TW201808636A - Resin composition for formation of composite, composite, and method for producing composite - Google Patents

Abstract

Disclosed is a composite comprising a substrate, and a resin adhering to the substrate. The resin contains a polymer containing, as a monomer unit, a radical polymerizable monomer including a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer. When the first monofunctional radical polymerizable monomer is homopolymerized, a homopolymer having a glass transition temperature of 20 DEG C or lower is formed. When the second monofunctional radical polymerizable monomer is homopolymerized, a homopolymer having a glass transition temperature of 50 DEG C or higher is formed.

Description

Resin composition for forming composite body, composite body, and method for manufacturing composite body

The present invention relates to a resin composition for forming a composite, a composite, and a method for producing a composite.

Attempts are now being made to suppress changes in shape due to use and leap years among various raw materials. In particular, wrinkles and wrinkles are likely to occur in flat materials and processed products, and thus wrinkle prevention functions may be provided. For example, the development of various clothes that have been provided with a wrinkle prevention function has been generally sold. For example, Patent Document 1 describes a handkerchief excellent in wrinkle resistance and gatherability.

A wrinkle removal device is used to prevent abnormal reading of banknotes in vending machines and the like. For example, Patent Document 2 describes a banknote wrinkle removing device having a simple structure. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-177708 [Patent Document 2] Japanese Patent Laid-Open No. 09-040262

[Problems to be Solved by the Invention] An object of one aspect of the present invention is to provide a composite body that has excellent shape reproducibility by heating and can be easily manufactured. [Means for solving problems]

One aspect of the present invention relates to a composite including a substrate and a resin adhered to the substrate. The resin contains a polymer including a radical polymerizable monomer as a monomer unit, and the radical polymerizable monomer includes a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer. The first monofunctional radical polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when it is polymerized alone. The second monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or higher when polymerized alone.

A composite including a resin containing a combination of two kinds of radical polymerizable monomers selected with the glass transition temperature of a homopolymer as described above, having excellent shape reversibility by heating as described above.

The composite can be easily produced by, for example, a method including the steps of radical polymerization including the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer. The radically polymerizable monomer is polymerized in a resin composition that is in contact with the base material and is in contact with the substrate. [Effect of the invention]

According to one aspect of the present invention, a composite having excellent shape reproducibility by heating is provided. In addition, composites of several forms can be produced by simple methods regardless of the material and shape of the base material, and therefore can easily have complicated three-dimensional structures such as unevenness and creases. The composites of several forms can be reshaped by simple methods such as heating with warm water or warm air. Therefore, they are also excellent in wrinkle prevention function and wrinkle acquisition function. By using the resin composition according to one aspect of the present invention, it is possible to easily produce a composite having a base material having various forms and having a shape reproducibility or a shape memory property.

Hereinafter, several embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

(Composite) The composite according to one embodiment includes a substrate and a resin adhered to the substrate. The resin can be formed from a resin composition (composite-forming resin composition) containing a radical polymerizable monomer including a first monofunctional radical polymerizable monomer and a second monofunctional free radical polymer. Group polymerizable monomer. Each of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer has one radical polymerizable group. By polymerizing a radical polymerizable monomer in the resin composition, a polymer containing each radical polymerizable monomer as a monomer unit is produced. Thereby, a resin composition is hardened, and the hardened | cured material of a resin as a composite body is produced | generated. That is, the resin of the composite may be a cured product of a curable resin composition.

The weight average molecular weight of the polymer formed from the radical polymerizable monomer may be 100,000 or more, or 200,000 or more. The higher the weight average molecular weight, the more the elongation at break of the resin tends to increase. In this specification, unless there is a special definition of weight average molecular weight, it shows the standard polystyrene conversion value calculated | required by gel permeation chromatography.

The substrate is not particularly limited, and can be arbitrarily selected according to the application. Examples of the material of the substrate include synthetic or natural resins, metals, glass, ceramics, wood, and natural sponges.

The substrate may be a fibrous substrate such as a nonwoven fabric, a woven fabric, or a mesh. Examples of the substrate include synthetic or natural fiber nonwoven or woven fabric, paper, glass cloth, glass wool, metal mesh, and steel wool. The substrate may be a porous substrate such as a sponge. When the base material is a base material containing voids that easily absorb liquid, such as a fibrous base material and a porous base material, part or all of the resin may be impregnated into the base material from the viewpoint of improving shape reproducibility. .

Alternatively, the resin of the composite may form a resin layer (for example, a coating layer) covering part or all of the surface of the substrate. For example, the composite may include a fiber (single yarn) as a base material and a resin layer covering part or all of the outer peripheral surface of the fiber.

The composite may include a resin layer formed of a resin, and a base material covering a part or all of the molded body. The composite may include two or more substrates which are the same or different, and a resin sandwiched between the substrates. For example, the composite may have a laminated structure having a resin layer sandwiched between substrates inside.

The shape of the substrate is not particularly limited, and may be, for example, planar, fibrous, or other three-dimensional shapes. The base material may have, for example, a curved portion such as a heel portion of a shoe, a folded portion such as a pleating process of clothes, or an uneven surface such as a banknote.

When the shape of the substrate is planar, the thickness may be, for example, 10 nm or more, 100 nm or more, or 1 μm or more, and may be 10 mm or less, 1 mm or less, or 500 μm or less.

From the viewpoint of excellent shape reproducibility, the amount of resin (adhesion amount of resin) in the composite may be, for example, 1 mass% or more, 5 mass% or more, or 10 mass% or more with respect to the quality of the substrate. And may be 1000% by mass or less, 500% by mass or less, or 100% by mass or less.

The resin composition of the resin (cured material) that can be used to form the composite contains two types of monofunctional radical polymerizable monomers (the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerization) having different glass transition temperatures. Sexual monomer). The first monofunctional radical polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when it is polymerized alone. The second monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or higher when polymerized alone. A resin formed from a resin composition containing these two types of monofunctional radically polymerizable monomers can impart excellent shape reversibility to the composite by heating. In addition, the resin has high breaking elongation and breaking strength. From the same viewpoint, the first radical polymerizable monomer may be a monomer that forms a homopolymer of 10 ° C. or lower or 0 ° C. during the single polymerization, and the second radical polymerizable monomer may also be a monomer A monomer that forms a homopolymer having a glass transition temperature of 60 ° C. or higher or 70 ° C. or higher when polymerized alone. The glass transition temperature of the homopolymer formed from the first monofunctional radical polymerizable monomer may be -70 ° C or higher. The glass transition temperature of the homopolymer formed from the second monofunctional radical polymerizable monomer may be 150 ° C. or lower.

In this specification, the glass transition temperature of a homopolymer formed from each radically polymerizable monomer means a temperature determined by differential scanning calorimetry. Those skilled in the art can also know the glass transition temperature of a homopolymer of a general radical polymerizable monomer in the form of literature values.

The content of the first monofunctional radical polymerizable monomer may be 5% by mass or more, 10% by mass or more, or 15% by mass or more, and may be 90% by mass based on the total amount of the radically polymerizable monomer. Or less, 85% by mass or less, or 80% by mass or less. When the content of the first radical polymerizable monomer is within these ranges, the cured product exhibits excellent shape reproducibility, and a more significant effect can be obtained from the viewpoint of taking into account both high elongation at break and high elastic modulus. .

The first monofunctional radical polymerizable monomer may be an alkyl (meth) acrylate which may have a substituent. The alkyl (meth) acrylate which may be used as the first monofunctional radical polymerizable monomer and which may have a substituent may be selected from, for example, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, and methyl. N-butyl acrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, methacrylic acid 2-Hydroxyethyl, 2-Hydroxypropyl methacrylate, 2-Hydroxy-1-methylethyl methacrylate, 2-methoxyethyl acrylate, and glycidyl methacrylate At least one of the group.

The first monofunctional radical polymerizable monomer may be 2-ethylhexyl acrylate. By using 2-ethylhexyl acrylate, the shape resilience and elongation at break of the resin are increased, and a more advantageous effect is obtained in terms of easy control of the elastic modulus.

The content of the second monofunctional radical polymerizable monomer may be 10% by mass or more, 15% by mass or more, or 20% by mass or more, and may be 95% by mass based on the total amount of the radically polymerizable monomer. Below 90% by mass, or below 85% by mass. When the content of the second monofunctional radical polymerizable monomer is within these ranges, a more significant effect is obtained in that the resin can achieve both high elongation at break and high elastic modulus.

The second monofunctional radical polymerizable monomer may be a (meth) acrylic acid such as an alkyl (meth) acrylate or a derivative thereof (such as an alkyl (meth) acrylate) which may have a substituent. The second monofunctional radical polymerizable monomer may be, for example, selected from the group consisting of adamantyl acrylate, adamantane methacrylate, 2-cyanomethyl acrylate, 2-cyanobutyl acrylate, acrylamide, and acrylic acid. At least one selected from the group consisting of methacrylic acid, acrylonitrile, dicyclopentyl acrylate, and methyl methacrylate.

The second monofunctional radical polymerizable monomer may be at least one selected from the group consisting of acrylonitrile, dicyclopentyl acrylate, and methyl methacrylate. By using these monomers, the shape resilience and the breaking strength of the resin are increased, and further advantageous effects are obtained in terms of making it easier to control the elastic modulus.

The ratio of the first monofunctional radical polymerizable monomer to the second monofunctional radical polymerizable monomer can be appropriately adjusted. The higher the ratio of the first monofunctional radical polymerizable monomer, the lower the elastic modulus and the glass transition temperature of the resin, and the elongation at break tends to increase. The higher the ratio of the second monofunctional radical polymerizable monomer, the higher the elastic modulus and glass transition temperature of the resin tend to be.

The monomer unit derived from the first monofunctional radically polymerizable monomer is considered to function in the resin as a soft segment that relaxes external forces such as extension and bending. The monomer unit derived from the second monofunctional radically polymerizable monomer is considered to function in the resin as a hard segment that generates a force that resists external forces such as extension and bending and restores the shape. By introducing these two monomer units having greatly different properties into the polymer chain forming the hardened material, the properties of both can be taken into consideration. However, the mechanism for expressing the physical properties of the resin is not necessarily limited to this.

Taking the above into consideration, the mass ratio of the first monofunctional radical polymerizable monomer to the second monofunctional radical polymerizable monomer can be 90:10 to 5: if the total of the two is 100. 95, or 85:15 to 30:70.

The resin composition may further contain, as the radical polymerizable monomer, monomers other than the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer. The total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer may be 60% by mass or more and 70% by mass based on the total amount of the radical polymerizable monomer. Or more, or 80% by mass or more. By keeping the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer within these ranges, the resin has high shape reversibility, elongation at break, and high elastic elongation. In terms of getting even more significant effects.

The radical polymerizable monomer in the resin composition may include a polyfunctional radical polymerizable monomer having two or more radical polymerizable groups, and / or a first monofunctional radical polymerizable monomer and a second free radical polymerizable monomer. Monofunctional radical polymerizable monomers (monomers that form a homopolymer of more than 20 ° C. and less than 50 ° C. when polymerized alone) other than the polymerizable monomers.

There is a tendency for the resin to have a high breaking strength and excellent solvent resistance by including a polyfunctional radical polymerizable monomer in the radical polymerizable monomer. The resin composition may include a difunctional radical polymerizable monomer and / or a trifunctional radical polymerizable monomer as the polyfunctional radical polymerizable monomer. The content of the polyfunctional radical polymerizable monomer may be 0.01% by mass or more, 0.05% by mass or more, or 0.1% by mass or more, and may be 10% by mass or less based on the total amount of the radically polymerizable monomer. 8.0% by mass or less, or 5.0% by mass or less. When the content of the polyfunctional radically polymerizable monomer is within these ranges, there is a tendency that the breaking strength and elongation at break of the resin can be taken into consideration at a particularly high level.

From the viewpoint of compatibility with other components, the polyfunctional radical polymerizable monomer may be a polyfunctional (meth) acrylate. The polyfunctional (meth) acrylate may be a difunctional (meth) acrylate and / or a trifunctional (meth) acrylate. By using a difunctional and / or trifunctional (meth) acrylate, it is possible to obtain a further advantageous effect in terms of both the breaking strength and the elongation at break of the resin. The difunctional and / or trifunctional (meth) acrylate may include a cyclic structure, and may also form a cyclic structure by a hardening reaction.

Examples of the difunctional or trifunctional (meth) acrylate include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6- Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, polypropylene glycol di (meth) acrylate, polytetraethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxy modified bisphenol A bis (methyl) ) Acrylate, tris (2- (meth) acryloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, and pentaerythritol tri (meth) acrylate. These compounds can be used alone or in combination of two or more.

The total content of the difunctional (meth) acrylate and trifunctional (meth) acrylate may be 0.1% by mass or more, 0.2% by mass or more, or 0.5% by mass based on the total amount of the radical polymerizable monomer. Above, and may be 10% by mass or less, 8.0% by mass or less, or 5.0% by mass or less.

The resin composition may contain a polymerization initiator for polymerizing a radical polymerizable monomer. The polymerization initiator may be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof. The content of the polymerization initiator may be appropriately adjusted within a normal range, but may be, for example, 0.01 to 5% by mass based on the mass of the resin composition.

Examples of thermal radical polymerization initiators include organic peroxides such as ketone peroxide, peroxyketal, dialkyl peroxide, difluorenyl peroxide, peroxyester, peroxydicarbonate, and hydrogen peroxide. Persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, 2,2'-azobis-isobutyronitrile (AIBN), 2,2-azobis-2,4-dimethylvaleronitrile ( ADVN), 2,2'-azobis-2-methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid and other azo compounds; alkyl groups such as sodium ethoxide and third butyl lithium Metals, silicon compounds such as 1-methoxy-1- (trimethylsilyloxy) -2-methyl-1-propene, and the like.

It is also possible to combine a thermal radical polymerization initiator with a catalyst. Examples of the catalyst include reducing compounds such as metal salts and tertiary amine compounds such as N, N, N ', N'-tetramethylethylenediamine.

Examples of the photo-radical polymerization initiator include benzophenone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl- 1- [4- (methylthio) phenyl] -2-morpholino-acetone-1,2,2'-dimethoxy-1,2-diphenylethane-1-one (Yanjia Solid (Irgacure) 651 (made by Japan Ciba-Geigy Co., Ltd.) and other aromatic ketones; quinone compounds such as alkyl anthraquinone; benzoin ether compounds such as benzoin alkyl ether; benzoin, alkyl benzoin Benzoin compounds such as benzoin dimethyl ketal; 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-fluorophenyl) -4,5-diphenylimidazole dimer, etc. 2,4,5-triarylimidazole dimer; 9-phenylacridine, 1,7- (9,9'-acridyl) heptane, etc. Acridine derivatives. The photopolymerization initiators may be used singly or in combination of two or more.

The resin composition may optionally include a binder polymer, a solvent, a photochromic agent, a thermal coloration inhibitor, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, an adhesiveness imparting agent, a leveling agent, Peeling accelerators, antioxidants, fragrances, developers, etc. These can be used alone or in combination of two or more. When the resin composition contains other components, the content may be 0.01% by mass or more and 20% by mass or less based on the mass of the resin composition.

The resin or the composite may or may not have shape memory, and may have shape memory by appropriately selecting the type of the radical polymerizable monomer and the like. In this specification, "shape memory" means that when a resin or a composite is deformed by an external force at room temperature (for example, 25 ° C), the resin or the composite maintains the deformed shape at room temperature under no load. When heated to a high temperature, it returns to its original shape. Among them, the resin or the composite body can also completely return to the original shape without heating. The heating temperature for the shape reply is, for example, 70 ° C.

The storage elastic modulus of the resin at 25 ° C is not particularly limited, and may be 0.5 MPa or more. A resin having a storage elastic modulus of 0.5 MPa or more generally has shape memory properties. The elastic modulus of the resin may be 1.0 MPa or more, or 10 MPa or more, and may be 10 GPa or less, 8 GPa or less, or 5 GPa or less. If the storage elastic modulus is high, the resin tends to easily retain the deformed shape. There is a tendency for the resin to easily return to its original shape when heated by having a storage elastic modulus of a moderate size. The elastic modulus of the resin can be controlled, for example, based on the type of the radical polymerizable monomer and its blending ratio, and the amount of the radical polymerization initiator. The elastic modulus of the resin can be appropriately adjusted according to the properties of the substrate.

The glass transition temperature of the resin is not particularly limited, and may be, for example, 30 ° C or higher, or 40 ° C or higher. When the glass transition temperature is room temperature or higher than the use temperature, it is easy to maintain a high elastic modulus during use and is advantageous in terms of excellent handling properties. The glass transition temperature can be adjusted, for example, by the mixing ratio of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer in the curable resin composition.

The elongation at break of the resin may be 10% or more, 100% or more, or 200% or more. When the breaking elongation of the resin falls within these ranges, a particularly significant effect is obtained in that the shape that can be changed is large. The breaking strength of the resin may be 1 MPa or more, 3 MPa or more, or 5 MPa or more.

(Method for Manufacturing Composite) The composite according to this embodiment can be manufactured, for example, by a method including the steps of: contacting the resin composition for forming a composite according to the embodiment with a substrate; and contacting the substrate with the substrate. In the resin composition, a step (curing step) of generating a cured product of the resin composition as a resin by polymerization of a radical polymerizable monomer.

In the contacting step, the resin composition can be brought into contact with the substrate by, for example, impregnating the resin composition with the substrate or applying the resin composition to the substrate. The method of impregnation and coating is not particularly limited. A resin composition layer that is in contact with or adheres to the substrate is formed by impregnation and coating. From the viewpoints of workability and the like, the polymerization reaction of the radical polymerizable monomer may be partially performed, and then the resin composition in a semi-hardened state may be brought into contact with the substrate.

In the hardening step, the radical polymerization of the radical polymerizable monomer can be initiated by heating or irradiating active light such as ultraviolet rays. The temperature of the resin composition in the hardening step is not particularly limited, and when the resin composition contains a solvent, it may be below its boiling point. Alternatively, after removing the solvent from the resin composition, the polymerization reaction may be started. The polymerization reaction can also be performed in an environment of an inert gas such as nitrogen, helium, or argon. This can suppress polymerization inhibition due to oxygen and stably obtain a resin of good quality.

When a resin or a composite has a shape memory property, a polymer is usually produced, and the shape of the resin or the composite at the time when the resin composition hardens becomes a basic shape. A resin or a composite body deformed by an external force is deformed in a manner close to its basic shape by heating.

Therefore, for example, after the step of contacting the resin composition with the substrate, the substrate is deformed into a predetermined shape, and then the resin composition is hardened, or the resin composition is contacted with the substrate deformed into a predetermined shape, and the resin is then By hardening the composition, a composite having a desired shape as a basic shape can be obtained.

The composite may have shape memory properties derived from the shape memory properties of the resin. Therefore, after the composite body provided with the basic shape is bent, elongated, or recessed, for example, the composite body is restored to the basic shape by heating. The temperature for heating to restore the basic shape is, for example, 70 ° C. [Example]

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.

1. Resin composition for composite formation Each raw material was mixed in a mass ratio shown in Table 1 to prepare each composite formation resin composition of the examples and comparative examples. The numerical values in the table are parts by mass.

2. Composite sample for shape reproducibility test Composite sample 1 A non-woven fabric impregnated with a nylon (registered trademark) fiber in a resin composition containing a thermal polymerization initiator (2,2'-azobisisobutyronitrile). The nonwoven fabric is sufficiently impregnated with the resin composition. The non-woven fabric impregnated with the resin composition was sandwiched by a stainless steel flat plate to remove excess resin composition. Thereafter, the resin composition was hardened by heating at 70 ° C. for 1 hour in an oven to obtain a structure 100 including two stainless steel flat plates 10 and a composite body 1 sandwiched therebetween as shown in FIG. 1. . The stainless steel flat plate 10 was removed from the structure 100 to obtain a flat composite sample 1 having a nonwoven fabric as a base material.

The composite sample 2 uses a curved stainless steel plate instead of a stainless steel flat plate. In addition, the same procedure as the composite sample 1 is used to obtain the two stainless steel plates 11 shown in FIG. 2 and the sandwiched between them. Structure 200 of complex 1. The stainless steel plate 11 was removed from the structure 200 to obtain a curved plate-like composite sample 2 having a nonwoven fabric as a base material.

Composite Sample 3 A resin composition containing a photopolymerization initiator (Yanjiagu 651) was coated on a paper substrate (copy paper), and a polyethylene terephthalate (PET) film was superposed thereon. A PET film was irradiated with ultraviolet rays at a cumulative light amount of 1000 mJ / cm ² to harden the resin composition. Thereafter, the PET film was peeled off to obtain a flat plate-like or sheet-like composite sample 3 having a paper substrate.

Composite Sample 4 A nonwoven fabric in which a nylon (registered trademark) fiber was impregnated into a resin composition containing a photopolymerization initiator (Yanjiagu 651), and the resin composition was sufficiently impregnated into the nonwoven fabric. The shape of the nonwoven fabric impregnated with the resin composition was adjusted to a flat plate shape, and then a polyethylene terephthalate (PET) film was superposed thereon. A PET film was irradiated with ultraviolet rays at a cumulative light amount of 1000 mJ / cm ² to harden the resin composition. Thereafter, the PET film was peeled off to obtain a flat plate-like or sheet-like composite sample 4 having a nonwoven fabric as a base material.

Composite sample 5 A glass cloth (made by Maeda Glass Co., Ltd., EP09E) with a thickness of 0.09 mm was impregnated in a resin composition containing a thermal polymerization initiator (2,2'-azobisisobutyronitrile), and the glass The cloth is sufficiently impregnated with the resin composition. The glass cloth impregnated with the resin composition was sandwiched between stainless steel flat plates, and the excess resin composition was removed. Thereafter, the resin composition was hardened by heating at 70 ° C. for 1 hour in an oven to obtain a structure 100 including two stainless steel flat plates 10 and a composite body 1 sandwiched therebetween as shown in FIG. 1. The stainless steel flat plate 10 was removed from the structure 100 to obtain a flat plate-like composite sample 5 having a glass cloth as a substrate.

Composite sample 6 An aluminum mesh (42 mesh) was impregnated with a resin composition containing a thermal polymerization initiator (2,2'-azobisisobutyronitrile), and the aluminum mesh was fully impregnated with the resin composition. The aluminum mesh impregnated with the resin composition was sandwiched between stainless steel flat plates to remove excess resin composition. Thereafter, the resin composition was hardened by heating at 70 ° C. for 1 hour in an oven to obtain a structure 100 including two stainless steel flat plates 10 and a composite body 1 sandwiched therebetween as shown in FIG. 1. The stainless steel flat plate 10 was removed from the structure 100 to obtain a flat composite sample 6 having an aluminum mesh as a base material.

Composite Sample 7 A resin composition containing a photopolymerization initiator (Yanjiagu 651) was coated on a polyimide film (25 μm thick), and polyethylene terephthalate ( PET) film. A PET film was irradiated with ultraviolet rays at a cumulative light amount of 1000 mJ / cm ² to harden the resin composition. After that, the PET film was peeled off to obtain a flat plate-like or sheet-like composite sample 7 having a polyimide substrate.

3. Shape reproducibility test Bend the flat composite sample 1, composite sample 3, composite sample 4, composite sample 5, composite sample 6, composite sample 7 to 180 °, and confirm the shape of the bend It does not substantially return to its original shape. The curved composite sample 2 was deformed in a direction opposite to the bending direction and bent 180 °, and it was confirmed that the bent shape did not substantially return to the original shape.

Each deformed composite sample was immersed in hot water at 80 ° C., and it was judged to be “good” when it was returned to its initial shape within 10 seconds, and “bad” when it was not responded.

4. Production of Resin Film A resin composition for forming a composite is dropped onto a polyethylene terephthalate (PET) film subjected to a release treatment to form a coating film of the resin composition. While a 0.2 mm gap was left between the coating film and the coating film, the coating film was covered with a PET film subjected to a mold release treatment. In the case of a resin composition containing a photopolymerization initiator, the PET film is irradiated with ultraviolet rays of 365 nm at a cumulative light amount of 1000 mJ / cm ² to harden the coating film. In the case of a curable resin composition containing a thermal polymerization initiator, the coating film is hardened by heating in an oven at 70 ° C. for 1 hour. After curing, the PET film was peeled to obtain a resin film for a tensile test.

5. Tensile test A strip-shaped test piece with a width of 5 mm and a length of 50 mm was punched from the resin film. This test piece was supplied to a tensile tester (made by Shimadzu Corporation, EZ-TEST) under the conditions of a measurement temperature of 25 ° C, a tensile speed of 10 mm / min, and a distance between chucks of 30 mm. test. The stress at the time of breaking was taken as the breaking strength, and the slope of the stress-strain curve at the beginning of stretching was taken as the tensile elastic modulus.

6. Measurement of glass transition temperature A strip-shaped test piece with a width of 5 mm and a length of 50 mm was punched from the resin film. Using a dynamic viscoelasticity measuring device (manufactured by TA Instruments Co., Ltd., RSA-G2), the temperature change of tan δ of the test piece was measured under conditions of a distance between chucks of 20 mm and a measurement frequency of 10 Hz. The temperature at which tan δ was shown as a peak was taken as the glass transition temperature.

[Table 1]

As shown in Table 1, it was confirmed that by using a resin composition containing a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer, a composite having excellent shape reproducibility can be easily produced. .

1‧‧‧ complex
10‧‧‧Stainless steel flat plate
11‧‧‧ curved stainless steel plate
100, 200‧‧‧ structure

FIG. 1 is a cross-sectional view showing a method of preparing a composite sample for a shape reproducibility test. FIG. 2 is a cross-sectional view showing a method of preparing a composite sample for a shape reproducibility test.

1‧‧‧ complex

10‧‧‧Stainless steel flat plate

100‧‧‧ Structure

Claims (13)

A composite comprising a base material and a resin attached to the base material, the resin containing a polymer including a radical polymerizable monomer as a monomer unit, and the radical polymerizable monomer including a first A monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer; the first monofunctional radical polymerizable monomer is a homopolymer having a glass transition temperature of 20 ° C. or less when independently polymerized; The second monofunctional radical polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or higher when polymerized alone. The composite according to item 1 of the scope of application, wherein the monomer unit derived from the first monofunctional radical polymerizable monomer and the monomer unit derived from the second monofunctional radical polymerizable monomer The total content of the body unit is 60% by mass or more based on the mass of the polymer. The composite according to item 1 or item 2 of the scope of patent application, wherein the first monofunctional radical polymerizable monomer comprises 2-ethylhexyl acrylate. The complex according to any one of claims 1 to 3, wherein the second monofunctional radical polymerizable monomer comprises a member selected from the group consisting of acrylonitrile, dicyclopentyl acrylate, and formazan At least one of the group consisting of methyl methacrylate. The complex according to any one of claims 1 to 4, wherein the radical polymerizable monomer further includes a difunctional radical polymerizable monomer and / or a trifunctional radical polymerizable polymer. monomer. The composite according to any one of claims 1 to 5, wherein the content of the monomer units derived from the first monofunctional radical polymerizable monomer is the total amount of the polymer. The amount is 5 mass% or more and 90 mass% or less based on the amount, and the content of the monomer unit derived from the second monofunctional radical polymerizable monomer is 10 based on the total amount of the polymer. Above mass% and below 95 mass%. A resin composition for forming a composite, which is used to form the resin including a substrate and a resin adhered to the substrate, and the resin composition for forming a composite contains a radically polymerizable monomer. Body, the radical polymerizable monomer includes a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer, and the first monofunctional radical polymerizable monomer is polymerized separately A monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or less, and the second monofunctional radical polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or more when separately polymerized . The resin composition for forming a complex according to item 7 of the scope of the patent application, wherein the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer is as follows The total amount of the radical polymerizable monomer is 60% by mass or more based on the reference. The resin composition for forming a complex according to claim 7 or claim 8, wherein the first monofunctional radical polymerizable monomer includes 2-ethylhexyl acrylate. The resin composition for forming a complex according to any one of claims 7 to 9, in which the second monofunctional radical polymerizable monomer includes a resin selected from the group consisting of acrylonitrile and dicyclopentyl acrylate. At least one of the group consisting of a methyl ester and methyl methacrylate. The resin composition for forming a complex according to any one of claims 7 to 10, wherein the radical polymerizable monomer further includes a difunctional radical polymerizable monomer and / or trifunctional Functional radical polymerizable monomer. The resin composition for forming a complex according to any one of claims 7 to 11, in which the content of the first monofunctional radical polymerizable monomer is the same as that of the radical polymerizable monomer. The total amount of the polymer is 5% by mass or more and 90% by mass or less, and the content of the second monofunctional radical polymerizable monomer is based on the total amount of the radical polymerizable monomer. 10% by mass or more and 95% by mass or less. A method for manufacturing a composite body is a method for manufacturing a composite body including a base material and a resin adhered to the base material, the method for manufacturing the composite body is included in the scope of the patent application in contact with the base material. In the resin composition for forming a composite according to any one of 7 to 11, a step of polymerizing a radical polymerizable monomer contained in the resin composition for forming a composite.