JP6075858B2 - Adhesive, laminated sheet using the same, and laminated structure - Google Patents

Description

  The present invention relates to an adhesive that can be applied to a heat-foamable sheet, a laminated sheet in which the adhesive is laminated, and a laminated structure that foams and carbonizes to protect a substrate when the temperature rises due to a fire or the like.

Conventionally, in a building structure, a main structure such as a pillar, a beam, a floor, or a wall is required to have a heat resistant structure for the purpose of protecting the building from a fire.
As one method for applying a heat resistant structure, there is a method in which a thermally foamable sheet is attached to a base material such as a main structure via an adhesive. (For example, Patent Document 1 etc.)
The heat-foamable sheet 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 sheet is characterized in that it can be applied relatively easily simply by sticking with an adhesive or the like, and an extra space is not required and the thickness can be made uniform.

JP-A-8-60763

  However, when a heat-foamable sheet is attached to a substrate via an adhesive, it may be difficult to retain the heat-insulating layer formed by heat, and it is difficult to maintain the desired heat-resistant protective performance. was there.

  As a result of intensive studies to solve the above problems, the present inventors have used a synthetic resin having a specific acid value and a specific hydroxyl value as an adhesive, thereby providing excellent adhesiveness in normal times. The present invention was completed by discovering that sufficient heat-resistant protection can be obtained by exhibiting excellent drop-off prevention and slip-off prevention at the time of temperature rise.

That is, the present invention has the following characteristics.
1. An adhesive applied to a thermally foamable sheet,
The adhesive is an acrylic adhesive;
Acrylic resin contained in the acrylic adhesive is,
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
An adhesive material characterized by satisfying any of the following conditions.
2. A laminate sheet in which a releasable sheet, an adhesive, and a thermally foamable sheet are laminated,
The thermally foamable sheet contains a synthetic resin, a flame retardant, a foaming agent, and a carbonizing agent,
The adhesive is an acrylic adhesive;
An acrylic resin contained in the acrylic adhesive is
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
A laminated sheet characterized by satisfying any of the following conditions .
3. A laminated structure in which an adhesive and a heat-foamable sheet are laminated to the base material surface side having heat resistance protection,
The thermally foamable sheet contains a synthetic resin, a flame retardant, a foaming agent, and a carbonizing agent,
The adhesive is an acrylic adhesive;
An acrylic resin contained in the acrylic adhesive is
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
A laminated structure satisfying any of the following conditions:

  The adhesive of the present invention contains a synthetic resin having a specific acid value and hydroxyl value, and is used for laminating a heat-foamable fireproof sheet. It has excellent adhesiveness during normal times, and is excellent when the temperature rises. Exhibits falling-off prevention and slip-off prevention, and sufficient heat-resistant protection is obtained.

It is sectional drawing which shows an example of this invention laminated sheet. It is a perspective view which shows an example of this invention laminated structure. It is an expanded sectional view of the A part of FIG.

1. 1. Thermally foamable sheet 2. Adhesive material Release sheet 4. Base material

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

The adhesive of the present invention is applied to the lamination of heat foamable sheets.
For example, it can be used as a laminate in which an adhesive and a heat-foamable sheet are laminated in order from the side of the substrate surface that has heat resistance protection.

In general, those containing a synthetic resin containing a cationic functional group are advantageous for a substrate surface that requires heat-resistant protection. This is overwhelmingly the case where the surface of the substrate has a negative charge, and the negative charge and the cation are easily connected electrically, which is advantageous for adhesion.
However, in the case of sticking a heat-foamable sheet as in the present invention, a synthetic resin having a specific acid value and hydroxyl value is advantageous. And found to be effective in preventing slippage.

That is, the present invention is characterized by using either the following first adhesive material or second adhesive material.
The first adhesive has an acid value of 30 KOH mg / g or more and 100 KOH mg / g or less (preferably 35 KOH mg / g or more and 90 KOH mg / g or less), and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g (preferably 25 KOH mg / g or more and 60 KOH mg or less). / G or less).
The second adhesive has an acid value of 10 KOH mg / g or more and less than 30 KOH mg / g (preferably 15 KOH mg / g or more and 25 KOH mg / g or less), and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less (preferably 80 KOH mg / g or more and 130 KOH mg or less). / G or less).
By using such an adhesive, it is possible to have excellent adhesiveness as well as excellent drop-off prevention and slip-off prevention.
When the acid value is too small or the acid value is too large, the adhesiveness is inferior, and excellent anti-drop-off and slip-off prevention properties cannot be obtained. On the other hand, when the hydroxyl value is too small or the hydroxyl value is too large, the drop-off prevention property and the slip-off prevention property are not improved.
In addition, the acid value said here is a value (KOHmg / g) represented by the number of mg of potassium hydroxide equimolar to the acid group contained in 1 g of solid content, and the hydroxyl value is 1 g of solid content. It is a value (KOHmg / g) represented by the number of mg of potassium hydroxide equimolar to the hydroxyl group contained.
The glass transition temperature of the synthetic resin is not particularly limited, but is preferably about −60 ° C. or higher and 30 ° C. or lower, more preferably −40 ° C. or higher and 0 ° C. or lower, and further preferably −35 ° C. or higher and −5 ° C. or lower. When the glass transition temperature is in such a region, it has excellent adhesiveness, and can have excellent drop-off preventing property and slip-off preventing property. In addition, a glass transition temperature is a value calculated | required from the calculation formula of FOX.

The synthetic resin in such an adhesive is not particularly limited as long as it has the above acid value and hydroxyl value, but is an aqueous dispersion type such as an acrylic resin, a urethane resin, an epoxy resin, a silicone resin, an alkyd resin, and a melamine resin. , Water soluble type, solvent type, solventless type and the like. In the present invention, a water dispersion type of acrylic resin is particularly suitable.
Examples of a method for obtaining a specific acid value and a specific hydroxyl value include, for example, one or more monomers selected from carboxyl group-containing monomers, and one or more monomers selected from hydroxyl group-containing monomers. And a monomer mixture containing other monomers can be obtained by copolymerization by a known method.
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 carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, and the like. In the present invention, it is particularly preferable to include (meth) acrylic acid.
In the present invention, there is no particular limitation as long as the carboxyl group-containing monomer is mixed with the monomer mixture so that the acid value stipulated in the present invention is obtained, but the mixing amount of the carboxyl group-containing monomer is the first adhesive. Then, it is preferably 5% by weight or more and 18% by weight or less, and more preferably 5.5% by weight or more and 15% by weight or less with respect to the total amount of monomers. In the second adhesive, it is preferably 1% by weight or more and less than 5% by weight, and more preferably 2% by weight or more and 4% by weight or less based on the total amount of monomers.

Examples of the hydroxyl group-containing monomer include primary hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- Secondary hydroxyl group-containing monomers such as hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate, tertiary hydroxyl group-containing monomers such as 2-hydroxy-2-methylpropyl (meth) acrylate, Glycerol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (meth) acrylate, caprolactone-modified (meth) acrylic acid ester, N-hydroxyethylacrylamide and the like.
In the present invention, in particular, the hydroxyl group-containing monomer includes a primary hydroxyl group-containing monomer and / or a tertiary hydroxyl group-containing monomer, and further includes a tertiary hydroxyl group-containing monomer and a primary hydroxyl group. Including a group-containing monomer is preferable in terms of improving adhesiveness.
In the present invention, there is no particular limitation as long as the hydroxyl group-containing monomer is mixed with the monomer mixture so as to have the hydroxyl value specified in the present invention, but the mixing amount of the hydroxyl group-containing monomer is the first adhesive. Then, it is preferably 5% by weight or more and less than 16% by weight, and more preferably 5.5% by weight or more and 15% by weight or less based on the total amount of the monomers. In the second adhesive, it is preferably 16% by weight or more and 35% by weight or less, more preferably 17% by weight or more and 32% by weight or less, based on the total amount of monomers.

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl ( Alkyl group-containing (meth) acrylic monomers such as (meth) acrylate,
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,
Among them, one or more of them can be used.

  The adhesive used in the present invention is not particularly limited as long as it contains the above synthetic resin, but other known additives may be included. Although it does not specifically limit as an additive, A filler, a coloring agent, a diluent, an adhesive imparting agent, a thickener, a dispersing agent, an antifoamer, an antiseptic, an antifungal agent, an antialgae, an ultraviolet absorber And light stabilizers.

  Examples of the thermally foamable sheet of the present invention include those containing a resin component, a flame retardant, a foaming agent, and a carbonizing agent.

  The resin component is not particularly limited, but a thermoplastic resin is preferably used. Examples of thermoplastic resins include polyethylene resins, polypropylene resins, polybutene resins, polypentene resins, polystyrene resins, polycarbonate resins, acrylic resins, polyphenylene ether resins, polyamide resins, and polyvinyl chloride resins. , Phenolic resin, polyurethane resin, chloroprene resin, polybutadiene, polyisobutylene, nitrile rubber, butyl rubber, vinyltoluene-butadiene copolymer, vinyltoluene-acrylic acid ester copolymer, vinyltoluene-methacrylic acid ester copolymer Styrene-butadiene copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, or two kinds of monomers constituting these copolymers and (meth) acrylic monomer, etc. It is possible to use a resin such as a copolymer. As the (meth) acrylic monomer constituting these copolymers, for example, one or more of the above monomers can be used.

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. When ammonium polyphosphate is used, the effects of dehydration and cooling and the incombustible gas generation effect can be more effectively exhibited, so the flame retardancy is high and the content of the blowing agent can be reduced. Is advantageous over other flame retardants.

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.
In the present invention, by including such a nitrogen-containing compound, an excellent carbonized heat insulating layer can be formed, and it has excellent adhesiveness with the adhesive of the present invention, and has excellent anti-drop-off and slip-off prevention properties. Can be obtained.
As content of a nitrogen-containing compound, it is preferable that the nitrogen-containing compound content rate in a thermally foamable sheet is 1 to 30 weight% (further 3 to 25 weight%). If the content of the nitrogen-containing compound is too small or too large, it may be difficult to obtain excellent adhesiveness, excellent drop-off preventing property, and slip-off preventing property.

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 blending ratio of each component of the heat-foamable sheet is not particularly limited, but the flame retardant 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) with respect to 100 parts by weight of the solid content of the resin component. The blowing agent is about 10 to 200 parts by weight (preferably 20 to 150 parts by weight), and the carbonizing agent is about 10 to 200 parts by weight (preferably 30 to 150 parts by weight). Is preferred.

The thermally foamable sheet of the present invention can further contain a filler, pigment, fiber and the like.
The filler generally has an effect of improving the strength of the carbonized heat insulating layer and enhancing the heat protection property. 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 sheet 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 thermally foamable sheet 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 in which an appropriate amount of the above-mentioned synthetic resin, flame retardant, foaming agent, carbonizing agent, etc. is blended, 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.

  A reinforcing sheet can be laminated on the thermally foamable sheet. Examples of the reinforcing sheet include woven or non-woven fabric, mesh, and the like. By laminating such a reinforcing sheet, it is possible to improve adhesion and adhesion, and to further prevent the falling off prevention and the slipping off prevention.

  The thickness of the thermally foamable sheet of the present invention 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.

  The laminated sheet of the present invention (FIG. 1) is obtained by forming an adhesive layer of the above-mentioned adhesive on one surface of a thermally foamable sheet and covering the surface with a release sheet. By setting it as such a laminated sheet, a thermally foamable sheet can be easily affixed and work efficiency improves.

The release sheet protects the adhesive layer during storage or transportation of the laminated sheet of the present invention, and can be easily peeled off from the adhesive layer when the laminated sheet is used. Such a releasable sheet is not particularly limited, and a known sheet can be used. For example, a paper or film coated or impregnated with a release agent such as silicon, wax, or fluorine resin, or a synthetic resin film such as polypropylene or polyethylene that does not contain the release agent and has release properties per se.

The production method of the laminated sheet is not particularly limited, but a method of applying an adhesive on one surface of the thermally foamable sheet and laminating the release sheet thereon, or an adhesive on the release sheet. Examples thereof include a method of applying and laminating a thermally foamable sheet thereon. In the above method, when an adhesive is applied and each sheet is laminated thereon, the sheets may be laminated as they are (undried) or may be laminated after being dried.
The amount of the adhesive is not particularly limited, smeared amount as long (solid content) of 25 g / ^{m 2} or more 300 g / ^{m 2} of the order or less.

  The laminated structure (FIGS. 2 and 3) of the present invention can be obtained by sticking a thermally foamable sheet to a base material via an adhesive. 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 substrate surface may be treated with a rust inhibitor or a rust inhibitor paint.

  In this invention, the laminated structure which has heat-resistant protection property can be obtained by laminating | stacking a thermally foamable sheet on such a base material through the said adhesive material.

The bonding method is not particularly limited, but a method of applying an adhesive on the substrate side and / or the heat-foamable sheet side and bonding it as it is, or a method of applying an adhesive on the substrate side and / or the heat-foamable sheet side. For example, there may be mentioned a method in which the adhesive is dried and then bonded by pressure bonding. The amount of the adhesive is not particularly limited, smeared amount as long (solid content) of 25 g / ^{m 2} or more 300 g / ^{m 2} of the order or less. In addition, when using a release sheet, an adhesive, and a laminated sheet laminated with a heat-foamable sheet, the release sheet may be peeled off and adhered to the substrate, and pressure bonding or the like is performed as necessary. You can also.

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

(Manufacture of adhesives)
The following synthetic resin emulsions 1 to 30 were used as adhesives 1 to 30, respectively.
(Production of synthetic resin emulsion 1)
A reaction vessel was charged with 104.4 parts by weight of deionized water, and the temperature was raised to 80 ° C. while stirring and purging with nitrogen. To this, separately prepared emulsion monomer (89.6 parts by weight of butyl acrylate, 5.2 parts by weight of methacrylic acid, 2 parts by weight of an aqueous solution in which 3.1 parts by weight of sodium dodecyl sulfate was dissolved in 42.2 parts by weight of deionized water) -Emulsified and dispersed with 5.2 parts by weight of hydroxyethyl methacrylate) and an aqueous initiator solution (aqueous solution in which 0.4 parts by weight of ammonium persulfate was dissolved in 7.6 parts by weight of deionized water), each over 3 hours. (See Table 1).
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 a synthetic resin emulsion 1. The resin solid content of the synthetic resin emulsion 1 was 40% by weight, Tg was −36 ° C., the acid value was 33 KOH mg / g, and the hydroxyl value was 22 KOH mg / g.
(Production of synthetic resin emulsions 2 to 30)
Synthetic resin emulsions 2 to 30 were produced by the same production method as synthetic resin emulsion 1 except for the monomer composition shown in Table 1.

(Manufacture of thermally foamable sheet 1)
As shown in Table 2, a raw material mixture containing 100 parts by weight of 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 was sufficiently kneaded using a kneader. Then, it processed into the sheet form with the extrusion molding machine, and produced the thermally foamable sheet 1 with a film thickness of 1 mm.
(Manufacture of thermally foamable sheets 2-6)
The thermally foamable sheets 2 to 6 were produced in the same manner as the thermally foamable sheet 1 except for the formulation shown in Table 2.

(Experimental example 1)
1. The adhesive 1 100 g / ^{m 2} coated on one side of half of the adhesion test heat foamable sheet 1 (25mm × 50mm) (25mm × 25mm), and dried for 3 hours at 23 ° C.. Similarly, 100 g / m ² of adhesive 1 was applied to one side of a steel plate (150 mm × 70 mm × 1.6 mm) and dried at 23 ° C. for 3 hours.
Next, the adhesive-coated surface of the thermally foamable sheet 1 and the adhesive-coated surface of the steel plate were bonded together by pressure bonding to obtain a test body. (In addition, this test body is an aspect in which the half surface of the thermally foamable sheet 1 is not bonded to the steel plate (has a non-bonded portion).)
In the adhesion test, the test specimen was placed horizontally so that the heat-foamable sheet 1 was on the lower side, the non-adhesive portion of the heat-foamable sheet 1 was bent at 90 °, and the heat-foamable sheet 1 was bent. A weight of 200 g was suspended at the tip, and the time until the thermally foamable sheet 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

2. Dropout test 1
100 g / m ² of the adhesive 1 was applied to the entire surface of one side of the thermally foamable sheet 1 (70 mm × 70 mm) and dried at 23 ° C. for 3 hours. Similarly, 100 g / m ² of adhesive 1 was applied to one side of a steel plate (150 mm × 70 mm × 1.6 mm) and dried at 23 ° C. for 3 hours.
Next, the adhesive-coated surface of the thermally foamable sheet 1 and the adhesive-coated surface of the steel plate were bonded together by pressure bonding to obtain a test body.
In the drop-off test 1, the heat-foamable sheet 1 is installed horizontally so that it is on the lower side, a heater (heater temperature 680 ° C.) is installed at a position 25 mm above the test body, and the test body is heated with the heater. The interface temperature between the steel plate and the heat-foamable sheet 1 when the heat-foamable sheet 1 dropped from 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

3. Dropout test 2
A specimen was obtained in the same manner as in the dropout test 1.
In the drop-off test 2, the test body was installed vertically, and a propane gas burner was installed at a position 50 cm laterally from the test body (one surface side of the thermally foamable sheet).
In the drop-off test 2, the specimen was heated for 1 minute with a propane gas burner, and the state of the thermally foamable sheet 1 was evaluated. Evaluation was performed in the following three stages. The results are shown in Table 3.
○: Not dropped △: Partially dropped ×: Dropped

(Experimental Examples 2-35)
Except for the combination of the adhesive and the heat-foamable sheet shown in Table 3, a test specimen was prepared in the same manner as in Experimental Example 1, and an adhesion test, a drop test 1 and a drop test 2 were performed. The evaluation is shown in Table 3.

(Manufacture of laminated sheet 1-1)
100 g / m ² of the adhesive material 3 was applied to one half (25 mm × 25 mm) of one side of the thermally foamable sheet 6 (25 mm × 50 mm) and dried at 23 ° C. for 3 hours. On the adhesive layer, release paper (25 mm × 50 mm) was laminated to obtain a laminated sheet 1-1.

(Manufacture of laminated sheet 1-2)
100 g / m ² of the adhesive 3 was applied to the entire surface of one side of the heat-foamable sheet 6 (70 mm × 70 mm) and dried at 23 ° C. for 3 hours. On the adhesive layer, release paper (70 mm × 70 mm) was laminated to obtain a laminated sheet 1-2.

(Example 36)
Adhesive 3 was applied to 100 g / m ² on one side of a steel plate (150 mm × 70 mm × 1.6 mm) and dried at 23 ° C. for 3 hours.
Next, the release sheet of the laminated sheet 1-1 or the laminated sheet 1-2 was peeled off, and the adhesive layer and the adhesive-coated surface of the steel plate were bonded by pressure bonding to obtain each test specimen. In the same manner as in Experimental Example 1, an adhesion test (laminated sheet 1-1), a dropout test 1, and a dropout test 2 (laminated sheet 1-2) were performed. The results are shown in Table 3.

(Experimental example 37)
Laminated sheets 2-1 and 2-2 were obtained in the same manner as the laminated sheets 1-1 and 1-2 except for the combination of the adhesive and the thermally foamable sheet shown in Table 3. Next, a test body was prepared in the same manner as in Experimental Example 36, and an adhesion test, a drop test 1 and a drop test 2 were performed. The evaluation is shown in Table 3.

Claims (3)

An adhesive applied to a thermally foamable sheet,
The adhesive is an acrylic adhesive;
Acrylic resin contained in the acrylic adhesive is,
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
An adhesive material characterized by satisfying any of the following conditions. A laminate sheet in which a releasable sheet, an adhesive, and a thermally foamable sheet are laminated,
The thermally foamable sheet contains a synthetic resin, a flame retardant, a foaming agent, and a carbonizing agent,
The adhesive is an acrylic adhesive;
An acrylic resin contained in the acrylic adhesive is
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
A laminated sheet characterized by satisfying any of the following conditions . A laminated structure in which an adhesive and a heat-foamable sheet are laminated to the base material surface side having heat resistance protection,
The thermally foamable sheet contains a synthetic resin, a flame retardant, a foaming agent, and a carbonizing agent,
The adhesive is an acrylic adhesive;
An acrylic resin contained in the acrylic adhesive is
An acid value of 30 KOH mg / g or more and 100 KOH mg / g or less and a hydroxyl value of 20 KOH mg / g or more and less than 70 KOH mg / g, or
An acid value of 10 KOH mg / g or more and less than 30 KOH mg / g and a hydroxyl value of 70 KOH mg / g or more and 150 KOH mg / g or less,
A laminated structure satisfying any of the following conditions:

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