Composition and sheet

Abstract

The invention relates to a composition and a sheet. The composition according to the present invention contains: first hollow particles that are thermally expandable hollow particles; second hollow particles which are hollow particles other than the first hollow particles; and a polymerizable compound.

Description

[0001] The present invention is a divisional application of the invention application with application number 202180085983.1 (international application number PCT / JP2021 / 047085), application date December 20, 2021, and invention name “Composition and sheet”. Technical Field

[0002] The invention relates to a composition and a sheet. Background Art

[0003] Non-volatile memory, which features low power consumption and high-speed read / write, has attracted much attention as a new generation of memory. For example, there are known phase change memory (PCM), magnetoresistive random access memory (MRAM), and resistive random access memory (ReRAM). Non-volatile memory is not heat-resistant, and quality maintenance when exposed to high temperature environment during the reflow process during installation has become an issue.

[0004] To address this problem, for example, Patent Document 1 discloses a nonvolatile semiconductor memory device comprising: an MRAM chip; and a peripheral device that covers a portion or the entirety of the MRAM chip and has a heat-insulating region that prevents thermal fluctuations in magnetization of a memory layer.

[0005] Previous technical literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2014-36192 Summary of the invention

[0008] Technical issues to be solved by the invention

[0009] However, the nonvolatile semiconductor memory device disclosed in Patent Document 1 includes a heat insulating region as one of its components, so after the reflow process, the device also includes the heat insulating region. However, from the perspective of miniaturization of the device and improvement of the degree of freedom in design, it is not preferable to leave the heat insulating material in the device even after the reflow process. Therefore, a heat insulating material that can be easily removed after the reflow process is required.

[0010] Therefore, an object of the present invention is to provide a composition and a sheet suitable for a thermal insulation material which can be suitably attached to a device during a reflow process and can be easily removed from the device after the reflow process.

[0011] Means for solving technical problems

[0012] As a result of intensive research, the present inventors have found that by using both heat-expandable hollow particles and hollow particles other than heat-expandable hollow particles, a composition and sheet suitable for use as a heat insulating material that can be attached to a device during a reflow process and can be easily removed from the device after the reflow process can be obtained. The present invention provides the following [1] to

[10] in several aspects.

[0013] [1] A composition comprising: first hollow particles that are heat-expandable hollow particles; second hollow particles that are hollow particles other than the first hollow particles; and a polymerizable compound.

[0014] [2] The composition according to [1], wherein the expansion start temperature of the first hollow particles is 70° C. or higher.

[0015] [3] The composition according to [1] or [2], wherein the expansion start temperature of the first hollow particles is 260° C. or lower.

[0016] [4] The composition according to any one of [1] to [3], wherein the maximum expansion temperature of the first hollow particles is 100° C. or higher.

[0017] [5] The composition according to any one of [1] to [4], wherein the maximum expansion temperature of the first hollow particles is 290° C. or lower.

[0018] [6] A sheet comprising: first hollow particles which are heat-expandable hollow particles; second hollow particles which are hollow particles other than the first hollow particles; and a matrix polymer.

[0019] [7] The composition according to [6], wherein the expansion start temperature of the first hollow particles is 70° C. or higher.

[0020] [8] The composition according to [6] or [7], wherein the expansion start temperature of the first hollow particles is 260° C. or lower.

[0021] [9] The composition according to any one of [6] to [8], wherein the maximum expansion temperature of the first hollow particles is 100° C. or higher.

[0022]

[10] The composition according to any one of [6] to [9], wherein the maximum expansion temperature of the first hollow particles is 290° C. or lower.

[0023] Effects of the Invention

[0024] According to the present invention, it is possible to provide a composition and a sheet suitable for a thermal insulation material that can be appropriately attached to a device during a reflow process and can be easily removed from the device after the reflow process. DETAILED DESCRIPTION

[0025] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

[0026] The term "(meth)acryloyl" in the present specification refers to "acryloyl" and its corresponding "methacryloyl", and the same also applies to "(meth)acrylate", "(meth)acrylic acid" and the like.

[0027] The weight average molecular weight (Mw) in this specification refers to a value determined by measuring using gel permeation chromatography (GPC) under the following conditions and using polystyrene as a standard substance.

[0028] ·Measurement equipment: HLC-8320GPC (product name, manufactured by TOSOH CORPORATION)

[0029] ·Analysis column: TSKgel SuperMultipore HZ-H (3 connected) (product name, manufactured by TOSOH CORPORATION)

[0030] Guard column: TSK guardcolumn SuperMP (HZ) -H (product name, manufactured by TOSOH CORPORATION)

[0031] Eluent: THF

[0032] ·Measurement temperature: 25℃

[0033] [Composition]

[0034] A composition according to one embodiment includes: first hollow particles that are thermally expandable hollow particles; second hollow particles that are hollow particles other than the first hollow particles; and a polymerizable compound.

[0035] (The first hollow particle)

[0036] The first hollow particle has a shell and a hollow portion. The first hollow particle is a (thermally expansive) hollow particle that expands due to heat. The thermally expansive hollow particles in this specification refer to hollow particles with a maximum volume ratio of 10 times or more relative to the volume at 25°C. When the first hollow particle is used, in the reflow process, the first hollow particle expands due to heat, thereby reducing the bonding area of ​​the interface between the thermal insulation material and the device, and the composition can be easily removed after the reflow process.

[0037] The maximum volume ratio of the first hollow particles is measured by thermomechanical analysis (TMA) as the ratio of the maximum volume of the first hollow particles when the temperature is increased at a temperature increase rate of 10° C. / min to the volume at 25° C. (maximum volume / volume at 25° C.). The maximum volume ratio of the first hollow particles may be, for example, 20 times or more, 30 times or more, or 40 times or more, or 120 times or less.

[0038] The shell of the first hollow particle is preferably composed of a thermoplastic polymer. At this time, since the shell softens due to heating, even if the liquid contained in the hollow portion is gasified and the internal pressure rises, the hollow particle is not easy to break and is easy to expand. The thermoplastic polymer can be, for example, a polymer containing acrylonitrile, vinylidene chloride, etc. as monomer units. The thickness of the shell can be more than 2 μm, or less than 15 μm.

[0039] 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 (for example, at least at atmospheric pressure and 30°C). The liquid is appropriately selected, for example, according to 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 can be, for example, a hydrocarbon having a boiling point (under atmospheric pressure) of 50°C or more, 100°C or more, 150°C or more, or 200°C or more. In addition to the above-mentioned liquid, the hollow portion of the first hollow particle may also contain a gas.

[0040] As the components contained in the hollow part of the first hollow particle, for example, there can be mentioned hydrocarbons such as propane, propylene, butene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, heptane, isooctane, n-octane, isoalkanes (carbon number: 10 to 13), and petroleum ether; low-boiling point compounds such as methane halides and tetraalkylsilanes; and compounds that are gasified by thermal decomposition such as azodicarbonamide.

[0041] The average particle size of the first hollow particles may be 5 μm or more, 10 μm or more, or 20 μm or more, or 50 μm or less, 40 μm or less, or 30 μm or less. The average particle size of the first hollow particles is measured by a laser diffraction / scattering method (for example, using "SALD-7500 nano" manufactured by Shimadzu Corporation).

[0042] From the viewpoint that the composition is more suitably used as an insulating material in a reflow process (generally heated to 260° C.), the expansion start temperature of the first hollow particles is preferably 70° C. or more, 100° C. or more, 130° C. or more, or 160° C. or more, and preferably 260° C. or less. The expansion start temperature of the first hollow particles refers to the temperature of the intersection of the tangent line of the point where a volume change of 3 times or more / 5° C. occurs in a curve of temperature (horizontal axis)-volume change (vertical axis) when the temperature is increased at a heating rate of 10° C. / min by thermomechanical analysis (TMA) and a straight line (horizontal axis) where the volume change is zero (initial volume).

[0043] From the viewpoint of better using the composition as a heat insulating material in the reflow process, the maximum expansion temperature of the first hollow particles is preferably 100° C. or more, 150° C. or more, 200° C. or more, or 220° C. or more, and preferably 290° C. or less, 280° C. or less, or 270° C. or less. The maximum expansion temperature of the first hollow particles refers to the temperature at which the first hollow particles exhibit the above-mentioned maximum volume expansion ratio.

[0044] From the viewpoint of making it easier to remove the composition after the reflow process, the content of the first hollow particles is preferably 1 mass % or more, more preferably 5 mass % or more, further preferably 8 mass % or more, and may also be 20 mass % or less, or 15 mass % or less, based on the total mass of the composition.

[0045] From the viewpoint of making it easier to remove the composition after the reflow process, the content of the first hollow particles is preferably 1 volume % or more, more preferably 2 volume % or more, further preferably 3 volume % or more, and particularly preferably 4 volume % or more, based on the total volume of the composition, and can be, for example, 10 volume % or less, 7 volume % or less, or 5 volume % or less.

[0046] (Second hollow particle)

[0047] The second hollow particle has a shell and a hollow portion. The second hollow particle is a hollow particle other than the first hollow particle. That is, the second hollow particle is a hollow particle with a maximum volume expansion ratio of less than 10 times relative to the volume at 25°C. By using the second hollow particle, the thermal insulation of the composition is improved, and the composition can be suitably used as a thermal insulation material. The maximum volume ratio of the second hollow particle is measured by the same method as the maximum volume ratio of the first hollow particle.

[0048] The shell of the second hollow particle can be made of a polymer or an inorganic material. The shell is preferably made of a polymer, more preferably made of a thermoplastic polymer. At this time, the hollow particle is not easy to break even if pressurized, and the hollow structure is maintained and thermal insulation can be maintained. Thermoplastic polymers can be, for example, polymers containing acrylonitrile, vinylidene chloride, etc. as monomer units. Inorganic materials can be, for example, inorganic glasses such as borosilicate glass (sodium borosilicate glass, etc.), aluminosilicate glass, and glass obtained by compounding them. The thickness of the shell can be more than 0.005 μm, or less than 15 μm.

[0049] The hollow part of the second hollow particle contains, for example, a gas. The second hollow particle is in this state at normal temperature and pressure (for example, at least at atmospheric pressure and 30° C.). The hollow part of the second hollow particle may contain a liquid in addition to a gas.

[0050] As the components contained in the hollow part of the second hollow particle, for example, there can be mentioned hydrocarbons such as propane, propylene, butene, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane, isohexane, heptane, isooctane, n-octane, isoalkanes (carbon number: 10 to 13), petroleum ether, etc.; low boiling point compounds such as methane halides and tetraalkylsilane; decomposition products of compounds gasified by thermal decomposition of azodicarbonamide, etc. In addition, the component contained in the hollow part of the second hollow particle may also be air.

[0051] 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, further preferably 100 μm or less, and for example, can be 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 measured by laser diffraction / scattering method (for example, using "SALD-7500nano" made by Shimadzu Corporation).

[0052] The density of the second hollow particle can be 500 kg / m 3 Below, 300kg / m 3 Below, 100kg / m 3 Below, 50kg / m 3 Below, or 40kg / m 3 Below, can also be 10kg / m 3 Above, or 20kg / m 3 The density of the second hollow particle in this specification refers to the density measured by the tap density method. That is, the second hollow particle (about 5 g) is put into a 10 mL measuring cylinder, tapped 50 times, and the volume at the top when stable is taken as the stable volume, and the density is calculated using the following formula.

[0053] Density = initial input (kg) / volume at stable state (m 3 )

[0054] From the viewpoint of improving the thermal insulation of the composition, the content of the second hollow particles is preferably 1 mass % or more, more preferably 3 mass % or more, further preferably 5 mass % or more, and for example may be 20 mass % or less, based on the total mass of the composition.

[0055] From the viewpoint of improving the thermal insulation properties 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 may be 95% by volume or less, based on the total volume of the composition.

[0056] The total content of the hollow particles (including the content of the first hollow particles and the second hollow particles) may be, for example, 5 mass % or more, 10 mass % or more, or 15 mass % or less, or 40 mass % or less, 30 mass % or less, or 20 mass % or less.

[0057] The total content of the hollow particles (including the content of the first hollow particles and the second hollow particles) based on the total mass of the composition may be, for example, 50% by volume or more, 60% by volume or more, or 70% by volume or more, or 95% by volume or less.

[0058] (Polymerizable compound)

[0059] The polymerizable compound is not particularly limited, and may include, for example, a compound represented by the following formula (1).

[0060]

[0061] In formula (1), R 11 and R 12 Each independently represents a hydrogen atom or a methyl group, R 13 It represents a divalent group having a polyoxyalkylene chain.

[0062] When the polymerizable compound is a compound represented by the above formula (1), the cured product of the composition has low elasticity and excellent elongation, and can improve the followability of the adherend.

[0063] In one embodiment, R 11 and R 12 One of them may be a hydrogen atom and the other may 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.

[0064] In one embodiment, the polyoxyalkylene chain includes a structural unit represented by the following formula (2): This can improve the strength of the cured product while suppressing an excessive increase in the viscosity of the composition.

[0065]

[0066] At this time, R 13 It may be a divalent group having a polyoxyethylene chain, and the compound represented by the formula (1) is preferably a compound represented by the following formula (1-2) (polyethylene glycol di(meth)acrylate).

[0067]

[0068] In formula (1-2), R 11 and R 12 The meaning of is the same as R in formula (1) 11 and R 12 and m is an integer greater than or equal to 2.

[0069] In another embodiment, the polyoxyalkylene chain includes a structural unit represented by the following formula (3).

[0070] Thereby, the composition can be easily handled.

[0071]

[0072] At this time, R 13 It may be a divalent group having a polyoxypropylene chain, and the compound represented by the formula (1) is preferably a compound represented by the following formula (1-3) (polypropylene glycol di(meth)acrylate).

[0073]

[0074] In formula (1-3), R 11 and R 12 The meaning of is the same as R in formula (1) 11 and R 12 , respectively, have the same meanings, and n is an integer greater than or equal to 2.

[0075] In another embodiment, from the viewpoint of easily taking into account the strength of the cured product of the compound represented by formula (1) and the handleability of the composition, the polyoxyalkylene chain is preferably a copolymer chain comprising the structural unit represented by the above-mentioned formula (2) and the structural unit represented by the formula (3). 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 handling of the composition easier, the copolymer chain is preferably a random copolymer chain.

[0076] In each of the above embodiments, the polyoxyalkylene chain may have, as a structural unit, an oxyalkylene group having 4 to 5 carbon atoms such as an oxymethylene group, an oxybutylene group, or an oxypentylene group, in addition to the structural unit represented by formula (2) and the structural unit represented by formula (3).

[0077] R 13 It may be a divalent group having other organic groups in addition to the above-mentioned polyoxyalkylene chain. Other organic groups may be chain groups other than the polyoxyalkylene chain, for example, a methylene chain (a chain with -CH2- as a structural unit), a polyester chain (a chain containing -COO- in a structural unit), a polyurethane chain (a chain containing -OCON- in a structural unit), etc.

[0078] For example, the compound represented by formula (1) may be a compound represented by the following formula (1-4).

[0079]

[0080] In formula (1-4), R 11 and R 12 The meaning of is the same as R in formula (1) 11 and R 12 The meanings are the same, R 14 and R 15 Each of k1, k2 and k3 is independently an alkylene group having 2 to 5 carbon atoms, and each of k1, k2 and k3 is independently an integer greater than 2. For example, k2 may be an integer less than 16.

[0081] Multiple R 14 and R 15 They may be the same as or different from each other. 14 and R 15 Preferably, they contain ethylene and propylene groups, respectively. 14 O) k1 The polyoxyalkylene chain represented by (R 15 O) k3 The polyoxyalkylene chains represented are preferably copolymer chains containing an oxyethylene group (a structural unit represented by the above formula (2)) and an oxypropylene group (a structural unit represented by the above formula (3)).

[0082] In each of 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 more excellent, 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.

[0083] The number of oxyalkylene 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 oxyalkylene groups in the polyoxyalkylene chain may be 600 or less, 570 or less, or 530 or less.

[0084] From the viewpoint of 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 easy adjustment of 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.

[0085] The compound represented by formula (1) may be in liquid form at 25°C. In this case, from the viewpoint of facilitating coating on the coating surface and improving the adhesion of the cured product 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 may 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.

[0086] The compound represented by formula (1) may be solid at 25°C. In this case, from the viewpoint of further improving the operability of the composition, the compound represented by formula (1) is preferably liquid at 50°C. Furthermore, in this case, 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, further 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 may be 0.1 Pa·s or more, 0.2 Pa·s or more, or 0.3 Pa·s or more.

[0087] The viscosity refers to a value measured according to JIS Z 8803, specifically, a value measured by an E-type viscometer (e.g., PE-80L manufactured by TOKISANGYO CO., LTD.). The viscometer can be calibrated according to JIS Z 8809-JS14000. The viscosity of the compound represented by formula (1) can be adjusted by adjusting the weight average molecular weight of the compound.

[0088] From the viewpoint of lower elasticity and better elongation of the cured product, 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. Based on the total mass of the composition, the content of the compound represented by formula (1) may 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.

[0089] The composition may contain only the compound represented by formula (1) as a polymerizable compound. The composition may further contain other polymerizable compounds other than the compound represented by formula (1) (details to be described later). At this time, from the viewpoint that the cured product has lower elasticity and better elongation, 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 polymerizable compounds (hereinafter referred to as "the total content of polymerizable components"). The content of the compound represented by formula (1) can be 80 parts by mass or less, 70 parts by mass or less, or 60 parts by mass or less relative to 100 parts by mass of the total of the polymerizable components.

[0090] The polymerizable compound may contain other polymerizable compounds other than the compound represented by formula (1).

[0091] Other polymerizable compounds may be, for example, compounds having one (meth)acryloyl group. Such compounds may be, for example, alkyl (meth)acrylates. Other polymerizable compounds may be compounds having, in addition to one (meth)acryloyl group, an aromatic hydrocarbon group, a group containing a polyoxyalkylene chain, a group containing a heterocycle, an alkoxy group, a phenoxy group, a group containing a silyl group, a group containing a siloxane bond, a halogen atom, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group. In particular, by making the composition contain alkyl (meth)acrylates, the viscosity of the composition can be adjusted. Furthermore, by making the composition contain compounds having, in addition to the (meth)acryloyl group, a hydroxyl group, a carboxyl group, an amino group, or an epoxy group, the adhesion of the composition and the thermal insulation material to the component can be further improved.

[0092] The alkyl group (alkyl part other than the (meth)acryloyl group) in the alkyl (meth)acrylate may be linear, branched, or alicyclic. The number of carbon atoms in the alkyl group may be, for example, 1 to 30. The number of carbon atoms in the alkyl group may be 1 to 11, 1 to 8, 1 to 6, or 1 to 4, or may be 12 to 30, 12 to 28, 12 to 24, 12 to 22, 12 to 18, or 12 to 14.

[0093] Examples of the alkyl (meth)acrylate having a linear alkyl group include alkyl (meth)acrylate having a linear alkyl group having 1 to 11 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, or undecyl (meth)acrylate, and alkyl (meth)acrylate having a linear alkyl group having 12 to 30 carbon atoms, such as dodecyl (meth)acrylate (lauryl (meth)acrylate), tetradecyl (meth)acrylate, hexadecyl (meth)acrylate (cetyl (meth)acrylate), octadecyl (meth)acrylate (stearyl (meth)acrylate), behenyl (meth)acrylate (behenyl (meth)acrylate), lauryl (meth)acrylate, hexacosyl (meth)acrylate, and octacosyl (meth)acrylate.

[0094] Examples of the alkyl (meth)acrylate having a branched alkyl group include secondary butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, isopentyl (meth)acrylate, isoamyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and the like. 1, isomyristyl (meth)acrylate, 2-propylheptyl (meth)acrylate, isoundecyl (meth)acrylate, isododecyl (meth)acrylate, isotridecyl (meth)acrylate, isopentadecyl (meth)acrylate, isohexadecyl (meth)acrylate, isoheptadecyl (meth)acrylate, isostearyl (meth)acrylate, decyltetradecyl (meth)acrylate, etc.

[0095] Examples of the alkyl (meth)acrylate having an alicyclic alkyl (cycloalkyl) group include cyclohexyl (meth)acrylate, 3,3,5-trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, terpene (meth)acrylate, and dicyclopentanyl (meth)acrylate.

[0096] Examples of the compound having a (meth)acryloyl group and an aromatic hydrocarbon group include benzyl (meth)acrylate and the like.

[0097] Examples of the compound having a (meth)acryloyl group and a group containing a polyoxyalkylene chain include polyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, polybutylene glycol (meth)acrylate, and methoxypolybutylene glycol (meth)acrylate.

[0098] Examples of the compound having a (meth)acryloyl group and a heterocyclic ring-containing group include tetrahydrofurfuryl (meth)acrylate and the like.

[0099] Examples of the compound having a (meth)acryloyl group and an alkoxy group include 2-methoxyethyl acrylate and the like.

[0100] As a compound which has a (meth)acryloyl group and a phenoxy group, phenoxyethyl (meth)acrylate etc. are mentioned.

[0101] Examples of the compound having a (meth)acryloyl group and a silyl group-containing group include 3-acryloxypropyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-acryloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, and 10-acryloxydecyltriethoxysilane.

[0102] As a compound which has a (meth)acryloyl group and a siloxane bond-containing group, siloxane (meth)acrylate etc. are mentioned.

[0103] Examples of the compound 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 perfluorobutyl methyl (meth)acrylate. (Meth)acrylates having fluorine atoms, such as perfluorotridecylmethyl (meth)acrylate, perfluorotetradecylmethyl (meth)acrylate, 2-(trifluoromethyl)ethyl (meth)acrylate, 2-(perfluoroethyl)ethyl (meth)acrylate, 2-(perfluoropropyl)ethyl (meth)acrylate, 2-(perfluorobutyl)ethyl (meth)acrylate, 2-(perfluoropentyl)ethyl (meth)acrylate, 2-(perfluorohexyl)ethyl (meth)acrylate, 2-(perfluoroheptyl)ethyl (meth)acrylate, 2-(perfluorooctyl)ethyl (meth)acrylate, 2-(perfluorononyl)ethyl (meth)acrylate, 2-(perfluorotridecyl)ethyl (meth)acrylate, and 2-(perfluorotetradecyl)ethyl (meth)acrylate.

[0104] Examples of the compound having a (meth)acryloyl group and a hydroxyl group include hydroxyalkyl (meth)acrylates such as 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, and 12-hydroxylauryl (meth)acrylate; and hydroxyalkylcycloalkyl (meth)acrylates such as (4-hydroxymethylcyclohexyl)methyl (meth)acrylate.

[0105] Examples of the compound having a (meth)acryloyl group and a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, monohydroxyethyl acrylate phthalate (e.g., “ARONIX M5400” manufactured by TOAGOSEI CO., LTD.), and 2-acryloyloxyethyl succinate (e.g., “NK ESTER A-SA” manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.).

[0106] Examples of the compound having a (meth)acryloyl group and an amino group include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate.

[0107] Examples of the compound having a (meth)acryloyl group and an epoxy group 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.

[0108] The composition may contain one of the above-mentioned other polymerizable compounds as a polymerizable compound, or may contain two or more of them. Furthermore, the composition may or may not further contain a compound represented by formula (1).

[0109] The content of other polymerizable compounds other than the compound represented by formula (1) can be, for example, 1% by mass or more, 5% by mass or more, 10% by mass or more, 20% by mass or more, or 30% by mass or less, or 60% by mass or less, 50% by mass or less, or 40% by mass or less, based on the total mass of the composition.

[0110] The content of the polymerizable compound (the total content of the compound represented by formula (1) and other polymerizable compounds) based on the total mass of the composition can be, for example, 40 mass % or more, 50 mass % or more, 60 mass % or more, or 70 mass % or less, or 95 mass % or less, or 90 mass % or less.

[0111] The composition may further contain a polymerization initiator. The polymerization initiator may be, for example, a thermal polymerization initiator that generates free radicals by heat, a photopolymerization initiator that generates free radicals by light, etc. The polymerization initiator is preferably a thermal polymerization initiator.

[0112] 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 of preferably 105° C. or higher, more preferably 110° C. or higher, and further preferably 115° C. or higher, and can be, for example, a composition that is cured by heating at a temperature of 200° C. or lower, 190° C. or lower, or 180° C. or lower. The heating time when heating the composition can be appropriately selected according to the composition of the composition so that the composition is appropriately cured.

[0113] Examples of the thermal polymerization initiator include azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile, azobisbenzoyl and other azo compounds, benzoyl peroxide, lauroyl peroxide, di-tert-butyl peroxide, di-tert-hexyl peroxide, di-tert-butyl peroxyhexahydroterephthalate, tert-butyl peroxy-2-ethylhexanoate, 1,1-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl peroxyisopropyl carbonate and other organic peroxides. The thermal polymerization initiator may be used alone or in combination of two or more.

[0114] When the composition contains a photopolymerization initiator, for example, a cured product of the composition can be obtained by irradiating the composition with light (for example, light containing at least a portion of wavelengths in the range of 200 to 400 nm (ultraviolet light)). The conditions for light irradiation can be appropriately set depending on the type of the photopolymerization initiator.

[0115] The photopolymerization initiator may be, for example, a benzoin ether-based photopolymerization initiator, an acetophenone-based photopolymerization initiator, an α-ketol-based photopolymerization initiator, an aromatic sulfonyl chloride-based photopolymerization initiator, a photoactive oxime-based photopolymerization initiator, a benzoin-based photopolymerization initiator, a benzyl-based photopolymerization initiator, a diphenyl ketone-based photopolymerization initiator, a ketal-based photopolymerization initiator, a thioxanthone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and the like.

[0116] Examples of the benzoin ether-based photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, "Irgacure 651" manufactured by BASF), and anisole methyl ether. Examples of the acetophenone-based photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (e.g., “Irgacure 184” manufactured by BASF), 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (e.g., “Irgacure 2959” manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., “Irgacure 1173” manufactured by BASF), and methoxyacetophenone.

[0117] Examples of α-ketol-based photopolymerization initiators include 2-methyl-2-hydroxyacetophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropan-1-one, and the like. Examples of aromatic sulfonyl chloride-based photopolymerization initiators include 2-naphthalenesulfonyl chloride, and the like. Examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime, and the like.

[0118] Examples of benzoin-based photopolymerization initiators include benzoin. Examples of benzyl-based photopolymerization initiators include benzyl. Examples of phenyl ketone-based photopolymerization initiators include phenyl ketone, benzoylbenzoic acid, 3,3'-dimethyl-4-methoxyphenyl ketone, polyvinyl phenyl ketone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of ketal-based photopolymerization initiators include benzyl dimethyl ketal, and the like. 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.

[0119] Examples of the acylphosphine-based photopolymerization initiator 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)-octylphosphine oxide. (2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4-dipentyloxy)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzilphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenyl 2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzilbutylphosphine oxide, 2,6-dimethoxybenzoylbenziloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6 2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine 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, tri(2-methylbenzoyl)phosphine oxide, and the like.

[0120] The above-mentioned photopolymerization initiators can be used alone or in combination of two or more.

[0121] From the viewpoint of appropriately promoting polymerization, the content of the polymerization initiator is preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, and further preferably 0.05 parts by mass or more, relative to 100 parts by mass of the total content of the polymerizable components. From the viewpoint of making the molecular weight of the polymer in the cured product of the composition within an appropriate range and suppressing decomposition products, the content of the polymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, further preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the total content of the polymerizable components.

[0122] The composition can contain a plasticizer as an additive. By containing a plasticizer in the composition, the adhesion of the composition and the elongation of the cured product can be further improved. As the plasticizer, tackifiers such as butadiene rubber, isoprene rubber, silicone rubber, styrene-butadiene rubber, chloroprene rubber, acrylonitrile-butadiene rubber, butyl rubber, ethylene-propylene rubber, polyurethane rubber, acrylic resin, rosin-based resin, terpene-based resin, or polyalkylene glycols can be cited. The content of the plasticizer can be more than 0.1 mass parts, more than 1 mass parts, or more than 3 mass parts relative to the total 100 mass parts of the content of the polymerizable component, or less than 20 mass parts, less than 15 mass parts, less than 12 mass parts, or less than 10 mass parts.

[0123] The composition may further contain other additives as required. As other additives, for example, antioxidants, surface treatment agents (such as silane coupling agents), dispersants, curing accelerators, colorants, crystal nucleating agents, thermal stabilizers, foaming agents, flame retardants, vibration damping agents, dehydrating agents, flame retardant aids (such as metal oxides), etc. can be cited. Based on the total amount of the composition, the content of other additives can be 0.1% by mass or more, and can be 30% by mass or less.

[0124] The composition is preferably liquid at 25°C. Thus, it can be well coated on the surface of an object such as a nonvolatile semiconductor storage device, and the adhesion to the coated surface can also be improved. The composition can be solid at 25°C, and in this case, it is preferably heated (for example, at 50°C or above) to become liquid. The composition can be cured after being coated in a liquid state, thereby suppressing dripping and pumping of the thermal insulation material precursor.

[0125] [Combination set]

[0126] The above-mentioned composition may be in the state of a multi-liquid composition (composition kit). The composition kit involved in one embodiment comprises a composition kit comprising a first liquid containing an oxidant and a second liquid containing a reducing agent. The above-mentioned first hollow particles, second hollow particles and polymerizable compounds are respectively contained in at least one of the first liquid and the second liquid. By mixing the first liquid and the second liquid, the oxidant and the reducing agent react to generate free radicals, and the polymerizable compound is polymerized. According to the composition kit involved in this embodiment, by mixing the first liquid and the second liquid, a solidified product of the mixture of the first liquid and the second liquid can be immediately obtained. That is, according to the composition kit, a solidified product of the composition can be quickly obtained.

[0127] In the composition kit, preferably, the first liquid contains an oxidizing agent, a polymerizable compound, first hollow particles and second hollow particles, and the second liquid contains a reducing agent, a polymerizable compound, first hollow particles and second hollow particles. More preferably, the first liquid contains an oxidizing agent, a polymerizable compound represented by formula (1), first hollow particles and second hollow particles, and the second liquid contains a reducing agent, a polymerizable compound represented by formula (1), first hollow particles and second hollow particles.

[0128] The content of the compound represented by formula (1) based on the total mass of the liquid constituting the composition set (for example, the total mass of the first liquid and the second liquid in the case of a two-liquid composition set) can be the same as the content of the compound represented by formula (1) based on the total mass of the above-mentioned composition. The same also applies to the content of the hollow particles contained in the composition set.

[0129] The oxidant contained in the first liquid plays the role of a polymerization initiator (free radical polymerization initiator). The oxidant may be, for example, an organic peroxide or an azo compound. The organic peroxide may be, for example, hydrogen peroxide, peroxydicarbonate, peroxyester, peroxyketal, dialkyl peroxide, diacyl peroxide, etc. The azo compound may be AIBN (2,2'-azobisisobutyronitrile), V-65 (azobisdimethylvaleronitrile), etc. The oxidant may be used alone or in combination of two or more.

[0130] Examples of hydrogen peroxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

[0131] Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, di(2-ethylhexylperoxy)dicarbonate, dimethoxybutyl peroxydicarbonate, and di(3-methyl-3-methoxybutylperoxy)dicarbonate.

[0132] Examples of the peroxyester include isopropyl peroxyneodecanoate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypentanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethyl peroxyneodecanoate, tert-hexyl peroxyneodecanoate, tert-butyl peroxypentanoate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethyl tert-Butyl peroxy-2-ethylhexanoate, tert-Hexyl peroxy-2-ethylhexanoate, tert-Butyl peroxy-2-ethylhexanoate, tert-Butyl peroxyisobutyrate, 1,1-bis(tert-butylperoxy)cyclohexane, tert-Butyl peroxy-3,5,5-trimethylhexanone, tert-Butyl peroxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, tert-Hexyl peroxybenzoate, tert-Butyl peroxyacetate, etc.

[0133] Examples of the peroxyketal include 1,1-bis(tert-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-hexylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclododecane, and 2,2-bis(tert-butylperoxy)decane.

[0134] Examples of the dialkyl peroxide include α,α′-bis(tert-butylperoxy)diisopropylbenzene, diisopropylphenyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, and tert-butylisopropylphenyl peroxide.

[0135] Examples of the diacyl peroxide include isobutyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinyl peroxide, benzoyl peroxytoluene, and benzoyl peroxide.

[0136] From the viewpoint of storage stability, the oxidizing agent is preferably a peroxide, more preferably hydrogen peroxide, and still more preferably cumene hydroperoxide.

[0137] The content of the oxidant may be 0.1 mass % or more, 0.5 mass % or more, or 10 mass % or less, 5 mass % or less, or 3 mass % or less, based on the total mass of the liquid constituting the composition kit.

[0138] The reducing agent contained in the second liquid may be, for example, a tertiary amine, a thiourea derivative, a transition metal salt, etc. Examples of the tertiary amine include triethylamine, tripropylamine, tributylamine, N,N-dimethyl-p-toluidine, etc. Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea, ethylenethiourea, etc. Examples of the transition metal salt include cobalt naphthenate, copper naphthenate, vanadium acetylacetonate, etc. The reducing agent may be used alone or in combination of two or more.

[0139] From the viewpoint of excellent curing speed, the reducing agent is preferably a thiourea derivative or a transition metal salt. For example, the thiourea derivative may be ethylenethiourea. From the same viewpoint, the transition metal salt is preferably vanadium acetylacetonate.

[0140] The content of the reducing agent may be 0.05 mass % or more, 0.1 mass % or more, or 0.3 mass % or less, or 5 mass % or less, or 3 mass % or less, or 1 mass % or less, based on the total mass of the liquid constituting the composition kit.

[0141] The composition kit may further contain the above-mentioned additives. These components may be contained in one or both of the first liquid and the second liquid, or in a third liquid different from the first liquid and the second liquid. The content of the additives based on the total mass of the liquid constituting the composition kit may be the same as the range of the content of the additives based on the total mass of the above-mentioned composition.

[0142] [Sheet]

[0143] The sheet of the present embodiment contains: first hollow particles that are heat-expandable hollow particles; second hollow particles that are hollow particles other than the first hollow particles; and a matrix polymer.

[0144] The type and content of the first and second hollow particles contained in the sheet can be the same as the type and content of the first and second hollow particles contained in the above-mentioned composition or composition set. In addition, regarding the content, "based on the total mass of the composition" can be replaced by "based on the total mass of the sheet", and "based on the total volume of the composition" can be replaced by "based on the total volume of the sheet".

[0145] The matrix polymer contained in the sheet is a polymer (binder polymer) for holding the matrix (forming a continuous phase) of other materials contained in the sheet. The matrix polymer is a polymer of the polymerizable compound contained in the above-mentioned composition or composition set.

[0146] The content of the matrix polymer based on the total mass of the sheet may be, for example, 40 mass % or more, 50 mass % or more, 60 mass % or more, or 70 mass % or less, or 95 mass % or less, or 90 mass % or less.

[0147] The thickness of the sheet is not particularly limited, and may be, for example, 200 μm or more, or 2000 μm or less.

[0148] The sheet may further contain additives that may be contained in the above-mentioned composition or combination set. In this case, the content of the additives contained in the sheet may be the same as the content of the additives contained in the above-mentioned composition or combination set (the replacement of the content is the same as above).

[0149] The sheet of the present embodiment is obtained, for example, by polymerizing the polymerizable component in the above-mentioned composition or composition set and curing it. That is, the sheet of the present embodiment can also be said to be a sheet of the polymer (cured product) of the above-mentioned composition or composition set.

[0150] Example

[0151] Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0152] In Examples and Comparative Examples, the following components were used.

[0153] (The first hollow particle)

[0154] A-1: "Matsumoto Microsphere (registered trademark) F-190SSD" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size: 10 to 15 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 155 to 165°C, maximum expansion temperature: 210 to 220°C)

[0155] A-2: "Matsumoto Microsphere (registered trademark) F-190D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size: 30 to 40 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 160 to 170°C, maximum expansion temperature: 210 to 220°C)

[0156] A-3: "D-210D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size: 35 to 40 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 200 to 210°C, maximum expansion temperature: 220 to 230°C)

[0157] A-4: "Matsumoto Microsphere (registered trademark) F-230D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size: 20 to 35 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 180 to 190°C, maximum expansion temperature: 220 to 240°C)

[0158] A-5: "Matsumoto Microsphere (registered trademark) F-260D" manufactured by Matsumoto Yushi-Seiyaku Co., Ltd. (average particle size: 20 to 35 μm, maximum volume expansion ratio: 50 times or more, expansion start temperature: 190 to 200°C, maximum expansion temperature: 250 to 260°C)

[0159] (Second hollow particle)

[0160] B: "Expancel (registered trademark) 920DE80d30" manufactured by Japan Fillite Co., Ltd. (average particle size 60 to 90 μm, density 30 ± 3 kg / m 3 , Maximum volume expansion ratio: less than 5 times)

[0161] (Polymerizable compound)

[0162] C-1: A compound represented by the following formula (1-5) synthesized by the steps shown below (weight average molecular weight: 15000, m1+m2 in formula (1-5) is about 252±5, n1+n2 is about 63±5 integers (wherein m1, m2, n1 and n2 are integers greater than 2, m1+n1≥100, m2+n2≥100) mixture, viscosity at 25°C: 50 Pa·s)

[0163]

[0164] In the formula (1-5), -r- represents a symbol for random copolymerization.

[0165] C-2: dicyclopentadienyl acrylate ("FANCRY L (registered trademark) FA-513A" manufactured by Resonac Holdings Corporation)

[0166] C-3: 4-Hydroxybutyl acrylate (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.)

[0167] (Other ingredients)

[0168] D: polymerization initiator ("Perbutyl (registered trademark) O" manufactured by NOF CORPORATION)

[0169] E: Phenolic antioxidant ("ADEKA STAB (registered trademark) AO-80" manufactured by ADEKA CORPORATION)

[0170] F: Surface conditioning agent (BYK (registered trademark) 350 manufactured by BYK)

[0171] [Synthesis of the compound represented by formula (1-5)]

[0172] A 500 mL flask consisting of a stirrer, a thermometer, a nitrogen inlet pipe, a discharge pipe and a heating jacket was used as a reactor. 225 g of a diol having a polyoxyalkylene chain ("NEWPOL 75H-90000" manufactured by SANYO CHEMICAL INDUSTRIES, LTD.) and 300 g of toluene were added to the reactor, stirred at 45°C and a stirring speed of 250 times / min, and nitrogen was flowed at 100 mL / min, and stirred for 30 minutes. Then, the temperature was lowered to 25°C, and after the temperature was lowered, 2.9 g of acryloyl chloride was added dropwise to the reactor and stirred for 30 minutes. Then, 3.8 g of triethylamine was added dropwise and stirred for 2 hours. Then, the temperature was raised to 45°C and the reaction was carried out for 2 hours. The reaction solution was filtered and the filtrate was desolvated to obtain the compound represented by formula (1-5).

[0173] [Production of Composition and Sheet]

[0174] The components are mixed according to the proportions shown in Table 1 to obtain a composition. Next, two substrates are prepared, on which the demolding-treated surface of the demolding-treated PET sheet ("A31" manufactured by TOYOBO CO., LTD.) is placed upward relative to the glass plate. A 10 cm × 15 cm × 1.0 mm silicone rubber mold is set on the PET sheet of one substrate, and the composition is filled inside the mold. Furthermore, the demolding-treated surface of the PET sheet of another substrate is made the composition side, and the other substrate is covered, and then heated at 135°C for 15 minutes to cure the composition precursor. Thus, a sheet (thickness 1.0 mm) of the cured product of the composition of Examples 1 to 10 and Comparative Example 1 is obtained.

[0175] [Measurement of thermal conductivity]

[0176] The prepared sheet was sandwiched between PET sheets, cut into 8 cm × 13 cm × 1.0 mm, and sandwiched between a reference plate and a measuring probe. The thermal conductivity was measured at 25°C using a fast thermal conductivity meter (KYOTO ELECTRONICS MANUFACTURING CO., LTD. "QTM-710", measuring probe PD-11N, thin film measurement mode). The reference was to overlap two pieces of PET with release treatment (TOYOBO CO., LTD. "A31") and sandwich them between a reference plate and a measuring probe for measurement.

[0177] [Measurement of adhesive relay strength]

[0178] The prepared sheet was attached to a glass slide and left for more than 15 minutes, and then

[0179] [1] At room temperature (20-25°C) without heating,

[0180] [2] Heating at 220°C for 120 seconds and then cooling to room temperature, and

[0181] [3] Heating at 260°C for 30 seconds and then cooling to room temperature

[0182] For each of these samples, the adhesive strength (90° peeling, tensile speed: 50 mm / min) was measured using "EZ Test EZ-S" manufactured by Shimadzu Corporation.

[0183] The results of measuring various physical properties of the sheets of Examples 1 to 10 and Comparative Example 1 are shown in Table 1. In Table 1, the expression "≥200" (N / m) for the adhesive strength means that the sheets failed to be peeled due to cohesive failure when peeling was attempted.

[0184] [Table 1]

[0185]

[0186] As described above, it can be seen that the sheets of Examples 1 to 10 have a larger adhesive strength when [2] heated at 220°C for 120 seconds and then cooled to room temperature, so they can be appropriately attached to the device during the reflow process, and have a smaller adhesive strength when [3] heated at 260°C for 30 seconds and then cooled to room temperature, so they can be easily removed after the reflow process.

Claims

1. A composition comprising: first hollow particles, which are heat-expandable hollow particles; second hollow particles, which are hollow particles other than the first hollow particles; and Polymeric compounds.

2. The composition according to claim 1, wherein The expansion start temperature of the first hollow particles is 70° C. or higher.

3. The composition according to claim 1 or 2, wherein The expansion start temperature of the first hollow particles is 260° C. or lower.

4. The composition according to any one of claims 1 to 3, wherein The maximum expansion temperature of the first hollow particles is 100° C. or higher.

5. The composition according to any one of claims 1 to 4, wherein The maximum expansion temperature of the first hollow particles is 290° C. or lower.

6. A sheet comprising: first hollow particles, which are heat-expandable hollow particles; second hollow particles, which are hollow particles other than the first hollow particles; and Matrix polymer.

7. The sheet material according to claim 6, wherein The expansion start temperature of the first hollow particles is 70° C. or higher.

8. The sheet material according to claim 6 or 7, wherein: The expansion start temperature of the first hollow particles is 260° C. or lower.

9. The sheet material according to any one of claims 6 to 8, wherein The maximum expansion temperature of the first hollow particles is 100° C. or higher.

10. The sheet material according to any one of claims 6 to 9, wherein The maximum expansion temperature of the first hollow particles is 290° C. or lower.

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