WO2019244395A1

WO2019244395A1 - Resin laminate and method of manufacturing resin laminate

Info

Publication number: WO2019244395A1
Application number: PCT/JP2019/005319
Authority: WO
Inventors: 博之香川; 剛資近藤
Original assignee: 株式会社日立製作所
Priority date: 2018-06-22
Filing date: 2019-02-14
Publication date: 2019-12-26
Also published as: TWI743495B; JP7038012B2; JP2019217738A; TW202000460A

Abstract

To provide a resin laminate that has excellent moldability and a method of manufacturing the resin laminate, the present invention is characterized by having a thermoplastic resin layer in tight contact between two arbitrary thermosetting resin layers. The present invention is also characterized in that, in at least one of the thermosetting resin layers, the molecules making up the thermosetting resin have dynamic covalent bonds which are covalent bonds that can reversibly break and reform. The present invention is further characterized in that at least one of the thermosetting resin layers is a fiber-containing thermosetting resin.

Description

Resin laminate and method for producing resin laminate

The present invention relates to a technique of a resin laminate and a method of manufacturing the resin laminate.

繊維 Fiber reinforced resin using fiber as a reinforcing material is used in many fields such as automobiles, railways, aircrafts, and building materials because of its excellent strength and elasticity while being lightweight. In particular, fiber-reinforced thermosetting resins in which thermosetting resins are combined with continuous fibers made of glass or carbon have been widely used because of their excellent strength and heat resistance.

Resin transfer molding, a method using an autoclave, a method using a vacuum bag, a compression molding method, and the like are known as methods for obtaining a molded article in which a thermosetting resin and fibers are composited. In either case, the fiber and the resin are impregnated with a resin varnish before curing and then heat-cured, or the fiber-resin composite material is once semi-cured (prepreg), formed into a desired shape, and then heated. It is a curing method.

向上 In the production of such fiber-reinforced resin in which the thermosetting resin and the fiber are combined, improvement in productivity is required. For example, Patent Literature 1 states that “Compared with a conventional epoxy resin composition, curing is completed in a short time even at a low temperature, and a sufficient usable period can be ensured even when stored at room temperature, which is suitable for a prepreg. An epoxy resin composition used for at least one of a reaction product of an epoxy resin and an amine compound having at least one sulfur atom in a molecule and an amine compound having at least one sulfur atom in a molecule, a urea compound, An epoxy resin composition comprising dicyandiamide, wherein the content of sulfur atom and urea compound in the epoxy resin composition is 0.2 to 7% by mass and 1 to 15% by mass, respectively. "Epoxy resin for prepreg, prepreg , Fiber reinforced composite materials and methods for their manufacture are disclosed (see abstract). Non-Patent Document 1 discloses a method of pressing a carbon fiber-reinforced thermosetting resin laminate after heat curing in the same manner as a metal.

On the other hand, recently, resin compositions using dynamic covalent bonds have been proposed. The dynamic covalent bond is a covalent bond that is capable of reversible dissociation-bonding in a molecule constituting the resin by an external stimulus such as heat or light while being a covalent bond. Patent Document 2 discloses “a thermosetting resin composition that is heat-transformable after curing and contains at least one thermosetting polymer precursor containing a hydroxyl group and / or an epoxy group. Is obtained by contacting with at least one curing agent selected from acid anhydrides in the presence of at least one transesterification catalyst (provided that the thermosetting polymer precursor and the acid anhydride have an equimolar ratio. The total molar amount of the transesterification catalyst should be between 5% and 25% of the total molar amount of hydroxyl groups and epoxy groups contained in the thermosetting polymer precursor of the thermosetting resin composition. Wherein said catalyst is selected from metal salts of zinc, tin, magnesium, cobalt, calcium, titanium and zirconium, said catalyst comprising said thermoset polymer precursor. And the amount of the curing agent is selected such that the thermosetting resin composition forms a network and satisfies 2NA <No + 2Nx. (Where, No represents the number of moles of hydroxyl groups in the thermosetting polymer precursor, Nx represents the number of moles of epoxy groups in the thermosetting polymer precursor, and NA represents the thermosetting polymer. The number of moles of anhydride groups of the above curing agent capable of forming a bond with the hydroxyl group or epoxy group of the precursor). Thermosetting and recyclable anhydrous epoxy thermosetting resin and thermosetting An active composition is disclosed (see claim 1). The thermosetting resin composition disclosed in Patent Document 2 comprises, in the presence of at least one transesterification catalyst, a precursor of at least one thermosetting resin containing a hydroxyl group and / or an epoxy group to an acid anhydride. And at least one curing agent selected from the group consisting of: Thereby, the amount of acid anhydride is selected such that a network is formed which is maintained by the ester groups and free hydroxyl groups remain after the reaction between the precursor and the curing agent.

International Publication No. WO 2004/48435 Japanese Patent No. 5749354

However, since the curing of the thermosetting resin is an exothermic reaction, it is difficult to control the temperature during curing with the technology described in Patent Document 1, and deformation after curing is likely to occur due to temperature unevenness. Further, the fiber-containing thermosetting resin is prepared by immersing a thermosetting resin raw material liquid in a fibrous material such as cloth. However, when the fiber-containing thermosetting resin is softened by heating, the fibers are disturbed due to the flow of the resin whose viscosity has been reduced by heating. Fiber turbulence leads to uneven strength. On the other hand, when a laminated body of the fiber-containing thermosetting resin after curing is molded from a metal plate as in the technique described in Non-Patent Document 1, deformation after effect due to temperature unevenness and disturbance of the fiber due to resin flow may occur. Can be suppressed. However, according to the technology described in Non-Patent Document 1, a phenomenon called peeling between the laminated fiber-containing thermosetting resin layers and a phenomenon called springback that returns to the original state after molding occurs.

The present invention has been made in view of such a background, and an object of the present invention is to provide a resin laminate excellent in moldability and a method for producing the resin laminate.

In order to solve the above-mentioned problem, the present invention is characterized in that a layer of a thermoplastic resin exists between two arbitrary layers of a thermosetting resin in close contact with each other.
Other solutions will be described in the embodiments as appropriate.

According to the present invention, a resin laminate excellent in moldability and a method for producing the resin laminate can be provided.

FIG. 2 is a schematic cross-sectional view (first example) of a resin laminate 1 according to the embodiment. FIG. 3 is a schematic cross-sectional view (second example) of a resin laminate 1 according to the embodiment. FIG. 4 is a schematic cross-sectional view (third example) of a resin laminate 1 according to the embodiment. FIG. 6 is a schematic cross-sectional view (fourth example) of a resin laminate 1 according to the present embodiment. FIG. 6 is a schematic cross-sectional view (fifth example) of a resin laminate 1 according to the present embodiment. It is a cross section of a resin layered product 1 concerning this embodiment (sixth example). FIG. 7 is a schematic cross-sectional view (seventh example) of a resin laminate 1 according to the present embodiment. It is a cross section schematic diagram (eighth example) of the resin layered product 1 concerning this embodiment. It is a cross section of a resin layered product 1 concerning this embodiment (a 9th example). It is a cross section of a resin layered product 1 concerning this embodiment (tenth example). It is a cross section of the resin layered product 1 concerning this embodiment (eleventh example). It is a cross section of a resin layered product 1 concerning this embodiment (a 12th example). It is a cross section of a resin layered product 1 concerning this embodiment (a 13th example). FIG. 14 is a schematic cross-sectional view (a fourteenth example) of a resin laminate 1 according to the present embodiment. It is a cross section schematic diagram (the 15th example) of resin layered product 1 concerning this embodiment. It is a cross section of resin laminate 1Z (CFRP resin laminate) in a comparative example. It is a figure showing the example of composition of resin laminated body manufacturing system 100 which manufactures resin laminated body 1 concerning this embodiment.

Next, a mode for carrying out the present invention (referred to as “embodiment”) will be described in detail with reference to the drawings as appropriate.
[Lamination example of resin laminate 1]
1 to 15 show examples of lamination of the resin laminate 1 according to the present embodiment.
1 to 15 are schematic sectional views of the resin laminate 1 according to the present embodiment. In FIGS. 1 to 15, hatched lines indicate a fiber-containing resin, dots indicate a thermosetting resin, and no dots indicate a thermoplastic resin.
That is, in FIG. 1 to FIG. 15, the non-hatched + dot indicates a fiber-free thermosetting resin, and the hatched + dot indicates a fiber-containing thermosetting resin. Further, “without hatching + no dot” indicates a fiber-free thermoplastic resin, and “with hatching + no dot” indicates a fiber-containing thermoplastic resin.
In the present embodiment, the fiber-free thermosetting resin and the fiber-containing thermosetting resin are referred to as thermosetting resins as appropriate. Similarly, the fiber-free thermoplastic resin and the fiber-containing thermoplastic resin are referred to as thermoplastic resins as appropriate. Here, the fiber-free thermoplastic resin and the fiber-free thermosetting resin are thermoplastic resins and thermosetting resins containing no fibers.
Further, in the present embodiment, it is assumed that the thermosetting resin (the thermosetting resin containing no fiber and the thermosetting resin containing the fiber) has a dynamic covalent bond. Resin may be used.

FIG. 1 is a schematic cross-sectional view (first example) of a resin laminate 1 according to the present embodiment.
As shown in FIG. 1, in the resin laminate 1 a (1), a fiber-free thermosetting resin layer (thermosetting resin layer) 11 has a fiber-free thermoplastic resin layer (thermoplastic resin layer) 21. It is pinched. That is, the fiber-free thermoplastic resin layer 21 exists between the two fiber-free thermosetting resin layers 11.

FIG. 2 is a schematic cross-sectional view (second example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 2, in the resin laminate 1 b (1), a fiber-free thermoplastic resin layer 21 is sandwiched between fiber-containing thermosetting resin layers (layers of fiber-containing thermosetting resin) 12. . That is, the fiber-free thermoplastic resin layer 21 exists between the two fiber-containing thermosetting resin layers 12.

FIG. 3 is a schematic cross-sectional view (third example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 3, the resin laminate 1c (1) has a fiber-containing thermosetting resin layer 12 between three fiber-free thermoplastic resin layers 21.

FIG. 4 is a schematic cross-sectional view (fourth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 4, the resin laminate 1d (1) is one in which two fiber-free thermoplastic resin layers 21 and two fiber-containing thermosetting resin layers 12 are alternately laminated.

FIG. 5 is a schematic cross-sectional view (fifth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 5, the resin laminate 1e (1) has a fiber-containing thermoplastic resin layer (a fiber-containing thermoplastic resin layer, a thermoplastic resin layer) between each of the three fiber-free thermosetting resin layers 11. (Layer) 22 is present.

FIG. 6 is a schematic cross-sectional view (sixth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 6, the resin laminate 1f (1) has a fiber-free thermosetting resin layer 11 between three fiber-containing thermoplastic resin layers 22.

FIG. 7 is a schematic cross-sectional view (seventh example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 7, the resin laminate 1g (1) has two fiber-containing thermoplastic resin layers 22 and two fiber-free thermosetting resin layers 11 alternately laminated.

FIG. 8 is a schematic cross-sectional view (eighth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 8, the resin laminate 1h (1) has a fiber-containing thermoplastic resin layer 22 between two fiber-containing thermosetting resin layers 12.

FIG. 9 is a schematic cross-sectional view (ninth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 9, the resin laminate 1 i (1) has a fiber-containing thermosetting resin layer 12 between three fiber-containing thermoplastic resin layers 22.

FIG. 10 is a schematic cross-sectional view (tenth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 10, the resin laminate 1j (1) has a fiber-containing thermoplastic resin layer 22 between each of the three fiber-containing thermosetting resin layers 12. The resin laminate 1j shown in FIG. 10 is obtained by stacking the resin laminate 1h shown in FIG. 8 in multiple stages.

FIG. 11 is a schematic cross-sectional view (eleventh example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 11, the resin laminate 1k (1) is one in which two fiber-containing thermosetting resin layers 12 and two fiber-containing thermoplastic resin layers 22 are alternately laminated.

FIG. 12 is a schematic cross-sectional view (a twelfth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 12, in the resin laminate 1 m (1), a fiber-free thermoplastic resin layer 21 exists between two fiber-containing thermosetting resin layers 12. Further, the fiber-containing thermoplastic resin layer 22 exists so as to sandwich the laminate of the fiber-containing thermosetting resin layer 12, the fiber-free thermoplastic resin layer 21, and the fiber-containing thermosetting resin layer 12 from above and below.

FIG. 13 is a schematic cross-sectional view (a thirteenth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 13, between the two fiber-containing thermosetting resin layers 12, the resin laminate 1 n (1) includes, in order from the top, a fiber-free thermoplastic resin layer 21, a fiber-containing thermoplastic resin layer 22, A fiber-free thermoplastic resin layer 21 is present.

FIG. 14 is a schematic cross-sectional view (a fourteenth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 14, the resin laminate 1p (1) includes a fiber-free thermoplastic resin layer 21 and a fiber-containing thermoplastic resin layer 22 between two fiber-containing thermosetting resin layers 12 in order from the top. Existing.

FIG. 15 is a schematic cross-sectional view (fifteenth example) of the resin laminate 1 according to the present embodiment.
As shown in FIG. 15, in the resin laminate 1q (1), a fiber-containing thermosetting resin layer 12, a fiber-free thermoplastic resin layer 21, and a fiber-free thermosetting resin layer 11 are laminated in this order from the top. I have.

[Comparative example]
FIG. 16 is a schematic cross-sectional view of a resin laminate 1Z (CFRP resin laminate) in a comparative example.
As shown in FIG. 16, the resin laminate 1Z in the comparative example has only the fiber-containing thermosetting resin layer 12 laminated (four layers in the example of FIG. 16).
If the resin laminate 1Z as shown in FIG. 16 is cured by heating and then pressed to perform bending, the peeling between the fiber-containing thermosetting resin layers 12 occurs at the bent portions.

As shown in FIGS. 1 to 15, the presence of the thermoplastic resin layer between any of the thermosetting resin layers softens the thermoplastic resin layer when the resin laminate 1 is heat-formed. Thereby, by heating and pressing the resin laminate 1, delamination and cracking of the thermosetting resin layer at a bent portion even after molding is suppressed. Further, as described above, it is assumed that the thermosetting resin in the present embodiment has a dynamic covalent bond. This makes it possible to alleviate stress due to a change in the network structure of the chemical bond in the resin, and to greatly reduce springback after molding. As described above, the dynamic supply bond is a covalent bond in which molecules constituting the resin are reversibly separated and bonded.
In addition, at least one of the thermosetting resin layers constituting the resin laminate 1 may have a dynamic supply connection.

Further, in the resin laminate 1 shown in FIGS. 1 to 15, the curing of the thermosetting resin layer has been completed. For this reason, there is no curing shrinkage or heat generation of the resin in the heat molding step of the resin laminate 1, and the dimensional accuracy of molding can be improved. Further, the dynamic covalent bond of the thermosetting resin has an ester bond. Further, by having a —C (C ＝ O) —O— bond in the thermoplastic resin, a chemical bond is generated between the thermosetting resin and the thermoplastic resin, and the adhesive strength between both layers is improved.
As the dynamic covalent bond, not only an ester bond but also an imine bond, a quaternary ammonium salt bond, an oxazoline bond, a spiro orthoester bond, a borate ester bond, a disulfide bond, a dioxoborane bond, and the like can be used.

Also, the resin laminate 1 shown in FIGS. 1, 2, 4, 5, 7, 8, 10, 10, 11, and 13 to 15 has at least one of the layers constituting the outermost layer. One is a thermosetting resin layer. By doing so, the resin laminate 1 having a high surface hardness can be provided. As a result, it is possible to provide the resin laminate 1 that is hardly damaged.
In addition, since the thermosetting resin has a chemical structure containing oxygen, nitrogen, and the like, it has a high polarity. Therefore, by providing the outermost layer with the thermosetting resin, it is possible to provide the resin laminate 1 that can be easily applied. be able to.
Further, the strength can be increased by using a fiber-containing thermosetting resin or a fiber-containing thermoplastic resin.

The resin laminate 1 shown in FIGS. 1 to 15 has a functional group that promotes recombination of the bond on the fiber surface, for example, a hydroxyl group or an ester bond, by using a known technique such as impregnation into a solution or vapor deposition. In addition, a layer containing a large amount of a transesterification catalyst described below can be formed. By doing so, stress can be alleviated, and cracking and peeling can be suppressed.
That is, the resin laminate 1 excellent in moldability can be provided.

In the resin laminate 1 of the present embodiment, a thermoplastic resin layer is always sandwiched between thermosetting resin layers. That is, the thermosetting resin layers are stacked discontinuously. That is, a thermoplastic resin exists between any thermosetting resin layers.
Various laminated structures are possible based on the resin laminate 1 shown in FIGS. 1 to 15 as a basic configuration. For example, the resin laminate 1 shown in FIGS. 1 to 15 can be further overlapped. However, it is necessary to ensure that a thermoplastic resin layer exists between arbitrary thermosetting resin layers. In other words, the thermosetting resin layer must not be continuous.

<Thermosetting resin>
The thermosetting resin in the present embodiment has an appropriate curing temperature range depending on the curing agent and the catalyst, but a monomer that forms a dynamic covalent bond during curing is considered. Further, as the thermosetting resin of the present embodiment, a monomer having a structure containing a dynamic covalent bond as a monomer skeleton and capable of forming a crosslinked structure is considered. Alternatively, a mixture of both of them can be considered as the thermosetting resin of the present embodiment. Further, as a monomer, a mixture of a monomer, a curing agent, and a catalyst capable of forming a dynamic covalent bond or a crosslinked structure with another monomer during curing is impregnated into a fiber having a catalyst or a curing agent layer on the surface, and heated. It is conceivable to obtain one obtained by curing by the method described above. Further, the catalyst may be added as needed or may not be added.

Curing time and curing temperature are appropriately adjusted according to the application. The fiber reinforced resin obtained after curing has a catalyst for promoting dynamic covalent bonding and recombination therein, and an exchange reaction occurs appropriately. As an example, chemical formula (1) shows a chemical formula of a transesterification reaction which is one of dynamic covalent bonds. The chemical formula shown in chemical formula (1) is a part of the structure obtained by the transesterification reaction.

において In the chemical formula (1), R, R1, and R2 have any chemical structures.

熱 As the thermosetting resin in the present embodiment, a resin having an ester bond, an imine bond, a quaternary ammonium salt bond, an oxazoline bond, a spiro orthoester bond, a borate ester bond, a disulfide bond, or the like can be used. From the viewpoint of mechanical strength, a monomer or a monomer skeleton that forms an ester bond at the time of curing preferably has a structure containing an ester bond. The monomer that forms an ester bond during curing is preferably composed of an epoxy compound having a polyfunctional epoxy group, and a carboxylic anhydride or a polycarboxylic acid as a curing agent. Further, as the epoxy compound, a bisphenol A type resin, a novolak type resin, an alicyclic resin, and a glycidylamine resin are preferable.

Examples of epoxy include bisphenol A diglycidyl ether phenol, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, resorcinol diglycidyl ether, hexahydrobisphenol A diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether. Glycidyl ether, diglycidyl phthalate, diglycidyl dimer, triglycidyl isocyanurate, tetraglycidyl diaminodiphenylmethane, tetraglycidyl metaxylene diamine, cresol novolak polyglycidyl ether, tetrabromobisphenol A diglycidyl ether, bisphenol hexafluoroacetone di Glycidyl ether, etc. The present invention is not limited to.

Examples of the carboxylic anhydride or polycarboxylic acid as a curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3-dodecenylsuccinic anhydride, octenylsuccinic anhydride, Methylhexahydrophthalic anhydride, methylnadic anhydride, dodecylsuccinic anhydride, chlorendic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis (anhydrotrimate), methylcyclohexenetetracarboxylic acid Anhydride, trimellitic anhydride, polyazelain anhydride, ethylene glycol dibisanhydrotrimellitate, 1,2,3,4-butanetetracarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, polyvalent fatty acid Etc. But it is not limited thereto.

The transesterification catalyst is preferably one that is uniformly dispersed in the mixture. For example, catalysts that promote the transesterification reaction include zinc (II) acetate, zinc (II) acetylacetonate, zinc (II) naphthenate, iron (III) acetylacetone, cobalt (II) acetylacetone, aluminum isopropoxide, Titanium isopropoxide, methoxide (triphenylphosphine) copper (I) complex, ethoxide (triphenylphosphine) copper (I) complex, propoxide (triphenylphosphine) copper (I) complex, isopropoxide (triphenylphosphine) Copper (I) complex, methoxide bis (triphenylphosphine) copper (II) complex, ethoxide bis (triphenylphosphine) copper (II) complex, propoxide bis (triphenylphosphine) copper (II) complex, isopropoxide bis (tri Phenyl phosphite ) Copper (II) complex, tris (2,4-pentanedionato) cobalt (III), tin (II) diacetate, tin (II) di (2-ethylhexanoate), N, N-dimethyl-4- Examples include, but are not limited to, aminopyridine, diazabicycloundecene, diazabicyclononene, triazabicyclodecene, triphenylphosphine, and the like.

Further, the resin composition having a covalent bond that reversibly dissociates and bonds may be composed of a vinyl monomer having a hydroxyl group, an ester bonding group and two or more vinyl groups, a polymerization initiation catalyst, and a transesterification reaction catalyst. .

Specific examples that can be used as vinyl monomers include 2-hydroxy methacrylate, hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, divinyl ethylene glycol, monomethyl fumarate, hydroxypropyl acrylate, ethyl 2- (hydroxymethyl) acrylate, glycerol dimethacrylate , Allyl acrylate, methyl crotonate, methyl methacrylate, methyl 3,3-dimethacrylate, diethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, dimethyl fumarate, fumaric acid, 1,4-butanediol Dimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butanediol dimethacrylate Tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, vinyl crotonate, crotonic anhydride, diallyl maleate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, trimethylol propane triacrylate, trimethylol Examples include, but are not limited to, propane trimethacrylate.

As the polymerization initiation catalyst, a peroxide-based compound, an azo-based compound, and the like are considered, and specific examples thereof include 2,2′-azobisisobutyronitrile, 2, 2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), 1,1'-azobis (cyclohexanecarbonitrile), 2,2'-azobis (2,4,4-trimethylpentane) and the like Azo compounds, dialkyl peroxides such as di-t-butyl peroxide, di-t-hexyl peroxide, dicumyl peroxide, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis ( t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) pro Peroxy ketals such as tert-butyl peroxybenzoate, t-hexyl peroxy benzoate, t-butyl peroxy acetate, t-butyl peroxy laurate, peroxy such as t-hexyl peroxy neodecanoate Esters, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, t-butylperoxyisopropyl monocarbonate, t-hexylperoxyisopropyl monocarbonate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di- Examples include, but are not limited to, peroxycarbonates such as 2-ethylhexyl peroxydicarbonate.

The transesterification catalyst is preferably one that is uniformly dispersed in the mixture to promote the transesterification reaction. For example, zinc (II) acetate, zinc (II) acetylacetonate, zinc (II) naphthenate, iron (III) acetylacetone, cobalt (II) acetylacetone, cobalt (III) acetylacetone, aluminum isopropoxide, titanium isopropoxide , Methoxide (triphenylphosphine) copper (I) complex, ethoxide (triphenylphosphine) copper (I) complex, propoxide (triphenylphosphine) copper (I) complex, isopropoxide (triphenylphosphine) copper (I) Complex, methoxide bis (triphenylphosphine) copper (II) complex, ethoxide bis (triphenylphosphine) copper (II) complex, propoxide bis (triphenylphosphine) copper (II) complex, isopropoxide bis (triphenylphosphine) (II) complex, tris (2,4-pentanedionato) cobalt (III), cobalt (II) naphthenate, cobalt (II) stearate, tin (II) diacetate, tin (2-ethylhexanoate) (II), N, N-dimethyl-4-aminopyridine, diazabicycloundecene, diazabicyclononene, triazabicyclodecene, triphenylphosphine, 2-phenylimidazole, 2-phenyl-4-methylimidazole, -Benzyl-2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and the like, but are not limited thereto.

Further, the resin composition having a reversibly dissociable and bonded covalent bond may be a thermoplastic resin into which a cross-linking component having a reversibly dissociated and bonded covalent bond is introduced. Examples of the thermoplastic resin include, but are not limited to, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyethylene terephthalate, and acrylic resin.
Examples of the cross-linking component having a covalent bond capable of reversibly dissociating and bonding include those having an alkoxyamine skeleton, a diarylbibenzofuran skeleton, and a dioxaborane skeleton, but are not limited thereto.

<Thermoplastic resin>
The thermoplastic resin used for the thermoplastic resin layer includes polyethylene, polypropylene, polystyrene, ABS resin, acrylic resin, polyvinyl chloride, polyamide, polyacetal, polycarbonate, polyester, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyphenylene oxide. And resins which soften and flow by heating, such as polyamideimide, polyether ether ketone, polyphenylene sulfide, and polytetrafluoroethylene. Among them, those having an ester bond or a carbonate group having a structure of —C (C ＝ O) ＝ O— in the chemical structure are particularly desirable. For example, polyester, polycarbonate, acrylic resin, and polyamide are desirable. These resins can improve the adhesiveness between layers by chemically reacting with the ester bond of the thermosetting resin.

<Fiber>
As the fibers used for the thermosetting resin in the present embodiment, inorganic fibers and organic fibers can be used. For example, examples of the inorganic fiber include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, alumina fiber, zirconia fiber, potassium titanate fiber, tyranno fiber, silicon carbide fiber, and metal fiber. Organic fibers include high-strength polyethylene fibers, polyacetal fibers, aliphatic or aromatic polyamide fibers, polyacrylate fibers, fluorine fibers, boron fibers, polyacrylonitrile fibers, aramid fibers, PBO (poly-p-phenylene benzobisoxazole) fibers, Fibers derived from plants (vegetable fibers) such as ramie, cellulose and the like. These fibers can be used alone or in combination of two or more. Among these fibers, inorganic fibers, particularly carbon fibers, are preferable in terms of mechanical strength and the like. Carbon fibers can be classified according to their raw materials into carbon fibers derived from synthetic polymers (polyacrylonitrile-based, polyvinyl alcohol-based, rayon-based carbon fibers, etc.) and mineral-derived carbon fibers (pitch-based carbon fibers, etc.). From the viewpoint of mechanical strength, carbon fibers derived from synthetic polymers are preferred.

These fibers are used in the form of a continuous fiber, a long fiber, a short fiber, chopped or the like, and are used in the form of a unidirectional material, a plain weave, a nonwoven cloth, or the like. In addition, it may be used by being directly added to a resin, but in the present embodiment, it is not limited to these fiber shapes and fiber states.
The resin laminate 1 of the present embodiment includes, for example, moving bodies such as automobiles, railway vehicles, ships, and aircraft, blades for wind power generators, fan blades, unit baths, septic tanks, printed boards, playground equipment, skis, and the like. It can be used for parts and bodies used in various fields.

(First specific example)
A thermosetting resin sheet is prepared according to the following procedure.
First, 100 parts by weight of “jER828 (trade name)”, an epoxy resin manufactured by Mitsubishi Chemical Corporation, and zinc (II) acetyl manufactured by Tokyo Chemical Industry Co., Ltd. 14.2 parts by weight of acetonate was added and dissolved. To this, 44.8 parts by weight of "HN-2200 (trade name)" manufactured by Hitachi Chemical Co., Ltd. was added as a curing agent, followed by stirring and mixing. The resulting liquid mixture is referred to as a thermosetting resin raw material liquid.
Then, the thermosetting resin raw material liquid is spread on a Teflon (registered trademark) sheet with a thickness of about 1 mm, and heat-cured at 160 ° C. for 2 hours to form a thermosetting resin sheet (fiber-free thermosetting resin). Layer 11) was prepared. The manufacturer sandwiched one PET film (the fiber-free thermoplastic resin layer 21) between the two produced thermosetting resin sheets and pressed it at 160 ° C. under reduced pressure to obtain a resin laminate 1.
The resin laminate 1 thus produced is a resin laminate 1 in which the fiber-free thermoplastic resin layer 21 exists between the fiber-free thermosetting resin layers 11. Note that the resin laminate 1 of the first specific example corresponds to the resin laminate 1a of FIG.

(Second specific example)
The manufacturer produced a fiber-containing resin body containing a thermosetting resin by the following procedure.
The manufacturer prepares the thermosetting resin raw material liquid described in the first specific example, and converts the thermosetting resin raw material liquid to “CO6343 (trade name)” manufactured by Toray Industries, Inc., which is a carbon fiber cloth, under reduced pressure. For impregnation. The manufacturer heat-cured the impregnated carbon fiber cloth at 160 ° C. for 2 hours to produce a carbon fiber-containing thermosetting resin sheet (fiber-containing thermosetting resin layer 12). Subsequently, the manufacturer inserts a polycarbonate film (fiber-free thermoplastic resin layer 21) one by one between the three layers of the prepared carbon fiber-containing thermosetting resin sheet and presses it at 160 ° C. under reduced pressure. Thus, a resin laminate 1 was obtained.
The resin laminate 1 thus produced is a resin laminate 1 having a fiber-free thermoplastic resin layer 21 between the fiber-containing thermosetting resin layers 12. Note that the resin laminate of the second specific example corresponds to the resin laminate 1b of FIG.

(Third specific example)
The manufacturer produced a fiber-containing thermosetting resin sheet in which the resin is in a semi-cured state by the following procedure. First, the manufacturer prepares a carbon fiber cloth (carbon fiber-containing thermosetting resin sheet; fiber-containing thermosetting resin layer 12) impregnated with a thermosetting resin raw material liquid in the same manner as described in the second specific example. Produced.
Then, the manufacturer heated the carbon fiber-containing thermosetting resin sheet at 80 ° C. for 1 hour. Thus, a fiber-containing thermosetting resin sheet in which the resin was in a semi-cured state was produced. A PET film (fiber-free thermoplastic resin layer 21) was sandwiched between each layer of four fiber-containing thermosetting resin sheets in a semi-cured state, and pressed at 180 ° C. under reduced pressure. Thus, a resin laminate 1 was obtained.
The resin laminate 1 produced in this manner is a resin laminate 1 in which the fiber-free thermoplastic resin layer 21 exists between the fiber-containing thermosetting resin layers 12 produced from a semi-cured state of the resin. is there. The resin laminate 1 of the third specific example corresponds to a resin laminate 1b shown in FIG. 2 manufactured using the fiber-containing thermosetting resin layer 12 in a semi-cured state.

(Fourth specific example)
Between each of the four fiber-containing thermosetting resin sheets (fiber-containing thermosetting resin layer 12) in which the resin is in a semi-cured state, a carbon fiber cloth manufactured by Toray Industries, Inc. And a fiber-containing thermoplastic resin sheet (fiber-containing thermoplastic resin layer 22) made of polycarbonate and manufactured by Ichimura Sangyo Co., Ltd. was sandwiched one by one. Thereafter, these laminates were pressed at 180 ° C. under reduced pressure to obtain a resin laminate 1.
The resin laminate 1 manufactured in this manner is a resin laminate 1 in which the fiber-containing thermoplastic resin layer 22 exists between the fiber-containing thermosetting resin layers 12. The resin laminate 1 of the fourth specific example corresponds to the resin laminate 1h of FIG.

(Fifth specific example)
The manufacturer provided 89.6 parts by weight of “HN-2200 (trade name)” manufactured by Hitachi Chemical Co., Ltd. as a curing agent, and “2E4MZ-CN” (trade name) manufactured by Shikoku Chemicals as a curing accelerator. ) "Was added, and the mixture was stirred and mixed. 100 parts by weight of “jER828 (trade name)” manufactured by Mitsubishi Chemical, which is an epoxy resin, was added to this mixed solution, and the mixture was stirred and mixed to obtain a resin raw material liquid. At this mixing ratio, the epoxy resin and the curing agent are mixed at an equal ratio. The manufacturer impregnated one carbon fiber cloth used in the second specific example with the obtained resin raw material liquid under reduced pressure. Further, the manufacturer heat-cured the impregnated carbon fiber cloth at 160 ° C. for 2 hours. The manufacturer inserts a PET film between the four layers of the prepared carbon fiber-containing thermosetting resin sheet (fiber-containing thermosetting resin layer 12) one by one, and presses it at 180 ° C. under reduced pressure to obtain a resin. The laminate 1 was obtained.

The resin laminate 1 manufactured in this manner is a resin laminate 1 in which the fiber-free thermoplastic resin layer 21 exists between the fiber-containing thermosetting resin layers 12. However, the resin laminate 1 manufactured in the fifth specific example is a resin laminate 1 having a non-dynamic covalent bond thermosetting resin layer.
The resin laminate 1 of the fifth specific example corresponds to the resin laminate 1b of FIG. 2 in which the fiber-containing thermosetting resin layer 12 has no dynamic bond.

(Comparative example)
In the following procedure, a resin laminate 1Z of FIG. 16 was produced as a comparative example.
The resin raw material liquid prepared in the first specific example was impregnated under reduced pressure with four carbon fiber cloths used in the second specific example being stacked. Then, the four impregnated carbon fiber cloths were heated and cured at 160 ° C. for 2 hours, thereby obtaining a resin laminate 1 </ b> Z including only the fiber-containing thermosetting resin layer 12.
The resin laminate 1Z produced in this manner is a resin laminate 1Z in which only four fiber-containing thermosetting resin layers 12 are laminated.

(Comparison result)
Reforming of the

resin laminates

1 and 1Z was performed according to the following method.
Each of the resin laminate 1 obtained in the third specific example and the resin laminate 1Z obtained in the comparative specific example was cut into a plate having a width of 5 cm and a length of 20 cm. Here, as described above, the resin laminate 1 of the third specific example has a fiber between the fiber-containing thermosetting resin layers 12 prepared from a semi-cured state of the resin between the fiber-containing thermoplastic resin layers 22. The resin laminate 1 includes the non-containing thermoplastic resin layer 21. Further, as described above, the resin laminate 1Z of the comparative specific example has only four fiber-containing thermosetting resin layers 12 shown in FIG.

{Circle around (1)} The obtained respective plate-shaped

resin laminates

1 and 1Z were heated to 180 ° C. in a thermostat. In addition, a SUS mold having a radius of curvature of 200 mm separated vertically was heated to 180 ° C. The heated resin laminate 1 of the third specific example and the resin laminate 1Z of the comparative specific example were sandwiched between the upper and lower molds, and left for 2 hours. Two hours later, the mold was taken out of the thermostat and allowed to cool. When each of the

resin laminates

1 and 1Z taken out of the mold was observed, delamination was observed in the concave portion (inside the bent portion) in the resin laminate 1Z of the comparative specific example. This is separation caused by stress between the layers generated when bending. On the other hand, no peeling was observed in the resin laminate 1 of the third specific example.

(5) Next, the bending angle was measured from the height of the curved portion of the plate-shaped

resin laminates

1 and 1Z taken out of the mold. The difference between the bending angle θon of the mold and the bending angle θoff of the

resin laminates

1 and 1Z after remolding was defined as the springback amount Δθ.

Next, the amount of springback of the resin laminate 1 of the fourth specific example (with dynamic covalent bonds) was compared with the resin laminate 1 of the fifth specific example (without dynamic covalent bonds). As a result, the springback of the resin laminate 1 of the fourth specific example was 5 °, whereas the springback of the resin laminate 1 of the fifth specific example was 15 °. As described above, the amount of springback of the resin laminate 1 of the fourth specific example (with dynamic covalent bonds) was smaller than that of the resin laminate 1 of the fifth specific example (without dynamic covalent bonds). .

(Resin laminate manufacturing system 100)
FIG. 17 is a diagram illustrating a configuration example of a resin laminate manufacturing system 100 that manufactures the resin laminate 1 according to the present embodiment.
The resin laminate manufacturing system 100 includes two first rolls 101, a second roll 102, a thermostat 111, and a cutter 112. The first roll 101 processes a fiber-containing thermosetting resin sheet (fiber-containing thermosetting resin layer 12) in which the resin is in a semi-cured state into, for example, a width of 5 cm and a length of 1 m, and winds the sheet into a cylinder having a diameter of 5 cm. It is turned. The second roll 102 is formed, for example, by winding a PET film (fiber-free thermoplastic resin layer 21) having a width of 5 cm and a length of 1 m around a cylinder having a diameter of 5 cm. The width and length of each sheet in the first roll 101 and the second roll 102 and the diameter of the wound tube are not limited to these sizes. Here, when the fiber-containing thermosetting resin sheet is in a semi-cured state, it can be wound into a roll.
Then, as shown in FIG. 17, two rolls of the fiber-containing resin sheet in a semi-cured state and one roll of the PET film are alternately stacked and heated in the thermostat 111, whereby the resin laminate 1 is heated. Are manufactured continuously. The resin laminate 1 manufactured by heating is cut into an appropriate length by the cutter 112.

In the example of FIG. 17, a resin laminate 1 (corresponding to the resin laminate 1b in FIG. 2) having a configuration in which one fiber-free thermoplastic resin layer 21 is sandwiched between fiber-containing thermosetting resin layers 12 is manufactured. But it is not limited to this. That is, the resin laminate 1 shown in FIGS. 1 and 3 to 15 and the resin laminate 1 shown in FIGS. 1 to 15 are further laminated with the resin laminate 1 (where the thermosetting resin layer is located between the thermosetting resin layers). (There is always a thermoplastic resin layer).
Further, in the example of FIG. 17, the thermosetting resin layer in the semi-cured state is wound in a roll shape, but the thermosetting resin layer in the cured state may be put into the thermostat 111.

The present invention is not limited to the above-described embodiment, and includes various modifications. For example, the above-described embodiments have been described in detail for easy understanding of the present invention, and are not necessarily limited to those having all the configurations described above.

1, 1a to 1q Resin laminate 11 Fiber-free thermosetting resin layer (thermosetting resin layer)
12 Fiber-containing thermosetting resin layer (fiber-containing thermosetting resin layer, thermosetting resin layer)
21 Fiber-free thermoplastic resin layer (thermoplastic resin layer)
22 Fiber-containing thermoplastic resin layer (fiber-containing thermoplastic resin layer, thermoplastic resin layer)
REFERENCE SIGNS LIST 100 Resin laminate production system 101 First roll (thermosetting resin layer in semi-cured state)
102 2nd roll

Claims

A resin laminate, wherein a layer of a thermoplastic resin is in close contact between any two layers of a thermosetting resin.
The molecule which comprises the said thermosetting resin has a dynamic covalent bond which is a covalent bond which detach | separates and couple | bonds reversibly in at least one of the layers of the said thermosetting resin. The Claim 1 characterized by the above-mentioned. Resin laminate.
The resin laminate according to claim 2, wherein the thermosetting resin having the dynamic covalent bond is a resin containing an ester bond.
The resin laminate according to claim 1, wherein at least one of the thermosetting resin layers is a fiber-containing thermosetting resin layer.
The resin laminate according to claim 4, wherein the fibers contained in the fiber-containing thermosetting resin include at least one of aramid fiber, glass fiber, carbon fiber, and plant fiber.
The resin laminate according to claim 1, wherein when a plurality of the thermoplastic resin layers are present, at least one of the thermoplastic resin layers is a fiber-containing thermoplastic resin layer.
The resin laminate according to claim 6, wherein the fibers contained in the fiber-containing thermoplastic resin include at least one of an aramid fiber, a glass fiber, a carbon fiber, and a plant fiber.
The resin laminate according to claim 1, wherein the thermoplastic resin is a resin having a -C (= O)-(O)-bond.
The resin laminate according to claim 1, wherein the thermoplastic resin is one of polyester, polycarbonate, polyamide, and acrylic resin.
An arranging step of closely arranging the layer of the thermosetting resin and the layer of the thermoplastic resin such that the thermoplastic resin is present between any two layers of the thermosetting resin,
A heating step of heating the layer of the thermosetting resin and the layer of the thermoplastic resin arranged in the arrangement step at a predetermined temperature or higher,
A method for producing a resin laminate, comprising:
In the disposing step,
The method for producing a resin laminate according to claim 10, wherein the thermosetting resin layer is in a semi-cured state.