WO2017030096A1 - 硬化性樹脂組成物、及びその硬化物 - Google Patents
硬化性樹脂組成物、及びその硬化物 Download PDFInfo
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- WO2017030096A1 WO2017030096A1 PCT/JP2016/073789 JP2016073789W WO2017030096A1 WO 2017030096 A1 WO2017030096 A1 WO 2017030096A1 JP 2016073789 W JP2016073789 W JP 2016073789W WO 2017030096 A1 WO2017030096 A1 WO 2017030096A1
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- 0 C*C1CCC(*C2CCC(*N)CC2)CC1 Chemical compound C*C1CCC(*C2CCC(*N)CC2)CC1 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
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- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/42—Nitriles
- C08F20/44—Acrylonitrile
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1806—C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/48—Acrylonitrile with nitrogen-containing monomers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
Definitions
- the present invention relates to a curable resin composition and a cured product thereof.
- Patent Document 1 discloses a cured product having a tensile modulus of 1 to 100 MPa and a tensile fracture elongation of 200% or more.
- Patent Document 2 discloses a material exhibiting a high elastic modulus.
- shape memory materials metals, resins, ceramics, etc. are known as shape memory materials.
- shape memory property is developed based on a phase transformation caused by a change in crystal structure or a change in molecular motion form.
- shape memory materials often have characteristics such as excellent vibration isolation characteristics.
- metal and resin have been mainly studied as shape memory materials.
- Shape memory resin is a resin that recovers its original shape when heated to a certain temperature or higher, even if it is deformed by applying force after molding. Compared to shape memory alloys, shape memory resins are generally superior in that they are inexpensive, have a high rate of change in shape, are light, are easy to process, and can be colored.
- Shape memory resin is soft at high temperatures and easily deforms like rubber. On the other hand, it is hard at low temperatures and hardly deforms like glass.
- the shape memory resin can be stretched to several times its original length by a small force at a high temperature, and can retain its deformed shape by cooling. If the material is heated under no load in this state, the material recovers to its original shape. At high temperatures, the material returns to its original shape simply by removing the force. Thus, energy absorption and storage characteristics at high temperatures can be utilized.
- Main shape memory resins include polynorbornene, transisoprene, styrene-butadiene copolymer, and polyurethane.
- Patent Document 3 describes norbornene resins
- Patent Document 4 describes trans-isoprene resins
- Patent Document 5 discloses polyurethane resins
- Patent Document 6 describes shape memory resins related to acrylic resins.
- An object of one aspect of the present invention is to provide a curable resin composition that has a high elongation at break and can form a cured product that is also excellent in shape recovery after being deformed under stress. is there.
- An object of another aspect of the present invention is to provide a resin molded body having a shape memory property excellent in a shape recovery property by heating.
- One aspect of the present invention relates to a curable resin composition containing 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 radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or higher when polymerized alone.
- the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer may be 60% by mass or more based on the total amount of the radical polymerizable monomer.
- This curable resin composition can form a cured product having high elongation at break and excellent shape recovery after being deformed by stress.
- the curable resin composition contains 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 radically polymerizable monomer is a monomer that forms a homopolymer having a glass transition temperature of 50 ° C. or higher when polymerized alone.
- the total content of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer may be 60% by mass or more based on the total amount of the radical polymerizable monomer.
- This cured product can have excellent shape recoverability after being deformed under stress as well as high elongation at break.
- Another aspect of the invention is a compound of formula (I):
- X, R 1 and R 2 are each independently a divalent organic group, and R 3 and R 4 are each independently a hydrogen atom or a methyl group, and a radically polymerizable compound and monofunctional radically polymerizable
- the present invention relates to a resin molded article containing a first polymer containing a monomer as a monomer unit and a linear or branched second polymer.
- This resin molded body may have a storage elastic modulus of 0.5 MPa or more at 25 ° C. Or the resin molding may have shape memory property. Such a resin molded body is excellent in shape recovery by heating.
- Another aspect of the present invention is a molding composition
- a molding composition comprising a radical polymerizable compound of formula (I), a radical polymerizable monomer (reactive monomer) containing a monofunctional radical polymerizable monomer, and a second polymer.
- This molding composition can form a resin molding having a storage modulus of 0.5 MPa or more at 25 ° C. when the radical polymerizable monomer is polymerized in the presence of the second polymer.
- this molding composition can form a resin molded product having shape memory properties when a radical polymerizable monomer is polymerized in the presence of the second polymerizable monomer.
- Still another aspect of the present invention relates to a method for producing a resin molded body containing a first polymer and a second polymer.
- This method comprises polymerizing a radically polymerizable monomer in a molding composition comprising a radically polymerizable compound of formula (I) and a radically polymerizable monomer containing a monofunctional radically polymerizable monomer and a second polymer.
- a step of producing a first polymer comprises polymerizing a radically polymerizable monomer in a molding composition comprising a radically polymerizable compound of formula (I) and a radically polymerizable monomer containing a monofunctional radically polymerizable monomer and a second polymer.
- a curable resin composition capable of forming a resin molded body having high breaking elongation and excellent shape recovery after being deformed under stress.
- the curable resin composition according to some embodiments, it is possible to achieve both a high elastic modulus and a high bending resistance at a high level.
- the cured product is excellent in shape recovery after being deformed under stress, it means that it is easy to recover to the shape before receiving the stress just by being released from the stress. It does not necessarily mean that it has shape memory property for recovering.
- a resin molded body having shape memory properties excellent in shape recovery by heating By controlling the elastic modulus of the resin molded body of the present invention, the shape recovery rate when heated can be easily increased.
- Resin molded bodies according to some forms are also excellent in terms of various characteristics such as transparency, flexibility, stress relaxation, and water resistance.
- the curable resin composition which concerns on one Embodiment contains the radically polymerizable monomer containing the 1st monofunctional radically polymerizable monomer and the 2nd monofunctional radically polymerizable monomer.
- Each of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer has one radical polymerizable group.
- 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.
- the combination of the first monofunctional radical polymerizable monomer and the second monofunctional radical polymerizable monomer allows the cured product to have excellent shape recovery after being deformed under stress along with high elongation at break. Can do. Moreover, there exists a tendency for the hardened
- 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.
- the glass transition temperature of a homopolymer formed by each radical 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.
- 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 radical polymerizable monomer may be 2-ethylhexyl acrylate.
- 2-ethylhexyl acrylate By using 2-ethylhexyl acrylate, the toughness and elongation at break of the cured product are increased, and a further advantageous effect is 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.
- the content of the second monofunctional radical polymerizable monomer is within these ranges, a more remarkable effect can be obtained in that the cured product can achieve both high elongation at break and high elastic modulus.
- the second monofunctional radically polymerizable monomer can be an alkyl (meth) acrylate which may have a substituent.
- alkyl (meth) acrylate optionally having a substituent used as the second monofunctional radically polymerizable monomer include adamantyl acrylate, adamantyl methacrylate, 2-cyanomethyl acrylate, 2-cyanobutyl acrylate, and acrylamide.
- the second monofunctional radical polymerization monomer may be at least one selected from the group consisting of acrylonitrile, dicyclopentanyl acrylate, and methyl methacrylate.
- the ratio of the first monofunctional radical polymerizable monomer to the second monofunctional radical polymerizable monomer can be adjusted as appropriate.
- the monomer unit derived from the first monofunctional radically polymerizable monomer is considered to function in the cured product 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 cured product as a hard segment that resists external forces such as elongation and bending. 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.
- the mechanism for expressing the physical properties of the cured product is not necessarily limited thereto.
- the curable 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.
- 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%.
- the radical polymerizable monomer in the curable resin composition is a polyfunctional radical polymerizable monomer having two or more radical polymerizable groups, and / or a first monofunctional radical polymerizable monomer and a second radical polymerizable monomer.
- Monofunctional radically polymerizable monomers other than monomers may be included.
- the curable 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 both the breaking strength and the breaking elongation of the cured product can be achieved 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.
- a bifunctional and / or trifunctional (meth) acrylate By using a bifunctional and / or trifunctional (meth) acrylate, a more advantageous effect can be obtained in terms of both the breaking strength and elongation at break of the cured product.
- the bifunctional and / or trifunctional (meth) acrylate may contain a cyclic structure and may form a cyclic structure by a curing reaction.
- bifunctional or trifunctional (meth) acrylates examples include 1,3-butylene diol 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 Rutori (meth) acrylate. These can be used alone or
- 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 curable resin composition may contain a radical polymerization initiator for polymerization of the radical polymerizable monomer.
- the radical polymerization initiator can be a thermal radical polymerization initiator, a photo radical polymerization initiator, or a combination thereof.
- the content of the radical polymerization initiator is appropriately adjusted within a normal range, and may be, for example, 0.001 to 5% by mass based on the mass of the curable 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.
- the catalyst include metal salts and reducing compounds such as tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine.
- photo radical polymerization initiators examples 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, Such as 5-diphenylimidazole dimer , 4,5-triary
- the curable resin composition is a binder polymer, a solvent, a photochromic agent, a thermochromic inhibitor, a plasticizer, a pigment, a filler, a flame retardant, a stabilizer, an adhesion-imparting agent, a leveling agent, and a peeling accelerator, if necessary Agents, antioxidants, fragrances, imaging agents, thermal crosslinking agents, and the like. These can be used alone or in combination of two or more. When the curable 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 curable resin composition. Also good.
- the cured product can be produced by a method including a step of radically polymerizing a radical polymerizable monomer in the curable resin composition to cure the curable resin composition.
- the radical polymerization of the radical polymerizable monomer can be initiated by heating or irradiation with actinic rays such as ultraviolet rays.
- radical polymerization generally, a polymer having a high molecular weight tends to be obtained by lowering the radical generation rate due to decomposition of the radical polymerization initiator.
- the radical generation rate can be controlled by radical polymerization conditions. There are methods such as reducing the amount of radical polymerization initiator in a small amount, lowering the heating temperature in thermal radical polymerization, and lowering the illuminance of actinic rays in radical photopolymerization.
- the conditions for radical polymerization for curing the curable resin composition are not particularly limited, but can be set in view of the above circumstances.
- the temperature of the thermal radical polymerization may be, for example, within 10 ° C. above or below the decomposition temperature of the radical polymerization initiator. When the curable resin composition contains a solvent, this temperature may be equal to or lower than the boiling point of the solvent.
- the illuminance of the photo radical polymerization may be 1 mW / cm 2 or less, for example. The higher the molecular weight of the polymer formed, the greater the tendency for the elongation at break of the cured product to increase, and it is easy to achieve both a high elastic modulus and a high elongation at break.
- the radical polymerization reaction can be performed in an atmosphere of an inert gas such as nitrogen gas, helium gas, or argon gas. Thereby, polymerization inhibition by oxygen is suppressed, and a cured product of good quality can be obtained stably.
- an inert gas such as nitrogen gas, helium gas, or argon gas.
- cured material is not restrict
- 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 elastic modulus (tensile elastic modulus) of the cured product may be 10 MPa or more, 100 MPa or more, 200 MPa or more, or 10 GPa or less, 7 GPa or less, 5 GPa or less.
- the elastic modulus 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 elongation at break of the cured product may be 10% or more, 100% or more, or 200% or more.
- a recoverable shape change is large, and a particularly remarkable effect is obtained in terms of characteristics such as bending resistance.
- the breaking strength of the cured product may be 1 MPa or more, 3 MPa or more, or 5 MPa or more.
- the weight average molecular weight of the polymer forming the cured product may be 100,000 or more, or 200,000 or more.
- the weight average molecular weight means a standard polystyrene equivalent value determined by gel permeation chromatography unless otherwise defined.
- a cured product excellent in shape recovery after being deformed under stress has a high elastic elongation. 60% or more, 70% or more, 80% or more may be sufficient as the elastic elongation rate of hardened
- the elastic elongation is measured, for example, by the following procedure.
- a test piece of a cured product having a size of 5 mm ⁇ 50 mm is prepared, and three portions aligned in the longitudinal direction are marked at portions corresponding to the chucks. The distance between the marks is L0 and L0 ′.
- the elongation at break is calculated by the formula: (L2-L0) / L0.
- the elongation at break is calculated by the formula: (L2 ⁇ L0 ′) / L0 ′.
- the elongation at break may be calculated by the formula: (L3 ⁇ L1) / L1 using the distance L3 between chucks at the time of breakage. (4) The test piece after breaking was heated at 70 ° C.
- the shape and size of the cured product are not particularly limited.
- a cured product having an arbitrary shape can be obtained by curing a curable resin composition filled in a predetermined mold.
- the cured product may be, for example, a fibrous shape, a rod shape, a cylindrical shape, a tubular shape, a flat plate shape, a disc shape, a spiral shape, a spherical shape, or a ring shape.
- the cured product may be further processed by various methods such as machining and melt molding.
- FIG. 1 is a perspective view showing an embodiment of a resin molded body.
- a resin molded body 1 in FIG. 1 is an example of a flat molded body.
- the molding composition has the formula (I): The radically polymerizable compound represented by these, the radically polymerizable monomer containing a monofunctional radically polymerizable monomer, and the 2nd polymer are contained.
- X, R 1 and R 2 are each independently a divalent organic group
- R 3 and R 4 are each independently a hydrogen atom or a methyl group.
- the first polymer may contain a cyclic monomer unit represented by the following formula (II) derived from the compound of the formula (I). It is considered that the cyclic monomer unit of the formula (II) contributes to the expression of unique characteristics such as the shape memory property of the resin molded body. However, the first polymer does not necessarily contain the monomer unit of the formula (II).
- X in the formulas (I) and (II) is, for example, the following formula (10): The group represented by these may be sufficient.
- Y is a cyclic group which may have a substituent
- Z 1 and Z 2 are each independently a functional group containing an atom selected from a carbon atom, an oxygen atom, a nitrogen atom and a sulfur atom.
- i and j are each independently an integer of 0-2. * Represents a bond (this also applies to other formulas).
- X is a group of the formula (10), it is considered that the cyclic monomer unit of the formula (II) is particularly easily formed.
- Z 1 and Z 2 with respect to the cyclic group Y may be a cis position or a trans position.
- Z 1 and Z 2 are —O—, —OC ( ⁇ O) —, —S—, —SC ( ⁇ O) —, —OC ( ⁇ S) —, —NR 10 — (R 10 is a hydrogen atom or An alkyl group), or a group represented by —ONH—.
- Y may be a cyclic group having 2 to 10 carbon atoms, or may contain a heteroatom selected from an oxygen atom, a nitrogen atom and a sulfur atom.
- the cyclic group Y is, for example, an alicyclic group, a cyclic ether group, a cyclic amine group, a cyclic thioether group, a cyclic ester group, a cyclic amide group, a cyclic thioester group, an aromatic hydrocarbon group, a heteroaromatic hydrocarbon group, or It can be a combination of these.
- the cyclic ether group may be a cyclic group possessed by a monosaccharide or polysaccharide.
- Y include, but are not particularly limited to, a cyclic group represented by the following formula (11), (12), (13), (14) or (15). From the viewpoint of stress relaxation properties of the resin molded body, Y may be a group of the formula (11) (particularly a 1,2-cyclohexanediyl group).
- R 1 and R 2 in the formulas (I) and (II) may be the same as or different from each other, and may be a group represented by the following formula (20).
- R 6 is a hydrocarbon group having 1 to 8 carbon atoms (an alkylene group or the like), and is bonded to the nitrogen atom in the formula (I) or (II).
- Z 3 is a group represented by —O— or —NR 10 — (R 10 is a hydrogen atom or an alkyl group).
- R 1 and R 2 are a group of the formula (20), it is considered that the cyclic monomer unit of the formula (II) is particularly easily formed.
- the number of carbon atoms in R 6 may be 2 or more, 6 or less, or 4 or less.
- radically polymerizable compound of the formula (I) is a compound represented by the following formula (Ia).
- Y, Z 1 , Z 2 , i, and j are defined in the same manner as in Expression (10).
- Examples of the compound of the formula (Ia) include the following formulas (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), ( And compounds represented by I-7) or (I-8).
- the proportion of the radically polymerizable compound of formula (I) in the molding composition is 0.01 mol% or more, 0.1 mol% or more, or 0.5 mol% or more, based on the total amount of the radical polymerizable monomer. It may be 10 mol% or less, 5 mol% or less, or 1 mol% or less. When the ratio of the radical polymerizable compound of the formula (I) is within these ranges, a further advantageous effect can be obtained in that a cured product having excellent mechanical properties such as elongation, strength, and bending resistance can be obtained.
- the compound of formula (I) can be synthesized by a usual synthesis method using a commonly available raw material as a starting material.
- the compound of formula (I) can be synthesized by reacting a cyclic diol compound or a cyclic diamine compound with a compound having a (meth) acryloyl group and an isocyanate group.
- the radical polymerizable monomer in the molding composition may contain alkyl (meth) acrylate and / or acrylonitrile as a monofunctional radical polymerizable monomer.
- the alkyl (meth) acrylate is an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms which may have a substituent ((meth) acrylic acid and optionally having 1 substituent). To 16 alkyl alcohol esters). The substituent that the alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms may have an oxygen atom and / or a nitrogen atom.
- the elastic modulus and glass transition temperature (Tg) of the cured product By including an alkyl (meth) acrylate having an alkyl group having 1 to 16 carbon atoms in the radical polymerizable monomer, the elastic modulus and glass transition temperature (Tg) of the cured product, and mechanical properties such as elongation and strength can be obtained. The effect that it can be controlled is obtained.
- the proportion of the alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent in the molding composition is 10 mol% or more, 15 mol% or more based on the total amount of the radical polymerizable monomer. Or 20 mol% or more, 95 mol% or less, 90 mol% or less, or 85 mol% or less.
- a cured product having excellent mechanical properties such as elongation and strength, and bending resistance can be obtained. In this respect, a further advantageous effect can be obtained.
- the radical polymerizable monomer may contain an alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms, which may have a substituent, as a monofunctional radical polymerizable monomer.
- the proportion of the alkyl (meth) acrylate having 10 or less carbon atoms that may have a substituent in the molding composition is 8 mol% or more, 10 mol% or more based on the total amount of the radical polymerizable monomer, Or 15 mol% or more may be sufficient, and 55 mol% or less, 45 mol% or less, or 25 mol% or less may be sufficient.
- the ratio of the alkyl (meth) acrylate having an alkyl group having 10 or less carbon atoms, which may have a substituent is within these ranges, a resin molded product having a certain degree of elasticity and shape memory properties is obtained. A further advantageous effect is obtained in that it is easily formed.
- the radical polymerizable monomer may contain a (meth) acrylate having an alkyl group having 8 or less carbon atoms, which may have a substituent, and the proportion thereof may be in the above numerical range. Good.
- alkyl (meth) acrylate having 1 to 16 carbon atoms which may have a substituent include ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, hexyl acrylate, Hexyl methacrylate, 2-ethylhexyl acrylate (EHA), 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-1-methylethyl methacrylate, 2-methoxyethyl acrylate (MEA), N, N -Dimethylaminoethyl acrylate, and glycidyl methacrylate. These can be used alone or in combination of two or more.
- the radical polymerizable monomer contains acrylonitrile, it tends to form a resin molded article having a high degree of elasticity and shape memory property while having excellent mechanical properties such as elongation and strength, and bending resistance.
- a combination of acrylonitrile and a (meth) acrylate having an alkyl group having 1 to 16 (or 1 to 10) carbon atoms is particularly advantageous in order to obtain a resin molded article having a high elastic modulus.
- the proportion of acrylonitrile in the molding composition may be 40 mol% or more, 50 mol% or more, or 70 mol% or more, based on the total amount of the radical polymerizable monomer, 90 mol% or less, 85 mol% % Or less, or 80 mol% or less.
- the ratio of acrylonitrile is within these ranges, a further advantageous effect can be obtained in that the shape recovery is quick.
- the radical polymerizable monomer may contain one or more compounds selected from vinyl ether, styrene and styrene derivatives as a monofunctional radical polymerizable monomer.
- vinyl ethers include vinyl butyl ether, vinyl octyl ether, vinyl-2-chloroethyl ether, vinyl isobutyl ether, vinyl dodecyl ether, vinyl kutadecyl ether, vinyl phenyl ether, and vinyl cresyl ether.
- styrene derivative examples include alkyl styrene, alkoxy styrene ( ⁇ -methoxystyrene, p-methoxystyrene, etc.), and m-chlorostyrene.
- the radical polymerizable monomer may contain other monofunctional radical polymerizable monomer and / or polyfunctional radical polymerizable monomer.
- examples of other monofunctional radically polymerizable monomers include vinylphenol, N-vinylcarbazole, 2-vinyl-5-ethylpyridine, isopropenyl acetate, vinyl isocyanate, vinyl isobutyl sulfide, 2-chloro-3-hydroxypropene, Vinyl stearate, p-vinylbenzylethyl carbinol, vinyl phenyl sulfide, allyl acrylate, ⁇ -chloroethyl acrylate, allyl acetate, 2,2,6,6-tetramethyl-piperidinyl methacrylate, N, N-diethyl vinyl Carbamate, vinyl isopropenyl ketone, N-vinyl caprolactone, vinyl formate, p-vinyl benzylmethyl carbinol, vinyl e
- the molding composition contains the radical polymerizable monomer described above and a linear or branched second polymer.
- the second polymer may be a polymer including two or more linear chains and a linking group that connects the ends thereof.
- This polymer includes a molecular chain represented by the following formula (B), for example.
- R 20 is a monomer unit constituting a linear chain
- n 1 , n 2 and n 3 are each independently an integer of 1 or more
- L is a linking group.
- a plurality of R 20 and L in the same molecule may be the same or different.
- Linear chain composed of monomer units R 20 are polyether, polyester, polyolefin, polyorganosiloxane, or a molecular chain derived from these combinations. Each linear chain may be a polymer or an oligomer.
- linear chains derived from polyether examples include polyoxyalkylene chains such as polyoxyethylene chains, polyoxypropylene chains, polyoxybutylene chains, and combinations thereof.
- Polyoxyethylene chains are derived from polyethers such as polyalkylene glycols.
- linear chains derived from polyolefins examples include polyethylene chains, polypropylene chains, polyisobutylene chains, and combinations thereof.
- linear chains derived from polyester include poly ⁇ -caprolactone chains.
- Examples of the linear chain derived from polyorganosiloxane examples include a polydimethylsiloxane chain.
- a 2nd polymer can contain these alone or the combination of 2 or more types chosen from these.
- the number average molecular weight of each of the linear molecular chains constituting the second polymer is not particularly limited, but may be, for example, 1000 or more, 3000 or more, or 5000 or more, and may be 80000 or less, 50000 or less, or 20000. It may be the following.
- the number average molecular weight means a standard polystyrene equivalent value obtained by gel permeation chromatography unless otherwise defined.
- the linking group L is an organic group containing a cyclic group or a branched organic group.
- the linking group L may be, for example, a divalent group represented by the following formula (30).
- R 30 is a cyclic group, a group containing two or more cyclic groups, which are bonded directly or via an alkylene group, or a carbon atom, and is selected from an oxygen atom, a nitrogen atom, a sulfur atom and a silicon atom
- the branched organic group which may contain the hetero atom is shown.
- Z 5 and Z 6 are divalent groups that bind R 30 and a linear chain, and include, for example, —NHC ( ⁇ O) —, —NHC ( ⁇ O) O—, —O—, —OC ( ⁇ O) —, —S—, —SC ( ⁇ O) —, —OC ( ⁇ S) —, or —NR 10 — (R 10 is a hydrogen atom or an alkyl group).
- R 10 is a hydrogen atom or an alkyl group.
- the atom at the end of the linear chain is not normally interpreted as an atom constituting Z 5 or Z 6 . If it is not clear whether the atom at the end of the linear chain is an atom derived from a monomer, the atom may be interpreted as being included in either the linear chain or the linking group.
- the cyclic group contained in the linking group L may contain a hetero atom selected from a nitrogen atom and a sulfur atom.
- the cyclic group included in the linking group L is, for example, an alicyclic group, a cyclic ether group, a cyclic amine group, a cyclic thioether group, a cyclic ester group, a cyclic amide group, a cyclic thioester group, an aromatic hydrocarbon group, or a heteroaromatic hydrocarbon. It can be a group or a combination thereof.
- cyclic group contained in the linking group L include 1,4-cyclohexanediyl group, 1,2-cyclohexanediyl group, 1,3-cyclohexanediyl group, 1,4-benzenediyl group, 1,3-benzene.
- examples include a diyl group, a 1,2-benzenediyl group, and a 3,4-furandiyl group.
- Examples of the branched organic group (for example, R 30 in the formula (30)) included in the linking group L include a lysine triyl group, a methylsilanetriyl group, and a 1,3,5-cyclohexanetriyl group.
- the linking group L represented by the formula (30) may be a group represented by the following formula (31).
- R 31 in the formula (31) represents a single bond or an alkylene group.
- R 31 may be an alkylene group having 1 to 3 carbon atoms. Defining Z 5 and Z 6 are the same as equation (30).
- the weight average molecular weight of the second polymer is not particularly limited, but may be, for example, 5000 or more, 7000 or more, or 9000 or more, or 100000 or less, 80000 or less, or 60000 or less. When the weight average molecular weight of the second polymer is within these numerical ranges, good compatibility with other components of the second polymer and good characteristics of the resin molded product tend to be easily obtained. is there.
- the second polymer can be obtained by an ordinary synthesis method using a commonly available raw material as a starting material.
- a polyalkylene glycol having a reactive end group such as a hydroxyl group
- a polyester such as a polyolefin, a polyorganosiloxane, or a mixture containing a combination thereof, a reactive functional group (such as an isocyanate group), and a cyclic or branched group
- the second polymer can be synthesized by reaction with a compound having the above group.
- the second polymer to be synthesized may contain a branched structure based on side reactions such as trimerization of isocyanate groups.
- the molding composition may contain a polymerization initiator for the 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.
- the content of the polymerization initiator is appropriately adjusted within a normal range, and may be, for example, 0.01 to 5% by mass based on the mass of the molding 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.
- the catalyst include metal salts and reducing compounds such as tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine.
- photoradical polymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one.
- Irgacure 651 manufactured by Ciba Geigy Japan.
- the molding composition may contain a solvent or may be substantially solvent-free.
- the molding composition may be liquid, semi-solid, or solid.
- the molding composition before curing may be in the form of a film.
- the resin molded body can be produced by a method including a step of forming a first polymer by radical polymerization of a radical polymerizable monomer in a molding composition.
- the radical polymerization of the radical polymerizable monomer can be initiated by heating or irradiation with actinic rays such as ultraviolet rays.
- the shape and size of the resin molded body (cured body) are not particularly limited.
- a resin molded body having an arbitrary shape can be obtained by curing a molding composition filled in a predetermined mold.
- the resin molded body may be, for example, a fiber shape, a rod shape, a columnar shape, a cylindrical shape, a flat plate shape, a disc shape, a spiral shape, a spherical shape, or a ring shape.
- the molded body after curing may be further processed by various methods such as machining.
- the temperature of the polymerization reaction is not particularly limited, but when the molding composition contains a solvent, it is preferably below the boiling point thereof.
- the polymerization reaction is preferably performed in an atmosphere of an inert gas such as nitrogen gas, helium gas, or argon gas. Thereby, the inhibition of polymerization due to oxygen is suppressed, and a molded article of good quality can be stably obtained.
- a radical polymerizable monomer containing a radical polymerizable compound of formula (I) is polymerized, a cyclic monomer unit of formula (II) is formed.
- the radically polymerizable monomer is polymerized in the presence of the first polymer, at least a part of the cyclic monomer unit of the formula (II) can form a structure in which the second polymer penetrates the cyclic part.
- the following formula (III) schematically shows a structure in which the second polymer (B) penetrates the cyclic portion of the monomer unit of the formula (II) of the first polymer (A).
- R 5 in formula (III) is a monomer unit derived from a radical polymerizable monomer other than the radical polymerizable compound of formula (I).
- a crosslinked network structure like a three-dimensional copolymer is formed by the first polymer and the second polymer.
- this network structure it is considered that the degree of freedom of movement of the second polymer penetrating the annular portion is kept relatively high.
- Such a structure is sometimes referred to as a ring structure by those skilled in the art, and the present inventors speculate that this contributes to the expression of unique properties such as shape memory properties of the resin molded body. Yes.
- a stress-strain curve obtained by a tensile test of a resin molding is a so-called J-shaped curve. This suggests the formation of a ring structure.
- the resin molded body does not necessarily include such a ring structure.
- the second polymer (B) has a plurality of polyoxyethylene chains and a linking group L that connects the ends thereof. Since the linking group L is bulky compared to the polyoxyethylene chain, it is easy to maintain a state in which the second polymer penetrates the cyclic portion of the monomer unit of the formula (II) as in the polyrotaxane.
- the second polymer can be appropriately selected based on the balance of the size of the cyclic monomer unit, the inclusion ability, and the properties of the polyrotaxane.
- the resin molded body produced and cured by the first polymer may or may not have shape memory, but the shape can be determined by appropriately selecting the type of radical polymerizable monomer.
- a resin molded body having memory properties can be obtained.
- shape memory property means that when a resin molded body is deformed by an external force at room temperature (for example, 25 ° C.), the resin molded body retains the deformed shape at room temperature, It means the property of returning to its original shape when heated to a high temperature. However, the resin molded body does not have to completely recover the same shape as the original shape by heating.
- the heating temperature for shape recovery is 70 ° C., for example.
- the first polymer is usually formed, and the shape of the resin molded body at the time of curing becomes the basic shape.
- the resin molded body deformed by an external force is deformed so as to approach this basic shape by heating.
- a resin molding having a desired shape as a basic shape can be obtained.
- the storage elastic modulus of the resin molded body at 25 ° C. is not particularly limited, but may be 0.5 MPa or more.
- a resin molded body having a storage elastic modulus of 0.5 MPa or more usually has shape memory.
- the elastic modulus of the resin molded body may be 1.0 MPa or more, or 10 MPa or more, or 10 GPa or less, 5 GPa or less, or 500 MPa or less. Since the storage elastic modulus is high, the resin molded body tends to easily retain the shape after deformation. By having an appropriate storage elastic modulus, the resin molded body tends to recover its original shape when heated.
- the elastic modulus of the resin molded body can be controlled based on, for example, the type of radical polymerizable monomer and the blending ratio thereof, the molecular weight of the second polymer, and the amount of radical polymerization initiator.
- Curable resin composition Each raw material was mixed by the mass ratio shown in Table 1, and the curable resin composition was prepared. The numerical value in a table
- surface is a mass part.
- the elongation at break is calculated by the formula: (L2-L0) / L0.
- the elongation at break may be calculated by the formula: (L3 ⁇ L1) / L1 using the distance L3 between chucks at the time of breakage.
- the test piece after fracture was heated at 70 ° C. for 3 minutes, and then the distance L4 between the marks was measured, and the elastic elongation indicating the ratio of elastic elongation to the elongation at break was expressed by the formula: (L2-L4) / (L2-L0 ).
- the stress at the time of breaking was defined as the breaking strength, and the slope of the stress-strain curve at the initial stage of tension was defined as the tensile modulus.
- the curable resin composition of the example containing the first radical polymerizable monomer and the second radical polymerizable monomer had a higher elongation at break and stress than the curable resin composition of Comparative Example 3. As a result, it was confirmed that a resin molded body having excellent shape recovery after being deformed can be formed.
- Synthesis Example 2 Synthesis of PEG-PPG oligomer 1 Polyethylene glycol (PEG 1500, 750 mg, 0.500 mmol, number average molecular weight 1500) and polypropylene glycol (PPG 4000, 2000 mg, 0.500 mmol, number average molecular weight 4000) were added to a 20 mL eggplant flask. After the addition, the inside of the flask was purged with nitrogen, and the contents were melted at 115 ° C. 4,4′-dicyclohexylmethane diisocyanate (262 mg, 1.00 mmol) was added to the melt, and the melt was stirred at 115 ° C. for 24 hours under a nitrogen atmosphere to obtain PEG-PPG oligomer 1 (polyoxyethylene chain, and A second polymer containing a polyoxypropylene chain) was obtained.
- PPG 4000 2000 mg, 0.500 mmol, number average mo
- the weight average molecular weight (Mw) of the obtained oligomer 1 was 9300, and the weight average molecular weight / number average molecular weight (Mw / Mn) of the oligomer 1 was 1.65.
- Synthesis Example 3 Synthesis of PEG-PPG oligomer 2 Polyethylene glycol (PEG 1500, 750 mg, 0.500 mmol, number average molecular weight 1500) and polypropylene glycol (PPG 4000, 2000 mg, 0.500 mmol, number average molecular weight 4000) were added to a 20 mL eggplant flask. After the addition, the inside of the flask was purged with nitrogen, and the contents were melted at 115 ° C.
- the weight average molecular weight (Mw) of the obtained oligomer 2 was 50000, and the weight average molecular weight / number average molecular weight (Mw / Mn) of the oligomer 2 was 1.95.
- the obtained compounded liquid was poured into a stainless steel mold having a length ⁇ width ⁇ depth of 46 mm ⁇ 10 mm ⁇ 1 mm, and a transparent sheet made of polyethylene terephthalate was placed thereon.
- the compounded solution was photocured by irradiating UV (ultraviolet rays) for 30 minutes at room temperature (25 ° C., the same applies hereinafter) from above the transparent sheet to obtain a film-like molded body.
- a polytetrafluoroethylene tube (trade name Naflon (registered trademark) BT tube 1 / 8B) having an inner diameter of 1.59 mm ⁇ , an outer diameter of 3.17 mm ⁇ , and a wall thickness of 0.79 mm was wound around a stainless steel tube having an outer diameter of 10 mm ⁇ .
- the wound tube was filled with the compounded solution, and the compounded solution was photocured in the tube by ultraviolet irradiation at room temperature for 30 minutes. Then, the helical molded body was taken out from the tube.
- the compounded liquid filled in a polyethylene cup-shaped mold was photocured by ultraviolet irradiation for 30 minutes at room temperature.
- a cup-shaped molded body was taken out from the mold as a three-dimensional molded body.
- Example 2-2 (Examples 2-2, 2-3, and Comparative Example 2-1) A blending solution was prepared at the blending ratio shown in Table 2. Using the resulting blended liquid, resin molded bodies having various shapes were produced in the same manner as in Example 2-1.
- Shape memory property The film-like molded body was folded twice, and in this state, the crease was pressed with a glass tube. It was confirmed that the folded shape did not substantially return to the original shape.
- the spiral shaped body was stretched and deformed into a rod shape.
- the cup-shaped molded body was sandwiched between two glass plates and deformed by crushing in the height direction. The case where the molded body of each shape retained the deformed shape was determined as “good”, and the case where it was not retained was determined as “bad”.
- the deformed molded body was immersed in water at 70 ° C., and it was visually confirmed that it returned to the initial shape within 10 seconds immediately after the immersion. The case where the molded body recovered the initial shape was determined as “good”, and the case where it did not recover was determined as “bad”.
- a polyethylene terephthalate (PET) film was laid on a stainless steel mold having a length x width x depth of 46 mm x 10 mm x 1 mm.
- the resin composition was poured therein, and a transparent sheet made of PET was placed thereon.
- a 2000 mJ / cm 2 ultraviolet ray was irradiated from above the transparent sheet at room temperature (25 ° C., the same applies hereinafter) to obtain a resin film.
- a strip-shaped test piece (width: 8 mm, thickness: 1 mm) was cut out from the obtained resin film.
- the test piece was measured for strength at break and elongation at break using a strograph T (manufactured by Toyo Seiki Seisakusho Co., Ltd.) at room temperature, a distance between chucks: 30 mm, and a tensile speed: 10.0 mm / min.
- the resin molded body of each example had excellent bending resistance and high elongation. Moreover, the resin molding of each Example had favorable shape memory property. From this result, according to one aspect of the present invention, it was confirmed that a resin molded body having shape memory property excellent in shape recovery property by heating was obtained.
Abstract
Description
一実施形態に係る硬化性樹脂組成物は、第一の単官能ラジカル重合性モノマー及び第二の単官能ラジカル重合性モノマーを含むラジカル重合性モノマーを含有する。第一の単官能ラジカル重合性モノマー及び第二の単官能ラジカル重合性モノマーは、それぞれ、1個のラジカル重合性基を有する。
(1)5mm×50mmのサイズを有する硬化物の試験片を準備し、そのチャック間に相当する部分において、長手方向に並ぶ3箇所に印を付ける。各印間の距離をL0及びL0’とする。
(2)引張試験機を用いて、測定温度が25℃、引張速度が10mm/min、チャック間距離L1が30mmの条件で引張試験を行う。
(3)破断直後の試験片において、3点の印のうち印の間に破断箇所が存在しない2点の印を選択し、それらの印の間の距離L2を測定する。この部分に対応する初期の長さがL0である場合、破断伸びは式:(L2-L0)/L0により計算される。初期の長さがL0’である場合、破断伸びは式:(L2-L0’)/L0’により計算される。あるいは、破断時のチャック間距離L3を用いて、式:(L3-L1)/L1により破断伸びを計算してもよい。
(4)破断後の試験片を70℃で3分間加熱し、その後の印間の距離L4を測定し、破断伸びに対する弾性伸びの割合を示す弾性伸び率を式:(L2-L4)/(L2-L0)により算出する。破断直後の距離L2は、チャック間距離L3を利用して式:L2=L3×(L0/L1)により算出してもよい。
一実施形態に係る成形用組成物は、式(I):
1.硬化性樹脂組成物
表1に示す質量比で各原料を混合して、硬化性樹脂組成物を調製した。表中の数値は質量部である。
得られた硬化性樹脂組成物を、離型処理が施されたポリエチレンテレフタレート(PET)フィルム上に滴下して、硬化性樹脂組成物の塗膜を形成した。塗膜との間に0.2mmのギャップを開けながら、離型処理が施されたPETフィルムで塗膜を被覆した。PETフィルムの上から365nmの紫外線を1000mJ/cm2の積算光量で照射することで塗膜を硬化させて、硬化物フィルムを形成させた。
比較例1では、評価に供するための自立した硬化物フィルムが得られず、各測定が行えなかった。比較例2では、硬化物が相分離してフィルム状にならず、各測定が行えなかった。
硬化物フィルムから5mm×50mmのサイズを有する試験片を打ち抜いた。試験片のチャック間に相当する部分に長手方向に並ぶ3箇所に油性マジックで印を付け、各印間の距離をL0及びL0’とした。引張試験機(島津製作所製、EZ-TEST)を用いて、測定温度が25℃、引張速度が10mm/min、チャック間距離L1が30mmの条件で引張試験を行った。破断直後の試験片において、3点の印のうち印の間に破断箇所が存在しない2点の印を選択し、それらの印の間の距離L2を測定した。この部分に対応する初期の長さがL0である場合、破断伸びは式:(L2-L0)/L0により計算される。あるいは、破断時のチャック間距離L3を用いて、式:(L3-L1)/L1により破断伸びを計算してもよい。
硬化物フィルム(50mm×50mm×0.2mm)を2回折りたたみ、その状態で折り目に垂直に1N/cm2の圧力を5分間加えた。折り目部分を元に戻してから、その部分を目視で観察した。折り曲げ前と比較して外観上の変化、白化及びボイドなどの異常が認められない場合を「良」、白化又はボイドが認められた場合を「不良」と判定した。
硬化物フィルムから幅5mm、長さ50mmの短冊状の試験片を打ち抜いた。試験片からPETフィルムを剥離してから、TAインスツルメント株式会社製の動的粘弾性測定装置(RSA-G2)を用いて、チャック間距離20mm、測定周波数10Hzの条件でtanδの温度変化を測定した。tanδがピークとなる温度をガラス転移温度とした。
1.合成合成例1:trans-1,2-ビス(2-アクリロイルオキシエチルカルバモイルオキシ)シクロヘキサン(BACH)の合成
100mL二口ナスフラスコにtrans-1,2-シクロヘキサンジオール(2.32g、20.0mmol)を加え、フラスコ内を窒素置換した。そこにジクロロメタン(40mL)、及びジラウリン酸ジブチル錫(11.8μL、0.10mol%:0.020mmol)を入れた。フラスコ中の反応液に2-アクリロイルオキシエチルイソシアネート(5.93g、42.0mmol)のジクロロメタン(4mL)溶液を滴下ロートから滴下し、反応液を30℃で24時間撹拌して、反応を進行させた。反応終了後、反応液にジエチルエーテルを加えて飽和食塩水で洗浄した。有機層を無水硫酸マグネシウムで乾燥した後、溶媒を減圧留去し、残渣からシリカゲルクロマトグラフィー(展開溶媒:クロロホルム)によって目的物を含む溶液を単離し、これを濃縮した。得られた粗生成物を、ジエチルエーテルとヘキサンからの再結晶により精製して、BACHの白色結晶を得た。収量は、3.78gであり、収率は、47.4質量%であった。
20mLナスフラスコにポリエチレングリコール(PEG1500、750mg、0.500mmol、数平均分子量1500)、及びポリプロピレングリコール(PPG4000、2000mg、0.500mmol、数平均分子量4000)を加えてからフラスコ内を窒素置換し、内容物を115℃で融解させた。融解液に4,4’-ジシクロヘキシルメタンジイソシアネート(262mg、1.00mmol)を加えて、窒素雰囲気下、115℃で融解液を24時間撹拌して、PEG-PPGオリゴマー1(ポリオキシエチレン鎖、及びポリオキシプロプレン鎖を含む第二の重合体)を得た。
20mLナスフラスコにポリエチレングリコール(PEG1500、750mg、0.500mmol、数平均分子量1500)、及びポリプロピレングリコール(PPG4000、2000mg、0.500mmol、数平均分子量4000)を加えてからフラスコ内を窒素置換し、内容物を115℃で融解させた。融解液に4,4’-ジシクロヘキシルメタンジイソシアネート(262mg、1.00mmol)、及びラウリル酸ジブチル錫(11.8μL、0.10mol%:0.020mmol)を加えて、窒素雰囲気下、115℃で融解液を24時間撹拌して、PEG-PPGオリゴマー2(ポリオキシエチレン鎖、及びポリオキシプロピレン鎖を有する第二の重合体)を得た。
10mMの臭化リチウムを含むDMF(N,N-ジメチルホルムアミド)を溶離液として用いて、流速1mL/分の条件でオリゴマーのGPCクロマトグラムを得た。得られたクロマトグラムから、オリゴマーの数平均分子量及び重量平均分子量をポリスチレン換算値として求めた。
(実施例2-1)
合成例1のBACH(27.7mg、69.5μmol)、合成例2のPEG-PPGオリゴマー1(34.5mg、2.88μmol)、2-エチルヘキシルアクリレート(2-EHA、553mg、3.00mmol)、アクリロニトリル(AN、390mg、3.00mmol)及びIrgacure 651(15.5mg、60.5μmol)をサンプル瓶中で加熱溶解し、配合液(成形用組成物)を調製した。
PEG-PPGオリゴマー1を用いないこと以外は、実施例1と同様にして配合液を調製した。得られた配合液を用いて、実施例2-1と同様に、各種形状の樹脂成形体を作製した。
表2に示した配合比で配合液を調製した。得られた配合液を用いて、実施例2-1と同様に、各種形状の樹脂成形体を作製した。
フィルム状の成形体から、5mm幅、長さ30mmの短冊状の試験片を切り出した。この試験片を用いて、TAインスツルメント株式会社社製動的粘弾性測定装置(RSA-G2)を用いて、25℃における貯蔵弾性率を測定した。測定条件は以下のとおりである。・チャック間距離:20mm
・測定周波数:10Hz
・昇温速度5℃/分
フィルム状の成形体を2回折りたたみ、その状態で折り目をガラス管で押さえた。折りたたまれた形状が実質的に元に戻らないことを確認した。螺旋状の成形体を、引き伸ばして棒状に変形させた。カップ状の成形体を、2枚のガラス板の間に挟み、高さ方向に押しつぶすことにより変形させた。各形状の成形体が変形後の形状を保持した場合を「良」、保持しなかった場合を「不良」と判定した。
実施例のフィルム状の成形体に関して、折り目部分を元に戻してから、その部分を目視と光学顕微鏡(100倍)で観察した。折り曲げ前と比較して外観上の変化がなかった場合を「良」、白化及びボイドなどの異常が発生した場合を「不良」と判定した。
長さ×幅×深さが46mm×10mm×1mmのステンレス金型にポリエチレンテレフタラート(PET)製フィルムを敷いた。そこに樹脂組成物を流し込み、その上にPET製の透明シートを被せた。透明シートの上から、室温(25℃、以下同様)で2000mJ/cm2の紫外線を照射し、樹脂フィルムを得た。
Claims (7)
- 第一の単官能ラジカル重合性モノマー及び第二の単官能ラジカル重合性モノマーを含むラジカル重合性モノマーを含有し、
前記第一の単官能ラジカル重合性モノマーが、単独で重合したときに20℃以下のガラス転移温度を有するホモポリマーを形成するモノマーであり、
前記第二の単官能ラジカル重合性モノマーが、単独で重合したときに50℃以上のガラス転移温度を有するホモポリマーを形成するモノマーである、
硬化性樹脂組成物。 - 前記第一の単官能ラジカル重合性モノマー及び前記第二の単官能ラジカル重合性モノマーの合計の含有量が、前記ラジカル重合性モノマーの全体量を基準として60質量%以上である、請求項1に記載の硬化性樹脂組成物。
- 前記第一の単官能ラジカル重合性モノマーが2-エチルヘキシルアクリレートを含む、請求項1又は2に記載の硬化性樹脂組成物。
- 前記第二の単官能ラジカル重合性モノマーが、アクリロニトリル、ジシクロペンタニルアクリレート、及びメチルメタクリレートからなる群より選ばれる少なくとも一種を含む、請求項1~3のいずれか一項に記載の硬化性樹脂組成物。
- 前記ラジカル重合性モノマーが、二官能ラジカル重合性モノマー及び/又は三官能ラジカル重合性モノマーを更に含む、請求項1~4のいずれか一項に記載の硬化性樹脂組成物。
- 前記第一の単官能ラジカル重合性モノマーの含有量が、前記ラジカル重合性モノマーの全体量を基準として5質量%以上、90質量%以下であり、
前記第二の単官能ラジカル重合性モノマーの含有量が、前記ラジカル重合性モノマーの全体量を基準として10質量%以上、95質量%以下である、
請求項1~5のいずれか一項に記載の硬化性樹脂組成物。 - 硬化性樹脂組成物の硬化物であって、
前記硬化性樹脂組成物が、第一の単官能ラジカル重合性モノマー及び第二の単官能ラジカル重合性モノマーを含むラジカル重合性モノマーを含有し、
前記第一の単官能ラジカル重合性モノマーが、単独で重合したときに20℃以下のガラス転移温度を有するホモポリマーを形成するモノマーであり、
前記第二の単官能ラジカル重合性モノマーが、単独で重合したときに50℃以上のガラス転移温度を有するホモポリマーを形成するモノマーである、
硬化物。
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