Patent Application
20180009955
The present invention relates to a resin composition, and an applied product of the resin composition.
In recent years, there is a growing interest in an equilibrium reaction of covalent bonds, in which reversible dissociation-bond can be easily realized while being a covalent bond, and chemistry utilizing this is referred to as dynamic covalent chemistry. In a structure formed based on dynamic covalent chemistry, there is a thermodynamically stable structure, but on the other hand, the structure can be altered by a specific external stimulus such as temperature, light, pressure, and presence or absence of catalyst and template. By utilizing such a “dynamic” covalent bond, supermolecular formation and polymer construction, which have not been able to be realized so far, can be realized. Particularly noteworthy is that since the involved bond is a covalent bond, the bond to be formed is significantly stronger than a weak bond such as a hydrogen bond that is observed in a conventional supermolecule or a polymer thereof, and this utilization can be an important means for constructing a new structure. PTL 1 is a patent concerning the study of a polymer having an alkoxyamine skeleton introduced into a polymer chain as a polymer utilizing such a dynamic covalent bond.
In PTL 2, there is a description that “The invention relates to thermosetting resins and to thermosetting composites containing same, wherein the materials are hot-formable. The compositions result from contacting at least one thermosetting resin precursor with at least one hardener selected from among the acid anhydrides in the presence of at least one transesterification catalyst”. In this PTL 2, for the purpose of developing a thermosetting resin that can be thermally deformed after curing, an ester bond exchange reaction is utilized as a dynamic covalent bond. This resin is characterized by being deformable and at the same time being capable of bonding, and relaxing a stress, while being a thermosetting resin. Accordingly, not only the recyclability described in PTL 2, but also improvement of the crack resistance, application to a maintenance free resin for a coating material having a self-repair function, life prolongation of the resin itself, and the like can be expected.
PTL 1: JP 5333975 B2
PTL 2: JP 2014-503670 A
A resin produced by a conventional technique has a weak nature in terms of hydrolysis resistance. For example, in a case where a resin produced by a conventional technique is used in an area with a highly humid climate such as Japan for a long period of time, deterioration of the resin due to hydrolysis becomes a concern.
The present invention is to provide a resin composition that is optimized in the molecular structure design of the resin and in the catalyst in order to improve the hydrolysis resistance. Specifically, a resin composition according to the present invention contains (1) a copolymer of a vinyl compound having two or more epoxy groups, a carboxylic acid anhydride, and a transesterification reaction catalyst, or (2) a copolymer of a vinyl compound having two or more carboxylic acid anhydride groups, an epoxy, and a transesterification reaction catalyst.
By employing the above-described constitution, a resin composition having improved hydrolysis resistance can be provided.
Hereinafter, the examples will be described with reference to the drawings.
The resin composition according to the present invention contains (1) a copolymer of a vinyl compound having two or more epoxy groups, a carboxylic acid anhydride, and a transesterification reaction catalyst, or (2) a copolymer of a vinyl compound having two or more carboxylic acid anhydride groups, an epoxy, and a transesterification reaction catalyst.
As a result of the reaction between the epoxy and the carboxylic acid anhydride, the resin composition according to the present invention has an ester bond and a hydroxyl group. Further, under the transesterification reaction catalyst, the ester bond and the hydroxyl group start the transesterification reaction by heating.
By setting the ester bond, the hydroxyl group, and the amount of the transesterification reaction catalyst in the predetermined ranges, and heating at an appropriate temperature, a thermally deformable resin can be synthesized.
The resin composition shown in
The vinyl compound having an epoxy group (precursor vinyl monomer) can be selected from 1,3-butadiene epoxide, 1,2-epoxy-5-hexene, allyl glycidyl ether, glycidyl methacrylate, and 1,2-epoxy-4-vinylcyclohexane.
The vinyl compound having a carboxylic acid anhydride (precursor vinyl monomer) can be selected from maleic anhydride, methyl maleic acid, allyl succinic acid, a 4-cyclohexene-1,2-dicarboxylic acid anhydride, and a 5-norbornene-2,3-dicarboxylic acid anhydride.
In the vinyl monomer described above, if the functional groups of the vinyl monomer are epoxy groups, the copolymerization reaction may be performed by mixing different kinds of vinyl monomers at an appropriate mixing ratio. Further, in the similar way, if the functional groups of the vinyl monomer are carboxylic acid anhydrides, the copolymerization reaction may be performed by mixing different kinds of vinyl monomers at an appropriate mixing ratio.
The precursor vinyl monomer can be selected from the group consisting of an aromatic vinyl compound, an aromatic allyl compound, a heterocycle-containing vinyl compound, a heterocycle-containing allyl compound, alkyl (meth)acrylate, an unsaturated monocarboxylic acid ester, fluoroalkyl (meth)acrylate, a siloxanyl compound, a mono-(meth)acrylate and di-(meth)acrylate of an alkylene glycol, an alkoxyalkyl (meth)acrylate, a cyanoalkyl (meth)acrylate, acrylonitrile, and methacrylonitrile, a hydroxyalkylester of an unsaturated carboxylic acid, an unsaturated alcohol, an unsaturated (mono) carboxylic acid, an unsaturated polycarboxylic acid, and an unsaturated polycarboxylic anhydrate; a monoester and diester of an unsaturated polycarboxylic acid or unsaturated polycarboxylic anhydrate; an epoxy group-containing unsaturated compound, a diene compound, vinyl chloride, vinyl acetate, sodium isoprene sulfonate, a cinnamic acid ester, a crotonic acid ester, dicyclopentadienyl, and ethylidene norbornene.
In the above-described vinyl monomer, by combining with a vinyl monomer having an epoxy group or a carboxylic acid anhydride, and performing a copolymerization reaction, the amount of the transesterification reaction site can be controlled. In this way, the control of the crosslinking density and the control of the flexibility of the main chain skeleton can be achieved. The elastic modulus can also be changed by controlling the crosslink density and the flexibility of the main chain skeleton, therefore, the thermal deformation characteristics can also be controlled.
In addition, by taking advantage of the characteristics of the above-described vinyl monomer itself, characteristics of heat resistance, hydrolysis resistance, optical properties, thermal conductivity, electric characteristics, and the like of the resin composition of the present invention can further be imparted.
For example, by combining dicyclopentadienyl, ethylidene norbornene, and the like, which are classified as cycloolefins, as a copolymerization monomer, the hydrolysis resistance can further be improved.
The resin composition according to the present invention is characterized in that the ratio of the transesterification reaction catalyst to the total vinyl compound is 0.23 to 11 mol %. By containing the transesterification reaction catalyst at this ratio, the conditions under which the transesterification reaction occurs can be satisfied. The proportions of the transesterification reaction catalyst shown in Table 2, which will be described later, are included in this range.
The transesterification reaction catalyst can be selected from the group consisting of zinc(II) acetate, zinc(II) acetylacetonate, zinc(II) naphthenate, iron (III) acetylacetone, cobalt(II) acetylacetone, aluminum isopropoxide, titanium isopropoxide, a methoxide(triphenylphosphine) copper(I) complex, an ethoxide(triphenylphosphine) copper(I) complex, a propoxide(triphenylphosphine) copper(I) complex, an isopropoxide(triphenylphosphine) copper(I) complex, a methoxidebis(triphenylphosphine) copper(II) complex, an ethoxidebis(triphenylphosphine) copper(II) complex, a propoxidebis(triphenylphosphine) copper(II) complex, an isopropoxidebis(triphenylphosphine) copper(II) complex, tris(2,4-pentanedionato)cobalt(III), tin(II) diacetate, tin(II) di(2-ethylhexanoate), N,N-dimethyl-4-aminopyridine, diazabicycloundecene, diazabicyclononene, triazabicyclodecene, and triphenylphosphine.
The resin composition according to the present invention is characterized by being a vinyl compound copolymer composition in which in a vinyl compound copolymer resin composition, an ester bond generated by adding a carboxylic acid anhydride or an epoxy compound and a catalyst selected from the above-described transesterification reaction catalysts, and a hydroxyl group are contained in a polymer obtained by polymerizing or copolymerizing a vinyl monomer selected from precursor vinyl monomers by radical polymerization.
As the radical polymerization initiator for polymerization of the main chain skeleton, an initiator such as a peroxide-based compound, and an azo-based compound can be used. Further, a living radical polymerization initiator can also be used, and a transition metal compound, a thiocarbonyl-based compound, and an alkylborane-based compound can be used.
In particular, when a living radical polymerization initiator is used, the block copolymerization and random copolymerization can be controlled, and the characteristics of the optical properties, the thermal conductivity, the electric characteristics, and the like of the resin composition of the present invention can be improved.
In a case where a monomer having an epoxy group as the functional group is selected as the precursor vinyl monomer, the precursor vinyl monomers are polymerized or copolymerized to form the main chain skeleton, and then a carboxylic acid anhydride and a transesterification reaction catalyst are added, and a resin composition of the present invention containing an ester bond and a hydroxyl group can be obtained.
Specific examples of the carboxylic acid anhydride include a phthalic anhydride, a nadic anhydride, a hexahydrophthalic anhydride, a dodecene succinic anhydride, and a glutaric anhydride, however, a carboxylic acid anhydride other than the anhydrides described above can also be used, and the carboxylic acid anhydride is not particularly limited.
In a case where a monomer having a carboxylic acid anhydride as the functional group is selected as the precursor vinyl monomer, the precursor vinyl monomers are polymerized or copolymerized to form the main chain skeleton, and then an epoxy compound and a transesterification reaction catalyst are added, and a resin composition of the present invention containing an ester bond and a hydroxyl group can be obtained.
The epoxy compound can be selected from a novolak.epoxy resin, bisphenol A diglycidyl ether (BADGE), bisphenol F diglycidyl ether, tetraglycidyl.methylene dianiline, pentaerythritol.tetraglycidyl.ether, tetrabromobisphenol A diglycidyl ether, or hydroquinone.diglycidyl ether, ethylene glycol.diglycidyl ether, propylene glycol.diglycidyl ether, butylene glycol.diglycidyl ether, neopentyl.glycol.diglycidyl ether, 1,4-butanediol.diglycidyl ether, 1,6-hexanediol.diglycidyl ether, cyclohexanedimethanol.diglycidyl ether, polyethylene glycol.diglycidyl ether, polypropylene glycol.diglycidyl ether, polytetramethylene.glycol.diglycidyl ether, resorcinol diglycidyl ether, neopentyl.glycol.diglycidyl ether, bisphenol A polyethylene glycol diglycidyl ether, bisphenol A polypropylene glycol.diglycidyl ether, terephthalic acid diglycidyl ester, poly(glycidyl.acrylate), poly(glycidyl methacrylate), an epoxidized polyunsaturated fatty acid, an epoxidized plant oil, an epoxidized fish oil, and epoxidized limonene, and a mixture thereof.
The resin composition of the present invention can be used for various kinds of coating materials. In a case where the resin composition is used as a coating material for a moving body such as a car, and a train, scratches can be repaired by moderate heating. This is because in the damaged part, by heating, the transesterification reaction occurs, and the bond site once cleaved can be bonded again, as a result the scratches are repaired. Further, the resin composition of the present invention can be used also for a coating material for a building material in a similar way.
The resin composition of the present invention can be used for a mold resin material for a transformer. In the mold resin material for a transformer, cracks are generated due to the distortion by the difference in the expansion coefficient with other members during the molding. When the crosslinking density of the resin is lowered in order to improve the crack resistance, the heat resistance is lowered. In addition, when an additive material such as rubber particles, and a filler is used, the resin viscosity increases, voids are easily generated at the time of molding casting, and there is a problem that cracks originating from the voids are generated and the electric insulation is lowered. On the other hand, with the resin according to the present invention, these problems can be overcome. In addition, in a case of small cracks, the cracks generated after use can also be repaired by heating.
The resin composition of the present invention can be used for a mold sealing material. In the mold sealing material, there is a problem of crack resistance by the difference in the expansion coefficient with other members such as a metal. As a technique for improving the crack resistance of the resin for a mold sealing material, decrease in the crosslinking density of the resin, decrease in the toughness value due to an additive material such as rubber particles, and a filler, or the like is generally used. In these techniques, once molded and processed, cracks occurring due to the distortion generated during the use of the product cannot be prevented. On the other hand, in the resin composition of the present invention, the distortion generated between the resin and other members after the molding by the heat generated during the use of the product can also prevent the occurrence of cracks due to the strain relaxation of bond recombination of transesterification reaction.
The electronic package 200 is constituted of a semiconductor element 24 arranged on a substrate 24a, a lead frame 22 extending outside the mold sealing material 23, and a bonding wire 25 for electrically connecting the lead frame 22 and the semiconductor element 24. Further, the lead frame 22, the semiconductor element 24, the substrate 24a, and the bonding wire 25 are sealed with the mold sealing material made of the resin composition of the present invention.
The lead frame 22, and the bonding wire 25 are both constituted of a good conductor, and specifically, made of copper, aluminum, or the like. Further, the form of the lead frame 22 and the bonding wire 25 may be any known form of, for example, a solid (solid) wire, a twisted wire, or the like.
In addition, as the shape of the semiconductor element 24, for example, a circular shape, a divided circular shape, a compressed shape, or the like can be applied. Further, the material for constituting the semiconductor element 24 is not particularly limited as long as the material can be sealed by the mold sealing material 23.
The resin composition of the present invention can be used for a protective material or varnish material for a motor coil. In the motor coil, there is a problem of the occurrence of cracks due to electromagnetic vibration or the like. In the resin composition of the present invention, the bond recombination occurs due to the heat generated during the use of the motor, therefore, the distortion, that is, stress, which causes cracks, can be relaxed.
The coil 300 for a motor is constituted of a magnetic core 36, a coated copper wire 37 wound around the magnetic core 36, and a motor coil protective material 38 made of the resin composition of the present invention. Further, to the coil 300, the resin composition of the present invention according to the present embodiment is uniformly applied as a varnish material for a motor coil protective material.
The magnetic core 36 is made of, for example, a metal such as iron. Further, as the coated copper wire 37, an enameled wire having a diameter of 1 mm is used.
The coil 300 is used for the motor 301 shown in
The resin composition of the present invention can be used for a coating layer or an insulating layer of a cable. When cracks are Generated due to the long-term use, the electric insulation of the coating material of the cable such as an electric wire is lowered. Since the cable is not easily replaced, there is a need for a material that can be repaired locally. In a case where the resin composition of the present invention is used for a cable, when the part where a crack has been generated is heated, the crack can be repaired by the bond regeneration function of the bond recombination of the transesterification reaction.
The cable 400 shown in
There is no particular limitation on the material constituting the inner semiconductive layer 44 and on the form, and any own material may be used.
Further, there is no particular limitation on the material constituting the insulating layer 45 and on the form, and for example, an oil-impregnated paper or oil-impregnated semi-synthetic paper material, a rubber material, a resin material, or the like can be used. Examples of the insulating material such as a rubber material and a resin material include ethylene-propylene rubber, butyl rubber, polypropylene, a thermoplastic elastomer, polyethylene, and crosslinked unsaturated polyethylene. Among them, polyethylene, and crosslinked polyethylene are suitable from the viewpoint of being generally used in an insulated cable.
The outer semiconductive layer (adhesive layer) 46 is arranged for the purpose of moderating the intense electric field generated at the periphery of the conductor 43. Examples of the material used for the outer semiconductive layer (adhesive layer) 46 include a semiconductive resin composition in which a resin material such as a styrene-butadiene-based thermoplastic elastomer, a polyester-based elastomer, and a soft polyolefin is mixed with a conductive carbon black, and conductive coating materials with a conductive carbon black added. However, the material is not particularly limited as long as the material satisfies the required performances. The method for forming the outer semiconductive layer (adhesive layer) 46 on the surface of the insulating layer 45 not particularly limited, and examples of the method include continuous extrusion, dipping, spray-coating, and coating, depending on the kind of the member.
The outer semiconductive layer (release layer) 47 is arranged for the purpose of moderating the intense electric field generated at the periphery of the conductor 43, and protecting the inner layers, in the similar manner as in the outer semiconductive layer (adhesive layer) 46. Further, in the application to the connection or the like, as the outer semiconductive layer (release layer) 47, any outer semiconductive layer may be used as long as it easily peels off from the outer semiconductive layer (adhesive layer) 46, or any outer semiconductive layer in which other layers interposed therebetween may be used. As the material used for the outer semiconductive layer (release layer) 47, a crosslinkable or non-crosslinkable resin composition in which a conductive carbon black is mixed in an amount of 30 to 100 parts by mass based on 100 parts by mass of a base material containing at least one among, for example, soft polyolefin, a rubber material such as ethylene-propylene rubber, and butyl rubber, a styrene-butadiene-based thermoplastic elastomer, a polyester-based elastomer, and the like, can be mentioned. However, the material is not particularly limited as long as the material satisfies the required performances. Further, as needed, for example, an additive such as a filler including graphite, a lubricant, a metal, an inorganic filler, and the like may be contained. In addition, the method for forming the outer semiconductive layer (release layer) 47 on the surface of the outer semiconductive layer (adhesive layer) 46 is not particularly limited, and is preferably extrusion molding.
As described above, when the resin composition of the present invention is used according to the characteristics of the transesterification reaction, the product life can be prolonged, and further, the hydrolysis resistance is higher than that of the conventional resin using the same reaction, therefore, a further long-term product life can be guaranteed.
In the present Example 1, a method for synthesizing the resin composition of the present invention will be described.
Synthesis of main chain skeleton First, synthesis of the main chain skeleton will be described. Glycidyl methyl methacrylate (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.) in an amount of 4.24 g (30 mmol), 15.6 g (150 mmol) of styrene (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), 0.8858 g (54 mmol) of 2,2′-azobis(isobutyronitrile) (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), and 30 ml of toluene (manufactured by Wako Pure Chemical Industries, Ltd.) were put into a separable flask, and were thoroughly stirred at room temperature with a mechanical stirrer. When it was confirmed that the 2,2′-azobis(isobutyronitrile) had been dissolved, the mixture was reacted at 60° C. for 3 hours under a N2 atmosphere. The sirup after the reaction was dissolved in tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.), and the resultant mixture was added dropwise to a large amount of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), and the reprecipitation was performed. The obtained reprecipitate and liquid were separated by suction filtration, and dried at room temperature using vacuum drying to obtain a copolymer A. The weight average molecular weight of the copolymer A was 50000, the molecular weight distribution (Mw/Mn) was 1.8, and the glass transition temperature (Tg) was 66° C. Note that the weight average molecular weight in the present specification is a standard polystyrene equivalent value by a gel permeation chromatography method. Further, from the integral ratio of the 1H-NMR spectrum, the incorporation ratio (molar ratio) of the glycidyl methyl methacrylate and the polystyrene in the copolymer A was determined to be 71:29.
With respect to the copolymers B to E synthesized by a synthesis method similar to the synthesis method described above, the results were summarized in Table 1 as to the type of monomers, the charged amount, and the incorporation ratio. Note that as dicyclopentenyloxyethyl methacrylate, a reagent manufactured by Hitachi Chemical Co., Ltd. was used.
Introduction of ester bond moiety The copolymer A in an amount of 1.5 g, which had been synthesized by the method described above, 0.34 of HN5500 (manufactured by Hitachi Chemical Company, Ltd.), and 0.53 g of zinc naphthenate (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), were dissolved in 2 g of tetrahydrofuran, and varnished. The tetrahydrofuran was dried under the airflow of N2 and the varnish was made into a film.
The prepared film was potted in a mold made of a Teflon sheet having a thickness of 0.5 mm, and a cured product A was obtained as strip test pieces with 20 mm×5 mm×0.5 mm and 20 mm×2 mm×0.5 mm by a vacuum press. The pressing pressure was 0.44 MPa, and the heating was performed at 90° C. for 1 hour and at 140° C. for 4 hours. The compositions of the cured products B to E prepared in the similar way are shown in Table 2.
In Example 2, the physical properties evaluation results of the resin composition in which bond recombination by the two types of transesterification reactions is generated, synthesized in Example 1 will be described.
Adhesion As shown in
Hydrolyzability A cured product of the test pieces with 20 mm×5 mm×0.5 mm was left to stand in a wet thermostat at a temperature of 85 degrees and at a humidity of 85%, and the changes in infrared absorption spectra were followed for 20 days. In the infrared absorption spectra, based on the aromatic region of 1509 cm−1, the changes in the absorption of carbonyl groups at 1736 cm−1, which are considered to be produced after the hydrolysis, were observed. As a result, as for the cured products A to E, as a result of the observation for 20 days, the absorption at 1736 cm−1 was hardly changed.
In Comparative Example 1, a method for synthesizing a conventional resin composition will be described. A jer825 epoxy resin (manufactured by The Dow Chemical Company, equivalent epoxy mass: 170 to 180 g/eq.) in an amount of 10.7 g, and 0.81 g of zinc acetylacetonate were put into a beaker made of Teflon. The reactant was heated by using a hot air gun (T=180° C.) and mixed until the complete dissolution was obtained. Next, into the resultant mixture, 4.4 g of HN5500 was added, and mixed until the complete dissolution was obtained. The resultant mixture solution was poured into a mold made of a Teflon sheet having a thickness of 0.5mm, and a cured product J was obtained as strip test pieces of 20 mm×5 mm×0.5 mm and 20 mm×2 mm×0.5 mm by a vacuum press. Two kinds of test pieces were obtained by pressing at a pressing pressure of 0.44 MPa and heating at 90° C. for 1 hour and at 140° C. for 8 hours.
By the adhesion test in the similar manner as in Example 2, it was confirmed that the characteristics of the resin composition in which bond recombination by the transesterification reaction is generated are shown in the similar manner as in the resin composition of the present invention.
On the other hand, in the 20-day hydrolysis test, as for the cured product J, based on the aromatic region of 1509 cm−1, the result that the absorption of carbonyl groups at 1736 cm−1 is increased was obtained. As a result, it can be understood that the cured product F is affected by hydrolysis.
As described above, according to Examples and Comparative Examples, it was proved that the hydrolysis resistance of the resin composition of the present invention is improved.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-007364 | Jan 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/050596 | 1/12/2016 | WO | 00 |
