JP2002220536A - Shape memory resin-forming composition and shape memory resin molded article molded from the composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a shape memory resin-forming composition, and to provide a shape memory resin molded article molded from the composition. SOLUTION: This shape memory resin-forming composition comprising a curable component and an ultraviolet light polymerization initiator is characterized in that a resin molded obtained by radically polymerizing the composition has a shape memory characteristic. The shape memory resin molded article obtained by molding the composition and then subjecting the molded article to a radical polymerization treatment is provided. The shape memory resin molded article does not contain such bubbles contained in a molded article as recognized when a conventional two-pack type composition is used, can perfectly be cured in a short time, and can improve workability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a shape-memory resin-forming composition and a shape-memory resin molded article formed from the composition.

[0002]

2. Description of the Related Art As a resin composition for producing a molded article such as reinforced plastic or artificial marble, a composition containing a resin component such as a polyester resin or an epoxy resin and a composition containing a curing agent are mixed. Thus, a two-pack type composition for starting the curing of a resin to produce a molded article has been conventionally used.

As a shape memory resin, Japanese Patent Application Laid-Open No. 2-225
No. 518 discloses a polynorbornene-based shape memory resin, a polyester-based shape memory resin, and the like. In addition, a shape-memory composition containing a shape-memory resin is also known. For example, Japanese Patent Application Laid-Open No. 4-77539 discloses a shape-memory resin composition containing a polyester-based shape-memory resin.

[0004]

In the two-pack type resin composition as described above, two liquids must be mixed at the time of manufacturing a molded article. In this case, air may be contained in the composition,
In some cases, gas is generated by the reaction of the curing agent, and air bubbles are formed on the surface of the molded product or the molding die. Although the two-part composition starts to cure quickly after mixing the two parts, the time until complete curing is relatively long, and may be as long as about one month. Is big. Also,
Due to the time required for molding, bending by the time of molding completion,
Deformation such as shrinkage may occur. Until the curing is completed, unreacted monomers continue to remain in the molded body, but this residual monomer not only causes a bad smell of monomer, but also has a health problem for workers. In some cases it can have a negative effect.

[0005] Further, since the above-mentioned two-pack type resin composition starts to harden immediately after mixing the two liquids, in terms of this quick hardening, there is no major problem in the molding operation in industrial production. However, there is a problem in molding a molded article by the hand lay-up method in that a molding operation needs to be performed in response to the rapid curing. Particularly when metal fibers or inorganic filled reinforcing fibers are used as molds and delicate work such as laminating them with a certain thickness is required, it is very difficult to operate within the curing time. It is. Therefore, only a part of skilled workers can perform such an operation using the two-pack type resin composition, so that the workability is lost and there is a problem from a human and economical point of view.

When transporting a molded article molded into a predetermined shape, and when removing the molded article from the mold after molding, the dents,
Although a distortion or the like may occur, such a damaged molded article cannot be used, which leads to a decrease in productivity as a whole. In particular, if a molded product that is not mass-produced, such as a molded product used for repairing a damaged part of an automobile, a machine, etc., and is manufactured only by order and is manufactured only one piece is damaged during transportation, it is extremely difficult. Loss. Such a custom-made product or a molded product that is easily damaged even if it is mass-produced needs to be handled carefully because once damaged, the damage is large.

Further, when molded as a fiber-reinforced plastic, even if no external force is applied, the characteristic of the molded article itself is that the more the molded article has a simple structure, the more the molded article is warped after being removed from the mold. And the use of the conventional resin composition has a problem that a molded article having a desired shape cannot be obtained. Further, in a case where a good appearance without scratches is desired, such as exterior parts of an automobile,
Eliminates inevitable scratches caused by use, such as, for example, fine scratches caused by friction from the brush of a machine wash,
A molded article capable of regaining the original good appearance is desired.

The present invention has been made in view of such circumstances, and the invention according to claim 1 has a simple shape even if deformed after molding, because the formed molded body has shape memory characteristics. It is an object of the present invention to provide a shape-memory resin-forming composition that can be easily returned to its original shape by a simple treatment, thereby facilitating the handling of a molded article. Further, the invention according to claim 2 eliminates the inclusion of bubbles in a molded article, shortens the time until complete curing, and improves workability, which is observed when a conventional two-part curable composition is used. Also, since the formed molded body has shape memory characteristics, even if it is deformed after molding, it can be returned to the original shape by a simple process, so that it is possible to easily handle the molded body. An object of the present invention is to provide a shape memory resin-forming composition. In addition, the invention according to claim 3 provides a two-component shape memory resin-forming composition in which the time required for complete curing is shortened because heat curing utilizing heat generated in ultraviolet polymerization is used in combination. The purpose is to do. Another object of the present invention is to provide a shape memory resin molded article which can be easily restored even when dents, distortions, and the like occur, and can be easily handled. Another object of the present invention is to provide a shape memory resin molded article containing a fibrous reinforcing material which can easily restore the deformation of a fiber-reinforced plastic which tends to deform after molding. Another object of the present invention is to provide a simple method for manufacturing a shape memory resin molded article. Another object of the present invention is to provide a method for producing a completely cured shape memory resin molded article in a short time from a two-component type shape memory resin forming composition.

[0009]

The present invention provides, as a first aspect, a composition comprising a curable component and a polymerization initiator, wherein a resin molded product obtained by subjecting the composition to radical polymerization is a shape memory. Provided is a shape memory resin-forming composition having characteristics. Further, the present invention provides, as a second aspect, the shape memory resin-forming composition according to the first aspect, wherein the polymerization initiator is an ultraviolet polymerization initiator or a mixture of an ultraviolet polymerization initiator and a thermal polymerization initiator. Further, the present invention provides a two-component composition comprising (a) a component containing a curable component and (b) a component containing a thermal polymerization initiator, wherein the components (a) and (b) ) Contains an ultraviolet polymerization initiator, and a resin molded article obtained by subjecting the two-component composition to radical polymerization has shape memory characteristics. A resin-forming composition is provided. The present invention provides, as a fourth aspect, a shape memory resin molded article obtained by subjecting the shape memory resin-forming composition according to any one of the first to third aspects to a radical polymerization treatment. Further, the present invention provides a shape memory resin molded article according to claim 4, further comprising a fibrous reinforcing material. In addition, the present invention provides a method for producing a shape memory resin molded article by irradiating a composition containing a curable component and an ultraviolet polymerization initiator with ultraviolet rays. Further, the present invention as claim 7 is a method for producing a shape memory resin molded article from the two-component type shape memory resin forming composition according to claim 3, wherein 1) components (a) and (b) And 2) molding the mixture of (a) and (b), and 3) irradiating the mixture with ultraviolet rays to provide a method for producing the shape memory resin molded article.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION As the curable component usable in the shape memory resin-forming composition of the present invention, any component can be used as long as the object of the present invention can be achieved. A mixture of compounds capable of free-radical addition polymerization or cross-linking, which contains a radical-polymerizable monomer and a radical-polymerizable prepolymer as main components is used. The radical polymerizable monomer is an acrylate or methacrylate of a monohydric alcohol or a polyhydric alcohol. Examples of the radical polymerizable prepolymer include polyester acrylate, epoxy acrylate, polyurethane acrylate, polyether acrylate, melamine acrylate, and alkyd. Acrylate,
Examples include silicon acrylate, but are not limited thereto.

Specific examples of the radical polymerizable monomer include 2-ethylhexyl acrylate, 2-hydroxyethylhexyl acrylate, 2-hydroxypropyl acrylate, 2-ethylhexyl acryloyl phosphate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate and dicyclopentenyl. Oxyethyl acrylate, 1,3-butanediol acrylate, 1,4-butanediol acrylate, 1,6
-Hexanediol acrylate, diethylene glycol acrylate, neopentyl glycol acrylate, polyethylene glycol acrylate, hydroxypivalic acid ester neopentyl glycol acrylate, tripropylene glycol acrylate, 1,3-
Bis (3'-acryloxyethoxy-3'-hydroxypropyl) -5,5-dimethylhydantoin, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, 2,2- Bis (4- (3-methacryloxy-2)
-Hydroxypropoxy) -phenyl) propane, di (methacryloxyethyl) trimethylhexamethylenediurethane, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, tetramethylolmethanetrimethacrylate, tetramethylolmethanetetramethacrylate, 4 -(Meth) acryloyloxymethoxycarbonylphthalic acid and its anhydride, 4- (meth) acryloyloxyethoxycarbonylphthalic acid and its anhydride, and the like, but are not limited thereto.

The radical polymerizable prepolymer includes those having an adipic acid / 1,6-hexanediol / acrylic acid structure, phthalic anhydride / propylene oxide /
Acrylic acid structure, trimellitic acid / diethylene glycol / acrylic acid structure, bisphenol A
Epichlorohydrin / acrylic acid structure, phenol novolak / epichlorohydrin / acrylic acid structure, alicyclic resin / acrylic acid structure, tolylene diisocyanate / hexanediol / acrylic acid structure etc. It is not something to be done.

The content of the curable component in the composition of the present invention is appropriately set according to the use in which the composition of the present invention is used, but is usually 20 to 99% by weight.
Preferably it is 20 to 80% by weight, more preferably,
It is 40 to 60% by weight.

As the polymerization initiator usable in the shape-memory resin-forming composition of the present invention, an ultraviolet-polymerization initiator, a heat-polymerization initiator, and the like can be used as long as they react with the above-mentioned curable component and cure the component. Any compound, such as an initiator, can be used. Preferably, the polymerization initiator is a UV polymerization initiator or a thermal polymerization initiator. A single UV polymerization initiator and a single thermal polymerization initiator may be used, or a plurality of initiators may be mixed and used. From the viewpoint that a shape memory resin molded article can be manufactured by a simple treatment of ultraviolet irradiation, and moreover, from the viewpoint that problems such as air bubble mixing at the time of mixing, which is a problem of the conventional two-part composition, do not occur, more preferably, The polymerization initiator is an ultraviolet polymerization initiator. It is also possible to use an ultraviolet polymerization initiator and a thermal polymerization initiator in combination. In this case, irradiation with ultraviolet light causes the ultraviolet polymerization initiator to react with the curable component to generate heat, and the heat polymerization initiator is reacted by using the heat, and the heat generated from the inside of the molded body is generated inside the molded body. Accelerates curing. Therefore, with the conventional two-pack type resin composition, the surface hardens relatively quickly, but the internal hardening is delayed, and the problem that the residual monomer remains in the molded body for a long time is solved. Is advantageous in the case of a thick material or a molded article containing a fibrous reinforcing material.

The shape-memory resin-forming composition of the present invention is prepared by individually preparing all the raw material components comprising a curable component, a polymerization initiator and other components, and measuring and mixing them all immediately before the radical polymerization treatment. Although it can be used, it is preferable to prepare a one- or several-component composition in advance from the viewpoint of easy use. When an ultraviolet polymerization initiator is used as the polymerization initiator, it does not cure if it blocks ultraviolet rays, so from the ease of handling, and also when using a conventional two-part curable composition,
The one-component type is more preferable because it eliminates the inclusion of bubbles in the molded article. When a thermal polymerization initiator is used as the polymerization initiator, the curing is started by mixing the curable component and the thermal polymerization initiator. Therefore, the component (a) containing the polymerization initiator as a main component and the thermal polymerization initiator are used. Component (b) containing an initiator as a main component
More preferably, the composition is at least a two-component composition, and still more preferably a two-component composition. Even when a thermal polymerization initiator and an ultraviolet polymerization initiator are used in combination as the polymerization initiator, the component (a) mainly containing the polymerization initiator and the component (b) mainly containing the thermal polymerization initiator are also referred to. More preferably, the composition is at least a two-component composition, and still more preferably a two-component composition.
In this case, the ultraviolet polymerization initiator may be contained in either component or both components. It is also possible to use an ultraviolet polymerization initiator separately as a three-component type.

Examples of the ultraviolet polymerization initiator in the composition of the present invention include, but are not limited to, benzoin ether compounds, benzophenone compounds, acetophenone compounds, thioxanthone compounds, and other aromatic ketone compounds. . Specifically, the UV polymerization initiator usable in the present invention includes N, N-tetraethyl-4,
4-diaminobenzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoinyl formate, α-hydroxyisobutylphenone, p-isopropyl-α-hydroxyisobutylphenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 2,2-dimethoxy-phenylacetophenone,
1-hydroxycyclohexyl phenyl ketone, α, α
-Dichloro-4-phenoxyacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-ethylanthraquinone, 4,4-bisdimethylaminobenzphenone, methyl orthobenzoylbenzoate, benzophenone, benzophenone acrylate, 1-phenyl-1, Examples include, but are not limited to, 2-propanediol-2- (o-ethoxycarbonyl) oxime.

The content of the ultraviolet polymerization initiator in the composition of the present invention is appropriately set according to the type and amount of the curable component used, the application target of the composition of the present invention, and the like. Generally, it will range from 0.1 to 5% by weight based on the weight of the composition.

As the thermal polymerization initiator that can be used in the composition of the present invention, any known thermal polymerization initiator can be used, for example, ketone peroxide such as cyclohexane peroxide or methyl ethyl ketone peroxide, di-t Di- (t-alkyl) peroxides such as -butyl peroxide, diacyl peroxides such as benzoyl peroxide, acetylalkylsulfonyl peroxide, dialkylperoxydicarbonates, t-alkylperoxyesters, t-alkyl-monoperoxycarbonates, t-alkyl Examples include, but are not limited to, hydroperoxides.

The amount of the thermal polymerization initiator to be added to the composition of the present invention is appropriately set according to the type and amount of the curable component used, the application target of the composition of the present invention, and the like.
Generally, it will range from 0.1 to 10% by weight based on the total weight of the composition.

The shape memory resin-forming composition of the present invention may optionally contain various resins other than those shown as the curable component. When the composition of the present invention contains the resin, the properties of the added resin are reflected on the molded article after curing. For example, according to the type of the resin to be added, the characteristics of the molded article such as the surface abrasion resistance, shape returnability, and adhesiveness are improved. For example, resins that can be included in the composition of the present invention include acrylonitrile acrylate styrene copolymer, ethylene vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorsulfonated polyethylene, adipic acid Polyester elastomers such as soft unsaturated polyester resin such as 4-butylene glycol-diallyl phthalate copolymer, nitrile-butadiene copolymer, polychloroprene, polyester-based and polyether-based urethane rubber, and polybutylene terephthalate-polytetramethylene ether glycol block copolymer , Polyamide elastomer such as polyamide 12 / polytetramethylene ether glycol block copolymer, polystyrene / polyisoprene copolymer etc. Tylene elastomers, caprolactone urethane elastomers, adipate urethane elastomers, ether urethane elastomers, ionomers such as ethylene-acrylic acid copolymers, polyester elastomers such as multiblock polymers of polybutylene terephthalate and polytetramethylene ether glycol, and the like. It is not limited to these.

The radical polymerization of the shape-memory resin-forming composition of the present invention may be performed by irradiating the composition with an ultraviolet ray when an ultraviolet ray polymerization initiator is used as the polymerization initiator of the composition. Is polymerized. The ultraviolet light usable in the treatment is an electromagnetic wave having a short wavelength end of visible light of 360 to 400 nm as an upper limit and a lower limit of about 1 nm. In the present invention, the wavelength of the ultraviolet light used is appropriately set according to the curable component and the ultraviolet polymerization initiator used. Further, the irradiation amount of the ultraviolet ray is appropriately set in consideration of the curable component and the ultraviolet polymerization initiator to be used, the shape of the molded article, and the like.

When a thermal polymerization initiator is used as the polymerization initiator of the composition, a radical polymerization treatment is performed by mixing the curable component and the thermal polymerization initiator and adjusting the temperature to a predetermined temperature. The polymerization temperature is appropriately set according to the curable component and the thermal polymerization initiator used. For example, when the curable component and the thermal polymerization initiator undergo a radical polymerization reaction at room temperature, polymerization starts at room temperature immediately after mixing, but in the present invention, the polymerization temperature is not limited to room temperature. Any temperature is possible. The processing time is appropriately set in consideration of the curable components and the thermal polymerization initiator to be used, the shape of the molded product, the processing temperature, and the like.

When an ultraviolet polymerization initiator and a thermal polymerization initiator are used in combination as the polymerization initiator of the composition, the ultraviolet irradiation is carried out in the same manner as when the above-mentioned ultraviolet polymerization initiator is used alone. Can be polymerized.
In this case, irradiation with ultraviolet light causes the ultraviolet polymerization initiator to react with the curable component to generate heat, and the heat polymerization initiator is reacted by using the heat, and the heat generated from the inside of the molded body is generated inside the molded body. Accelerates curing. In the polymerization treatment in this case, the polymerization treatment may be performed at room temperature or by heating to room temperature or higher.

[0024] The composition of the present invention may be used as a UV polymerization initiator and / or a thermal polymerization initiator,
Optionally, an oxygen scavenger and an active hydrogen donor chain transfer agent can be included. Examples of such oxygen scavengers include, but are not limited to, phosphine, phosphite, phosphonate, stannous salts, and other compounds that are easily oxidized by oxygen. Examples of the chain transfer agent include N-substituted N-phenylglycine such as N-phenylglycine and methacryloxy-β-hydropropyl-N-phenylglycine, trimethylbarbituric acid, 2-mercaptobenzoxazole, and 2-mercaptobenzothiazole. , N, N-dialkylaniline and the like, but are not limited thereto. N,
Examples of N-dialkylanilines include ortho, meta,
Or, at least one of the para positions is substituted with an alkyl group, a phenyl group, an acetyl group, an ethoxycarbonyl group, a carbonyl group, a carboxylate group, a silyl group, an alkoxyl group, a phenoxy group, an acetyloxy group, a hydroxy group, a halogen group, or the like. Things. More preferred N, N-dialkylanilines include 2,6-diisopropyl-
N, N-dimethylaniline, 2,6-diethyl-N, N
-Dimethylaniline, N, N, 2,4,6-pentamethylaniline and p-tert-butyl-N, N-dimethylaniline.

The composition of the present invention may contain, in addition to the above components, any other additives such as a coatability improver, an anti-striation agent, a plasticizer, a speed-increasing agent, and an inorganic filler as long as the object of the present invention can be achieved. Can be contained. Since the compositions of the present invention are UV curable, it is preferred that these additional additives do not have the property of absorbing the UV radiation being irradiated. For example,
When an inorganic filler is used as an additive, the durability and toughness of the molded article are achieved. As inorganic fillers,
Aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, magnesium carbonate, silica,
Examples include, but are not limited to, barium sulfate, calcium oxide, magnesium oxide, titanium oxide, talc, glass beads, glass powder, clay, kaolin, mica, carbon black, diatomaceous earth, metal powder, metal fiber, and the like.

When the composition of the present invention is of the two-component or higher-component type, the above-described oxygen scavenger and active hydrogen donor chain transfer agent, and additives do not contradict the object of the present invention. As long as it is mixed with any of the components. For example, a component (a) containing a polymerization initiator as a main component,
In the case of the two-component type of the component (b) containing a thermal polymerization initiator as a main component, the above-described oxygen removing agent, active hydrogen donor chain transfer agent, and additives are (a) unless they are contrary to the object of the present invention. ) Or (b).

By subjecting the shape-memory resin-forming composition of the present invention to radical polymerization treatment, the curable component in the composition undergoes radical polymerization to form a cured shape-memory resin, that is, a shape-memory resin molded article. Is done. As mentioned above,
When the composition contains components other than the curable component and the polymerization initiator, it is possible to form a molded article containing components other than the shape memory resin. In the shape memory resin molded article of the present invention, the shape formed by radical polymerization is the initial shape in the shape memory characteristics of the molded article that should be recovered.

The resin molded article of the present invention has "shape memory" characteristics. Here, “shape memory” means that, when the resin molded body is deformed by an external load, when the deformed molded body is heated to a certain temperature or higher, the resin molded body is restored to a shape immediately after molding. Preferably, as a mode of "shape memory", after the resin molded article of the present invention is molded and removed from the mold, when the obtained molded article is warped, the deformed molded article is heated to a certain temperature or higher. By heating, it returns to the original shape immediately after molding, and after molding, if the surface of the molded body is damaged, by heating the molded body to a certain temperature or more, the wound disappears and the original But it is not limited to this. In particular, when the molded body contains a fiber reinforcing material, more preferably as a mode of "shape memory", the resin molded body of the present invention is molded,
When the obtained molded body warps after being removed from the mold, the deformed molded body may be heated to a certain temperature or higher to return to the original shape immediately after molding.

The shape memory resin molded article of the present invention exhibits the above shape memory characteristics without heating up to the glass transition point. Although it is not desired to be bound by theory as this cause, in the shape memory resin molded article of the present invention, after the polymer structure formed by radical polymerization is deformed by an external load, the polymer Is considered to exhibit the property of returning to the initial molecular arrangement by polymerization when heated.

The heating condition for restoring the shape memory resin molded article of the present invention is preferably from 40 ° C. to 100 ° C., more preferably from 50 ° C. to 80 ° C. It can be changed depending on the composition of the composition.

In order to form a shape memory resin molded article by subjecting the composition of the present invention to a radical polymerization treatment, the composition is subjected to a molding treatment. As used herein, the term “molding treatment” includes any treatment for imparting the shape of a molded article to the composition. For example, processing of filling the composition with the composition, processing of applying the composition to the mold, processing of spraying the composition on the mold, and
For example, glass fiber mats, carbon fiber mats, treatments such as a treatment of impregnating the composition of the present invention into a mat formed from inorganic reinforcing fibers such as Kepra mat and laminating them in a mold, and the like, include, but are not limited to, these. Not something. The mold into which the composition is filled can have any shape. The molding process of the present invention may be mechanical molding, hand lay-up molding, or molding by a casting method.

The composition of the present invention is subjected to a radical polymerization treatment after or simultaneously with the molding treatment. When the polymerization initiator in the composition is an ultraviolet polymerization initiator, the composition is filled in the mold, applied to the mold, sprayed on the mold, impregnated on a mat and laminated on the mold. By irradiating with ultraviolet rays in such a state, radical polymerization is performed, and the resin is completely cured. When the polymerization initiator was a thermal polymerization initiator, the composition was filled in a mold, applied to the mold, sprayed on the mold, impregnated in a mat and laminated on the mold. Radical polymerization treatment is performed under heating or at room temperature in a state or the like, and the resin is completely cured. The same applies to the case where the polymerization initiator uses a thermal polymerization initiator and an ultraviolet polymerization initiator in combination.

A two-component composition comprising (a) a component containing a curable component and (b) a component containing a thermal polymerization initiator, wherein one or both of components (a) and (b) are used. Contains a UV polymerization initiator, and a resin molded product obtained by subjecting the two-component composition to a radical polymerization treatment has shape-memory characteristics, wherein a two-component shape-memory resin-forming composition is used. In this case, a method for producing a shape memory resin molded article from the composition includes: 1) mixing the components (a) and (b), and 2) a mixture of the above (a) and (b). And 3) irradiating the mixture with ultraviolet rays to produce the shape-memory resin molded article.

The composition of the present invention can be molded together with a reinforcing material, particularly a fibrous reinforcing material, to give a fiber-reinforced plastic molded article. By using the composition of the present invention in the production of a fiber-reinforced plastic molded article, the use of a conventional resin composition results in a large warpage after removal from the mold, and a molded article of a desired shape cannot be obtained. Problem is solved. Examples of the fibrous reinforcing material include, but are not limited to, metal fibers, plant fibers, mineral fibers, inorganic fibers (such as glass fibers), carbon fibers, and organic fibers (such as aramid fibers). The fibrous reinforcing material that can be included in the molded article of the present invention may be a single type, or may include a plurality of types of fibrous reinforcing materials. The diameter of the fiber used for the fibrous reinforcement is, for example, 1 to 10
0 μm, preferably 5 to 50 μm, more preferably
The thickness is 10 to 20 μm, but is not limited thereto. As the fibrous reinforcing material, a fiber having the above diameter is used as it is, or in the form of a yarn, cloth, or mat. As a method for molding a molded article containing a fibrous reinforcing material, for example, a glass fiber mat, a carbon fiber mat, a mat formed from inorganic reinforcing fibers such as Keplemat is impregnated with the composition of the present invention and laminated on a mold. It is also possible to form by this.

When the fiber-reinforced plastic molded article is formed by molding together with the fibrous reinforcing material, and the fibrous reinforcing material is a substance which does not transmit ultraviolet light, the composition of the present invention is suitably used. From the viewpoint of curing, it is preferable that a thermal polymerization initiator and an ultraviolet polymerization initiator are used in combination as the polymerization initiator. The composition of the present invention is a two-component composition comprising (a) a component containing a curable component and (b) a component containing a thermal polymerization initiator, wherein the components (a) and (b)
One or both of which contains an ultraviolet polymerization initiator, and wherein a resin molded product obtained by subjecting the two-component composition to radical polymerization has shape memory characteristics, a two-component shape memory resin More preferably, it is a formable composition.

The fiber-reinforced molded article molded from the composition of the present invention and the fibrous reinforcing material may be a molded article comprising a single layer in which the composition has penetrated into the fibrous reinforcing material and cured. One or more arbitrarily selected from the group consisting of the composition of the present invention, the fibrous reinforcing material, and a substance other than the composition of the present invention, in addition to the layer containing the composition of the present invention and the fibrous reinforcing material, It may be a laminate formed of a plurality of layers, including a layer made of the above substance.

The composition of the present invention can be molded into a shape memory resin decorative plywood, a shape memory resin part, a shape memory resin film, a shape memory resin panel and the like. These molded articles may be those in which a molded article of the same shape is mass-produced, or may be a car, a repair part of a machine, or the like.
It may be a one-piece molded article. When the shape memory resin molded article of the present invention is an exterior part of an automobile or the like, a repair part, or the like, for example, when a scratch is generated by use, such as a fine scratch caused by friction by a brush of a machine car wash. By heating with hot water or the like at a certain temperature or higher, it is possible to easily restore the original good appearance. Hereinafter, the present invention will be described in detail with reference to examples, but the examples do not limit the scope of the present invention.

[0038]

EXAMPLES 97% by weight of a curable component (bisphenol-based vinyl ester resin) and an ultraviolet polymerization initiator (2-hydroxy-2-methyl-1-phenyl-propan-1-one; Darocure (registered trademark) 1173, Ciba) ) 3
% By weight of the composition containing ultraviolet light (wavelength 360 to 420 n).
m) to obtain a sheet-like molded product having a thickness of about 0.5 mm (the glass transition temperature of the resin constituting the molded product is 100).
° C). The hardness of the molded body was evaluated using pencil hardness, and when a flaw, dent, or the like was formed on the evaluation surface by the evaluation method, the restoration of the shape was examined. Evaluation by pencil hardness is as follows. Pencils having various hardnesses (manufactured by Mitsubishi Pencil Co., Ltd.) are exposed at a 45-degree angle with respect to the evaluation surface by exposing the lead and shaving the tip so that the tip of the lead becomes flat. As described above, a line of 1 cm was drawn by pressing with human power, and by this operation, the depression and flaw formed on the evaluation surface were visually confirmed. The hardness of the composition was H hardness (pencil hardness conversion). A line having a length of 1 cm was drawn on the molded body with a pencil of various hardness. When the pencil had a hardness of 4H to 7H, scratches were observed on the surface of the molded body. The molded body with the flaw was immersed in water at a temperature of 0 ° C. to 100 ° C., and the state of the flaw on the surface of the molded body was observed. As a result, 0
No recovery of the damage was observed at a temperature of from 30 ° C to 30 ° C, but at a temperature of from 40 ° C to 100 ° C, the damage on the surface of the molded body disappeared.

[0039]

As described above, the composition of the present invention is molded and subjected to radical polymerization,
It is possible to produce a resin molded body exhibiting shape memory characteristics such that when heated to a certain temperature or higher, the shape is restored to the shape immediately after molding. In addition, since a one-part composition can be obtained by using an ultraviolet polymerization initiator, the inclusion of bubbles in a molded article, which is observed when a conventional two-part composition is used, is eliminated. , Shortening the time to complete curing and improving workability. Furthermore, by using a two-component type shape memory resin-forming composition in which an ultraviolet polymerization initiator and a thermal polymerization initiator are used in combination, heat curing is promoted by utilizing heat generated in a radical polymerization reaction by ultraviolet irradiation. This makes it possible to shorten the time until complete curing, which is particularly advantageous for forming a thick molded article and a molded article containing a fibrous reinforcing material. In addition, when the formed body obtained by subjecting the composition of the present invention to radical polymerization treatment has shape memory characteristics, even if the molded body is dented and deformed such as distortion, by applying heat at a certain temperature or higher, Since it is possible to restore the original shape, it is possible to obtain a molded body that is easy to handle and a molded body that can easily regain the initial good appearance. In particular, by using the composition of the present invention in the production of a fiber-reinforced plastic molded article, the use of the conventional resin composition results in a large warpage after removal from the mold, and a molded article of a desired shape is obtained. The problem of not being able to be solved is solved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 290/06 C08F 290/06 4J027 C08J 5/00 CEY C08J 5/00 CEY 4J100 5/04 5/04 / / C08L 33:08 C08L 33:08 F term (reference) 4F071 AA01 AD01 AE17 AF60 AH07 AH17 BB12 BC03 4F072 AA02 AD03 AG04 AK13 AK20 AL01 AL16 4F204 AB04 EA03 EA04 EB01 EF27 EK18 EK25 E01 CB25 EA25 EH126 EK006 EK016 EK036 EK046 EK066 EK086 EN096 ES016 EV306 FD010 FD146 GM00 GN00 4J011 GB07 GB08 QA03 QA13 QA18 QA22 QA23 QA24 QA33 QA34 QA35 QA37 QA38 QA39 QA42 QB11 QB22 SAB16 SAB15 SAB SA61 SA63 SA64 TA06 TA09 UA01 UA08 VA04 WA07 4J027 AB03 AB10 AB12 AB18 AB23 AB24 AB26 AC03 AC06 AE03 AE04 AF05 AG14 AG23 AG27 AG33 AH02 CA02 CA03 CA04 CA05 CA06 CA07 CA08 CA10 CA12 CA14 CA18 CA19 CA36 CA38 CB03 CB10 CC02 CC05 CD01 CD02 4J100 AL03P AL04P AL08P AL09P AL62P AL63P AL66P AL67P AR28P BAPPBC02P BC55P BC73P CA01 JA28

Claims (7)

[Claims] 1. A composition comprising a curable component and a polymerization initiator, wherein a resin molded article obtained by subjecting the composition to a radical polymerization treatment has shape memory characteristics. Composition. 2. The shape memory resin-forming composition according to claim 1, wherein the polymerization initiator is an ultraviolet polymerization initiator or a mixture of an ultraviolet polymerization initiator and a thermal polymerization initiator. 3. A composition comprising: (a) a component containing a curable component; and (b)
A two-component composition comprising a component containing a thermal polymerization initiator, wherein one or both of components (a) and (b) contain an ultraviolet-ray polymerization initiator, and the two-component composition is subjected to radical polymerization. A two-component shape memory resin-forming composition, wherein the resin molded product obtained by the treatment has shape memory characteristics. 4. A shape memory resin molded article obtained by subjecting the shape memory resin-forming composition according to claim 1 to a radical polymerization treatment. 5. The shape memory resin molded article according to claim 4, further comprising a fibrous reinforcing material. 6. A method for producing a shape memory resin molded article by subjecting a composition containing a curable component and an ultraviolet polymerization initiator to a molding treatment and irradiating the composition with ultraviolet rays. 7. A method for producing a shape-memory resin molded article from the two-component type shape-memory resin-forming composition according to claim 3, comprising: 1) mixing components (a) and (b); 3) A method for producing the shape memory resin molded article by subjecting the mixture of (a) and (b) to a molding treatment, and 3) irradiating the mixture with ultraviolet rays.