Thin film polymer laminate capacitor, use of the same and method for manufacturing the same

Abstract

To provide a thin-film polymer laminate capacitor exhibiting excellent characteristics even at low temperatures.SOLUTION: In a thin-film polymer laminate capacitor having a structure in which resin thin-film layers and internal electrode metal layers are alternately laminated, the resin thin-film layers have a glass transition temperature of 150°C or less, have a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, and satisfy at least one of the following conditions 1 and 2. Under the condition 1, when measured at -85°C and 1 kHz, the tan δ is 0.8% or less. Under the condition 2, based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.SELECTED DRAWING: Figure 2

Description

Technical Field

[0001] The present invention relates to a thin-film polymer laminated capacitor, its use, and a method for manufacturing the same.

Background Art

[0002] As a capacitor, a capacitor having a structure in which a dielectric layer containing a resin and an electrode layer containing a metal are alternately laminated is known. When manufacturing such a thin-film polymer laminated capacitor, in many cases, a resin thin-film layer is formed using a monomer having an acryloyl group or a methacryloyl group (for example, an acrylate monomer or a methacrylate monomer).

[0003] Patent Document 1 describes a thin-film polymer laminated film capacitor and a method for manufacturing the same. This manufacturing method includes a step of forming a monomer layer by vapor-depositing a monomer in a vacuum chamber and then irradiating the monomer layer with an electron beam to cure the monomer layer to form a resin thin-film layer, and a step of forming a metal thin-film layer by vapor-depositing a metal material, and alternately repeating these steps on a rotating drum to manufacture a laminate in which a resin thin-film layer and a metal thin-film layer are alternately laminated on the rotating drum. In the examples, it is described that tricyclodecane dimethanol dimethacrylate was used as the monomer.

[0004] Patent Document 2 discloses a capacitor including two electrodes separated by a dielectric member. This document describes that the dielectric member includes a polymer of a polyfunctional acrylate having a specific chemical structure.

[0005] Patent Document 3 describes a resin layer forming apparatus for forming a resin layer on a support. As the resin material, those mainly composed of an acrylate resin or a vinyl resin are preferably used. In the examples, it is described that dicyclopentadiene dimethanol diacrylate was used.

[0006] Patent Document 4 describes a method for manufacturing a capacitor in which a resin layer that becomes a dielectric and an electrode metal are alternately laminated on a cooling roll in a vacuum to form a roll-shaped laminate, the roll-shaped laminate is removed from the cooling roll and divided into a curved laminate, and the curved laminate is heat-treated while being pressed. According to this document, the resin of the dielectric may have thermosetting properties. In the examples, it is described that dimethyloltricyclodecane diacrylate and 1,9-nonanediol diacrylate were used for the resin layer.

[0007] Patent Document 5 describes a method for manufacturing a capacitor, and it is described that during the lamination process, the number of laminations to be laminated thereafter is determined according to the lamination status up to that point. In the examples, it is described that dicyclopentadiene dimethanol diacrylate was used as the resin layer material.

[0008] Patent Document 6 describes a capacitor having a dielectric formed by polymerizing a divinyl compound containing no polar group. In the examples, it is described that a dielectric film was formed by a high-frequency sputtering method using 1,6-divinylnaphthalene as a sputtering target.

[0009] Patent Document 7 describes a laminated film capacitor, which has a dielectric formed from a compound having at least two functional groups selected singly or in combination from allyloxy groups or vinyloxy groups represented by a specific general formula. In the examples, it is described that 1,9-divinyloxynonane was used to form the dielectric layer.

[0010] Patent Document 8 describes a method for manufacturing a capacitor, and it is described that after curing the residual vinyl group rate of the resin to 40 to 20% for each layer, the laminated board removed from this cooling roll is heat-treated while applying pressure and heat. In the examples, it is described that dimethyloltricyclodecane diacrylate, 1,9-nonanediol diacrylate, and cyclohexane dimethylol divinyl ether were used singly or in combination.

[0011] Here, in the case of capacitors for in-vehicle use, etc. that are used in a harsh outdoor environment, good characteristics may be required even at low temperatures (for example, 0°C or lower, or even -20°C or lower).

[0012] Furthermore, particularly in circuits utilizing superconductivity at extremely low temperatures, quantum computers, and even in space applications, capacitors that can operate stably even at temperatures lower than -20°C (especially -80°C or lower) have come to be required.

[0013] Patent Document 9 describes a multilayer ceramic capacitor having a two-component substance composed of lead iron tungstate and lead iron niobate as a dielectric. Although this document is not related to the field of thin-film polymer multilayer capacitors, it describes the use of multilayer ceramic capacitors at extremely low temperatures.

Prior Art Documents

Patent Documents

[0014]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

Summary of the Invention

Problems to be Solved by the Invention

[0015] An object of the present invention is to provide a thin-film polymer laminated capacitor that exhibits good characteristics even at low temperatures (for example, less than 0 ° C, particularly -20 ° C or lower, and further -80 ° C or lower).

Means for Solving the Problems

[0016] The above problems can be solved by the following aspects according to the present invention. <Aspect 1> A thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated, wherein the resin thin-film layer has a glass transition temperature of 150 ° C or lower and has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, A capacitor that satisfies at least one of the following Condition 1 and Condition 2: Condition 1: tan δ at -85 ° C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20 ° C and 1 kHz, the capacitance reduction rate at -85 ° C is 9% or less. <Aspect 2> The capacitor according to Aspect 1, wherein the resin thin-film layer has a polymer structure formed by polymerizing a mixed monomer containing at least a bifunctional monomer and a monofunctional monomer. <Aspect 3> The capacitor according to Aspect 2, wherein the resin thin-film layer has a polymer structure formed by polymerizing a mixed monomer further containing a trifunctional and / or tetrafunctional monomer. <Aspect 4> The capacitor according to Aspect 2 or 3, wherein the ratio M1 / M2 of the molar amount M1 of the monofunctional monomer to the molar amount M2 of the bifunctional monomer is 0.1 to 1.5. <Aspect 5> The capacitor according to Aspect 3, wherein the ratio (M3 + M4) / M2 of the total molar amount M3 + M4 of the trifunctional monomer M3 and the tetrafunctional monomer M4 to the molar amount M2 of the bifunctional monomer is 0.02 to 0.4. <Aspect 6> The capacitor according to any one of Aspects 2 to 5, wherein both the bifunctional monomer and the monofunctional monomer contain an acryloyl group or a methacryloyl group. <Aspect 7> The capacitor according to any one of Aspects 1 to 6, for use at a temperature of 0°C or lower. <Aspect 8> The capacitor according to any one of Aspects 1 to 7, for space applications. <Aspect 9> The capacitor according to any one of Aspects 1 to 8, having a capacitor water absorption rate of 0.2 to 0.9%. <Aspect 10> A method for manufacturing a thin-film polymer laminated capacitor having a laminated structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated, forming a resin thin-film layer by curing a monomer layer containing at least a bifunctional monomer, depositing a metal on the resin thin-film layer to form an internal electrode metal layer, and forming the laminated structure by alternately repeating the formation of the resin thin-film layer and the formation of the internal electrode metal layer, comprising the glass transition temperature of the resin thin-film layer being 150°C or lower, the capacitor satisfying at least one of the following Condition 1 and Condition 2: Method: Condition 1: tanδ at -85°C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less. <Aspect 11> A use of a capacitor, comprising using a thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated at a temperature of 0°C or lower, wherein the resin thin-film layer has a glass transition temperature of 150°C or lower and has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer. The capacitor is used when it satisfies any one of the following Condition 1 and Condition 2: Condition 1: When measured at 1 kHz, tan δ at -85°C is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a thin-film polymer laminated capacitor that exhibits good characteristics even at low temperatures. In particular, according to the present invention, it is possible to provide a capacitor that has a small capacitance reduction at low temperatures and exhibits a relatively small tan δ at low temperatures.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0019] ≪Thin-Film Polymer Laminated Capacitor≫ The capacitor according to the present invention is a thin-film polymer laminated capacitor having a structure in which a resin thin film layer and an internal electrode metal layer are alternately laminated, the resin thin film layer having a glass transition temperature of 150°C or lower and having a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, and satisfies at least any one of the following Condition 1 and Condition 2: Condition 1: When measured at 1 kHz, tan δ at -85°C is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

[0020] As described above, there is a demand for capacitors suitable for use at low temperatures. On the other hand, conventional capacitors may not have sufficient low-temperature characteristics.

[0021] In the present invention, by studying and selecting a dielectric material used in a thin-film polymer laminated capacitor, a capacitor with excellent low-temperature characteristics has been invented. That is, the thin-film polymer laminated capacitor according to the present invention uses a resin thin-film layer made of a material having excellent low-temperature characteristics, and thereby can exhibit excellent low-temperature characteristics. In the capacitor according to the present invention, for example, the capacitance reduction at low temperatures is suppressed, and the tanδ at low temperatures is relatively small.

[0022] In the present invention, the glass transition temperature of the resin thin-film layer is set relatively low, whereby a relatively low tanδ and suppressed capacitance reduction at low temperatures can be obtained. Although not intended to be limited by theory, in the capacitor according to the present invention, since the glass transition temperature of the resin thin-film layer is set relatively low, it has a molecular structure that is easy to move in which the bond angle can change or rotate within the molecule even at low temperatures, and as a result, excellent low-temperature characteristics are considered to be obtained.

[0023] The thin-film polymer laminated capacitor is considered to be particularly suitable for space applications and the like for the following reasons: · It is a completely solid capacitor (can be used regardless of the atmospheric pressure); · It can be used as a surface-mount component that can be reflow-mounted; · While having good characteristics as a film capacitor, it is small in size and large in capacitance; · The characteristic variation is relatively small, and it exhibits stable performance; · The loss is small, and it has excellent electrical characteristics; · It is lightweight.

[0024] Hereinafter, the method according to the present disclosure will be described in more detail below.

[0025] In the capacitor according to the present disclosure, the glass transition temperature of the resin thin film layer is 150°C or lower.

[0026] A resin thin film layer having a glass transition temperature of 150°C or lower can be obtained, for example, by selecting the monomers constituting the polymer structure of the resin thin film layer.

[0027] Specifically, for example, a mixed monomer of a bifunctional monomer that produces a polymer having a relatively high glass transition temperature and a monofunctional monomer that produces a polymer having a relatively low glass transition temperature is used to form the polymer structure of the resin thin film layer, whereby a resin thin film layer having a glass transition temperature of 150°C or lower can be obtained.

[0028] Also, for example, a resin thin film layer having a glass transition temperature of 150°C or lower can be obtained by forming the polymer structure of the resin thin film layer using a bifunctional monomer that produces a polymer having a glass transition temperature of 150°C or lower.

[0029] In the capacitor according to the present disclosure, the glass transition temperature of the resin thin film layer may be 145°C or lower, 140°C or lower, 135°C or lower, 130°C or lower, 125°C or lower, 120°C or lower, 110°C or lower, 105°C or lower, or 100°C or lower, and / or may be 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 85°C or higher, or 90°C or higher. The glass transition temperature of the resin thin film layer is preferably 80 to 130°C, more preferably 85 to 125°C, and particularly preferably 90 to 120°C.

[0030] The glass transition temperature of the resin thin film layer can be determined by differential scanning calorimetry (DSC).

[0031] More specifically, for a 4 mm × 4 mm polymer sample with a thickness of 0.5 mm obtained by UV-curing a monomer, using a differential scanning calorimeter, under the following measurement conditions, heating and cooling are repeated according to the following measurement temperature profile, and the glass transition temperature is read during the third cooling process, whereby the glass transition temperature of the resin thin film layer can be determined. By reading the glass transition temperature during the third cooling process, variations in the measured values due to uncured components in UV-curing can be eliminated. <Measurement conditions> · Heating and cooling rate: 10 °C / min. · Modulated temperature amplitude: ±1.0 °C · Modulation period: 30 seconds · Nitrogen flow rate: 50 mL / min. <Measurement temperature profile> First time: Starting from 0 °C (holding for 5 minutes) → 260 °C → -40 °C → 25 °C Second time: Starting from 0 °C (holding for 5 minutes) → 340 °C → -40 °C → 25 °C Third time: Starting from 0 °C (holding for 5 minutes) → 340 °C → -40 °C → 25 °C

[0032] As an example, the glass transition temperatures of the resin thin film layers measured as described above using polymers obtained by curing various monomers (or mixed monomers having a specific composition) are shown below: DCPA: 165 °C DCPA(50)+A-LEN-10(50): 94 °C DCPA(45)+A-LEN-10(45)+TAIC(10): 99 °C DCPA(67.5)+S(22.5)+TAIC(10): 114 °C DCPA(67.5)+SA(22.5)+TAIC(10): 118 °C DCP: 154 °C 「DCPA」 represents 「tricyclodecane dimethanol diacrylate」. 「DCP」 represents tricyclodecane dimethanol dimethacrylate. "A-LEN-10" represents 2-(biphenyl-2-yloxy)-ethyl acrylate. "S" represents n-stearyl methacrylate. "SA" represents stearyl acrylate. The numbers in parentheses represent molar ratios.

[0033] <Tan δ or capacitance change rate at low temperature> The capacitor according to the present disclosure satisfies at least one of the following conditions 1 and 2: Condition 1: Tan δ at -85°C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

[0034] (Condition 1) Preferably, in the capacitor according to the present disclosure, tan δ at -85°C measured at 1 kHz may be 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less. The lower limit of this value is not particularly limited, but may be, for example, more than 0%, 0.01% or more, or 0.05% or more.

[0035] "Tan δ at -85°C measured at 1 kHz" can be measured using an LCR meter. More specifically, it can be measured as follows: (1) Connect the capacitor to be measured to a measurement cable; (2) Place the capacitor in a thermostatic bath maintained at -85°C and let it stand for 30 minutes or more; (3) Connect the other end of the measurement cable to the LCR meter; (4) Measure tan δ at -85°C and 1 kHz with the LCR meter.

[0036] (Condition 2) Preferably, based on the capacitance measured at 20 °C and 1 kHz, the capacitance reduction rate at -85 °C is 8% or less, 7% or less, 6% or less, or 5% or less. The lower limit of this value is not particularly limited, and may be, for example, 1% or more, or 2% or more.

[0037] The "capacitance reduction rate at -85 °C based on the capacitance measured at 20 °C and 1 kHz" can be measured using an LCR meter. More specifically, it can be measured as follows: (1) Connect the capacitor to be measured to the measurement cable; (2) Place the capacitor in a thermostatic bath maintained at 20 °C and let it stand for 30 minutes or more; (3) Connect the other end of the measurement cable to the LCR meter; (4) Measure the capacitance at 20 °C and 1 kHz with the LCR meter; (5) Disconnect the other end of the measurement cable from the LCR meter; (6) Set the temperature of the thermostatic bath to -85 °C and let it stand for 30 minutes or more after reaching -85 °C; (7) Connect the other end of the measurement cable to the LCR meter; (8) Measure the capacitance at -85 °C and 1 kHz with the LCR meter; (9) Calculate the capacitance reduction rate from the capacitance measurement values at 20 °C and -85 °C.

[0038] <Resin thin film layer> The resin thin film layer of the capacitor according to the present disclosure has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer.

[0039] The bifunctional monomer has two polymerizable functional groups in one molecule.

[0040] (Polymerizable functional group) Examples of the polymerizable functional group include a vinyl group, an acrylonitrile group, an isopropenyl group, and an epoxy group.

[0041] The vinyl group is represented by CH2=CH-. Specific examples of the polymerizable functional group include, in particular, an acryloyl group (CH2=CH-C(=O)), a methacryloyl group (CH2=C(CH3)-C(=O)), an acrylate group (CH2=CH-C(=O)-O), a methacrylate group ((CH2=C(CH3)-C(=O)-O), an allyl group (CH2=CH-CH2-), and a group represented by CH2=CH-R- (R is a hydrocarbon group containing 2 to 12 carbon atoms). R may be, for example, an alkylene group, or a hydrocarbon group containing an alicyclic structure or a benzene ring. R particularly contains 2 to 8, more particularly 2 to 4 carbon atoms.

[0042] The bifunctional monomer, as well as the monofunctional monomer and polyfunctional monomer having three or more functional groups described later, can polymerize via the polymerizable functional group under conditions such as electron beam irradiation to form a polymer structure (polymer).

[0043] (Bifunctional monomer) The bifunctional monomer preferably includes a monomer having an acryloyl group or a methacryloyl group, or consists of a monomer having an acryloyl group or a methacryloyl group.

[0044] In one embodiment according to the present disclosure, the bifunctional monomer can have a chemical structure represented by the following general formula (2).

[0045] [Chemical formula]

[0046] In formula (2), R 1 is a group containing 1 to 20 carbon atoms; R 2 are each independently H or CH3.

[0047] In formula (2), R 1 preferably contains 3 to 20, more preferably 6 to 20, and still more preferably 8 to 20 carbon atoms.

[0048] R in formula (2) 1 may contain an oxygen atom. In this case, R 1 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, or 1 to 2 oxygen atoms, or can contain one oxygen atom.

[0049] R in formula (2) 1 can particularly contain an ether bond. In this case, R 1 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, or 1 to 2 ether bonds, or can contain one ether bond.

[0050] Preferably, R in formula (2) 1 consists of carbon atoms, hydrogen atoms, and optional oxygen atoms.

[0051] In formula (2), R 1 can contain an (unbranched or branched) aliphatic moiety, an alicyclic moiety, and / or an aromatic moiety.

[0052] R in formula (2) 1 When it contains an alicyclic moiety, the bulkiness of the molecule increases, so the molar volume increases, and it may have the effect of lowering the tanδ of the capacitor. Also, due to the bulkiness and rigidity, the micro-Brownian motion of the main chain segments in the three-dimensional network structure of the polymer due to temperature rise is inhibited, and as a result, it may lead to a capacitor with a relatively high glass transition point and excellent heat resistance. Furthermore, since the curing shrinkage of the resin thin film layer is relatively suppressed, the interlayer adhesion of the capacitor can be further improved.

[0053] R in formula (2) 1 When it contains an aromatic moiety, since it has a π-electron conjugation system, the polarization due to the dipole orientation becomes larger than that of a simple alkyl skeleton, and a relatively large dielectric constant can be obtained. Furthermore, especially when R 1When it contains a bulky structure such as a biphenyl structure, as described above for the alicyclic portion, it may have an effect of lowering the tanδ of the capacitor. Further, since the curing shrinkage of the resin thin film layer is relatively suppressed, the interlayer adhesion of the capacitor can be further improved.

[0054] In formula (2), R 1 preferably does not contain an unsaturated bond. By not containing an unsaturated bond, it may be possible to suppress an increase in the tanδ of the capacitor.

[0055] Examples F1 to F6 of the chemical structures of the bifunctional monomers that can be used in the present invention are shown below.

[0056] [Chemical formula]

[0057] In chemical formulas F3 and F4, n may each be from 1 to 20, preferably from 5 to 18, more preferably from 8 to 15, and still more preferably from 9 to 12.

[0058] In chemical formulas F5 and F6, n may each be from 1 to 20, preferably from 1 to 10, more preferably from 2 to 6, and still more preferably from 3 to 4.

[0059] Particularly preferred bifunctional monomers include tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, and the like.

[0060] Preferably, among all the monomer units constituting the polymer structure of the resin thin film layer, the proportion occupied by the bifunctional monomer is 40% or more in terms of molar ratio. The upper limit is not particularly limited, but for example, it may be 90% or less, or even 80% or less in terms of molar ratio.

[0061] (monofunctional monomer) In one preferred embodiment according to the present disclosure, the resin thin film layer has a polymer structure formed by polymerizing a mixed monomer containing at least a bifunctional monomer and a monofunctional monomer.

[0062] By using a monofunctional monomer in addition to the bifunctional monomer, a resin thin film layer having a relatively low glass transition temperature can be easily formed.

[0063] When a monofunctional monomer is added to the bifunctional monomer, it is also possible to reduce the water absorption rate of the capacitor.

[0064] The monofunctional monomer has one polymerizable functional group in one molecule.

[0065] The monofunctional monomer preferably includes a monomer having an acryloyl group or a methacryloyl group, or consists of a monomer having an acryloyl group or a methacryloyl group.

[0066] In one embodiment according to the present disclosure, the monofunctional monomer can have a chemical structure represented by the following general formula (1).

[0067]

Chemical formula

[0068] In formula (1), R 3 is a group containing 1 to 20 carbon atoms; R 2 is H or CH3.

[0069] R in formula (1) 2 is preferably H.

[0070] R in formula (1) 3 preferably contains 3 to 20, more preferably 6 to 20, and still more preferably 8 to 20 carbon atoms.

[0071] R in formula (1) 3can contain an oxygen atom. In this case, R 3 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, 1 to 2, or one oxygen atom.

[0072] R in formula (1) 3 can particularly contain an ether bond. In this case, R 3 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, 1 to 2, or one ether bond.

[0073] Preferably, R in formula (1) 3 consists of carbon atoms, hydrogen atoms, and optional oxygen atoms.

[0074] In formula (1), R 3 can contain an aliphatic moiety (linear or branched), an alicyclic moiety, and / or an aromatic moiety.

[0075] R in formula (1) 3 When it contains an alicyclic moiety, the steric bulk of the molecule increases, so the molar volume increases, and it may have an effect of lowering the tanδ of the capacitor. Also, due to the steric bulk and rigidity, the micro-Brownian motion of the main chain segments in the three-dimensional network structure of the polymer caused by temperature rise is inhibited, and as a result, it may lead to a capacitor with a relatively high glass transition temperature and excellent heat resistance. Furthermore, since the curing shrinkage of the resin thin film layer is relatively suppressed, the interlayer adhesion of the capacitor may be further improved.

[0076] R in formula (1) 3 When it contains an aromatic moiety, since it has a π-electron conjugation system, the polarization due to the dipole orientation becomes larger than that of a simple alkyl skeleton, and a relatively large dielectric constant can be obtained. Furthermore, especially when R 3 contains a bulky structure such as a biphenyl structure, as described above for the alicyclic moiety, it may have an effect of lowering the tanδ of the capacitor. Furthermore, since the curing shrinkage of the resin thin film layer is relatively suppressed, the interlayer adhesion of the capacitor may be further improved.

[0077] R3 Preferably has a biphenyl structure.

[0078] In formula (1), R 3 Preferably does not contain an unsaturated bond. By not containing an unsaturated bond, an increase in the tanδ of the capacitor may be suppressed.

[0079] Examples S1 to S8 of the chemical structures of the monofunctional monomers that can be used in the present invention are shown below.

[0080]

Chemical formula

[0081] In chemical formulas S1 and S2, n may each be from 0 to 20, preferably from 1 to 10, more preferably from 1 to 5, still more preferably from 1 to 3 or 1 to 2, and most preferably n = 1.

[0082] In chemical formulas S5 and S6, n may each be from 1 to 20, preferably from 5 to 18, more preferably from 12 to 17.

[0083] In chemical formulas S7 and S8, n may each be from 1 to 20, preferably from 10 to 20, more preferably from 12 to 18, still more preferably from 14 to 16.

[0084] Examples of the chemical structures of preferred monofunctional monomers are shown below.

[0085]

Chemical formula

[0086] Particularly preferred monofunctional monomers include 2-(Biphenyl-2-yloxy)-ethyl acrylate, 4-Phenylbenzyl acrylate, Stearyl acrylate, and n-Stearyl methacrylate include the following.

[0087] (Ratio of monofunctional monomer units) Preferably, with respect to the monofunctional monomer and the bifunctional monomer constituting the polymer structure of the resin thin film layer, the ratio M1 / M2 of the molar amount M1 of the monofunctional monomer to the molar amount M2 of the bifunctional monomer is 0.1 to 1.5.

[0088] This molar ratio M1 / M2 is more preferably 0.1 to 1.2, and particularly preferably 0.2 to 1.0. In one preferred embodiment, the molar ratio M1 / M2 is 0.8 to 1.2, or even 0.9 to 1.1. Also, in another preferred embodiment, the molar ratio M1 / M2 is 0.1 or more and less than 0.5, 0.1 to 0.4, 0.1 to 0.3, or even 0.1 to 0.2.

[0089] (Trifunctional monomer and / or tetrafunctional monomer) In a particularly preferred embodiment according to the present disclosure, the resin thin film layer has a polymer structure formed by polymerizing a mixed monomer further containing a trifunctional and / or tetrafunctional monomer in addition to the bifunctional monomer and the monofunctional monomer.

[0090] The trifunctional monomer has three polymerizable functional groups in one molecule. The tetrafunctional monomer has four polymerizable functional groups in one molecule.

[0091] In a particularly preferred embodiment according to the present disclosure, the trifunctional and tetrafunctional monomers include a monomer having a polymerizable functional group other than an acryloyl group and a methacryloyl group, or consist of a monomer having a polymerizable functional group other than an acryloyl group and a methacryloyl group. This polymerizable functional group is particularly a nonpolar functional group.

[0092] This polymerizable functional group other than the acryloyl group and the methacryloyl group preferably has a smaller polarity than the acryloyl group and the methacryloyl group.

[0093] Examples of the polymerizable functional group having a polarity smaller than that of an acryloyl group and a methacryloyl group include an allyl group (CH2=CH-CH2-), and a group represented by CH2=CH-R- (R is a hydrocarbon group containing 2 to 12 carbon atoms). R may be, for example, an alkylene group or a hydrocarbon group containing a benzene ring. R particularly contains 2 to 8 carbon atoms, more particularly 2 to 4 carbon atoms.

[0094] Examples of the trifunctional monomer having an allyl group include triallyl isocyanurate (commercially available as "TAIC" (registered trademark)).

[0095] [Chemical formula]

[0096] When a monomer containing a polymerizable functional group (particularly an allyl group) having a polarity smaller than that of an acryloyl group and a methacryloyl group is used as the trifunctional and / or tetrafunctional monomer, particularly good low-temperature characteristics of the capacitor may be obtained. Although not intended to be limited by theory, in this case, it is considered that the small polarity of the polymerizable functional group suppresses tanδ to a low level.

[0097] Here, polymerizable functional groups with relatively small polarity (such as allyl groups) are generally considered to be less likely to undergo a curing reaction by electron beams or light. However, the inventors of the present invention have found that when mixed in a monomer that cures by electron beams or light, a polymerization reaction occurs at a certain ratio, and a crosslinked structure is formed by subsequent heat treatment or the like.

[0098] In one embodiment according to the present disclosure, the trifunctional monomer and / or tetrafunctional monomer may include a monomer having an acryloyl group or a methacryloyl group, or may consist of a monomer having an acryloyl group or a methacryloyl group.

[0099] In this case, the trifunctional monomer and the tetrafunctional monomer may have, for example, a chemical structure represented by the following general formula (3).

[0100]

Chem.

[0101] In formula (3), R 4 is a group containing 1 to 20 carbon atoms; R 2 are each independently H or CH3; n is 3 or 4.

[0102] In formula (3), n is preferably 3.

[0103] In formula (3), R 4 preferably contains 1 to 20, more preferably 2 to 12, and even more preferably 3 to 8 carbon atoms.

[0104] R in formula (3) 4 can also contain an oxygen atom. In this case, R 4 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, or 1 to 2 oxygen atoms, or can contain one oxygen atom. Preferably, R 4 does not contain an oxygen atom.

[0105] R in formula (3) 4 can also contain an ether bond. In this case, R 4 can contain 1 to 20, 1 to 10, 1 to 5, 1 to 3, or 1 to 2 ether bonds, or can contain one ether bond.

[0106] Preferably, R in formula (3) 4 consists of carbon atoms, hydrogen atoms, and optional oxygen atoms. Particularly preferably, R in formula (3) 4 is a hydrocarbon group consisting only of carbon atoms and hydrogen atoms, particularly a hydrocarbon group having 3 to 8 carbon atoms.

[0107] In formula (3), R 4It can contain an aliphatic moiety, an alicyclic moiety, and / or an aromatic moiety (linear or branched).

[0108] In formula (3), R 4 Preferably, it does not contain an unsaturated bond. By not containing an unsaturated bond, an increase in the tanδ of the capacitor may be suppressed.

[0109] Among the compounds represented by the above formula (3), as an example of a trifunctional monomer, the chemical structure of trimethylolpropane triacrylate is shown below.

[0110] [Chemical formula]

[0111] (Ratio of trifunctional and / or tetrafunctional monomer units) Preferably, regarding the monomer constituting the polymer structure forming the resin thin film layer, the ratio (M3 + M4) / M2 of the total molar amount M3 + M4 of the trifunctional monomer and the molar amount M4 of the tetrafunctional monomer to the molar amount M2 of the bifunctional monomer is 0.02 to 0.4.

[0112] When using a trifunctional monomer and not using a tetrafunctional monomer, that is, when the polymer structure forming the resin thin film layer is composed of monofunctional, bifunctional, and trifunctional monomers, the ratio M3 / M2 of the molar amount M3 of the trifunctional monomer to the molar amount M2 of the bifunctional monomer is preferably 0.02 to 0.4.

[0113] The molar ratio (M3 + M4) / M2, or the molar ratio M3 / M2, is more preferably 0.02 to 0.35, or even more preferably 0.03 to 0.3.

[0114] (Combination of monomers) As combinations of monofunctional, bifunctional, and trifunctional monomers, in particular, the following combinations can be mentioned: · 2-(Biphenyl-2-yloxy)-ethyl acrylate, stearyl acrylate, or n-stearyl methacrylate as monofunctional monomers · Tricyclodecane dimethanol diacrylate as difunctional monomer · Triallyl isocyanurate as trifunctional monomer (Composition of monomers) Also, regarding the combination of monofunctional and difunctional monomers, and the combination of monofunctional, difunctional, and trifunctional monomers, the relative molar ratio is preferably as follows: Monofunctional monomer: Difunctional monomer = 10 - 60:90 - 40, more preferably 15 - 50:85 - 50 Monofunctional monomer: Difunctional monomer: Trifunctional monomer = 15 - 60:40 - 85:1 - 20, more preferably 20 - 50:40 - 75:5 - 15

[0115] <Thin film polymer laminated capacitor> The thin film polymer laminated capacitor according to the present disclosure has a structure in which a resin thin film layer and an internal electrode metal layer are alternately laminated.

[0116] Figure 1 is a perspective schematic view of the thin film polymer laminated capacitor 1. The thin film polymer laminated capacitor 1 has a laminate 2 in which a resin thin film layer and a metal thin film layer (internal electrode metal layer) are alternately laminated, and two external electrodes 3 and 4 are attached to this laminate 2.

[0117] The thin film polymer laminated capacitor can have 10 to 10,000 layers, 50 to 5000 layers, or 100 to 2,000 layers.

[0118] The resin thin film layer may have a thickness of 10 nm to 3000 nm, preferably 100 to 1500 nm.

[0119] As the metal material constituting the internal electrode metal layer, at least one selected from the group consisting of Al, Cu, Zn, Sn, Au, Ag, Pt, and combinations thereof can be mentioned. The metal material constituting the internal electrode metal layer is preferably aluminum.

[0120] The internal electrode metal layer may have a thickness of 1 nm to 100 nm, preferably a thickness of 10 to 40 nm. Further, the metal thin film layer preferably has a deposition resistance value of 1 to 50 Ω / □, 5 to 40 Ω / □, or 5 to 30 Ω / □.

[0121] (Water absorption rate) In one embodiment, the capacitor according to the present disclosure exhibits a water absorption rate (referred to as "capacitor water absorption rate" in the present disclosure) of 0.2 to 0.9% when measured by the method described below. This water absorption rate is particularly 0.25 to 0.80%, more particularly 0.25 to 0.75 or even 0.30 to 0.70%: The weight change rate (%) of the capacitor after performing a moisture absorption test in which the capacitor with the external electrode portion cut off is placed in a thermo-hygrostat chamber at a temperature of 60°C and a relative humidity of 90% and left standing for 100 hours is measured, and this is taken as the water absorption rate (%) of the capacitor: Weight change rate (%) = 100 × (weight after moisture absorption test - weight before moisture absorption test) / weight before moisture absorption test.

[0122] Further, the capacitor according to the present disclosure exhibits a water absorption rate (referred to as "capacitor resin sample water absorption rate" in the present disclosure) of 0.2 to 0.9% when measured by the following method using a resin sample. This water absorption rate is particularly 0.25 to 0.80%, more particularly 0.30 to 0.70%: (a) Provide a test monomer of the same type and composition as that used when forming the resin thin film layer of the capacitor, Mix a photoinitiator (2-benzyl-2-dimethylamino-4'-morpholinobutyrophenone, manufactured by Tokyo Chemical Industry Co., Ltd.) at a ratio of 0.2 ± 0.01 mol per 100 mol of the test monomer to form a mixture, Inject the mixture into a round dish, and The mixture injected into the dish was irradiated with UV in a nitrogen atmosphere under the conditions of 120 W and a distance of 250 mm until the polymerization stopped, to produce a disc-shaped resin film having dimensions of 30 mm in diameter and 1 mm in depth. (b) After conducting a moisture absorption test in which the resin film as a resin sample was placed in a thermo-hygrostat chamber at a temperature of 60°C and a relative humidity of 90% and left standing for 100 hours, the weight change rate of the resin film was measured according to the following formula, and this was taken as the water absorption rate (%): Weight change rate (%) = 100 × (weight after moisture absorption test - weight before moisture absorption test) / weight before moisture absorption test.

[0123] <Method for manufacturing a capacitor> The method for manufacturing the thin film polymer laminated capacitor according to the present disclosure is not particularly limited.

[0124] For example, the thin film polymer laminated capacitor according to the present disclosure can be manufactured by a method including alternately repeating, on a rotating drum, a step of forming a resin thin film layer and a step of depositing a metal material to form a metal thin film layer, thereby manufacturing a laminate in which the resin thin film layer and the metal thin film layer are alternately laminated on the rotating drum.

[0125] The laminate formed on the rotating drum can be removed from the rotating drum and pressed under heating to be flattened. Then, after cutting the flattened laminate into a stick shape, an external electrode is formed, and this is further cut into a chip shape, whereby a thin film polymer laminated capacitor can be obtained.

[0126] (One aspect of the manufacturing method) The present disclosure includes a method for manufacturing a thin film polymer laminated capacitor having a laminated structure in which a resin thin film layer and an internal electrode metal layer are alternately laminated, and this method includes hardening a monomer layer containing at least a bifunctional monomer to form a resin thin film layer, depositing a metal on the resin thin film layer to form an internal electrode metal layer, and By alternately repeating the formation of the resin thin film layer and the formation of the internal electrode metal layer, a laminated structure is formed. including The glass transition temperature of the resin thin film layer is 150°C or lower. The capacitor satisfies at least one of the following Condition 1 and Condition 2: Condition 1: When measured at 1 kHz, tan δ at -85°C is 0.8% or less. Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

[0127] This manufacturing method according to the present disclosure is particularly suitable for manufacturing the above capacitor according to the present disclosure. For details of each component (monomer, resin thin film layer, internal electrode metal layer, glass transition temperature, etc.) in this manufacturing method and the preferred ranges of numerical values such as the glass transition temperature, reference can be made to the above description regarding the capacitor of the present disclosure.

[0128] (Monomer) The molar amount of the monomer used in the manufacturing process is considered to correspond to the molar amount of the monomer units in the formed resin thin film layer. Therefore, regarding the molar amounts of the monofunctional monomer, bifunctional monomer, trifunctional monomer, and tetrafunctional monomer used in the manufacturing process, reference can be made to the description regarding the molar amounts M1, M2, M3, and M4 of the monofunctional monomer, bifunctional monomer, trifunctional monomer, and tetrafunctional monomer described above for the capacitor of the present disclosure.

[0129] The step of curing the monomer layer to form the resin thin film layer can be performed according to a known method. For example, it can be performed according to the method described in International Publication No. 2015 / 118693. Specifically, for example, after depositing a monomer in a vacuum chamber to form a monomer layer, the monomer layer can be cured by irradiating the monomer layer with an electron beam.

[0130] For the method of forming a metal thin film layer and the method of alternately laminating a resin thin film layer and a metal thin film layer, known methods can also be used. For example, the method described in International Publication No. 2015 / 118693 can be used.

[0131] (Vapor deposition) In one embodiment of the manufacturing method according to the present disclosure, the resin thin film layer and the internal electrode metal layer are formed into films by a vapor deposition method.

[0132] Also, in one embodiment of the manufacturing method according to the present disclosure, when forming a monomer layer, a mixture of a monofunctional monomer and a bifunctional monomer and a trifunctional and / or tetrafunctional monomer are vapor-deposited from separate evaporation sources, respectively.

[0133] (Additional curing treatment by heating) In one embodiment of the manufacturing method according to the present disclosure, by heating the laminated structure formed as described above, the curing of the uncured components in the resin thin film layer is advanced.

[0134] In particular, when using a monomer having a polymerizable functional group (for example, an allyl group) with a lower polarity than an acryloyl group and a methacryloyl group as the trifunctional and / or tetrafunctional monomer, by further performing a heat treatment after forming the laminated structure, particularly good curing degree can be obtained.

[0135] The temperature during this heating may be 150 to 250°C, and the heating time may be 1 to 10 hours.

[0136] (Applications) The applications of this capacitor are not particularly limited. This capacitor is particularly suitable for applications at low temperatures (for example, 0°C or lower, particularly -10°C or lower, or even -20°C or lower, -40°C or lower, -60°C or lower, or -80°C or lower).

[0137] In addition, the capacitor according to the present disclosure is also suitable for space applications. Examples of space applications include artificial satellites, space stations, and space vehicles (such as spacecraft and space vehicles).

[0138] (Use) The present disclosure includes the use of the capacitor according to the present disclosure.

[0139] In particular, the present disclosure includes the following uses: Using a thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated at a temperature of 0 °C or lower (in particular, a temperature of -10 °C or lower, or even -20 °C or lower, -40 °C or lower, -60 °C or lower, or -80 °C or lower), which is a use of a capacitor, The resin thin-film layer has a glass transition temperature of 150 °C or lower and has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, The use of the capacitor, wherein the capacitor satisfies any one of the following conditions 1 and 2: Condition 1: tanδ at -85 °C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20 °C and 1 kHz, the capacitance reduction rate at -85 °C is 9% or less.

[0140] In addition, the present disclosure includes the following uses: Using a thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated in space applications, which is a use of a capacitor, The capacitor is The resin thin-film layer has a glass transition temperature of 150 °C or lower and has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, The use of the capacitor, wherein the capacitor satisfies any one of the following conditions 1 and 2: Condition 1: tanδ at -85 °C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

[0141] For the details of each component in these uses and the preferred ranges of numerical values such as the glass transition temperature, reference can be made to the descriptions in the capacitor and the method for manufacturing a capacitor according to the above present disclosure.

Example

[0142] Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited by the examples.

[0143] <<Examples 1 to 4 and Comparative Examples 1 to 2>> Thin-film polymer multilayer capacitors according to Examples 1 to 4 and Comparative Examples 1 to 2 were manufactured and their characteristics were evaluated.

[0144] <Example 1> (Manufacture of thin-film polymer multilayer capacitor) In a vacuum chamber, the step of forming a resin thin film layer and the step of forming a metal thin film layer were alternately repeated on a rotating drum, whereby a laminate in which a resin thin film layer and a metal thin film layer (internal electrode metal layer) were alternately laminated in a total of 2500 layers was manufactured on the rotating drum.

[0145] In the step of forming the resin thin film layer, the following Monomer 1 and Monomer 2 were used at a molar ratio of 50:50. · Monomer 1 (monofunctional monomer): 2-(biphenyl-2-yloxy)-ethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-LEN-10) · Monomer 2 (bifunctional monomer): tricyclodecane dimethanol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-DCP)

[0146] After forming a monomer layer by vapor-depositing the mixture of the above monomers in a vacuum chamber, the monomer layer was irradiated with an electron beam to cure the monomer layer, thereby forming a resin thin film layer. The irradiation with the electron beam was performed under the conditions of an acceleration voltage of 5 kV and an irradiation current of 50 mA. The thickness of the resin thin film layer was 0.5 μm.

[0147] In the step of forming the metal thin film layer, aluminum (Al) as a metal material was vapor-deposited on the resin thin film layer in which a part of the region was masked by vapor-depositing and coating fluorine oil to form a metal thin film layer. The vapor deposition resistance value of the metal thin film layer was 15 Ω / □.

[0148] The manufactured laminate was removed from the rotating drum and pressed and flattened under heating at 160 °C. Then, after cutting the flattened laminate into a stick shape, an external electrode (spray deposit of brass metallicon, copper plating, and tin plating) was attached, and this was further cut into a chip shape to obtain the thin film polymer laminate capacitor according to Example 1. The size of the capacitor was 4.5 mm × 3.2 mm.

[0149] (Glass transition temperature of the resin thin film layer) The glass transition temperature of the resin thin film layer of the capacitor according to Example 1 was measured as follows: Regarding a 4 mm × 4 mm and 0.5 mm thick polymer sample obtained by UV-curing the mixture of monomers used in Example 1, using a differential scanning calorimeter, under the following measurement conditions, heating and cooling were repeated according to the following measurement temperature profile, and the glass transition temperature was read in the third cooling process to determine the glass transition temperature of the resin thin film layer: <Measurement conditions> · Heating and cooling rate: 10 °C / min. · Modulated temperature amplitude: ±1.0 °C · Modulation period: 30 seconds · Nitrogen flow rate: 50 mL / min. <Measurement temperature profile> First time: Starting from 0 °C (holding for 5 minutes) → 260 °C → -40 °C → 25 °C Second time: Start at 0°C (hold for 5 minutes) → 340°C → -40°C → 25°C Third time: Start at 0°C (hold for 5 minutes) → 340°C → -40°C → 25°C The results are shown in Table 1 below.

[0150] (tanδ) For the capacitor according to Example 1 obtained as described above, using an LCR meter, at the condition of 1 kHz shown in the graph of Figure 2, the tanδ (%) corresponding to each temperature was measured. Specifically, the capacitor was placed in a thermostat through a measurement cable and the tanδ (%) at each temperature was measured. The results are shown in Figure 2 and Table 1 below.

[0151] (Evaluation of tanδ at low temperature) The tanδ at low temperature was evaluated according to the following evaluation criteria: (++) - The value of tanδ at -85°C was less than 0.55%. (+) - The value of tanδ at -85°C was 0.55% or more and 0.8% or less. (--) - The value of tanδ at -85°C was more than 0.8%.

[0152] (Rate of change of capacitance) For the capacitor according to Example 1 obtained as described above, the rate of change of capacitance (%) when the capacitor was placed in a specific environment was measured. Specifically, at each temperature shown in Figure 3, the capacitance (μF) when the capacitor was left standing for 30 minutes was measured at 1 kHz using an LCR meter, and the rate of change of capacitance (%) with respect to the initial capacitance measured at 20°C was calculated. The results are shown in Figure 3 and Table 1. The initial capacitance was approximately 1 μF.

[0153] (Evaluation of rate of change of capacitance at low temperature) The rate of change of capacitance (rate of capacitance decrease) at low temperature was evaluated according to the following evaluation criteria: (++) - The above rate of capacitance decrease at -85°C was significantly small and less than 4%. (+) - The rate of capacitance decrease at -85°C was relatively small and 4% or more and 9% or less. (--) The capacitance reduction rate at 85 °C was relatively large, exceeding 9%.

[0154] (Water absorption rate) The weight change rate (%) of the capacitor after conducting a moisture absorption test in which a capacitor with the external electrode portion removed was placed in a thermo-hygrostat chamber at a temperature of 60 °C and a relative humidity of 90% and allowed to stand for 100 hours was measured, and this was defined as the water absorption rate (%) of the capacitor: Weight change rate (%) = 100 × (weight after moisture absorption test - weight before moisture absorption test) / weight before moisture absorption test.

[0155] <Example 2> A capacitor according to Example 2 was manufactured and evaluated in the same manner as in Example 1 above. However, in the step of forming the resin thin film layer, the following Monomer 1, Monomer 2, and Monomer 3 were used at a molar ratio of 45:45:10. · Monomer 1 (monofunctional monomer): 2-(biphenyl-2-yloxy)-ethyl acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: A-LEN-10)

Chemical formula

Chemical formula

Chemical formula

[0156] <Example 3> A capacitor according to Example 3 was manufactured and evaluated in the same manner as in Example 1 above. However, in the step of forming the resin thin film layer, the following Monomer 1, Monomer 2, and Monomer 3 were used at a molar ratio of 22.5:67.5:10. · Monomer 1 (monofunctional monomer): Stearyl acrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Acrylate S-A)

Chemical formula

[0157] <Example 4> A capacitor according to Example 4 was manufactured and evaluated in the same manner as in Example 1 above. However, in the step of forming the resin thin film layer, the following Monomer 1, Monomer 2, and Monomer 3 were used at a molar ratio of 22.5:67.5:10. · Monomer 1 (monofunctional monomer): n-Stearyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester S)

Chemical formula

[0158] (Comparative Example 1) As a monomer, a capacitor according to Comparative Example 1 was produced and evaluated in the same manner as in Example 1, except that only tricyclodecane dimethanol diacrylate, which is a bifunctional monomer, was used. The results are shown in the graphs of FIGS. 2 to 3 and Table 1.

[0159] (Comparative Example 2) As a monomer, a capacitor according to Comparative Example 2 was produced and evaluated in the same manner as in Example 1, except that only tricyclodecane dimethanol dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., product name: DCP), which is a bifunctional monomer, was used. The results are shown in the graphs of FIGS. 2 to 3 and Table 1.

[0160] [Table 1]

[0161] As can be seen from Table 1 and FIGS. 2 to 3, the thin-film polymer laminated capacitors of Examples 1 to 4 having a polymer structure formed by polymerizing a monomer having a glass transition temperature of 94°C to 118°C and containing at least a bifunctional monomer in the resin thin-film layer have a polymer structure formed by polymerizing a bifunctional monomer, while having a glass transition temperature of the resin thin-film layer of 154°C to 165°C. Compared with the thin-film polymer laminated capacitors according to Comparative Examples 1 and 2, they showed excellent low-temperature characteristics at least in the range of -10°C to -85°C. Such capacitors are considered to exhibit good capacitor characteristics even in vehicles operated under severe cold conditions and in outer space.

[0162] As can be seen from FIGS. 2 to 3, the capacitors according to Examples 1 and 2 using 2-(biphenyl-2-yloxy)-ethyl acrylate as a monofunctional monomer showed particularly reduced tanδ values in the extremely low-temperature region. Although not intended to be limited by theory, this is considered to be due to the use of a monofunctional monomer having an aromatic ring.

Claims

1. A thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated, wherein the resin thin-film layer has a glass transition temperature of 150 ° C or lower and has a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, A capacitor satisfying at least one of the following Conditions 1 and 2: Condition 1: The tan δ at -85 ° C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20 ° C and 1 kHz, the capacitance reduction rate at -85 ° C is 9% or less.

2. The capacitor according to claim 1, wherein the resin thin-film layer has a polymer structure formed by polymerizing a mixed monomer containing at least a bifunctional monomer and a monofunctional monomer.

3. The capacitor according to claim 2, wherein the resin thin-film layer has a polymer structure formed by polymerizing a mixed monomer further containing a trifunctional and / or tetrafunctional monomer.

4. The capacitor according to claim 2 or 3, wherein the ratio M1 / M2 of the molar amount M1 of the monofunctional monomer to the molar amount M2 of the bifunctional monomer is 0.1 to 1.

5.

5. The capacitor according to claim 3, wherein the ratio (M3 + M4) / M2 of the total molar amount M3 + M4 of the trifunctional monomer M3 and the tetrafunctional monomer M4 to the molar amount M2 of the bifunctional monomer is 0.02 to 0.

4.

6. The capacitor according to claim 2, 3 or 5, wherein both the bifunctional monomer and the monofunctional monomer contain an acryloyl group or a methacryloyl group.

7. The capacitor according to claim 1, 2, 3 or 5, for use at a temperature of 0 ° C or lower.

8. The capacitor according to claim 1, 2, 3 or 5, for space applications.

9. The capacitor according to claim 1, 2, 3 or 5, having a capacitor water absorption rate of 0.2 to 0.9%.

10. A method for manufacturing a thin-film polymer laminated capacitor having a laminated structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated, forming a resin thin-film layer by curing a monomer layer containing at least a bifunctional monomer, depositing a metal on the resin thin-film layer to form an internal electrode metal layer, and forming the laminated structure by alternately repeating the formation of the resin thin-film layer and the formation of the internal electrode metal layer, including the glass transition temperature of the resin thin-film layer being 150°C or lower, the capacitor satisfying at least one of the following Condition 1 and Condition 2, Method: Condition 1: tanδ at -85°C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

11. The use of a capacitor, including using a thin-film polymer laminated capacitor having a structure in which a resin thin-film layer and an internal electrode metal layer are alternately laminated at a temperature of 0°C or lower, the resin thin-film layer having a glass transition temperature of 150°C or lower and having a polymer structure formed by polymerizing a monomer containing at least a bifunctional monomer, the capacitor satisfying any one of the following Condition 1 and Condition 2, Use: Condition 1: tanδ at -85°C measured at 1 kHz is 0.8% or less; Condition 2: Based on the capacitance measured at 20°C and 1 kHz, the capacitance reduction rate at -85°C is 9% or less.

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