Reinforcing materials and reinforcing structures

Abstract

The reinforcing material has a resin layer and a constraint layer. The resin layer contains a resin component and a foaming agent, and the resin layer can be a reinforcing layer that reinforces an object to be reinforced. The constraint layer is disposed on the resin layer. The reinforcing layer contains a matrix resin that is cured from the resin component, and a plurality of bubbles that are generated by foaming of the foaming agent. A proportion of a total area of the plurality of bubbles in a cross section of the reinforcing layer is 83% or more, and an elastic modulus of the matrix resin of the reinforcing layer is 1.4 GPa or more.

Description

Technical Field

[0001] This invention relates to reinforcing materials and reinforcing structures. Background Technology

[0002] Previously, reinforcing materials (reinforcing sheets) having a restraining layer and a reinforcing layer were known. The reinforcing layer contains at least styrene-butadiene rubber, epoxy resin, and a foaming agent (for example, see Patent Document 1).

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2005-41210 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] In the reinforcing material described in the aforementioned Patent Document 1, it is required to further improve the reinforcing performance.

[0008] Therefore, the present invention provides a reinforcing material and a reinforcing structure that can achieve improved enhancement performance.

[0009] Methods for solving problems

[0010] The present invention [1] includes a reinforcing material for reinforcing a reinforced object, the reinforcing material comprising: a resin layer containing a resin component and a foaming agent, which can serve as a reinforcing layer for reinforcing the reinforced object; and a restraining layer disposed on the resin layer, the reinforcing layer containing a base resin formed by curing the resin component and a plurality of bubbles generated by foaming with the foaming agent, wherein the proportion of the total area of ​​the plurality of bubbles in the cross section of the reinforcing layer is 83% or more, and the elastic modulus of the base resin of the reinforcing layer is 1.4 GPa or more.

[0011] The present invention [2] includes the reinforcing material of [1] above, wherein the resin component contains a thermosetting resin and a rubber, and the proportion of the thermosetting resin is more than 100 parts by mass relative to 100 parts by mass of the rubber.

[0012] The present invention [3] includes the reinforcing material of [2] above, wherein the thermosetting resin contains a flexible epoxy resin and an epoxy resin other than the flexible epoxy resin, and the proportion of the flexible epoxy resin in the thermosetting resin is 10% by mass or more and less than 50% by mass.

[0013] The present invention [4] includes the reinforcing material of [3] above, wherein the rubber contains acrylonitrile-butadiene rubber and the proportion of acrylonitrile-butadiene rubber is 60 parts by mass or more relative to 100 parts by mass of the flexible epoxy resin.

[0014] [5] of the present invention includes a reinforcement structure comprising: a reinforcement object; and a reinforcement member having the reinforcement layer and the constraint layer described in [1] above.

[0015] Invention Effects

[0016] The reinforcing material and reinforcing structure according to the present invention can improve the reinforcing performance. Attached Figure Description

[0017] Figure 1 This is a cross-sectional view of the reinforcing material as one embodiment of the present invention.

[0018] Figure 2 is used for illustration. Figure 1 The diagram illustrates a reinforcement method where the reinforcing material is used to reinforce the object. Figure 2A This refers to the process of attaching reinforcing material to the object being reinforced. Figure 2B This refers to the curing process that involves foaming and curing a reinforced object to which the reinforcing material has been applied.

[0019] Figure 3 yes Figure 2B An enlarged view of the cross-section of the reinforcing layer shown. Detailed Implementation

[0020] 1. Reinforcing Material 1

[0021] Figure 1 The reinforcing material 1 shown is used for reinforcing the object P (refer to) Figure 2B The component being reinforced (P) can be made of metal sheets such as aluminum, stainless steel, iron, copper, zinc, and brass. It should be noted that these metal sheets can be used in transportation equipment such as automobiles, railway vehicles, ships, and aircraft, as well as in buildings. The preferred reinforcing material 1 is a reinforcing sheet. The reinforcing material 1 has a resin layer 2 and a restraining layer 3. The reinforcing material 1 may, if necessary, have a release sheet 4.

[0022] (1) Resin layer 2

[0023] The resin layer 2 has a specified thickness. In the thickness direction of the resin layer 2, the resin layer 2 has a first surface S1 and a second surface S2.

[0024] The thickness of the resin layer 2 is, for example, 0.1 mm or more, preferably 0.2 mm or more, for example, 10 mm or less, and preferably 5 mm or less.

[0025] With the reinforcing material 1 attached to the reinforced object P, the resin layer 2 foams and cures, thereby the resin layer 2 becomes the reinforcing layer 5 (see reference). Figure 2B The reinforcing layer 5 will be explained later. Resin layer 2 contains resin components and a foaming agent. Resin layer 2 may contain vulcanizing agents, vulcanization accelerators, thermosetting resin curing agents, and other additives as needed.

[0026] (1-1) Resin composition

[0027] The resin composition preferably contains thermosetting resin and rubber. The resin composition may contain tackifiers as needed.

[0028] The viscosity of the resin component at the decomposition temperature of the foaming agent is, for example, 500 Pa·s or more, preferably 1000 Pa·s or more, for example, 4000 Pa·s or less, and preferably 3500 Pa·s or less. The decomposition temperature of the foaming agent will be explained later.

[0029] (1-1-1) Thermosetting resins

[0030] Thermosetting resins preferably contain flexible epoxy resins and epoxy resins other than flexible epoxy resins. More preferably, thermosetting resins consist only of flexible epoxy resins and epoxy resins other than flexible epoxy resins. In the following description, epoxy resins other than flexible epoxy resins are referred to as other epoxy resins.

[0031] Flexible epoxy resins exhibit higher flexibility than bisphenol A type epoxy resins. Preferably, the flexible epoxy resin, after curing, exhibits higher flexibility than the aromatic epoxy resins described later. More preferably, the flexible epoxy resin, after curing, exhibits higher flexibility than other epoxy resins described later.

[0032] Flexible epoxy resins do not contain cyclic structures in their main chain, or contain fewer cyclic structures than other epoxy resins described later. Examples of cyclic structures include aromatic rings, aliphatic hydrocarbon rings, and nitrogen-containing rings. Preferably, flexible epoxy resins have a flexible component in their main chain. Examples of flexible components include long-chain aliphatic hydrocarbon components, rubber components, and polyol components. Examples of long-chain aliphatic hydrocarbon components include alkylene groups derived from dimer acids (dimeric acids) of long-chain unsaturated fatty acids. Examples of long-chain unsaturated fatty acids include unsaturated fatty acids with 12 or more carbon atoms. Examples of unsaturated fatty acids with 12 or more carbon atoms include linoleic acid.

[0033] The epoxy equivalent of the flexible epoxy resin is, for example, 220 g / eq or more, preferably 300 g / eq or more, and more preferably 500 g / eq or more. If the epoxy equivalent is at or above the aforementioned lower limit, the reinforcing member 11 (see reference) can be improved. Figure 2B The flexibility of the reinforcing member 11 will be explained later.

[0034] Furthermore, the epoxy equivalent of the flexible epoxy resin is, for example, 2000 g / eq or less, preferably 1200 g / eq or less, more preferably 1000 g / eq or less, and even more preferably 800 g / eq or less. If the epoxy equivalent is below the above-mentioned upper limit, it is possible to suppress excessive reduction in the reinforcing performance of the reinforcing member 11.

[0035] It should be noted that, in this embodiment, the reinforcing performance of the reinforcing member 11 is evaluated using the 1mm bending strength. The 1mm bending strength is measured using the method described in the embodiments described later.

[0036] Examples of flexible epoxy resins include aliphatic modified epoxy resins, ε-caprolactone modified epoxy resins, thiol-based epoxy resins, rubber-modified epoxy resins, dimer acid modified epoxy resins, urethane modified epoxy resins, polyol modified epoxy resins, and amine modified epoxy resins. Examples of rubber-modified epoxy resins include butadiene-based epoxy resins. Examples of butadiene-based epoxy resins include acrylonitrile-butadiene rubber-modified epoxy resins, carboxyl-terminated acrylonitrile-butadiene rubber-modified epoxy resins, and amino-terminated acrylonitrile-butadiene rubber-modified epoxy resins.

[0037] From the viewpoint of compatibility with rubber and adhesion to resin layer 2, aliphatic modified epoxy resins, rubber modified epoxy resins, and dimer acid modified epoxy resins are preferred as flexible epoxy resins, and dimer acid modified epoxy resins are more preferred. Resin layer 2 may contain a variety of flexible epoxy resins.

[0038] Commercially available flexible epoxy resins include, for example, the jER (registered trademark) series (manufactured by Mitsubishi Chemical Corporation) and the YD series (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.). Examples of flexible epoxy resins in the jER series include jER871, jER872, and jER872X75. Examples of flexible epoxy resins in the YD series include YD-172.

[0039] Other epoxy resins include, for example, aromatic epoxy resins, alicyclic epoxy resins, and nitrogen-containing epoxy resins.

[0040] Examples of aromatic epoxy resins include bisphenol type epoxy resins, linear phenolic type epoxy resins, naphthalene type epoxy resins, and biphenyl type epoxy resins.

[0041] Examples of bisphenol-type epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin.

[0042] Examples of linear phenolic epoxy resins include phenolic linear phenolic epoxy resin and cresol linear phenolic epoxy resin.

[0043] Examples of alicyclic epoxy resins include bicyclic epoxy resins and hydrogenated bisphenol A type epoxy resins.

[0044] Examples of nitrogen-containing epoxy resins include triglycidyl isocyanurate, hydantoin epoxy resin, and triglycidyl isocyanurate resin.

[0045] The epoxy equivalent of other epoxy resins is less than that of flexible epoxy resins. The epoxy equivalent of other epoxy resins is, for example, less than 220 g / eq, preferably less than 200 g / eq, for example, more than 150 g / eq, and preferably more than 160 g / eq.

[0046] The proportion of thermosetting resin in resin layer 2 is, for example, 10% by mass or more, preferably 15% by mass or more, for example, 50% by mass or less, preferably 30% by mass or less.

[0047] The proportion of thermosetting resin in the resin composition is, for example, 30% by mass or more, preferably 40% by mass or more, for example, 80% by mass or less, preferably 60% by mass or less.

[0048] The proportion of thermosetting resin relative to 100 parts by weight of rubber is, for example, greater than 100 parts by weight, preferably 150 parts by weight or more. If the proportion of thermosetting resin relative to rubber is at or above the aforementioned lower limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0049] The proportion of thermosetting resin relative to 100 parts by weight of rubber is, for example, 300 parts by weight or less, preferably 200 parts by weight or less. If the proportion of thermosetting resin relative to rubber is below the above-mentioned upper limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0050] The proportion of flexible epoxy resin in the thermosetting resin is, for example, 10% by mass or more, preferably 20% by mass or more, for example, less than 50% by mass, preferably 45% by mass or less, and more preferably 40% by mass or less. If the proportion of flexible epoxy resin in the thermosetting resin is at or above the lower limit and less than the upper limit, the reinforcing properties of the reinforcing material 1 can be further improved.

[0051] (1-1-2) Rubber

[0052] Examples of rubbers include diene-based rubbers. Examples of diene-based rubbers include styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), isoprene rubber, and butadiene rubber.

[0053] As rubbers, styrene-butadiene rubber and acrylonitrile-butadiene rubber are preferred examples. Rubbers preferably contain acrylonitrile-butadiene rubber. Rubbers more preferably contain both styrene-butadiene rubber and acrylonitrile-butadiene rubber.

[0054] The proportion of rubber in the resin layer 2 is, for example, 3% by mass or more, preferably 8% by mass or more, for example, 40% by mass or less, preferably 20% by mass or less.

[0055] The proportion of rubber in the resin component is, for example, 20% by mass or more, preferably 25% by mass or more, for example, 40% by mass or less, preferably 35% by mass or less.

[0056] When the thermosetting resin contains flexible epoxy resin and the rubber contains acrylonitrile-butadiene rubber, the proportion of acrylonitrile-butadiene rubber relative to 100 parts by mass of flexible epoxy resin is, for example, 60 parts by mass or more, preferably 100 parts by mass or more. If the proportion of acrylonitrile-butadiene rubber relative to flexible epoxy resin is at or above the aforementioned lower limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0057] The proportion of acrylonitrile-butadiene rubber relative to 100 parts by weight of flexible epoxy resin is, for example, 150 parts by weight or less, preferably 130 parts by weight or less. If the proportion of acrylonitrile-butadiene rubber relative to flexible epoxy resin is below the above-mentioned upper limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0058] When the rubber contains styrene-butadiene rubber and acrylonitrile-butadiene rubber, the proportion of acrylonitrile-butadiene rubber relative to 100 parts by mass of styrene-butadiene rubber is, for example, 40 parts by mass or more, preferably 60 parts by mass or more, and more preferably 75 parts by mass or more. If the proportion of acrylonitrile-butadiene rubber relative to styrene-butadiene rubber is at or above the aforementioned lower limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0059] The proportion of acrylonitrile-butadiene rubber relative to 100 parts by weight of styrene-butadiene rubber is, for example, less than 100 parts by weight, preferably 80 parts by weight or less. If the proportion of acrylonitrile-butadiene rubber relative to styrene-butadiene rubber is below the above-mentioned upper limit, the reinforcing properties of the reinforcing material 1 can be improved.

[0060] (1-1-3) Tackifying resin

[0061] The tackifying resin imparts adhesiveness to resin layer 2.

[0062] Tackifying resins are classified, for example, as natural resin-based tackifying resins and synthetic resin-based tackifying resins.

[0063] Examples of natural resin-based tackifying resins include rosin-based resins, aromatic modified terpene resins, and terpene-based resins. Examples of rosin-based resins include rosin esters. Examples of terpene-based resins include terpene phenol resins.

[0064] Examples of synthetic resin-based tackifying resins include aliphatic petroleum resins, aromatic petroleum resins, and aliphatic-aromatic copolymer petroleum resins. In the following description, aliphatic petroleum resins will be referred to as C5 series petroleum resins, aromatic petroleum resins as C9 series petroleum resins, and aliphatic-aromatic copolymer petroleum resins as C5 / C9 series petroleum resins.

[0065] C5 series petroleum resins mainly contain structural units derived from aliphatic hydrocarbons with 5 carbon atoms. Examples of 5-carbon aliphatic hydrocarbons include isoprene and isoprene. C5 series petroleum resins are manufactured by polymerizing a mixture of 5-carbon aliphatic hydrocarbons produced as a byproduct of the thermal decomposition of naphtha. In the following description, the mixture of 5-carbon aliphatic hydrocarbons produced as a byproduct of the thermal decomposition of naphtha will be referred to as the C5 fraction.

[0066] C9 series petroleum resins primarily contain structural units derived from aromatic hydrocarbons with nine carbon atoms. Examples of nine-carbon aromatic hydrocarbons include styrene, vinyltoluene, and indene. C9 series petroleum resins are manufactured by polymerizing a mixture of nine-carbon aromatic hydrocarbons produced as a byproduct of the thermal decomposition of naphtha. In the following description, the mixture of nine-carbon aromatic hydrocarbons produced as a byproduct of the thermal decomposition of naphtha will be referred to as the C9 fraction.

[0067] C5 / C9 series petroleum resins mainly contain structural units from aliphatic hydrocarbons with 5 carbon atoms and aromatic hydrocarbons with 9 carbon atoms. C5 / C9 series petroleum resins are manufactured by polymerizing C5 fractions and C9 fractions.

[0068] As a tackifying resin, synthetic resin-based tackifying resins are preferred, and C5 / C9 petroleum resins are more preferred.

[0069] The proportion of the tackifying resin in the resin layer 2 is, for example, 1% by mass or more, preferably 5% by mass or more, for example, 15% by mass or less, and preferably 10% by mass or less.

[0070] The proportion of the tackifying resin in the resin composition is, for example, 10% by mass or more, preferably 15% by mass or more, for example, 30% by mass or less, preferably 25% by mass or less.

[0071] The proportion of tackifying resin relative to 100 parts by weight of thermosetting resin is, for example, 20 parts by weight or more, preferably 40 parts by weight or more, for example, 70 parts by weight or less, preferably 60 parts by weight or less.

[0072] The proportion of tackifying resin relative to 100 parts by weight of rubber is, for example, 50 parts by weight or more, preferably 70 parts by weight or more, for example, 150 parts by weight or less, preferably 100 parts by weight or less.

[0073] (1-2) Foaming agent

[0074] The foaming agent foams upon heating. By including the foaming agent in the resin layer 2, the reinforcing layer 5 can be enlarged (see reference). Figure 2B The thickness of the reinforcing member 11 is increased (see reference). Figure 2B The intensity of ).

[0075] Foaming agents are classified, for example, into inorganic foaming agents and organic foaming agents.

[0076] Examples of inorganic foaming agents include ammonium carbonate (decomposition temperature: 58℃), ammonium bicarbonate (decomposition temperature: 35℃~60℃), sodium bicarbonate (decomposition temperature: 140℃~170℃), ammonium nitrite (decomposition temperature: 210℃), and azides.

[0077] Examples of organic blowing agents include N-nitroso compounds, azo compounds, fluoroalkanes, hydrazine compounds, aminourea compounds, and triazole compounds. Examples of N-nitroso compounds include N,N'-dinitrospentamethylenetetramine (decomposition temperature: 205°C). Examples of azo compounds include azobisisobutyronitrile (decomposition temperature: approximately 50°C). Examples of hydrazine compounds include 4,4'-oxobis(benzenesulfonylhydrazine) (decomposition temperature: 155°C–165°C). Examples of aminourea compounds include p-toluenesulfonylaminourea. Examples of triazole compounds include 5-morpholino-1,2,3,4-thiatriazole.

[0078] The decomposition temperature of the foaming agent is preferably above 80°C, more preferably above 100°C, more preferably below 300°C, and even more preferably below 200°C.

[0079] As a foaming agent, organic foaming agents are preferred, hydrazine compounds are more preferred, and 4,4'-oxobis(benzenesulfonylhydrazine) (OBSH) is even more preferred.

[0080] The proportion of the foaming agent in the resin layer 2 is, for example, 0.1% by mass or more, preferably 0.5% by mass or more, for example, 2% by mass or less, preferably 1% by mass or less.

[0081] The proportion of foaming agent relative to 100 parts by weight of resin is, for example, 1 part by weight or more, preferably 1.5 parts by weight or more, for example, 3 parts by weight or less, preferably 2 parts by weight or less.

[0082] (1-3) Vulcanizing agent

[0083] The vulcanizing agent crosslinks (vulcanizes) the diene rubber by heating.

[0084] Examples of sulfiding agents include sulfur, sulfur compounds, and organic peroxides. Sulfur is preferred as a sulfiding agent.

[0085] The proportion of vulcanizing agent relative to 100 parts by weight of diene rubber is, for example, 2 parts by weight or more, preferably 10 parts by weight or more, more preferably 20 parts by weight or more, more preferably 40 parts by weight or more, for example, 80 parts by weight or less, preferably 70 parts by weight or less, more preferably 60 parts by weight or less.

[0086] (1-4) Vulcanization accelerators

[0087] Vulcanization accelerators promote vulcanization based on vulcanizing agents.

[0088] Examples of vulcanization accelerators include thiazole-based vulcanization accelerators, thiourea-based vulcanization accelerators, thiuram-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators, guanidine-based vulcanization accelerators, aldehyde-amine-based vulcanization accelerators, and sulfenamide-based vulcanization accelerators. Thiazole-based vulcanization accelerators are preferred as vulcanization accelerators.

[0089] The proportion of vulcanizing accelerator relative to 100 parts by weight of vulcanizing agent is, for example, 10 parts by weight or more, preferably 30 parts by weight or more, for example, 100 parts by weight or less, preferably 70 parts by weight or less.

[0090] (1-5) Thermosetting resin curing agent

[0091] Thermosetting resin curing agents promote the curing of thermosetting resins.

[0092] Examples of thermosetting resin curing agents include cyanamide, amine, acid anhydride, amide, acylhydrazine, imidazole and imidazoline.

[0093] Examples of cyanamides include dicyandiamide.

[0094] Examples of amines include ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, their amine adducts, m-phenylenediamine, diaminodiphenylmethane, and diaminodiphenyl sulfone.

[0095] Examples of acid anhydrides include phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, dichlorosuccinic anhydride, benzophenone tetracarboxylic anhydride, and chloramphenicol anhydride.

[0096] Examples of amides include polyamides.

[0097] Examples of acylhydrazides include, for instance, diacylhydrazides.

[0098] Examples of imidazoles include methylimidazolium, 2-ethyl-4-methylimidazolium, ethylimidazolium, isopropylimidazolium, 2,4-dimethylimidazolium, phenylimidazolium, undecylimidazolium, heptadecanylimidazolium, and 2-phenyl-4-methylimidazolium.

[0099] Examples of imidazolines include methylimidazoline, 2-ethyl-4-methylimidazoline, ethylimidazoline, isopropylimidazoline, 2,4-dimethylimidazoline, phenylimidazoline, undecylimidazoline, heptadecanylimidazoline, and 2-phenyl-4-methylimidazoline.

[0100] The proportion of the thermosetting resin curing agent relative to 100 parts by weight of the thermosetting resin is, for example, 1 part by weight or more, preferably 3 parts by weight or more, for example, 10 parts by weight or less, preferably 7 parts by weight or less.

[0101] (1-6) Other additives

[0102] Resin layer 2 may further contain other additives. Examples of other additives include fillers and pigments.

[0103] Examples of fillers include calcium carbonate, talc, and organobentonite.

[0104] The proportion of filler relative to 100 parts by weight of resin is, for example, 50 parts by weight or more, preferably 110 parts by weight or more, for example, 300 parts by weight or less, preferably 200 parts by weight or less.

[0105] Examples of pigments include carbon black and zinc oxide.

[0106] The proportion of pigment relative to 100 parts by mass of resin is, for example, 1 part by mass or more, preferably 3 parts by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass or less.

[0107] (2) Constraint Layer 3

[0108] A restraining layer 3 is disposed on the first surface S1 of the resin layer 2. The restraining layer 3 restrains the reinforcing layer 5, which will be described later. By restraining the reinforcing layer 5 with the restraining layer 3, the toughness of the reinforcing layer 5 is improved. The restraining layer 3 has a predetermined thickness in the thickness direction of the resin layer 2.

[0109] The thickness of the constraint layer 3 is, for example, 0.01 mm or more, preferably 0.05 mm or more, for example, 3 mm or less, preferably 1 mm or less.

[0110] Materials used for the constraint layer 3 include, for example, metals and glass fibers. Examples of metals include aluminum and copper. Aluminum is preferred as a metal. Resin-impregnated glass fiber cloth is preferred as a glass fiber.

[0111] (3) Release sheet 4

[0112] The release sheet 4 is disposed on the second surface S2 of the resin layer 2. The release sheet 4 protects the resin layer 2 while disposed on the second surface S2 of the resin layer 2. The release sheet 4 can be peeled off from the resin layer 2. For example, a known release paper can be used as the release sheet 4.

[0113] 2. Enhancement Methods

[0114] Next, the reinforcement method for the reinforced object P based on the reinforcing material 1 will be explained.

[0115] like Figure 2A and Figure 2B As shown, the reinforcement method includes: an attachment process of attaching the reinforcing material 1 to the reinforced object P (refer to...). Figure 2A ), and a curing process in which the resin layer 2 is thermo-cured while the reinforcing material 1 is attached to the reinforced object P (see reference). Figure 2B ).

[0116] like Figure 2A As shown, in the bonding process, the operator peels the release sheet 4 from the resin layer 2, bringing the second surface S2 of the resin layer 2 into contact with the reinforced object P. The reinforcing material 1 is bonded to the reinforced object P by the adhesive force of the resin layer 2.

[0117] Next, in the curing process, the operator heats the reinforced object P to which the reinforcing material 1 is attached.

[0118] The heating temperature is, for example, above the decomposition temperature of the foaming agent. The heating temperature is, for example, below a temperature 100°C higher than the decomposition temperature of the foaming agent.

[0119] When the foaming agent is OB SH, the heating temperature is, for example, 130°C or higher, preferably 150°C or higher, and also, for example, 265°C or lower, preferably 220°C or lower.

[0120] The heating time is, for example, 5 minutes or more, preferably 10 minutes or more, and also, for example, 60 minutes or less, preferably 30 minutes or less.

[0121] In the curing process, such as Figure 2A and Figure 2B As shown, resin layer 2 is foamed and cured.

[0122] In detail, during the curing process, the resin components in resin layer 2 are softened by heating. As described above, the viscosity of the softened resin components at the decomposition temperature of the foaming agent is, for example, 500 Pa·s or more, preferably 1000 Pa·s or more, for example, 4000 Pa·s or less, and preferably 3500 Pa·s or less.

[0123] While the resin components are softened, the foaming agent decomposes, causing resin layer 2 to foam. While resin layer 2 is foamed, the resin components solidify, thus solidifying resin layer 2. Once the solidification of resin layer 2 is complete, it becomes reinforcing layer 5. That is, reinforcing layer 5 is the cured form of resin layer 2. Reinforcing layer 5 is fixed to the reinforced object P.

[0124] like Figure 3 As shown, the reinforcing layer 5 contains a base resin 51 cured from resin components and multiple air bubbles 52 generated by foaming with a foaming agent.

[0125] The proportion (porosity) of the total area of ​​the plurality of bubbles 52 in the cross-section of the reinforcing layer 5 is 83% or more. The proportion of the total area of ​​the plurality of bubbles 52 in the cross-section of the reinforcing layer 5 is determined by the method described in the embodiments described later. The proportion of the total area of ​​the plurality of bubbles 52 in the cross-section of the reinforcing layer 5 can be adjusted by the viscosity of the softened resin component and the proportion of the foaming agent in the resin layer 2.

[0126] The proportion of the total area of ​​the plurality of bubbles 52 in the cross section of the reinforcing layer 5 is preferably 83% or more, for example, 90% or less, and preferably 88% or less.

[0127] If the ratio of the total area of ​​the multiple bubbles 52 in the cross section of the reinforcing layer 5 is above the aforementioned lower limit, then the thickness of the reinforcing layer 5 can be increased.

[0128] The foaming ratio of resin layer 2 (thickness of reinforcing layer 5 / thickness of resin layer 2) is, for example, more than 3 times, and less than 5 times.

[0129] The average diameter of the plurality of bubbles 52 is, for example, 100 μm or more, preferably 200 μm or more, for example, 2000 μm or less, preferably 1000 μm or less. It should be noted that when the proportion of the total area of ​​the plurality of bubbles 52 in the cross-section of the reinforcing layer 5 is the same, the average diameter of the plurality of bubbles 52 will affect the fracture strength of the reinforcing member 11, etc. However, regarding the 1 mm flexural elasticity, the bending of the reinforcing member 11 is small, therefore the average diameter of the plurality of bubbles 52 has almost no effect on the 1 mm flexural elasticity.

[0130] Furthermore, the elastic modulus of the base resin 51 of the reinforcing layer 5 is 1.4 GPa or higher. The elastic modulus of the base resin 51 of the reinforcing layer 5 can be adjusted by the ratio of thermosetting resin to rubber.

[0131] The elastic modulus of the parent resin 51 of the reinforcing layer 5 is, for example, 5.0 GPa or less, preferably 4.5 GPa or less.

[0132] If the proportion of resin components in resin layer 2 is the same, then when the elastic modulus of the parent resin 51 of reinforcing layer 5 is high and the proportion of the total area of ​​multiple bubbles 52 in the cross section of reinforcing layer 5 is high, the 1mm bending elasticity tends to be higher.

[0133] Therefore, by making the elastic modulus of the parent resin 51 of the reinforcing layer 5 1.4 GPa or more, and making the proportion of the total area of ​​the plurality of bubbles 52 in the cross section of the reinforcing layer 5 83% or more, the reinforcing performance of the reinforcing member 11 can be improved.

[0134] This is accomplished through a curing process, thus... Figure 2B As shown, a reinforcement structure 10 is formed. The reinforcement structure 10 includes a reinforcement object P and a reinforcement member 11. The reinforcement member 11 includes a reinforcement layer 5 and a constraint layer 3. The reinforcement member 11 reinforces the reinforcement object P. The reinforcement layer 5 is disposed on the reinforcement object P. The constraint layer 3 is disposed on the reinforcement layer 5. The constraint layer 3 is disposed on the opposite side of the reinforcement object P in the thickness direction of the reinforcement layer 5.

[0135] 3. Effects

[0136] According to the reinforcing material 1, such as Figure 2B As shown, for the reinforcing layer 5 obtained by foaming and curing the resin layer 2, the elastic modulus of the parent resin 51 of the reinforcing layer 5 is 1.4 GPa or more, and the proportion of the total area of ​​the plurality of bubbles 52 in the cross section of the reinforcing layer 5 is 83% or more.

[0137] Therefore, it is possible to improve the reinforcing properties of reinforcing material 1.

[0138] Example

[0139] Next, the present invention will be described based on embodiments and comparative examples. The present invention is not limited to the embodiments described below. In addition, the specific numerical values ​​of physical property values, parameters, etc. used in the following description can replace the upper limit values ​​(defined as "below") or lower limit values ​​(defined as "above") of physical property values, parameters, etc. corresponding to them described in the "Specific Embodiments" above.

[0140] (1) Preparation of resin layer

[0141] For each embodiment and comparative example, the materials shown in Tables 1 and 2 were mixed to prepare resin compositions.

[0142] The obtained resin composition was calendered to a thickness of 0.4 mm using a stamping machine to create a resin layer. A 0.2 mm thick resin-impregnated fiberglass cloth was adhered to one side of the resin layer as a restraining layer, and release paper was adhered to the other side of the resin layer (the side opposite to the first side). This yielded a reinforcing material.

[0143] Table 1

[0144]

[0145] Table 2

[0146]

[0147] The following is an explanation of the materials in Tables 1 and 2.

[0148] SBR: Styrene-butadiene rubber (trade name: TUFDENE 2003, manufactured by Asahi Kasei Chemicals Co., Ltd.)

[0149] NBR: Acrylonitrile-butadiene rubber (trade name: Nipol1052J, manufactured by ZEON Corporation, Japan)

[0150] Epoxy resin: Bisphenol A type epoxy resin (trade name: jER-828, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 190g / eq)

[0151] Flexible epoxy resin: Dimer acid modified epoxy resin (trade name: YD-172, manufactured by NIPPON STEEL Chemical & Material, epoxy equivalent: 650 g / eq)

[0152] Tackifying resin 1: C5 / C9 series petroleum resin (trade name: Petrotack 90HM, manufactured by Tosoh Corporation)

[0153] Heavy calcium carbonate (manufactured by Maruo Calcium Co., Ltd.)

[0154] Carbon black (trade name: Asahi #50, manufactured by Asahi Carbon)

[0155] Sulfur (trade name: Jinhua Yinwei powder sulfur, manufactured by Tsurumi Chemical Industry Co., Ltd.)

[0156] Vulcanization accelerator (trade name: DM, manufactured by Ouchi Shinsei Chemical Co., Ltd.)

[0157] Epoxy resin curing agent (thermosetting resin curing agent): Dicyandiamide (manufactured by NIPPON CARBIDE)

[0158] Foaming agent: 4,4'-oxobis(benzenesulfonyl hydrazine) (trade name: Neocellborn N#1000S, manufactured by Yung Ho Chemical Industry Co., Ltd.)

[0159] (2) Determination of porosity

[0160] The reinforcing materials of each embodiment and each comparative example were peeled off the release paper and attached to the entire surface of the cold-rolled steel sheet (manufactured by Nippon Testpanel, SPCC-SD, width: 25mm, length: 150mm, thickness: 0.8mm) that was to be reinforced.

[0161] Next, the steel plate with the reinforcing material attached is heated at 180°C for 20 minutes. As a result, the resin layer foams and cures, and a reinforcing member (a reinforcing member having a reinforcing layer and a constraint layer as the cured resin layer) is obtained on the steel plate.

[0162] The obtained reinforcing member was peeled off from the steel plate, and the cross-section of the reinforcing layer was magnified 100 times under a microscope for observation.

[0163] In the cross-sectional image (3000 μm × 3000 μm) obtained using a microscope, the proportion of the total area of ​​multiple bubbles in the cross-section of the reinforcing layer was calculated using the following formula. The results are shown in Tables 1 and 2.

[0164] Formula: Porosity = Total area of ​​multiple bubbles / Total area of ​​the reinforcing layer in the cross-sectional image × 100

[0165] (3) Determination of the elastic modulus of the parent resin

[0166] Reinforcing members were obtained on steel plates under the same conditions as those used for porosity determination. The resulting reinforcing members were peeled off the steel plates, and the elastic modulus of the matrix resin of the reinforcing layer was determined using a nanoindenter (Triboindenter, Hysitron Inc.).

[0167] Using a Glass indenter, the matrix resin of the reinforcing layer was pressed under a maximum load of 11000 μN, and the elastic modulus was calculated based on the slope of the unloading curve from 20% to 85%. The results are shown in Tables 1 and 2.

[0168] (4) Determination of 1mm bending strength

[0169] Reinforcing members were obtained on steel plates under the same conditions as those used for porosity determination.

[0170] The test specimens, which consist of steel plates and reinforcing members, are supported on the testing machine (tensile and compression testing machine: Technograph TG-5KN, manufactured by Minebea Mitsumi) with the steel plates facing upwards at 100 mm intervals. The test bar is then lowered from above towards the center of the test specimen along its length at a speed of 1 mm / min.

[0171] After the test bar comes into contact with the steel plate, the bending strength (N) when the test bar drops 1 mm is the bending strength at 1 mm. The results are shown in Tables 1 and 2.

[0172] It should be noted that the above-described invention is provided as an illustrative embodiment of the present invention, but this is merely an example and not intended to be limiting. Modifications of the present invention that will be apparent to those skilled in the art are included within the scope of protection of the present invention.

[0173] Industrial availability

[0174] The reinforcing materials and reinforcing structures of the present invention are used to reinforce metal plates used in transportation equipment such as automobiles, railway vehicles, ships, and aircraft, as well as in buildings.

[0175] Explanation of reference numerals in the attached figures

[0176] 1. Reinforcing materials

[0177] 2 Resin layer

[0178] 3. Constraint Layer

[0179] 5. Reinforcement layer

[0180] 51. Parent resin

[0181] 52 bubbles

[0182] 10. Reinforced Structure

[0183] 11 Reinforcing Components

[0184] P Enhanced Object

Claims

1. A reinforcing material for reinforcing a reinforced object, said reinforcing material comprising: A resin layer, containing resin components and a foaming agent, can serve as a reinforcing layer for reinforcing the reinforced object; and A constraint layer, disposed on the resin layer, The reinforcing layer contains a base resin formed by curing the resin components and multiple air bubbles generated by foaming with the foaming agent. The resin composition contains thermosetting resin and rubber. The proportion of thermosetting resin is greater than 100 parts by weight relative to 100 parts by weight of the rubber. The thermosetting resin contains dimer acid-modified epoxy resin and epoxy resins other than flexible epoxy resin. The proportion of the dimer acid-modified epoxy resin in the thermosetting resin is more than 10% by mass and less than 40% by mass. The proportion of the total area of ​​the multiple bubbles in the cross-section of the reinforcing layer is more than 83%. The elastic modulus of the parent resin in the reinforcing layer is 1.4 GPa or higher.

2. The reinforcing material according to claim 1, wherein, The rubber contains acrylonitrile-butadiene rubber. The proportion of acrylonitrile-butadiene rubber is 60 parts by mass or more, relative to 100 parts by mass of the dimer acid modified epoxy resin.

3. A reinforcing structure comprising: Enhanced objects; and enhanced components, The reinforcing member has a reinforcing layer for reinforcing the object being reinforced and a constraint layer disposed on the reinforcing layer. The reinforcing layer contains a base resin formed by the curing of resin components and multiple air bubbles generated by foaming with a foaming agent. The resin composition contains thermosetting resin and rubber. The proportion of thermosetting resin is greater than 100 parts by weight relative to 100 parts by weight of the rubber. The thermosetting resin contains dimer acid-modified epoxy resin and epoxy resins other than flexible epoxy resin. The proportion of the dimer acid-modified epoxy resin in the thermosetting resin is more than 10% by mass and less than 40% by mass. The proportion of the total area of ​​the multiple bubbles in the cross-section of the reinforcing layer is more than 83%. The elastic modulus of the parent resin in the reinforcing layer is 1.4 GPa or higher.

Images