JP2019156861A - Resin composition for forming composite, composite, and method for producing composite - Google Patents

Abstract

To provide a composite that has excellent shape recoverability by heating and can be easily produced.SOLUTION: A composite comprising a substrate and a resin attached to the substrate is disclosed. The resin contains a polymer containing, as monomer units, a radical polymerizable monomer including 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 polymerized alone. 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.SELECTED DRAWING: None

Description

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

  In the past, attempts have been made to suppress changes in shape due to use and aging in various materials. In particular, a flat material and a processed product thereof are likely to be wrinkled and twisted, and thus may have a wrinkle prevention function. For example, clothes with various wrinkle prevention functions have been developed and are generally sold. For example, Patent Document 1 describes a handkerchief excellent in wrinkle resistance and pleatability.

  A wrinkle removing device may be used for the purpose of preventing a reading failure in a bill vending machine or the like. For example, Patent Document 2 describes a banknote wrinkle removal apparatus having a simple configuration.

JP 2013-177708 A Japanese Patent Laid-Open No. 09-040262

  An object of one aspect of the present invention is to provide a composite that is excellent in shape recovery by heating and can be easily manufactured.

  One aspect of the present invention relates to a composite including a base material and a resin attached to the base material. The resin contains a polymer containing, as monomer units, a radical polymerizable monomer including a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer. The first monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when 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 having a resin containing a combination of two kinds of radically polymerizable monomers selected by paying attention to the glass transition temperature of the homopolymer as described above can have excellent shape recoverability by heating.

  The composite includes, for example, a radical polymerizable monomer including the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer, and is in a resin composition in contact with a substrate. It can be easily produced by a method comprising a step of polymerizing the radical polymerizable monomer.

  According to one aspect of the present invention, a composite having excellent shape recovery by heating is provided. In addition, since the composite according to some embodiments can be produced by a simple method regardless of the material and shape of the base material, it can easily have a complicated three-dimensional structure such as irregularities and folds. Since the composites according to some forms can be recovered in shape by a simple method such as heating with warm water or warm air, they are excellent in terms of a wrinkle prevention function, a wrinkle removal function, and the like. By using the resin composition according to one aspect of the present invention, it is possible to easily produce a composite having various forms of base materials and having shape recovery properties or shape memory properties.

It is sectional drawing which shows the method of producing the composite sample for a shape recoverability test. It is sectional drawing which shows the method of producing the composite sample for a shape recoverability test.

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

(Complex)
The composite according to one embodiment includes a base material and a resin attached to the base material. The resin can be formed from a resin composition (resin composition for forming a complex) containing a radical polymerizable monomer including a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer. . Each of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer has one radical polymerizable group. A polymer containing each radical polymerizable monomer as a monomer unit is generated by polymerization of the radical polymerizable monomer in the resin composition. Thereby, a resin composition hardens | cures and forms hardened | cured material as resin of a composite_body | complex. That is, the composite resin can be a cured product of the curable resin composition.

  The polymer formed from the radical polymerizable monomer may have a weight average molecular weight of 100,000 or more, or 200,000 or more. As the weight average molecular weight is higher, the elongation at break of the resin tends to increase. In this specification, the weight average molecular weight means a standard polystyrene equivalent value determined by gel permeation chromatography unless otherwise defined.

  The substrate is not particularly limited and can be arbitrarily selected depending on the application. Examples of the material of the base material include synthetic or natural resin, metal, glass, ceramics, wood, and natural sponge.

  The substrate may be a fiber substrate such as a nonwoven fabric, woven fabric, network, examples of which are synthetic or natural fiber nonwoven fabric or woven fabric, paper, glass cloth, glass wool, metal mesh, and Steel wool is mentioned. The substrate may be a porous substrate such as a sponge. When the base material is a base material including voids that easily absorb liquid, such as a fiber base material and a porous base material, a part or all of the resin is impregnated into the base material from the viewpoint of improving shape recoverability. It may be.

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

  There is no restriction | limiting in particular in the shape of a base material, For example, planar shape, fiber shape, or another three-dimensional shape may be sufficient. The base material may have, for example, a curved portion such as a heel portion of a shoe, a bent portion such as pleating of clothes, or an uneven surface such as a banknote.

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

  The amount of resin in the composite (resin adhesion amount) is, for example, 1% by mass or more, 5% by mass or more, or 10% by mass or more with respect to the mass of the substrate from the viewpoint of excellent shape recoverability. It may be 1000 mass% or less, 500 mass% or less, or 100 mass% or less.

  The resin composition that can be used to form a composite resin (cured product) is composed of two monofunctional radical polymerizable monomers having different glass transition temperatures (a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer). Monofunctional radically polymerizable monomer). The first monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when 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 recovery by heating to the composite. Furthermore, the resin can have a 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. or lower when polymerized alone, and the second radical polymerizable monomer is a single monomer. It may be a monomer that forms a homopolymer having a glass transition temperature of 60 ° C. or higher, or 70 ° C. or higher when polymerized at. The glass transition temperature of the homopolymer formed by the first monofunctional radically polymerizable monomer may be −70 ° C. or higher. The glass transition temperature of the homopolymer formed by the second monofunctional radically polymerizable monomer may be 150 ° C. or lower.

  In this specification, the glass transition temperature of the homopolymer formed by each radically polymerizable monomer means a temperature determined by differential scanning calorimetry. A person skilled in the art can know the glass transition temperature of a homopolymer of a general radical polymerizable monomer as a literature value.

  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 based on the total amount of the radical polymerizable monomer, and 90% by mass or less. 85 mass% or less, or 80 mass% or less. When the content of the first radical polymerizable monomer is within these ranges, the cured product exhibits excellent shape recovery and can achieve both a high elongation at break and a high elastic modulus. It is done.

  The first monofunctional radically polymerizable monomer can be an alkyl (meth) acrylate which may have a substituent. The alkyl (meth) acrylate optionally having a substituent used as the first monofunctional radically polymerizable monomer is, for example, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, Isobutyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-methoxyethyl acrylate, and glycidyl methacrylate It can be at least one selected from the group consisting of:

  The first monofunctional radically polymerizable monomer may be 2-ethylhexyl acrylate. By using 2-ethylhexyl acrylate, the shape recovery property and elongation at break of the resin are increased, and a more advantageous effect can be obtained in that the elastic modulus can be easily controlled.

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

  The second monofunctional radically polymerizable monomer can be (meth) acrylic acid or a derivative thereof (alkyl (meth) acrylate etc.) such as alkyl (meth) acrylate which may have a substituent. Examples of the second monofunctional radical polymerizable monomer include adamantyl acrylate, adamantyl methacrylate, 2-cyanomethyl acrylate, 2-cyanobutyl acrylate, acrylamide, acrylic acid, methacrylic acid, acrylonitrile, dicyclopentanyl acrylate, and methyl methacrylate. It can be at least one selected from the group consisting of:

  The second monofunctional radical polymerization monomer may be at least one selected from the group consisting of acrylonitrile, dicyclopentanyl acrylate, and methyl methacrylate. By using these monomers, a more advantageous effect can be obtained in that the shape recovery property and breaking strength of the resin are increased and the elastic modulus can be easily controlled.

  The ratio of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer can be adjusted as appropriate. The higher the ratio of the first monofunctional radical polymerizable monomer, the lower the elastic modulus and glass transition temperature of the resin, and the higher the elongation at break. The higher the ratio of the second monofunctional radical polymerizable monomer, the higher the elastic modulus and glass transition temperature of the resin.

  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 elongation 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 resists external forces such as stretching and bending and generates a force for restoring the shape. It is considered that both properties can be achieved by introducing these two types of monomer units having greatly different properties into the polymer chain forming the cured product. However, the mechanism by which the physical properties of the resin are manifested is not necessarily limited to this.

  Considering the above points, the mass ratio of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer is 90:10 to 5:95, or 85: 15-30: 70 may be sufficient.

  The resin composition may further contain a monomer other than the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer as the radical polymerizable monomer. However, the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer is 60% by mass or more, 70% by mass or more, or 80% based on the total amount of the radical polymerizable monomer. It may be greater than or equal to mass%. Since the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer is within these ranges, the resin has high shape recovery property, elongation at break and high elastic elongation. Thus, an even more remarkable effect can be obtained.

  The radical polymerizable monomer in the resin composition is a polyfunctional radical polymerizable monomer having two or more radical polymerizable groups and / or other than the first monofunctional radical polymerizable monomer and the second radical polymerizable monomer. A monofunctional radically polymerizable monomer (a monomer that forms a homopolymer of more than 20 ° C. and less than 50 ° C. when polymerized alone).

  When the radical polymerizable monomer contains a polyfunctional radical polymerizable monomer, the resin tends to have high breaking strength and excellent solvent resistance. The resin composition may contain a bifunctional 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 based on the total amount of the radical polymerizable monomer. It may be less than mass%, less than 8.0 mass%, or less than 5.0 mass%. When the content of the polyfunctional radically polymerizable monomer is within these ranges, there is a tendency that the breaking strength and breaking elongation of the resin can be compatible at a particularly high level.

  The polyfunctional radical polymerizable monomer may be a polyfunctional (meth) acrylate from the viewpoint of compatibility with other components. The polyfunctional (meth) acrylate may be a bifunctional (meth) acrylate and / or a trifunctional (meth) acrylate. By using bifunctional and / or trifunctional (meth) acrylate, a more advantageous effect can be obtained in terms of both the breaking strength and breaking elongation of the resin. The bifunctional and / or trifunctional (meth) acrylate may contain a cyclic structure and may form a cyclic structure by a curing reaction.

  Examples of difunctional or trifunctional (meth) acrylates include 1,3-butylenediol 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 di (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, trimethylolpropane tri (meth) acrylate, and pentaerythritol Tri (meth) acrylate. These can be used alone or in combination of two or more.

  The total content of the bifunctional (meth) acrylate and trifunctional (meth) acrylate is 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. % 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 polymerization of the radical polymerizable monomer. The polymerization initiator can be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof. Although content of a polymerization initiator is suitably adjusted in a normal range, for example, 0.01-5 mass% may be sufficient on the basis of the mass of a resin composition.

  Thermal radical polymerization initiators include ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, hydroperoxides and other organic peroxides, sodium persulfate, potassium persulfate Persulfates such as ammonium persulfate, 2,2′-azobis-isobutyronitrile (AIBN), 2,2′-azobis-2,4-dimethylvaleronitrile (ADVN), 2,2′-azobis-2 -Azo compounds such as methylbutyronitrile, 4,4'-azobis-4-cyanovaleric acid, alkyl metals such as sodium ethoxide, tert-butyllithium, 1-methoxy-1- (trimethylsiloxy) -2- Examples thereof include silicon compounds such as methyl-1-propene.

  A thermal radical polymerization initiator and a catalyst may be combined. Examples of the catalyst include metal salts and compounds having reducibility such as tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine.

  Examples of the photo radical polymerization initiator include benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Aromatic ketones such as propanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one (Irgacure 651 (manufactured by Ciba Geigy Japan)); quinone compounds such as alkylanthraquinones; benzoin alkyl ethers and the like Benzoin ether compounds; benzoin compounds such as benzoin and alkylbenzoin; benzyl derivatives such as benzyldimethyl ketal; 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2-fluorophenyl) -4, 2 such as 5-diphenylimidazole dimer 4,5 triarylimidazole dimer; 9-phenyl acridine, 1,7 (9,9'-acridinyl) include acridine derivatives such as heptane. A photoinitiator can be used individually by 1 type or in combination of 2 or more types.

  Resin composition is, if necessary, binder polymer, solvent, photochromic agent, thermochromic inhibitor, plasticizer, pigment, filler, flame retardant, stabilizer, adhesion imparting agent, leveling agent, release accelerator, You may contain antioxidant, a fragrance | flavor, an imaging agent, etc. These can be used alone or in combination of two or more. When the resin composition contains other components, the content thereof 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 properties, but can have shape memory properties by appropriately selecting the type of radical polymerizable monomer. In this specification, “shape memory property” means that when a resin or composite is deformed by an external force at room temperature (for example, 25 ° C.), the resin or composite retains the deformed shape at room temperature. It means the property of returning to its original shape when heated to high temperature under load. However, it is not necessary for the resin or the composite to completely recover the same shape as the original shape by heating. The heating temperature for shape recovery is 70 ° C., for example.

  The storage elastic modulus at 25 ° C. of the resin is not particularly limited, but may be 0.5 MPa or more. A resin having a storage elastic modulus of 0.5 MPa or more usually has shape memory properties. The elastic modulus of the resin may be 1.0 MPa or more, or 10 MPa or more, or 10 GPa or less, 8 GPa or less, or 5 GPa or less. Since the storage elastic modulus is high, the resin tends to easily retain the shape after deformation. By having an appropriate storage modulus, the resin tends to recover its original shape when heated. The elastic modulus of the resin can be controlled based on, for example, the type of radical polymerizable monomer, the blending ratio thereof, and the amount of radical polymerization initiator. The elastic modulus of the resin can be appropriately adjusted according to the properties of the substrate.

  Although the glass transition temperature of resin is not specifically limited, For example, 30 degreeC or more may be sufficient and 40 degreeC or more may be sufficient. When the glass transition temperature is room temperature or a use temperature or higher, it is advantageous in that a high elastic modulus is easily maintained during use and the handling property is excellent. The glass transition temperature can be adjusted by, for example, the blending ratio of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer in the curable resin composition.

  The breaking elongation of the resin may be 10% or more, 100% or more, or 200% or more. When the breaking elongation of the resin is within these ranges, a particularly remarkable effect is obtained in that the recoverable shape change 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 producing composite)
The composite according to the present embodiment includes, for example, a step of bringing the composite-forming resin composition according to the above-described embodiment into contact with a substrate, and a radical polymerizable monomer in the resin composition in contact with the substrate. The process of producing | generating the hardened | cured material of a resin composition as resin by superposition | polymerization of (a hardening process) can manufacture by a method provided.

  In the contacting step, for example, the resin composition can be brought into contact with the substrate by impregnating the substrate with the resin composition or by coating the resin composition on the substrate. There are no particular limitations on the impregnation and coating methods. By impregnation and coating, a layer of the resin composition in contact with or adhering to the substrate is formed. From the viewpoint of workability and the like, the polymerization reaction of the radical polymerizable monomer may be partially advanced, and then the semi-cured resin composition may be brought into contact with the substrate.

  In the curing step, radical polymerization of the radical polymerizable monomer can be initiated by heating or irradiation with actinic rays such as ultraviolet rays. The temperature of the resin composition during the curing step is not particularly limited, but may be equal to or lower than the boiling point when the resin composition contains a solvent. Alternatively, the polymerization reaction may be started after removing the solvent from the resin composition. The polymerization reaction may be performed in an atmosphere of an inert gas such as nitrogen gas, helium gas, or argon gas. Thereby, the polymerization inhibition by oxygen is suppressed and a resin of good quality can be obtained stably.

  When the resin or the composite has shape memory, the shape of the resin or the composite at the time when the polymer is formed and the resin composition is cured becomes the basic shape. The resin or composite deformed by an external force is deformed so as to approach this basic shape by heating.

  Therefore, for example, after the step of bringing the resin composition into contact with the base material, the base material is deformed into a predetermined shape and then the resin composition is cured, or the base material deformed into the predetermined shape is resinized. By bringing the composition into contact and then curing the resin composition, a composite having a desired shape as a basic shape can be obtained.

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

1. Complex Forming Resin Composition Each raw material was mixed at a mass ratio shown in Table 1 to prepare each complex forming resin composition of Examples and Comparative Examples. The numerical value in a table | surface is a mass part.

2. Composite sample for shape recovery test Composite sample 1
A nonwoven fabric of nylon (registered trademark) fibers was dipped in a resin composition containing a thermal polymerization initiator (2,2-azobisisobutyronitrile), and the nonwoven fabric was sufficiently impregnated with the resin composition. The nonwoven fabric impregnated with the resin composition is sandwiched between stainless steel plates, and after removing the excess resin composition, it is heated in an oven at 70 ° C. for 1 hour to cure the resin composition, as shown in FIG. A structure 100 including two stainless steel flat plates 10 and the composite 1 sandwiched therebetween was obtained. The stainless steel plate 10 was removed from the structure 100 to obtain a plate-like composite sample 1 having a nonwoven fabric as a base material.

Complex sample 2
In place of the stainless steel plate, a stainless steel plate curved in a curved surface was used, and the same procedure as that of the composite sample 1 was performed, and the two stainless steel plates 11 as shown in FIG. A structure 200 including the composite 1 was obtained. 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.

Complex sample 3
A resin composition containing a photopolymerization initiator (Irgacure 651) was applied to a paper substrate (copy paper), and a polyethylene terephthalate (PET) film was overlaid thereon. The resin composition was cured by irradiating ultraviolet rays with an integrated light amount of 1000 mJ / cm ² from above the PET film. Thereafter, the PET film was peeled off to obtain a plate-like or sheet-like composite sample 3 having a paper substrate.

Complex sample 4
A nonwoven fabric of nylon (registered trademark) fibers was dipped in a resin composition containing a photopolymerization initiator (Irgacure 651), and the nonwoven fabric was sufficiently impregnated with the resin composition. After adjusting the shape of the nonwoven fabric impregnated with the resin composition into a flat plate shape, a polyethylene terephthalate (PET) film was laminated thereon. The resin composition was cured by irradiating ultraviolet rays with an integrated light amount of 1000 mJ / cm ² from above the PET film. Thereafter, the PET film was peeled off to obtain a plate-like or sheet-like composite sample 4 having a nonwoven fabric as a base material.

3. Shape recovery test The flat composite samples 1, 3, and 4 were bent at 180 °, and it was confirmed that the bent shape did not substantially return to the original shape. The composite sample 2 having a curved shape was deformed in a direction opposite to the bending direction and bent at 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 the case where it was restored to the initial shape within 10 seconds was judged as “good”, and the case where it was not restored was judged as “bad”.

4). Production of Resin Film The resin composition for forming a composite was dropped onto a polyethylene terephthalate (PET) film that had been subjected to a release treatment to form a coating film of the resin composition. The coating film was covered with a PET film that had been subjected to a mold release treatment, with a gap of 0.2 mm between the coating film and the coating film. In the case of a resin composition containing a photopolymerization initiator, the coating film was cured by irradiating 365 nm ultraviolet light from the top of the PET film with an integrated light amount of 1000 mJ / cm ² . In the case of a curable resin composition containing a thermal polymerization initiator, the coating film was cured by heating in an oven at 70 ° C. for 1 hour. After curing, the PET film was peeled off to obtain a resin film for a tensile test.

5). Tensile test A strip-shaped test piece having a width of 5 mm and a length of 50 mm was punched from the resin film. This test piece was subjected to a tensile test using a tensile tester (manufactured by Shimadzu Corporation, EZ-TEST) under the conditions of a measurement temperature of 25 ° C., a tensile speed of 10 mm / min, and a chuck distance of 30 mm. The stress at the time of rupture was defined as the rupture strength, and the slope of the stress-strain curve at the initial stage of tension was defined as the tensile modulus.

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

  As shown in Table 1, by using a resin composition containing the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer, a composite having excellent shape recoverability can be easily obtained. It was confirmed that it could be manufactured.

  DESCRIPTION OF SYMBOLS 1 ... Composite body, 10 ... Stainless steel flat plate, 11 ... Curved stainless steel plate, 100, 200 ... Structure.

Claims (13)

A base material, and a resin attached to the base material,
The resin contains a polymer containing a radical polymerizable monomer including a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer as a monomer unit,
The first monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when polymerized alone;
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.
Complex.   The total content of the monomer unit derived from the first monofunctional radical polymerizable monomer and the monomer unit derived from the second monofunctional radical polymerizable monomer is 60% by mass or more based on the mass of the polymer. The composite according to claim 1, wherein   The composite according to claim 1 or 2, wherein the first monofunctional radically polymerizable monomer comprises 2-ethylhexyl acrylate.   The composite according to any one of claims 1 to 3, wherein the second monofunctional radically polymerizable monomer includes at least one selected from the group consisting of acrylonitrile, dicyclopentanyl acrylate, and methyl methacrylate.   The composite according to any one of claims 1 to 4, wherein the radical polymerizable monomer further comprises a bifunctional radical polymerizable monomer and / or a trifunctional radical polymerizable monomer. The content of the monomer unit derived from the first monofunctional radical polymerizable monomer is 5% by mass or more and 90% by mass or less based on the total amount of the polymer,
The content of the monomer unit derived from the second monofunctional radical polymerizable monomer is 10% by mass or more and 95% by mass or less based on the total amount of the polymer.
The complex according to any one of claims 1 to 5. A resin composition for forming a complex, which is used for forming the resin of a complex including a substrate and a resin attached to the substrate,
Containing a radical polymerizable monomer comprising a first monofunctional radical polymerizable monomer and a second monofunctional radical polymerizable monomer;
The first monofunctional radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 20 ° C. or lower when polymerized alone;
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.
A resin composition for forming a complex.   The total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer is 60% by mass or more based on the total amount of the radical polymerizable monomer. The resin composition for complex formation as described.   The resin composition for forming a complex according to claim 7 or 8, wherein the first monofunctional radically polymerizable monomer contains 2-ethylhexyl acrylate.   The complex formation according to any one of claims 7 to 9, wherein the second monofunctional radically polymerizable monomer includes at least one selected from the group consisting of acrylonitrile, dicyclopentanyl acrylate, and methyl methacrylate. Resin composition.   The resin composition for forming a complex according to any one of claims 7 to 10, wherein the radical polymerizable monomer further comprises a bifunctional radical polymerizable monomer and / or a trifunctional radical polymerizable monomer. The content of the first monofunctional radical polymerizable monomer is 5% by mass or more and 90% by mass or less based on the total amount of the radical polymerizable monomer,
The content of the second monofunctional radical polymerizable monomer is 10% by mass or more and 95% by mass or less based on the total amount of the radical polymerizable monomer.
The resin composition for complex formation as described in any one of Claims 7-11. A method for producing a composite comprising a base material and a resin attached to the base material,
The process of superposing | polymerizing the radically polymerizable monomer which the said resin composition for complex formation contains in the resin composition for complex formation as described in any one of Claims 7-11 currently contacting the said base material. A method comprising:

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