JP2017087727A - Method for forming laminated structure, and laminated structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To efficiently obtain a laminated structure having stable adhesive strength, and to allow the laminated structure to exhibit more excellent heat resistant protection properties.SOLUTION: Provided is a method for forming a laminated structure, in which an adhesive material layer and a heat foamable covering material are laminated to a base material face, the method including: a step where the first adhesive material layer is provided on the base material face; and a step where the first adhesive material layer and the second adhesive material layer provided at the rear face of the heat foamable covering material are crimped. In the first adhesive material layer and the second adhesive material layer, either is formed with a specified adhesive material (M), the other is formed with a specified adhesive material (N), and, before curing of the adhesive material layer formed with the adhesive material (M), the first adhesive material layer and the second adhesive material laye are crimped.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for forming a novel laminated structure. The laminated structure obtained by the present invention can protect the substrate when the temperature rises due to a fire or the like.

  Conventionally, in a building structure, in order to protect the building from a fire, it is required to make a main part such as a pillar, a beam, a floor, and a wall a heat resistant structure. As one method for applying a heat resistant structure, there is a method in which a thermally foamable coating material is attached to a base material such as a main part via an adhesive (for example, Patent Document 1).

  The heat-foamable covering material is normally thin and light, and has the effect of exhibiting heat-resistant protection by foaming and carbonizing to form a heat-insulating layer when the temperature rises due to a fire or the like. Such a heat-foamable covering material can usually be constructed by sticking with an adhesive or the like, and does not require an extra space and can be made uniform in thickness.

JP-A-8-60763

  However, in the structure obtained by the above method, it may be difficult to efficiently obtain sufficient adhesion due to the influence of moisture or the like, or it may be difficult to hold the heat insulating layer formed during heating. In such a case, there is a possibility that the desired heat-resistant protective performance by the heat-foamable coating material is not sufficiently exhibited.

  The present invention has been made in view of the above problems, and aims to efficiently obtain a laminated structure having a stable adhesive force, and to exhibit excellent heat protection properties by the laminated structure. .

  As a result of diligent research to solve the above problems, the present inventors have come up with a forming method using an adhesive layer containing a specific component when a thermally foamable coating material is attached to a substrate. The present invention has been completed.

That is, the present invention has the following characteristics.
1. A method for forming a laminated structure in which an adhesive layer and a thermally foamable coating material are laminated on a base material surface,
Providing a first adhesive layer on the substrate surface;
A step of pressure-bonding the first adhesive layer and the second adhesive layer provided on the back surface of the thermally foamable covering material;
One of the first adhesive layer and the second adhesive layer includes a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound, and an NCO / OH equivalent ratio of 10/100 to It is formed from an adhesive (M) included at 120/100, and the other is formed from an adhesive (N) including a hydroxyl group-containing synthetic resin,
A method for forming a laminated structure, wherein the first adhesive layer and the second adhesive layer are pressure-bonded before the adhesive layer formed of the adhesive (M) is cured.
2. 1. The hydroxyl group-containing synthetic resin in the adhesive (M) contains a hydroxyl group and a carboxyl group. A method for forming a laminated structure according to 1.
3. The hydroxyl group-containing synthetic resin in the adhesive (M) is a copolymer of a monomer group including a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. 1. Or 2. A method for forming a laminated structure according to 1.
4). The polyisocyanate compound is a biuret type polyisocyanate compound. ~ 3. A method for forming a laminated structure according to any one of the above.
5. A laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a substrate surface,
The adhesive layer has a first adhesive layer in contact with the substrate surface and a second adhesive layer in contact with the thermally foamable coating material,
One of the first adhesive layer and the second adhesive layer includes a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound, and an NCO / OH equivalent ratio of 10/100 to A laminated structure characterized in that it is formed of an adhesive (M) containing 120/100, and the other is formed of an adhesive (N) containing a hydroxyl group-containing synthetic resin.

  ADVANTAGE OF THE INVENTION According to this invention, the laminated structure which has the stable adhesive force can be formed efficiently. The laminated structure of the present invention is capable of maintaining excellent adhesiveness in normal times and exhibiting excellent anti-drop-off and slip-off prevention at the time of temperature rise, thereby achieving heat-resistant protection of the substrate. is there.

It is sectional drawing which shows an example of this invention laminated structure. It is a schematic diagram which shows an example of the formation method of a laminated structure. It is sectional drawing which shows an example of a laminated body.

1: Base material 2: First adhesive layer 3: Thermally foamable coating material 4: Second adhesive layer 5: Laminate 6: Release sheet

  Hereinafter, modes for carrying out the present invention will be described.

The present invention relates to a method for forming a laminated structure in which an adhesive layer and a thermally foamable coating material are laminated on a substrate surface.

[Base material]
As the base material, materials mainly constituting columns, beams, floors, walls, etc. of building structures can be mentioned. For example, H steel, steel round column, steel square column, mortar, concrete, silica Examples include calcium acid plates, gypsum boards, calcium carbonate foam plates, incombustible volcanic glassy multilayer plates, fiber reinforced cement plates, lightweight cement plates, and the like. The surface of such a substrate may be treated with a rust inhibitor, a rust preventive paint or the like.

[Adhesive layer]
The adhesive layer of the present invention is used for adhering and fixing the heat-foamable coating material to the base material, and is in contact with the first adhesive material layer in contact with the base material surface and the heat-foamable coating material. It has a 2nd adhesive material layer (FIG. 1). In the present invention, one of the first adhesive layer and the second adhesive layer is formed from the adhesive (M), and the other is formed from the adhesive (N). The adhesive material in the present invention includes an adhesive material.

・ Adhesive (M)
In the present invention, the adhesive (M) includes a liquid (I) containing a hydroxyl group-containing synthetic resin (a) (hereinafter also simply referred to as “synthetic resin (a)”) and a polyisocyanate compound (b) (II). Use liquid containing a specific ratio.

  The synthetic resin (a) of the present invention is not particularly limited as long as it is a copolymer of a monomer mixture containing a hydroxyl group-containing monomer. The hydroxyl group-containing monomer in the present invention desirably contains a primary hydroxyl group-containing monomer. Examples of the primary hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 1-methyl-4-hydroxybutyl (meth). Acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyheptyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 2-methyl-8-hydroxyoctyl (meth) acrylate , 7-methyl-8-hydroxyoctyl (meth) acrylate, 9-hydroxynonyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate and the like. In the present invention, 2-hydroxyethyl (meth) acrylate is particularly preferred. Including Embodiment is preferably used.

Further, as a hydroxyl group-containing monomer other than the above, a tertiary hydroxyl group-containing monomer may be included. Examples of such a tertiary hydroxyl group-containing monomer include 2-hydroxy-2-methylpropyl (meth) acrylate and 3-ethyl-3-hydroxyhexyl (meth) acrylate. The ratio of the hydroxyl group-containing monomer in the synthetic resin (a) is preferably 0.1 to 10% by weight (more preferably 0.5 to 8% by weight) with respect to the total amount of monomers. In such a case, better adhesion can be obtained.

In addition, the synthetic resin (a) of the present invention preferably contains a carboxyl group, and is preferably a copolymer of a monomer group containing a carboxyl group-containing monomer and the above hydroxyl group-containing monomer. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, etc. Among them, (meth) acrylic acid is particularly preferable. The ratio of the carboxyl group-containing monomer in the synthetic resin (a) is preferably 0.5 to 20% by weight (more preferably 1 to 10% by weight) with respect to the total amount of monomers. In such a case, the adhesiveness can be further improved.

  Furthermore, the synthetic resin (a) of the present invention is preferably a copolymer of a monomer group including a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. In the present invention, the acrylic acid alkyl ester and the methacrylic acid alkyl ester are collectively referred to as (meth) acrylic acid alkyl ester.

Examples of (meth) acrylic acid alkyl esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-amyl (meth) acrylate. , Isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, cyclohexyl (meta) ) Acrylate and the like. These can be used alone or in combination of two or more. In this invention, the aspect containing the (meth) acrylic acid ester whose carbon number of an alkyl group is 4-14 (preferably 4-10) is suitable, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate The aspect containing 1 or more types chosen from is used suitably. In particular, an embodiment containing at least one selected from n-butyl acrylate and 2-ethylhexyl acrylate is most preferably used. The ratio of the (meth) acrylic acid alkyl ester in the synthetic resin (a) is preferably 70% by weight or more (more preferably 80 to 99.9% by weight, still more preferably 82 to 99% by weight) based on the total amount of monomers. Particularly preferred is 85 to 95% by weight).

Moreover, another monomer can also be used as needed. Examples of other monomers include amino group-containing (meth) acrylic monomers such as dimethylaminoethyl (meth) acrylate and dimethylaminopropyl (meth) acrylate,
Amide-containing (meth) acrylic monomers such as (meth) acrylamide and ethyl (meth) acrylamide,
Nitrile group-containing (meth) acrylic monomers such as acrylonitrile,
Epoxy group-containing (meth) acrylic monomers such as glycidyl (meth) acrylate,
γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, etc. Hydrolyzable silyl group-containing vinyl monomers,
Fluorine-containing (meth) acrylic monomers such as trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate,
Fluoroolefins such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoroethylene, hexafluoropropylene,
Aromatic hydrocarbon vinyl monomers such as styrene, methylstyrene, chlorostyrene, vinyltoluene,
Sulfonic acid-containing vinyl monomers such as styrene sulfonic acid and vinyl sulfonic acid,
Chlorine-containing monomers such as vinyl chloride, vinylidene chloride, chloroprene,
Α-olefins such as ethylene, propylene and isobutylene,
Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate,
Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether,
Allyl ethers such as ethyl allyl ether and butyl allyl ether,
These can be used alone or in combination of two or more.

  The glass transition temperature of the synthetic resin (a) of the present invention is not particularly limited, but is preferably −60 ° C. or higher and 30 ° C. or lower (more preferably −55 ° C. or higher and 0 ° C. or lower, more preferably −50 ° C. or higher and −5 ° C.). The following). When the glass transition temperature is in such a region, the effect of the present invention can be stably obtained. In addition, a glass transition temperature is a value calculated | required from the calculation formula of FOX.

The synthetic resin (a) of the present invention is preferably, for example, a water-dispersed resin in which a monomer mixture containing the above monomers is copolymerized by a known method and dispersed in an aqueous medium. As the polymerization method, a known method may be employed, and soap-free emulsion polymerization, feed emulsion polymerization, seed emulsion polymerization, etc. may be employed in addition to ordinary emulsion polymerization. Moreover, an emulsifier, an initiator, a dispersant, a polymerization inhibitor, a polymerization inhibitor, a buffering agent, a chain transfer agent and the like can also be used during polymerization. A reactive emulsifier can also be used as an emulsifier.

Examples of the polyisocyanate compound (b) of the present invention include aromatic polyisocyanates such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate,
Aliphatic polyisocyanates such as tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate,
Cycloaliphatic polyisocyanates such as isophorone diisocyanate, hydrogenated xylylene diisocyanate,
Etc. As the polyisocyanate compound (b) of the present invention, for example, a polyisocyanate compound having a biuret structure, an isocyanurate structure, a urethane structure, a uretdione structure, an allophanate structure, a trimer structure, or the like can be used. In particular, in the present invention, a polyisocyanate compound having a biuret structure is preferable.

Furthermore, the polyisocyanate compound (b) is preferably a water-dispersible polyisocyanate compound. The water-dispersible polyisocyanate compound is obtained by introducing a hydrophilic compound into the polyisocyanate compound. For example, a polyisocyanate compound is added with an emulsifier, and a polyoxyalkylene group-containing compound is added to the polyisocyanate compound. Examples include those obtained by addition reaction (modification) and those obtained by addition reaction (modification) of a water-soluble resin to a polyisocyanate compound.

 In the present invention, a polyisocyanate compound obtained by addition reaction (modification) of a polyoxyalkylene group-containing compound is preferred, and its production method is not particularly limited. However, the polyisocyanate compound has an isocyanate group and a polyoxyalkylene group-containing compound. It can be easily produced by reacting the terminal hydroxyl group.

  Examples of the polyoxyalkylene group-containing compound include polyoxyethylene glycol, polyoxyethylene glycol monoalkyl ether, polyoxyethylene glycol monoaryl ether, polyoxyethylene-propylene glycol, polyoxyethylene-propylene glycol monoalkyl ether, polyoxyethylene glycol Examples thereof include oxyethylene-propylene glycol monoaryl ether, polyoxyethylene-tetramethylene glycol, polyoxyethylene-tetramethylene glycol monoalkyl ether, and polyoxyethylene-tetramethylene glycol monoaryl ether.

The adhesive (M) of the present invention comprises a liquid (I) containing the hydroxyl group-containing synthetic resin (a) and a liquid (II) containing the polyisocyanate compound (b) in an NCO / OH equivalent ratio of 10/100 to 120. / 100 (preferably 20/100 to 100/100, more preferably 40/100 to 90/100). By mixing the polyisocyanate compound (b) so as to be in the above range, good tackiness can be obtained. As a result, excellent adhesiveness can be sufficiently maintained during normal times, and excellent drop-off prevention and slip-off prevention can be achieved when the temperature rises, thereby protecting the substrate. On the other hand, when the NCO / OH equivalent ratio is outside the above range, the adhesiveness may be inferior. The NCO / OH equivalent ratio is calculated by dividing the number of equivalents of isocyanate groups (—NCO) in (b) by the number of equivalents of hydroxyl groups (—OH) in (a).

  In the adhesive (M) used in the present invention, the (I) liquid containing the synthetic resin (a) and the (II) liquid containing the polyisocyanate compound (b) may contain known additives. Good. Examples of additives include fillers, colorants, diluents, tackifiers, thickeners, dispersants, wetting agents, antifoaming agents, plasticizers, film-forming aids, antifreeze agents, and preservatives. , Antifungal agents, antialgae agents, ultraviolet absorbers, light stabilizers and the like.

・ Adhesive (N)
In the present invention, an adhesive (N) containing a hydroxyl group-containing synthetic resin (a ′) “(hereinafter also simply referred to as“ synthetic resin (a ′) ”) is used. The synthetic resin (a ′) is not particularly limited as long as it is a synthetic resin containing a hydroxyl group. For example, a copolymer of a monomer mixture containing a hydroxyl group-containing monomer is preferable.

The synthetic resin (a ′) of the present invention preferably contains a carboxyl group, and is preferably a copolymer of a monomer group containing a carboxyl group-containing monomer and the hydroxyl group-containing monomer. Furthermore, the synthetic resin (a ′) of the present invention is a copolymer of a monomer group including a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. preferable. The glass transition temperature of the synthetic resin (a ′) of the present invention is not particularly limited, but is preferably −60 ° C. or higher and 30 ° C. or lower (more preferably −55 ° C. or higher and 0 ° C. or lower, more preferably −50 ° C. or higher and −5). ° C or lower). The synthetic resin (a ′) of the present invention is preferably a water-dispersed resin. As the hydroxyl group-containing monomer, carboxyl group-containing monomer, and (meth) acrylic acid alkyl ester in the synthetic resin (a ′), those described above can be used. As the synthetic resin (a ′) of the present invention, it is preferable to use the same synthetic resin (a) as the liquid (I) of the adhesive (M). When the synthetic resin (a) and the synthetic resin (a ′) contain the same (meth) acrylic acid alkyl ester, and when they have the same composition, the adhesion can be further improved.

  Furthermore, a polyisocyanate compound can also be mixed as the adhesive material (N) of the present invention. The polyisocyanate compound is preferably mixed at an NCO / OH equivalent ratio so that the hydroxyl group of the synthetic resin (a ′) remains. Furthermore, the equivalent ratio of NCO / OH in the adhesive (N) is preferably smaller than the equivalent ratio of NCO / OH in the adhesive (M), specifically, preferably less than 40/100 (more preferably An embodiment that is less than 20/100, more preferably less than 10/100, most preferably 0/100 or more and 8/100 or less) and does not contain NCO (polyisocyanate compound) is also suitable. As a polyisocyanate compound, the thing similar to the above-mentioned thing can be used.

  The adhesive (N) used in the present invention may contain a known additive. Examples of additives include fillers, colorants, diluents, tackifiers, thickeners, dispersants, wetting agents, antifoaming agents, plasticizers, film-forming aids, antifreeze agents, and preservatives. , Antifungal agents, antialgae agents, ultraviolet absorbers, light stabilizers and the like.

[Heat-foaming coating]
As the heat-foamable coating material in the present invention, a material that forms a heat insulating layer by foaming and carbonizing when the temperature rises can be used. As a suitable heat-foamable coating material, for example, a sheet-like material containing a synthetic resin, a flame retardant, a foaming agent, a carbonizing agent and the like can be mentioned.

  As the synthetic resin in the thermally foamable coating material, a thermoplastic resin is preferably used. Examples of such thermoplastic resins include polyethylene resins, polypropylene resins, polybutene resins, polypentene resins, polystyrene resins, polycarbonate resins, acrylic resins, polyphenylene ether resins, polyamide resins, polyvinyl chloride resins, phenol resins, polyurethane resins, Chloroprene resin, polybutadiene, polyisobutylene, nitrile rubber, butyl rubber, vinyl toluene-butadiene copolymer, vinyl toluene-acrylic acid ester copolymer, vinyl toluene-methacrylic acid ester copolymer, styrene-butadiene copolymer, ethylene- Examples thereof include a methacrylic acid ester copolymer and an ethylene-vinyl acetate copolymer.

  In general, a flame retardant exhibits at least one effect such as a dehydration cooling effect, an incombustible gas generation effect, and a binder carbonization promoting effect in a fire, and has an action of preventing or suppressing combustion of a resin component. Examples of the flame retardant include tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, tri (β-chloroethyl) phosphate, tributyl phosphate, tri (dichloropropyl) phosphate, triphenyl phosphate, triphenyl Organic phosphorus such as (dibromopropyl) phosphate, chlorophosphonate, bromophosphonate, diethyl-N, N-bis (2-hydroxyethyl) aminomethyl phosphate, di (polyoxyethylene) hydroxymethyl phosphonate Compounds: Chlorinated polyphenyl, chlorinated polyethylene, diphenyl chloride, triphenyl chloride, pentachloride fatty acid ester, perchloropentacyclodecane, chlorinated naphthalene, tetrachlorophthalic anhydride, etc. Compounds; antimony compounds such as antimony trioxide and antimony pentachloride; phosphorus compounds such as phosphorus trichloride, phosphorus pentachloride, ammonium phosphate and ammonium polyphosphate; and other inorganic compounds such as zinc borate and sodium borate . These can be used alone or in combination of two or more. In the present invention, ammonium polyphosphate is particularly preferable. In the case of using ammonium polyphosphate, the dehydration cooling effect and the incombustible gas generation effect can be more effectively exhibited, so that the flame retardancy effect is high and the content of the foaming agent can be reduced.

  In general, the blowing agent generates a non-flammable gas in the event of a fire, foams the carbonized resin component and the carbonizing agent, and forms a carbonized heat insulation layer having pores. Examples of the foaming agent include nitrogen-containing compounds such as melamine and derivatives thereof, dicyandiamide and derivatives thereof, azodicarbonamide, urea and thiourea. Moreover, these can be used individually or in mixture of 2 or more types. Among these, melamine, dicyandiamide, azodicarbonamide and the like are preferable because they are excellent in generating efficiency of nonflammable gas.

  The carbonizing agent generally has a function of forming a carbonized heat insulating layer having a thickness superior in heat insulating properties by dehydrating and carbonizing itself with the carbonization of the resin component due to a fire. Examples of the carbonizing agent include starch, casein and the like, in addition to polyhydric alcohols such as dipentaerythritol, pentaerythritol, and trimethylolpropane. These can be used alone or in combination of two or more.

  The composition ratio of each component in the thermally foamable coating material is 200 parts by weight or more and 600 parts by weight or less (preferably 250 parts by weight or more and 500 parts by weight or less) of the flame retardant with respect to 100 parts by weight of the solid content of the resin component. It is preferable that they are 10 parts by weight or more and 200 parts by weight or less (preferably 30 parts by weight or more and 150 parts by weight or less).

  In addition to the above-mentioned components, the heat-foamable coating material further comprises fillers, pigments, fibers, wetting agents, plasticizers, lubricants, antiseptics, antifungal agents, anti-algae agents, antibacterial agents, thickeners, leveling agents, dispersions An agent, an antifoaming agent, a crosslinking agent, an ultraviolet absorber, an antioxidant, a catalyst and the like can also be contained.

  Among these, the filler generally has an effect of improving the strength of the carbonized heat insulating layer and increasing the heat resistance protection. The filler is not particularly limited as long as it has such an action, and the same filler as that in a known thermally foamable coating material can be used. Examples thereof include silicates such as talc; carbonates such as calcium carbonate and sodium carbonate; metal oxides such as aluminum oxide, titanium dioxide and zinc oxide; natural minerals such as clay, clay, shirasu and mica. These can be used alone or in combination of two or more. Of these fillers, titanium dioxide is more preferred.

  As the pigment, general color pigments (organic pigments / inorganic pigments) can be used. In the present invention, inorganic pigments such as bengara, yellow lead, yellow iron oxide, titanium yellow, chrome green, ultramarine blue, cobalt blue and cadmium red are particularly preferable. Further, in order to further improve the heat resistance protection, expandable graphite, unexpanded vermiculite, etc. may be blended.

  The heat-foamable coating material used in the present invention can be produced by a known method. For example, a method in which an appropriate solvent is added to a composition containing an appropriate amount of the above-described synthetic resin, flame retardant, foaming agent, carbonizing agent, etc., if necessary, poured into a mold, and demolded after drying; A method of winding the composition after being applied to a release paper by a warming coater; a method of processing the composition kneaded by a kneader into a sheet shape by an extrusion molding machine; and the composition kneaded by a kneader between a pair of rolls A method of supplying and processing into a sheet; a method of forming the composition into a pellet and then processing into a sheet with an extrusion molding machine; a calendar comprising a plurality of heat rolls of the composition kneaded by a Banbury mixer, a mixing roll, or the like And a method of rolling and processing into a sheet.

  In addition, a reinforcing sheet can be laminated on the thermally foamable covering material. Examples of the reinforcing sheet include woven fabric, non-woven fabric, mesh, and composites thereof. The reinforcing sheet is desirably laminated at least on the back side of the thermally foamable coating material. A heat-foamable coating material having such a reinforcing sheet is suitable in terms of improving effects such as adhesion, drop-off prevention, and slip-off prevention.

  The thickness of the thermally foamable coating material is not particularly limited, but is preferably 0.2 mm or more and 10 mm or less, more preferably 0.5 mm or more and 6 mm or less.

-Laminated body In this invention, the laminated body which has the said thermally foamable coating | covering material and a 2nd adhesive material layer can be used. Such a laminate can be obtained by applying an adhesive to the back surface of the thermally foamable coating material to form a second adhesive layer. Furthermore, the surface of the second adhesive layer can be covered with a release sheet. FIG. 3 is an example of a laminate, which has a second adhesive layer and a release sheet on the back surface of the thermally foamable coating material. By using such a laminated body, working efficiency can be improved.

  The releasable sheet protects the second adhesive layer during storage or transportation of the heat-foamable coating material, and can be easily peeled off from the second adhesive layer when using the heat-foamable coating material It is. As such a release sheet, a known sheet can be used, for example, a paper or film coated or impregnated with a release agent such as silicon, wax, fluorine resin, or the like, or does not contain the release agent. Examples thereof include synthetic resin films such as polypropylene and polyethylene having releasability.

Although the manufacturing method of a laminated body is not specifically limited, About the laminated body of FIG. 3, the method of apply | coating an adhesive material to one surface of a thermally foamable coating | covering material, and laminating a release sheet on it, or, Examples thereof include a method of applying an adhesive on the releasable sheet and laminating a heat-foamable coating material thereon. In such a laminate, the adhesive forming the second adhesive layer may be either the adhesive (M) or the adhesive (N), but in the present invention, the adhesive ( N) is preferably used. The laminated body using the adhesive (N) can maintain the adhesiveness even when stored for a long period of time, and can form a laminated structure having a stable adhesive force. The coating amount (solid content) of the adhesive is preferably 25 g / m ² or more and 300 g / m ² or less, and the coating thickness of the second adhesive layer is preferably 12 to 150 μm (more preferably 25 to 100 μm). ). Moreover, it is desirable that the adhesive is dried after application. However, the adhesive (M) is before curing. Desirably, the adhesive (M) is dried at room temperature (for example, 5 to 40 ° C.), and the adhesive (N) is desirably dried at room temperature or under heating (for example, 50 to 100 ° C.).

[Method for forming laminated structure]
In the laminated structure of the present invention, the first adhesive layer is provided on the substrate surface, the second adhesive layer is provided on the back surface of the thermally foamable coating material, the first adhesive layer on the substrate surface, and the thermal foaming property. It can form by crimping | bonding with the 2nd adhesive material layer of the back surface of a coating | covering material (FIG. 2). Specifically, a thermally foamable coating material (laminated body) having a second adhesive layer provided on the back surface is prepared. On the other hand, an adhesive is applied to the surface of the substrate to form a first adhesive layer, and a laminate (second adhesive layer side) is attached and pressure-bonded. When the laminate has a releasable sheet, the releasable sheet may be peeled off and the second adhesive layer may be exposed and attached.

In the present invention, one of the first adhesive layer and the second adhesive layer is formed from the adhesive (M), and the other is formed from the adhesive (N). Is. In this invention, it is preferable that a 1st adhesive material layer is an adhesive material layer (M) and a 2nd adhesive material layer is an adhesive material layer formed from an adhesive material (N). Further, the laminate is affixed before the adhesive (M) is cured. Thereby, it has excellent adhesiveness at the interface between the base material surface and the adhesive (M), and a cross-linking reaction occurs at the interface between the first adhesive layer and the second adhesive layer, so that it has a stable adhesive force. It is thought that the body can be formed efficiently.

  The term “before curing of the adhesive (M)” means that the isocyanate group (—NCO) of the polyisocyanate compound (b) contained in the adhesive (M) remains. For example, the adhesive (M) is a base material or a heat-foamable coating material, preferably within 4 hours (more preferably within 3 hours) at 25 ° C. after mixing the liquid (I) and the liquid (II). The laminated body is applied so that the first adhesive layer and the second adhesive layer are in contact with each other, preferably within 10 hours (more preferably within 10 minutes to 6 hours) after application. The state in which the isocyanate group (—NCO) remains can be confirmed with an infrared spectrophotometer (FT-IR). Moreover, when crimping | bonding, pressing tools, such as a roller and a trowel, can be used as needed.

When applying the first adhesive to the substrate, for example, a tool such as a brush, a roller, a trowel, a spatula, or a spray can be used. The coating amount (solid content) of the first adhesive is preferably 25 g / m ² or more and 300 g / m ² or less, and the coating thickness of the first adhesive layer is preferably 12 to 150 μm (more preferably 25). ~ 100 μm). The first adhesive is preferably dried after application. However, the adhesive (M) is before curing. Desirably, the adhesive (M) is dried at room temperature (for example, 5 to 40 ° C.), and the adhesive (N) is desirably dried at room temperature or under heating (for example, 50 to 100 ° C.).

  The laminated structure of the present invention can be used by laminating two or more of the above heat-foamable coating materials. When two or more thermally foamable coating materials are laminated, a thermally foamable coating material previously laminated with an adhesive or the like can also be used.

  In the present invention, a decorative layer can also be formed on the surface of the thermally foamable coating material. The decorative layer may be formed by a known method. For example, various paints can be applied, or a decorative film, a decorative sheet, or the like can be laminated. The decorative layer may be a laminate of a plurality of materials.

  Hereinafter, an Example is shown and the characteristic of this invention is clarified more.

(Synthetic resin emulsion 1-6)
The reaction vessel was charged with deionized water, and the temperature was raised to 80 ° C. while stirring and nitrogen substitution. Separately prepared emulsion monomers (in which an aqueous solution obtained by dissolving sodium dodecyl sulfate in deionized water was emulsified and dispersed in the monomer shown in Table 1), an initiator aqueous solution (ammonium persulfate was dissolved in deionized water). Aqueous solution) was continuously added dropwise over 3 hours.
After completion of dropping, the mixture was aged for 3 hours, cooled to 30 ° C., and then added with aqueous ammonia to adjust the pH to 8 to obtain synthetic resin emulsions 1 to 5. The resin solid content of these synthetic resin emulsions 1 to 5 was 50% by weight.

(Manufacture of adhesives 1-15)
4 parts by weight of additives (pigments, wetting agents, thickeners, antifoaming agents, preservatives, etc.) were blended with 100 parts by weight of the synthetic resin emulsion to prepare a liquid (I). Subsequently, the (II) liquid which consists of a polyisocyanate compound was prepared, and it mixed with the said (I) liquid, and manufactured the adhesives 1-15. Adhesives 1 to 15 were prepared by adding an appropriate amount of water to a solid content of 50% by weight. Table 2 shows the synthetic resin emulsion, polyisocyanate compound, and NCO / OH equivalent ratio used for each adhesive.
Moreover, the following was used as a polyisocyanate compound.
Polyisocyanate compound 1: Biuret type water-dispersed isocyanate (solid content: 80% by weight, NCO%: 13.4% by weight)
Polyisocyanate compound 2: isocyanurate type water-dispersed isocyanate (solid content: 100% by weight, NCO%: 14.3% by weight)

(Manufacture of thermal foaming covering material 1)
A raw material mixture containing 100 parts by weight of an acrylic resin, 75 parts by weight of melamine, 75 parts by weight of dipentaerythritol, 370 parts by weight of ammonium polyphosphate and 105 parts by weight of titanium oxide is sufficiently kneaded using a kneader, and then sheeted by an extruder. The heat-foamable covering material 1 having a film thickness of 1 mm was produced.

(Manufacture of heat-foamable covering material 2)
A raw material mixture containing 100 parts by weight of an ethylene-vinyl acetate resin, 75 parts by weight of melamine, 75 parts by weight of dipentaerythritol, 370 parts by weight of ammonium polyphosphate and 105 parts by weight of titanium oxide is sufficiently kneaded using a kneader and then extruded. It processed into the sheet form with the machine, and produced the heat-foamable coating material 2 with a film thickness of 1 mm.

Example 1
<Adhesion evaluation>
Adhesive 1 is applied at 100 g / m ^{2 on} one side (25 mm × 25 mm) of thermal foaming coating 1 (25 mm × 50 mm) and dried at 25 ° C. for 3 hours or 24 hours on the back side of the thermal foaming coating material. The laminated body 1 which provided the 2nd adhesive material layer was manufactured.
On the other hand, 100 g / m ² of the adhesive 2 was applied to one side of a steel plate (150 mm × 70 mm × 1.6 mm) to form a first adhesive layer. Note that both the adhesive 1 and the adhesive 2 were used within 3 hours after mixing the liquids (I) and (II).
Next, the first adhesive layer of the steel plate and the second adhesive of the laminate 1 are cured before the first adhesive layer of the steel plate (the surface to which the adhesive 2 is applied) (after drying, dried at 25 ° C. for 2 hours). The layers were pressure-bonded and bonded together to obtain a specimen A. (In addition, this test body is an aspect in which the half surface of the heat-foamable coating material 1 is not bonded to the steel plate (has a non-bonded portion).)
In the adhesion test, the test body A is placed horizontally so that the heat-foamable coating material 1 is on the lower side, the non-adhesive portion of the heat-foamable coating material 1 is bent at 90 °, and the heat-foamable coating material A weight of 200 g was hung at the tip of one bent portion, and the time until the thermally foamable coating material 1 was peeled off from the steel plate was measured. Evaluation was performed in the following five stages. The results are shown in Table 3.
A: 2 hours or more B: 1 hour or more and less than 2 hours C: 30 minutes or more and less than 1 hour D: 15 minutes or more and less than 30 minutes E: Less than 15 minutes

<Water resistance evaluation>
Adhesive 1 was applied to 100 g / m ² on the entire surface of one side of thermal foamable covering material 1 (150 mm × 70 mm) and dried at 25 ° C. for 3 hours to provide a second adhesive layer on the back surface of the thermal foamable covering material A laminate 2 was produced.
On the other hand, 100 g / m ² of the adhesive 2 was applied to one side of a steel plate (150 mm × 70 mm × 1.6 mm) to form a first adhesive layer. Note that both the adhesive 1 and the adhesive 2 were used within 3 hours after mixing the liquids (I) and (II).
Next, the first adhesive layer of the steel plate and the second adhesive of the laminate 2 before curing of the first adhesive layer of the steel plate (the surface to which the adhesive 2 is applied) (after drying, drying at 25 ° C. for 2 hours) The layers were pressure bonded together.
Further, a decorative layer (urethane resin paint layer) was laminated on the surface of the heat-foamable coating material 1 to obtain a specimen B.
The obtained test body B was immersed in 25 degreeC water for 4 days (water resistance evaluation 1), and the external appearance of the laminated body was evaluated. Evaluation criteria were evaluated in the following four stages.
Further, for the water resistance evaluation 1 that was a good result (◎), the test specimen B was immersed in water at 25 ° C. for 7 days (water resistance evaluation 2), and the same evaluation was performed. The results are shown in Table 3.
◎: No change at all ○: Almost no change △: Some peeling occurred ×: Some peeling occurred

<Falling prevention evaluation>
Adhesive 1 was applied to 100 g / m ² on the entire surface of one side of thermal foamable covering material 1 (70 mm × 70 mm) and dried at 25 ° C. for 3 hours to provide a second adhesive layer on the back surface of the thermally foamable covering material The laminated body 3 was manufactured.
On the other hand, 100 g / m ² of the adhesive 2 was applied to one side of a steel plate (150 mm × 70 mm × 1.6 mm) to form a first adhesive layer. Note that both the adhesive 1 and the adhesive 2 were used within 3 hours after mixing the liquids (I) and (II).
Next, the first adhesive layer of the steel plate and the second adhesive of the laminate 3 before curing of the first adhesive layer of the steel plate (surface where the adhesive 2 is applied) (after drying, drying at 25 ° C. for 2 hours) The layers were pressure bonded and bonded together to obtain a test body C.
In the drop-off prevention test, the heat-foamable covering material 1 is installed horizontally so that it is on the lower side, a heater (heater temperature 680 ° C.) is installed at the position 25 mm above the test body, and the test body is heated by the heater. Then, the interface temperature between the steel plate and the heat-foamable coating material 1 when the heat-foamable coating material 1 dropped out of the steel plate was measured. Evaluation was performed in the following four stages. The results are shown in Table 3.
◎: Drop-off temperature 320 ° C or higher ○: Drop-off temperature 300 ° C or higher and lower than 320 ° C △: Drop-off temperature 280 or higher and lower than 300 ° C ×: Drop-off temperature 280 ° C or lower

(Examples 2 to 17, Comparative Examples 1 and 2)
In Examples 2 to 17 and Comparative Examples 1 and 2, the type of adhesive used and the type of thermally foamable coating used were as shown in Table 3. Other than that, by the same method as Example 1, the test body was produced and each test was done. The results are shown in Table 3.

Claims (5)

A method for forming a laminated structure in which an adhesive layer and a thermally foamable coating material are laminated on a base material surface,
Providing a first adhesive layer on the substrate surface;
A step of pressure-bonding the first adhesive layer and the second adhesive layer provided on the back surface of the thermally foamable covering material;
One of the first adhesive layer and the second adhesive layer includes a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound, and an NCO / OH equivalent ratio of 10/100 to It is formed from an adhesive (M) included at 120/100, and the other is formed from an adhesive (N) including a hydroxyl group-containing synthetic resin,
A method for forming a laminated structure, wherein the first adhesive layer and the second adhesive layer are pressure-bonded before the adhesive layer formed of the adhesive (M) is cured.   The method for forming a laminated structure according to claim 1, wherein the hydroxyl group-containing synthetic resin in the adhesive (M) contains a hydroxyl group and a carboxyl group.   The hydroxyl group-containing synthetic resin in the adhesive (M) is a copolymer of a monomer group including a (meth) acrylic acid alkyl ester, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer. The method for forming a laminated structure according to claim 1 or 2.   The method for forming a laminated structure according to any one of claims 1 to 3, wherein the polyisocyanate compound is a biuret type polyisocyanate compound. A laminated structure in which an adhesive layer and a heat-foamable coating material are laminated on a substrate surface,
The adhesive layer has a first adhesive layer in contact with the substrate surface and a second adhesive layer in contact with the thermally foamable coating material,
One of the first adhesive layer and the second adhesive layer includes a liquid (I) containing a hydroxyl group-containing synthetic resin and a liquid (II) containing a polyisocyanate compound, and an NCO / OH equivalent ratio of 10/100 to A laminated structure characterized in that it is formed of an adhesive (M) containing 120/100, and the other is formed of an adhesive (N) containing a hydroxyl group-containing synthetic resin.

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