more waxes having different melting points can be used in combination.

  As the wax (E), a wax dispersed in an organic solvent may be used from the viewpoint of improving the surface curability. Since the wax (E) is in a dispersed state in the organic solvent and is finely divided, the air blocking effect can be effectively exhibited. A commercially available wax can be used as the wax in the dispersed state, and the resin composition can be prepared by adding the wax as it is. In this case, the resin composition also contains an organic solvent.

  The wax (E) in a dispersed state may be one in which the wax is dispersed in the components (A) and (B) without containing any organic solvent.

  The content of the wax (E) is 100 parts by mass in total of the component (A), the component (B), the component (C), and the component (D) from the viewpoint of the balance between the air curability and the physical properties of the coating film. Is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass.

  When the content of the wax (E) is equal to or more than the lower limit, a sufficient air blocking effect can be obtained when the resin composition is applied and cured, and the surface curability can be improved. When the content of the wax (E) is equal to or less than the upper limit, the viscosity of the resin composition does not become too high, and the curing rate and the physical properties of the coating film tend to be good. To disperse the resin composition, and to improve the stain resistance when the resin composition is cured by coating.

<Curing accelerator (F)>
The resin composition for an adhesive protective layer preferably contains a curing accelerator (F).

  Examples of the curing accelerator (F) include tertiary amines, organometallic compounds, and metal soaps.

  Specific examples of the tertiary amine include N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, -(N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis ( N, N-substituted anilines such as 2-hydroxypropyl) -p-toluidine, triethanolamine, diethylenetriamine, phenylmorpholine, N, N-bis (hydroxyethyl) aniline and diethanolaniline, and N, N-substituted-p-toluidine , 4- (N, N-substituted amino) benzaldehyde and the like.

  Among tertiary amines, aromatic tertiary amines are preferred. As the aromatic tertiary amine, those in which at least one aromatic residue is directly bonded to a nitrogen atom are preferable.

  Examples of the aromatic tertiary amine include N, N-dimethyl-p-toluidine, N, N-diethylaniline, N, N-diethyl-p-toluidine, N- (2-hydroxyethyl) N-methyl-p-toluidine. Toluidine, N, N-di (2-hydroxyethyl) -p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine; N, N-di (2-hydroxyethyl) -p-toluidine or Examples thereof include ethylene oxide or propylene oxide adducts of N, N-di (2-hydroxypropyl) -p-toluidine. Further, instead of the p (para) body, an o (ortho) body or an m (meta) body may be used.

  Among the aromatic tertiary amines, N, N-dimethyl-p-toluidine, N, N-diethyl-p-toluidine, N, N-di (2- (Hydroxyethyl) -p-toluidine and N, N-di (2-hydroxypropyl) -p-toluidine are preferred.

  One of the above tertiary amines may be used alone, or two or more of them may be used in combination.

  A curing accelerator such as a tertiary amine may be added immediately before curing the resin composition, or may be added to the resin composition in advance.

  The addition amount of a curing accelerator such as a tertiary amine is determined in consideration of the balance between curability and pot life (workability), from the components (A), (B), (C) and (D). Is preferably 0.05 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and particularly preferably 0.3 to 5 parts by mass with respect to 100 parts by mass in total. When the amount of the tertiary amine is equal to or more than the lower limit, the surface curability can be improved.

  In addition, the preferable range of the addition amount of the tertiary amine varies depending on the type of the curing accelerator used and the temperature environment, and it is preferable to appropriately adjust the addition amount according to the use temperature.

  Examples of the organic metal compound include organic metal compounds such as cobalt naphthenate, manganese naphthenate, nickel octylate, cobalt octylate, and cobalt acetoacetylate. The surface curability can be improved by adding these organometallic compounds to the resin composition.

  The addition amount of the organometallic compound or the metal soap is determined by considering the balance between the curability and the pot life (workability) and the like, and is based on the sum of the components (A), (B), (C), and (D). The content of the metal derived from the organometallic compound is preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass or less based on 100 parts by mass.

  The preferred range of the amount of the organometallic compound varies depending on the type of the curing accelerator used and the temperature environment, and it is preferable to appropriately adjust the amount of the organometallic compound depending on the use temperature.

<Curing agent>
When the resin composition for an adhesion protective layer is cured, it is preferable that a redox catalyst is obtained by combining a curing agent with the curing accelerator.

  Examples of the curing agent include known curing agents that can initiate radical polymerization. Specific examples of such a curing agent include ketone peroxides such as methyl ethyl ketone peroxide; 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di ( Peroxy ketals such as t-hexylperoxy) cyclohexane and 1,1-di (t-butylperoxy) cyclohexane; 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p- Hydroperoxides such as menthane hydroperoxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide; di (4-t-butyl) Cyclohexyl) peroxydicarbonate And peroxydicarbonates such as di (2-ethylhexyl) peroxydicarbonate; and peroxydicarbonates such as t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate and t-butylperoxybenzoate. Oxyester and the like.

  Among the above curing agents, diacyl peroxide, peroxyester and hydroperoxide are preferable, and benzoyl peroxide is particularly preferable.

  The benzoyl peroxide is preferably in a liquid, paste or powder form diluted with an inert liquid or solid to a concentration of about 30 to 55% by mass from the viewpoint of handleability.

  One of the curing agents may be used alone, or two or more thereof may be used in combination.

  It is preferable that the addition amount of the curing agent is appropriately adjusted so that the pot life of the resin composition is 5 to 60 minutes. If the curing agent is added in this range, the polymerization reaction starts immediately after the addition, and the curing of the resin composition can be advanced.

  When benzoyl peroxide is used as a curing agent, the amount of addition is 0.25 to 5 parts by mass with respect to 100 parts by mass of the components (A), (B), (C) and (D) in total. Parts by mass, more preferably 0.25 to 4 parts by mass. If the amount of benzoyl peroxide is not less than the lower limit, the curability is good, and if it is not more than the upper limit, the coating workability of the resin composition and various physical properties of the obtained coating film tend to be improved. is there. It is preferable that the amount of the curing agent is appropriately adjusted according to the use temperature.

<Oligomers other than urethane acrylate oligomer (D)>
In order to improve the surface curability, an oligomer having a (meth) acryloyl group, other than urethane (meth) acrylate, may be added to the resin composition for an adhesion protective layer.

  Such oligomers include epoxy (meth) acrylate and polyester (meth) acrylate.

  Epoxy (meth) acrylate is obtained by reacting a polybasic acid anhydride, a partially esterified product of a hydroxyl group-containing (meth) acrylate, a bifunctional bisphenol A type epoxy resin, and an unsaturated monobasic acid by a known method. It is something that can be done. The bifunctional bisphenol A type epoxy resin is a general-purpose epoxy resin obtained by reacting bisphenol A with epichlorohydrin.

  The polyester (meth) acrylate is obtained by reacting a polybasic acid or its anhydride, a polyhydric alcohol compound, a (meth) acrylic acid adduct or glycidyl (meth) acrylate by a known method. Examples of the polybasic acid anhydride include phthalic acid, isophthalic acid, tetrahydrophthalic acid, succinic acid, maleic acid, fumaric acid, adipic acid and the like. Examples of the polyhydric alcohol include ethylene glycol and propylene glycol.

  The addition amount of the oligomer other than the urethane acrylate oligomer (D) is preferably 10 parts by mass or less based on 100 parts by mass of the total of the components (A), (B), (C), and (D). 5 parts by mass or less is more preferable. When the addition amount of the oligomer other than the urethane acrylate oligomer (D) is equal to or less than the upper limit, the coating workability and various physical properties of the obtained coating film tend to be improved without impairing the flexibility of the resin composition. is there.

<Other polymer components>
The resin composition for an adhesive protective layer includes a resin (C), a urethane acrylate oligomer (D), other oligomers and other polymer components other than the wax (E), such as a vinyl chloride-vinyl acetate copolymer and an epoxy resin. Etc. can be contained.

<Other additive components>
In the resin composition for an adhesive protective layer according to the embodiment of the present invention, if necessary, as other additive components, a polymerization inhibitor, a silane coupling agent, an ultraviolet absorber, a light resistance stabilizer, a thixotropic agent, reinforcement Materials, plasticizers, aggregates, inorganic pigments such as chromium oxide and red iron oxide, and organic pigments such as phthalocyanine blue can be used. In addition, the resin composition may contain an antifoaming agent, a defoaming agent, a leveling agent, and the like as additive components for the purpose of improving coating workability and appearance. As this aggregate, the same aggregate as the aggregate to be scattered described later can be used, and a part of the final amount of aggregate used may be added in advance.

  As the polymerization inhibitor, for the purpose of improving storage stability, it is preferable to add hydroquinone, 2-methylhydroquinone, hydroquinone monomethyl ether, 2-6-di-t-butyl 4-methylphenol and the like.

  The silane coupling agent is other than the monomer (a-10), for example, γ- (glycidoxypropyl) trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. Is mentioned. The silane coupling agent can be used for the purpose of improving the adhesion to inorganic substances.

  The content of the silane coupling agent other than the monomer (a-10) is 5 parts by mass with respect to 100 parts by mass in total of the components (A), (B), (C) and (D). Or less, more preferably 3 parts by mass or less from the viewpoint of curability and cost. When the content of the silane coupling agent is equal to or less than the upper limit, the surface curability is improved while the adhesiveness of the resin composition to the inorganic component is improved.

  The ultraviolet absorber is used for the purpose of improving the weather resistance of the coating film.

  Examples of ultraviolet absorbers include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-octyloxybenzophenone, 2-hydroxy-4-decyloxybenzophenone, 2-hydroxy-4,4'-dimethoxybenzophenone, and 2-hydroxy-4. Derivatives of 2-hydroxybenzophenone such as 4,4'-dibutoxybenzophenone or 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-ditert-butyl) (Phenyl) benzotriazole, a halide thereof, phenyl salicylate, p-tert-butylphenyl salicylate and the like. These may be used alone or in combination of two or more.

  Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2 -[3- (3,5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6, -tetramethylpiperidine and the like. These may be used alone or in combination of two or more.

  The thixotropic agent imparts thixotropic properties to the resin composition. Specifically, when a thixotropic agent is contained, structural viscosity is imparted to the resin composition, thixotropy is increased, additives in the resin composition can be uniformly distributed, and the storage stability of the resin composition Is improved. In addition, it is possible to improve coating workability when the resin composition is applied to, for example, an inclined surface.

  As the thixotropic agent, an organic thixotropic agent such as urethane urea, fatty acid amide, organic bentonite, and oxidized polyethylene wax, and fine particle silica are preferable.

  Examples of combinations of thixotropic agents include a combination of fatty acid amide and fine silica, a combination of organic bentonite and fine silica, a combination of fatty acid amide, organic bentonite and fine silica, and a combination of polyethylene oxide wax and fine silica.

  The average primary particle diameter of the fine silica is preferably 7 to 40 μm.

  The thixotropic agent may be added to the resin composition or may be used by being mixed with the aggregate. Two or more thixotropic agents may be used in combination.

  The content of the thixotropic agent is such that the urethane urea, fatty acid amide and / or organic bentonite are 0 in total with respect to 100 parts by mass of the components (A), (B), (C) and (D) in total. 0.2 to 5 parts by mass, and the fine silica is preferably 0.5 to 10 parts by mass.

  Thereby, the TI value (thixotropic index) obtained by the measurement method specified in JIS-K6833 can be set to 1.5 or more, and it is possible to prevent the resin composition from flowing out when applied to an inclined surface. .

  If the content of the thixotropic agent is too small, the effect of the addition becomes insufficient. On the other hand, if the content of the thixotropic agent is too large, the fluidity of the resin composition decreases, and the coating workability decreases, so that a uniform coating film may not be obtained. From these viewpoints, it is preferable to set the content within the above range.

  The reinforcing material is preferably used when the flexibility and tensile elongation at break of the resin composition are excessive with respect to the usage scene.

  Examples of the reinforcing material include chopped strand or roving net-like glass fiber, vinylon fiber, and nylon fiber.

  The plasticizer is for reducing shrinkage during curing.

  Examples of the plasticizer include phthalic acid esters such as dibutyl phthalate, di-2-ethylhexyl phthalate and diisodecyl phthalate, adipic esters such as di-2-ethylhexyl adipate and octyl adipate, dibutyl sebacate, and di-2-ethylhexyl seba. Dibasic fatty acid esters such as sebacic esters such as keto; azelaic esters such as di-2-ethylhexyl azelate and octyl azelate; and paraffins such as chlorinated paraffin. One type of plasticizer may be used alone, or two or more types may be used in combination.

  The content of the plasticizer is preferably 10 parts by mass or less based on 100 parts by mass of the total of the components (A), (B), (C) and (D). When the content of the plasticizer is 10 parts by mass or less, the mechanical strength of the coating film can be sufficiently ensured, and the plasticizer can be prevented from seeping out on the surface of the coating film.

<Aggregate>
Examples of the aggregate include calcium carbonate, silica fume, fly ash, talc, clay, titanium oxide, and aluminum hydroxide. Among them, calcium carbonate is preferably used.

The specific surface area of the aggregate is preferably 5,000 to 15,000 cm ² / g. The upper limit of the specific surface area is more preferably from 12,000cm ² / g, and particularly preferably 10,000 cm ² / g. The specific surface area referred to herein is a value measured by a Blaine transmission method.

  When the specific surface area of the aggregate is equal to or more than the lower limit, separation of the aggregate and the resin component is less likely to occur, the coating thickness is easily secured, and a coating film having good properties such as flexibility tends to be obtained. It is in. This is because the resin component is uniformly present between the aggregate particles, and the original physical properties of the resin component can be sufficiently exhibited. On the other hand, when the specific surface area of the aggregate is equal to or less than the upper limit, separation of the aggregate and the resin component is less likely to occur, and the tensile elongation at break of the cured product is further increased. This is because the resin component exists evenly between the aggregate particles without being excessively reduced, and the original physical properties of the resin component can be sufficiently exhibited.

  The content of the aggregate in the adhesive protective layer is 50 parts by mass or less and 45 parts by mass or less with respect to 100 parts by mass in total of the components (A), (B), (C), and (D). It is preferred that The aggregate content may be 0 parts by mass. When the content of the aggregate is 50 parts by mass or less, the tensile elongation at break at -10 ° C can be increased. In addition, it is easy to secure a sufficient coating film thickness, the coating workability at the time of coating is improved, and the flexibility at low temperatures tends not to be impaired.

<TI value>
The resin composition for an adhesion protective layer preferably has a thixotropic index (hereinafter, referred to as “TI value”) of 1.5 or more determined by a measurement method specified in JIS-K6833.

  The TI value can be determined by the following formula (9) from a viscosity measured using a Brookfield viscometer (BM type, manufactured by Tokimec) when the temperature of the composition is 23 ± 1 ° C.

  TI value = [viscosity at rotation speed of 6 rpm (mPa · s)] / [viscosity at rotation speed of 60 rpm (mPa · s)] (9)

  When the TI value is 1.5 or more, the coating workability is good, and when the base is inclined or the surface of the base has irregularities, it flows after the resin coating is applied. Can be prevented. Therefore, even if the substrate surface has a slope or an uneven shape, it can be coated so as to cover the surface uniformly, and a uniform coating thickness can be obtained.

  If the TI value is too low, the resin composition will flow even when coated, and it will be difficult to cover the surface evenly when the substrate is inclined or when the substrate surface has irregularities. It becomes difficult to form a coating film having an appropriate thickness. Therefore, the ability of the laminate to follow the opening and closing of cracks generated in the base tends to decrease.

<Formation of scattered aggregate layer>
To provide a scattered aggregate layer containing an aggregate as an adhesive protective layer, before the applied adhesive protective layer resin composition is cured, it is coated with an inorganic aggregate, an asphalt-coated aggregate, or a thermoplastic resin. It is preferable to spray a granular material such as a coated aggregate such as a coated aggregate.

  Aggregates include, for example, natural inorganic ores such as silica sand, river sand, cold water stone, emery, marble, alumina, slag, glass, ceramic aggregate, pottery, porcelain, tile, glass beads, inorganic aggregates such as colored aggregate, Organic aggregates and coated aggregates coated with such aggregates may be mentioned. One of these aggregates may be used alone, or two or more thereof may be used in combination. The aggregate particle size is preferably from 0.5 to 3 mm, more preferably from 0.5 to 2 mm.

  Examples of the aggregate coated with asphalt include those obtained by coating the above-mentioned aggregate mainly with, for example, straight asphalt or blown asphalt.

  The aggregate coated with a thermoplastic resin can be used as the aggregate coated with the thermoplastic resin. Examples of the thermoplastic resin for coating include thermoplastic elastomers such as olefin-based thermoplastic elastomers, polybutadiene-based thermoplastic elastomers, styrene-butadiene thermoplastic elastomers, styrene-isoprene thermoplastic elastomers, polyester-based resins, polyamide-based, and ethylene-based thermoplastic elastomers. Examples thereof include a vinyl acetate copolymer, an ethylene acrylic copolymer, and a petroleum resin, and a resin having a softening temperature of 60 to 120 ° C can be used.

(Waterproof layer)
A resin having a tensile elongation at break measured at a test temperature of −10 ° C. of preferably 80% or more, more preferably 100% or more, according to a measurement method specified in JIS K6251: 2010 (resin for a waterproof layer) Cured product of the composition) can be used. When the tensile elongation at break of the resin (cured product) satisfies the above range, the crack followability of the laminate, particularly the crack followability at a low temperature, can be further improved.

  Further, in order to further improve the crack followability, the resin used for the waterproof layer (the cured product of the waterproof layer resin composition) is measured at a test temperature of 23 ° C. in accordance with the measurement method specified in JIS K6251: 2010. The tensile elongation at break is preferably 200% or more, and more preferably 250% or more.

  The tensile elongation at break of the resin used for the waterproof layer is preferably larger than the tensile elongation at break of the resin of the adhesive protective layer, from the viewpoint of further improving crack followability at low temperatures.

  The resin composition for a waterproof layer preferably has a viscosity of 100 to 3,000 mPa · s measured at 23 ° C. with a Brookfield viscometer specified in JIS-Z8803. When the viscosity is within the above range, the coating workability is improved.

  If the viscosity of the resin composition for a waterproof layer is too low, when the resin composition for a waterproof layer is applied to an inclined surface such as a slope or a slope or a standing surface such as a wall surface, the resin composition drips after painting. I will.

  When coating a resin composition on an inclined base such as a slope or a slope or a standing surface such as a wall surface, a thixotropic agent (for example, aerosil such as hydrophilic silica and hydrophobic silica, montmorillonite, synthetic mica, organic mica) Additives such as inorganic layered compounds such as bentonite, fibrous minerals such as sepiolite, etc.), thixotropic agents, thickeners, and extender pigments such as extender pigments are added to increase the TI value to 1.5 or more. It is preferable to make it viscous.

  When the viscosity of the resin composition for a waterproof layer is too high, the coating workability is deteriorated.

  Examples of the curable resin composition that forms a cured resin that satisfies the above-described tensile elongation at break include an acrylic resin composition, an unsaturated polyester resin composition, and a vinyl ester resin composition. Among these, an acrylic resin composition is preferred because of its high curing rate and excellent curability at low temperatures.

  As the acrylic resin composition that forms a cured resin that satisfies the tensile elongation at break, the acrylic resin composition includes the monomer (A), the monomer (B), and the resin A resin composition containing (C) is preferred. This resin composition can further contain the urethane acrylate oligomer (D). Examples of such a resin composition include the following resin compositions (i) to (iii).

(I) Resin containing monomer (A) having one (meth) acryloyl group, polybutylene glycol di (meth) acrylate (b-1) as monomer (B), and resin (C) Composition.
(Ii) A monomer (A) having one (meth) acryloyl group and two (meth) acryloyl groups other than polybutylene glycol di (meth) acrylate (b-1) as monomer (B) A resin composition comprising a monomer (b-2) having at least one resin and a resin (C).
(Iii) A resin composition containing a monomer (A) having one (meth) acryloyl group, a urethane acrylate oligomer (D), a monomer (B), and a resin (C).

  Examples of the monomer (A) include (a-1) to (a-11) described above. Among these, (a-3) and (a-6) are selected in that the viscosity of the resin composition can be easily adjusted and the mechanical strength of the cured coating film formed from the resin composition can be easily adjusted. Is preferred.

  As the monomer (A), one type may be used alone, or two or more types may be used in combination.

  The content of the monomer (A) may be 55 to 85 parts by mass when the total of the components (A), (B), (C), and (D) is 100 parts by mass. More preferably, it is 60 to 85 parts by mass. When the content of the monomer (A) is at least the lower limit, the surface curability of the resin composition and the strength of the cured coating film can be improved, and the coating workability can be improved. On the other hand, if the content of the monomer (A) is equal to or less than the upper limit, the cured coating film can be prevented from being hard and brittle.

In the monomer (A), the glass transition temperature (Tg _S ) of the cured product obtained from the Fox equation shown in the above equation (3) may satisfy the range of −25 ° C. to 15 ° C. preferable.

Tg _S of the cured product of the monomer (A) is equal to or -25 ° C. or higher, the mechanical strength can be maintained while improving the surface curing property of the coating film. On the other hand, if the Tg _S of the cured product of the monomer (A) is 15 ° C. or lower, the flexibility of the cured coating film can be maintained.

  In the resin composition (i) for a waterproof layer, the content of the component (b-1) is 0 when the total of the components (A), (B), and (C) is 100 parts by mass. It is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 2 to 15 parts by mass. If the content of the component (b-1) is equal to or more than the lower limit, the tensile elongation at break at low temperature is higher. If the content is equal to or less than the upper limit, the tensile elongation at break is increased and the maximum tensile strength is also increased. Get higher.

  The monomer (b-2) may or may not be used together with the monomer (b-1) to such an extent that the elongation at break and the flexibility are not impaired.

  In the resin composition (ii) for the waterproof layer, the content of the monomer (b-2) is 20 when the total of the component (A), the component (B), and the component (C) is 100 mass. It is preferably at most 15 parts by mass, more preferably at most 15 parts by mass, further preferably at most 10 parts by mass, particularly preferably at most 7 parts by mass. When the content of the monomer (b-2) is equal to or less than the upper limit, the time required for curing is not too short, the coating workability is improved, and the flexibility of the cured product is not impaired. The lower limit of the content of the monomer (b-2) is not particularly limited, but is preferably 0.1 parts by mass or more, and more preferably 1 part by mass or more, from the viewpoint of obtaining a sufficient effect of addition. .

Tg _C of the resin (C) is preferably from 20 to 110 ° C., more preferably from 20 to 90 ° C.. When the Tg _{C of the} resin (C) is at least 20 ° _C , the surface curability of the resin composition will be good. On the other hand, if Tg _C of the resin (C) is 110 ° C. or lower, the coating film can be prevented from being hard and brittle. In addition, when the resin composition is produced, the solubility in the monomer (A) and the monomer (B) is improved. The Tg _C of the resin (C) is determined from the equation (4) based on the Fox equation.

The type of the resin (C) is not particularly limited as long as it is soluble in the components (A) and (B) and the Tg _C is within the above range. For example, the resins (c-1) and (c-2) ) And (c-3).

  As the resin (c-1), a homopolymer or copolymer of an alkyl (meth) acrylate and a cellulose acetate butyrate resin are preferable.

  As the resin (c-1), one type may be used alone, or two or more types may be used in combination.

  The mass average molecular weight (hereinafter, referred to as “Mw”) of the resin (c-1) is preferably from 5,000 to 200,000, more preferably from 10,000 to 180,000, and from 30,000 to 160,000. Is particularly preferred. When Mw is equal to or more than the lower limit, the strength of the cured coating film of the resin composition can be improved. When Mw is equal to or less than the above upper limit, the solubility in the component (A) and the component (B) becomes good when the resin composition is produced.

  The content of the resin (c-1) is preferably 3 to 30 parts by mass when the total of the components (A), (B), and (C) is 100 parts by mass. When the content of the resin (c-1) is equal to or less than the upper limit, the pot life of the resin composition (the time when the composition has fluidity and the coating operation can be performed) can be sufficiently obtained, and the coating workability can be improved. Can be improved. On the other hand, when the content of the resin (c-1) is equal to or more than the lower limit, the viscosity of the resin composition can be balanced, the curability thereof can be improved, and the curing time can be appropriately shortened.

  The content of the resin (c-1) is within the above range (3 to 30 parts by mass) when the total of the components (A), (B), and (C) is 100 parts by mass. It is more preferable that the ratio be within the range satisfying the following expression (11). When the following formula (11) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <Mw of resin (c-1) × content of resin (c-1) <1,600,000 (11)

  In the formula (11), the “content of the resin (c-1)” refers to the content of the resin (c-1) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  When the resin (c-1) is a mixture of the resins (c-1-1), (c-1-2),..., The following formula (11 ') is used.

  200,000 <{Mw of resin (c-1-1) × content of resin (c-1-1)} + {Mw of resin (c-1-2) × of resin (c-1-2) Content｝ + ... <1,600,000 (11 ')

  The content of the resin (c-2) in the resin composition is such that the total number of the components (A), (B), and (C) is 3 to 30 parts by mass when the total of the components is 100 parts by mass. More preferably, it is within the above range (3 to 30 parts by mass) and within the range satisfying the following formula (12). When the following formula (12) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <Mw of resin (c-2) × content of resin (c-2) <1,600,000 (12)

  In the formula (12), the “content of the resin (c-2)” refers to the content of the resin (c-2) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  When the resin (c-2) is a mixture of the resins (c-2-1), (c-2-2), and so on, the following formula (12 ') is used.

  200,000 <{Mw of resin (c-2-1) × content of resin (c-2-1)} + {Mw of resin (c-2-2) × of resin (c-2-2) Content｝ + ... <1,600,000 (12 ')

  Also, in the case of a mixture of the resin (c-1) and the resin (c-2)..., It is also preferably within the range satisfying the following formula (13). When the following formula (13) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained well.

  200,000 <{Mw of resin (c-1) × content of resin (c-1)} + {Mw of resin (c-2) × content of resin (c-2)} +... < 1,600,000 ・ ・ ・ (13)

  The mixing amount of the resin (c-3) in the resin composition is 3 to 30 parts by mass assuming that the total of the components (A), (B), and (C) is 100 parts by mass. It is more preferable that it is within the above range (3 to 30 parts by mass) and within the range satisfying the following formula (14). When the following formula (14) is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <Mw of resin (c-3) × content of resin (c-3) <1,600,000 (14)

  In the formula (14), the “content of the resin (c-3)” refers to the content of the resin (c-3) when the total of the components (A), (B), and (C) is 100 parts by mass. Content (parts by mass).

  Similarly, the mixture of the resin (c-1), the resin (c-2) and the resin (c-3) preferably falls within the range satisfying the following formula (14 '). When the following formula (14 ') is satisfied, the viscosity of the resin composition does not become too high, and the coating workability can be maintained satisfactorily.

  200,000 <{Mw of resin (c-1) × content of resin (c-1)} + {Mw of resin (c-2) × content of resin (c-2)} + {resin (c -3) Mw × content of resin (c-3)｝ <1,600,000 (14 ′)

  As the component (D), the urethane acrylate oligomer (D) mentioned in the description of the adhesion protective layer can be used. The mass average molecular weight of the urethane acrylate oligomer (D) is preferably 1,000 or more, more preferably 5,000 or more, from the viewpoint of imparting good flexibility to an appropriate distance between crosslinking points. From the viewpoint of improving the coating workability, the weight average molecular weight is preferably 50,000 or less, more preferably 20,000 or less.

  In the resin composition (iii) for the waterproof layer, the content of the component (D) is defined assuming that the total of the components (A), (B), (C), and (D) is 100 parts by mass. The amount is preferably 0 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, still more preferably 1 to 15 parts by mass, and particularly preferably 2 to 15 parts by mass. If the content of the component (D) is at least the lower limit (0.1 parts by mass), the tensile elongation at break at low temperatures tends to be higher. And the maximum tensile strength tends to increase.

  The resin composition for the waterproof layer preferably contains a wax (E) in order to block the air on the surface of the coating film during the curing reaction and improve the surface curability. As the wax (E), those that do not dissolve in the components (A) and (B) can be used. As the wax (E), the wax (E) mentioned in the description of the adhesive protective layer can be used.

  The content of the wax (E) is 100 parts by mass in total of the component (A), the component (B), the component (C), and the component (D) from the viewpoint of the balance between the air curability and the physical properties of the coating film. Is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 2 parts by mass.

  When the content of the wax (E) is equal to or more than the lower limit, a sufficient air blocking effect can be obtained when the resin composition is applied and cured, and the surface curability can be improved. When the content of the wax (E) is equal to or less than the upper limit, the viscosity of the resin composition does not become too high, and the curing rate and the physical properties of the coating film tend to be good. To disperse the resin composition, and to improve the stain resistance when the resin composition is cured by coating.

  The resin composition for the waterproof layer preferably contains a curing accelerator (F), and the curing accelerator (F) described in the description of the adhesive protective layer can be used.

  Examples of the curing accelerator (F) include a tertiary amine, an organometallic compound, and a metal soap as described above. Among the tertiary amines, aromatic tertiary amines are preferable, and one kind may be used alone or two or more kinds may be used in combination.

  A curing accelerator such as a tertiary amine may be added immediately before curing the resin composition, or may be added to the resin composition in advance.

  The addition amount of a curing accelerator such as a tertiary amine is determined based on the balance between the curability and the pot life (workability), etc., from the components (A), (B), (C), and (D). Is preferably 0.05 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, and particularly preferably 0.3 to 5 parts by mass with respect to 100 parts by mass in total. When the amount of the tertiary amine is equal to or more than the lower limit, the surface curability can be improved.

  In addition, the preferable range of the addition amount of the tertiary amine varies depending on the type of the curing accelerator used and the temperature environment, and it is preferable to appropriately adjust the addition amount according to the use temperature.

  The addition amount of the metal soap or the organometallic compound is determined by considering the balance between the curability and the pot life (workability) and the like, and is based on the sum of the components (A), (B), (C), and (D). The content of the metal derived from the metal soap or the organometallic compound is preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass or less based on 100 parts by mass.

  In addition, the preferable range of the addition amount of the metal soap and the organometallic compound varies depending on the type of the curing accelerator used and the temperature environment, and it is preferable to appropriately adjust the addition amount according to the use temperature.

  When curing the resin composition for a waterproof layer, it is preferable to combine the curing accelerator with a curing agent to form a redox catalyst. As the curing agent, the curing agents described in the description of the adhesive protective layer can be used.

  Among the above curing agents, diacyl peroxide, peroxyester and hydroperoxide are preferred, and benzoyl peroxide is particularly preferred.

  The benzoyl peroxide is preferably in a liquid, paste or powder form diluted with an inert liquid or solid to a concentration of about 30 to 55% by mass from the viewpoint of handleability.

One of the curing agents may be used alone, or two or more thereof may be used in combination.

  It is preferable that the addition amount of the curing agent is appropriately adjusted so that the pot life of the resin composition is 5 to 60 minutes. If the curing agent is added in this range, the polymerization reaction starts immediately after the addition, and the curing of the resin composition can be advanced.

  When benzoyl peroxide is used as a curing agent, the amount of addition is 0.25 to 5 parts by mass with respect to 100 parts by mass of the components (A), (B), (C) and (D) in total. Parts by mass, more preferably 0.25 to 4 parts by mass. If the amount of benzoyl peroxide is not less than the lower limit, the curability is good, and if it is not more than the upper limit, the coating workability of the resin composition and various physical properties of the obtained coating film tend to be improved. is there. It is preferable that the amount of the curing agent is appropriately adjusted according to the use temperature.

  An oligomer having a (meth) acryloyl group and an oligomer other than urethane (meth) acrylate may be added to the resin composition for the waterproof layer in order to improve surface curability.

  Examples of such an oligomer include epoxy (meth) acrylate and polyester (meth) acrylate, which have already been described in the description of the adhesive protective layer.

  The addition amount of the oligomer other than the urethane acrylate oligomer (D) is preferably 10 parts by mass or less based on 100 parts by mass of the total of the components (A), (B), (C), and (D). 5 parts by mass or less is more preferable. When the addition amount of the oligomer other than the urethane acrylate oligomer (D) is equal to or less than the upper limit, the coating workability and various physical properties of the obtained coating film tend to be improved without impairing the flexibility of the resin composition. is there.

  The resin composition for the waterproof layer includes, as resin (C), urethane acrylate oligomer (D), other oligomers and other polymer components other than wax (E), vinyl chloride / vinyl acetate copolymer, epoxy resin, etc. Can also be contained.

  In the resin composition for the waterproof layer, if necessary, as other additive components, a polymerization inhibitor, a silane coupling agent, an ultraviolet absorber, a light stabilizer, a thixotropic agent, a reinforcing material, a plasticizer, a bone Materials, inorganic pigments such as chromium oxide and red iron, and organic pigments such as phthalocyanine blue can be used. In addition, the resin composition may further contain an antifoaming agent, a defoaming agent, a leveling agent, and the like as other additive components for the purpose of improving coating workability and appearance. Those described in the description of the additive component of the resin composition for the adhesive protective layer can be used.

  The silane coupling agent is other than the monomer (a-10), for example, γ- (glycidoxypropyl) trimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. Is mentioned. The silane coupling agent can be used for the purpose of improving the adhesion to inorganic substances.

  The content of the silane coupling agent other than the monomer (a-10) is 5 parts by mass with respect to 100 parts by mass in total of the components (A), (B), (C) and (D). Or less, more preferably 3 parts by mass or less from the viewpoint of curability and cost. When the content of the silane coupling agent is equal to or less than the upper limit, the surface curability is improved while the adhesiveness of the resin composition to the inorganic component is improved.

  The content of the thixotropic agent is such that the urethane urea, fatty acid amide and / or organic bentonite are in total with respect to 100 parts by mass in total of the component (A), the component (B), the component (C) and the component (D). It is preferable that 0.5 to 5 parts by mass and 1 to 10 parts by mass of the fine silica be used.

  Thereby, the TI value (thixotropic index) obtained by the measurement method specified in JIS-K6833 can be set to 1.5 or more, and it is possible to prevent the resin composition from flowing out when applied to an inclined surface. .

  If the content of the thixotropic agent is too small, the effect of the addition becomes insufficient. On the other hand, if the content of the thixotropic agent is too large, the fluidity of the resin composition decreases, and the coating workability decreases, so that a uniform coating film may not be obtained. From these viewpoints, it is preferable to set the content within the above range.

  The content of the plasticizer is preferably 10 parts by mass or less based on 100 parts by mass of the total of the components (A), (B), (C) and (D). When the content of the plasticizer is 10 parts by mass or less, the mechanical strength of the coating film can be sufficiently ensured, and the plasticizer can be prevented from seeping out on the surface of the coating film.

  The content of the aggregate in the waterproof layer is not more than 50 parts by mass and not more than 45 parts by mass with respect to 100 parts by mass of the components (A), (B), (C) and (D) in total. Preferably, there is. The aggregate content may be 0 parts by mass. When the content of the aggregate is 50 parts by mass or less, the tensile elongation at break at -10 ° C can be increased. In addition, it is easy to secure a sufficient coating film thickness, the coating workability at the time of coating is improved, and the flexibility at low temperatures tends not to be impaired.

  The waterproof layer can be formed by applying the resin composition for a waterproof layer on the surface of the substrate or the surface of the primer layer on the substrate.

  As a method of applying the resin composition for forming the waterproof layer, a normal application method using a roller, a gold trowel, a brush, a universal broom, a coating machine (a spray coating machine, a two-liquid airless coating machine, etc.) or the like is applied. be able to. In the case of using a two-component airless coating machine, it is preferable to divide the two components into a main component and a curing agent, to add a curing accelerator to the main component, and to add a peroxide such as benzoyl peroxide to the curing agent.

  On the surface of the waterproof layer, it is preferable to provide an adhesive protective layer and an aggregate dispersed on the adhesive protective layer, further provide a paving adhesive layer for bonding the paving material and the adhesive protective layer, and thereafter provide the paving material.

<Pavement adhesive>
The pavement adhesive can be provided for the purpose of strengthening the adhesion between the adhesive protective layer, which has been integrally cured by spraying the aggregate, and the pavement material.

  The form of the adhesive forming the pavement adhesive is not particularly limited, and may be, for example, any of liquid, powder, granule, and sheet / film. The material for the pavement adhesive is not particularly limited as long as it improves the adhesion between the adhesive protective layer and the dispersed aggregate in the embodiment of the present invention and the pavement material. Specific examples of the pavement adhesive include solid materials such as resin, rubber and asphalt, and liquid materials such as petroleum asphalt and asphalt emulsion. When the paving adhesive is in a liquid state, the liquid material may be applied on the cured coating film of the syrup composition by brush, roller, spray or the like. When the pavement adhesive is solid, it may be heated and melted and liquefied before coating.

<Paving material (paving layer)>
The paving material (paving layer) is provided on the adhesive protective layer, or on the paving adhesive layer on the adhesive protective layer. Examples of the material of the pavement layer include asphalt mixture (asphalt-containing pavement such as asphalt-based pavement obtained by mixing asphalt with an aggregate, drainage pavement including modified asphalt, etc.), concrete-based pavement, resin Paving materials and the like.

<Effects>
As described above, since the laminate according to the embodiment of the present invention has the waterproof layer and the adhesive protective layer, the laminate has a high ability to follow the cracks of the base, and particularly, the base has a low temperature of about −20 ° C. High ability to follow cracks. Specifically, Table 2.5.1 Performance check of 2.5 floor slabs of “Hokkaido Development Bureau Road Design Guidelines Vol. 3 Bridges” (issued in April 2013) issued by the Hokkaido Development Bureau of the Ministry of Land, Infrastructure, Transport and Tourism When the “crack following test I” described in the method is performed at a test temperature of −20 ° C., breakage can be prevented.

  Further, the waterproof layer and the adhesive protective layer can be formed to have excellent coating workability at the time of their formation, have a moderately high curing speed, and have both flexibility and strength. In addition, a waterproof layer having high adhesion to the primer can be formed, and an adhesive protective layer having high adhesion to the waterproof layer can be formed.

  Hereinafter, the present invention will be described specifically with reference to examples.

  Note that the present invention is not limited to these examples.

  In the following examples, all “parts” indicate “parts by mass”, and all “%” other than the degree of saponification and humidity indicate “% by mass”.

[Synthesis Example 1: Synthesis of polymer (P-1)]
In a polymerization apparatus equipped with a stirrer, a cooling pipe, and a thermometer, 135 parts of deionized water and 0.4 part of polyvinyl alcohol (80 mol% of saponification degree, 1,700 degree of polymerization) as a dispersant were added and stirred. After completely dissolving the polyvinyl alcohol, the stirring was temporarily stopped. 60 parts of n-butyl methacrylate (hereinafter abbreviated as “n-BMA”), 40 parts of methyl methacrylate (hereinafter abbreviated as “MMA”), and 2,2′-azobis-2-methylbutyro as a polymerization initiator 0.2 parts of nitrile (hereinafter abbreviated as "AMBN"), 0.5 parts of n-dodecylmercaptan (hereinafter abbreviated as "n-DM") as a chain transfer agent, and 0.1 part of sodium carbonate as an electrolyte. The mixture was stirred again, heated to 75 ° C., and reacted for 2.5 hours. After the temperature was further raised to 98 ° C. and maintained for 1.5 hours, the reaction was terminated.

  After cooling to 40 ° C., the resulting aqueous suspension was filtered through a 45 μm mesh nylon filter cloth, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours. A granular vinyl polymer (polymer P-1) was obtained.

  The glass transition temperature (Tg) of the obtained granular vinyl polymer was 49 ° C., and the mass average molecular weight was 60,000.

  The Tg of the granular vinyl polymer was calculated from the Tg of the homopolymer described in the Polymer Handbook using the Fox equation.

[Synthesis Example 2: Synthesis of polymer (P-2)]
In the reaction of Synthesis Example 1, the amount of MMA was changed from 40 parts to 80 parts, the amount of n-BMA was changed from 60 parts to 20 parts, and the amount of n-DM was changed from 0.5 part to 0 part. Changed to .35 copies. Other than that, it was synthesized in the same manner as the polymer (P-1) of Synthesis Example 1 to obtain a granular vinyl polymer (polymer P-2) having a Tg of 82 ° C and a weight average molecular weight of 80,000.

[Synthesis Example 3: Preparation of composition (S-1) containing polymer (C)]
First, the first stage reaction was performed.

  That is, 135 parts of deionized water and 0.4 part of polyvinyl alcohol (degree of saponification 80%, degree of polymerization 1,700) were added to a polymerization apparatus equipped with a stirrer, a cooling pipe, and a thermometer, and stirred. After completely dissolving the polyvinyl alcohol, stirring was once stopped, and 40 parts of MMA, 59 parts of n-BMA, 1 part of methacrylic acid (hereinafter abbreviated as “MAA”), and 2 parts of a polymerization initiator were used. 0.2 parts of 2'-azobis 2-methylbutyronitrile (hereinafter abbreviated as "AMBN"), 0.5 part of n-dodecyl mercaptan (hereinafter abbreviated as "n-DM") as a chain transfer agent, 0.1 parts of sodium carbonate as an electrolyte was added and the mixture was stirred again, heated to 75 ° C. and reacted for 2.5 hours, and heated to 98 ° C. and held for 1.5 hours to complete the reaction.

  After cooling to 40 ° C., the resulting aqueous suspension was filtered through a 45 μm mesh filter cloth made of nylon, and the filtrate was washed with deionized water, dehydrated, and dried at 40 ° C. for 16 hours to obtain a granular vinyl suspension. A system polymer (first copolymer) was obtained.

  The Tg of the obtained granular vinyl polymer was 50 ° C., and the weight average molecular weight was 60,000.

  The Tg of the granular vinyl polymer was calculated from the Tg of the homopolymer described in the Polymer Handbook using the Fox equation.

  Then, the second stage reaction was performed.

  That is, 1.65 parts of glycidyl methacrylate (hereinafter abbreviated as "GMA"), 1.5 parts of tetrabutylammonium bromide as an esterification catalyst, and a polymerization inhibitor in a polymerization apparatus provided with a stirrer, a cooling pipe, and a thermometer. 0.1 part of 2,6-di-t-butyl-4-methylphenol (hereinafter abbreviated as “BHT”) and 135.54 parts of 2-ethylhexyl acrylate (hereinafter abbreviated as “2-EHA”) , MMA, 101.65 parts. Next, 100 parts of the granular vinyl polymer (first copolymer) obtained above was gradually charged with stirring, and after charging the whole amount, the temperature was raised to 90 ° C. and maintained for 2 hours, and the acid value was 0.3 mg KOH. / G of polymer (C), 2-EHA and MMA (hereinafter abbreviated as “S-1”).

  The molar ratio of GMA used in the second-stage reaction to 1.0 mole of MAA used in the first-stage reaction was 1.0 / 1.0.

The composition of the obtained S-1 was as follows.
S-1: First copolymer / GMA + (2-EHA + MMA) = 100 / 1.65 + (135.54 + 101.65) (parts).

  First copolymer = MMA / n-BMA / MAA = 40/59/1 (parts), Tg: 50 ° C., Mw: 60,000.

[Synthesis Example 4: Preparation of urethane acrylate oligomer composition (UA-1)]
In a container equipped with a stirrer, a temperature controller, and a condenser, 3,139.2 parts of polyester polyol F7-67 having a weight average molecular weight of 810 (product name: Adeka New Ace F7-67, manufactured by Asahi Denka Kogyo Co., Ltd.), 784 parts of MMA, 21.3 parts of diethylaminoethyl methacrylate and 3.61 parts of BHT were charged and heated to 65 ° C. with stirring. While maintaining this temperature, 348 parts of tolylene diisocyanate was added dropwise over 1 hour, then 87 parts of MMA was added, and the reaction was allowed to proceed at 65 ° C. for another 2 hours. Thereafter, while dropping 120.7 parts of 2-hydroxyethyl acrylate over 30 minutes, the temperature was raised to 90 ° C, 30.2 parts of MMA was added, and the reaction was allowed to proceed while maintaining 90 ° C. The reaction was terminated when the reaction rate of the isocyanate group became 97% or more, and the mixture was cooled to obtain a urethane acrylate oligomer composition (UA-1) containing 20% by mass of MMA.

[Preparation of resin composition for primer layer (PR-1)]
A resin composition for a primer layer was prepared according to the formulation shown in Table 1.

  30 parts of MMA as monomer (B), 36.5 parts of 2-EHA, KBM-503 (product name KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.) in a 1 L flask equipped with a stirrer, thermometer, and cooling tube 7.5 parts of NK ester 14G (product name: NK ester 14G, manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.06 part of BHT as a polymerization inhibitor, P-115 (product name: paraffin wax 115, manufactured by Nippon Seiro Co., Ltd.) 0.3 parts of P-130 (product name: paraffin wax 130, manufactured by Nippon Seiro Co., Ltd., melting point: 55 ° C.) (hereinafter, “P-130”). 0.5 part) and 0.2 part of P-150 (product name Paraffin Wax 150, manufactured by Nippon Seiro Co., Ltd., melting point 66 ° C.) (hereinafter abbreviated as “P-150”). N, N-di (2-hydroxyethyl) -p- 0.8 parts of Luisin (hereinafter abbreviated as "PTEO"), 0.5 parts of BYK-1752 (manufactured by BYK Japan) as an antifoaming agent (hereinafter abbreviated as "BYK-1752"), and an ultraviolet absorber 0.2 parts of JF-77 (manufactured by Johoku Chemical Co., Ltd.) (hereinafter, abbreviated as “JF-77”). Thereafter, 25 parts of the polymer P-1 of Synthesis Example 1 was further added with stirring, heated at 60 ° C. for 2 hours to dissolve, and then cooled to obtain a resin composition for a primer layer (PR-1). .

(viscosity)
Primer composition (PR-1) prepared as described above, Acrylicup DR-90 (product name, hereinafter abbreviated as "DR-90") manufactured by Ryokosha Co., Ltd., PD primer (product name) manufactured by Misyu Kosan Co., Ltd. , Hereinafter abbreviated as “PD primer”), the viscosity was measured by the following measurement method. Table 1 shows the results.

  The viscosity was measured at 23 ° C. (viscosity at 60 rpm) using a B-type (Brookfield type) viscometer (BM type, manufactured by Tokimec).

[Performance evaluation]
As described below, a resin composition for a primer layer containing a curing agent was prepared and evaluated.

  For 100 parts of the primer layer composition (PR-1) and DR-90 prepared as described above, BPO-50 (product name: BPO-50, manufactured by Kayaku Akzo, 50% benzoyl peroxide) was used as a curing agent. (Hereinafter, abbreviated as “BPO-50”). 2 parts were added and mixed well to obtain a resin composition for a primer layer containing a curing agent. The PD primer was used as it was because it was a moisture-curable one-component urethane resin.

  As a sample for measuring the curing characteristics at -10 ° C, 100 parts of the primer layer composition (PR-1) and DR-90 prepared as described above were used as an accelerator, AC-103 (product name Acrysilap AC). -103, manufactured by Ryokosha Co., Ltd. (hereinafter abbreviated as "AC-103") 1.5 parts, and 8 parts of BPO-50 as a curing agent were added and mixed well to obtain a resin composition containing a curing agent. . The PD primer was used as it was because it was a moisture-curable one-component urethane resin.

  The curing properties and the tensile test of the resin composition for a primer layer containing a curing agent were measured and evaluated as follows. Table 1 shows the results.

<Curing characteristics (23 ° C)>
(Gel time)
In a variable environment room at an indoor temperature of 23 ° C. and a humidity of 50%, 50 g of the resin composition for a primer layer containing each of the above-mentioned curing agents was put into a 100 ml polypropylene cup, and required from the addition of the curing agent to the disappearance of fluidity of the resin. The time was defined as the gel time. The PD primer was a moisture-curable one-component urethane resin, and therefore did not have a gel time (described in the table as "-").

(Drying time)
The resin composition for a primer layer containing each curing agent was applied to a thickness of 300 μm on a polyethylene terephthalate film using an applicator in an environment variable room at an indoor temperature of 23 ° C. and a humidity of 50%. Gauze was brought into contact with the surface of the obtained coating film, and the time required until the gauze did not adhere to the coating film was defined as the drying time. The PD primer was also applied to a thickness of 100 μm using an applicator and evaluated in the same manner as described above.

<Curing characteristics (-10 ° C)>
(Gel time)
In a thermostatic chamber controlled at −10 ° C., 50 g of the above-described primer layer-containing resin composition containing each curing agent was put into a 100 ml polypropylene cup, and the time required from the addition of the curing agent to the loss of fluidity of the resin. Was taken as the gel time. The PD primer was a moisture-curable one-component urethane resin, and therefore did not have a gel time (described in the table as "-").

(Drying time)
In a thermo-hygrostat controlled at −10 ° C., the resin composition for a primer layer containing each curing agent was applied on a polyethylene terephthalate film to a thickness of 300 μm using an applicator. Gauze was brought into contact with the surface of the obtained coating film, and the time required until the gauze did not adhere to the coating film was defined as the drying time. The PD primer was also applied to a thickness of 100 μm using an applicator and evaluated in the same manner as described above.

<Tensile test>
The resin composition for a primer layer containing a curing agent prepared as described above was defoamed in an environment-variable room at an indoor temperature of 23 ° C. and a humidity of 50%, and then poured into a mold and cured and cured. After releasing from the mold the next day after curing, a casting plate (test sample) having a thickness of 3 mm was obtained.

These test samples were subjected to a tensile test at −10 ° C. and −20 ° C. in accordance with JIS-K6251: 2010, and the tensile strength at break (N / mm ² ) was measured. This tensile breaking strength is one of the indexes of the mechanical strength of the cured coating film. In the tensile test, the tensile elongation at break was also measured. Table 1 shows the results. In addition, about PD primer, since the coating film thickness similar to the above could not be obtained, the tensile test was not evaluated.

[Preparation of Resin Composition SH-1 for Adhesive Protection Layer]
With the composition shown in Table 2, a resin composition for an adhesive protective layer was prepared.

  That is, in a container equipped with a stirrer, a temperature control device, and a condenser, as a monomer (A), 38 parts of MMA, 28 parts of 2-EHA, 1 part of KBM-503, and as a monomer (B), NK-ester 14G: 10 parts of polyethylene glycol dimethacrylate (product name: NK-ester 14G, manufactured by Shin-Nakamura Chemical Co., Ltd.) (hereinafter abbreviated as "NK-ester 14G"), 0.06 part of BHT as a polymerization inhibitor, P 0.3 parts of -115, 0.5 parts of P-130, 0.2 parts of P-150, 0.6 parts of PTEO as a curing accelerator, 0.5 parts of BYK-1752 as a defoamer, After adding 0.2 parts of JF-77 as an ultraviolet absorber, while stirring, the thixotropic agent AG-200 (trade name: AG-200, manufactured by Ryoko Corp.) (hereinafter abbreviated as "AG-200"). ) And 25 parts of polymer (P-1) I was painting. Next, the mixture was heated at 60 ° C. for 2 hours to dissolve, and then cooled to obtain a resin composition (SH-1) for an adhesive protective layer.

[Preparation of Resin Composition (SH-2), (SH-3), (SH-5) to (SH-14) for Adhesive Protective Layer]
Except for changing to the composition shown in Table 2 and Table 3, in the same manner as the method for preparing the resin composition for an adhesive protective layer (SH-1), the resin composition for an adhesive protective layer (SH-2), (SH-3) ) And (SH-5) to (SH-14). In addition, PBOA-2000, TR-2000, and BYK-410 in Tables 2 and 3 are as follows.
-PBOA-2000: polybutylene glycol diacrylate (the weight average molecular weight of the repeating unit of polybutylene glycol is about 2,000) (hereinafter abbreviated as "PBOA-2000").
TR-2000: manufactured by JSR Corporation: trade name JSR TR-2000 (hereinafter abbreviated as "TR-2000").
-BYK-410: BYK-410 manufactured by BYK Japan KK (hereinafter abbreviated as "BYK-410").

[Preparation of Resin Composition (SH-4) for Adhesive Protection Layer]
Using the urethane acrylate oligomer composition (UA-1) obtained in Synthesis Example 4, a resin composition SH-4 was prepared according to the formulation shown in Table 2.

  In addition, the compounding amount (unit: parts by mass) of UA-1 described in Table 2 is the total amount of the oligomer (D) and MMA contained in the composition, and the value in parentheses shown together is And the amount (unit: parts by mass) of the oligomer (D) contained in the compounded UA-1.

  Therefore, in the resin composition for an adhesive protective layer (SH-4), although the amount of MMA blended separately from the urethane acrylate oligomer composition (UA-1) is 38.7 parts by mass, the resin composition for an adhesive protective layer (SH-4) The content of all MMA contained in SH-4) is 39.3 parts by mass.

(Viscosity, TI value)
About the resin composition for adhesive protection layers (SH-1 to SH-14) prepared as described above, the viscosity and the TI value were measured by the following measurement methods. The results are shown in Tables 2 and 3, respectively.

  The viscosity was measured at 23 ° C. (viscosity at 60 rpm) using a B-type (Brookfield type) viscometer (BM type, manufactured by Tokimec).

  The TI value was determined from the measured viscosity when the viscosity at 23 ° C. was measured using a B-type viscometer (BM type, manufactured by Tokimec) according to the above formula (9).

[Performance evaluation]
As described below, a resin composition for an adhesive protective layer containing a curing agent was prepared and evaluated.

  To 100 parts (parts excluding calcium carbonate) of the resin composition for adhesive protection layer (SH-1 to SH-14) prepared as described above, add 2 parts of BPO-50 as a curing agent and mix well. Thus, a resin composition for an adhesive protective layer containing a curing agent was obtained. The curing properties of these resin compositions for an adhesive protective layer containing a curing agent were measured and evaluated as follows. The results are shown in Tables 2 and 3.

<Curing characteristics (23 ° C)>
(Gel time)
The gelation time at 23 ° C. of each of the resin compositions for an adhesive protective layer containing a curing agent was measured in the same manner as in the measurement of the gelation time of the resin composition for a primer layer containing a curing agent.

(Drying time)
The drying time at 23 ° C. of each of the resin compositions for an adhesive protective layer containing a curing agent was measured in the same manner as the measurement of the drying time for the resin composition for a primer layer containing a curing agent.

<Tensile test>
The resin composition for an adhesive protective layer containing a curing agent prepared as described above was defoamed in an environment-variable room at an indoor temperature of 23 ° C. and a humidity of 50%, and then poured into a mold and cured and cured. After releasing from the mold the next day after curing, a casting plate (test sample) having a thickness of 3 mm was obtained.

These test samples were subjected to a tensile test at 23 ° C., −10 ° C., and −20 ° C. in accordance with JIS-K6251: 2010, and the tensile strength at break (N / mm ² ) was measured. This tensile breaking strength is one of the indexes of the mechanical strength of the cured coating film. In the tensile test, the tensile elongation at break was also measured. Tables 2 and 3 show the results.

[Preparation of resin composition BS-1 for waterproof layer]
With the composition shown in Table 4, a resin composition (BS-1) for a waterproof layer was prepared as follows.

  In a container equipped with a stirrer, temperature controller and condenser, 28 parts of MMA, 42 parts of 2-EHA as monomer (A), 5 parts of PBOA-2000 as monomer (B), polymerization inhibition 0.05 parts of BHT, 0.2 parts of P-115, 0.2 parts of P-130, 0.2 parts of P-150, 0.6 parts of PTEO as a curing accelerator, BYK as a defoamer After 0.5 parts of -1752 and 0.2 parts of JF-77 as an ultraviolet absorber were added, 25 parts of the polymer (P-1) was added with stirring. Next, the mixture was heated at 60 ° C. for 2 hours to dissolve, and then cooled to obtain a resin composition for a waterproof layer (BS-1).

[Resin compositions for waterproof layer (BS-2) to (BS-6), (BS-8) to (BS-14), (BS-16), (BS-18), (BS-19A), ( Preparation of BS-19B)]
Except having changed to the composition shown in Table 4 and Table 5, similarly to the preparation method of the resin composition for waterproof layers (BS-1), the resin compositions for waterproof layers (BS-2) to (BS-6), (BS-8) to (BS-14), (BS-16), (BS-18), (BS-19A) and (BS-19B) were prepared. In addition, BPE-4, APG-700, PBOM-1000, PBOM, TR-2000, and SIS-5002 in Tables 4 and 5 are as follows.
BPE-4: manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name New Frontier BPE-4 (hereinafter abbreviated as "BPE-4").
APG-700: manufactured by Shin-Nakamura Chemical Co., Ltd., trade name NK ester APG-700 (hereinafter abbreviated as "APG-700").
-PBOM-1000: polybutylene glycol dimethacrylate (the mass average molecular weight of the repeating unit of polybutylene glycol is about 1,000) (hereinafter abbreviated as "PBOM-1000").
PBOM: polybutylene glycol dimethacrylate (the weight average molecular weight of the repeating unit of polybutylene glycol is about 650) (hereinafter abbreviated as "PBOM").
TR-2000: JSR Corporation, trade name JSR TR-2000 (hereinafter abbreviated as "TR-2000").
-SL-700: Calcium carbonate SL-700 (trade name; hereinafter, abbreviated as "SL-700") manufactured by Takehara Chemical Co., Ltd.
-P-300: manufactured by ADEKA, trade name Adecaizer P-300 (hereinafter abbreviated as "P-300").

[Preparation of resin composition for waterproof layer (BS-7)]
Using the urethane acrylate oligomer composition (UA-1) obtained in Synthesis Example 4, a resin composition (BS-7) was prepared according to the formulation shown in Table 4.

  The amount (unit: parts by mass) of UA-1 described in Table 4 is the total amount of the oligomer (D) and MMA contained in the composition, and the value in parentheses shown together is And the amount (unit: parts by mass) of the oligomer (D) contained in the compounded UA-1.

  Therefore, in the resin composition for a waterproof layer (BS-7), MMA blended separately from the urethane acrylate oligomer composition (UA-1) is 10 parts by mass, but the resin composition for a waterproof layer (BS-7) Is 20 parts by mass.

[Preparation of Resin Compositions for Waterproof Layer (BS-15) and (BS-17)]
A resin composition for a waterproof layer (BS-15) and (BS-17) were prepared in the same manner as the method for preparing a resin composition for a waterproof layer (BS-7), except that the composition was changed to the composition shown in Table 5.

(Viscosity, TI value)
About the resin composition for waterproof layers (BS-1 to BS-18, BS-19A, BS-19B) prepared as described above, the viscosity and the TI value were measured by the following measuring methods. The results are shown in Tables 4 and 5, respectively.

  The viscosity was measured at 23 ° C. (viscosity at 60 rpm) using a B-type viscometer (BM type, manufactured by Tokimec).

  The TI value was determined from the measured viscosity when the viscosity at 23 ° C. was measured using a B-type viscometer (BM type, manufactured by Tokimec) according to the above formula (9).

[Performance evaluation]
As described below, a resin composition for a waterproofing layer containing a curing agent was prepared and evaluated.

  To 100 parts (parts excluding calcium carbonate) of the resin composition for a waterproof layer BS-1 to BS-18 prepared as described above, add 2 parts of BPO-50 as a curing agent, mix well, and cure. Thus, a resin composition for a waterproof layer containing an agent was obtained.

  Further, 4 parts of BPO-50 as a curing agent was added to 100 parts of the resin composition for a waterproof layer (BS-19B) prepared as described above, mixed well, and further mixed with the resin composition for a waterproof layer (BS-19B). 100 parts of BS-19A) were added and mixed well to obtain a resin composition for a waterproofing layer containing a curing agent.

  As a sample for measuring curing characteristics at −10 ° C., an accelerator was used for 100 parts (parts excluding calcium carbonate) of the resin composition for a waterproof layer (BS-1 to BS-18) prepared as described above. Of AC-103 and 8 parts of BPO-50 as a curing agent were added and mixed well to obtain a resin composition for a waterproofing layer containing a curing agent.

  Further, 16 parts of BPO-50 as a curing agent was added to 100 parts of the resin composition for a waterproof layer (BS-19B) and mixed well. -19A) 3 parts of AC-103 were added to 100 parts of an accelerator as an accelerator, and the mixture was mixed well. These were mixed well to obtain a resin composition for a waterproofing layer containing a curing agent.

  The curing properties of the resin composition for a waterproofing layer containing a curing agent were measured and evaluated as follows. The results are shown in Tables 4 and 5.

<Curing characteristics (23 ° C)>
(Gel time)
The gelation time at 23 ° C. of each of the above-mentioned resin compositions for a waterproofing layer containing a curing agent was measured in the same manner as in the measurement of the gelation time of the resin composition for a primer layer containing a curing agent.

(Drying time)
The drying time at 23 ° C. of each of the above-mentioned resin compositions for a waterproofing layer containing a curing agent was measured in the same manner as in the measurement of the drying time of the resin composition for a primer layer containing a curing agent.

<Tensile test>
Each of the resin compositions for a waterproofing layer containing a curing agent prepared as described above was defoamed in an environment-variable room at an indoor temperature of 23 ° C. and a humidity of 50%, and then poured into a mold and cured and cured. After releasing from the mold the next day after curing, a casting plate (test sample) having a thickness of 3 mm was obtained.

These test samples were subjected to a tensile test at 23 ° C., −10 ° C., and −20 ° C. in accordance with JIS-K6251: 2010, and the tensile strength at break (N / mm ² ) was measured. This tensile breaking strength is one of the indexes of the mechanical strength of the cured coating film. In the tensile test, the tensile elongation at break was also measured. Tables 4 and 5 show the results.

[Example 1]
<Formation of primer layer>
A steel plate of 150 mm x 30 mm x 0.5 mm thickness was prepared, and the surface was degreased with acetone.

  On the other hand, 2 parts of BPO-50 as a curing agent is added to 100 parts of the resin composition for a primer layer prepared as described above (PR-1), mixed well, and then mixed well with a curing agent-containing resin composition for a primer layer. I got

The resin composition for a primer layer containing a curing agent was applied to the surface of the steel sheet so that the dry coating amount was 0.4 kg / m ^2, and the coating was cured to form a primer layer.

At that time, the coating workability was evaluated based on the following criteria. Table 6 shows the results.
Good (O): The resin composition was sufficiently leveled with a brush, and was uniformly applied.
Poor (x): When leveling the resin composition with a brush, the viscosity was high and it was difficult to level, or a long time was required to obtain a uniform surface.

<Formation of waterproof layer>
To 100 parts of the waterproofing layer resin composition (BS-10) prepared as described above, 2 parts of BPO-50 was added as a curing agent and mixed well to obtain a curing agent-containing waterproofing layer resin composition. .

The resin composition for a waterproofing layer containing a curing agent was applied to the surface of the primer layer so that the dry coating amount was 1.5 kg / m ^2, and the coating was cured to form a waterproofing layer.

At that time, the coating workability was evaluated based on the following criteria. Table 6 shows the results.
Good (O): The resin composition was sufficiently leveled with a spatula, and was uniformly applied.
Poor (x): When leveling the resin composition with a spatula, the viscosity was high and difficult to level, or a long time was required to obtain a uniform surface.

<Formation of adhesion protective layer>
To 100 parts of the resin composition for adhesive protection layer (SH-1) prepared as described above, 2 parts of BPO-50 as a curing agent is added and mixed well, and the resin composition for adhesion protection layer containing a curing agent is added. I got

The resin composition for an adhesive protective layer containing a curing agent was applied to the surface of the waterproof layer so that the dry coating amount was 0.3 kg / m ² . Then, before the resin composition for the adhesive protective layer containing the curing agent of the coating film is cured, 1 kg / m ² of silica sand No. 5 is sprayed on the surface of the coating film as a scattered aggregate to be integrated. To form an adhesive protective layer. Thereafter, the dispersed aggregate that was not integrated with the resin for the adhesive protective layer was removed from the surface.

At that time, the coating workability was evaluated based on the following criteria. Table 6 shows the results of Example 1. Tables 6 to 10 show the results of other examples and comparative examples described later.
Good (O): The resin composition was sufficiently leveled with a brush, and was uniformly applied.
Poor (x): When leveling the resin composition with a brush, the viscosity was high and it was difficult to level, or a long time was required to obtain a uniform surface.
No coating film left: The cured resin (coating film) did not remain at the interface with the waterproof layer because the coated resin composition for the adhesive protective layer migrated to the spraying aggregate side due to the capillary action of the spraying aggregate.
Sedimentation: When aggregate was sprayed on the coated resin composition for an adhesive protective layer, the aggregate was settled in the resin composition for an adhesive protective layer, and no aggregate appeared on the surface of the cured coating film.

<Crack Followability Test I (-20 ° C)>
The laminated body formed on the steel sheet was used as a test sample, and the 2.5 floor version waterproof of "Hokkaido Development Bureau Road Design Guidebook 3rd Bridge" (issued in April 2013) issued by Hokkaido Development Bureau of the Ministry of Land, Infrastructure, Transport and Tourism. Pass / Fail was determined by performing a "crack following test I" (test temperature -20 ° C) described in Table 2.5.1 Performance checking method.

  Regarding the crack followability test I at −20 ° C., the test temperature was set to −20 in the test method of the crack followability test I (low-temperature flexibility test) described in the Road Bridge Deck Waterproof Handbook (Japan Road Association). ° C.

The pass / fail judgment is based on the following criteria. Table 6 shows the results. Tables 6 to 9 show the results of other examples and comparative examples described later.
Pass (O): The waterproof layer is not broken. However, fine cracks in the upper part of the waterproof layer are also considered to be acceptable.
Failed (x): The waterproof layer is broken.

(Crack tracking test II)
The following substrate was prepared, and a laminate similar to the above was formed on the substrate according to the following. Using this as a test sample, Table 2.5.1 of the 2.5-floor slab of “Hokkaido Development Bureau Road Design Guidelines Vol. 3 Bridges” (issued in April 2013) issued by the Hokkaido Development Bureau of the Ministry of Land, Infrastructure, Transport and Tourism The evaluation was performed by performing a “crack following test II” (test temperature −20 ° C.) described in the performance checking method. Table 6 shows the results. Tables 6 to 9 show the results of other examples and comparative examples described later.

  The crack followability test II at −20 ° C. is the test method of the crack followability test II described in the Road Bridge Deck Waterproof Handbook (Japan Road Association) with the test temperature changed to −20 ° C. .

<Preparation of base>
A mortar plate of 40 mm × 120 mm × 10 mm thickness prepared in accordance with JIS-R5201 was cut into a 5-mm-depth cut by a diamond cutter on a surface on the side on which a laminate was formed, and was cut into two pieces. Next, the mortar plates cut into two pieces were arranged on a steel plate, the side surfaces of the mortar plates were butted, and an adhesive tape was wound around the entire side surface of the mortar plate in the butted state and fixed to obtain a base.

<Formation of primer layer>
To 100 parts of the primer layer resin composition (PR-1) prepared as described above, 2 parts of BPO-50 as a curing agent is added and mixed well to obtain a curing agent-containing primer layer resin composition. Was. The resin composition for a primer layer containing a curing agent was applied to the surface of the mortar plate so that the dry coating amount was 0.4 kg / m ^2, and the coating was cured to form a primer layer.

<Formation of waterproof layer>
To 100 parts of the resin composition for a waterproof layer (BS-10) prepared as described above, 2 parts of BPO-50 as a hardener is added and mixed well to obtain a resin composition for a waterproof layer containing a hardener. Was. The resin composition for a waterproofing layer containing a curing agent was applied to the surface of the primer layer so that the dry coating amount was 1.5 kg / m ^2, and cured to form a waterproofing layer.

<Formation of adhesion protective layer>
To 100 parts of the resin composition for adhesive protection layer (SH-1) prepared as described above, 2 parts of BPO-50 as a curing agent is added and mixed well, and the resin composition for adhesion protection layer containing a curing agent is added. I got The resin composition for an adhesive protective layer containing a curing agent was applied to the surface of the waterproof layer so that the dry coating amount was 0.3 kg / m ² . Subsequently, before the resin composition for the adhesive protective layer containing the curing agent of the coating film is cured, 1 kg / m ² of silica sand No. 5 is sprayed on the surface of the coating film as a scattered aggregate so as to be integrated. To form an adhesive protective layer. Thereafter, the dispersed aggregate that was not integrated with the resin for the adhesive protective layer was removed from the surface.

(Examples 2 to 8 and Comparative Examples 1 to 6)
The resin composition for an adhesive protective layer (SH-1) of Example 1 was used as the resin composition for an adhesive protective layer (SH-2 to SH-8, SH-9 to SH-14) shown in Tables 6 and 9. A laminate was formed and a test was performed in the same manner as in Example 1 except that the test piece was changed to. The results are shown in Tables 6 and 9.

(Examples 9 and 10)
A laminate was prepared in the same manner as in Example 2 except that the resin composition for a primer layer (PR-1) of Example 2 was changed to the resin composition for a primer layer (DR-90, PD primer) shown in Table 6. Was formed and tested. Table 6 shows the results.

(Examples 11 to 22 and Comparative Examples 7 to 11)
The resin composition for waterproof layer (BS-10) of Example 2 was combined with the resin composition for waterproof layer (BS-1 to BS-9, BS-11 to BS-13) described in Tables 6, 7, and 9. , BS-14 to BS-18), except that a laminate was formed and tested in the same manner as in Example 2. The results are shown in Tables 6, 7, and 9.

(Example 23)
The resin composition for waterproof layer (BS-10) of Example 2 was added to 100 parts of the resin composition for waterproof layer (BS-19: resin composition for waterproof layer (BS-19B)) described in Table 7. A resin composition for a waterproofing layer containing a curing agent, obtained by adding 4 parts of BPO-50 as a curing agent, mixing well, and further adding and mixing 100 parts of a resin composition for a waterproofing layer (BS-19A). ), And a test was performed in the same manner as in Example 2 except that a laminate was formed. Table 7 shows the results.

(Examples 24 and 25)
Example 2 was repeated except that the dry coating amount (1.0 kg / m ² , 2.0 kg / m ² ) shown in Table 8 was changed in the resin composition for a waterproof layer (BS-10) of Example 2. A laminate was formed in the same manner as described above, and a test was performed. Table 8 shows the results.

(Examples 26 and 27)
Adhesive protective layer resin composition of Example 2 at (SH-2), except for changing the dry coating amount shown in Table ^{8 (0.2kg / m 2, 0.5kg} / m 2), Example A laminate was formed in the same manner as in Example 2, and a test was performed. Table 8 shows the results.

(Example 28)
A laminate was formed and tested in the same manner as in Example 2, except that the primer layer resin composition (PR-1) of Example 2 was not applied. Table 8 shows the results.

(Examples 29 and 30)
Laminating was carried out in the same manner as in Example 28 except that the waterproofing layer resin composition (BS-10) of Example 28 was changed to the waterproofing layer resin composition (BS-1, BS-8) shown in Table 8. The body was formed and tested. Table 8 shows the results.

(Comparative Examples 12, 13)
Except for changing the dry coating amount (0.1 kg / m ² , 1.0 kg / m ² ) shown in Table 9 in the resin composition for an adhesive protective layer (SH-2) of Example 2, A laminate was formed in the same manner as in Example 2, and a test was performed. Table 9 shows the results.

(Example 31)
<Preparation of base>
The surface of a JIS concrete plate (30cm x 30cm x 6cm thickness specified in JIS-A5371 (precast unreinforced concrete product), is sufficiently polished with No. 150 abrasive paper specified in JIS-R6252 "Abrasive paper". Was used as a substrate.

<Formation of primer layer>
To 100 parts of the primer layer resin composition (PR-1) prepared as described above, 2 parts of BPO-50 as a curing agent is added and mixed well to obtain a curing agent-containing primer layer resin composition. Was. The resin composition for a primer layer containing a curing agent was applied to the surface of the concrete plate so that the dry coating amount was 0.4 kg / m ^2, and cured to form a primer layer.

<Formation of waterproof layer>
To 100 parts of the resin composition for a waterproof layer (BS-10) prepared as described above, 2 parts of BPO-50 as a hardener is added and mixed well to obtain a resin composition for a waterproof layer containing a hardener. Was. The resin composition for a waterproofing layer containing a curing agent was applied onto the surface of the primer layer so that the dry coating amount was 2.0 kg / m ^2, and the coating was cured to form a waterproofing layer.

<Formation of adhesion protective layer>
To 100 parts of the resin composition for adhesive protection layer (SH-1) prepared as described above, 2 parts of BPO-50 as a curing agent is added and mixed well, and the resin composition for adhesion protection layer containing a curing agent is added. I got The resin composition for an adhesive protective layer containing a curing agent was applied to the surface of the waterproof layer so that the dry coating amount was 0.3 kg / m ² . Then, before the resin composition for the adhesive protective layer containing the curing agent of the coating film is cured, 1 kg / m ² of silica sand No. 5 is sprayed on the surface of the coating film as a scattered aggregate to be integrated. To form an adhesive protective layer. Thereafter, the dispersed aggregate that was not integrated with the resin for the adhesive protective layer was removed from the surface.

<Pavement>
On the surface of the adhesive protective layer, 0.5 kg / m ^{2 of} rubber-coated asphalt emulsion for tack coat PKR-T (a modified asphalt emulsion conforming to JEAAS-2006 association standard of Japan Asphalt Association) is applied. Asphalt pavement. As a type of pavement, a dense grain asphalt mixture 13F (straight asphalt) was used, and paving was performed by a compactor in which the pavement temperature was adjusted to 140 ° C. and the linear pressure was 30 kg / cm.

(Waterproof test II)
The above samples (laminates) were tested according to the test method of the waterproof test II described in the Road Bridge Deck Waterproof Handbook (Japan Road Association). Table 10 shows the results.
Good (O): No leakage of test liquid is observed in concrete.
Poor (x): Water leakage of the test liquid was observed in concrete.

(Crack switching load test)
The above samples (laminates) were tested according to the test method of crack opening / closing load test described in the Road Bridge Floor Slab Waterproof Handbook (Japan Road Association). Table 10 shows the test results up to the waterproof test II.
Good (O): No leakage of test liquid is observed in concrete.
Poor (x): Water leakage of the test liquid was observed in concrete.

(Examples 32-35, Comparative Examples 14, 15)
A laminated body was prepared in the same manner as in Example 31 except that the configuration shown in Table 10 was used, and a test was performed in the same manner as in Example 31. Table 10 shows the results.

  As shown in Tables 1 to 8, the laminates of Examples 1 to 30 have a high tensile elongation at −10 ° C. of the resin constituting the waterproof layer and the resin constituting the adhesive protective layer, and have a temperature of −20 ° C. In addition, good results were obtained in which no breakage occurred even when the crack following test I was carried out at -20 ° C, and the following limit crack width as a criterion for pass / fail judgment in the crack following test II at −20 ° C. was 0.3 mm or more. Very good results were obtained. Further, the curing time was in an appropriate range, and the coating workability was good.

  On the other hand, as shown in Table 9, Comparative Examples 1, 2, 5 and 6 showed that the curing time of the resin composition for the waterproof layer was within an appropriate range, the coating workability was good, and the low temperature of the cured coating film was low. Tensile elongation at break is high. However, on the other hand, the liquid properties (viscosity and TI value) of the resin composition for an adhesive protective layer are insufficient (the coating workability is poor if the viscosity is too high, and the coated resin is too low if the resin viscosity is too low). The resin composition migrated to the scattered aggregate side due to the capillary action of the scattered aggregate, and the resin composition hardly remained at the interface with the waterproof layer, and a desired coating film could not be formed. Neither the followability test I nor the crack followability test II could be evaluated.

  In Comparative Example 3, as shown in Table 9, the curing time of the resin composition for the waterproof layer was in an appropriate range, the coating workability was good, and the tensile elongation at break of the cured coating film at low temperature was high. However, on the other hand, the tensile elongation at -10 ° C of the cured film of the resin composition (SH-11) for the adhesive protective layer was low. As a result, in the laminate of Comparative Example 3, breakage occurred in the crack followability test I at -20 ° C.

  Comparative Example 4 was inferior in workability because the drying time of the curing characteristics of the resin composition for an adhesive protective layer (SH-12) exceeded 60 minutes.

  In Comparative Examples 7 to 10, the curing time of the resin composition for the adhesive protective layer was within an appropriate range, the coating workability was good, and the tensile strength at break of the cured coating film at low temperature was high. However, on the other hand, the tensile elongation at -10 ° C of the cured film of the resin composition for the waterproof layer was low. As a result, all of Comparative Examples 7 to 10 were broken in the crack followability test I at −20 ° C., and were poor when the limit crack width was less than 0.3 mm in the crack followability test II at −20 ° C. Results.

  In Comparative Example 11, the curing time of the resin composition for the adhesive protective layer was within an appropriate range, the coating workability was good, and the tensile strength at break of the cured coating film at low temperature was high. However, on the other hand, the liquid properties (viscosity, TI value) of the resin composition for the waterproof layer were insufficient (the coating workability was poor because the viscosity was too high, and a smooth coating film was not obtained. The performance could not be evaluated because the protective layer could not be painted).

In Comparative Examples 12 and 13, the application amount of the resin composition for the adhesive protective layer is out of the preferred range. That is, when the application amount of the resin composition for an adhesive protective layer is less than 0.2 kg / m ² , the resin for the adhesive protective layer is sufficiently sucked up by the sprinkled aggregate or the like by capillary action, and the resin for the adhesive protective layer is sufficiently left on the waterproof layer. When the application amount of the resin composition for an adhesive protective layer exceeds 0.5 kg / m ² , the dispersed aggregate sinks into the adhesive protective layer, making it difficult for the aggregate to appear on the surface. It is. As a result, a desired coating film could not be formed, and neither the crack following test I nor the crack following test II could be evaluated.

  As shown in Table 10, the laminates of Examples 31 to 35 had good evaluation results in the waterproof test II. Further, in Example 31, a favorable evaluation result was also obtained in a crack opening / closing load test.

  On the other hand, in Comparative Examples 14 and 15 having no adhesive protective layer, the waterproof test II resulted in water leakage.

  The laminate according to the embodiment of the present invention can be formed on the surface of a substrate (structure such as a floor or a road) made of concrete or asphalt, and can have a waterproof function or the like. Further, the laminate according to the embodiment of the present invention may be formed on the surface of a metal base.

DESCRIPTION OF SYMBOLS 1 Base 2 Primer layer 3 Waterproof layer 4 Adhesive protective layer 5 Aggregate

Claims (11)

A waterproof laminated structure provided between the base and the paving material,
The waterproof laminated structure includes a waterproof layer and an adhesive protective layer in order from the base side,
The waterproof layer is a coating film of a resin composition for a waterproof layer,
The resin composition for a waterproof layer has a cured product having a tensile elongation at break of 80% or more measured at −10 ° C. according to a measurement method defined in JIS K6251: 2010,
The adhesive protective layer is a coating film in which the coating amount of the resin composition for an adhesive protective layer is 0.2 to 0.5 kg / m ² (excluding aggregate), and is 0.5 to 2.0 kg / m ² . Including aggregate,
The resin composition for an adhesive protective layer has a cured product having a tensile elongation at break of 10% or more measured at −10 ° C. according to a measurement method defined in JIS K6251: 2010 and a tensile strength measured at 23 ° C. A waterproof laminated structure having a breaking elongation of 100% or more.   The waterproof laminated structure according to claim 1, wherein the aggregate has a specific gravity of 2.2 to 3.5, and a ratio of the aggregate having a particle size of 0.5 to 2.0 mm is 90% by mass or more. .   The resin composition for an adhesive protective layer has a solution viscosity of 300 to 1,500 mPa · s measured at 23 ° C. with a Brookfield viscometer specified in JIS-Z8803, and a measuring method specified in JIS-K6833. The waterproof laminated structure according to claim 1 or 2, wherein the determined TI value (thixotropic index) is 1.5 or more.   The laminated structure according to any one of claims 1 to 3, wherein the resin composition for an adhesion protective layer is a radically polymerizable acrylic resin composition. The radical polymerization type acrylic resin composition,
A monomer (A) having one (meth) acryloyl group,
A monomer (B) having two or more (meth) acryloyl groups, and a resin (C) soluble in the monomers (A) and (B) and having a glass transition temperature of 110 ° C. or lower Including
The total of the monomer (A), the monomer (B) and the resin (C) is 80% by mass or more;
With respect to the total of the monomer (A), the monomer (B) and the resin (C), the monomer (A) is 60 to 80% by mass, the monomer (B) is 20% by mass or less, and the resin The waterproof laminated structure according to claim 4, wherein (C) is 5 to 30% by mass.   The waterproof laminated structure according to claim 5, wherein the cured product of the radical polymerization type acrylic resin composition has a glass transition temperature of -25 to 15 ° C.   The waterproof laminated structure according to any one of claims 1 to 6, wherein the resin composition for a waterproof layer is a radically polymerizable acrylic resin composition.   The waterproof laminated structure according to any one of claims 1 to 7, further comprising a primer layer on the base side of the waterproof layer.   The waterproof laminated structure according to any one of claims 1 to 8, further comprising a pavement adhesive layer on the pavement side of the adhesive protection layer. It is a manufacturing method of the waterproof laminated structure according to any one of claims 1 to 9,
A step of applying the resin composition for a waterproof layer on the surface of a substrate or a surface of a primer layer provided on the surface of the substrate, and curing to form a waterproof layer,
A method for producing a waterproof laminated structure, comprising a step of applying the resin composition for an adhesive protective layer on the surface of the waterproof layer, dispersing an aggregate before curing, and then curing to form an adhesive protective layer. . A waterproof pavement laminate comprising a substrate, a pavement material, and the waterproof laminate structure according to any one of claims 1 to 9 between the substrate and the pavement material.