WO2023171798A1 - 制振材用積層体 - Google Patents

制振材用積層体 Download PDF

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Publication number
WO2023171798A1
WO2023171798A1 PCT/JP2023/009328 JP2023009328W WO2023171798A1 WO 2023171798 A1 WO2023171798 A1 WO 2023171798A1 JP 2023009328 W JP2023009328 W JP 2023009328W WO 2023171798 A1 WO2023171798 A1 WO 2023171798A1
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Prior art keywords
mass
parts
resin layer
less
resin composition
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PCT/JP2023/009328
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English (en)
French (fr)
Japanese (ja)
Inventor
冬子 波元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2024506427A priority Critical patent/JP7837395B2/ja
Publication of WO2023171798A1 publication Critical patent/WO2023171798A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to a laminate for vibration damping material. More specifically, vibration-damping coatings are used to prevent vibrations and noise in various structures, especially under the floors of vehicles, to maintain quietness, and vibration-damping coatings are formed on surfaces.
  • This invention relates to a base material with a damping material.
  • Vibration damping materials are used to prevent vibrations and noise in various structures and maintain quietness.For example, they are used under the floors of automobiles, as well as in railway vehicles, ships, aircraft, electrical equipment, etc. It is also widely used in building structures, construction equipment, etc.
  • molded products such as plate-shaped molded bodies and sheet-shaped molded bodies made of materials with vibration-absorbing properties have been used as materials for such vibration damping materials.
  • paint-type damping material compositions paint-type damping material compositions (paints) have been developed.
  • various damping coatings have been proposed that are formed by spraying or applying any method to the relevant location. ing.
  • Patent Document 1 describes a vibration-damping coating film formed on a base material, the coating film having an average thickness of 1 mm or less, and consisting of a lower layer on the base material side and an upper layer, and the upper layer describes a vibration-damping coating film characterized by containing an acrylic resin, zinc oxide, and calcium carbonate, and describes that it can exhibit excellent vibration-damping properties even though it is a thin film.
  • Patent Document 2 describes a vibration-damping coating film formed on a base material, the coating film having a hardness on the side in contact with the base material that is lower than the hardness of the coating film surface on the side in contact with the base material.
  • a vibration-damping coating film is described in which the hardness of the coating film surface on the side is high, and the difference in hardness is two or more levels on the pencil hardness scale.
  • JP2021-160210A Japanese Patent Application Publication No. 2015-196118
  • the present inventor conducted studies in view of the above problems, and provided a laminate for vibration damping material having a resin layer A and a resin layer B, where the resin layer A may contain an inorganic filler.
  • Resin layer B contains an inorganic filler, and the content of the inorganic filler in 100 parts by mass of nonvolatile content of resin layer A is 30 parts by mass or less, and the content of the inorganic filler in 100 parts by mass of nonvolatile content of resin layer B.
  • the amount is 50 parts by mass or more and 90 parts by mass or less, and resin layer A and resin layer B may each contain zinc oxide, and the content of zinc oxide in 100 parts by mass of nonvolatile content of resin layer A is 5 parts by mass.
  • the content of zinc oxide in 100 parts by mass of the nonvolatile content of resin layer B is 5 parts by mass or less, and the average film thickness of the laminate is 1.5 mm or more,
  • the present invention (1) is a laminate for vibration damping material having a resin layer A and a resin layer B, where the resin layer A may contain an inorganic filler, and the resin layer B may contain an inorganic filler.
  • the content of the inorganic filler in 100 parts by mass of non-volatile content of resin layer A is 30 parts by mass or less, and the content of the inorganic filler in 100 parts by mass of non-volatile content of resin layer B is 50 parts by mass or more and 90 parts by mass.
  • the resin layer A and the resin layer B may each contain zinc oxide, and the content of zinc oxide in 100 parts by mass of the nonvolatile content of the resin layer A is 5 parts by mass or less, and the resin layer B The content of zinc oxide in 100 parts by mass of nonvolatile matter is 5 parts by mass or less, and the laminate has an average film thickness of 1.5 mm or more.
  • the present invention (2) is a laminate for vibration damping material, wherein the laminate for vibration damping material has a resin layer A on the base material and a resin layer B on the upper layer of the resin layer A,
  • the laminate for damping material according to the present invention (1) has a ratio of the average thickness of layer A to the average thickness of resin layer B of 50/50 to 10/90.
  • the present invention (3) is the laminate for a damping material according to the present invention (1) or (2), wherein the resin layer A has an average thickness of 0.15 mm or more.
  • the present invention (4) is the laminate for a damping material according to any one of the present inventions (1) to (3), wherein the resin layer A has an average thickness of 3 mm or less.
  • the present invention (5) is the laminate for a damping material according to any one of the present inventions (1) to (4), wherein the resin layer B has an average thickness of 0.7 mm or more.
  • the present invention (6) is the laminate for a damping material according to any one of the present inventions (1) to (5), wherein the resin layer B has an average thickness of 5 mm or less.
  • the content of the inorganic filler in 100 parts by mass of the nonvolatile content of the resin layer A is 10 parts by mass or less
  • the content of the inorganic filler in 100 parts by mass of the nonvolatile content of the resin layer B is 10 parts by mass or less.
  • the present invention (8) is the laminate for a damping material according to any one of the present inventions (1) to (7), wherein the content of zinc oxide is 1 part by mass or less based on 100 parts by mass of the nonvolatile content of the resin layer A. .
  • the present invention (9) is the laminate for a damping material according to any one of the present inventions (1) to (8), wherein the storage modulus of the resin layer B at 25° C. is 1.0E+07 MPa or more.
  • the present invention (10) is a vehicle including the laminate of any one of the present inventions (1) to (9).
  • the present invention (11) is for damping materials in which resin composition B is applied on top of resin layer A derived from resin composition A after applying resin composition A or at the same time as applying resin composition A.
  • a method for producing a laminate wherein resin composition A may contain an inorganic filler, resin composition B contains an inorganic filler, and the inorganic filler in 100 parts by mass of nonvolatile content of resin composition A.
  • the content of the inorganic filler is 50 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of nonvolatile content of resin composition B, and resin composition A and resin composition B are , each may contain zinc oxide, the content of zinc oxide per 100 parts by mass of nonvolatile content of resin composition A is 5 parts by mass or less, and the content of zinc oxide per 100 parts by mass of nonvolatile content of resin composition B.
  • the present invention (12) is the present invention ( 11) is a method for manufacturing a laminate for vibration damping material.
  • the present invention (13) is the present invention (13) in which the storage modulus of the coating film at 25°C after coating the resin composition B with a film thickness of 0.6 mm and drying at 140°C for 60 minutes is 1.0E + 07 MPa or more. 11) or (12), the method for producing a laminate for damping material.
  • the present invention (14) provides the damping material according to any one of the present inventions (11) to (13), wherein the storage elastic modulus of the resin composition B is higher than the storage elastic modulus of the resin composition A by 1.0E+07 MPa or more. This is a method for manufacturing a laminate for use in the manufacturing process.
  • the present invention provides a vibration damping material laminate according to any one of the present inventions (11) to (14), which has a step of drying the applied resin composition A and/or the applied resin composition B. This is the manufacturing method.
  • the present invention is the laminate for a vibration damping material according to any one of the present inventions (1) to (9), wherein the content of zinc oxide is 1 part by mass or less based on 100 parts by mass of the nonvolatile content of the resin layer B.
  • the present invention is a laminate for vibration damping material having a resin layer A and a resin layer B
  • the resin layer A may contain an inorganic filler
  • the resin layer B contains an inorganic filler
  • the content of the inorganic filler in 100 parts by mass of nonvolatile content of A is 30 parts by mass or less
  • the content of the inorganic filler in 100 parts by mass of nonvolatile content of resin layer B is 50 parts by mass or more and 90 parts by mass or less
  • It is also a laminate for vibration damping material in which the average thickness of the laminate is 1.5 mm or more. Such a laminate for vibration damping material has excellent vibration damping properties.
  • a laminate for a vibration damping material in which the resin composition as a raw material has excellent stability and the resulting resin layer has excellent vibration damping properties.
  • the laminate for vibration damping material of the present disclosure is a laminate for vibration damping material having a resin layer A and a resin layer B, where the resin layer A may contain an inorganic filler and the resin layer B has an inorganic filler.
  • the resin layer A may contain an inorganic filler and the resin layer B has an inorganic filler.
  • Contains a filler the content of the inorganic filler in 100 parts by mass of non-volatile content of resin layer A is 30 parts by mass or less, and the content of the inorganic filler in 100 parts by mass of non-volatile content of resin layer B is 50 parts by mass or more 90 parts by mass or less
  • resin layer A and resin layer B may each contain zinc oxide, and the content of zinc oxide in 100 parts by mass of nonvolatile content of resin layer A is 5 parts by mass or less
  • the resin layer B is characterized in that the content of zinc oxide is 5 parts by mass or less based on 100 parts by mass of nonvolatile content, and the average film thickness of the laminate
  • the storage modulus of resin layer A and resin layer B It is thought that the difference between the storage elastic modulus of
  • the content of zinc oxide within a low range in resin layers A and B gelation due to the crosslinking agent occurs in the resin composition that is the raw material for resin layers A and B before the resin layer is formed. can be sufficiently prevented, and the storage stability of the resin composition can be improved.
  • the components of these two layers may be partially mixed with each other.
  • the term "resin” refers to a broader concept than polymer.
  • the resin may contain one or more kinds of polymers, and may further contain materials other than the polymers, such as additives, if necessary.
  • resin layer A resin layer B
  • a laminate for vibration damping material resin composition A for forming resin layer A
  • resin composition B for forming resin layer B will be described in this order.
  • Resin layer A of the present disclosure is formed using resin composition A.
  • the resin layer A may be formed immediately after applying the resin composition A to the base material, etc., but it may be formed by applying the resin composition A to the base material, etc. and then performing a drying process and/or a curing process. It is preferable that the
  • the content of zinc oxide in 100 parts by mass of nonvolatile content of resin layer A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and substantially It does not have to be included.
  • the content of zinc oxide includes not only zinc oxide that has not yet been crosslinked, but also zinc oxide that has been crosslinked in the resin layer or resin composition.
  • the non-volatile content of the resin layer A of the present disclosure may be calculated as a component excluding the volatile components used, or 1 g of the resin layer A is weighed and dried in a hot air dryer at a temperature of 110°C. The residue obtained by drying for a period of time may be used as a non-volatile component.
  • [Nonvolatile content (mass%) in resin layer A] ([mass of residue] ⁇ [resin layer A 1 g]) x 100
  • the nonvolatile content per 100 parts by mass of the resin layer A of the present disclosure is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and particularly preferably 100 parts by mass. .
  • the volatile content per 100 parts by mass of the resin layer A of the present disclosure is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less.
  • the resin layer A contains substantially no volatile matter.
  • the resin layer A of the present disclosure may contain a crosslinking agent other than zinc oxide.
  • crosslinking agents other than zinc oxide of the present disclosure include metal oxides other than zinc oxide, (block) isocyanate compounds, melamine compounds, epoxy compounds, oxazoline compounds, vinyl ether compounds, and the like.
  • metal oxides other than zinc oxide of the present disclosure include zinc chloride, zinc sulfide, alumina, titanium oxide, magnesium oxide, zirconium oxide, and the like.
  • Examples of the epoxy compound of the present disclosure include ADEKA RIN EMN-26-60 and EM-101-50 (both trade names, manufactured by ADEKA).
  • Examples of the oxazoline compound of the present disclosure include Epocross WS-500, WS-700, K-2010, 2020, and 2030 (all trade names, manufactured by Nippon Shokubai Co., Ltd.).
  • the content of the crosslinking agent other than zinc oxide in 100 parts by mass of the nonvolatile content of the resin layer A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, It does not have to be substantially contained.
  • the content of crosslinking agents other than zinc oxide includes not only uncrosslinked crosslinking agents but also crosslinking agents crosslinked in the resin layer or resin composition.
  • the total content of zinc oxide and crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin layer A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass or less. is even more preferable. It is particularly preferable that the nonvolatile content of the resin layer A of the present disclosure does not substantially contain zinc oxide and a crosslinking agent other than zinc oxide.
  • Resin layer A of the present disclosure typically includes polymer A.
  • the polymer A of the present disclosure is not particularly limited, but is preferably an acrylic polymer from the viewpoint of damping properties.
  • the acrylic polymer of the present disclosure may have a structural unit derived from a (meth)acrylic monomer, and may or may not be derived from a (meth)acrylic monomer.
  • (Meth)acrylic monomers include, for example, (meth)acrylic acid alkyl ester monomers and (meth)acrylic acid monomers.
  • a (meth)acrylic acid alkyl ester monomer is a monomer having a carboxylic acid ester group obtained by esterifying the carboxyl group of (meth)acrylic acid with an alkyl alcohol, and has an acryloyloxy group or a methacryloyloxy group.
  • Examples of the (meth)acrylic acid alkyl ester monomers of the present disclosure include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, Isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, pentyl acrylate, pentyl methacrylate, isoamyl acrylate, isoamyl methacrylate, hexyl acrylate, hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, octyl acrylate, octyl methacrylate, isooctyl acryl
  • the content of the structural unit derived from the (meth)acrylic acid alkyl ester monomer in 100 parts by mass of the acrylic polymer of the present disclosure is preferably 20 parts by mass or more, more preferably 40 parts by mass or more. It is preferably 60 parts by mass or more, more preferably 65 parts by mass or more, and particularly preferably 65 parts by mass or more. From the viewpoint of polymerization stability, the content is preferably 99.9 parts by mass or less, more preferably 99.8 parts by mass or less, even more preferably 99.6 parts by mass or less, It is particularly preferred that the amount is 99.5 parts by mass or less.
  • the acrylic polymer of the present disclosure preferably further includes a structural unit derived from a (meth)acrylic acid monomer.
  • the acrylic resin has a structural unit derived from a (meth)acrylic acid monomer, it can be used as a filler such as calcium carbonate in the vibration damping material formulation that is the raw material for the damping coating film of the present invention.
  • the dispersibility of the coating film is improved, and the resulting coating film has better functionality.
  • the (meth)acrylic acid monomer is preferably (meth)acrylic acid (salt).
  • (Meth)acrylic acid refers to acrylic acid and/or methacrylic acid.
  • the salt of the (meth)acrylic acid monomer is preferably a metal salt, an ammonium salt, an organic amine salt, or the like.
  • metal atoms forming metal salts include monovalent metal atoms such as alkali metal atoms such as lithium, sodium, and potassium; divalent metal atoms such as calcium and magnesium; trivalent metal atoms such as aluminum and iron. Atoms are preferred.
  • organic amine salt alkanolamine salts such as ethanolamine salt, diethanolamine salt, triethanolamine salt, etc., and triethylamine salt are suitable.
  • the content of the structural unit derived from the (meth)acrylic acid monomer in 100 parts by mass of the acrylic polymer of the present disclosure is preferably obtained by copolymerizing 0.1 to 5 parts by mass. .
  • the amount of the (meth)acrylic acid monomer is 0.3 parts by mass or more, and it is more preferable that the amount of the (meth)acrylic acid monomer is 0.5 parts by mass or more. More preferably, the amount of the (meth)acrylic acid monomer is 0.7 parts by mass or more.
  • the (meth)acrylic acid monomer is 5 parts by mass or less, and it is more preferable that the (meth)acrylic acid monomer is 4 parts by mass or less, It is more preferable that the amount of the (meth)acrylic acid monomer is 3 parts by mass or less.
  • the acrylic polymer of the present disclosure further includes structural units derived from a (meth)acrylic acid alkyl ester monomer and other copolymerizable unsaturated monomers other than the (meth)acrylic acid monomer. It may have.
  • other copolymerizable unsaturated monomers include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, diallyl phthalate, triallyl cyanurate, and ethylene glycol.
  • Diacrylate ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol diacrylate Methacrylate, allyl acrylate, allyl methacrylate, etc.; Esterified products of (meth)acrylic acid monomers other than these; Acrylamide, methacrylamide, etc.: Amidated products of (meth)acrylic acid monomers other than these; acrylonitrile, , polyfunctional unsaturated monomers such as trimethylolpropane diallyl ether; vinyl acetate, etc., and it is preferable to use one or more of these.
  • the acrylic polymer of the present disclosure may include, for example, a polymer having a structural unit derived from an unsaturated monomer having an aromatic ring.
  • unsaturated monomer having an aromatic ring include divinylbenzene, styrene, ⁇ -methylstyrene, vinyltoluene, and ethylvinylbenzene, with styrene being preferred.
  • the acrylic polymer of the present disclosure contains a structural unit derived from an unsaturated monomer having an aromatic ring
  • the structural unit derived from the unsaturated monomer having an aromatic ring in 100 parts by mass of the acrylic polymer is The content is preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 15 parts by mass or more, and particularly preferably 25 parts by mass or more.
  • the acrylic polymer of the present disclosure preferably contains 80 parts by mass or less, and 70 parts by mass of the structural unit derived from the unsaturated monomer having an aromatic ring, based on 100 parts by mass of the acrylic polymer. It is more preferable to contain up to 60 parts by mass, even more preferably up to 40 parts by mass.
  • the resin layer A of the present disclosure may contain one type of polymer A, or may contain two or more types of polymer A. Furthermore, the polymer A may be composed of two or more kinds of polymers and may be in the form of a composite.
  • the glass transition temperature of the polymer (more preferably acrylic polymer) of the present disclosure is preferably -30 to 40°C. When a polymer having such a glass transition temperature is used, the vibration damping material can effectively exhibit vibration damping performance in the practical temperature range.
  • the glass transition temperature of the above polymer is more preferably -20 to 35°C, still more preferably -15 to 30°C. Note that the glass transition temperature (Tg) is calculated from the monomer composition used using the following calculation formula (1).
  • Tg' is the Tg (absolute temperature) of the polymer.
  • W 1 ′, W 2 ′, . . . W n ′ are the mass fractions of each monomer relative to the total monomer component.
  • T 1 , T 2 , . . . T n are glass transition temperatures (absolute temperatures) of homopolymers (homopolymers) made of each monomer component.
  • the resin layer A of the present disclosure contains two or more types of polymers, or when at least one type of polymer is obtained by multistage polymerization (for example, an emulsion having a core part and a shell part) In the case of resin particles), the above-mentioned glass transition temperature means Tg (total Tg) calculated from the monomer composition used in all stages.
  • the total amount of monomers whose glass transition temperature is unknown in the monomer components is the mass fraction. If the amount is 10% by mass or less, the glass transition temperature is determined using only monomers whose glass transition temperatures are known. If the total amount of monomers whose glass transition temperatures are unknown in the monomer components exceeds 10% by mass, the glass transition temperature of the polymer can be determined by differential scanning calorimetry (DSC) or differential calorimetry. (DTA), thermomechanical analysis (TMA), etc. The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer components.
  • DSC differential scanning calorimetry
  • DTA differential calorimetry.
  • TMA thermomechanical analysis
  • the composition of the monomer component used as a raw material for the polymer forming the particles can be determined in consideration of the glass transition temperature of the polymer forming the particles.
  • the glass transition temperature of the polymer is, for example, -70°C for a homopolymer of 2-ethylhexyl acrylate, -56°C for a homopolymer of n-butyl acrylate, 20°C for a homopolymer of n-butyl methacrylate, and 20°C for a homopolymer of n-butyl methacrylate.
  • the temperature is -15°C for the homopolymer of 2-hydroxyethyl methacrylate, and 55°C for the homopolymer of 2-hydroxyethyl methacrylate.
  • the glass transition temperature of one of the polymers is preferably 0 to 60°C. More preferably, the temperature is 10 to 50°C.
  • the other glass transition temperature of the polymer is preferably -30 to 30°C. More preferably, it is -20 to 20°C.
  • the difference in glass transition temperature between the two polymers is preferably 5 to 60°C.
  • the difference in glass transition temperature is more preferably 5 to 50°C, even more preferably 5 to 40°C.
  • At least one of the above polymers A (polymer) is composed of two or more kinds of polymers, and when they are in a composite form, the monomer component forming one of the polymers and the other of the polymers are formed.
  • the mass ratio of the monomer component to the monomer component is preferably 30/70 to 70/30.
  • the mass ratio is more preferably 35/65 to 55/45.
  • the weight average molecular weight of the polymer A of the present disclosure is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, from the viewpoint of heat resistance, and preferably 600,000 or less from the viewpoint of baking property. It is more preferably 400,000 or less, and even more preferably 200,000 or less.
  • the weight average molecular weight of the polymer A of the present disclosure can be measured using a known method, for example, by GPC (gel permeation chromatography) measurement under the following measurement conditions.
  • Measuring equipment HLC-8120GPC (product name, manufactured by Tosoh Corporation)
  • Molecular weight column TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) were connected in series and used
  • Eluent Tetrahydrofuran (THF)
  • Standard material for calibration curve Polystyrene (manufactured by Tosoh Corporation)
  • Measurement method The object to be measured is dissolved in THF so that the solid content is approximately 0.2% by mass, and the resulting solution is filtered through a filter, and the molecular weight is measured using the sample as a measurement sample.
  • the content of the polymer A in 100 parts by mass of the resin layer A of the present disclosure is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 60 parts by mass or more. Moreover, the content of polymer A is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 80 parts by mass or less.
  • the resin layer A of the present disclosure may contain an inorganic filler.
  • Inorganic fillers of the present disclosure include calcium carbonate, mica, wollastonite, talc, and the like.
  • the resin layer A of the present disclosure preferably contains at least one of calcium carbonate, mica, wollastonite, and talc as an inorganic filler.
  • the inorganic filler of the present disclosure preferably has an average particle diameter of 0.1 to 200 ⁇ m, more preferably 0.5 to 100 ⁇ m, and even more preferably 1 to 50 ⁇ m.
  • the average particle diameter of the inorganic filler can be measured using a laser diffraction particle size distribution analyzer, and is the value of the 50% diameter by weight from the particle size distribution.
  • the content of the inorganic filler contained in 100 parts by mass of the nonvolatile content of the resin layer A of the present disclosure is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass. It is particularly preferable that the amount is below, and most preferably that it is substantially 0 part by weight.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin layer A of the present disclosure is preferably 55 parts by mass or less, more preferably 40 parts by mass or less, and preferably 15 parts by mass or less. More preferably, the amount is 10 parts by weight or less, particularly preferably 10 parts by weight or less, and most preferably substantially 0 parts by weight. Since the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin layer A of the present disclosure is specified within a low range, the difference in elastic modulus between the resin layer A and the resin layer B becomes large. , the vibration damping effect can be fully exhibited.
  • the resin layer A of the present disclosure may further contain other components.
  • Other components include, for example, organic fillers (polyethylene, polystyrene, acrylic resins, silicone resins, urethane resins, etc.); fibers (carbon fibers, glass fibers, cellulose nanofibers, metal fibers, etc.); surfactants; dispersants. Thickener; Foaming agent; Gelling agent; Antifoaming agent; Plasticizer; Stabilizer; Wetting agent; Preservative; Antifoaming agent; Antiaging agent; Antifungal agent; Ultraviolet absorber; Antistatic agent; These agents These components can be used alone or in combination of two or more.
  • the resin layer A of the present disclosure preferably has a storage modulus at 25°C of 1.0E+05 MPa or more, more preferably 1.0E+06 MPa or more, and even more preferably 1.0E+07 MPa or more.
  • the storage modulus is preferably 5.0E+08 MPa or less, more preferably 5.0E+07 MPa or less.
  • the storage modulus of the resin layer A is measured by the same method as the method for measuring the storage modulus of the resin composition A after heating and drying described in the Examples.
  • the average thickness of the resin layer A of the present disclosure is preferably 0.15 mm or more, more preferably 0.2 mm or more, even more preferably 0.3 mm or more, even more preferably 0.4 mm or more, and even more preferably 0.5 mm or more. It is preferably 0.8 mm or more, even more preferably 1.0 mm or more.
  • the average thickness of the resin layer A is preferably 3.0 mm or less, more preferably 2.0 mm or less, and even more preferably 1.5 mm or less from the viewpoint of coating suitability. As a method for calculating the average thickness of the resin layer A of the present disclosure, it can be measured under the conditions described in the Examples described later.
  • the loss coefficient at 30° C. of the resin layer A of the present disclosure is preferably 0.1 or more, more preferably 0.15 or more, and from the viewpoint of coating suitability, 0.9 or less is preferable, and more preferably 0.8 or less. More preferably, it is 0.75 or less.
  • a resonance method in which measurement is performed near a resonance frequency is generally used, and there are a half-width method, a damping factor method, and a mechanical impedance method.
  • the loss coefficient of the damping coating film is preferably measured by a resonance method (3 dB method) using a cantilever beam method. Measurement using the cantilever method can be performed using, for example, a damping material evaluation system manufactured by Spectris Co., Ltd.
  • Resin layer B of the present disclosure is formed using resin composition B.
  • the resin layer B may be formed by applying the resin composition A to a base material, etc., but it is also possible to apply the resin composition A to a base material, etc. and then perform a drying process and/or a curing process. It is preferable that it be formed by
  • the content of zinc oxide in 100 parts by mass of the nonvolatile content of resin layer B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and substantially It does not have to be included.
  • the non-volatile content of the resin layer B of the present disclosure may be calculated as a component excluding the volatile components used, or 1 g of the resin layer B is weighed and dried in a hot air dryer at a temperature of 110°C. The residue obtained by drying for a period of time may be used as a non-volatile component.
  • [Nonvolatile content (mass%) in resin layer B] ([mass of residue] ⁇ [resin layer B 1 g]) x 100
  • the nonvolatile content per 100 parts by mass of the resin layer B of the present disclosure is preferably 80 parts by mass or more, more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, and particularly preferably 100 parts by mass. .
  • the volatile content per 100 parts by mass of the resin layer B of the present disclosure is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 1 part by mass or less.
  • the resin layer B contains substantially no volatile matter.
  • the resin layer B of the present disclosure may contain a crosslinking agent other than zinc oxide.
  • the crosslinking agent other than zinc oxide of the present disclosure is as described above in the resin layer A of the present disclosure.
  • the content of crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin layer B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, It does not have to be substantially contained.
  • the total content of zinc oxide and crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin layer B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass or less. is even more preferable. It is particularly preferable that the nonvolatile content of the resin layer B of the present disclosure does not substantially contain zinc oxide and a crosslinking agent other than zinc oxide.
  • Resin layer B of the present disclosure typically includes polymer B.
  • the polymer B of the present disclosure is not particularly limited, but is preferably an acrylic polymer from the viewpoint of damping properties.
  • the acrylic polymer is as described above.
  • the resin layer B of the present disclosure may contain one type of polymer B, or may contain two or more types of polymer B.
  • the polymer B may be composed of two or more kinds of polymers and may be in the form of a composite.
  • the glass transition temperature of one of the polymers is preferably 0 to 60°C. More preferably, the temperature is 10 to 50°C.
  • the other glass transition temperature of the polymer is preferably -30 to 30°C. More preferably, it is -20 to 20°C. Further, the difference in glass transition temperature between the two polymers is preferably 5 to 60°C. By creating a difference in glass transition temperature in this way, for example, when applied to a vibration damping material, it is possible to exhibit higher vibration damping properties over a wide temperature range, especially within a practical range of 20. The damping performance in the range of ⁇ 60°C will be further improved.
  • the difference in glass transition temperature is more preferably 5 to 50°C, even more preferably 5 to 40°C.
  • At least one of the polymers B (polymer) forming the emulsion resin particles is composed of two or more kinds of polymers, and when they are in a composite form, the monomer component forming one of the polymers and the polymer
  • the mass ratio with the monomer component forming the other side of the combination is preferably 30/70 to 70/30.
  • the mass ratio is more preferably 35/65 to 55/45.
  • the weight average molecular weight of the polymer B of the present disclosure is preferably 20,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, from the viewpoint of heat resistance, and preferably 600,000 or less from the viewpoint of baking property. It is more preferably 400,000 or less, and even more preferably 200,000 or less.
  • the weight average molecular weight of the polymer B of the present disclosure can be measured using a known method, for example, by GPC (gel permeation chromatography) measurement under the following measurement conditions.
  • Measuring equipment HLC-8120GPC (product name, manufactured by Tosoh Corporation)
  • Molecular weight column TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) were connected in series and used
  • Eluent Tetrahydrofuran (THF)
  • Standard material for calibration curve Polystyrene (manufactured by Tosoh Corporation)
  • Measurement method The object to be measured is dissolved in THF so that the solid content is approximately 0.2% by mass, and the resulting solution is filtered through a filter, and the molecular weight is measured using the sample as a measurement sample.
  • the content of the polymer B in 100 parts by mass of the resin layer B of the present disclosure is preferably 10 parts by mass or more from the viewpoint of damping properties, more preferably 12 parts by mass or more, even more preferably 15 parts by mass or more, and the content of the polymer B is preferably 10 parts by mass or more from the viewpoint of damping properties. From the viewpoint, the amount is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less.
  • the content ratio of polymer B in 100 parts by mass of non-volatile content of resin composition B of the present disclosure is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 20 parts by mass or more. It is even more preferable.
  • the content ratio is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 27 parts by mass or less.
  • Resin layer B of the present disclosure includes an inorganic filler.
  • the inorganic filler of the present disclosure is the same as the inorganic filler in the resin layer A described above. That is, the resin layer B of the present disclosure preferably contains at least one of calcium carbonate, mica, wollastonite, and talc as an inorganic filler.
  • the content of the inorganic filler contained in 100 parts by mass of the nonvolatile content of the resin layer B of the present disclosure is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, and 60 parts by mass or more from the viewpoint of damping properties. It is more preferably 65 parts by mass or more, even more preferably 70 parts by mass or more.
  • the content is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less from the viewpoint of coating suitability.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B contained in the resin layer B of the present disclosure is preferably 150 parts by mass or more, more preferably 200 parts by mass or more, and 250 parts by mass or more. It is more preferable that the amount is 300 parts by mass or more, and particularly preferably 300 parts by mass or more.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B contained in the resin layer B of the present disclosure is preferably 600 parts by mass or less, and more preferably 500 parts by mass or less.
  • the content ratio of the inorganic filler in 100 parts by mass of non-volatile content of resin layer B of the present disclosure is more preferably 30 parts by mass or more than the content ratio of inorganic filler in 100 parts by mass of non-volatile content of resin layer A, and 35 parts by mass or more. It is more preferable that the amount is at least 40 parts by weight, even more preferably at least 50 parts by weight, and particularly preferably at least 55 parts by weight.
  • the content ratio of the inorganic filler in 100 parts by mass of non-volatile content of resin layer B of the present disclosure is preferably 90 parts by mass or less greater than the content ratio of inorganic filler in 100 parts by mass of non-volatile content of resin layer A.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B in the resin layer B of the present disclosure is more preferably 100 parts by mass or more than the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin layer A, and 200 parts by mass or more.
  • the amount is at least 250 parts by weight, even more preferably at least 280 parts by weight, and particularly preferably at least 300 parts by weight.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B in the resin layer B of the present disclosure is preferably 400 parts by mass or less greater than the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin layer A. , more preferably 300 parts by mass or less. In this way, by increasing the content ratio of the inorganic filler to 100 parts by mass of polymer B in resin layer B relative to the content ratio of inorganic filler to 100 parts by mass of polymer A in resin layer A, the combination with resin layer B can be improved. Therefore, it is expected that vibration damping performance will be improved over a wide temperature range within the practical temperature range.
  • the resin layer B of the present disclosure may further contain other components.
  • Other components include, for example, organic fillers (polyethylene, polystyrene, acrylic resins, silicone resins, urethane resins, etc.); fibers (carbon fibers, glass fibers, cellulose nanofibers, metal fibers, etc.); surfactants; dispersants. Thickener; Foaming agent; Gelling agent; Antifoaming agent; Plasticizer; Stabilizer; Wetting agent; Preservative; Antifoaming agent; Antiaging agent; Antifungal agent; Ultraviolet absorber; Antistatic agent; These agents These components can be used alone or in combination of two or more.
  • the storage elastic modulus of the resin layer B of the present disclosure at 25° C. is preferably 1.0E+07MPa or more, more preferably 1.0E+08MPa or more, even more preferably 1.0E+09MPa or more, particularly 2.0E+09MPa or more. preferable.
  • the storage modulus is preferably 1.0E+11 MPa or less, more preferably 1.0E+10 MPa or less, even more preferably 5.0E+09 MPa or less.
  • the storage modulus of the resin layer B of the present disclosure is preferably higher than the storage modulus of the resin layer A of the present disclosure by 1.0E+07MPa or more, more preferably higher than 1.0E+08MPa, and higher than the storage modulus of the resin layer A of the present disclosure by 1.0E+09MPa or more. It is even more preferable that the pressure is higher than 2.0E+09 MPa.
  • the storage modulus of the resin layer B is preferably higher than the storage modulus of the resin layer A by 1.0E+11 MPa or less, more preferably 1.0E+10 MPa or less, and even more preferably 5.0E+09 MPa or less higher.
  • the difference in the modulus of elasticity between the resin layer A and the resin layer B can be increased.
  • the storage modulus of the resin layer B is measured by the same method as the storage modulus method after heating and drying the resin composition B described in the Examples.
  • the average thickness of the resin layer B of the present disclosure is preferably 0.7 mm or more, more preferably 1.0 mm or more, even more preferably 1.5 mm or more, and particularly preferably 2.0 mm or more.
  • the average thickness of the resin layer B is preferably 5.0 mm or less, more preferably 4.0 mm or less, even more preferably 3.7 mm or less, and particularly preferably 3.0 mm or less from the viewpoint of damping properties.
  • the loss coefficient at 30° C. of the resin layer B of the present disclosure is preferably 0.05 or more, more preferably 0.075 or more, and even more preferably 0.1 or more.
  • the loss coefficient of the resin layer B at 30° C. is preferably 0.7 or less, more preferably 0.6 or less, and even more preferably 0.5 or less from the viewpoint of coating suitability.
  • the method for measuring the loss coefficient of the present disclosure is as described above.
  • the damping material laminate of the present disclosure is a damping material laminate having a resin layer A and a resin layer B.
  • the laminate for vibration damping material of the present disclosure may have a resin layer A on a base material and a resin layer B on top of the resin layer A, or may have a resin layer B on the base material.
  • the resin layer A may be provided on the base material
  • the resin layer B may be provided on the resin layer A. It is preferable that it is an aspect.
  • the laminate for vibration damping material of the present disclosure may have another resin layer between the resin layer A and the resin layer B, but from the viewpoint of productivity, the layer in contact with the resin layer A may have a resin layer.
  • the laminate for vibration damping material of the present disclosure is not particularly limited as long as it includes resin layer A and resin layer B, and may have two layers or three or more layers, but it should be two layers. is preferred.
  • the average thickness of the laminate for vibration damping material of the present disclosure is preferably 1.5 mm or more, more preferably 2.0 mm or more, and even more preferably 2.5 mm or more from the viewpoint of vibration damping properties.
  • the average film thickness is preferably 7.0 mm or less, more preferably 5.0 mm or less, and even more preferably 4.0 mm or less from the viewpoint of coating suitability.
  • the ratio of the average thickness of resin layer A to the average thickness of resin layer B in the laminate for vibration damping material of the present disclosure is preferably 50/50 to 10/90, more preferably 50/50 to 20/80, More preferably 50/50 to 30/70, particularly preferably 40/60 to 30/70.
  • the average thickness of the resin layer A and the average thickness of the resin layer B in the laminate for vibration damping material of the present disclosure can be used. Measurements can be made by cutting out a section and analyzing the cross section using a microscope.
  • the average thickness of the base material, the lower layer of the base material and the damping coating film (base material + resin layer A), and the average thickness of the base material and the vibration damping coating film (base material + resin layer A + resin layer B) can be arbitrarily determined using calipers.
  • the average thickness ratio of resin layer A/resin layer B can be calculated by measuring at five locations, subtracting from each, and averaging.
  • the average film thickness of the laminate for vibration damping material of the present disclosure can be calculated by adding up all the average thicknesses of the respective resin layers that constitute the laminate for vibration damping material.
  • the damping properties of the laminate for damping material of the present disclosure can be evaluated by measuring the loss coefficient of the film.
  • the loss coefficient is usually expressed as ⁇ , and indicates how much vibration applied to the coating is attenuated. The higher the loss coefficient, the better the damping performance.
  • the above-mentioned loss coefficient can be measured by the method described in Examples described later.
  • the loss coefficient at 30°C of the laminate for vibration damping material of the present disclosure is preferably 0.15 or more, more preferably 0.2 or more, even more preferably 0.25 or more, and 0.6 from the viewpoint of coatability. The following is preferable, 0.55 or less is more preferable, and 0.525 or less is still more preferable.
  • the method for measuring the loss coefficient of the present disclosure is as described above.
  • the base material of the present disclosure is not particularly limited, but includes, for example, steel, aluminum, plastic materials, and the like. Among these, one preferred embodiment of the vehicle of the present invention is for the base material to be made of a metal material.
  • the average thickness of the base material of the present disclosure is preferably 0.1 to 3 mm, more preferably 0.3 to 2 mm, and even more preferably 0.5 to 1.6 mm.
  • the average thickness of the metal base material of the present disclosure is preferably thicker than the average thickness of the resin layer B.
  • the average thickness of the resin layer B is preferably 0.1 mm or more thinner than the average thickness of the metal base material, more preferably 0.3 mm or more thinner, still more preferably 0.5 mm or more thinner, and even more preferably 0.1 mm or more thinner than the average thickness of the metal base material. It is particularly preferable that the thickness be 7 mm or more.
  • the average thickness of the metal base material can be measured in the same manner as the average thickness of the resin layer described above.
  • the content of zinc oxide in 100 parts by mass of nonvolatile content of the resin composition A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and substantially It does not have to be included in
  • the non-volatile content of the resin composition A of the present disclosure may be calculated as a component excluding the volatile components used, or 1 g of the resin composition A is weighed from the total mass of the resin composition A, and 1 g of the resin composition A is weighed and dried in a hot air dryer to It may be dried for 1 hour at a temperature of .degree. C., and the resulting residue may be used as a nonvolatile component.
  • [Nonvolatile content (mass%) in resin composition A] ([mass of residue] ⁇ [1 g of resin composition A]) x 100
  • the nonvolatile content per 100 parts by mass of the resin composition A of the present disclosure is preferably 50 parts by mass or more from the viewpoint of productivity, more preferably 55 parts by mass or more, even more preferably 60 parts by mass or more, and From the viewpoint, the amount is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 87 parts by mass or less.
  • the resin composition A of the present disclosure may contain a crosslinking agent other than zinc oxide.
  • the crosslinking agent other than zinc oxide of the present disclosure is the same as the crosslinking agent other than zinc oxide described above in the resin layer A of the present disclosure.
  • the content of the crosslinking agent other than zinc oxide in 100 parts by mass of nonvolatile content of the resin composition A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. .
  • the nonvolatile content of the resin composition A of the present disclosure does not need to contain substantially any crosslinking agent other than zinc oxide.
  • the total content of zinc oxide and crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin composition A of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass. The following are more preferred.
  • the nonvolatile content of resin composition A does not need to substantially contain zinc oxide and crosslinking agents other than zinc oxide.
  • the resin composition A of the present disclosure may contain the polymer A.
  • the polymer A of the present disclosure is the same as the polymer A described above in the resin layer A of the present disclosure.
  • the resin composition A of the present disclosure may contain one type of polymer A, or may contain two or more types of polymer A.
  • the polymer A may be composed of two or more kinds of polymers and may be in the form of a composite.
  • the polymer A has a form having a core part and a shell part, which will be described later, the polymer A is composed of two types of polymers, and one of the two types of polymers is the core part and the other is the shell part. It may also be formed.
  • Polymer A is an acrylic polymer
  • the (meth)acrylic acid alkyl ester monomer and the other monomer copolymerizable with the (meth)acrylic acid alkyl ester monomer are used in the emulsion.
  • the emulsion resin particles may be contained in either the monomer component forming the core part or the monomer component forming the shell part, or it may be used in both. Further, it is preferable that at least one of the polymers (also referred to as polymers) forming the emulsion resin particles is in the form of emulsion resin particles having a core portion and a shell portion. Thereby, the number of interfaces between polymers can be increased, and effects such as improved vibration damping properties can be further enhanced.
  • the core part and the shell part may be completely compatible with each other and may have a homogeneous structure in which they cannot be distinguished. , a core-shell composite structure or a microdomain structure in which these structures are not completely compatible and are formed heterogeneously, but even among these structures, it is possible to fully bring out the characteristics of the emulsion and create a stable emulsion.
  • a core-shell composite structure is preferred.
  • Emulsions with a core-shell composite structure have excellent vibration damping properties over a wide range of practical temperatures. In particular, it exhibits superior vibration damping performance compared to other types of damping material compounds, even at high temperatures.As a result, within the practical temperature range, it exhibits vibration damping performance over a wide range from room temperature to high temperature. can demonstrate.
  • the surface of the core portion is covered with the shell portion.
  • the surface of the core part is completely covered with the shell part, but it may not be completely covered, for example, the surface of the core part may be covered in a mesh shape, or the surface of the core part may be covered with the shell part in places. It may also be in a form where the portion is exposed.
  • the glass transition temperature of the polymer of the present disclosure preferably an acrylic polymer
  • the glass transition temperature of the above polymer is more preferably -20 to 35°C, still more preferably -15 to 30°C. Note that the glass transition temperature (Tg) is calculated or measured as described above.
  • the glass transition temperature of the polymer in the core portion is preferably 0 to 60°C. More preferably, the temperature is 10 to 50°C.
  • the glass transition temperature of the polymer of the shell portion is preferably -30 to 30°C. More preferably, it is -20 to 20°C.
  • the difference in glass transition temperature between the core polymer and the shell polymer is preferably 5 to 60°C.
  • the damping performance in the range of ⁇ 60°C will be further improved.
  • the difference in glass transition temperature is more preferably 5 to 50°C, even more preferably 5 to 40°C.
  • the monomer component forming the core part and the shell part are formed.
  • the mass ratio to the monomer component (monomer component forming the core portion/monomer component forming the shell portion) is preferably from 30/70 to 70/30. With such a mass ratio, the effect of the structure having a core portion and a shell portion can be more fully exhibited.
  • the mass ratio of the monomer component forming the core portion to the monomer component forming the shell portion is more preferably 35/65 to 55/45.
  • the weight average molecular weight of the polymer A of the present disclosure is as described above as the weight average molecular weight of the polymer A in the resin layer A.
  • the average particle diameter of the emulsion resin particles is preferably 80 to 450 nm.
  • the average particle diameter of the emulsion resin particles is more preferably 400 nm or less, still more preferably 350 nm or less.
  • the average particle diameter is more preferably 100 nm or more.
  • the average particle diameter of the emulsion resin particles of the present disclosure is measured in accordance with JIS Z 8828, is measured by a dynamic light scattering method, and is defined as a cumulant average particle diameter, specifically as described in Examples. It can be measured by the following method.
  • the emulsion resin particles having the above average particle diameter preferably have a particle size distribution defined by the standard deviation divided by the average particle diameter (standard deviation/volume average particle diameter x 100) of 40% or less. More preferably it is 30% or less. When the particle size distribution is 40% or less, coarse particles are not included, and as a result, the damping material composition can exhibit sufficient heat drying properties.
  • the content of the polymer A (preferably, an acrylic polymer) in 100 parts by mass of the resin composition A of the present disclosure is preferably 45 parts by mass or more from the viewpoint of productivity, more preferably 50 parts by mass or more, and 60 parts by mass or more. Parts by mass or more are more preferable.
  • the content is preferably 95 parts by mass or less, more preferably 90 parts by mass or less, and even more preferably 87 parts by mass or less from the viewpoint of coating suitability.
  • the content of polymer A in 100 parts by mass of nonvolatile content of resin composition A of the present disclosure is more preferably 65 parts by mass or more, even more preferably 70 parts by mass or more, and 75 parts by mass or more. More preferably, the amount is 80 parts by weight or more, particularly preferably 95 parts by weight or more, even more preferably 98 parts by weight or more, even more preferably 99 parts by weight or more, and most preferably 100 parts by weight.
  • the resin composition A of the present disclosure may contain an inorganic filler.
  • examples of the inorganic filler of the present disclosure include those similar to the inorganic filler in the resin layer A of the present disclosure.
  • the inorganic filler of the present disclosure preferably has an average particle diameter of 0.1 to 200 ⁇ m, more preferably 0.5 to 100 ⁇ m, and even more preferably 1 to 50 ⁇ m.
  • the average particle diameter of the inorganic filler can be measured using a laser diffraction particle size distribution analyzer, and is the value of the 50% diameter by weight from the particle size distribution.
  • the content of the inorganic filler in 100 parts by mass of the resin composition A of the present disclosure is preferably 30 parts by mass or less, more preferably 25 parts by mass or less, and even more preferably 20 parts by mass or less from the viewpoint of damping properties.
  • the content of the inorganic filler contained in 100 parts by mass of the nonvolatile content of the resin composition A of the present disclosure is preferably 30 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, and 5 parts by mass. Parts by weight or less are particularly preferred, and most preferably substantially 0 parts by mass.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin composition A of the present disclosure is preferably 55 parts by mass or less, more preferably 40 parts by mass or less, and 15 parts by mass or less. is more preferable, particularly preferably 10 parts by weight or less, and most preferably substantially 0 parts by weight.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin composition A of the present disclosure is specified within a low range, the difference in elastic modulus between the resin layer A and the resin layer B becomes large. Therefore, the vibration damping effect can be fully exhibited.
  • the resin composition A of the present disclosure includes an aqueous solvent, and the polymer A is preferably dispersed or dissolved in the aqueous solvent, and preferably dispersed in the aqueous solvent. More preferred. That is, it is more preferable that the resin composition A is an emulsion.
  • being dispersed in an aqueous solvent means being dispersed without being dissolved in an aqueous solvent.
  • the above-mentioned polymer A can be polymerized by a known method such as solution polymerization or suspension polymerization, but its form is obtained by emulsion polymerization of monomer components in the damping material formulation Preferably, they are emulsion resin particles (resin particles present in an emulsion).
  • the aqueous solvent of the present disclosure may include organic solvents such as ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, etc. as long as it contains water, but water is preferable.
  • the blending amount of the solvent may be appropriately set in order to appropriately adjust the solid content concentration of the resin composition A of the present invention.
  • the content of the aqueous solvent in 100 parts by mass of the resin composition A of the present disclosure is preferably 30 parts by mass or more, more preferably 35 parts by mass or more, and even more preferably 40 parts by mass or more from the viewpoint of coating suitability. From the viewpoint of productivity, the content of the aqueous solvent is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and even more preferably 40 parts by mass or less.
  • the resin composition A of the present disclosure may further contain other components.
  • Other components include, for example, organic fillers (polyethylene, polystyrene, acrylic resins, silicone resins, urethane resins, etc.); fibers (carbon fibers, glass fibers, cellulose nanofibers, metal fibers, etc.); surfactants; dispersants. Thickener; Foaming agent; Gelling agent; Antifoaming agent; Plasticizer; Stabilizer; Wetting agent; Preservative; Antifoaming agent; Antiaging agent; Antifungal agent; Ultraviolet absorber; Antistatic agent; These agents These components can be used alone or in combination of two or more.
  • the resin composition A of the present disclosure preferably has a storage modulus of 1.0E+05 MPa or more at room temperature after being dried at 140° C. for 60 minutes after coating with a film thickness of 0.3 mm. 0E+06 MPa or more is more preferable, and 1.0E+07 MPa or more is even more preferable.
  • the storage modulus is preferably 5.0E+08 MPa or less, more preferably 5.0E+07 MPa or less.
  • the storage elastic modulus of the resin composition A after heating and drying corresponds to the storage elastic modulus of the resin layer A after substantially drying, and serves as an index of the vibration damping properties of the resin layer A.
  • the storage modulus of the resin composition A after heat drying is measured by the method described in Examples.
  • the resin composition A of the present disclosure preferably has a storage elastic modulus of 1.0E+04MPa or more at room temperature after being left at room temperature for 60 minutes after coating with a film thickness of 0.6mm, and preferably 2.0E+04MPa. The above is more preferable, and 3.0E+04MPa or more is even more preferable.
  • the storage modulus is preferably 5.0E+08 MPa or less, more preferably 5.0E+07 MPa or less.
  • the storage modulus of the resin composition A after drying at room temperature becomes an index of the drying properties of the resin composition A, since the storage modulus increases as the moisture in the resin composition A evaporates. If the drying property is excellent, drying at room temperature can be performed suitably, for example. In order to increase the storage modulus after drying at room temperature, it is possible to reduce the amount of water in the resin composition, reduce the water retention component, increase the content rate of the inorganic filler, etc. In this specification, room temperature is intended to be 25°C.
  • the pH of the resin composition A of the present disclosure is not particularly limited, but is preferably from 2 to 10, more preferably from 3 to 9.5, and even more preferably from 7 to 9.
  • the pH can be adjusted by adding ammonia water, water-soluble amines, alkali hydroxide aqueous solution, etc. to the acrylic resin.
  • the pH of the resin composition A of the present disclosure can be measured by the method described in the Examples below.
  • the viscosity of the resin composition A of the present disclosure is not particularly limited, but is preferably from 1 to 10,000 mPa ⁇ s, more preferably from 10 to 4,000 mPa ⁇ s, and even more preferably from 20 to 3,000 mPa ⁇ s. , 40 to 1000 mPa ⁇ s is particularly preferable.
  • the viscosity of the resin composition A of the present disclosure can be measured under the conditions described in the Examples below.
  • the content of zinc oxide in 100 parts by mass of the nonvolatile content of the resin composition B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1 part by mass or less, and It does not have to be included in
  • the non-volatile content of the resin composition B of the present disclosure may be calculated as a component excluding the volatile components used, or 1 g of the resin composition B is weighed from the total mass of the resin composition B, and 1 g of the resin composition B is weighed and dried in a hot air dryer to It may be dried for 1 hour at a temperature of .degree. C., and the resulting residue may be used as a nonvolatile component.
  • the resin composition B of the present disclosure may contain a crosslinking agent other than zinc oxide.
  • the crosslinking agent other than zinc oxide of the present disclosure is the same as the crosslinking agent other than zinc oxide described above in the resin layer B of the present disclosure.
  • the content of crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin composition B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less. .
  • the nonvolatile content of the resin composition B of the present disclosure does not need to contain substantially any crosslinking agent other than zinc oxide.
  • the total content of zinc oxide and crosslinking agents other than zinc oxide in 100 parts by mass of nonvolatile content of resin composition B of the present disclosure is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and 1 part by mass. The following are more preferable, and the content may not be substantially included.
  • the nonvolatile content per 100 parts by mass of the resin composition B of the present disclosure is preferably 60 parts by mass or more from the viewpoint of drying properties, more preferably 70 parts by mass or more, even more preferably 75 parts by mass or more, and From this viewpoint, the amount is preferably 90 parts by mass or less, more preferably 88 parts by mass or less, and even more preferably 85 parts by mass or less.
  • the resin composition B of the present disclosure may include a polymer B.
  • the polymer B of the present disclosure is not particularly limited, but is preferably an acrylic polymer from the viewpoint of damping properties.
  • the acrylic polymer is as described above.
  • the resin composition B of the present disclosure may contain one type of polymer B, or may contain two or more types of polymer B.
  • the polymer B may be composed of two or more kinds of polymers and may be in the form of a composite.
  • the polymer B has a form having a core part and a shell part, which will be described later, the polymer B is composed of two types of polymers, and one of the two types of polymers is the core part and the other is the shell part. It may also be formed.
  • the (meth)acrylic acid alkyl ester monomer and other monomers copolymerizable with the (meth)acrylic acid alkyl ester monomer are the monomer components forming the core of the emulsion, the shell It may be contained in any of the monomer components forming the part, or it may be used in both of them. Further, it is preferable that at least one of the polymers forming the emulsion resin particles is in the form of emulsion resin particles having a core portion and a shell portion. Thereby, the number of interfaces between the polymers can be increased, and effects such as improved vibration damping properties can be further enhanced.
  • the core part and the shell part may be completely compatible with each other and may have a homogeneous structure in which they cannot be distinguished.
  • a core-shell composite structure is preferred.
  • Emulsions with a core-shell composite structure have excellent vibration damping properties over a wide range of practical temperatures. In particular, it exhibits superior vibration damping performance compared to other types of damping material compounds, even at high temperatures.As a result, within the practical temperature range, it exhibits vibration damping performance over a wide range from room temperature to high temperature. can demonstrate.
  • the surface of the core portion is covered with the shell portion. In this case, it is preferable that the surface of the core part is completely covered with the shell part, but it may not be completely covered, for example, the surface of the core part may be covered in a mesh shape, or the surface of the core part may be covered with the shell part in places.
  • the glass transition temperature of the polymer in the core portion is preferably 0 to 60°C. More preferably, the temperature is 10 to 50°C.
  • the glass transition temperature of the polymer of the shell portion is preferably -30 to 30°C. More preferably, it is -20 to 20°C. Further, the difference in glass transition temperature between the core polymer and the shell polymer is preferably 5 to 60°C.
  • the difference in glass transition temperature is more preferably 5 to 50°C, even more preferably 5 to 40°C.
  • the mass ratio to the monomer component is preferably from 30/70 to 70/30. With such a mass ratio, the effect of the structure having a core portion and a shell portion can be more fully exhibited.
  • the mass ratio of the monomer component forming the core portion to the monomer component forming the shell portion is more preferably 35/65 to 55/45.
  • the weight average molecular weight of the polymer B of the present disclosure is as described above as the weight average molecular weight of the polymer B in the resin layer B.
  • the average particle diameter of the emulsion resin particles is preferably 80 to 450 nm.
  • the average particle diameter of the emulsion resin particles is more preferably 400 nm or less, still more preferably 350 nm or less.
  • the average particle diameter is more preferably 100 nm or more.
  • the average particle diameter of the emulsion resin particles of the present disclosure is measured in accordance with JIS Z 8828, is measured by a dynamic light scattering method, and is defined as a cumulant average particle diameter, specifically as described in Examples. It can be measured by the following method.
  • the emulsion resin particles having the above average particle size preferably have a particle size distribution defined by the standard deviation divided by the volume average particle size (standard deviation/volume average particle size x 100) of 40% or less. . More preferably it is 30% or less. When the particle size distribution is 40% or less, coarse particles are not included, and as a result, the damping material composition can exhibit sufficient heat drying properties.
  • the content of the polymer B in 100 parts by mass of the resin composition B of the present disclosure is preferably 10 parts by mass or more from the viewpoint of damping properties, more preferably 12 parts by mass or more, even more preferably 15 parts by mass or more, and coating suitability. From this viewpoint, the amount is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 25 parts by mass or less.
  • the content ratio of polymer B in 100 parts by mass of non-volatile content of resin composition B of the present disclosure is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and 20 parts by mass or more. More preferably, from the viewpoint of coating suitability, the amount is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably 27 parts by mass or less. is more preferable.
  • Resin composition B of the present disclosure includes an inorganic filler.
  • the inorganic filler of the present disclosure include those similar to the inorganic filler in the resin layer B of the present disclosure.
  • the content of the inorganic filler in 100 parts by mass of the resin composition B of the present disclosure is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, even more preferably 57 parts by mass or more from the viewpoint of vibration damping. From the viewpoint of properties, the amount is preferably 80 parts by mass or less, more preferably 75 parts by mass or less, and even more preferably 70 parts by mass or less.
  • the content of the inorganic filler contained in 100 parts by mass of the nonvolatile content of the resin composition B of the present disclosure is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, and 60 parts by mass or more from the viewpoint of damping properties. is more preferred, 65 parts by mass or more is even more preferred, and 70 parts by mass or more is particularly preferred.
  • the content of the inorganic filler is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and even more preferably 80 parts by mass or less from the viewpoint of coating suitability.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B contained in the resin composition B of the present disclosure is preferably 150 parts by mass or more, more preferably 200 parts by mass or more, and 250 parts by mass or more. It is more preferable that it is, and it is especially preferable that it is 300 parts by mass or more.
  • the content ratio of the inorganic filler to 100 parts by mass of the acrylic resin contained in the resin composition B of the present disclosure is preferably 400 parts by mass or less, and more preferably 380 parts by mass or less.
  • the content ratio of the inorganic filler in 100 parts by mass of the resin composition B of the present disclosure is more preferably 30 parts or more, more preferably 35 parts by mass or more than the content ratio of the inorganic filler in 100 parts by mass of the resin composition A. is more preferred, more preferably 40 parts by mass or more, even more preferably 50 parts by mass or more, particularly preferably 55 parts by mass or more.
  • the content ratio of the inorganic filler in 100 parts by mass of the resin composition B of the present disclosure is preferably 90 parts by mass or less, and 80 parts by mass or less more than the content ratio of the inorganic filler in 100 parts by mass of the resin composition A. More preferably, the amount is 70 parts by mass or less. In this way, by increasing the content of the inorganic filler in the resin composition B compared to the content of the inorganic filler in the resin composition A, in combination with the lower layer, it can be controlled over a wide temperature range within the practical temperature range. The vibration properties can be improved.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B in the resin composition B of the present disclosure is more preferably 100 parts by mass or more than the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin composition A. , more preferably 200 parts by mass or more, even more preferably 250 parts by mass or more, even more preferably 280 parts by mass or more, particularly preferably 300 parts by mass or more.
  • the content ratio of the inorganic filler to 100 parts by mass of the polymer B in the resin composition B of the present disclosure is 400 parts by mass or less greater than the content ratio of the inorganic filler to 100 parts by mass of the polymer A in the resin composition A. is preferred, and more preferably 300 parts by mass or less.
  • the resin composition B of the present disclosure contains an aqueous solvent, and the polymer B is preferably dispersed or dissolved in the aqueous solvent, and preferably dispersed in the aqueous solvent. More preferred. That is, it is more preferable that the damping material compound is an emulsion.
  • being dispersed in an aqueous solvent means being dispersed without being dissolved in an aqueous solvent.
  • the above-mentioned polymer B can be polymerized by a known method such as solution polymerization or suspension polymerization, but its form in the damping material formulation is obtained by emulsion polymerization of monomer components.
  • the aqueous solvent of the present disclosure may include organic solvents such as ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, etc. as long as it contains water, but water is preferable.
  • the blending amount of the solvent may be appropriately set in order to appropriately adjust the solid content concentration of the resin composition A of the present invention.
  • the content of the aqueous solvent in 100 parts by mass of the resin composition B of the present disclosure is preferably 10 parts by mass or more from the viewpoint of coating suitability, more preferably 13 parts by mass or more, even more preferably 15 parts by mass or more, and from the viewpoint of drying property.
  • the content of the aqueous solvent in resin composition B is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, even more preferably 25 parts by mass or less.
  • the resin composition B of the present disclosure may further contain other components.
  • Other components include, for example, organic fillers (polyethylene, polystyrene, acrylic resins, silicone resins, urethane resins, etc.); fibers (carbon fibers, glass fibers, cellulose nanofibers, metal fibers, etc.); surfactants; dispersants. Thickener; Foaming agent; Gelling agent; Antifoaming agent; Plasticizer; Stabilizer; Wetting agent; Preservative; Antifoaming agent; Antiaging agent; Antifungal agent; Ultraviolet absorber; Antistatic agent; These agents These components can be used alone or in combination of two or more.
  • the resin composition B of the present disclosure has a storage modulus of 1.0E+07 MPa or more at 25° C. after coating with a film thickness of 0.6 mm and drying in an oven at 140° C. for 60 minutes.
  • 0E+08MPa or more is more preferable, 1.0E+09MPa or more is even more preferable, and particularly preferably 2.0E+09MPa or more.
  • the storage modulus is preferably 1.0E+11 MPa or less, more preferably 1.0E+10 MPa or less, even more preferably 5.0E+09 MPa or less.
  • the storage elastic modulus of the resin composition B after heating and drying corresponds to the storage elastic modulus of the resin layer B after substantially drying, and serves as an index of the damping properties of the resin layer B.
  • the storage modulus of the resin composition B after heat drying is measured by the method described in Examples.
  • the storage elastic modulus of the resin composition B after heating and drying is preferably higher than the storage elastic modulus of the resin composition A after heating and drying by 1.0E+07 MPa or more, more preferably 1.0E+08 MPa or more, It is more preferably higher than 1.0E+09MPa, and particularly preferably higher than 2.0E+09MPa.
  • the storage modulus is preferably as high as 1.0E+11 MPa, more preferably as high as 1.0E+10 MPa, and even more preferably as high as 5.0E+09 MPa.
  • the resin composition B of the present disclosure preferably has a storage modulus of storage elasticity at room temperature of 1.8E+08MPa or more, preferably 1.9E+08MPa or more after being left at room temperature for 60 minutes after coating with a film thickness of 0.6mm. is more preferable, more preferably 2.0E+08MPa or more, preferably 5.0E+09MPa or less, more preferably 3.0E+09MPa or less, even more preferably 2.0E+09MPa or less.
  • the storage modulus of the resin composition B after drying at room temperature becomes an index of the drying properties of the resin composition B, since the storage modulus increases as the moisture in the resin composition B evaporates. If the drying property is excellent, drying at room temperature can be performed suitably, for example.
  • the storage modulus of the resin composition B after drying at room temperature is measured by the method described in Examples.
  • the pH of the resin composition B of the present disclosure is not particularly limited, but is preferably from 2 to 10, more preferably from 3 to 9.5, and even more preferably from 7 to 9.
  • the pH can be adjusted by adding ammonia water, water-soluble amines, alkali hydroxide aqueous solution, etc. to the acrylic resin.
  • the pH of the resin composition B of the present disclosure can also be measured by the method described in the Examples below.
  • the viscosity of the resin composition B of the present disclosure is not particularly limited, but is preferably from 1 to 10,000 mPa ⁇ s, more preferably from 10 to 4,000 mPa ⁇ s, and even more preferably from 20 to 3,000 mPa ⁇ s. , 40 to 1000 mPa ⁇ s is particularly preferable.
  • the viscosity of the resin composition B of the present disclosure can be measured using a known method, but can also be measured under the conditions described in the Examples below.
  • the resin composition A may contain an inorganic filler
  • the resin composition B contains an inorganic filler
  • the nonvolatile content of the resin composition A is The content of the inorganic filler in 100 parts by mass is 30 parts by mass or less
  • the content of the inorganic filler in 100 parts by mass of the nonvolatile content of resin composition B is 50 parts by mass or more and 90 parts by mass or less
  • the resin composition A and resin composition B may each contain zinc oxide
  • the content of zinc oxide per 100 parts by mass of nonvolatile content of resin composition A is 5 parts by mass or less
  • the nonvolatile content of resin composition B The content of zinc oxide per 100 parts by mass is 5 parts by mass or less.
  • the laminate for vibration damping material of the present disclosure As a manufacturing method of the laminate for vibration damping material of the present disclosure, it can be obtained by applying resin composition A on a base material and applying resin composition B on the upper layer of resin layer A.
  • the laminate for vibration damping material of the present disclosure includes, for example, a first step of forming a resin layer A and a second step of forming a resin layer B, a second step of forming a further coating film may be used. 3 steps may be included. Note that the first step and the second step may be performed simultaneously.
  • the method for producing a damping material laminate (damping coating film) according to the second step of the present invention includes the steps of forming the resin layer A and the resin layer B, as well as drying these coating films. It is preferable to include a step of causing.
  • a resin layer A may be formed and dried, and then a resin layer B may be formed thereon and dried. After forming layer A and resin layer B, these coating films may be dried at once. More preferably, the method is such that after forming the resin layer A and the resin layer B, these coating films are dried at once. That is, it is preferable to perform the step of drying the coating film after performing the step of forming the resin layer A and the step of forming the resin layer B.
  • the drying process is performed by drying all the coating films. It is preferable to perform this after performing the forming step and dry all the formed coating films at once.
  • the preferred temperature for drying the coating film is preferably 0°C to 200°C, more preferably 5°C to 150°C, and 10°C to The temperature is more preferably 100°C, and particularly preferably 15°C to 90°C.
  • the preferred time for drying the coating film is preferably 10 to 240 minutes.
  • the preferred temperature and time for drying the coating film are as follows: The temperature and time are the same as those described in the method for producing a laminate (damping coating film). Furthermore, in the method for manufacturing a laminate for vibration damping material of the present disclosure, vibration damping is achieved by performing a step of drying the coating film at once after performing the step of forming the resin layer A and the step of forming the resin layer B. In the method for producing a coating film, the preferable temperature and time for drying the coating film are the same as those described in the method for producing a damping coating film according to the first step of the present invention.
  • the method of application is not particularly limited, and for example, a method of applying using a brush, spatula, air spray, airless spray, mortar gun, ricing gun, etc. can be used.
  • the damping coating film of the present invention can also be obtained by a process of laminating a coating film on a release paper, laminating a base material thereon, and finally peeling off the release paper, or a process of molding. is possible. In these cases, the layer that is applied first becomes the upper layer on the surface side.
  • the damping coating film of the present invention is preferably obtained by heating and drying the applied damping material composition.
  • the present invention can be suitably used even under milder drying conditions than those in conventional manufacturing processes.
  • the surface hardness that is, the storage modulus of the upper layer can be quickly improved even at a temperature of around 100°C or even lower, compared to the conventional drying process at around 150°C.
  • a coating film with high vibration damping properties can be formed.
  • the laminate for vibration damping material of the present disclosure exhibits excellent vibration damping properties, and is therefore preferably used in vehicles. Specifically, it can be suitably used by forming a coating film on the surface of materials such as steel plates that constitute various structures such as automobiles, railway vehicles, ships, aircraft, and electrical equipment.
  • the present disclosure also relates to the use of the damping material (laminate) of the present disclosure as a damping material.
  • ⁇ Cumulant average particle diameter> The average particle diameter of the emulsion resin particles was measured using a dynamic light scattering particle size distribution analyzer (FPAR-1000 manufactured by Otsuka Electronics Co., Ltd.). ⁇ Nonvolatile content (N.V.)> Approximately 1 g of the obtained resin composition was weighed and dried in a hot air dryer at 150° C. for 1 hour, and the remaining amount after drying was expressed as non-volatile matter, expressed as a percentage of the mass before drying (% by mass). [Nonvolatile content (mass%) in resin composition] ([mass of residue] ⁇ [resin composition 1 g]) x 100
  • ⁇ pH> The value was measured at 25° C. using a pH meter (“F-23” manufactured by Horiba, Ltd.).
  • ⁇ Viscosity> Measurement was performed using a B-type rotational viscometer ("VISCOMETER TUB-10" manufactured by Toki Sangyo Co., Ltd.) at 25° C. and 20 rpm.
  • VISCOMETER TUB-10 B-type rotational viscometer
  • Measuring equipment HLC-8120GPC (product name, manufactured by Tosoh Corporation)
  • Molecular weight column TSK-GEL GMHXL-L and TSK-GELG5000HXL (both manufactured by Tosoh Corporation) were connected in series and used
  • Eluent Tetrahydrofuran (THF)
  • Standard material for calibration curve Polystyrene (manufactured by Tosoh Corporation)
  • Measurement method The object to be measured is dissolved in THF so that the solid content is approximately 0.2% by mass, and the resulting solution is filtered through a filter, and the molecular weight is measured using the sample as a measurement sample.
  • the glass transition temperature (Tg) is calculated from the monomer composition constituting the polymer component using the following formula (1).
  • Tg' is the Tg (absolute temperature) of the polymer.
  • W1', W2', . . . Wn' are the mass fractions of each monomer relative to the total monomer component.
  • T1, T2, . . . Tn are glass transition temperatures (absolute temperatures) of homopolymers (homopolymers) made of each monomer component.
  • the resin composition A of the present disclosure contains two or more types of polymers, or when at least one type of polymer is obtained by multistage polymerization (for example, a resin composition having a core part and a shell part) In the case of emulsion resin particles), the Tg calculated from the monomer composition used in all stages was described as "total Tg".
  • Tg glass transition temperature
  • Production example 1 (resin composition A1) 285 parts of deionized water was charged into a polymerization vessel equipped with a stirrer, a reflux condenser, a thermometer, a nitrogen introduction tube, and a dropping funnel. Thereafter, the internal temperature was raised to 75° C. while stirring under a nitrogen gas stream.
  • styrene 60 parts of styrene, 140 parts of methyl methacrylate, 190 parts of butyl acrylate, 100 parts of 2-ethylhexyl acrylate, 10 parts of acrylic acid, 3.0 parts of t-dodecyl mercaptan, and Hitenol, which had been adjusted to a 20% aqueous solution in advance, were added.
  • a resin composition with a molecular weight of 51,000, a first stage Tg of 16°C, a second stage Tg of -13°C, and a total Tg of 0°C was obtained.
  • the emulsion obtained in Production Example 1 was also used as resin composition A1.
  • Production example 2 100 parts by mass of resin composition A1 and 23 parts of calcium carbonate (NN#200, manufactured by Nitto Funka Kogyo Co., Ltd.) as an inorganic filler were mixed to obtain resin composition A2.
  • N#200 manufactured by Nitto Funka Kogyo Co., Ltd.
  • Resin composition B1 was obtained by mixing 50 parts of resin composition A1, 1.5 parts of zinc oxide, and 72 parts of calcium carbonate (NN#200, manufactured by Nitto Funka Kogyo Co., Ltd.) as an inorganic filler.
  • Epocross used in Production Example 4 was prepared by adding 2 parts by mass of Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd., non-volatile content: 39% by mass).
  • Example 1 A first layer of 2 mm thick was formed on the base material (cold rolled steel plate, 250*10*1.0 mm) using the resin composition A1 obtained in Production Example 1, and then heated for 15 minutes at room temperature (25°C). Dry for an hour. Thereafter, a 2 mm thick second layer was formed using the resin composition B1 obtained above and dried at room temperature (25°C) for 15 hours, so that the thickness ratio was 50 on the base material.
  • a test piece for evaluation was obtained on which a damping coating film consisting of a first layer and a second layer of /50 was formed.
  • Examples 2 to 7 A damping coating consisting of the first layer/second layer was prepared in the same manner as in Example 1, except that the compounding ratio and the thickness of the first layer and second layer were changed as shown in Tables 2 and 3 below. A test piece for evaluation on which a film was formed was obtained.
  • Comparative example 1 A 4 mm layer was formed on the base material (cold rolled steel plate, 250*10*1.0 mm) using the damping material composition 3 obtained in Example 3, and the layer was dried. A test piece for evaluation was obtained on which a damping coating film consisting of a single layer was formed.
  • Comparative example 2 A test piece for evaluation was obtained in the same manner as in Example 1 except that the amount of zinc oxide was changed to 6.0 parts and the thickness and ratio of the first layer and second layer were changed.
  • Evaluation method (coating film thickness)
  • the thickness of the dry coating film of each layer and the total thickness of the dry coating film (first layer + second layer) described in the examples and comparative examples can be determined by measuring any five points with a caliper and calculating the average value. Calculated.
  • the ratio of the average thickness of the lower layer to the average thickness of the upper layer was measured by cutting out the cross section of the damping coating film at five arbitrary points and analyzing the cross section with a microscope.
  • Resin composition A (A1, A2): A coating film with a thickness of 0.3 mm is formed on a glass plate using a resin composition corresponding to resin composition A in each example. After drying in an oven at 140°C for 60 minutes, it was cut into strips of 5.0 mm x 50.0 mm to obtain test pieces for storage modulus measurement. The obtained test piece was measured using a dynamic viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments) in tensile mode, frequency 1 Hz, strain 0.1%, temperature increase condition 3°C/min, from -20°C to 100°C. The storage modulus was measured at 25°C, and the storage modulus at 25°C was evaluated.
  • ARES-G2 dynamic viscoelasticity measuring device
  • Resin composition B (B1 to B5): A coating film with a thickness of 0.6 mm is formed on a glass plate using a resin composition corresponding to resin composition B in each example. After drying in an oven at 140°C for 60 minutes, it was cut into strips of 2.5 mm x 50.0 mm to obtain test pieces for storage modulus measurement. The obtained test piece was measured using a dynamic viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments) in tensile mode, frequency 10.0 Hz, strain 0.1%, temperature increase condition 3°C/min, -20°C. The storage modulus was measured at 100°C, and the storage modulus at 25°C was evaluated.
  • ARES-G2 dynamic viscoelasticity measuring device
  • a coating film with a thickness of 0.6 mm is formed on a glass plate using a resin composition corresponding to resin composition B in each example. After drying in a constant temperature room at 25° C. for 60 minutes, it was cut into strips of 2.5 mm x 50.0 mm to obtain test pieces for storage modulus measurement. The storage elasticity of the obtained test piece was measured using a dynamic viscoelasticity measuring device ARES-G2 (manufactured by TA Instruments) under the conditions of tensile mode, frequency 10.0Hz, strain 0.1%, and 25°C. The rate was evaluated.
  • ARES-G2 dynamic viscoelasticity measuring device

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JPH10202775A (ja) * 1997-01-23 1998-08-04 Cosmo Sogo Kenkyusho:Kk 制振シート
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JP2011231184A (ja) * 2010-04-26 2011-11-17 Nippon Shokubai Co Ltd 制振材用エマルション及び制振材配合物
JP2017071106A (ja) * 2015-10-06 2017-04-13 積水化学工業株式会社 樹脂積層体

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JP7455320B2 (ja) * 2020-03-31 2024-03-26 国立大学法人東京工業大学 制振性塗膜

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JPS5588876A (en) * 1978-12-07 1980-07-04 Teroson Gmbh Preparation of coating with improved vibration buffer property and sound absorbing property on rigid base material
JPH06254483A (ja) * 1993-03-04 1994-09-13 Aisin Chem Co Ltd 耐チッピング塗膜
JPH10202775A (ja) * 1997-01-23 1998-08-04 Cosmo Sogo Kenkyusho:Kk 制振シート
JP2007504014A (ja) * 2003-08-29 2007-03-01 バイヤリッシェ モトーレン ベルケ アーゲー 吸音塗装、その製造方法およびその使用方法
JP2011231184A (ja) * 2010-04-26 2011-11-17 Nippon Shokubai Co Ltd 制振材用エマルション及び制振材配合物
JP2017071106A (ja) * 2015-10-06 2017-04-13 積水化学工業株式会社 樹脂積層体

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