WO2019159672A1 - Copolymère séquencé contenant un groupe anhydride d'acide, composition de résine, feuille de résine et verre feuilleté - Google Patents

Copolymère séquencé contenant un groupe anhydride d'acide, composition de résine, feuille de résine et verre feuilleté Download PDF

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Publication number
WO2019159672A1
WO2019159672A1 PCT/JP2019/002801 JP2019002801W WO2019159672A1 WO 2019159672 A1 WO2019159672 A1 WO 2019159672A1 JP 2019002801 W JP2019002801 W JP 2019002801W WO 2019159672 A1 WO2019159672 A1 WO 2019159672A1
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Prior art keywords
block copolymer
acid anhydride
structural unit
anhydride group
derived
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PCT/JP2019/002801
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English (en)
Japanese (ja)
Inventor
春樹 上村
洋平 小出
竜太 栗原
小原　禎二
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日本ゼオン株式会社
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Priority to JP2020500376A priority Critical patent/JPWO2019159672A1/ja
Publication of WO2019159672A1 publication Critical patent/WO2019159672A1/fr

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    • 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
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/04—Reduction, e.g. hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to an acid anhydride group-containing block copolymer, a resin composition, a resin sheet, and laminated glass.
  • a hydride of a block copolymer (hereinafter sometimes referred to as “block copolymer hydride”) and an acid anhydride group, an alkoxysilyl group, etc. introduced into the block copolymer hydride,
  • block copolymer hydride an acid anhydride group, an alkoxysilyl group, etc.
  • Useful for applications requiring excellent flexibility and transparency such as interlayer films for laminated glass, sealing materials for solar cells, sealing materials for organic electroluminescence elements (for example, Patent Documents 1 to 3). reference).
  • the resin composition obtained by mixing the block copolymer hydride with an additive is usually processed into a sheet by extrusion molding, calendar molding, or the like after being made into a pellet state. And the resin sheet obtained by processing the resin composition into a sheet shape is laminated on the base material, so that an interlayer film for laminated glass, a sealing material for solar cells, a sealing material for organic electroluminescence elements, etc. It is used for
  • the laminated glass is excellent in safety because it has less scattering of glass fragments even when it is broken by a collision object and can resist the penetration of the collision object. Therefore, laminated glass is widely used as window glass for automobiles, airplanes, and buildings.
  • Patent Document 4 a monomer block derived from a polymer block mainly composed of a monomer unit derived from an aromatic vinyl compound and a chain conjugated diene compound (linear conjugated diene or branched conjugated diene) is used.
  • Modified block copolymer hydride obtained by introducing alkoxysilyl group into block copolymer hydride obtained by hydrogenating block copolymer containing polymer block as main component at a predetermined ratio is used for the intermediate film.
  • Patent Document 5 30 to 55% by mass of a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound and 45 to 70 polymer blocks mainly composed of a structural unit derived from a chain conjugated diene compound.
  • a block copolymer hydride obtained by introducing an acid anhydride group into a block copolymer hydride obtained by hydrogenating a block copolymer comprising mass%, and a function of shielding infrared rays in a predetermined wavelength region By using a sheet made of a resin composition containing a metal oxide fine particle and / or a near-infrared absorbing dye having an excellent heat shielding function and excellent moisture resistance and durability It has been proposed to provide glass.
  • the sheet made of the resin composition containing the conventional modified block copolymer hydride has room for improvement in terms of improving adhesiveness while ensuring transparency.
  • an object of the present invention is to provide a resin sheet that can achieve both excellent adhesiveness and transparency. Moreover, an object of this invention is to provide the acid anhydride group containing block copolymer and resin composition which can provide the resin sheet which can make the outstanding adhesiveness and transparency compatible. Furthermore, an object of this invention is to provide a laminated glass provided with the resin sheet which can make the outstanding adhesiveness and transparency compatible.
  • the present inventor has intensively studied for the purpose of solving the above problems. And, the present inventor has excellent adhesion by using an acid anhydride group-containing block copolymer having predetermined two kinds of polymer blocks at a predetermined mass fraction and containing a predetermined structural unit.
  • the present invention has been completed by finding that a resin sheet capable of satisfying both properties and transparency can be provided.
  • the present invention aims to advantageously solve the above problems, and the acid anhydride group-containing block copolymer of the present invention comprises a structural unit [a1] derived from an aromatic vinyl compound, and Derived from a polymer block [A] containing as a main component a structural unit [a2] obtained by hydrogenating at least a part of unsaturated bonds in a structure derived from an aromatic vinyl compound and a chain conjugated diene compound
  • the structural unit [b1] and / or the structural unit [b2] formed by hydrogenating unsaturated bonds in the structure derived from the chain conjugated diene compound are the main components.
  • a polymer block [B], and the structural unit [a1] and [a2] account for the mass fraction of the entire block copolymer as wA, and the structural units [b1] and [b] ],
  • the ratio of wA to wB is 5/95 or more and 29/71 or less when the mass fraction of the entire block copolymer is wB, and the structural unit [a2] and It contains at least one of [b2].
  • the polymer block [A] containing the predetermined structural unit [a1] and / or [a2] as the main component and the predetermined structural unit [b1] and / or [b2] as the main component are contained.
  • the acid anhydride group preferably contains a maleic anhydride group and / or an itaconic anhydride group. If a maleic anhydride group and / or an itaconic anhydride group are included as the acid anhydride group, the resin sheet formed using the resin composition containing the acid anhydride group-containing block copolymer has a further excellent adhesive property. It can be demonstrated.
  • the chain conjugated diene compound is isoprene
  • a structural unit derived from isoprene and an unsaturated bond in the structure derived from isoprene are hydrogenated.
  • the structural unit derived only from 1,2-addition polymerization and the structural unit formed by hydrogenating unsaturated bonds in the structure derived only from 1,2-addition polymerization are the entire block copolymer.
  • the block comprises a structural unit derived only from 3,4-addition polymerization and a structural unit obtained by hydrogenating an unsaturated bond in the structure derived only from 3,4-addition polymerization, wherein the mass fraction in w is wP
  • the formula: Structural unit ratio S (wP + wQ) / (wP + wQ + wR) It is preferable that the value of the structural unit ratio S represented by is 0.3 or more.
  • a resin sheet formed using a resin composition containing an acid anhydride group-containing block copolymer can satisfactorily achieve both adhesiveness and transparency, and can also exhibit excellent sound insulation.
  • the resin composition of the present invention comprises any of the above-mentioned acid anhydride group-containing block copolymers and a metal oxide. And at least one additive (X) selected from the group consisting of fine particles, metal boride fine particles, and near-infrared absorbing dyes.
  • X additive selected from the group consisting of fine particles, metal boride fine particles, and near-infrared absorbing dyes.
  • the additive (X) includes metal oxide fine particles, and the metal oxide includes cesium-doped tungsten oxide. If the additive (X) contains fine particles of metal oxide and the metal oxide contains cesium-doped tungsten oxide, the resin sheet formed using the resin composition has both good adhesion and transparency. In addition, it is possible to exhibit further excellent heat shielding properties.
  • the additive (X) contains fine particles of metal boride, and the metal boride contains lanthanum boride. If the additive (X) includes fine particles of metal boride and the metal boride includes lanthanum boride, the resin sheet formed using the resin composition has both excellent adhesion and transparency. In addition, it can exhibit further excellent heat shielding properties.
  • the present invention aims to solve the above-mentioned problem advantageously, and the resin sheet of the present invention comprises at least one resin layer comprising any one of the resin compositions described above. To do.
  • the resin sheet containing at least one resin layer made of any of the resin compositions described above can achieve both excellent adhesiveness and transparency.
  • the present invention aims to advantageously solve the above problems, and the laminated glass of the present invention is characterized by comprising at least one resin sheet as described above.
  • the laminated glass of the present invention is characterized by comprising at least one resin sheet as described above.
  • the laminated glass of the present invention preferably has a region with a light transmittance of 50% or less within a wavelength range of 800 nm or more and 2000 nm or less, and further has a light transmittance of 60% or more at a wavelength of 500 nm. More preferably. If it is a laminated glass having a region with a light transmittance of 50% or less within a wavelength range of 800 nm or more and 2000 nm or less, it is possible to exhibit excellent heat shielding properties while achieving both good adhesion and transparency, Furthermore, if the light transmittance at a wavelength of 500 nm of the laminated glass is 60% or more, it is possible to exhibit further excellent transparency while exhibiting excellent heat shielding properties. In the present invention, the light transmittance can be measured using an integrating sphere spectrophotometer.
  • an acid anhydride group-containing block copolymer and a resin composition that can provide a resin sheet that can achieve both excellent adhesion and transparency.
  • the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.
  • a laminated glass provided with the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.
  • the acid anhydride group-containing block copolymer of the present invention is used for the preparation of the resin composition of the present invention.
  • the resin sheet of this invention contains at least 1 layer of the resin layer which consists of a resin composition of this invention.
  • the laminated glass of the present invention includes at least one resin sheet of the present invention.
  • the acid anhydride group-containing block copolymer of the present invention is a block copolymer containing an acid anhydride group, derived from a structural unit [a1] derived from an aromatic vinyl compound and / or an aromatic vinyl compound.
  • the acid anhydride group-containing block copolymer contains at least one of the above-described structural units [a2] and [b2]
  • the weather resistance of the obtained resin sheet can be secured sufficiently high.
  • the acid anhydride group enhances the dispersibility of the additive that can be added to the resin composition containing the acid anhydride group-containing block copolymer, and improves the transparency of the resin sheet to be produced. It has the function of exhibiting excellent adhesiveness.
  • the acid anhydride group include a maleic anhydride group, a citraconic anhydride group, an itaconic anhydride group, an anhydrous 2,3-dimethylmaleic acid group, an anhydrous 5-norbornene-2,3-dicarboxylic acid group, an allyl succinic anhydride group, Examples thereof include a 2-phenylmaleic anhydride group and a cis-aconitic anhydride group.
  • the acid anhydride groups include maleic anhydride groups, itaconic anhydride groups, anhydrous 5-norbornene-2, It is preferably a 3-dicarboxylic acid group, and more preferably a maleic anhydride group and an itaconic anhydride group from the viewpoint of further satisfying both the adhesiveness and transparency of the resin sheet.
  • the content ratio of the acid anhydride group in the acid anhydride group-containing block copolymer is not particularly limited, but 0.01 mass when the total acid anhydride group-containing block copolymer is 100 mass% % Or more, preferably 0.1% by weight or more, more preferably 0.3% by weight or more, preferably 9% by weight or less, and 6.5% by weight or less. It is more preferable that it is 3.8% by mass or less. If the content ratio of the acid anhydride group in the acid anhydride group-containing block copolymer is 0.01% by mass or more, the transparency of the resulting resin sheet can be further enhanced. On the other hand, if the content ratio of the acid anhydride group in the acid anhydride group-containing block copolymer is 9% by mass or less, the low water absorption of the resulting resin sheet can be increased.
  • the polymer block [A] is a structural unit [a2] obtained by hydrogenating at least part of an unsaturated bond in a structural unit [a1] derived from an aromatic vinyl compound and / or a structure derived from an aromatic vinyl compound. ] As a main component.
  • ⁇ Structural Unit [a1] Examples of the aromatic vinyl compound capable of forming the structural unit [a1] derived from the aromatic vinyl compound include styrene and derivatives thereof. Specifically, styrene, ⁇ -methylstyrene, 2-methylstyrene, 3- Methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, 4-monochlorostyrene, dichlorostyrene, 4- Examples thereof include monofluorostyrene and 4-phenylstyrene.
  • styrene ⁇ -methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4- Dimethyl styrene, 4-t-butyl styrene, 5-t-butyl-2-methyl styrene, and 4-phenyl styrene are preferably used, and styrene is particularly preferable in terms of industrial availability. One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the structural unit [a2] is a structural unit obtained by hydrogenating at least part of unsaturated bonds in the structure derived from the aromatic vinyl compound. And as an aromatic vinyl compound, the same thing as what was mentioned above as an aromatic vinyl compound which can form structural unit [a1] is mentioned. In the structural unit [a2], only part of the unsaturated bonds in the structure derived from the aromatic vinyl compound may be hydrogenated, or all of the unsaturated bonds may be hydrogenated. However, from the viewpoint of enhancing the weather resistance of the resulting resin sheet, it is preferable that all of the unsaturated bonds in the structure derived from the aromatic vinyl compound are hydrogenated.
  • the structural unit [a2] may be a structural unit derived only from addition polymerization of a vinyl group of a compound obtained by hydrogenating at least a part of unsaturated bonds in the aromatic ring of an aromatic vinyl compound.
  • compounds obtained by hydrogenating at least part of unsaturated bonds in the aromatic ring of an aromatic vinyl compound include vinylcyclohexane, 1-vinyl-1-cyclohexene, 3-vinyl-1-cyclohexene, 4- Vinyl-1-cyclohexene, 1-vinyl-1,3-cyclohexadiene, 2-vinyl-1,3-cyclohexadiene, 5-vinyl-1,3-cyclohexadiene, 3-vinyl-1,4-cyclohexadiene, Examples thereof include compounds such as 4-vinyl-1,4-cyclohexadiene and derivatives thereof.
  • the polymer block [A] may contain structural units other than the structural units [a1] and [a2], and such other structural units are structures derived from a chain conjugated diene compound described later. It may be a unit [b1] and / or a structural unit [b2] formed by hydrogenating an unsaturated bond in the structure derived from a chain conjugated diene compound. As other compounds that can form a structural unit, those not containing a polar group are preferable.
  • ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -Chain olefins such as nonene, 1-decene, 1-dodecene, 1-eicosene, 4-methyl-1-pentene, 4,6-dimethyl-1-heptene;
  • cyclic compounds other than compounds formed by hydrogenating at least part of unsaturated bonds in the aromatic ring of the aromatic vinyl compound described above in the section of “structural unit [a2]” are used. Olefin can also be used.
  • the content ratio of the structural units [a1] and [a2] in the polymer block [A] is preferably 80% by mass or more when the total repeating unit in the polymer block [A] is 100% by mass. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more, Most preferably, it is 100 mass%.
  • the content ratio of the structural units [a1] and [a2] in the polymer block [A] is 80% by mass or more, the heat resistance of the obtained resin sheet can be secured sufficiently high.
  • the number of polymer blocks [A] in the acid anhydride group-containing block copolymer is usually 5 or less, preferably 4 or less, more preferably 3 or less, and preferably 2 That's it.
  • the acid anhydride group-containing block copolymer has a plurality of polymer blocks [A]
  • the composition of the structural units in the plurality of polymer blocks [A] may be the same or different. Good.
  • the polymer block [B] includes a structural unit [b1] derived from a chain conjugated diene compound and / or a structural unit [b2] formed by hydrogenating an unsaturated bond in a structure derived from a chain conjugated diene compound. Contains as a main component.
  • the chain conjugated diene compound that can form the structural unit [b1] derived from the chain conjugated diene compound is not particularly limited, but from the viewpoint of enhancing the low water absorption of the resulting resin sheet, those that do not contain a polar group are available.
  • 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like are preferable.
  • 1,3-butadiene and isoprene are particularly preferable from the viewpoint of industrial availability, and isoprene is most preferable from the viewpoint of producing a resin sheet excellent in sound insulation.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the structural unit [b2] is a structural unit obtained by hydrogenating an unsaturated bond in a structure derived from a chain conjugated diene compound. And as a chain conjugated diene compound, the same thing as what was mentioned above as a chain conjugated diene compound which can form structural unit [b1] is mentioned.
  • the polymer block [B] may contain structural units other than the structural units [b1] and [b2], and such other structural units are structural units derived from the above-described aromatic vinyl compound. [A1] and / or a structural unit [a2] formed by hydrogenating at least a part of unsaturated bonds in the structure derived from the aromatic vinyl compound may be used. Further, the other structural unit may be formed from the chain olefin and cyclic olefin described above in the section “Polymer block [A]”.
  • the content ratio of the structural units [b1] and [b2] in the polymer block [B] is preferably 60% by mass or more when all repeating units in the polymer block [B] are 100% by mass. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more, Most preferably, it is 100 mass%. If the content ratio of the structural units [b1] and [b2] in the polymer block [B] is 80% by mass or more, the flexibility of the resulting resin sheet is increased. Also, it is difficult to cause defects such as cracks even when the environment changes rapidly.
  • the number of polymer blocks [B] in the acid anhydride group-containing block copolymer is usually 4 or less, preferably 3 or less, more preferably 2 or less, and still more preferably 1.
  • the acid anhydride group-containing block copolymer has a plurality of polymer blocks [B]
  • the composition of the structural units in the plurality of polymer blocks [B] may be the same or different.
  • wA represents the mass fraction of the structural units [a1] and [a2] in the entire acid anhydride group-containing block copolymer
  • structural units [b1] and [b2] represent the acid anhydride group-containing block copolymer.
  • the ratio of wA to wB (wA / wB) when the mass fraction in the whole coalescence is wB needs to be 5/95 or more, preferably 7/93 or more, / 85 or more, more preferably 10/90 or more, further preferably 29/71 or less, preferably 27/73 or less, and 25/75 or less. Is more preferable.
  • the ratio of wA / wB is 5/95 or more, the heat resistance of the resin sheet can be secured sufficiently high.
  • the ratio of wA / wB is 29/71 or less, the adhesiveness of the resin sheet at a low temperature can be secured sufficiently high.
  • the acid anhydride group-containing block copolymer of the present invention is formed by hydrogenating a structural unit derived from isoprene and an unsaturated bond in the structure derived from isoprene when the above-described chain conjugated diene compound is isoprene.
  • structural units a structural unit derived only from 1,2-addition polymerization and a structural unit obtained by hydrogenating an unsaturated bond in a structure derived only from 1,2-addition polymerization are blocks containing an acid anhydride group.
  • the block structure of the acid anhydride group-containing block copolymer may be a chain type block or a radial type block, but is preferably a chain type block from the viewpoint of mechanical strength.
  • the acid anhydride group-containing block copolymer has at least one structure in which the polymer block [A] is bonded to both ends of the polymer block [B] (that is, a structure arranged in the order of ABA). It is preferable to have.
  • a particularly preferred structure of the acid anhydride group-containing block copolymer is a triblock copolymer (ABA) in which the polymer block [A] is bonded to both ends of the polymer block [B].
  • the polymer block [B] is bonded to both ends of the polymer block [A], and the polymer block [A] is bonded to the other end of the two polymer blocks [B].
  • a block copolymer (ABABABA) can be mentioned, and a triblock copolymer (ABA) is most preferred.
  • the physical properties of the acid anhydride group-containing block copolymer are not particularly limited.
  • the weight average molecular weight (Mw) of the acid anhydride group-containing block copolymer is preferably 20,000 or more. 25,000 or more, more preferably 30,000 or more, preferably 90,000 or less, more preferably 85,000 or less, and 80,000 or less. More preferably, it is more preferably 75,000 or less. If the polymerization average molecular weight of the acid anhydride group-containing block copolymer is 20,000 or more, the mechanical strength of the resulting resin sheet can be increased, and if it is 90,000 or less, the processability of the resin sheet is increased. Can be improved.
  • the molecular weight distribution (Mw / Mn) of the acid anhydride group-containing block copolymer is preferably 3.5 or less, more preferably 2.5 or less, and further preferably 2.0 or less. preferable. If molecular weight distribution is 3.5 or less, the mechanical strength of the resin sheet obtained can be raised.
  • a weight average molecular weight (Mw) and a number average molecular weight (Mn) can be measured as a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as a solvent.
  • the method for preparing the acid anhydride group-containing block copolymer of the present invention is not particularly limited.
  • a block copolymer [C] is prepared, then the block copolymer [C] is hydrogenated, and the resulting hydride [D] is modified with an acid anhydride to obtain an acid anhydride.
  • an acid anhydride modified product of the block copolymer [C ′] that is, acid anhydride modified product [D ′])
  • a part of the acid anhydride group of the block copolymer [C ′′] may be decomposed. Therefore, the acid anhydride group in the finally obtained acid anhydride group-containing block copolymer may be decomposed.
  • the block copolymers [C], [C ′] and [C ′′] used in the preparation methods (1) to (3) described above, and methods for hydrogenation and acid anhydride modification will be described in detail below. .
  • Block copolymer [C] and [C '] mainly comprise a polymer block [A ′] containing a structural unit derived from an aromatic vinyl compound as a main component and a structural unit derived from a chain conjugated diene compound. It is necessary to be a block copolymer containing a polymer block [B ′] contained as a component at a predetermined mass fraction.
  • Polymer block [A ']] As an aromatic vinyl compound that can form a structural unit derived from an aromatic vinyl compound suitably contained in the polymer block [A ′], an “anhydride group-containing block copolymer“ polymer block [A] ”can be used. The same thing as the above-mentioned thing in the term of this is mentioned. And the content rate of the structural unit derived from the aromatic vinyl compound in polymer block [A '] is the structural unit [a1 in polymer block [A] mentioned above in the section of "polymer block [A]". ] And [a2] can be adjusted in the same range as the content ratio range.
  • the polymer block [A ′] may contain a structural unit other than the structural unit derived from the aromatic vinyl compound, and such other structural unit is a structural unit derived from the chain conjugated diene compound. There may be. Further, the other structural unit may be formed from the chain olefin and cyclic olefin described in the section “Polymer block [A]”.
  • the number of polymer blocks [A ′] in the block copolymer [C] or [C ′] is also the same as the number of polymer blocks [A] in the acid anhydride group-containing block copolymer described above. It can be adjusted within the range.
  • the composition of the structural units in the plurality of polymer blocks [A ′] may be the same or different. It may be.
  • Polymer block [B ′] As the chain conjugated diene compound capable of forming a structural unit derived from the chain conjugated diene compound preferably contained in the polymer block [B ′], an acid anhydride group-containing block copolymer “polymer block [B ] "Is the same as described above.
  • the content ratio of the structural unit derived from the chain conjugated diene compound in the polymer block [B ′] is the structural unit in the polymer block [B] described above in the section “Polymer block [B]”.
  • b1] and [b2] can be adjusted in the same range as the range of the content ratio.
  • the polymer block [B ′] may contain a structural unit other than the structural unit derived from the chain conjugated diene compound, and such other structural unit is a structural unit derived from the aromatic vinyl compound. There may be. Further, the other structural unit may be formed from the chain olefin and cyclic olefin described in the section “Polymer block [A]”.
  • the number of polymer blocks [B ′] in the block copolymer [C] or [C ′] is also the same as the number of polymer blocks [B] in the acid anhydride group-containing block copolymer described above. It can be adjusted within the range.
  • the composition of the structural units in the plurality of polymer blocks [B ′] may be the same or different. It may be.
  • wA ′ represents the mass fraction of the structural unit derived from the aromatic vinyl compound in the entire block copolymer [C] or [C ′], and the structural unit derived from the chain conjugated diene compound is block copolymerized.
  • the ratio (wA ′ / wB ′) between wA ′ and wB ′ when the mass fraction of the combined [C] or [C ′] is wB ′ is the above-described acid anhydride group-containing block copolymer weight. It can be adjusted within the same range as the range of wA to wB ratio (wA / wB) in coalescence.
  • the ratio of wA ′ to wB ′ (wA ′ / wB ′) in the block copolymer [C] is an acid anhydride obtained by hydrogenating the block copolymer [C] and then modifying the acid anhydride. This coincides with the ratio (wA / wB) of wA and wB in the product-modified hydride [E] (an acid anhydride group-containing block copolymer).
  • the ratio of wA ′ to wB ′ (wA ′ / wB ′) in the block copolymer [C ′] is an acid obtained by hydrogenating the block copolymer [C ′] after acid anhydride modification. This corresponds to the ratio (wA / wB) between wA and wB in the anhydride-modified hydride [E ′] (an acid anhydride group-containing block copolymer).
  • Structural unit ratio S ′ (wP ′ + wQ ′) / (wP ′ + wQ ′ + wR ′) Is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, and more preferably 0.55 or more. Is more preferable, and it is preferable that it is 0.65 or less.
  • the resin sheet formed using the resin composition containing the acid anhydride group-containing block copolymer exhibits excellent sound insulation. Can do.
  • the structural unit ratio S ′ can be determined by the method described in the examples of this specification.
  • the structural unit ratio S ′ in the block copolymer [C] is determined by the acid anhydride-modified hydride [E] (acid anhydride) obtained by hydrogenating the block copolymer [C] and then modifying the acid anhydride. This corresponds to the structural unit ratio S in the physical group-containing block copolymer).
  • the structural unit ratio S ′ in the block copolymer [C ′] is determined based on the acid anhydride modified hydride [E ′] obtained by hydrogenating the block copolymer [C ′] after the acid anhydride modification. This corresponds to the structural unit ratio S in (an acid anhydride group-containing block copolymer).
  • the polymer block containing the structural unit derived only from the 1,2-addition polymerization and / or the structural unit derived only from the 3,4-addition polymerization is composed of a chain conjugated diene compound and, if necessary,
  • a compound capable of forming other structural units such as an aromatic vinyl compound, a chain olefin, and a cyclic olefin is a specific compound having an electron donating atom (hereinafter sometimes referred to as a “randomizing agent”). Can be obtained by polymerization in the presence of.
  • the value of the unit ratio S ′ can be controlled by the amount of randomizing agent added.
  • Examples of the compound having an electron donor atom (for example, oxygen (O), nitrogen (N)) that can be used as a randomizing agent include ether compounds, amine compounds, and phosphine compounds.
  • an ether compound is preferable from the viewpoint that the molecular weight distribution of the polymer block can be reduced and the hydrogenation reaction is hardly inhibited.
  • randomizing agent examples include, for example, diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol diisopropyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl phenyl ether, propylene glycol dimethyl ether.
  • the amount of these randomizing agents used in the preparation of the block copolymer [C] or [C ′] is preferably 0.001 part by mass or more with respect to 100 parts by mass of the chain conjugated diene compound, The amount is more preferably 0.01 parts by mass or more, preferably 10 parts by mass or less, and more preferably 1 part by mass or less.
  • the block structure of the block copolymer [C] or [C ′] may be a chain block or a radial block, but is preferably a chain block from the viewpoint of mechanical strength.
  • the block copolymer [C] or [C ′] has a structure in which the polymer block [A ′] is bonded to both ends of the polymer block [B ′] (that is, in the order of A′-B′-A ′). It is preferable to have at least one side-by-side structure.
  • a particularly preferable structure of the block copolymer [C] or [C ′] is a triblock copolymer (A) in which the polymer block [A ′] is bonded to both ends of the polymer block [B ′].
  • '-B'-A') and the polymer block [B '] are bonded to both ends of the polymer block [A'], and the other ends of the two polymer blocks [B '] are respectively overlapped with each other.
  • Examples include pentablock copolymers (A′-B′-A′-B′-A ′) formed by combining the combined blocks [A ′], and triblock copolymers (A′-B′-A ′). ) Is most preferred.
  • the method for preparing the block copolymer [C] or [C ′] is not particularly limited.
  • a composition containing an aromatic vinyl compound and a composition containing a chain conjugated diene compound using living anion polymerization. are alternately polymerized, whereby the block copolymer [C] or [C ′] can be prepared.
  • Block copolymer [C "] contains a polymer block [A ′′] containing a structural unit derived from an aromatic vinyl compound as a main component and a structural unit derived from a chain conjugated diene compound as a main component. It is necessary to be a block copolymer containing a polymer block [B ′′] at a predetermined mass fraction and containing an acid anhydride group-containing structural unit.
  • acid anhydride group-containing structural unit examples include maleic anhydride, citraconic anhydride, itaconic anhydride, 2,3-dimethylmaleic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, Examples thereof include ethylenically unsaturated carboxylic acid anhydrides such as allyl succinic anhydride, 2-phenylmaleic anhydride, and cis-aconitic anhydride.
  • maleic anhydride, itaconic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride are preferably used as the acid anhydride, and the resin sheet has adhesiveness and transparency. It is more preferable to use maleic anhydride and itaconic anhydride from the viewpoint of achieving better compatibility. In addition, these may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
  • the content ratio of the acid anhydride group-containing structural unit in the block copolymer [C ′′] is not particularly limited, but when the total amount of the block copolymer [C ′′] is 100% by mass, 0.01% It is preferably at least mass%, more preferably at least 0.1 mass%, even more preferably at least 0.3 mass%, preferably at most 9 mass%, and at most 6.5 mass% More preferably, it is more preferably 3.8% by mass or less.
  • the content ratio of the acid anhydride group-containing structural unit in the block copolymer [C ′′] is 0.01% by mass or more, the transparency of the resulting resin sheet can be further enhanced.
  • the content ratio of the acid anhydride group-containing structural unit in the coalescence [C ′′] is 9% by mass or less, the low water absorption of the obtained resin sheet can be increased.
  • polymer block [A "]] As an aromatic vinyl compound that can form a structural unit derived from an aromatic vinyl compound suitably contained in the polymer block [A ′′], an acid anhydride group-containing block copolymer “polymer block [A]” is used. The same thing as the above-mentioned thing in the term of this is mentioned.
  • the polymer block [A ′′] may contain a structural unit other than the structural unit derived from the aromatic vinyl compound, and such other structural unit is a structural unit derived from the chain conjugated diene compound.
  • the other structural unit may be formed from the chain olefin and cyclic olefin described above in the section of “polymer block [A]”, or may be formed from the acid anhydride described above. .
  • the number of polymer blocks [A ′′] in the block copolymer [C ′′] is also adjusted within the same range as the number of polymer blocks [A] in the acid anhydride group-containing block copolymer described above. can do.
  • the block copolymer [C ′′] has a plurality of polymer blocks [A ′′]
  • the composition of the structural units in the plurality of polymer blocks [A ′′] may be the same or different. .
  • polymer block [B "] As the chain conjugated diene compound capable of forming a structural unit derived from the chain conjugated diene compound preferably contained in the polymer block [B ′′], an “anhydride group-containing block copolymer“ polymer block [B ” ] "Is the same as described above.
  • the polymer block [B ′′] may contain a structural unit other than the structural unit derived from the chain conjugated diene compound, and such other structural unit is a structural unit derived from the aromatic vinyl compound.
  • the other structural unit may be formed from the chain olefin and cyclic olefin described above in the section of “polymer block [A]”, or may be formed from the acid anhydride described above. .
  • the number of polymer blocks [B ′′] in the block copolymer [C ′′] is also adjusted within the same range as the number of polymer blocks [B] in the acid anhydride group-containing block copolymer described above. can do.
  • the block copolymer [C ′′] has a plurality of polymer blocks [B ′′]
  • the composition of the structural units in the plurality of polymer blocks [B ′′] may be the same or different. .
  • Mass fraction the mass fraction of the structural unit derived from the aromatic vinyl compound in the entire block copolymer [C ′′] is wA ′′, and the structural unit derived from the chain conjugated diene compound is the block copolymer [C ′′.
  • the ratio (wA ′′ / wB ′′) of wA ′′ and wB ′′ in the block copolymer [C ′′] is an acid anhydride group-containing hydride obtained by hydrogenating the block copolymer [C ′′]. It corresponds to the ratio (wA / wB) of wA and wB in [E ′′] (an acid anhydride group-containing block copolymer).
  • the block copolymer [C ′′] is a structural unit derived only from 1,2-addition polymerization among structural units derived from isoprene.
  • C ′′] represents a mass fraction in the whole, wP ′′, and a structural unit derived only from 3,4-addition polymerization represents a mass fraction in the entire block copolymer [C ′′] as wQ ′′.
  • Structural unit ratio S ′′ (wP ′′ + wQ ′′) / (wP ′′ + wQ ′′ + wR ′′) Is preferably 0.3 or more, more preferably 0.4 or more, still more preferably 0.5 or more, and more preferably 0.55 or more. More preferably, it is preferably 0.65 or less. If the value of the structural unit ratio S ′′ is within the predetermined range, a resin composition containing an acid anhydride group-containing block copolymer is used. The formed resin sheet can exhibit excellent sound insulation.
  • the value of the structural unit ratio S ′′ can be obtained by a method similar to the method for calculating the structural unit ratio S ′ described in the examples of the present specification. Further, the structural unit ratio S ′′ in the block copolymer [C ′′] is determined based on the acid anhydride group-containing hydride [E ′′] (acid anhydride group-containing) obtained by hydrogenating the block copolymer [C ′′]. This corresponds to the structural unit ratio S in the block copolymer). The value of the structural unit ratio S ′′ can be controlled by using the randomizing agent described in the section “Block copolymer [C] and [C ′]”. Can be adjusted within the range described above.
  • the block structure of the block copolymer [C ′′] may be a chain block or a radial block, but is preferably a chain block from the viewpoint of mechanical strength.
  • C ′′] has at least one structure in which the polymer block [A ′′] is bonded to both ends of the polymer block [B ′′] (that is, a structure arranged in the order of A ′′ -B ′′ -A ′′). preferable.
  • a particularly preferable structure of the block copolymer [C ′′] is a triblock copolymer (A ′′ -B ′′) in which the polymer block [A ′′] is bonded to both ends of the polymer block [B ′′].
  • the method for preparing the block copolymer [C ′′] is not particularly limited.
  • the composition (A) containing the aromatic vinyl compound and the acid anhydride, the chain conjugated diene compound, and the living anion polymerization are used.
  • a block copolymer [C ′′] can be prepared by alternately polymerizing the composition (B) containing an acid anhydride.
  • the method for hydrogenating is not particularly limited, and a known method can be adopted, but a hydrogenation method capable of suppressing the polymer chain scission reaction while increasing the hydrogenation rate is preferable. Examples of such a hydrogenation method include the methods described in International Publication No. 2011/096389, International Publication No. 2012/043708, etc.
  • the weather resistance and heat resistance of the resulting resin sheet From the viewpoint of enhancing the properties, it is preferable to use a method of selectively hydrogenating only unsaturated bonds in the structural unit derived from the chain conjugated diene compound in the block copolymer or acid anhydride modified product.
  • hydrogenation process such as, for example, can be mentioned methods as described in, JP 2015-78090.
  • the hydride obtained by the above-described method is usually obtained by removing the hydrogenation catalyst and / or the polymerization catalyst and recovering from the reaction solution containing the hydride.
  • recovered hydride is not limited, For example, it can be set as a pellet shape.
  • the hydrogenation rate of the hydride obtained by hydrogenation is preferably 90% or more, more preferably 97% or more, and further preferably 99% or more. If the hydrogenation rate is 90% or more, the weather resistance of the resulting resin sheet can be secured sufficiently high. In addition, a hydrogenation rate can be measured by the method as described in the Example of this specification.
  • Acid anhydride modification a hydride of a block copolymer [C] (ie, a hydride [D]) or a block copolymer [C ′] and an ethylenically unsaturated carboxylic acid anhydride are usually peroxidized.
  • the reaction is carried out in the presence of a product (anhydride modification) to introduce an acid anhydride group into the hydride [D] or block copolymer [C ′].
  • ethylenically unsaturated carboxylic acid anhydride examples include reaction with hydride [D] or block copolymer [C ′] (for example, graft polymerization), and the hydride or block copolymer.
  • an acid anhydride group can be introduced into the coalescence.
  • an ethylenically unsaturated carboxylic acid anhydride for example, those described above in the section of the block copolymer [C ′′] can be used.
  • the introduced acid anhydride group corresponds to the ethylenically unsaturated carboxylic acid anhydride to be used.
  • the amount of the ethylenically unsaturated carboxylic acid anhydride used is preferably 0.01 parts by mass or more with respect to 100 parts by mass of the hydride [D] or the block copolymer [C ′], and 0.1 mass. Part or more, preferably 0.3 part by weight or more, more usually 10 parts by weight or less, preferably 7 parts by weight or less, and more preferably 4 parts by weight or less. If the usage-amount of an ethylenically unsaturated carboxylic acid anhydride is 0.01 mass part or more, the transparency of the resin sheet obtained can be improved further. On the other hand, if the usage-amount of ethylenically unsaturated carboxylic acid anhydride is 10 mass parts or less, the low water absorption of the resin sheet obtained can be improved.
  • peroxide As the peroxide used for acid anhydride modification, those having a one-minute half-life temperature of 170 ° C. or higher and 190 ° C. or lower are preferably used.
  • Organic peroxides such as peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, di-t-butylperoxide, di- (2-t-butylperoxyisopropyl) benzene Things.
  • One of these may be used alone, or two or more of these may be used in combination at any ratio.
  • the amount of the peroxide used is usually 0.05 parts by mass or more, preferably 0.1 parts by mass or more with respect to 100 parts by mass of the hydride [D] or the block copolymer [C ′]. More preferably, it is 0.2 parts by mass or more, usually 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less.
  • reaction method The method of reacting the hydride [D] or the block copolymer [C ′] with the ethylenically unsaturated carboxylic acid anhydride in the presence of peroxide is not particularly limited.
  • an acid anhydride group can be introduced into the hydride or polymer.
  • the kneading temperature is usually 180 ° C or higher, preferably 185 ° C or higher, more preferably 190 ° C or higher, usually 220 ° C or lower, preferably 210 ° C or lower, more preferably 200 ° C or lower. is there.
  • the kneading time is usually 0.1 minutes or more, preferably 0.2 minutes or more, more preferably 0.3 minutes or more, usually 10 minutes or less, preferably 5 minutes or less, more Preferably it is 2 minutes or less. What is necessary is just to perform kneading
  • the amount of the acid anhydride group introduced into the hydride [D] or the block copolymer [C ′] by performing the acid anhydride modification as described above is the same as that of the hydride [D] or the block copolymer [ C ′] per 100 parts by mass, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, still more preferably 0.3 parts by mass or more, and 10 parts by mass or less. Preferably, it is 7 parts by mass or less, more preferably 4 parts by mass or less.
  • the introduction amount of the acid anhydride group is 0.01 parts by mass or more per 100 parts by mass of the hydride or block copolymer, the transparency of the resulting resin sheet can be further improved. On the other hand, if the introduction amount of the acid anhydride group is 10 parts by mass or less per 100 parts by mass of the hydride or block copolymer, the low water absorption of the resulting resin sheet can be increased.
  • the amount of acid anhydride group introduced per 100 parts of hydride [D] or block copolymer [C ′] is the acid anhydride obtained from the hydride or block copolymer.
  • the modified product is measured with a Fourier transform infrared spectrophotometer (FT-IR), and can be calculated from the peak intensity of 1790 cm ⁇ 1 derived from the acid anhydride group in the obtained IR spectrum.
  • FT-IR Fourier transform infrared spectrophotometer
  • the resin composition of the present invention comprises at least one additive selected from the group consisting of the above-described acid anhydride group-containing block copolymer, metal oxide fine particles, metal boride fine particles, and near-infrared absorbing dye. Agent (X) and optionally further other components. If the resin composition containing the above-mentioned acid anhydride group-containing block copolymer and additive (X) is used, a resin capable of achieving both excellent adhesiveness and transparency and exhibiting excellent heat shielding properties. A sheet can be obtained.
  • the method for preparing the resin composition of the present invention is not particularly limited.
  • an additive (X) or the like is added to a pellet containing an acid anhydride group-containing block copolymer as a main component. It can be prepared by mixing with a known mixer.
  • the content of the acid anhydride group-containing block copolymer in the pellet is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 99% by mass or more.
  • the additive (X) is at least one additive selected from the group consisting of metal oxide fine particles, metal boride fine particles, and near-infrared absorbing dyes, and imparts excellent heat shielding properties to the resin sheet. It is an ingredient to obtain.
  • Metal oxide fine particles include fine particles of tin oxide such as tin oxide, aluminum-doped tin oxide, indium-doped tin oxide, and antimony-doped tin oxide; zinc oxide, aluminum-doped zinc oxide, indium-doped zinc oxide, gallium-doped zinc oxide Zinc oxide fine particles such as tin-doped zinc oxide and silicon-doped zinc oxide; fine particles of titanium oxide such as titanium oxide and niobium-doped titanium oxide; tungsten oxide, sodium-doped tungsten oxide, cesium-doped tungsten oxide, thallium-doped tungsten oxide, Examples thereof include fine particles of tungsten oxide such as rubidium-doped tungsten oxide; fine particles of indium oxide such as indium oxide and tin-doped indium oxide.
  • fine particles of cesium-doped tungsten oxide as the fine particles of metal oxide.
  • These metal oxide fine particles can be used singly or in combination of two or more.
  • the average particle size of the metal oxide fine particles is usually 0.001 ⁇ m or more, preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and usually 0.2 ⁇ m or less. Is 0.15 ⁇ m or less, more preferably 0.1 ⁇ m or less. If the average particle diameter of the metal oxide fine particles is 0.001 ⁇ m or more, the resin sheet can exhibit further excellent heat shielding properties. On the other hand, if the average particle diameter of the metal oxide fine particles is 0.2 ⁇ m or less, the transparency of the resin sheet can be secured sufficiently high.
  • the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
  • the content of the metal oxide fine particles in the resin composition is usually 0.001 parts by mass or more, preferably 0.002 parts by mass with respect to 100 parts by mass of the acid anhydride group-containing block copolymer. Or more, more preferably 0.005 parts by mass or more, still more preferably 0.25 parts by mass or more, still more preferably 0.5 parts by mass or more, and usually 2.0 parts by mass or less, Preferably it is 1.5 mass parts or less, More preferably, it is 1.25 mass parts or less.
  • the content of the metal oxide fine particles in the resin composition is 0.001 part by mass or more with respect to 100 parts by mass of the acid anhydride group-containing block copolymer, the resin sheet exhibits further excellent heat shielding properties. be able to.
  • the content of the metal oxide fine particles in the resin composition is 2.0 parts by mass or less with respect to 100 parts by mass of the acid anhydride group-containing block copolymer, the transparency of the resin sheet is sufficiently high. Can be secured.
  • metal boride fine particles examples include fine particles of lanthanum boride (lanthanum hexaboride, LaB 6 ), cerium boride (CeB 6 ), tungsten boride (W 2 B 5 ), and the like.
  • lanthanum boride lanthanum hexaboride, LaB 6
  • CeB 6 cerium boride
  • W 2 B 5 tungsten boride
  • fine particles of lanthanum boride from the viewpoint of further improving the heat shielding property of the resin sheet.
  • These metal boride fine particles can be used singly or in combination of two or more.
  • the average particle diameter of the metal boride fine particles is usually 0.001 ⁇ m or more, preferably 0.005 ⁇ m or more, more preferably 0.01 ⁇ m or more, and usually 0.2 ⁇ m or less, preferably It is 0.15 ⁇ m or less, more preferably 0.1 ⁇ m or less. If the average particle diameter of the metal boride fine particles is 0.001 ⁇ m or more, the resin sheet can exhibit further excellent heat shielding properties. On the other hand, if the average particle diameter of the metal boride fine particles is 0.15 ⁇ m or less, the transparency of the resin sheet can be secured sufficiently high.
  • the content of the metal boride fine particles in the resin composition is usually 0.001 parts by mass or more, preferably 0.002 parts by mass with respect to 100 parts by mass of the acid anhydride group-containing block copolymer. Or more, more preferably 0.005 parts by mass or more, usually 1.0 parts by mass or less, preferably 0.5 parts by mass or less, more preferably 0.3 parts by mass or less, Preferably it is 0.2 mass part or less. If the content of the metal boride fine particles in the resin composition is 0.001 part by mass or more with respect to 100 parts by mass of the acid anhydride group-containing block copolymer, the resin sheet exhibits further excellent heat shielding properties. be able to.
  • the content of the metal boride fine particles in the resin composition is 1.0 part by mass or less with respect to 100 parts by mass of the acid anhydride group-containing block copolymer, the transparency of the resin sheet is sufficiently high. Can be secured.
  • the near-infrared absorbing dye has a function of shielding infrared rays in any region within a wavelength range of 800 nm to 2000 nm.
  • “having a function of shielding infrared rays in any region within the wavelength range of 800 nm or more and 2000 nm or less” means “the near-infrared absorbing dye is in any wavelength range of 800 nm or more and 2000 nm or less. It has the function of absorbing infrared rays in the region and blocking the passage of infrared rays as a result.
  • the near-infrared absorbing dye has a maximum absorption wavelength in any region within the wavelength range of 800 nm or more and 2000 nm or less, but the maximum in any region outside the wavelength range of 800 nm or more and 2000 nm or less. It may have an absorption wavelength.
  • Examples of the near-infrared absorbing dye include phthalocyanine compounds, naphthatocyanine compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds, and azomethine compounds.
  • the content of the near-infrared absorbing dye in the resin composition is usually 0.001 part by mass or more, preferably 0.002 part by mass or more with respect to 100 parts by mass of the acid anhydride group-containing block copolymer. More preferably, it is 0.005 parts by mass or more, usually 1.0 parts by mass or less, preferably 0.7 parts by mass or less, more preferably 0.5 parts by mass or less. If the content of the near-infrared absorbing pigment in the resin composition is 0.001 part by mass or more with respect to 100 parts by mass of the acid anhydride group-containing block copolymer, the resin sheet exhibits a further excellent heat shielding property. Can do.
  • the transparency of the resin sheet is sufficiently high. can do.
  • the resin composition of the present invention may contain other components other than the above-described acid anhydride group-containing block copolymer and additive (X) within a range in which a desired effect is obtained.
  • the other components include additives remaining in the resin composition as a result of being used when preparing the acid anhydride group-containing block copolymer.
  • other components include an adhesive, an ultraviolet absorber, a light stabilizer, and an antioxidant.
  • a phenolic antioxidant such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] can be used.
  • the resin sheet of the present invention includes at least one resin layer made of the resin composition described above. If it is a resin sheet containing at least one resin layer made of the resin composition described above, both excellent adhesiveness and transparency can be achieved. Therefore, the resin sheet of the present invention can be suitably used as an interlayer film for laminated glass.
  • the resin sheet of the present invention is not particularly limited as long as it includes at least one resin layer composed of the above-described resin composition.
  • the resin sheet is composed only of a resin layer obtained by molding the above-described resin composition. A single layer sheet or a multilayer sheet may be sufficient, and the laminated sheet formed by laminating
  • the said resin layer may be formed with the same resin composition, and may be formed with a mutually different resin composition.
  • the method for forming a resin composition (single layer sheet) by molding a resin composition is not particularly limited, and examples thereof include a melt extrusion molding method, a calendar molding method, and an inflation molding. Can do.
  • the temperature and die of the resin composition are preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and 160 ° C. or higher. Is particularly preferably 220 ° C. or lower, more preferably 210 ° C. or lower, and particularly preferably 200 ° C. or lower.
  • the temperature of the resin composition and the die is not particularly limited, and examples thereof include a melt extrusion molding method, a calendar molding method, and an inflation molding. Can do.
  • the temperature and die of the resin composition are preferably 140 ° C. or higher, more preferably 150 ° C. or higher, and 160 ° C. or higher. Is particularly preferably 220 ° C. or lower, more preferably 210 ° C. or lower, and particularly preferably 200 ° C. or lower
  • the fluidity is prevented from deteriorating, and the surface of the resin layer (single layer sheet) is prevented from being defective such as the skin or die line.
  • the extrusion speed can be increased and the molding can be advantageously carried out industrially.
  • the thickness of the resin layer (single layer sheet) is not particularly limited, and is preferably, for example, 0.01 mm or more, more preferably 0.05 mm or more, and preferably 0.1 mm or more. It is preferably 0.0 mm or less, more preferably 2.5 mm or less, and particularly preferably 2.0 mm.
  • the thickness of the resin layer (single layer sheet) is 3 By setting the thickness to 0.0 mm or less, the transparency of the resin layer (single layer sheet) can be secured sufficiently high.
  • an adhesive layer can be used as the functional layer.
  • the method for producing the laminated sheet is not particularly limited. For example, (i) a method in which the resin layer and the adhesive layer are bonded together by a heating means such as a hot press, and (ii) an adhesive on the resin layer. A method of spraying and applying the composition to remove the solvent; (iii) a method of removing the solvent by dipping the resin layer on the adhesive composition; and (iv) an adhesive layer prepared in advance while extruding the resin layer.
  • Known methods such as a method of laminating at least one surface of the resin layer and (v) a method of coextrusion molding of the resin layer and the adhesive layer during melt molding can be used.
  • the adhesive composition used for forming the adhesive layer is not particularly limited, and it is possible to use one containing a known adhesive having good adhesion to the resin layer and the adherend. it can.
  • a polymer block mainly composed of a structural unit derived from an aromatic vinyl compound such as styrene and a chain conjugated diene compound such as isoprene are used as an adhesive suitable when the adherend is glass.
  • examples include hydrides of block copolymers composed of a polymer block as a main component, and alkoxysilane-modified / acid anhydride-modified products of hydrides.
  • the acid anhydride modified body of the hydride of the said block copolymer shall not correspond to the acid anhydride group containing block copolymer of this invention.
  • a polymer block mainly composed of an aromatic vinyl compound such as styrene and a heavy chain composed mainly of a chain conjugated diene compound such as isoprene it is preferable to use an alkoxysilane-modified product of a hydride of a block copolymer composed of a combined block.
  • the thickness of the adhesive layer is not particularly limited and is preferably 0.02 mm or more, more preferably 0.05 mm or more, further preferably 0.1 mm or more, and 5 mm or less. It is preferably 3 mm or less, more preferably 1 mm or less.
  • the laminated glass of the present invention comprises at least one resin sheet as described above.
  • the laminated glass of the present invention includes a resin sheet that can achieve both excellent adhesiveness and transparency.
  • a window glass for a building a glass for a roof, a thermal barrier wall material for a room, an automobile It is useful as a windshield, side glass, rear glass, sunroof glass, and window glass for railway vehicles and ships.
  • the laminated glass of the present invention is not particularly limited as long as it includes at least one of the above-described resin sheets, but is usually a laminate in which the above-described resin sheet is integrated between two glass plates. It is.
  • an adhesive sheet may be interposed between the glass plate and the resin sheet.
  • the adhesive sheet can be formed by a known method using the adhesive composition described above in the section “Resin sheet”.
  • ⁇ Manufacturing method> There is no restriction
  • the heating temperature is preferably 100 ° C.
  • the heating time is preferably 15 minutes or more and 60 minutes or less
  • the pressure (gauge pressure) is 0. .3 MPa or more is preferable, and 1.1 MPa or less is preferable.
  • the heating temperature is preferably 130 ° C. or higher, preferably 170 ° C. or lower, and the pressure is preferably 0.01 MPa or higher, and 0.1 MPa or lower. It is preferable that
  • Glass plate Although there is no restriction
  • the material of the glass plate is not particularly limited.
  • aluminosilicate glass, aluminoborosilicate glass, uranium glass, potassium glass, silicate glass, crystallized glass, germanium glass, quartz glass, soda glass, lead glass, barium borosilicate examples thereof include glass and borosilicate glass.
  • the two or more glass plates used for the laminated glass may be the same or different in thickness and material.
  • the laminated glass of the present invention preferably has a region with a light transmittance of 50% or less within a wavelength range of 800 nm to 2000 nm. If the laminated glass has a region with a light transmittance of 50% or less within a wavelength range of 800 nm or more and 2000 nm or less, excellent heat shielding properties can be exhibited. Furthermore, the laminated glass of the present invention preferably has a light transmittance at a wavelength of 500 nm of 60% or more. If the laminated glass has a light transmittance of 60% or more at a wavelength of 500 nm, further excellent transparency can be exhibited.
  • ⁇ Structural unit ratio S '> The structural unit ratio S ′ in the block copolymer was calculated based on the 1 H-NMR spectrum of the block copolymer (measuring solvent: deuterated chloroform, measuring instrument: “AVANCE 500” manufactured by BRUKER). Specifically, in the acquired 1 H-NMR spectrum, the peak area of 1 H bonded to the carbon of the carbon-carbon unsaturated bond portion in the polymer main chain is represented by a structure derived only from 1,2-addition polymerization.
  • the weight average molecular weight (Mw) of the acid anhydride group-modified hydride is a standard polystyrene conversion value by gel permeation chromatography (GPC) using tetrahydrofuran (THF) as an eluent. As sought. GPC was measured at 38 ° C. As the measuring device, “HLC8020GPC” manufactured by Tosoh Corporation was used. Further, in the same manner as described above, after measuring the number average molecular weight (Mn), the molecular weight distribution (Mw / Mn) of the acid anhydride group-modified hydride was determined.
  • Total light transmittance The total light transmittance of the laminated glass was measured using an integrating sphere spectrophotometer (“V-670” manufactured by JASCO Corporation) within a wavelength range of 300 nm to 2500 nm.
  • a test piece having a length of 300 mm and a width of 25 mm was cut out from the resin sheet, and the test piece was sandwiched between two soda glass plates having a length of 300 mm, a width of 25 mm, and a thickness of 1.2 mm, for sound insulation evaluation.
  • a laminated glass test piece was produced. With respect to the laminated glass, a loss factor corresponding to the frequency was measured by a central excitation method using a vibration damping test device (“SA-02” manufactured by Rion Co.) according to JIS K7391. The sound insulation property of the resin sheet provided in the laminated glass was evaluated by obtaining the sound transmission loss corresponding to the frequency from the ratio between the loss coefficient obtained here and the resonance frequency of the laminated glass.
  • the sound insulation of the resin sheet is A (good) when there is no region where the sound transmission loss is less than 35 dB in the frequency range of 2000 to 4000 Hz, and B when there is a region where the sound transmission loss is less than 35 dB. It was evaluated as (bad).
  • the transparency of the resin sheet was evaluated by measuring the haze of the laminated glass.
  • the haze of the laminated glass was measured using a haze meter (“NDH7000SP” manufactured by Nippon Denshoku Industries Co., Ltd.). It can be said that the smaller the haze value of the laminated glass, the better the transparency of the resin sheet provided in the laminated glass.
  • the transparency of the resin sheet was evaluated according to the following criteria.
  • B The haze of the laminated glass is 1 or more and 3 or less.
  • C The haze of the laminated glass is more than 3.
  • Adhesiveness to soda glass plate >> Resin sheet produced by superposing one soda glass plate having a thickness of 1.1 mm, a length of 100 mm and a width of 100 mm and a single resin sheet cut out in the same vertical and horizontal length as the soda glass plate / Put the soda glass plate laminate in a 75 ⁇ m thick bag made of NY (nylon) / PP (polypropylene), heat seal both sides with a heat sealer, leaving 200 mm width at the center of the opening of the bag, then seal Using a pack device (Panasonic “BH-951”), the inside of the bag is degassed and the opening is heat-sealed to seal and wrap the laminate, and then the sealed and wrapped laminate is placed in an autoclave.
  • a pack device Panasonic “BH-951”
  • test piece for evaluating adhesiveness.
  • the test piece was subjected to a 180 ° peel test in accordance with the test method JIS K6854-2 to evaluate the adhesiveness of the resin sheet included in the test piece.
  • the adhesiveness of the resin sheet to the soda glass plate was evaluated as A (good) when the adhesive strength of the test piece was 10 N or more, and B (defect) when the adhesive strength of the test piece was less than 10 N.
  • Adhesiveness to acrylic resin board In place of the soda glass plate having a thickness of 1.1 mm, a length of 100 mm, and a width of 100 mm, except for using an acrylic resin plate having a thickness of 1 mm, a length of 50 mm, and a width of 100 mm, Similarly, the adhesiveness of the resin sheet to the acrylic resin plate was evaluated.
  • the reaction solution was filtered to remove the hydrogenation catalyst, and the filtrate was then subjected to pentaerythritol tetrakis [3- (3,5-di-t-butyl-4] which is a phenolic antioxidant.
  • -Hydroxyphenyl) propionate (“Songnox (registered trademark) 1010” manufactured by Koyo Chemical Research Co., Ltd.) 0.1 part of xylene solution was added and dissolved.
  • the above solution is removed from the solution by using a cylindrical concentrator / dryer (“Contro” manufactured by Hitachi, Ltd.) at a temperature of 260 ° C. and a pressure of 0.001 MPa or less. did.
  • the molten polymer was continuously extruded from the die into a strand, and after cooling, 93 parts of hydride [D1] pellets were obtained by a pelletizer.
  • the hydrogenation rate of the obtained pellet-like hydride [D1] was almost 100%.
  • a hydride [D3] was obtained in the same manner as in the production of the hydride [D1] in Production Example 1.
  • the hydrogenation rate of the obtained pellet-like hydride [D3] was almost 100%.
  • Example 1 ⁇ Production of acid anhydride-modified hydride [E1]> To 100 parts of the hydride [D1] pellets obtained in Production Example 1, 2.0 parts of maleic anhydride as an ethylenically unsaturated carboxylic acid anhydride and 2,5-dimethyl-2,5-di ( 0.2 part of t-butylperoxy) hexane (“Perhexa (registered trademark) 25B” manufactured by NOF Corporation, 1 minute half-life: 179.8 ° C.) was added. This mixture is kneaded with a twin screw extruder (“TEM-37B” manufactured by Toshiba Machine Co., Ltd.) at a resin temperature of 200 ° C. and a residence time of 60 to 70 seconds, extruded into a strand, air cooled, and then cut by a pelletizer. As a result, 96 parts of pellets of acid anhydride-modified hydride [E1] were obtained.
  • TEM-37B twin screw ex
  • CWO cesium-doped tungsten oxide
  • X additive
  • YMDS-874 average particle size: 55 nm
  • This mixture was extruded using a twin screw extruder (“TEM-37B” manufactured by Toshiba Machine Co., Ltd.) equipped with a T die having a width of 400 mm under conditions of a molten resin temperature of 200 ° C. and a T die temperature of 200 ° C.
  • a resin sheet [E1S1] (thickness: 760 ⁇ m) composed of a resin composition [E1C1] in which CWO as additive (X) was blended with acid anhydride-modified hydride [E1] was prepared. And the sound insulation and adhesiveness of the obtained resin sheet were evaluated. The results are shown in Table 1.
  • a test piece having a length of 290 mm and a width of 290 mm was cut out from the obtained resin sheet [E1S1].
  • a hydride of a block copolymer (styrene-derived structural unit / isoprene-derived structural unit content ratio: 50/50 (mass ratio)) separately prepared according to the method described in International Publication No. 2012/043708.
  • a 300 mm long and 300 mm wide sheet was cut out from an adhesive sheet having a thickness of 100 ⁇ m consisting of a modified alkoxysilane (alkoxysilyl group content: 1.8%, weight average molecular weight (Mw): 39,000).
  • the test piece of the resin sheet [E1S1] and the adhesive sheet are placed between two soda glass plates having a thickness of 1.1 mm, a length of 300 mm, and a width of 300 mm, soda glass plate / adhesion sheet / resin sheet [ E1S1] / adhesive sheet / soda glass plate were laminated in this order to form a laminate.
  • the resin sheet [E1S1] is disposed at the center of the adhesive sheet and is made of laminated glass
  • the end of the resin sheet [E1S1] is located on the inner side of the end of the adhesive sheet over the entire circumference. It was made to be enclosed in the sheet.
  • This laminate was put into a 75 ⁇ m thick bag made of NY (nylon) / PP (polypropylene), and the both sides of the bag were heat sealed with a heat sealer leaving 200 mm width at the center of the opening.
  • BH-951 manufactured by Panasonic Corporation
  • the opening was heat-sealed while the inside of the bag was deaerated, and the laminate was hermetically packaged.
  • the hermetically sealed laminate was put in an autoclave and heated and pressurized at a temperature of 140 ° C. and a pressure of 0.8 MPa for 30 minutes to produce a laminated glass [E1G1].
  • Example 2 to 4 The amount of CWO added as additive (X) was changed from 0.5 parts to 0.25 parts, 1.25 parts, and 2 parts with respect to 100 parts of the anhydride-modified hydride pellet [E1].
  • Resin sheets [E1S2], [E1S3], and [E1S4] (each thickness: similar to Example 1) except that the resin compositions [E1C2], [E1C3], and [E1C4] were used. 760 ⁇ m).
  • laminated glass [E1G2], [E1G3], and [E1G4] were produced in the same manner as in Example 1 except that the resin sheets [E1S2], [E1S3], and [E1S4] were used, respectively. The items were measured and evaluated. The results are shown in Table 1.
  • Example 5 Instead of 2.0 parts of maleic anhydride, 2.0 parts of itaconic anhydride is added as an ethylenically unsaturated carboxylic acid anhydride to 100 parts of the hydride [D1] pellets obtained in Production Example 1. Except for the above, 96 parts of acid anhydride-modified hydride [E2] pellets were obtained in the same manner as in Example 1, and the same items were measured. The weight average molecular weight (Mw) was 75,000. The molecular weight distribution (Mw / Mn) was 1.59. In addition, when measured by the same method as in Example 1, it was confirmed that 0.17 part of itaconic anhydride was bonded to 100 parts of hydride [D1].
  • Example 1 the acid anhydride-modified hydride [E2] was added in the same manner as in Example 1 except that the acid anhydride-modified hydride [E2] was used instead of the acid anhydride-modified hydride [E1].
  • a resin sheet [E2S1] (thickness: 760 ⁇ m) made of a resin composition [E2C1] containing CWO as the agent (X) was produced.
  • a laminated glass [E2G1] was produced in the same manner as in Example 1 except that the resin sheet [E2S1] was used instead of the resin sheet [E1S1], and the same items were measured and evaluated. The results are shown in Table 1.
  • Example 6 As an additive (X), 0.2 parts of lanthanum hexaboride (“KHDS-06” manufactured by Sumitomo Metal Mining Co., Ltd., average particle size: 40 nm) is added instead of 0.5 parts of cesium-doped tungsten oxide (CWO)
  • KHDS-06 lanthanum hexaboride
  • CWO cesium-doped tungsten oxide
  • a resin sheet [E1S5] (thickness: 760 ⁇ m) was produced in the same manner as in Example 1 except that the resin composition [E1C5] was used.
  • a laminated glass [E1G5] was produced in the same manner as in Example 1 except that the resin sheet [E1S5] was used, and the same items were measured and evaluated. The results are shown in Table 1.
  • Example 7 Instead of 100 parts of the hydride [D1] pellets obtained in Production Example 1, the hydride [D2] obtained in Production Example 2 and the hydride [D4] obtained in Production Example 4 were used. Except for this, 96 parts of the acid anhydride-modified hydride [E3] and [E4] pellets were obtained in the same manner as in Example 1, and the same items were measured. The acid anhydride-modified hydride was obtained.
  • the weight average molecular weight (Mw) is 74,000 and the molecular weight distribution (Mw / Mn) is 1.61
  • the acid anhydride-modified hydride [E4] the weight average molecular weight (Mw) was 75,000 and the molecular weight distribution (Mw / Mn) was 1.59.
  • the acid anhydride-modified hydride [E3] was measured by the same method as in Example 1. As a result, 0.18 parts of maleic anhydride was bonded to 100 parts of hydride [D2], and the acid anhydride was added. In the modified hydride [E4], it was confirmed that 0.17 part of maleic anhydride was bonded to 100 parts of the hydride [D4].
  • the polymer block [A] containing the predetermined structural unit [a1] and / or [a2] as the main component and the predetermined structural unit [b1] and / or [b2] as the main component are contained.
  • [B] at a predetermined mass fraction and using an acid anhydride group-containing block copolymer containing at least one of the structural units [a2] and [b2].
  • the resin sheet can achieve both excellent adhesion and transparency.
  • the resin sheet of Comparative Example 1 using the acid anhydride group-containing block copolymer in which the mass fraction of the polymer block [A] and the polymer block [B] is out of the predetermined range is transparent. Although it is favorable, it turns out that it is inferior to adhesiveness. Furthermore, it turns out that the resin sheet of the comparative example 2 using the block copolymer which does not contain an acid anhydride group is inferior to both adhesiveness and transparency.
  • an acid anhydride group-containing block copolymer and a resin composition that can provide a resin sheet that can achieve both excellent adhesion and transparency.
  • the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.
  • a laminated glass provided with the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
  • Laminated Bodies (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Le but de la présente invention est de fournir un copolymère séquencé contenant un groupe anhydride d'acide capable de donner une feuille de résine pouvant présenter une adhésivité et une transparence élevées. Le copolymère séquencé contenant un groupe anhydride d'acide selon la présente invention contient un groupe anhydride d'acide et est caractérisé en ce qu'il comporte, en fractions en masse prédéterminées : une séquence polymère [A] contenant, en tant que composants principaux, un motif structural [a1] dérivé d'un composé vinylique aromatique et/ou un motif structural [a2] qui est obtenu par hydrogénation d'au moins une partie des liaisons insaturées d'une structure dérivée d'un composé vinylique aromatique ; et une séquence polymère [B] contenant, en tant que composants principaux, un motif structural [b1] dérivé d'un composé diène conjugué à chaîne et/ou un motif structural [b2] qui est obtenu par hydrogénation des liaisons insaturées d'une structure dérivée d'un composé diène conjugué à chaîne, au moins l'un des motifs structuraux [a2] et [b2] étant contenu.
PCT/JP2019/002801 2018-02-14 2019-01-28 Copolymère séquencé contenant un groupe anhydride d'acide, composition de résine, feuille de résine et verre feuilleté WO2019159672A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021172189A1 (fr) * 2020-02-27 2021-09-02 Ｍｃｐｐイノベーション合同会社 Copolymère séquencé hydrogéné modifié

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Publication number Priority date Publication date Assignee Title
JPS4891186A (fr) * 1971-11-05 1973-11-27
JPS60188451A (ja) * 1984-03-09 1985-09-25 Mitsui Petrochem Ind Ltd 熱可塑性を有するエラストマ−
JPH06192350A (ja) * 1992-05-12 1994-07-12 Mitsubishi Petrochem Co Ltd 塗料用樹脂組成物
JPH06200086A (ja) * 1993-01-07 1994-07-19 Sumitomo Bakelite Co Ltd 水添ブロック共重合体エラストマー組成物
JPH06230725A (ja) * 1993-02-03 1994-08-19 Oji Yuka Synthetic Paper Co Ltd ヒートシール性ラベル
JPH07173390A (ja) * 1992-05-26 1995-07-11 Asahi Chem Ind Co Ltd 耐衝撃性に優れたポリアミド樹脂組成物
JPH11335430A (ja) * 1998-02-25 1999-12-07 Mitsubishi Chemical Corp グラフト共重合体およびその製造方法
WO2009084308A1 (fr) * 2007-12-27 2009-07-09 Zeon Corporation Copolymère statistique hydrocarboné alicyclique, procédé pour le produire, composition de résine et article moulé
JP2011126033A (ja) * 2009-12-15 2011-06-30 Japan Polypropylene Corp 表面保護用フィルム
WO2012165120A1 (fr) * 2011-05-27 2012-12-06 旭化成ケミカルズ株式会社 Procédé pour la fabrication de copolymère de diène conjugué hydrogéné
JP2017159590A (ja) * 2016-03-10 2017-09-14 日本ゼオン株式会社 接合体及び複合接合体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4891186A (fr) * 1971-11-05 1973-11-27
JPS60188451A (ja) * 1984-03-09 1985-09-25 Mitsui Petrochem Ind Ltd 熱可塑性を有するエラストマ−
JPH06192350A (ja) * 1992-05-12 1994-07-12 Mitsubishi Petrochem Co Ltd 塗料用樹脂組成物
JPH07173390A (ja) * 1992-05-26 1995-07-11 Asahi Chem Ind Co Ltd 耐衝撃性に優れたポリアミド樹脂組成物
JPH06200086A (ja) * 1993-01-07 1994-07-19 Sumitomo Bakelite Co Ltd 水添ブロック共重合体エラストマー組成物
JPH06230725A (ja) * 1993-02-03 1994-08-19 Oji Yuka Synthetic Paper Co Ltd ヒートシール性ラベル
JPH11335430A (ja) * 1998-02-25 1999-12-07 Mitsubishi Chemical Corp グラフト共重合体およびその製造方法
WO2009084308A1 (fr) * 2007-12-27 2009-07-09 Zeon Corporation Copolymère statistique hydrocarboné alicyclique, procédé pour le produire, composition de résine et article moulé
JP2011126033A (ja) * 2009-12-15 2011-06-30 Japan Polypropylene Corp 表面保護用フィルム
WO2012165120A1 (fr) * 2011-05-27 2012-12-06 旭化成ケミカルズ株式会社 Procédé pour la fabrication de copolymère de diène conjugué hydrogéné
JP2017159590A (ja) * 2016-03-10 2017-09-14 日本ゼオン株式会社 接合体及び複合接合体

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021172189A1 (fr) * 2020-02-27 2021-09-02 Ｍｃｐｐイノベーション合同会社 Copolymère séquencé hydrogéné modifié

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