Composition and sheet comprising a cured product thereof

Abstract

A composition containing: a compound represented by the following formula (1); and a hollow particle. In formula (1), R 11 and R 12 each independently represent a hydrogen atom or a methyl group, R 13 represents a divalent group having a polyoxyalkylene chain.

Description

Technical Field

[0001] This invention relates to a composition and a sheet comprising a cured product thereof. Background Technology

[0002] Thermal insulation materials are used in various applications to protect heat-sensitive components and improve energy efficiency. In thermal insulation materials, hollow particles with low thermal conductivity are sometimes used to improve their insulation performance. For example, Patent Document 1 describes an insulation layer formed on the surface of a substrate, comprising a plurality of hollow particles and an adhesive embedded between the hollow particles and holding them on the substrate. The adhesive is characterized by being a silicone resin containing T units and D units as basic constituent units.

[0003] Previous technical documents

[0004] Patent documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-065155 Summary of the Invention

[0006] The technical problem to be solved by the invention

[0007] According to the research of the inventors, there is sometimes a need for thermal insulation materials with low elasticity and excellent elongation so that the thermal insulation materials can be applied to components of various shapes.

[0008] Therefore, the object of the present invention is to provide a composition suitable for a thermal insulation material with low elasticity and excellent elongation, and a sheet containing the cured product thereof.

[0009] means for solving technical problems

[0010] The inventors have conducted in-depth research and discovered that by using a composition containing a specific compound having a polyoxyalkylene chain and two (meth)acryloyl groups and hollow particles, it is possible to obtain a composition suitable for insulating materials with low elasticity and excellent elongation, and a sheet containing the cured form thereof. The present invention provides the following [1] to [7] in several aspects.

[0011] [1] A composition comprising: a compound represented by the following formula (1); and hollow particles.

[0012]

[0013] In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This indicates a divalent group with a polyoxyalkylene chain.

[0014] [2] The composition as described in [1], wherein the polyoxyalkylene chain contains oxyethylene.

[0015] [3] The composition as described in [1], wherein the polyoxyalkylene chain contains an oxypropylidene group.

[0016] [4] The composition as described in [1], wherein the polyoxyalkylene chain is a copolymer chain containing oxyethylene and oxypropylene.

[0017] [5] The composition as described in [4], wherein the copolymer chain is a random copolymer chain.

[0018] [6] The composition according to any one of [1] to [5], wherein the hollow particles comprise: a first hollow particle that is a thermally expandable hollow particle; and a second hollow particle that is a hollow particle other than the first hollow particle.

[0019] [7] A sheet comprising a cured product of any one of the compositions described in [1] to [6].

[0020] Invention Effects

[0021] According to the present invention, it is possible to provide a composition suitable for thermal insulation materials with low elasticity and excellent elongation, as well as a sheet containing the cured product thereof. Detailed Implementation

[0022] The embodiments of the present invention will now be described in detail. However, the present invention is not limited to these embodiments.

[0023] In this specification, "(meth)acryloyl" refers to "acryloyl" and its corresponding "methacryloyl", and the same applies to similar terms such as "(meth)acrylate" and "(meth)acrylic acid".

[0024] The weight-average molecular weight (Mw) in this specification refers to the value determined using gel permeation chromatography (GPC) under the following conditions, with polystyrene as the standard.

[0025] • Measuring equipment: HLC-8320GPC (product name, manufactured by TOSOH CORPORATION)

[0026] • Analytical column: TSKgel SuperMultipore HZ-H (3-connection) (Product name, manufactured by TOSOHCORPORATION)

[0027] • Protective tubing: TSKguardcolumn SuperMP(HZ)-H (product name, manufactured by TOSOH CORPORATION)

[0028] • Elution buffer: THF

[0029] • Measurement temperature: 25℃

[0030] [Composition]

[0031] One embodiment of the composition includes: a compound represented by the following formula (1); and hollow particles.

[0032]

[0033] In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This indicates a divalent group having a polyoxyalkylene chain.

[0034] (The compound represented by formula (1))

[0035] In one embodiment, by having the composition containing the compound represented by the above formula (1), the cured composition has low elasticity and excellent elongation, which can improve the conformability of the adhered object.

[0036] In one embodiment, R 11 and R 12 One of them can be a hydrogen atom, and the other can be a methyl group. In another embodiment, R 11 and R 12 These two can be hydrogen atoms; in another embodiment, R 11 and R 12 Both of these can be methyl groups.

[0037] In one embodiment, the polyoxyalkylene chain comprises the structural unit represented by the following formula (2). This allows for the improvement of the strength of the cured product while suppressing excessive increase in the viscosity of the composition.

[0038]

[0039] At this time, R 13 It can be a divalent group having a polyoxyethylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formula (1-2) (polyethylene glycol di(meth)acrylate).

[0040]

[0041] In equation (1-2), R 11 and R 12 The meaning of R in equation (1) 11 and R 12 The meanings are the same, and m is an integer greater than 2.

[0042] In another embodiment, the polyoxyalkylene chain comprises the structural unit represented by the following formula (3). This allows for easy processing of the composition.

[0043]

[0044] At this time, R 13 It can be a divalent group having a polyoxypropylene chain, and the compound represented by formula (1) is preferably a compound represented by the following formulas (1-3) (polypropylene glycol di(meth)acrylate).

[0045]

[0046] In equation (1-3), R 11 and R 12 The meaning of R in equation (1) 11 and R 12 The meanings are the same, and n is an integer greater than or equal to 2.

[0047] In another embodiment, from the viewpoint of easily balancing the strength of the cured product of the compound represented by formula (1) and the processability of the composition, the polyoxyalkylene chain is preferably a copolymer chain comprising the structural units represented by formula (2) and formula (3) above. The copolymer chain can be any of an alternating copolymer chain, a block copolymer chain, or a random copolymer chain. From the viewpoint of further reducing the crystallinity of the compound represented by formula (1) and making the composition easier to process, the copolymer chain is preferably a random copolymer chain.

[0048] In the above embodiments, in addition to the structural units represented by formula (2) and formula (3), the polyoxyalkylene chain may also have oxyalkylene groups with 4 to 5 carbon atoms, such as oxymethylene, oxybutylene, and oxypentylene, as structural units.

[0049] R 13 It can be a divalent group that has other organic groups besides the polyoxyalkylene chain mentioned above. Other organic groups can be chain-like groups other than the polyoxyalkylene chain, such as methylene chains (chains with -CH2- as structural units), polyester chains (chains containing -COO- in structural units), polyurethane chains (chains containing -OCON- in structural units), etc.

[0050] For example, the compound represented by formula (1) can be the compound represented by the following formulas (1-4).

[0051]

[0052] In equation (1-4), R 11 and R 12 The meaning of R in equation (1) 11and R 12 The meanings are the same, R 14 and R 15 Each of the following is an alkylene group having 2 to 5 carbon atoms, and k1, k2, and k3 are each an integer greater than or equal to 2. For example, k2 can be an integer less than or equal to 16.

[0053] Multiple R 14 and R 15 Each can be the same as the others, or they can be different from each other. Multiple Rs 14 and R 15 Preferably, it contains ethylene and propylene groups respectively. That is, (R 14 O) k1 The polyoxyalkylene chain and (R) are represented 15 O) k3 The polyoxyalkylene chains represented are preferably vinyl oxide (the structural unit represented by formula (2) above) and copolymer chains containing propylene oxide (the structural unit represented by formula (3) above).

[0054] In the above embodiments, the number of oxyalkylene groups in the polyoxyalkylene chain is preferably 100 or more. If the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more, the main chain of the compound represented by formula (1) becomes longer, the elongation of the cured product is better, and the strength of the cured product can also be improved. The number of oxyalkylene groups corresponds to m in formula (1-2), n in formula (1-3), and k1 and k3 in formula (1-4), respectively.

[0055] The number of alkylene groups in the polyoxyalkylene chain is more preferably 130 or more, 180 or more, 200 or more, 220 or more, 250 or more, 270 or more, 300 or more, or 320 or more. The number of alkylene groups in the polyoxyalkylene chain can be less than 600, less than 570, or less than 530.

[0056] From the viewpoint of achieving lower elasticity and better elongation of the cured product, the weight-average molecular weight of the compound represented by formula (1) is preferably 5000 or more, 6000 or more, 7000 or more, 8000 or more, 9000 or more, 10000 or more, 11000 or more, 12000 or more, 13000 or more, 14000 or more, or 15000 or more. From the viewpoint of easily adjusting the viscosity of the composition, the weight-average molecular weight of the compound represented by formula (1) is preferably 100000 or less, 80000 or less, 60000 or less, 34000 or less, 31000 or less, or 28000 or less.

[0057] The compound represented by formula (1) can be in liquid form at 25°C. From the viewpoint of facilitating coating application and improving the adhesion of the cured material to the coating surface, the viscosity of the compound represented by formula (1) at 25°C is preferably 1000 Pa·s or less, 800 Pa·s or less, 600 Pa·s or less, 500 Pa·s or less, 350 Pa·s or less, 300 Pa·s or less, or 200 Pa·s or less. The viscosity of the compound represented by formula (1) at 25°C can be 0.1 Pa·s or more, 0.2 Pa·s or more, 0.3 Pa·s or more, 1 Pa·s or more, 2 Pa·s or more, or 3 Pa·s or more.

[0058] The compound represented by formula (1) can be in a solid state at 25°C. From the viewpoint of further improving the operability of the composition, the compound represented by formula (1) is preferably in a liquid state at 50°C. Furthermore, from the viewpoint of further improving the operability of the composition, the viscosity of the compound represented by formula (1) at 50°C is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, even more preferably 30 Pa·s or less, and particularly preferably 20 Pa·s or less. The viscosity of the compound represented by formula (1) at 50°C can be 0.1 Pa·s or more, 0.2 Pa·s or more, or 0.3 Pa·s or more.

[0059] Viscosity refers to the value measured according to JIS Z 8803, specifically, the value measured by an E-type viscometer (e.g., TOKISANGYO CO.,LTD., PE-80L). Furthermore, the viscometer can be calibrated according to JIS Z 8809-JS14000. The viscosity of the compound represented by equation (1) can be adjusted by adjusting the weight-average molecular weight of the compound.

[0060] From the viewpoint that the cured product has lower elasticity and excellent elongation, the content of the compound represented by formula (1) is preferably 10% by mass or more, 20% by mass or more, 30% by mass or more, or 40% by mass or more, based on the total mass of the composition. The content of the compound represented by formula (1) can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total mass of the composition.

[0061] The composition may further contain other polymeric compounds besides the compound represented by formula (1) (details to be described later). In this case, from the viewpoint of lower elasticity and better elongation of the cured product, the content of the compound represented by formula (1) is preferably 20 parts by mass or more, 30 parts by mass or more, or 40 parts by mass or more, relative to 100 parts by mass of the total of the compound represented by formula (1) and other polymeric compounds (hereinafter referred to as "total content of polymeric components"). The content of the compound represented by formula (1) relative to 100 parts by mass of the total polymeric components may be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less.

[0062] (Hollow particles)

[0063] Hollow particles have an outer shell and a hollow portion. By containing hollow particles, the thermal insulation properties of the composition can be improved, and the composition can be suitably used as a thermal insulation material. Examples of hollow particles include: a first hollow particle, which is a thermally expanding hollow particle; and a second hollow particle, which is a hollow particle other than the first hollow particle. The hollow particles may include either the first hollow particle or the second hollow particle, or both, preferably both the first hollow particle and the second hollow particle.

[0064] (First hollow particle)

[0065] The first hollow particle is a thermally expandable hollow particle. In this specification, thermally expandable hollow particles refer to hollow particles with a maximum volume ratio of 10 times or more relative to their volume at 25°C. When using the first hollow particle, during the reflow process, the first hollow particle expands due to heat, thereby reducing the bonding area at the interface between the insulation material and the device, allowing for easy removal of the composition after the reflow process.

[0066] The maximum volume ratio of the first hollow particle is determined by thermomechanical analysis (TMA) as the ratio of the maximum volume of the first hollow particle when heated at a rate of 10°C / min to its volume at 25°C (maximum volume / volume at 25°C). The maximum volume ratio of the first hollow particle can be, for example, more than 10 times, more than 20 times, more than 30 times, or more than 40 times, or less than 120 times.

[0067] The outer shell of the first hollow particle is preferably made of a thermoplastic polymer. In this case, because the outer shell softens upon heating, the hollow particle is less prone to rupture and expands easily even if the internal pressure increases due to the vaporization of the liquid contained within the hollow portion. The thermoplastic polymer can be, for example, a polymer containing acrylonitrile, vinylidene chloride, or similar monomer units. The thickness of the outer shell can be 2 μm or more, or 15 μm or less.

[0068] The hollow portion of the first hollow particle contains, for example, a liquid. The first hollow particle is in this state at normal temperature and pressure (e.g., at least atmospheric pressure and 30°C). The liquid is appropriately selected, for example, based on the heating temperature in the reflux process. The liquid is, for example, a liquid that vaporizes at a temperature below the highest heating temperature in the reflux process. The liquid may, for example, be a hydrocarbon with a boiling point (at atmospheric pressure) of 50°C or higher, 100°C or higher, 150°C or higher, or 200°C or higher. In addition to the aforementioned liquid, the hollow portion of the first hollow particle may also contain a gas.

[0069] Examples of components contained within the hollow portion of the first hollow particle include hydrocarbons such as propane, propylene, butene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, heptane, isooctane, n-octane, isoalkanes (carbon number: 10-13), and petroleum ether; low-boiling-point compounds such as methane halides and tetraalkylsilanes; and compounds that are vaporized through thermal decomposition, such as azodicarbonamide.

[0070] The average particle size of the first hollow particle can be greater than 5 μm, greater than 10 μm, or greater than 20 μm, or less than 50 μm, less than 40 μm, or less than 30 μm. The average particle size of the first hollow particle is determined by laser diffraction / scattering (e.g., using a Shimadzu Corporation "SALD-7500na no".)

[0071] From the viewpoint that the composition is more suitable as an insulation material in the reflux process (typically heated to 260°C), the expansion initiation temperature of the first hollow particle is preferably 70°C or higher, 100°C or higher, 130°C or higher, or 160°C or higher, and preferably 260°C or lower. The expansion initiation temperature of the first hollow particle refers to the temperature at the intersection of the tangent line to the curve of temperature (horizontal axis) versus volume change (vertical axis) when the temperature is increased at a heating rate of 10°C / min by thermomechanical analysis (TMA) and the straight line (horizontal axis) where the volume change is zero (initial volume).

[0072] From the viewpoint of better using the composition as an insulation material in the reflow process, the maximum expansion temperature of the first hollow particles is preferably 100°C or higher, 150°C or higher, 200°C or higher, or 220°C or higher, and preferably 290°C or lower, 280°C or lower, or 270°C or lower. The maximum expansion temperature of the first hollow particles refers to the temperature at which the volume expansion ratio reaches its maximum when measured by thermomechanical analysis (TMA) at a heating rate of 10°C / minute.

[0073] From the viewpoint of making the removal after the reflow process of the composition easier, the content of the first hollow particles is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 8% by mass or more, and may also be 20% by mass or less, or 15% by mass or less, based on the total mass of the composition.

[0074] From the viewpoint of making the removal after the reflow process of the composition easier, the content of the first hollow particles is preferably 1% by volume or more, more preferably 2% by volume or more, further preferably 3% by volume or more, especially preferably 4% by volume or more, and for example, it can be 10% by volume or less, 7% by volume or less, or 5% by volume or less.

[0075] (Second hollow particle)

[0076] The second hollow particle is a hollow particle other than the first hollow particle. That is, the second hollow particle is a hollow particle whose maximum volume expansion ratio relative to 25°C is less than 10 times. By using the second hollow particle, the thermal insulation properties of the composition are improved, and the composition can be suitably used as a thermal insulation material. The maximum volume expansion ratio of the second hollow particle is determined by the same method as that of the first hollow particle.

[0077] The outer shell of the second hollow particle can be made of a polymer or an inorganic material. Preferably, the outer shell is made of a polymer, more preferably of a thermoplastic polymer. In this case, the hollow particle is less prone to rupture even under pressure, maintains its hollow structure, and retains its thermal insulation properties. Thermoplastic polymers can be, for example, polymers containing acrylonitrile, vinylidene chloride, etc., as monomer units. Inorganic materials can be, for example, borosilicate glass (sodium borosilicate glass, etc.), aluminosilicate glass, or glass formed by combining these materials. The thickness of the outer shell can be 0.005 μm or more, or 15 μm or less.

[0078] The hollow portion of the second hollow particle may contain, for example, a gas. The second hollow particle exists in this state at normal temperature and pressure (e.g., at least atmospheric pressure and 30°C). In addition to gas, the hollow portion of the second hollow particle may also contain a liquid.

[0079] Examples of components contained within the hollow portion of the second hollow particle include hydrocarbons such as propane, propylene, butene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, heptane, isooctane, n-octane, isoalkanes (carbon number: 10-13), and petroleum ether; low-boiling-point compounds such as methane halides and tetraalkylsilanes; and decomposition products of compounds that vaporize through thermal decomposition, such as azodicarbonamide. Furthermore, the component contained within the hollow portion of the second hollow particle can also be air.

[0080] From the viewpoint of improving thermal insulation, the average particle size of the second hollow particles is preferably 150 μm or less, more preferably 120 μm or less, and even more preferably 100 μm or less, and can be, for example, 5 μm or more, 10 μm or more, 20 μm or more, or 30 μm or more. The average particle size of the second hollow particles is determined by laser diffraction / scattering (for example, using a Shimadzu Corporation "SALD-7500nano").

[0081] The density of the second hollow particle can be 500 kg / m³. 3 Below, 300kg / m 3 Below, 100kg / m 3 Below, 50kg / m 3 Below, or 40kg / m 3 The following can also be 10kg / m 3 Above, or 20kg / m 3 That's all. The density of the second hollow particle in this instruction manual refers to the density determined by the tap density method. That is, the second hollow particle (about 5g) is added to a 10mL graduated cylinder, tapped 50 times, and the volume at which the top stabilizes is taken as the stable volume. The density is then calculated using the following formula.

[0082] Density = Initial input (kg) / Steady volume (m³) 3 )

[0083] From the viewpoint of improving the thermal insulation of the composition, the content of the second hollow particles is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, and for example, it can be 20% by mass or less, based on the total mass of the composition.

[0084] From the viewpoint of improving the thermal insulation of the composition, the content of the second hollow particles is preferably 50% by volume or more, more preferably 60% by volume or more, and for example, 95% by volume or less, based on the total volume of the composition.

[0085] The total content of hollow particles (including the content of the first hollow particle and the second hollow particle) can be, for example, more than 5% by mass, more than 10% by mass, or more than 15% by mass, or less than 40% by mass, less than 30% by mass, or less than 20% by mass.

[0086] Based on the total mass of the composition, the total content of hollow particles (including the content of the first hollow particle and the second hollow particle) can be, for example, 50% or more by volume, 60% or more by volume, or 70% or more by volume, or less than 95% by volume.

[0087] The composition may further contain other polymerizable compounds that can copolymerize with the compound represented by the above formula (1) for the purpose of adjusting the physical properties of the composition.

[0088] Other polymerizable compounds may be, for example, compounds having a (meth)acrylyl group. This compound may be, for example, an alkyl (meth)acrylate. Other polymerizable compounds may be compounds having, in addition to a (meth)acrylyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a heterocyclic group, an alkoxy group, a phenoxy group, a silyl group, a siloxane group, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. In particular, by including an alkyl (meth)acrylate in the composition, the viscosity of the composition can be adjusted. Furthermore, by including a compound having a hydroxyl, carboxyl, amino, or epoxy group in addition to a (meth)acrylyl group in the composition, the adhesion between the composition and the insulation material and the component can be further improved.

[0089] The alkyl group (the alkyl portion other than the (meth)acryloyl group) in alkyl (meth)acrylates can be linear, branched, or alicyclic. The number of carbon atoms in the alkyl group can be, for example, 1 to 30. The number of carbon atoms in the alkyl group can be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0090] Examples of alkyl methacrylates having straight-chain alkyl groups include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, n-hexyl methacrylate, n-heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, or undecyl methacrylate, etc., which have straight-chain alkyl groups with 1 to 11 carbon atoms; dodecyl methacrylate (laurate methacrylate); tetradecyl methacrylate; hexadecyl methacrylate (cetyl methacrylate); octadecyl methacrylate (stearyl methacrylate); behenyl methacrylate; tetradecyl methacrylate; hexadecyl methacrylate; octadecyl methacrylate, etc., which have straight-chain alkyl groups with 12 to 30 carbon atoms.

[0091] Examples of alkyl (meth)acrylates having branched alkyl groups include: butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, and isodecanyl (meth)acrylate, etc., having 1 to 1 carbon atom. Alkyl methacrylates with branched alkyl groups having 12 to 30 carbon atoms, such as isomyrmine methacrylate, 2-propylheptyl methacrylate, isoundecyl methacrylate, isododecyl methacrylate, isotridecyl methacrylate, isopentadecanyl methacrylate, isohexadecyl methacrylate, isoheptadecyl methacrylate, isostearyl methacrylate, and decyltetradecyl methacrylate.

[0092] Examples of alkyl (meth)acrylates having an alicyclic alkyl (cycloalkyl) form include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isocamphenyl (meth)acrylate, terpene (meth)acrylate, and dicyclopentyl (meth)acrylate.

[0093] Examples of compounds containing (meth)acryloyl and aromatic hydrocarbon groups include benzyl (meth)acrylate.

[0094] Examples of compounds having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, polybutylene glycol (meth)acrylate, and methoxy polybutylene glycol (meth)acrylate.

[0095] Examples of compounds having a (meth)acryloyl group and heterocyclic groups include tetrahydrofurfuryl methacrylate.

[0096] Examples of compounds containing (meth)acryloyl and alkoxy groups include 2-methoxyethyl acrylate.

[0097] Examples of compounds having (meth)acryloyl and phenoxy groups include (meth)acrylate phenoxyethyl ester.

[0098] Examples of compounds having a (meth)acryloyl group and a silyl group include 3-acryloyloxypropyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, and 10-acryloyloxydecyltriethoxysilane.

[0099] Examples of compounds having a (meth)acryloyl group and a group containing a siloxane bond include siloxane (meth)acrylates.

[0100] Examples of compounds having a (meth)acryloyl group and a halogen atom include trifluoromethyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 1,1,1,3,3,3-hexafluoro-2-propyl (meth)acrylate, perfluoroethyl methyl (meth)acrylate, perfluoropropyl methyl (meth)acrylate, perfluorobutyl methyl (meth)acrylate, perfluoropentyl methyl (meth)acrylate, perfluorohexyl methyl (meth)acrylate, perfluoroheptyl methyl (meth)acrylate, perfluorooctyl methyl (meth)acrylate, perfluorononyl methyl (meth)acrylate, perfluorodecyl methyl (meth)acrylate, perfluoroundecyl methyl (meth)acrylate, perfluorododecyl methyl (meth)acrylate, and so on. Perfluorotridecyl methyl acrylate, perfluorotetradecyl methyl acrylate, 2-(trifluoromethyl)ethyl acrylate, 2-(perfluoroethyl)ethyl acrylate, 2-(perfluoropropyl)ethyl acrylate, 2-(perfluorobutyl)ethyl acrylate, 2-(perfluoropentyl)ethyl acrylate, 2-(perfluorohexyl)ethyl acrylate, 2-(perfluoroheptyl)ethyl acrylate, 2-(perfluorooctyl)ethyl acrylate, 2-(perfluorononyl)ethyl acrylate, 2-(perfluorotridecyl)ethyl acrylate, 2-(perfluorotetradecyl)ethyl acrylate, and other (meth)acrylates containing fluorine atoms, etc.

[0101] Examples of compounds having (meth)acryloyl and hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylaurate (meth)acrylate, and other hydroxyalkyl (meth)acrylate esters; and methyl (4-hydroxymethylcyclohexyl)acrylate and other hydroxyalkyl cycloalkyl (meth)acrylate esters.

[0102] Examples of compounds having (meth)acryloyl and carboxyl groups include (meth)acrylic acid, carboxyethyl (meth)acrylic acid, carboxypentyl (meth)acrylic acid, monohydroxyethyl phthalate (e.g., "ARONIX M5400" manufactured by TOAGOSEI CO.,LTD.), and 2-acryloyloxyethyl succinate (e.g., "NK ESTER A-SA" manufactured by SHIN-NAKAMURA CHEMICALCO,LTD.).

[0103] Examples of compounds having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminopropyl methacrylate, and N,N-diethylaminopropyl methacrylate.

[0104] Examples of compounds having (meth)acryloyl and epoxy groups include glycidyl (meth)acrylate, α-ethyl glycidyl (meth)acrylate, α-n-propyl glycidyl (meth)acrylate, α-n-butyl glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 4,5-epoxypentyl (meth)acrylate, 6,7-epoxyheptyl (meth)acrylate, α-ethyl(meth)acrylate-6,7-epoxyheptyl (meth)acrylate, 3-methyl-3,4-epoxybutyl (meth)acrylate, 4-methyl-4,5-epoxypentyl (meth)acrylate, 5-methyl-5,6-epoxyhexyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, and α-ethyl(meth)acrylate-β-methyl glycidyl (meth)acrylate.

[0105] The composition is a polymeric compound, and in addition to the compound represented by formula (1), it may contain one or more of the other polymeric compounds mentioned above.

[0106] Based on the total amount of the composition, the content of other polymeric compounds besides the compound represented by formula (1) may be, for example, more than 1% by mass, more than 5% by mass, more than 10% by mass, more than 20% by mass, or more than 30% by mass, or less than 60% by mass, less than 50% by mass, or less than 40% by mass.

[0107] Based on the total amount of the composition, the content of the polymeric compound (the total content of the compound represented by formula (1) and other polymeric compounds) can be, for example, 40% or more by mass, 50% or more by mass, 60% or more by mass, or 70% or more by mass, or 95% or less by mass, or 90% or less by mass.

[0108] The composition may also contain a polymerization initiator. The polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals through heat, or a photopolymerization initiator that generates free radicals through light. A thermal polymerization initiator is preferred.

[0109] When the composition contains a thermal polymerization initiator, a cured product of the composition can be obtained by heating the composition. In this case, the composition can be a composition that is cured by heating at a temperature preferably 105°C or higher, more preferably 110°C or higher, and even more preferably 115°C or higher, and for example, a composition that is cured by heating at a temperature below 200°C, below 190°C, or below 180°C. The heating time when heating the composition can be appropriately selected according to the composition to ensure proper curing of the composition.

[0110] Examples of thermal polymerization initiators include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylpentanonitrile, azobiscyclohexanone-1-nitrile, azobisbenzoyl, and other azo compounds; benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, di-tert-butyl peroxide hexahydroterephthalate, tert-butyl peroxide-2-ethylhexanoate, 1,1-tert-butyl peroxide-3,3,5-trimethylcyclohexane, and tert-butyl peroxyisopropyl carbonate, among other organic peroxides. One or more of these initiators can be used alone or in combination.

[0111] When the composition contains a photopolymerization initiator, a cured product of the composition can be obtained, for example, by irradiating the composition with light (e.g., light containing at least a portion of the wavelengths in the range of 200 to 400 nm (ultraviolet light)). The light irradiation conditions can be appropriately set depending on the type of photopolymerization initiator.

[0112] Photopolymerization initiators can be, for example, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-keto alcohol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, photoactive oxime-based photopolymerization initiators, benzoin-based photopolymerization initiators, benzoinyl-based photopolymerization initiators, diphenyl ketone-based photopolymerization initiators, ketal-based photopolymerization initiators, thioxanone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, etc.

[0113] Examples of benzoin ether-based photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (e.g., "Irgacure 651" manufactured by BASF), and anethole methyl ether. Examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone (e.g., BASF's "Irgacure 184"), 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-prop-1-one (e.g., BASF's "Irgacure 2959"), 2-hydroxy-2-methyl-1-phenyl-prop-1-one (e.g., BASF's "Irgacure 1173"), and methoxyacetophenone.

[0114] Examples of α-ketool-based photopolymerization initiators include 2-methyl-2-hydroxyacetophenone and 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylprop-1-one. Examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride. Examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

[0115] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzoyl-based photopolymerization initiators include benzoyl. Examples of diphenyl ketone-based photopolymerization initiators include diphenyl ketone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, polyvinyl diphenyl ketone, and α-hydroxycyclohexylphenyl ketone. Examples of ketal-based photopolymerization initiators include benzoyl dimethyl ketal. Examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and dodecylthioxanthone.

[0116] Examples of acylphosphine-based photopolymerization initiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1-methylprop-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-tert-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octylphosphine oxide, and bis(2-methoxybenzoyl)... (2-Methylprop-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylprop-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylprop-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentoxy)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzoinophosphine oxide, bis(2,6-dimethoxybenzoyl)-2-benzylphosphine oxide 2,6-Dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzoylazoline butylphosphine oxide, 2,6-dimethoxybenzoylbenzoylazoline octylphosphine oxide, 2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, 2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, 2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, 2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, 2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, 2,4,6-dimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, 2,4,6-dimethylbenzoyl)-2,5-diethyl ...5-diethylphenylphosphine oxide, 2,4,6-dimethylbenzoyl)-2,5-diethylphenylphosphine oxide, 2,4,6-dimethylbenzoyl)-2,5-diethylphenylphosphine oxide, 2,4,6-dimethylbenzoyl)-2,5-diethylphenylphosphine oxide (-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4,6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1,10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tris(2-methylbenzoyl)phosphine oxide, etc.

[0117] The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

[0118] From the viewpoint of appropriately promoting polymerization, the content of the polymerization initiator relative to 100 parts by mass of the total content of the polymerizable components is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and even more preferably 0.05 parts by mass or more. From the viewpoint of ensuring that the molecular weight of the polymer in the cured composition is within an appropriate range and suppressing decomposition products, the content of the polymerization initiator relative to 100 parts by mass of the total content of the polymerizable components is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less.

[0119] The composition may contain a plasticizer as an additive. The presence of a plasticizer in the composition can further improve the adhesion and elongation of the cured product. Examples of plasticizers include butadiene rubber, isoprene rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, nitrile rubber, butyl rubber, ethylene propylene rubber, polyurethane rubber, acrylic resin, rosin-based resin, terpene-based resin, and other tackifiers, or polyalkylene glycols. The content of the plasticizer relative to 100 parts by weight of the total polymerizable components can be 0.1 parts by weight or more, 1 part by weight or more, or 3 parts by weight or more, or 20 parts by weight or less, 15 parts by weight or less, 12 parts by weight or less, or 10 parts by weight or less.

[0120] The composition may further contain other additives as needed. Examples of other additives include, for instance, antioxidants, surface treatment agents (e.g., silane coupling agents), dispersants, curing accelerators, colorants, nucleating agents, heat stabilizers, foaming agents, flame retardants, damping agents, dehydrating agents, and flame retardant auxiliaries (e.g., metal oxides). The content of other additives may be 0.1% by mass or more, or 30% by mass or less, based on the total amount of the composition.

[0121] The composition is preferably in a liquid state at 25°C. This allows for good coating onto the surface of objects such as non-volatile semiconductor memory devices and improves adhesion to the coated surface. The composition can also be in a solid state at 25°C, but it is preferable to become liquid upon heating (e.g., above 50°C). The composition can be cured after being coated in a liquid state, thereby suppressing dripping and pumping out of the thermal insulation material precursor.

[0122] [Composition Set]

[0123] The above composition can be in the form of a multi-liquid composition (composition kit). One embodiment of the composition kit includes a first liquid containing an oxidizing agent and a second liquid containing a reducing agent. At least one of the first and second liquids contains a compound represented by formula (1) above. Furthermore, at least one of the first and second liquids contains the aforementioned hollow particles. By mixing the first and second liquids, the oxidizing agent and reducing agent react to generate free radicals, thereby polymerizing the polymerizable components. According to the composition kit of this embodiment, by mixing the first and second liquids, a cured mixture of the first and second liquids can be obtained immediately. That is, according to the composition kit, a cured composition can be obtained rapidly.

[0124] In the composition kit, the first liquid preferably contains an oxidizing agent, a polymeric compound represented by formula (1), and hollow particles, and the second liquid preferably contains a reducing agent, a polymeric compound represented by formula (1), and hollow particles.

[0125] The content of the compound represented by formula (1) based on the total amount of liquids constituting the composition kit (e.g., the combined amount of the first and second liquids in a two-liquid composition kit) can be in the same range as the content of the compound represented by formula (1) based on the total amount of the composition. The content of hollow particles contained in the composition kit is also the same.

[0126] The oxidant in the first solution acts as a polymerization initiator (free radical polymerization initiator). The oxidant can be, for example, an organic peroxide or an azo compound. Examples of organic peroxides include hydrogen peroxide, dicarbonate peroxide, ester peroxide, ketal peroxide, dialkyl peroxide, and acyl peroxide. Examples of azo compounds include AIBN (2,2'-azobisisobutyronitrile) and V-65 (azobisdimethylpentanonitrile). One oxidant can be used alone or in combination of two or more.

[0127] Examples of hydrogen peroxide include diisopropylbenzene hydrogen peroxide and isopropylbenzene hydrogen peroxide.

[0128] Examples of peroxide dicarbonates include di-n-propyl peroxide dicarbonate, diisopropyl peroxide dicarbonate, bis(4-tert-butylcyclohexyl) peroxide dicarbonate, di-2-ethoxymethoxy peroxide dicarbonate, di(2-ethylhexyl peroxide) dicarbonate, dimethoxybutyl peroxide dicarbonate, and di(3-methyl-3-methoxybutyl peroxide) dicarbonate.

[0129] Examples of peroxide esters include isopropylphenyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypentaenoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexyl peroxide)hexane, and 1-cyclohexyl-1-methyl ethyl peroxide. 2-Ethylhexanoate peroxide, tert-hexylhexanoate peroxide, tert-butylhexanoate peroxide, tert-butyl isobutyrate peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butylperoxy-3,5,5-trimethylhexanone, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di(m-toluylperoxy)hexane, tert-hexyl peroxide, tert-butyl peroxyacetate, etc.

[0130] Examples of peroxide ketals include 1,1-bis(tert-hexylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxide)cyclohexane, 1,1-bis(tert-butylperoxide)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxide)cyclododecane, and 2,2-bis(tert-butylperoxide)decane.

[0131] Examples of dialkyl peroxides include α,α'-bis(tert-butylperoxide)diisopropylbenzene, diisopropylphenyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and tert-butylisopropylphenyl peroxide.

[0132] Examples of diacyl peroxides include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearyl peroxide, succinyl peroxide, benzoyl peroxide, and benzoyl peroxide.

[0133] From the viewpoint of storage stability, the oxidant is preferably a peroxide, more preferably hydrogen peroxide, and even more preferably isopropylbenzene hydrogen peroxide.

[0134] Based on the total amount of liquid constituting the composition kit, the content of oxidant can be 0.1% by mass or more, 0.5% by mass or more, or 1% by mass or more, or less than 10% by mass, less than 5% by mass or less than 3% by mass.

[0135] The reducing agent contained in the second solution can be, for example, a tertiary amine, a thiourea derivative, or a transition metal salt. Examples of tertiary amines include triethylamine, tripropylamine, tributylamine, and N,N-dimethyl-p-toluidine. Examples of thiourea derivatives include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, and ethylidene thiourea. Examples of transition metal salts include cobalt naphthenate, copper naphthenate, and vanadium acetylacetonate. One reducing agent can be used alone or in combination of two or more.

[0136] From the viewpoint of excellent curing speed, the reducing agent is preferably a thiourea derivative or a transition metal salt. For example, a thiourea derivative can be ethylene thiourea. Similarly, from the same viewpoint, a transition metal salt is preferably vanadium acetylacetonate.

[0137] Based on the total amount of liquid constituting the composition kit, the content of reducing agent can be 0.05% by mass or more, 0.1% by mass or more, or 0.3% by mass or more, and can be less than 5% by mass, less than 3% by mass or less than 1% by mass.

[0138] The composition kit may also contain other polymerizable compounds and additives that can be used in the above-described compositions. These components may be contained in one or both of the first and second liquids, or in a third liquid different from the first and second liquids. The content of these components, based on the total amount of liquids constituting the composition kit, may be in the same range as the content of their components based on the total amount of the above-described compositions.

[0139] [Sheet]

[0140] One embodiment involves a sheet comprising a cured product of the above-described composition or a cured product of a mixture of the compositions.

[0141] The sheet of this embodiment is obtained, for example, by polymerizing the polymerizable components in the above-described composition or composition kit and then curing it.

[0142] There are no particular restrictions on the thickness of the sheet; for example, it can be above 200μm or below 2000μm.

[0143] Example

[0144] The present invention will now be described in more detail with reference to embodiments, but the present invention is not limited to these embodiments.

[0145] The following components were used in the examples and comparative examples.

[0146] (The compound represented by formula (1))

[0147] A: A mixture of compounds represented by formula (1-5) synthesized by the steps shown below (weight average molecular weight: 15000, m1+m2 in formula (1-5) is approximately 252±5, n1+n2 is approximately 63±5 (where m1, m2, n1 and n2 each independently represent integers greater than 2, m1+n1≥100, m2+n2≥100), viscosity at 25°C: 50 Pa·s).

[0148]

[0149] In equation (1-5), -r- represents the symbol for random copolymerization.

[0150] (Compounds having two acryloyl groups but no polyoxyalkylene chains)

[0151] a: Modified epoxy acrylate (Daicel Allnex Co., Ltd. "EBECRYL 3708")

[0152] (First hollow particle)

[0153] B-1: "Matsumoto Microsphere (registered trademark) F-190SSD" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (Average particle size: 10-15μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 155-165℃, maximum expansion temperature: 210-220℃)

[0154] B-2: "Matsumoto Microsphere (registered trademark) F-190D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (Average particle size: 30-40 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 160-170℃, maximum expansion temperature: 210-220℃)

[0155] B-3: "D-210D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (Average particle size: 35-40 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 200-210℃, maximum expansion temperature: 220-230℃)

[0156] B-4: "Matsumoto Microsphere (registered trademark) F-230D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (Average particle size: 20-35 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 180-190℃, maximum expansion temperature: 220-240℃)

[0157] B-5: "Matsumoto Microsphere (registered trademark) F-260D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (Average particle size: 20-35 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 190-200℃, maximum expansion temperature: 250-260℃)

[0158] (Second hollow particle)

[0159] C-1: Japan Fillite Co., Ltd. manufactures "Expancel (registered trademark) 920DE80d30" (average particle size 60-90μm, density 30±3kg / m³). 3 Maximum volume expansion ratio: less than 5 times

[0160] C-2: Hollow glass beads "Q-CEL (registered trademark) 5020" manufactured by Potters-Ballotini Co., Ltd. (particle size 5-110μm, density 200kg / m³). 3 Maximum volume expansion ratio: less than 5 times

[0161] (Other polymeric compounds)

[0162] D-1: Dicyclopentadienyl acrylate (manufactured by Resonac Holdings Corporation, "FANCRY L (registered trademark) FA-513A")

[0163] D-2: 4-Hydroxybutyl acrylate (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)

[0164] (Other ingredients)

[0165] E: Polymerization initiator (NOF CORPORATION. "Perbutyl (registered trademark) О")

[0166] F: Phenolic antioxidant (ADEKA CORPORATION's "ADEKA STAB (registered trademark) AO-80")

[0167] G: Surface Conditioner (BYK Corporation "BYK (Registered Trademark) 350")

[0168] [Synthesis of compounds represented by formulas (1-5)]

[0169] A 500 mL flask, consisting of a stirrer, thermometer, nitrogen inlet tube, outlet tube, and heating mantle, was used as a reactor. 225 g of a diol with a polyoxyalkylene chain (SANYO CHEMICAL INDUSTRIES, LTD., "NEWPOL 75H-90000") and 300 g of toluene were added to the reactor. The mixture was stirred at 45 °C and 250 rpm with nitrogen flowing at 100 mL / min for 30 minutes. The temperature was then lowered to 25 °C, and after cooling, 2.9 g of acryloyl chloride was added dropwise, followed by stirring for 30 minutes. Then, 3.8 g of triethylamine was added dropwise, and the mixture was stirred for 2 hours. The temperature was then raised to 45 °C, and the reaction was carried out for 2 hours. The reaction mixture was filtered to remove solvents, yielding the compound represented by formula (1-5).

[0170] [Preparation of the composition and sheet]

[0171] The components were mixed according to the proportions shown in Table 1 to obtain the composition. Next, two substrates were prepared, with the demolded surface of a PET sheet (manufactured by TOYOBO CO.,LTD., “A31”) facing upwards relative to a glass plate. A 10cm × 15cm × 1.0mm silicone rubber mold was placed on the PET sheet of one substrate, and the composition was filled into the inside of the mold. Then, the demolded surface of the PET sheet of the other substrate was placed on top of the other substrate with the composition side facing it, and the substrate was heated at 135°C for 15 minutes to cure the composition precursor. Thus, sheets (1.0mm thick) of cured compositions of Examples 1-12 and Comparative Example 1 were obtained.

[0172] [Determination of thermal conductivity]

[0173] The prepared sheet was sandwiched between PET sheets and cut into 8cm × 13cm × 1.0mm pieces. It was then held in place with a reference plate and a measuring probe, and its thermal conductivity was measured at 25°C using a rapid thermal conductivity meter (KYOTO ELECTRONICS MANUFACTURING CO.,LTD. "QTM-710", measuring probe PD-11N, thin film measurement mode). The reference was achieved by overlapping two PET sheets (TOYOBO CO.,LTD. "A31") with release treatment, and then holding them together with a reference plate and measuring probe for measurement.

[0174] [Determination of elongation at break and tensile modulus]

[0175] The elongation at break and tensile modulus of elasticity of sheets containing various cured materials at 25°C were determined using a tensile testing machine (Autograph EZ-TEST EZ S, manufactured by Shimadzu Corporation). In the tests, cured materials with a shape of 0.2 mm (film thickness) × 5 mm (width) × 30 mm (length) were measured according to JIS K7161 under conditions of a clamping distance of 20 mm and a tensile speed of 5 mm / min.

[0176] [Determination of adhesive bonding strength]

[0177] Attach the prepared sheet to the glass slide and let it sit for at least 15 minutes, then prepare...

[0178] [1] Room temperature (20-25°C) without heating

[0179] [2] The state after adding oil at 220℃ for 120 seconds and then cooling to room temperature, and

[0180] [3] Heated at 260℃ for 30 seconds and then cooled to room temperature.

[0181] Three types of samples were tested. For each of these samples, the adhesive strength (90° peel, tensile speed: 50 mm / min) was determined using the Shimadzu Corporation's "EZ Tes t EZ-S".

[0182] The results of the physical properties of the sheets in Examples 1-12 and Comparative Example 1 are shown in Table 1. Additionally, in Table 1, an adhesive strength of "≥200" (N / m) indicates that the sheet agglomerated and failed to peel when attempted.

[0183] [Table 1]

[0184]

[0185] As described above, the sheets of Examples 1 to 12 have low elasticity and excellent elongation. Furthermore, it is known that the sheets of Examples 2 to 11 have a large adhesive strength when heated at 220°C for 120 seconds and then cooled to room temperature, thus they can be properly adhered to the device during the reflow process, and have a small adhesive strength when heated at 260°C for 30 seconds and then cooled to room temperature, thus they can be easily removed after the reflow process.

Claims

1. A composition comprising: The compound represented by the following formula (1); and Hollow particles, In equation (1), R 11 and R 12 Each can be used independently to represent a hydrogen atom or a methyl group, R 13 This indicates a divalent group having a polyoxyalkylene chain, wherein the number of oxyalkylene groups in the polyoxyalkylene chain is 100 or more. The hollow particles contain: The first hollow particle, which is a thermally expandable hollow particle, has a maximum volume ratio of more than 10 times its volume at 25°C; and The second hollow particle, which is a hollow particle other than the first hollow particle, has a maximum volume expansion ratio of less than 10 times relative to its volume at 25°C. The expansion start temperature of the first hollow particle is 130℃~260℃, and the maximum expansion temperature is 150℃~290℃.

2. The composition according to claim 1, wherein, The polyoxyalkylene chain contains oxyethylene.

3. The composition according to claim 1, wherein, The polyoxyalkylene chain contains oxypropylidene.

4. The composition according to claim 1, wherein, The polyoxyalkylene chain is a copolymer chain containing oxyethylene and oxypropylene groups.

5. The composition according to claim 4, wherein, The copolymer chain is a random copolymer chain.

6. A sheet comprising a cured product of the composition according to any one of claims 1 to 5.

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