Resin composition, and molded article and film using resin composition

Abstract

The present invention provides a resin composition capable of providing a film or the like which can suppress coloring even after heating. Also provided are a molded article, a film, a conductive film, a film capacitor, a polarizing material, an electrostatic induction type conversion element, and a touch panel, each of which uses the resin composition. A resin composition containing a copolymer (A) and a Bronsted acidic compound (B), the copolymer (A) containing a structural unit (a1) derived from 1, 1-dicyanoethylene and a structural unit (a2) derived from a compound represented by general formula (I), and the content of the Bronsted acidic compound (B) in the resin composition being 0.1-95000 ppm by mass.

Description

Technical Field

[0001] The present invention relates to a resin composition containing a copolymer and a Bronsted acid compound, wherein the copolymer contains a structural unit derived from 1,1-dicyanoethylene and a structural unit derived from a specific polymerizable monomer. Background Art

[0002] A resin composition comprising a copolymer obtained by radical polymerization of 1,1-dicyanoethylene and a polymerizable monomer has excellent transparency when processed into a film and is therefore suitable for use in various materials such as optical components, lighting components, signboard components, and decorative components (eg, Patent Document 1).

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 01-103614 Summary of the invention

[0006] Problems to be solved by the invention

[0007] As described above, a film made of a resin composition containing a copolymer of 1,1-dicyanoethylene and a polymerizable monomer has excellent transparency and dielectric properties, but has a problem of being colored by heating and thus impairing the appearance.

[0008] The present invention is completed in view of the above-mentioned existing problems, and its subject is to provide a resin composition that can provide a film that can suppress coloring even after heating and has excellent dielectric properties. In addition, the subject of the present invention is to provide a molded product, a film, a conductive film, a film capacitor, a polarizing material, an electrostatic induction conversion element, and a touch panel using the above-mentioned resin composition.

[0009] Methods used to solve problems

[0010] The present inventors have conducted research and have found that a cross-linked structure is formed between nitrile groups in the side chains of the copolymer (nitrile groups derived from 1,1-dicyanoethylene) and between the nitrile groups and substituents in the side chains of other monomers constituting the copolymer, forming a conjugated structure in which some double bonds are connected, resulting in coloration due to heating. Further research has been repeated to suppress this coloration, and as a result, it has been found that by adding a specific amount of a Bronsted acidic compound to a resin composition, the conjugated structure can be stabilized, the coloration can be improved, and the dielectric properties are also excellent, thereby completing the present invention.

[0011] That is, the present invention provides the following [1] to

[21] .

[0012] [1] A resin composition, characterized in that the resin composition is a resin composition containing a copolymer (A) and a Bronsted acidic compound (B), wherein the copolymer (A) contains a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from a compound represented by the following general formula (I), and the content of the Bronsted acidic compound (B) in the resin composition is 0.1 to 95000 ppm by mass.

[0013] CH2=CR 1 R 2 (I)

[0014] (In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom,

[0015] R 2 is selected from hydrogen, alkyl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms. ) represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. ) is one or more of the acyloxy groups represented by

[0016] [2] The resin composition according to [1] above, wherein the compound represented by the general formula (I) is at least one selected from the group consisting of vinyl esters, (meth)acrylates, styrene derivatives, isobutylene and propylene.

[0017] [3] The resin composition according to [1] or [2] above, wherein the Bronsted acidic compound (B) has an acid dissociation constant (pKa) of 4.8 or less.

[0018] [4] The resin composition according to any one of [1] to [3] above, wherein the Bronsted acidic compound (B) is a compound having one or more selected from the group consisting of a phosphoric acid group, a carboxyl group, a sulfonic acid group and a phosphorous acid group.

[0019] [5] A resin composition according to any one of [1] to [4] above, wherein the structural unit (a2) comprises two different structural units: a structural unit (a21) derived from a compound represented by the general formula (I) above and a structural unit (a22) derived from a compound represented by the general formula (I) above.

[0020] [6] The resin composition according to any one of [1] to [5], wherein the composition ratio [S / N] of sulfur atoms to nitrogen atoms is 3.5×10 -8 ~0.3.

[0021] [7] The resin composition according to any one of [1] to [6], wherein the composition ratio [P / N] of phosphorus atoms to nitrogen atoms is 1.4×10 -8 ~0.3.

[0022] [8] A molded product using the resin composition according to any one of [1] to [7] above.

[0023] [9] A film using the resin composition according to any one of [1] to [7] above.

[0024]

[10] The film according to [9] above, wherein the yellowness after heating at 160° C. for 1 hour under normal pressure is 3.0% or less.

[0025]

[11] A conductive film comprising a conductive layer stacked on the film according to [9] or

[10] .

[0026]

[12] A thin film capacitor comprising the thin film described in [9] or

[10] above.

[0027]

[13] A thin film capacitor comprising the conductive film described in

[11] above.

[0028]

[14] A polarizing material comprising the resin composition according to any one of [1] to [7] above.

[0029]

[15] A polarizing material comprising the thin film described in [9] or

[10] above.

[0030]

[16] The polarizing material according to

[14] , wherein R in the general formula (I) 1 Contains H, R 2 Contains -OCOR 5 (R 5 It is an alkyl group having 1 to 12 carbon atoms. ) is a resin composition comprising an acyloxy group represented by

[0031]

[17] The polarizing material according to

[15] , wherein R in the general formula (I) 1 Contains H, R 2 Contains -OCOR 5 (R 5 It is an alkyl group having 1 to 12 carbon atoms. ) is a resin composition comprising an acyloxy group represented by

[0032]

[18] An electrostatic induction conversion element comprising the polarizing material described in

[14] above.

[0033]

[19] An electrostatic induction conversion element comprising the polarizing material described in

[15] above.

[0034]

[20] A touch panel comprising the electrostatic induction conversion element described in

[18] above.

[0035]

[21] A touch panel comprising the electrostatic induction conversion element described in

[19] above.

[0036] Effects of the Invention

[0037] According to the present invention, a resin composition can be provided, which can provide a film that can suppress coloring even after heating and has excellent dielectric properties, etc. In addition, the present invention can provide a molded product, a film, a conductive film, a film capacitor, a polarizing material, an electrostatic induction conversion element, and a touch panel using the above resin composition. DETAILED DESCRIPTION

[0038] [Resin composition]

[0039] The resin composition of the present invention is a resin composition containing a copolymer (A) and a Bronsted acidic compound (B), wherein the copolymer (A) contains a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from a compound represented by the following general formula (I), and the content of the Bronsted acidic compound (B) in the resin composition is 0.1 to 95000 ppm by mass.

[0040] The resin composition of the present invention contains a specific amount of a Bronsted acidic compound, and therefore can stabilize the partial conjugated structure of the side chain of the copolymer (A) that causes coloration, and as a result, can suppress coloration due to heating.

[0041] CH2=CR 1 R 2 (I)

[0042] (In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom,

[0043] R 2 is selected from the group consisting of a hydrogen atom, an alkyl group, an alkoxy group, a carboxyl group, a -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4is an alkyl group having 1 to 12 carbon atoms. ) represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. ) is one or more of the acyloxy groups represented by

[0044] <Copolymer (A)>

[0045] The copolymer (A) used in the present invention contains a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from the compound represented by the above general formula (I).

[0046] [Structural unit derived from 1,1-dicyanoethylene (a1)]

[0047] The copolymer (A) used in the present invention contains a structural unit (a1) derived from 1,1-dicyanoethylene. 1,1-dicyanoethylene provides a highly transparent copolymer by radical polymerization, and thus can be suitably used as a material for molded products requiring transparency.

[0048] 1,1-Dicyanoethylene can be produced by the production method described in J. Am. Chem. Soc., 1989, 111, 9078-9081 and U.S. Patent No. 2476270.

[0049] [Structural unit (a2) derived from the compound represented by general formula (I)]

[0050] The copolymer (A) used in the present invention contains a structural unit (a2) derived from a compound represented by the following general formula (I).

[0051] CH2=CR 1 R 2 (I)

[0052] (In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom,

[0053] R 2 is selected from hydrogen, alkyl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms. ) represented by -OCOR 5 (R 5 is an alkyl group having 1 to 12 carbon atoms. ) is one or more of the acyloxy groups represented by

[0054] In the general formula (I), R1 is at least one selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom.

[0055] As R 1 The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0056] As R 1 The cycloalkyl group is preferably a cycloalkyl group having 3 to 12 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

[0057] As R 1 The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, tolyl, xylyl and naphthyl.

[0058] As R 1 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0059] As R 1 The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0060] Among them, from the viewpoint of suppressing the coloration of the molded product using the resin composition of the present invention after heating, R 1 Preferred are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms, more preferred are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and a phenyl group, and still more preferred are a hydrogen atom, a methyl group, and a phenyl group.

[0061] In the general formula (I), R 2 is selected from hydrogen, alkyl, alkoxy, carboxyl, -COOR 3 (R 3 is an alkyl group having 1 to 12 carbon atoms. 4 (R 4 is an alkyl group having 1 to 12 carbon atoms. ) represented by -OCOR 5 (R 5 It is an alkyl group having 1 to 12 carbon atoms. One or more of the acyloxy groups represented by ).

[0062] As R 2The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0063] As R 2 The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and examples thereof include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy.

[0064] R 2 Can be made by -COOR 3 The ester group represented by R 3 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0065] As R 2 Examples of the acid anhydride groups include those derived from phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, glutaric anhydride, dimethylglutaric anhydride, diethylglutaric anhydride, succinic anhydride, methylhexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride.

[0066] R 2 Can be made by -COR 4 The acyl group represented by R 4 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0067] R 2 Can be by-OCOR 5 The acyloxy group represented by R 5 Examples of the alkyl group having 1 to 12 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, heptyl, octyl, decyl and dodecyl.

[0068] Among them, from the viewpoint of suppressing the coloration of the molded product using the resin composition of the present invention after heating, R 2 It is preferably selected from a hydrogen atom, an alkyl group, a -COOR 3 The ester group represented by -OCOR 5One of the group consisting of acyloxy groups represented by, more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a group represented by -COOR 3 The ester group represented by 3 is an alkyl group having 1 to 6 carbon atoms. ) is -OCOR 5 The acyloxy group represented by 5 is an alkyl group having 1 to 6 carbon atoms. ), more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a group represented by -COOR 3 The ester group represented by 3 is an alkyl group having 1 to 4 carbon atoms. ) is -OCOR 5 The acyloxy group represented by 5 is an alkyl group having 1 to 4 carbon atoms. ), and more preferably -OCOR 5 The acyloxy group represented by 5 is an alkyl group having 1 to 4 carbon atoms. ).

[0069] More specifically, from the viewpoint of suppressing coloration, the compound represented by the general formula (I) is preferably one or more selected from the group consisting of vinyl esters, (meth)acrylates, styrene derivatives, isobutylene and propylene, and specifically, more preferably one or more selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutylene, methyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, styrene, isobutylene and propylene, and further preferably one or more selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, isobutylene and propylene. By using these compounds, discoloration can be more effectively suppressed. When used as a polarizing material, from the viewpoint of excellent piezoelectricity, it is particularly preferred to be one or more selected from the group consisting of vinyl acetate, vinyl propionate and vinyl butyrate.

[0070] The compound represented by the above general formula (I) can be easily obtained from commercial products, or can be produced by a known method.

[0071] In addition, in this specification, "(meth)acrylate" means "acrylate or methacrylate".

[0072] The copolymer (A) may have two or more different structural units (a2), and from the viewpoint of the balance between the effect of suppressing coloration and the manufacturing cost, the structural unit (a2) preferably includes two different structural units, namely, a structural unit (a21) derived from the compound represented by the general formula (I) and a structural unit (a22) derived from the compound represented by the general formula (I). When the structural unit (a2) includes both the structural unit (a21) and the structural unit (a22), the compound represented by the general formula (I) constituting each structural unit is preferably two selected from the group consisting of vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, isobutylene and propylene.

[0073] [Content of each structural unit in the copolymer (A)]

[0074] The content of the structural unit (a1) in the copolymer (A) is preferably 20 to 80 mol %, more preferably 30 to 70 mol %, and more preferably 40 to 60 mol %.

[0075] On the other hand, the content of the structural unit (a2) is preferably 20 to 80 mol %, more preferably 30 to 70 mol %, and more preferably 40 to 60 mol %.

[0076] When the content of each structural unit is within the above range, a molded product using the copolymer (A) is unlikely to be colored even after heating.

[0077] It should be noted that the content of the above-mentioned structural units can be 1 H-NMR can be measured, and specifically, it can be measured by the method described in Examples.

[0078] [Other structural units]

[0079] The copolymer (A) may also contain structural units derived from other monomers in addition to the structural unit (a1) derived from 1,1-dicyanoethylene and the structural unit (a2) derived from the compound represented by the above general formula (I). The other structural units are not particularly limited, and examples thereof include aromatic vinyl compounds such as α-methylstyrene and tert-butylstyrene.

[0080] When the copolymer (A) contains a structural unit derived from other monomers, the content thereof in the copolymer is preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less.

[0081] [Triad structure of each structural unit in copolymer (A)]

[0082] The copolymer (A) may contain the following four triad structures (U-1) to (U-4) composed of the structural unit (a1) and the structural unit (a2). As described above, the structural unit (a2) may be two or more.

[0083] (a1)-(a1)-(a1) … (U-1)

[0084] (a1)-(a1)-(a2) … (U-2)

[0085] (a2)-(a1)-(a1) … (U-3)

[0086] (a2)-(a1)-(a2) … (U-4)

[0087] "(a1)-(a1)-(a1)" as one of the above four triad structures refers to a triad structure in which three structural units (a1) derived from 1,1-dicyanoethylene are continuously bonded, and "(a1)-(a1)-(a2)" refers to a triad structure in which two structural units (a1) derived from 1,1-dicyanoethylene are continuously bonded and then bonded to a structural unit (a2) derived from the compound represented by the above general formula (I). The same applies to other triad structures.

[0088] The amount of the triad structure (U-1) refers to "the content (mol %) of (a1) bonded between two (a1)s in the structure (a1)-(a1)-(a1) constituting (U-1)". Similarly, the content of the triad structure (U-2) refers to "the content (mol %) of (a1) bonded between (a1) and (a2) in the structure (a1)-(a1)-(a2) constituting (U-2)", and the contents of other triad structures have the same meaning.

[0089] It should be noted that the contents of the triad structures (U-1) to (U-4) in the present invention can be adjusted by 13 C-NMR can be measured, and specifically, it can be measured by the method described in the Examples.

[0090] The total content of (U-2) and (U-3) in the total amount of the above-mentioned four triad structures of the copolymer (A) is usually 25.0 mol% or less. From the viewpoint of suppressing the amount of the arrangement that will cause the coloring caused by heat, specifically the continuous arrangement of (a1), and effectively suppressing the coloring by combining the effect of the Bronsted acidic compound, the total content of (U-2) and (U-3) in the total amount of the above-mentioned four triad structures is more preferably 9.0 mol% or less, more preferably 8.5 mol% or less, more preferably 8.0 mol% or less, more preferably 7.5 mol% or less, more preferably 7.0 mol% or less, more preferably 6.0 mol% or less, more preferably 5.5 mol% or less, more preferably 5.3 mol% or less, more preferably 5.0 mol% or less, more preferably 4.8 mol% or less, and further preferably 4.3 mol% or less. Usually, the lower limit is 0.1 mol% or more, but it may be less than it.

[0091] The total content of (U-2) and (U-3) can be adjusted by controlling the amount of monomers added at a relatively low temperature of less than 50°C.

[0092] In the total amount of the above-mentioned 4 triad structures, the content of (U-1) is preferably 1.8 mol% or less. When the content of (U-1) is below the above-mentioned upper limit, the continuous arrangement of (a1) in the copolymer becomes less, and therefore, as a result, the coloring after heating of the molded product using the copolymer of the present invention can be further suppressed. From the above viewpoint, the content of (U-1) in the total amount of the above-mentioned 4 triad structures is preferably 1.7 mol% or less, more preferably 1.5 mol% or less, more preferably 1.0 mol% or less, more preferably 0.5 mol% or less, and further preferably substantially 0 mol%.

[0093] Of the total amount of the four types of triad structures, (U-4) is preferably 90 mol % or more, more preferably 94 mol % or more, and even more preferably 99 mol % or more.

[0094] [Glass transition temperature of copolymer (A)]

[0095] The glass transition temperature of the copolymer (A) is not particularly limited and can be appropriately selected depending on the intended use.

[0096] [Method for producing copolymer (A)]

[0097] The method for producing the copolymer (A) is not particularly limited, but the copolymer (A) is preferably produced at a polymerization temperature of less than 50° C. in the presence of a free radical initiator and a Bronsted acidic compound (B). By producing the copolymer under the above conditions, the coloring of the film produced from the resin composition can be suppressed. From this viewpoint, the polymerization temperature is preferably 47° C. or less, and more preferably 45° C. or less.

[0098] (Free Radical Polymerization Initiator)

[0099] Examples of the radical polymerization initiator used to produce the copolymer (A) include azo compounds such as azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis[2-(2-imidazolin-2-yl)propane], and 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine] hydrate; inorganic peroxides such as sodium persulfate, potassium persulfate, and hydrogen peroxide; organic peroxides such as tert-butyl hydroperoxide, cumene hydroperoxide, and p-menthane hydroperoxide; and redox initiators such as a combination of an oxidizing agent and a reducing agent such as hydrogen peroxide and an iron (II) salt, a persulfate and sodium bisulfite. These may be used alone or in combination of two or more.

[0100] As described above, the copolymer (A) can be arranged in a less colored arrangement by free radical polymerization at low temperature. Therefore, among these free radical polymerization initiators, azo compounds such as azobisisobutyronitrile and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), redox initiators, etc., which are easy to use at low temperatures, are preferred.

[0101] The amount of the radical polymerization initiator used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.08 to 3 parts by mass, based on 100 parts by mass of all monomers serving as raw materials of the copolymer (A).

[0102] (Ratio of input amount when producing copolymer (A))

[0103] In the production of copolymer (A), the input amount of the compound represented by the general formula (I) is preferably 0.9 equivalents or more, more preferably 1.0 equivalents or more relative to the input amount of 1,1-dicyanoethylene, and is usually preferably 5.0 equivalents or less from the viewpoint of the transparency of the film. When the input amount of the compound represented by the general formula (I) is greater than the above lower limit relative to the input amount of 1,1-dicyanoethylene, the reaction can be efficiently carried out.

[0104] (Brønsted acidic compound (B) for producing copolymer (A))

[0105] In the present invention, when manufacturing the copolymer (A), the Bronsted acidic compound (B) described later may be used. By the presence of the Bronsted acidic compound (B) when manufacturing the copolymer (A), the partial conjugated structure of the side chain that causes coloration can be stabilized immediately after the copolymer (A) is generated. When the Bronsted acidic compound (B) is used, the amount used is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and further preferably 0.08 to 3 parts by mass relative to 100 parts by mass of all monomers that are raw materials of the copolymer (A).

[0106] [Content of copolymer (A) in resin composition]

[0107] The content of the copolymer (A) in the resin composition of the present invention is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. When the content of the copolymer (A) in the resin composition is within the above range, a film with little coloration during heating can be obtained.

[0108] <Brønsted acid compound (B)>

[0109] The resin composition of the present invention further contains a Bronsted acidic compound. When the resin composition of the present invention contains a Bronsted acidic compound, the conjugated structure of the copolymer (A) can be stabilized, and coloration of a film produced using the resin composition during heating can be suppressed.

[0110] The content of the Bronsted acidic compound (B) in the resin composition of the present invention is 0.1 to 95000 mass ppm, preferably 0.5 to 90000 mass ppm, more preferably 0.8 to 85000 mass ppm, more preferably 0.8 to 50000 mass ppm, more preferably 1 to 30000 mass ppm, more preferably 5 to 10000 mass ppm, more preferably 5 to 9000 mass ppm, more preferably 10 to 5000 mass ppm, and further preferably 20 to 2000 mass ppm. When the content of the Bronsted acidic compound (B) is within the above range, the conjugated structure of the copolymer (A) can be stabilized, and the coloring of the film produced using the resin composition during heating can be suppressed.

[0111] The acid dissociation constant (pKa) of the Bronsted acidic compound (B) used in the present invention is preferably 4.8 or less, more preferably 3.0 or less, further preferably 2.5 or less, and further preferably 2.0 or less. When the acid dissociation constant (pKa) of the Bronsted acidic compound (B) is within the above range, the copolymer (A) is more easily stabilized and coloration can be suppressed.

[0112] It should be noted that the pKa value refers to the acid dissociation constant of the conjugate acid in water at 25°C, and can be calculated from the concentration of the substance and the hydrogen ion concentration by measuring the hydrogen ion concentration using a pH meter.

[0113] The Bronsted acidic compound that can be used in the present invention is not particularly limited, and examples thereof include inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, hydrobromic acid, and partially neutralized salts thereof, organic acids such as formic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, dichloroacetic acid, phenylphosphonic acid, ethylphosphinic acid, methanesulfonic acid, ethanesulfonic acid, 2-propanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid, and combinations thereof. In addition, compounds that react with water and exhibit Bronsted acidity, such as sulfur dioxide and phosphorus pentoxide, can also be used.

[0114] Among them, compounds having one or more selected from the group consisting of a phosphoric acid group, a carboxyl group, a sulfonic acid group and a phosphite group are preferred, and specifically, phosphoric acid, acetic acid, methanesulfonic acid, p-toluenesulfonic acid and the like are preferred, and methanesulfonic acid and p-toluenesulfonic acid are more preferred.

[0115] <Optional Ingredients>

[0116] The resin composition of the present invention is not particularly limited as long as it contains the copolymer (A) and the Bronsted acid compound (B), and may contain other synthetic resins.

[0117] Other synthetic resins include polyethylene, polypropylene, copolymers of ethylene and one or more α-olefins having 3 to 20 carbon atoms (e.g., propylene, 1-butene, 1-pentene, 1-hexene, etc.), ethylene-propylene-diene copolymers (EPDM), ethylene-vinyl acetate copolymers, ethylene-acrylic acid copolymers and other polyolefin resins, polyurethane resins, polyamide resins, polyester resins and polycarbonate resins.

[0118] In addition, the resin composition of the present invention may further contain other components as required, such as solvents, fillers, thickeners, antioxidants, plasticizers, flame retardants, stabilizers, antioxidants, and the like.

[0119] When the resin composition of the present invention contains optional components, that is, the above-mentioned synthetic resin and other components, their total content is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less in the total amount of the resin composition.

[0120] <Method for producing resin composition>

[0121] The resin composition can be produced by a method including a mixing step of mixing the copolymer (A), the Bronsted acidic compound (B) and the optional components as required. The method of mixing the components is not particularly limited and the components can be mixed by a known method.

[0122] <Composition ratio of elements in resin composition>

[0123] In the resin composition of the present invention, the composition ratio of sulfur atoms to nitrogen atoms [S / N] is preferably 3.5×10 -8 ~0.3, more preferably 0.5×10 -5 ~0.25, more preferably 0.5×10 -4 When the composition ratio [S / N] of sulfur atoms to nitrogen atoms in the resin composition is within the above range, the transparency of the film can be maintained even after long-term heating.

[0124] In addition, in the resin composition of the present invention, the composition ratio of phosphorus atoms to nitrogen atoms [P / N] is preferably 1.4×10 -8 ~0.3, more preferably 1.0×10 -5 ~0.05, more preferably 1.0×10 -4 When the composition ratio [P / N] of phosphorus atoms to nitrogen atoms in the resin composition is within the above range, the transparency of the film can be maintained even after long-term heating.

[0125] It should be noted that the above composition ratio can be measured by elemental analysis.

[0126] [Molded products and films]

[0127] The molded product and film of the present invention use the resin composition of the present invention. As the shape of the molded product, there is no restriction as long as it is a shape made using the resin composition of the present invention, and various shapes such as films, pellets, sheets, plates, pipes, tubes, fibers, nonwoven fabrics, rods, and granules can be cited.

[0128] The method for producing the molded product is not particularly limited, and the molded product can be formed by various conventionally known molding methods, such as solution casting, injection molding, blow molding, press molding, extrusion molding, calendaring molding, etc. In addition, the molded product of the present invention may also be a laminate with other materials.

[0129] Examples of molded products using the resin composition of the present invention include thin film capacitors, insulating layers of EL elements, electrostatic induction conversion elements, sensors (e.g., touch sensors, vibration sensors, biosensors, tire sensors (sensors provided on the inner surface of tires)), actuators, touch panels, tactile devices (devices having the function of providing tactile feedback to users), vibration power generation devices (e.g., vibration power generation floors, vibration power generation tires), speakers, microphones, vibration-damping sheets, hollow fiber membranes for water purification, anti-corrosion films, and the like.

[0130] The molded product of the present invention is preferably a film. As described above, the molded product using the resin composition of the present invention can suppress coloring even after heating, so by processing into a film, a film with a better appearance can be obtained.

[0131] The film of the present invention can suppress coloration even after heating, and therefore the difference in yellowness between the film before heating and the film after heating at 50° C. under normal pressure for 24 hours is preferably 1.5% or less, more preferably 1.0% or less, and even more preferably 0.8% or less.

[0132] In addition, in the case of the solution casting method, the "film before heating" refers to a film produced after applying the resin composition of the present invention and then vacuum drying at 40° C. and 1 kPa for 7 days.

[0133] In addition, the difference in yellowness between the film before heating and the film after heating at 160° C. for 1 hour under normal pressure is preferably 3.0% or less, more preferably 2.6% or less, more preferably 2.0% or less, more preferably 1.8% or less, more preferably 1.6% or less, more preferably 1.5% or less, and further preferably 1.1% or less.

[0134] The yellowness of the film in the present invention is a yellowness measured in accordance with JIS Z8722:2009, and can be specifically measured by the method described in Examples.

[0135] The film of the present invention before heating preferably has a low yellowness, and the yellowness after heating at 40° C. and 1 kPa for 7 days at normal pressure is preferably 1.0% or less, more preferably 0.8% or less, more preferably 0.5% or less, and further preferably 0.4% or less.

[0136] The film of the present invention preferably has a low yellowness after heating, and the yellowness after heating at 160° C. for 1 hour under normal pressure is preferably 3.0% or less, more preferably 2.8% or less, more preferably 2.7% or less, more preferably 2.5% or less, more preferably 2.3% or less, more preferably 2.1% or less, more preferably 2.0% or less, more preferably 1.9% or less, and further preferably 1.6% or less.

[0137] The thickness of the film of the present invention is not particularly limited, but is preferably 0.001 to 5.0 mm, more preferably 0.005 to 1.5 mm, and even more preferably 0.01 to 1.0 mm from the viewpoint of achieving both transparency and cutting processability of the film.

[0138] The manufacture method of film of the present invention is not particularly limited, and can be formed by known methods in the past. As forming method, for example solution casting, melt extrusion, calendering, compression molding, injection molding etc. can be enumerated. In addition, formed product of the present invention can also be a laminate with other materials.

[0139] [Conductive films, film capacitors]

[0140] In the conductive film of the present invention, a conductive layer is stacked on the above-mentioned film, and the film capacitor of the present invention includes the above-mentioned film or the above-mentioned conductive film.

[0141] The conductive film of the present invention uses the thin film of the present invention having an excellent relative dielectric constant, and therefore exhibits excellent performance as a thin film capacitor.

[0142] The conductive layer constituting the conductive film is not particularly limited, and is generally preferably a layer composed of conductive metals such as aluminum, zinc, gold, platinum and copper, and is a metal foil or a metal coating (e.g., a vapor-deposited metal coating), or both. Among these, vapor-deposited metal coatings are preferred from the viewpoints of making the conductive layer thinner and increasing the capacity relative to the volume, improving the adhesion with the dielectric, and further reducing the fluctuation of the thickness.

[0143] Regarding the vapor-deposited metal film, for the purpose of imparting moisture resistance, a semiconductor aluminum oxide layer may be further formed on an aluminum layer to form a multilayer structure as described in, for example, Japanese Patent Application Laid-Open No. 2-250306.

[0144] The thickness of the vapor-deposited metal film is not particularly limited, but is preferably 10 to 200 nm, more preferably 20 to 100 nm. When the thickness of the vapor-deposited metal film is within the above range, both the capacitance and the strength of the capacitor can be achieved, which is preferred.

[0145] When a deposited metal film is used as the conductive layer, the method for forming the film is not particularly limited, and for example, vacuum deposition, sputtering, ion plating, etc. may be used, and generally, vacuum deposition is preferred.

[0146] As the formation method of the conductive layer, for example, a batch method suitable for formed products, a semi-continuous method suitable for long strip products, and a continuous (air to air) method can be listed, and the semi-continuous method as the mainstream is preferred. The metal vapor deposition method of the semi-continuous method is a method as follows: metal vapor deposition is performed in a vacuum system, and after winding, the vacuum system is restored to an atmospheric system, and the vapor-deposited film is taken out.

[0147] As a film for film capacitors, from the viewpoint of easily increasing the electrostatic capacitance of the capacitor, it is preferred that the relative dielectric constant is high. The film containing the resin composition of the present invention has a high relative dielectric constant and is therefore suitable for film capacitor applications. The relative dielectric constant of the film measured under the conditions of 1kHz and 25°C is preferably 3 or more, more preferably 3.5 or more, more preferably 3.6 or more, more preferably 3.7 or more, more preferably 3.8 or more, more preferably 4.0 or more, more preferably 4.2 or more, more preferably 4.4 or more, more preferably 4.5 or more, more preferably 4.6 or more, more preferably 4.8 or more, and further preferably 5.0 or more. The dielectric constant of the film can be formed into a film capacitor by forming a metal coating on both sides and measured by the method described later.

[0148] In the use of film capacitors, the compound represented by the above general formula (I) constituting the copolymer (A) is preferably vinyl ester, (meth)acrylate, styrene derivative, isobutylene and propylene, more preferably vinyl ester, (meth)acrylate, styrene derivative, isobutylene, more preferably vinyl acetate, vinyl propionate, vinyl butyrate, isopropenyl acetate, vinyl chloroacetate, methyl methacrylate, methyl acrylate, butyl acrylate, styrene, α-methylstyrene, isobutylene, and from the viewpoint of being less susceptible to changes in relative dielectric constant, vinyl acetate, vinyl propionate, vinyl butyrate, methyl methacrylate, styrene, isobutylene are further preferred.

[0149] [Polarized Materials]

[0150] The polarizing material of the present invention comprises the resin composition of the present invention or the film of the present invention.

[0151] The polarized material of the present invention refers to a material showing piezoelectricity (d 33 ) materials. It should be noted that in materials such as fibers, d cannot be directly measured. 33 In the case of the above, the fibers can be stacked and processed into a film, or a film can be made of the same resin composition as that used in the above fibers, and the d value of the film can be measured. 33 , thus confirming the piezoelectricity of the above-mentioned fibers.

[0152] The polarized material can be obtained, for example, by subjecting the film of the present invention to polarization treatment. As the polarization treatment, the following method can be cited: heating the heat-treated formed article to a predetermined temperature, applying a DC high electric field or a DC high electric field superimposed with an AC electric field from the front and back sides of the formed article for a certain period of time in this state, and then slowly cooling or rapidly cooling. In addition, the following method can also be cited: while performing the above-mentioned heat treatment, applying a DC high electric field or a DC high electric field superimposed with an AC electric field from the front and back sides of the formed article for a certain period of time, and then slowly cooling or rapidly cooling.

[0153] The treatment temperature of the polarization treatment is preferably carried out at a temperature 30°C or higher than the glass transition temperature (Tg) of the heat-treated molded article. The polarization treatment is usually preferably carried out using a metal foil, a metal plate, a conductive paste, a vacuum-deposited or chemically-plated metal coating film that is closely attached to both sides of the molded article as an electrode. The applied voltage is generally 10KV / cm or more, preferably with an electric field strength that does not produce insulation breakdown, more preferably 100 to 1500KV / cm. The treatment time is not particularly limited, and for the heat-treated molded article, it is preferably 1 minute to 5 hours, more preferably 10 minutes to 2 hours.

[0154] In the application of polarizing materials, the compound represented by the above general formula (I) constituting the copolymer (A) is preferably vinyl ester or (meth)acrylate, more preferably vinyl ester, and particularly preferably vinyl acetate, vinyl propionate and vinyl butyrate from the perspective of excellent polarizing properties.

[0155] Polarization treatment may also be performed by corona discharge treatment. Corona discharge may be either negative corona or positive corona, but negative corona is preferably used from the viewpoint of easy polarization of the non-polarized film.

[0156] The corona discharge treatment is not particularly limited, and examples thereof include a method of applying the corona discharge to a non-polar thin film using a linear electrode, a method of applying the corona discharge to a non-polar thin film using a needle electrode, or a method of applying the corona discharge to a non-polar thin film using a grid electrode as described in Japanese Patent Application Laid-Open No. 2011-181748.

[0157] The conditions for the corona discharge treatment can be appropriately set based on common knowledge in the technical field. If the conditions for the corona discharge treatment are too weak, the piezoelectricity of the obtained film may be insufficient, while if the conditions for the corona discharge treatment are too strong, the obtained film may have point defects.

[0158] In order to suppress the piezoelectric constant d of the obtained polarized film 33In order to prevent in-plane fluctuations, it is preferred that the distance between each needle-shaped electrode and / or linear electrode and the film is constant, that is, the distance between the electrode and the film does not have in-plane fluctuations (or is extremely small). Specifically, the difference between the longest distance and the shortest distance is preferably within 6 mm, more preferably within 4 mm, and even more preferably within 3 mm.

[0159] In addition, for example, when continuously applying the film from roll to roll, it is preferred that the film be brought into close contact with the roll appropriately and uniformly so that a constant tension is applied to the film. For example, when continuously applying the film from roll to roll using a linear electrode, the DC electric field is preferably -50 to -1 kV, and the processing speed is preferably 10 to 1200 cm / min, although it also varies depending on the distance between the linear electrode and the non-polarized film, the film thickness, etc.

[0160] In addition to corona discharge, polarization treatment can also be applied by clamping a non-polarized film on both sides with flat electrodes. In this case, it is preferably carried out using a DC electric field in the range of preferably 0 to 400 MV / m, more preferably 50 to 400 MV / m, with an application time in the range of 0.1 seconds to 60 minutes.

[0161] [Electrostatic induction conversion element, touch panel]

[0162] The electrostatic induction conversion element of the present invention includes the polarizing material of the present invention, and the touch panel of the present invention includes the electrostatic induction conversion element of the present invention.

[0163] The electrostatic induction conversion element can be assembled in a touch panel and also in a vibration generator, an actuator, a sensor, etc. The electrostatic induction conversion element and the touch panel of the present invention are derived from the resin composition or film of the present invention and are particularly useful in terms of durability when used outdoors.

[0164] Example

[0165] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[0166] <Example 1>

[0167] In a 100 ml four-necked flask equipped with a stirring device, a Dimroth condenser and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above document, 5.5 g (0.064 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 25 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 68 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and heated and stirred at 40°C for 6 hours under a nitrogen flow to carry out free radical polymerization.

[0168] After the polymerization, the precipitated copolymer (A) was filtered, washed with ethyl acetate and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried at 40° C. under reduced pressure overnight to obtain a product (powder of a resin composition containing the copolymer (A)).

[0169] The obtained resin composition containing the copolymer (A) was subjected to spectrum measurement by NMR by the method described later.

[0170] The obtained resin composition containing the copolymer (A) was subjected to elemental analysis, and the result was that the resin composition contained 10 mass ppm of p-toluenesulfonic acid. The balance of the resin composition was the copolymer (A).

[0171] Next, the obtained resin composition containing the copolymer (A) was dissolved in a solvent (N,N-dimethylacetamide [manufactured by Tokyo Chemical Industry Co., Ltd.]), applied by a solution casting method in a thickness of 50 μm using an applicator (manufactured by Tester Industry Co., Ltd.), and vacuum dried at 40° C. and 1 kPa for 7 days to prepare a film (1) [film before heating].

[0172] The obtained film (1) was subjected to 1 As a result of H-NMR and elemental analysis, the content of p-toluenesulfonic acid was 10 mass ppm.

[0173] Furthermore, the yellowness of the film (1) was measured using a haze meter SH7000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS Z8722: 2009. The values ​​of three locations of the film (1) were measured, and the average value was used as the yellowness. The results are shown in Table 1.

[0174] Then, the film (1) was heated in a clean oven DE-41 (manufactured by Yamato Scientific Co., Ltd.) at 50° C. under atmospheric pressure for 24 hours to obtain a film (2). The yellowness of the film (2) was measured in the same manner as the film (1). The results are shown in Table 1.

[0175] Film (2) was further heated at 160°C for 1 hour under atmospheric pressure to obtain film (3). The yellowness of film (3) was measured in the same manner as film (1). The results are shown in Table 1.

[0176] <Example 2>

[0177] The product obtained in Example 1 (powder of the resin composition containing copolymer (A)) was further repeatedly washed several times with ethyl acetate and n-hexane and dried, and then films (1) to (3) were prepared in the same manner as in Example 1. The obtained films (1) to (3) were measured in the same manner as in Example 1. 1 The obtained results of H-NMR, elemental analysis and yellowness are shown in Table 1.

[0178] <Example 3>

[0179] The product obtained in Example 1 (powder of the resin composition containing copolymer (A)) and p-toluenesulfonic acid monohydrate were dissolved in a solvent (N,N-dimethylacetamide [manufactured by Tokyo Chemical Industry Co., Ltd.]) so that the p-toluenesulfonic acid content in the film was 100 mass ppm, and films (1) to (3) were prepared in the same manner as in Example 1. The obtained films (1) to (3) were measured in the same manner as in Example 1. 1 The obtained results of H-NMR, elemental analysis and yellowness are shown in Table 1.

[0180] <Examples 4 to 12>

[0181] Films (1) to (3) were prepared in the same manner as in Example 1 except that the materials listed in Tables 1 to 2 were used to produce copolymers (A) in the compositions and molar ratios listed in Tables 1 to 2 to obtain resin compositions having the compositions listed in Tables 1 to 2. The obtained films (1) to (3) were measured in the same manner as in Example 1. 1 H-NMR, elemental analysis and yellowness. The results are shown in Tables 1 and 2.

[0182] <Example 13>

[0183] In a 100-ml four-necked flask equipped with a stirring device, a serpentine condenser and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above-mentioned document, 2.7 g (0.026 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 17 ml of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 34 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated and stirred at 40°C for 4 hours under a nitrogen flow to carry out free radical polymerization.

[0184] After the polymerization, the precipitated copolymer (A) was filtered, washed with toluene and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried at 40° C. under reduced pressure overnight to obtain a product (powder of a resin composition containing the copolymer (A)).

[0185] Films (1) to (3) were prepared in the same manner as in Example 1 except for the above. 1 The results of H-NMR, elemental analysis and yellowness measurement are shown in Table 3.

[0186] <Example 14>

[0187] Into a 300 ml autoclave equipped with a stirring device and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above document, 2.7 g (0.064 mol, manufactured by Takachiho Chemical Industry Co., Ltd.), 8.9 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 34 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated and stirred at 40°C for 6 hours under a nitrogen flow to carry out free radical polymerization.

[0188] After the polymerization was completed, the precipitated copolymer (A) was filtered. Then, it was washed with toluene and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 40°C under reduced pressure to obtain a product (a powder of a resin composition containing the copolymer (A)). Films (1) to (3) were prepared in the same manner as in Example 1, and the results were measured. 1 The results of H-NMR, elemental analysis and yellowness are shown in Table 3.

[0189] <Example 15>

[0190] Into a 300 ml autoclave equipped with a stirrer and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above document, 3.6 g of isobutylene (0.064 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), 6.7 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 18 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and heated and stirred at 40°C for 6 hours under a nitrogen flow to carry out free radical polymerization.

[0191] After the polymerization was completed, the precipitated copolymer (A) was filtered. Then, it was washed with ethyl acetate and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 40°C under reduced pressure to obtain a product (a powder of a resin composition containing the copolymer (A)). Films (1) to (3) were prepared in the same manner as in Example 1. 1 The results of H-NMR, elemental analysis and yellowness measurement are shown in Table 3.

[0192] <Example 16>

[0193] In a 100-ml four-necked flask equipped with a stirring device, a serpentine condenser and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above document, 2.8 g of vinyl acetate (0.032 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 3.7 g of vinyl butyrate (0.032 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 25 ml of ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), and 18 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and heated and stirred at 40°C for 6 hours under a nitrogen flow to carry out free radical polymerization.

[0194] After the polymerization was completed, the precipitated copolymer (A) was filtered. Then, it was washed with ethyl acetate and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried overnight at 40°C under reduced pressure to obtain a product (a powder of a resin composition containing the copolymer (A)). Films (1) to (3) were prepared in the same manner as in Example 1. 1 The results of H-NMR, elemental analysis and yellowness measurement are shown in Table 3.

[0195] <Example 17>

[0196] Films (1) to (3) were prepared in the same manner as in Example 16 except that the amount of vinyl acetate used was changed to 3.6 g (0.039 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 3.9 g of vinyl propionate (0.039 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of vinyl butyrate. 1 The results of H-NMR, elemental analysis and yellowness measurement are shown in Table 3.

[0197] <Example 18>

[0198] Thin films (1) to (3) were prepared in the same manner as in Example 17 except that 68 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The obtained thin films (1) to (3) were measured in the same manner as in Example 1. 1 Table 3 shows the results of H-NMR, elemental analysis and yellowness.

[0199] <Example 19>

[0200] In a 100-ml four-necked flask equipped with a stirring device, a serpentine condenser and a thermometer, 2.0 g (0.026 mol) of 1,1-dicyanoethylene synthesized by the method described in the above document, 1.4 g (0.013 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) of styrene, 1.3 g (0.013 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 17 ml of toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 18 mg of 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile) and 18 mg of p-toluenesulfonic acid monohydrate (manufactured by Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was heated and stirred at 40°C for 4 hours under a nitrogen flow to carry out free radical polymerization.

[0201] After the polymerization, the precipitated copolymer (A) was filtered, washed with toluene and n-hexane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in that order, and then dried at 40° C. under reduced pressure overnight to obtain a product (powder of a resin composition containing the copolymer (A)).

[0202] Films (1) to (3) were prepared in the same manner as in Example 4. 1 The results of H-NMR, elemental analysis and yellowness measurement are shown in Table 3.

[0203] <Examples 20 to 24, Comparative Examples 1 to 4>

[0204] Films (1) to (3) were prepared in the same manner as in Example 1 except that the materials listed in Tables 4 to 5 were used and the copolymer (A) was produced in the composition and molar ratio listed in Tables 4 to 5 to obtain resin compositions with the compositions listed in Tables 4 to 5. Comparative Example 1 was performed without using p-toluenesulfonic acid monohydrate to prepare films (1) to (3). The obtained films were subjected to 1 H-NMR, elemental analysis and yellowness measurement. The results are shown in Tables 4 and 5.

[0205] The relative dielectric constant of the obtained thin film was further measured by the method described below. The results are shown in Tables 1 to 5.

[0206] As shown in Tables 1 to 5, the film of the present invention can suppress yellowness to a low level and has a high relative dielectric constant. Such a material with a high relative dielectric constant is suitable for use in film capacitors as described in Japanese Patent Application Laid-Open No. 2008-034189.

[0207] Furthermore, the obtained thin film was subjected to polarization treatment, and the piezoelectricity of the obtained thin film was evaluated by the method described later. The results are shown in Table 6.

[0208] As shown in Table 6, the film of the present invention can suppress yellowness to a low level and has excellent piezoelectric properties. Therefore, it is suitable as a transparent piezoelectric film for applications requiring transparency such as touch panels.

[0209] <Measurement method>

[0210] (1) Spectral measurement of resin composition containing copolymer (A) by NMR

[0211] The product (powder of the resin composition containing the copolymer (A)) was measured using a nuclear magnetic resonance spectrometer (NMR) under the following conditions: 1 H-NMR spectrum.

[0212] [ 1 H-NMR measurement conditions]

[0213] Device: JEOL Ltd. JNM-ECX400

[0214] Determination solvent: dimethyl sulfoxide-d6

[0215] Measuring temperature: 65℃

[0216] Chemical shift value standard: tetramethylsilane

[0217] [ 13 C-NMR measurement conditions]

[0218] Device: JEOL Ltd. JNM-ECX400

[0219] Determination solvent: dimethyl sulfoxide-d6

[0220] Measuring temperature: 65℃

[0221] Determination method: proton decoupling method

[0222] Pulse width: 45 degrees

[0223] Pulse repetition time: 10 seconds

[0224] Chemical shift value standard: tetramethylsilane

[0225] (2) Elemental analysis of thin films

[0226] The thin film was analyzed for sulfur using a trace sulfur analyzer TS-2100H (manufactured by Nitto Seiko Analytech Co., Ltd.), phosphorus using iCAP7400 Duo (manufactured by Thermo Fisher), and carbon, hydrogen, oxygen, and nitrogen using FLASH2000 (manufactured by Thermoscientific).

[0227] (3) Determination of yellowness of film

[0228] The yellowness of the obtained film was measured using a haze meter SH7000 (manufactured by Nippon Densho Kogyo Co., Ltd.) in accordance with JIS Z8722: 2009. The values ​​of three locations of each film were measured, and the average value was used as the yellowness. It should be noted that in each table, "film (1)" refers to a film after vacuum drying at 40°C and 1 kPa for 7 days, "film (2)" refers to a film after film (1) was heated at 50°C under atmospheric pressure for 24 hours in a clean oven DE-41 (manufactured by Yamato Scientific Co., Ltd.), and "film (3)" refers to a film after film (2) was heated at 160°C under atmospheric pressure for 1 hour.

[0229] (4) Determination of relative dielectric constant of thin films

[0230] After the thin films obtained in the examples and comparative examples were humidified at 26°C and 60% RH, Au-Pd alloy with a diameter of 30 mm was vapor-deposited on the surface of the film until the surface was conductive, and a conductive layer was also vapor-deposited on the opposite side to prepare a thin film capacitor sample.

[0231] The electrostatic capacitance (C) of the sample was measured using an LCR meter (manufactured by Keysight), and the relative dielectric constant (25°C, 1 kHz) was calculated from the electrostatic capacitance, electrode area (S), and film thickness (d) using the formula C = ε × ε0 × S / d (ε0 is the dielectric constant of vacuum).

[0232] (5) Evaluation of piezoelectricity

[0233] The thin films obtained in the examples and comparative examples were polarized at 160°C via vacuum-deposited gold electrodes on both sides, and the piezoelectric properties of the obtained polarized materials were evaluated. The piezoelectric constant d was measured using a piezoelectric measurement system PM300 from PIEZOTEST. 33 The determination of the piezoelectric constant d 33 The sample is clamped at 1.0 N and the generated charge is read when a force of 2.0 N is applied at a frequency of 110 Hz. 33 The piezoelectricity of the material having a value of 1 pC / N or more and having the positive and negative signs of the charges reversed on both sides of the film was considered "acceptable".

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240] As is clear from the results of Tables 1 to 5, the film using the resin composition of the present invention is able to suppress coloring even after heating and is excellent in dielectric properties.

[0241] As is clear from the results in Table 6, the film of the present invention has piezoelectricity and can therefore be suitably used for touch panel applications and the like.

Claims

1. A resin composition, characterized in that The resin composition is a resin composition containing a copolymer (A) and a Bronsted acidic compound (B), wherein the copolymer (A) contains a structural unit (a1) derived from 1,1-dicyanoethylene and a structural unit (a2) derived from a compound represented by the following general formula (I), and the content of the Bronsted acidic compound (B) in the resin composition is 0.1 to 95000 ppm by mass, CH2=CR 1 R 2 (I) In the general formula (I), R 1 is one or more selected from the group consisting of a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group and a halogen atom, R 2 is selected from hydrogen, alkyl, alkoxy, carboxyl, -COOR 3 Ester group, anhydride group, -COR 4 Acyl represented by -OCOR 5 One or more acyloxy groups represented by 3 is an alkyl group having 1 to 12 carbon atoms, R 4 is an alkyl group having 1 to 12 carbon atoms, R 5 It is an alkyl group having 1 to 12 carbon atoms.

2. The resin composition according to claim 1, wherein The compound represented by the general formula (I) is at least one selected from the group consisting of vinyl esters, (meth)acrylates, styrene derivatives, isobutylene and propylene.

3. The resin composition according to claim 1 or 2, wherein The acid dissociation constant (pKa) of the Bronsted acidic compound (B) is 4.8 or less.

4. The resin composition according to claim 1 or 2, wherein The Bronsted acidic compound (B) is a compound having one or more selected from the group consisting of a phosphoric acid group, a carboxyl group, a sulfonic acid group, and a phosphorous acid group.

5. The resin composition according to claim 1 or 2, wherein The structural unit (a2) includes two different structural units: a structural unit (a21) derived from the compound represented by the general formula (I) and a structural unit (a22) derived from the compound represented by the general formula (I).

6. The resin composition according to claim 4, wherein The composition ratio of sulfur atoms to nitrogen atoms [S / N] is 3.5×10 -8 ~0.

3.

7. The resin composition according to claim 4, wherein The composition ratio of phosphorus atoms to nitrogen atoms [P / N] is 1.4×10 -8 ~0.

3.

8. A molded product using the resin composition according to claim 1 or 2. 9 . A film using the resin composition according to claim 1 .

10. The film according to claim 9, wherein The yellowness after heating at 160°C for 1 hour under normal pressure is 3.0% or less. 11 . A conductive film comprising the film according to claim 9 and a conductive layer laminated thereon. 12 . A film capacitor comprising the film according to claim 9 . 13 . A thin film capacitor comprising the conductive film according to claim 11 .

14. A polarizing material comprising the resin composition according to claim 1 or 2.

15. A polarized material comprising the thin film according to claim 9.

16. The polarized material according to claim 14, wherein Containing R in the general formula (I) 1 Contains H, R 2 Contains -OCOR 5 The acyloxy resin composition represented by R 5 It is an alkyl group having 1 to 12 carbon atoms.

17. The polarized material according to claim 15, wherein Containing R in the general formula (I) 1 Contains H, R 2 Contains -OCOR 5 The acyloxy resin composition represented by R 5 It is an alkyl group having 1 to 12 carbon atoms. 18 . An electrostatic induction conversion element comprising the polarizing material according to claim 14 . 19 . An electrostatic induction conversion element comprising the polarizing material according to claim 15 . 20 . A touch panel comprising the electrostatic induction conversion element according to claim 18 . 21 . A touch panel comprising the electrostatic induction conversion element according to claim 19 .

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