WO2019159672A1 - Acid anhydride group-containing block copolymer, resin composition, resin sheet, and laminated glass - Google Patents

Acid anhydride group-containing block copolymer, resin composition, resin sheet, and laminated glass 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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French (fr)
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/en
Publication of WO2019159672A1 publication Critical patent/WO2019159672A1/en

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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.

Abstract

The purpose of the present invention is to provide an acid anhydride group-containing block copolymer capable of providing a resin sheet which can have both superior adhesiveness and transparency. The acid anhydride group-containing block copolymer according to the present invention contains an acid anhydride group, and is characterized by having, in predetermined mass fractions: a polymer block [A] containing, as main components, a structural unit [a1] derived from an aromatic vinyl compound and/or a structural unit [a2] which is obtained by hydrogenating at least a portion of the unsaturated bonds of a structure derived from an aromatic vinyl compound; and a polymer block [B] containing, as main components, a structural unit [b1] derived from a chain conjugated diene compound and/or a structural unit [b2] which is obtained by hydrogenating the unsaturated bonds of a structure derived from a chain conjugated diene compound, wherein at least one of the structural units [a2] and [b2] is contained.

Description

酸無水物基含有ブロック共重合体、樹脂組成物、樹脂シート、および合わせガラスAcid anhydride group-containing block copolymer, resin composition, resin sheet, and laminated glass
　本発明は、酸無水物基含有ブロック共重合体、樹脂組成物、樹脂シート、および合わせガラスに関するものである。 The present invention relates to an acid anhydride group-containing block copolymer, a resin composition, a resin sheet, and laminated glass.
　ブロック共重合体の水素化物（以下、「ブロック共重合体水素化物」と称することがある。）および該ブロック共重合体水素化物に酸無水物基、アルコキシシリル基等が導入されたものは、合わせガラス用の中間膜、太陽電池用の封止材、有機エレクトロルミネッセンス素子用の封止材等の優れた柔軟性および透明性が要求される用途に有用である（例えば、特許文献１～３参照）。 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, 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).
　上記ブロック共重合体水素化物を添加剤と混合して得られた樹脂組成物は、通常、ペレット状態にされた後に押出成形やカレンダー成形等によりシート状に加工される。そして、樹脂組成物をシート状に加工して得られる樹脂シートは、基材上に積層されることによって、合わせガラス用中間膜、太陽電池用封止材、有機エレクトロルミネッセンス素子用封止材等の用途に使用されている。 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
　ところで、合わせガラスは、衝突物により割れた場合にもガラス破片の飛散が少なく、また、衝突物の貫通に対しても抵抗することができるため、安全性に優れている。そのため、合わせガラスは、自動車、航空機、および建築物の窓ガラス等として広く使用されている。 By the way, 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.
　また、近年、自動車等の快適性を高めるため、遮音性、遮熱性等の特性に優れた合わせガラスが求められている。そのため、合わせガラス用中間膜として使用される樹脂シートに対しても、上記特性に優れることが要求される。そこで、上記特性を高めることを目的として、樹脂シートに使用されるブロック共重合体水素化物およびブロック共重合体水素化物を含む樹脂組成物の改良が行なわれている。 In recent years, in order to enhance the comfort of automobiles and the like, laminated glass excellent in properties such as sound insulation and heat insulation has been demanded. Therefore, it is requested | required that the said characteristic is excellent also with respect to the resin sheet used as an intermediate film for laminated glasses. Accordingly, for the purpose of enhancing the above characteristics, a block copolymer hydride used for the resin sheet and a resin composition containing the block copolymer hydride have been improved.
　例えば特許文献４では、芳香族ビニル化合物由来の単量体単位を主成分とする重合体ブロックおよび鎖状共役ジエン化合物（直鎖状共役ジエン、分岐鎖状共役ジエン）由来の単量体単位を主成分とする重合体ブロックを所定の比率で含んでなるブロック共重合体を水素化したブロック共重合体水素化物にアルコキシシリル基を導入してなる変性ブロック共重合体水素化物を中間膜に使用することにより、得られる合わせガラスの遮音性能を向上させることが提案されている。
　また、特許文献５では、芳香族ビニル化合物由来の構造単位を主成分とする重合体ブロック３０～５５質量％と、鎖状共役ジエン化合物由来の構造単位を主成分とする重合体ブロック４５～７０質量％とを含んでなるブロック共重合体を水素化したブロック共重合体水素化物に酸無水物基を導入してなる変性ブロック共重合体水素化物と、所定の波長領域の赤外線を遮蔽する機能を有する金属酸化物微粒子および／または近赤外線吸収色素とを配合してなる樹脂組成物からなるシートを用いることで、優れた遮熱機能を有し、且つ、耐湿性および耐久性にも優れる合わせガラスを提供することが提案されている。 For example, in 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. Thus, it has been proposed to improve the sound insulation performance of the obtained laminated glass.
In 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.
国際公開第２０１１／０９６３８９号International Publication No. 2011/096389 国際公開第２０１３／１７６２５８号International Publication No. 2013/176258 国際公開第２０１４／０９１９４１号International Publication No. 2014/091941 国際公開第２０１６／１０４７４０号International Publication No. 2016/104740 国際公開第２０１７／１３５１７７号International Publication No. 2017/135177
　しかし、上記従来の変性ブロック共重合体水素化物を含む樹脂組成物からなるシートには、透明性を確保しつつ接着性を向上させるという点において改善の余地があった。 However, 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.
　そこで、本発明は、優れた接着性および透明性を両立し得る樹脂シートを提供することを目的とする。また、本発明は、優れた接着性および透明性を両立し得る樹脂シートを提供可能な酸無水物基含有ブロック共重合体、および樹脂組成物を提供することを目的とする。さらに、本発明は、優れた接着性および透明性を両立し得る樹脂シートを備える合わせガラスを提供することを目的とする。 Therefore, 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.
　本発明者は、上記課題を解決することを目的として鋭意検討を行った。そして、本発明者は、所定の２種類の重合体ブロックを所定の質量分率で有し、且つ、所定の構造単位を含有する酸無水物基含有ブロック共重合体を用いれば、優れた接着性および透明性を両立し得る樹脂シートを提供できることを見出し、本発明を完成させた。 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.
　即ち、本発明は、上記課題を有利に解決することを目的とするものであり、本発明の酸無水物基含有ブロック共重合体は、芳香族ビニル化合物に由来する構造単位［ａ１］、および／または芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位［ａ２］を主成分として含有する重合体ブロック［Ａ］と、鎖状共役ジエン化合物に由来する構造単位［ｂ１］、および／または鎖状共役ジエン化合物（直鎖状共役ジエン、分岐鎖状共役ジエン）に由来する構造中の不飽和結合を水素化してなる構造単位［ｂ２］を主成分として含有する重合体ブロック［Ｂ］と、を有し、前記構造単位［ａ１］および［ａ２］が前記ブロック共重合体全体に占める質量分率をｗＡとし、前記構造単位［ｂ１］および［ｂ２］が前記ブロック共重合体全体に占める質量分率をｗＢとしたときの、ｗＡとｗＢとの比（ｗＡ／ｗＢ）が５／９５以上２９／７１以下であり、前記構造単位［ａ２］および［ｂ２］の少なくとも一方を含有することを特徴とする。このように、所定の構造単位［ａ１］および／または［ａ２］を主成分として含有する重合体ブロック［Ａ］と、所定の構造単位［ｂ１］および／または［ｂ２］を主成分として含有する重合体ブロック［Ｂ］とを所定の質量分率で含み、且つ、前記構造単位［ａ２］および［ｂ２］の少なくとも一方を含有する酸無水物基含有ブロック共重合体を用いれば、優れた接着性および透明性を両立し得る樹脂シートを提供することができる。 That is, 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 (linear conjugated diene, branched conjugated diene) 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 (wA / 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]. Thus, 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. Excellent adhesion by using an acid anhydride group-containing block copolymer containing a polymer block [B] at a predetermined mass fraction and containing at least one of the structural units [a2] and [b2] It is possible to provide a resin sheet that can satisfy both the properties and transparency.
　ここで、本発明の酸無水物基含有ブロック共重合体は、前記酸無水物基が無水マレイン酸基および／または無水イタコン酸基を含むことが好ましい。酸無水物基として無水マレイン酸基および／または無水イタコン酸基を含めば、酸無水物基含有ブロック共重合体を含む樹脂組成物を用いて形成された樹脂シートは、更に優れた接着性を発揮することができる。 Here, in the acid anhydride group-containing block copolymer of the present invention, 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.
　また、本発明の酸無水物基含有ブロック共重合体は、前記鎖状共役ジエン化合物がイソプレンであり、イソプレンに由来する構造単位、およびイソプレンに由来する構造中の不飽和結合を水素化してなる構造単位のうち、１，２－付加重合のみに由来する構造単位と、１，２－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＰとし、３，４－付加重合のみに由来する構造単位と、３，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＱとし、１，４－付加重合のみに由来する構造単位と、１，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＲとしたときの、下記式：
　構造単位比Ｓ＝（ｗＰ＋ｗＱ）／（ｗＰ＋ｗＱ＋ｗＲ）
で表わされる構造単位比Ｓの値が０．３以上であることが好ましい。鎖状共役ジエンがイソプレンである場合の上記式で表わされる構造単位比Ｓが０．３以上であれば、酸無水物基含有ブロック共重合体を含む樹脂組成物を用いて形成された樹脂シートは、接着性および透明性を良好に両立することができると共に、優れた遮音性を発揮することもできる。 In the acid anhydride group-containing block copolymer of the present invention, the chain conjugated diene compound is isoprene, and a structural unit derived from isoprene and an unsaturated bond in the structure derived from isoprene are hydrogenated. Among the structural units, 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 A structural unit obtained by hydrogenating an unsaturated bond in a structure derived only from 1,4-addition polymerization and a structural unit derived only from 1,4-addition polymerization, where wQ is a mass fraction in the entire copolymer And the block When the mass fraction of total copolymer was wR, 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. If the structural unit ratio S represented by the above formula when the chain conjugated diene is isoprene 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.
　また、本発明は、上記課題を有利に解決することを目的とするものであり、本発明の樹脂組成物は、上述したいずれかの酸無水物基含有ブロック共重合体と、金属酸化物の微粒子、金属ホウ化物の微粒子、および近赤外線吸収色素からなる群から選択される少なくとも１種の添加剤（Ｘ）とを含むことを特徴とする。このように、上述したいずれかの酸無水物基含有ブロック共重合体と、所定の添加剤とを含む樹脂組成物を用いれば、優れた接着性および透明性を両立し得ると共に、優れた遮熱性を発揮し得る樹脂シートを提供することができる。 Another object of the present invention is to advantageously solve the above-mentioned problems, and 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. As described above, if a resin composition containing any of the above-mentioned acid anhydride group-containing block copolymers and a predetermined additive is used, it is possible to achieve both excellent adhesiveness and transparency as well as excellent shielding. A resin sheet capable of exhibiting thermal properties can be provided.
　ここで、本発明の樹脂組成物は、前記添加剤（Ｘ）が金属酸化物の微粒子を含み、前記金属酸化物がセシウムドープ酸化タングステンを含むことが好ましい。添加剤（Ｘ）が金属酸化物の微粒子を含み、当該金属酸化物がセシウムドープ酸化タングステンを含めば、当該樹脂組成物を用いて形成された樹脂シートは、接着性および透明性を良好に両立することができると共に、更に優れた遮熱性を発揮することができる。
　また、本発明の樹脂組成物は、前記添加剤（Ｘ）が金属ホウ化物の微粒子を含み、前記金属ホウ化物がホウ化ランタンを含むことが好ましい。添加剤（Ｘ）が金属ホウ化物の微粒子を含み、当該金属ホウ化物がホウ化ランタンを含めば、当該樹脂組成物を用いて形成された樹脂シートは、接着性および透明性を良好に両立することができると共に、更に優れた遮熱性を発揮することができる。 Here, in the resin composition of the present invention, it is preferable that 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.
In the resin composition of the present invention, it is preferable that 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.
　さらに、本発明は、上記課題を有利に解決することを目的とするものであり、本発明の樹脂シートは、上述したいずれかの樹脂組成物からなる樹脂層を少なくとも１層含むことを特徴とする。このように、上述したいずれかの樹脂組成物からなる樹脂層を少なくとも１層含む樹脂シートは、優れた接着性および透明性を両立することができる。 Furthermore, 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. Thus, 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.
　また、本発明は、上記課題を有利に解決することを目的とするものであり、本発明の合わせガラスは、上述した樹脂シートを少なくとも１枚備えることを特徴とする。このように、上述した樹脂シートを少なくとも１枚用いれば、優れた接着性および透明性を両立し得る樹脂シートを備える合わせガラスを提供することができる。 Also, 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. As described above, when at least one of the above-described resin sheets is used, a laminated glass including a resin sheet that can achieve both excellent adhesiveness and transparency can be provided.
　ここで、本発明の合わせガラスは、８００ｎｍ以上２０００ｎｍ以下の波長の範囲内に光線透過率が５０％以下の領域を有することが好ましく、さらに、５００ｎｍの波長での光線透過率が６０％以上であることがより好ましい。８００ｎｍ以上２０００ｎｍ以下の波長の範囲内に光線透過率が５０％以下の領域を有する合わせガラスであれば、接着性および透明性を良好に両立しつつ、優れた遮熱性を発揮することができ、さらに、当該合わせガラスの５００ｎｍの波長での光線透過率が６０％以上であれば、優れた遮熱性を発揮しつつ、更に優れた透明性を発揮することができる。
　なお、本発明において、光線透過率は積分球式分光光度計を用いて測定することができる。 Here, 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.
　本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを提供可能な酸無水物基含有ブロック共重合体、および樹脂組成物を提供することができる。そして、本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを提供することができる。さらに、本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを備える合わせガラスを提供することができる。 According to the present invention, it is possible to provide 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. And according to this invention, the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided. Furthermore, according to this invention, a laminated glass provided with the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.
　以下、本発明の実施形態について詳細に説明する。
　ここで、本発明の酸無水物基含有ブロック共重合体は、本発明の樹脂組成物の調製に用いられる。そして、本発明の樹脂シートは、本発明の樹脂組成物からなる樹脂層を少なくとも１層含む。さらに、本発明の合わせガラスは、本発明の樹脂シートを少なくとも１枚備える。 Hereinafter, embodiments of the present invention will be described in detail.
Here, the acid anhydride group-containing block copolymer of the present invention is used for the preparation of the resin composition of the present invention. And the resin sheet of this invention contains at least 1 layer of the resin layer which consists of a resin composition of this invention. Furthermore, the laminated glass of the present invention includes at least one resin sheet of the present invention.
（酸無水物基含有ブロック共重合体）
　本発明の酸無水物基含有ブロック共重合体は、酸無水物基を含有するブロック共重合体であり、芳香族ビニル化合物に由来する構造単位［ａ１］、および／または芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位［ａ２］を主成分として含有する重合体ブロック［Ａ］と、鎖状共役ジエン化合物に由来する構造単位［ｂ１］、および／または鎖状共役ジエン化合物に由来する構造中の不飽和結合を水素化してなる構造単位［ｂ２］を主成分として含有する重合体ブロック［Ｂ］とを所定の質量分率で有し、且つ、前記構造単位［ａ２］および［ｂ２］の少なくともいずれか一方を含有することを特徴とする。なお、酸無水物基含有ブロック共重合体が、上述した構造単位［ａ２］および［ｂ２］の少なくとも一方を含有することで、得られる樹脂シートの耐候性を十分に高く確保することができる。 (Acid anhydride group-containing block copolymer)
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. A polymer block [A] containing as a main component a structural unit [a2] formed by hydrogenating at least a part of unsaturated bonds in the structure to be formed, a structural unit [b1] derived from a chain conjugated diene compound, and And / or a polymer block [B] containing as a main component a structural unit [b2] formed by hydrogenating an unsaturated bond in a structure derived from a chain conjugated diene compound, and having a predetermined mass fraction, and And at least one of the structural units [a2] and [b2]. In addition, when 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.
＜酸無水物基＞
　酸無水物基は、酸無水物基含有ブロック共重合体を含む樹脂組成物中に添加され得る添加剤の分散性を高めて、製造される樹脂シートの透明性を向上させると共に、当該樹脂シートに優れた接着性を発揮させる機能を有する。
　酸無水物基としては、無水マレイン酸基、無水シトラコン酸基、無水イタコン酸基、無水２，３－ジメチルマレイン酸基、無水５－ノルボルネン－２，３－ジカルボン酸基、無水アリルコハク酸基、無水２－フェニルマレイン酸基、無水ｃｉｓ－アコニット酸基などが挙げられる。中でも、酸無水物基の導入に用いる不飽和カルボン酸無水物の工業的入手の容易さの観点から、酸無水物基は、無水マレイン酸基、無水イタコン酸基、無水５－ノルボルネン－２，３－ジカルボン酸基であることが好ましく、樹脂シートの接着性および透明性を更に良好に両立する観点から、無水マレイン酸基および無水イタコン酸基であることがより好ましい。 <Acid anhydride group>
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.
Examples of 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. Among these, from the viewpoint of industrial availability of unsaturated carboxylic acid anhydrides used for introducing acid anhydride groups, 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.
　そして、酸無水物基含有ブロック共重合体中の酸無水物基の含有割合は、特に限定されないが、酸無水物基含有ブロック共重合体全体を１００質量％とした場合に、０．０１質量％以上であることが好ましく、０．１質量％以上であることがより好ましく、０．３質量％以上であることが更に好ましく、９質量％以下であることが好ましく、６．５質量％以下であることがより好ましく、３．８質量％以下であることが更に好ましい。酸無水物基含有ブロック共重合体中の酸無水物基の含有割合が０．０１質量％以上であれば、得られる樹脂シートの透明性を更に高めることができる。一方、酸無水物基含有ブロック共重合体中の酸無水物基の含有割合が９質量％以下であれば、得られる樹脂シートの低吸水性を高めることができる。 And 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.
＜重合体ブロック［Ａ］＞
　重合体ブロック［Ａ］は、芳香族ビニル化合物に由来する構造単位［ａ１］、および／または芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位［ａ２］を主成分として含有する。 <Polymer block [A]>
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.
＜＜構造単位［ａ１］＞＞
　芳香族ビニル化合物に由来する構造単位［ａ１］を形成し得る芳香族ビニル化合物としては、スチレンおよびその誘導体が挙げられ、具体的には、スチレン、α－メチルスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、２，４－ジイソプロピルスチレン、２，４－ジメチルスチレン、４－ｔ－ブチルスチレン、５－ｔ－ブチル－２－メチルスチレン、４－モノクロロスチレン、ジクロロスチレン、４－モノフルオロスチレン、および４－フェニルスチレンなどが挙げられる。これらの中でも、得られる樹脂シートの低吸水性を高める観点から、スチレン、α－メチルスチレン、２－メチルスチレン、３－メチルスチレン、４－メチルスチレン、２，４－ジイソプロピルスチレン、２，４－ジメチルスチレン、４－ｔ－ブチルスチレン、５－ｔ－ブチル－２－メチルスチレン、および４－フェニルスチレンを用いることが好ましく、工業的な入手の容易さから、スチレンを用いることが特に好ましい。これらは、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 << 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, α-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. Among these, from the viewpoint of increasing the low water absorption of the obtained resin sheet, styrene, α-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.
＜＜構造単位［ａ２］＞＞
　構造単位［ａ２］は、芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位である。そして、芳香族ビニル化合物としては、構造単位［ａ１］を形成し得る芳香族ビニル化合物として上述したものと同じものが挙げられる。また、構造単位［ａ２］においては、芳香族ビニル化合物に由来する構造中の不飽和結合の一部のみが水素化されていてもよいし、不飽和結合の全部が水素化されていてもよいが、得られる樹脂シートの耐候性を高める観点から、芳香族ビニル化合物に由来する構造中の不飽和結合の全部が水素化されていることが好ましい。なお、構造単位［ａ２］は、芳香族ビニル化合物の芳香環中の不飽和結合の少なくとも一部を水素化してなる化合物のビニル基の付加重合のみに由来する構造単位であってもよい。具体的に、芳香族ビニル化合物の芳香環中の不飽和結合の少なくとも一部を水素化してなる化合物としては、ビニルシクロヘキサン、１－ビニル－１－シクロヘキセン、３－ビニル－１－シクロヘキセン、４－ビニル－１－シクロヘキセン、１－ビニル－１，３－シクロヘキサジエン、２－ビニル－１，３－シクロヘキサジエン、５－ビニル－１，３－シクロヘキサジエン、３－ビニル－１，４－シクロヘキサジエン、４－ビニル－１，４－シクロヘキサジエン等の化合物およびそれらの誘導体などが挙げられる。 << Structural Unit [a2] >>
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. Specifically, 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.
＜＜その他の構造単位＞＞
　なお、重合体ブロック［Ａ］は、構造単位［ａ１］および［ａ２］以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、後述する鎖状共役ジエン化合物に由来する構造単位［ｂ１］、および／または鎖状共役ジエン化合物に由来する構造中の不飽和結合を水素化してなる構造単位［ｂ２］であってもよい。また、その他の構造単位を形成しうる化合物としては、極性基を含有しないものが好ましく、例えば、エチレン、プロピレン、１－ブテン、１－ペンテン、１－ヘキセン、１－ヘプテン、１－オクテン、１－ノネン、１－デセン、１－ドデセン、１－エイコセン、４－メチル－１－ペンテン、４，６－ジメチル－１－ヘプテンなどの鎖状オレフィン；などが挙げられる。なお、その他の構造単位を形成しうる化合物として、「構造単位［ａ２］」の項で上述した芳香族ビニル化合物の芳香環中の不飽和結合の少なくとも一部を水素化してなる化合物以外の環状オレフィンを用いることもできる。 << Other structural units >>
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. For example, 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; As other compounds that can form structural units, 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.
＜＜組成等＞＞
　そして、重合体ブロック［Ａ］中の構造単位［ａ１］および［ａ２］の含有割合は、重合体ブロック［Ａ］中の全繰り返し単位を１００質量％とした場合に、好ましくは８０質量％以上、より好ましくは９０質量％以上、更に好ましくは９５質量％以上、特に好ましくは１００質量％である。重合体ブロック［Ａ］中の構造単位［ａ１］および［ａ２］の含有割合が８０質量％以上であれば、得られる樹脂シートの耐熱性を十分に高く確保できる。 << Composition etc. >>
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%. When 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.
　ここで、酸無水物基含有ブロック共重合体中の重合体ブロック［Ａ］の数は、通常５つ以下、好ましくは４つ以下、より好ましくは３つ以下であり、また、好ましくは２つ以上である。
　なお、酸無水物基含有ブロック共重合体が重合体ブロック［Ａ］を複数有する場合は、複数の重合体ブロック［Ａ］中の構造単位の組成は同一であってもよく、異なっていてもよい。 Here, 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.
When 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.
＜重合体ブロック［Ｂ］＞
　重合体ブロック［Ｂ］は、鎖状共役ジエン化合物に由来する構造単位［ｂ１］、および／または鎖状共役ジエン化合物に由来する構造中の不飽和結合を水素化してなる構造単位［ｂ２］を主成分として含有する。 <Polymer block [B]>
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.
＜＜構造単位［ｂ１］＞＞
　鎖状共役ジエン化合物に由来する構造単位［ｂ１］を形成し得る鎖状共役ジエン化合物としては、特に限定されないが、得られる樹脂シートの低吸水性を高める観点から、極性基を含有しないものが好ましく、具体的には、１，３－ブタジエン、イソプレン（２－メチル－１,３－ブタジエン）、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエンなどが好ましく挙げられる。これらの中でも、工業的な入手の容易さから１，３－ブタジエン、イソプレンが特に好ましく、遮音性に優れた樹脂シートを製造する観点から、イソプレンが最も好ましい。これらは、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 << Structural unit [b1] >>
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. Specifically, 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like are preferable. Among these, 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.
＜＜構造単位［ｂ２］＞＞
　構造単位［ｂ２］は、鎖状共役ジエン化合物に由来する構造中の不飽和結合を水素化してなる構造単位である。そして、鎖状共役ジエン化合物としては、構造単位［ｂ１］を形成し得る鎖状共役ジエン化合物として上述したものと同じものが挙げられる。 << Structural unit [b2] >>
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.
＜＜その他の構造単位＞＞
　なお、重合体ブロック［Ｂ］は、構造単位［ｂ１］および［ｂ２］以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、上述した芳香族ビニル化合物に由来する構造単位［ａ１］、および／または芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位［ａ２］であってもよい。また、その他の構造単位は「重合体ブロック［Ａ］」の項で上述した鎖状オレフィンおよび環状オレフィンから形成されてもよい。 << Other structural units >>
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]”.
＜＜組成等＞＞
　そして、重合体ブロック［Ｂ］中の構造単位［ｂ１］および［ｂ２］の含有割合は、重合体ブロック［Ｂ］中の全繰り返し単位を１００質量％とした場合に、好ましくは６０質量％以上、より好ましくは８０質量％以上、更に好ましくは９０質量％以上、特に好ましくは１００質量％である。重合体ブロック［Ｂ］中の構造単位［ｂ１］および［ｂ２］の含有割合が８０質量％以上であれば、得られる樹脂シートの柔軟性が高まるため、例えば、当該樹脂シートを備える合わせガラスは、環境の急激な温度変化に対しても割れ等の不具合を発生し難い。 << Composition etc. >>
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.
　ここで、酸無水物基含有ブロック共重合体中の重合体ブロック［Ｂ］の数は、通常４つ以下、好ましくは３つ以下、より好ましくは２つ以下、更に好ましくは１つである。
　なお、酸無水物基含有ブロック共重合体が重合体ブロック［Ｂ］を複数有する場合は、複数の重合体ブロック［Ｂ］中の構造単位の組成は同一であっても異なっていてもよい。 Here, 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.
When 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.
＜質量分率＞
　ここで、構造単位［ａ１］および［ａ２］が酸無水物基含有ブロック共重合体全体に占める質量分率をｗＡとし、構造単位［ｂ１］および［ｂ２］が酸無水物基含有ブロック共重合体全体に占める質量分率をｗＢとしたときの、ｗＡとｗＢとの比（ｗＡ／ｗＢ）は、５／９５以上であることが必要であり、７／９３以上であることが好ましく、１５／８５以上であることがより好ましく、１０／９０以上であることが更に好ましく、２９／７１以下であることが必要であり、２７／７３以下であることが好ましく、２５／７５以下であることがより好ましい。ｗＡ／ｗＢの比が５／９５以上であれば、樹脂シートの耐熱性を十分に高く確保できる。一方、ｗＡ／ｗＢの比が２９／７１以下であれば、樹脂シートの低温での接着性を十分に高く確保できる。 <Mass fraction>
Here, wA represents the mass fraction of the structural units [a1] and [a2] in the entire acid anhydride group-containing block copolymer, and the 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. If the ratio of wA / wB is 5/95 or more, the heat resistance of the resin sheet can be secured sufficiently high. On the other hand, if 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.
＜構造単位比Ｓ＞
　本発明の酸無水物基含有ブロック共重合体は、上述した鎖状共役ジエン化合物がイソプレンである場合、イソプレンに由来する構造単位、およびイソプレンに由来する構造中の不飽和結合を水素化してなる構造単位のうち、１，２－付加重合のみに由来する構造単位と、１，２－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが酸無水物基含有ブロック共重合体全体に占める質量分率をｗＰとし、３，４－付加重合のみに由来する構造単位と、３，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが酸無水物基含有ブロック共重合体全体に占める質量分率をｗＱとし、１，４－付加重合のみに由来する構造単位と、１，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが酸無水物基含有ブロック共重合体全体に占める質量分率をｗＲとしたときの、下記式：
　構造単位比Ｓ＝（ｗＰ＋ｗＱ）／（ｗＰ＋ｗＱ＋ｗＲ）
で表わされる構造単位比Ｓの値が０．３以上であることが好ましく、０．４以上であることがより好ましく、０．５以上であることが更に好ましく、０．５５以上であることが一層好ましく、０．６５以下であることが好ましい。上記構造単位比Ｓの値が上記所定の範囲内であれば、酸無水物基含有ブロック共重合体を含む樹脂組成物を用いて形成された樹脂シートは、優れた遮音性を発揮することができる。 <Structural unit ratio S>
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. Among 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. A structural unit obtained by hydrogenating an unsaturated bond in a structure derived only from 3,4-addition polymerization and a structural unit derived only from 3,4-addition polymerization, wherein the mass fraction in the entire copolymer is wP And wQ represents the mass fraction of the entire acid anhydride group-containing block copolymer, and structural units derived only from 1,4-addition polymerization and unsaturation in structures derived only from 1,4-addition polymerization Hydrogenated bond The mass fraction of the concrete units to the total acid anhydride group-containing block copolymer when formed into a wR, the formula:
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 sheet formed using a resin composition containing an acid anhydride group-containing block copolymer can exhibit excellent sound insulation. it can.
＜ブロック構造＞
　酸無水物基含有ブロック共重合体のブロックの構造は、鎖状型ブロックでもラジアル型ブロックでも良いが、機械的強度の観点から、鎖状型ブロックであることが好ましい。また、酸無水物基含有ブロック共重合体は、重合体ブロック［Ｂ］の両端に重合体ブロック［Ａ］が結合した構造（すなわち、Ａ－Ｂ－Ａの順に並んだ構造）を少なくとも１箇所有することが好ましい。
　そして、酸無水物基含有ブロック共重合体の特に好ましい構造としては、重合体ブロック［Ｂ］の両端に重合体ブロック［Ａ］が結合してなるトリブロック共重合体（Ａ－Ｂ－Ａ）、および、重合体ブロック［Ａ］の両端に重合体ブロック［Ｂ］が結合し、さらに、該２つの重合体ブロック［Ｂ］の他端にそれぞれ重合体ブロック［Ａ］が結合してなるペンタブロック共重合体（Ａ－Ｂ－Ａ－Ｂ－Ａ）が挙げられ、トリブロック共重合体（Ａ－Ｂ－Ａ）が最も好ましい。 <Block structure>
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.
＜物性＞
　酸無水物基含有ブロック共重合体の物性は特に限定されることはないが、例えば、酸無水物基含有ブロック共重合体の重量平均分子量（Ｍｗ）は、２０,０００以上であることが好ましく、２５,０００以上であることがより好ましく、３０,０００以上であることが更に好ましく、９０，０００以下であることが好ましく、８５,０００以下であることがより好ましく、８０,０００以下であることが更に好ましく、７５，０００以下であることが一層好ましい。酸無水物基含有ブロック共重合体の重合平均分子量が２０,０００以上であれば、得られる樹脂シートの機械的強度を高めることができ、９０，０００以下であれば、当該樹脂シートの加工性を向上させることができる。
　また、酸無水物基含有ブロック共重合体の分子量分布（Ｍｗ／Ｍｎ）は、３．５以下であることが好ましく、２．５以下であることが好ましく、２．０以下であることが更に好ましい。分子量分布が３．５以下であれば、得られる樹脂シートの機械的強度を高めることができる。
　なお、重量平均分子量（Ｍｗ）および数平均分子量（Ｍｎ）は、テトラヒドロフラン（ＴＨＦ）を溶媒とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）による、標準ポリスチレン換算値として測定することができる。 <Physical properties>
The physical properties of the acid anhydride group-containing block copolymer are not particularly limited. For example, 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.
In addition, 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.
＜調製方法＞
　本発明の酸無水物基含有ブロック共重合体を調製する方法としては、特に限定されないが、例えば、
（１）まず、ブロック共重合体［Ｃ］を調製し、次いで、当該ブロック共重合体［Ｃ］を水素化し、さらに、得られた水素化物［Ｄ］を酸無水物変性させて酸無水物変性水素化物［Ｅ］を得ることにより調製する方法；
（２）まず、ブロック共重合体［Ｃ’］を調製し、次いで、当該ブロック共重合体［Ｃ’］を酸無水物変性させて、さらに、得られた酸無水物変性体［Ｄ’］を水素化して酸無水物変性体水素化物［Ｅ’］を得ることにより調製する方法；
（３）まず、酸無水物基含有構造単位を含むブロック共重合体［Ｃ”］を調製し、次いで、当該ブロック共重合体［Ｃ”］を水素化して酸無水物基含有水素化物［Ｅ”］を得ることにより調製する方法；
等が挙げられる。 <Preparation method>
The method for preparing the acid anhydride group-containing block copolymer of the present invention is not particularly limited.
(1) First, 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. A method of preparing by obtaining a modified hydride [E];
(2) First, a block copolymer [C ′] is prepared, then, the block copolymer [C ′] is modified with an acid anhydride, and the resulting acid anhydride modified product [D ′] is further obtained. A method for preparing an acid anhydride modified hydride [E ′] by hydrogenating
(3) First, a block copolymer [C ″] containing an acid anhydride group-containing structural unit is prepared, and then the block copolymer [C ″] is hydrogenated to obtain an acid anhydride group-containing hydride [E]. ”] To prepare by obtaining;
Etc.
　ここで、（２）または（３）の調製方法の場合、水素化反応の条件によっては、ブロック共重合体［Ｃ’］の酸無水物変性体（即ち、酸無水物変性体［Ｄ’］）、またはブロック共重合体［Ｃ”］が有する酸無水物基の一部が分解されるおそれがある。したがって、最終的に得られる酸無水物基含有ブロック共重合体中の酸無水物基の含有量を十分に高く確保し、更に優れた透明性および接着性を有する樹脂シートを製造する観点から、（１）の調製方法を用いることが特に好ましい。
　以下に、上述した（１）～（３）の調製方法に用いられるブロック共重合体［Ｃ］、［Ｃ’］および［Ｃ”］、ならびに水素化および酸無水物変性の方法について詳述する。 Here, in the case of the preparation method of (2) or (3), depending on the conditions of the hydrogenation reaction, an acid anhydride modified product of the block copolymer [C ′] (that is, acid anhydride modified product [D ′]) ), Or 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. It is particularly preferable to use the preparation method (1) from the viewpoint of securing a sufficiently high content and producing a resin sheet having excellent transparency and adhesiveness.
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. .
＜＜ブロック共重合体［Ｃ］および［Ｃ’］＞＞
　ブロック共重合体［Ｃ］および［Ｃ’］は、芳香族ビニル化合物に由来する構造単位を主成分として含有する重合体ブロック［Ａ’］と、鎖状共役ジエン化合物に由来する構造単位を主成分として含有する重合体ブロック［Ｂ’］とを所定の質量分率で含むブロック共重合体であることが必要である。 << Block copolymer [C] and [C '] >>
The block copolymers [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.
［重合体ブロック［Ａ’］］
　重合体ブロック［Ａ’］に好適に含まれる芳香族ビニル化合物に由来する構造単位を形成し得る芳香族ビニル化合物としては、酸無水物基含有ブロック共重合体の「重合体ブロック［Ａ］」の項で上述したものと同じものが挙げられる。そして、重合体ブロック［Ａ’］中の芳香族ビニル化合物に由来する構造単位の含有割合は、「重合体ブロック［Ａ］」の項で上述した重合体ブロック［Ａ］中の構造単位［ａ１］および［ａ２］の含有割合の範囲と同じ範囲で調整することができる。また、重合体ブロック［Ａ’］は芳香族ビニル化合物に由来する構造単位以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、鎖状共役ジエン化合物に由来する構造単位であってもよい。また、その他の構造単位は、「重合体ブロック［Ａ］」の項で上述した鎖状オレフィンおよび環状オレフィンから形成されてもよい。
　そして、ブロック共重合体［Ｃ］または［Ｃ’］中の重合体ブロック［Ａ’］の数も、上述した酸無水物基含有ブロック共重合体中の重合体ブロック［Ａ］の数と同じ範囲内で調整することができる。
　なお、ブロック共重合体［Ｃ］または［Ｃ’］が重合体ブロック［Ａ’］を複数有する場合は、複数の重合体ブロック［Ａ’］中の構造単位の組成は同一であっても異なっていてもよい。 [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.
When the block copolymer [C] or [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. It may be.
［重合体ブロック［Ｂ’］］
　重合体ブロック［Ｂ’］に好適に含まれる鎖状共役ジエン化合物に由来する構造単位を形成し得る鎖状共役ジエン化合物としては、酸無水物基含有ブロック共重合体の「重合体ブロック［Ｂ］」の項で上述したものと同じものが挙げられる。そして、重合体ブロック［Ｂ’］中の鎖状共役ジエン化合物に由来する構造単位の含有割合は、「重合体ブロック［Ｂ］」の項で上述した重合体ブロック［Ｂ］中の構造単位［ｂ１］および［ｂ２］の含有割合の範囲と同じ範囲で調整することができる。また、重合体ブロック［Ｂ’］は鎖状共役ジエン化合物に由来する構造単位以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、芳香族ビニル化合物に由来する構造単位であってもよい。また、その他の構造単位は、「重合体ブロック［Ａ］」の項で上述した鎖状オレフィンおよび環状オレフィンから形成されてもよい。
　そして、ブロック共重合体［Ｃ］または［Ｃ’］中の重合体ブロック［Ｂ’］の数も、上述した酸無水物基含有ブロック共重合体中の重合体ブロック［Ｂ］の数と同じ範囲内で調整することができる。
　なお、ブロック共重合体［Ｃ］または［Ｃ’］が重合体ブロック［Ｂ’］を複数有する場合は、複数の重合体ブロック［Ｂ’］中の構造単位の組成は同一であっても異なっていてもよい。 [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.
In the case where the block copolymer [C] or [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. It may be.
［質量分率］
　ここで、芳香族ビニル化合物に由来する構造単位がブロック共重合体［Ｃ］または［Ｃ’］全体に占める質量分率をｗＡ’とし、鎖状共役ジエン化合物に由来する構造単位がブロック共重合体［Ｃ］または［Ｃ’］全体に占める質量分率をｗＢ’としたときの、ｗＡ’とｗＢ’との比（ｗＡ’／ｗＢ’）は、上述した酸無水物基含有ブロック共重合体におけるｗＡとｗＢとの比（ｗＡ／ｗＢ）の範囲と同じ範囲で調整することができる。
　なお、ブロック共重合体［Ｃ］におけるｗＡ’とｗＢ’との比（ｗＡ’／ｗＢ’）は、当該ブロック共重合体［Ｃ］を水素化した後に酸無水物変性して得られる酸無水物変性水素化物［Ｅ］（酸無水物基含有ブロック共重合体）におけるｗＡとｗＢとの比（ｗＡ／ｗＢ）と一致する。また、ブロック共重合体［Ｃ’］におけるｗＡ’とｗＢ’との比（ｗＡ’／ｗＢ’）は、当該ブロック共重合体［Ｃ’］を酸無水物変性した後に水素化して得られる酸無水物変性体水素化物［Ｅ’］（酸無水物基含有ブロック共重合体）におけるｗＡとｗＢとの比（ｗＡ／ｗＢ）と一致する。 [Mass fraction]
Here, 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).
［構造単位比Ｓ’］
　ブロック共重合体［Ｃ］または［Ｃ’］は、上述した鎖状共役ジエン化合物がイソプレンである場合、イソプレンに由来する構造単位のうち、１，２－付加重合のみに由来する構造単位がブロック共重合体［Ｃ］または［Ｃ’］全体に占める質量分率をｗＰ’とし、３，４－付加重合のみに由来する構造単位がブロック共重合体［Ｃ］または［Ｃ’］全体に占める質量分率をｗＱ’とし、１，４－付加重合のみに由来する構造単位がブロック共重合体［Ｃ］または［Ｃ’］全体に占める質量分率をｗＲ’としたときの、下記式：
　構造単位比Ｓ’＝（ｗＰ’＋ｗＱ’）／（ｗＰ’＋ｗＱ’＋ｗＲ’）
で表わされる構造単位比Ｓ’の値が、０．３以上であることが好ましく、０．４以上であることがより好ましく、０．５以上であることが更に好ましく、０．５５以上であることが一層好ましく、０．６５以下であることが好ましい。上記構造単位比Ｓ’の値が上記所定の範囲内であれば、酸無水物基含有ブロック共重合体を含む樹脂組成物を用いて形成された樹脂シートは、優れた遮音性を発揮することができる。
　なお、構造単位比Ｓ’は、本明細書の実施例に記載の方法により求めることができる。
　また、ブロック共重合体［Ｃ］における構造単位比Ｓ’は、当該ブロック共重合体［Ｃ］を水素化した後に酸無水物変性して得られる酸無水物変性水素化物［Ｅ］（酸無水物基含有ブロック共重合体）における構造単位比Ｓと一致する。また、ブロック共重合体［Ｃ’］における構造単位比Ｓ’は、当該ブロック共重合体［Ｃ’］を酸無水物変性した後に水素化して得られる酸無水物変性体水素化物［Ｅ’］（酸無水物基含有ブロック共重合体）における構造単位比Ｓと一致する。 [Structural unit ratio S ′]
In the block copolymer [C] or [C ′], when the above-mentioned chain conjugated diene compound is isoprene, among the structural units derived from isoprene, structural units derived only from 1,2-addition polymerization are blocked. The mass fraction occupying the entire copolymer [C] or [C ′] is wP ′, and the structural unit derived only from 3,4-addition polymerization occupies the entire block copolymer [C] or [C ′]. When the mass fraction is wQ ′ and the mass fraction of the structural units derived only from 1,4-addition polymerization in the block copolymer [C] or [C ′] is wR ′, the following formula:
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. When the value of the structural unit ratio S ′ is within the predetermined range, 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). Further, 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).
　ここで、上述した１，２－付加重合のみに由来する構造単位および／または３，４－付加重合のみに由来する構造単位を含有する重合体ブロックは、鎖状共役ジエン化合物と、必要に応じて、芳香族ビニル化合物、鎖状オレフィン、環状オレフィン等のその他の構造単位を形成し得る化合物とを、電子供与原子を有する特定の化合物（以下、「ランダム化剤」と称することがある。）の存在下で重合させることにより得ることができる。１，２－付加重合のみに由来する構造単位と３，４－付加重合のみに由来する構造単位との含有量の合計は、ランダム化剤の種類と添加量に依存することから、上述した構造単位比Ｓ’の値はランダム化剤の添加量によって制御することができる。 Here, 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. Since the total content of structural units derived only from 1,2-addition polymerization and structural units derived only from 3,4-addition polymerization depends on the type and amount of randomizing agent, the structure described above The value of the unit ratio S ′ can be controlled by the amount of randomizing agent added.
　ランダム化剤として使用し得る電子供与原子（例えば、酸素（Ｏ）、窒素（Ｎ））を有する化合物としては、エーテル化合物、アミン化合物、ホスフィン化合物、などが挙げられる。これらの中でも、重合体ブロックの分子量分布を小さくすることができ、その水素添加反応を阻害し難いという観点から、エーテル化合物が好ましい。 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. Among these, 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.
　ランダム化剤の具体例としては、例えば、ジエチルエーテル、ジイソプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジイソプロピルエーテル、エチレングリコールジブチルエーテル、エチレングリコールメチルフェニルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジイソプロピルエーテル、プロピレングリコールジブチルエーテル、ジ（２－テトラヒドロフリル）メタン、ジエチレングリコールジブチルエーテル、ジプロピレングリコールジブチルエーテル、テトラメチルエチレンジアミン、などが挙げられる。中でも、１，２－付加重合のみに由来する構造単位および／または３，４－付加重合のみに由来する構造単位の質量分率を高め、構造単位比Ｓ’の値を増大させ、得られる樹脂シートの遮音性を更に高める観点から、エチレングリコールジブチルエーテルを用いることが好ましい。 Specific examples of the randomizing agent 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. Propylene glycol diethyl ether, propylene glycol diisopropyl ether, propylene glycol dibutyl ether, di (2-tetrahydrofuryl) methane, diethylene glycol dibutyl ether, dipropylene glycol dibutyl ether, tetramethylethylenediamine, and the like. Among them, the resin obtained by increasing the mass fraction of structural units derived only from 1,2-addition polymerization and / or structural units derived only from 3,4-addition polymerization and increasing the value of the structural unit ratio S ′ From the viewpoint of further improving the sound insulation of the sheet, it is preferable to use ethylene glycol dibutyl ether.
　ブロック共重合体［Ｃ］または［Ｃ’］の調製時におけるこれらのランダム化剤の使用量は、鎖状共役ジエン化合物１００質量部に対して、０．００１質量部以上であることが好ましく、０．０１質量部以上であることがより好ましく、１０質量部以下であることが好ましく、１質量部以下であることがより好ましい。 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.
［ブロック構造］
　ブロック共重合体［Ｃ］または［Ｃ’］のブロックの構造は、鎖状型ブロックでもラジアル型ブロックでも良いが、機械的強度の観点から、鎖状型ブロックであるものが好ましい。また、ブロック共重合体［Ｃ］または［Ｃ’］は、重合体ブロック［Ｂ’］の両端に重合体ブロック［Ａ’］が結合した構造（すなわち、Ａ’－Ｂ’－Ａ’の順に並んだ構造）を少なくとも１箇所有することが好ましい。
　そして、ブロック共重合体［Ｃ］または［Ｃ’］の特に好ましい構造としては、重合体ブロック［Ｂ’］の両端に重合体ブロック［Ａ’］が結合してなるトリブロック共重合体（Ａ’－Ｂ’－Ａ’）、および、重合体ブロック［Ａ’］の両端に重合体ブロック［Ｂ’］が結合し、さらに、該２つの重合体ブロック［Ｂ’］の他端にそれぞれ重合体ブロック［Ａ’］が結合してなるペンタブロック共重合体（Ａ’－Ｂ’－Ａ’－Ｂ’－Ａ’）が挙げられ、トリブロック共重合体（Ａ’－Ｂ’－Ａ’）が最も好ましい。 [Block structure]
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.
［調製方法］
　ブロック共重合体［Ｃ］または［Ｃ’］の調製方法は特に限定されず、例えば、リビングアニオン重合を用いて、芳香族ビニル化合物を含有する組成物と鎖状共役ジエン化合物を含有する組成物とを交互に重合させることで、ブロック共重合体［Ｃ］または［Ｃ’］を調製することができる。 [Preparation method]
The method for preparing the block copolymer [C] or [C ′] is not particularly limited. For example, 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.
＜＜ブロック共重合体［Ｃ”］＞＞
　ブロック共重合体［Ｃ”］は、芳香族ビニル化合物に由来する構造単位を主成分として含有する重合体ブロック［Ａ”］と、鎖状共役ジエン化合物に由来する構造単位を主成分として含有する重合体ブロック［Ｂ”］とを所定の質量分率で含み、且つ、酸無水物基含有構造単位を含むブロック共重合体であることが必要である。 << Block copolymer [C "] >>
The 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.
［酸無水物基含有構造単位］
　酸無水物基含有構造単位を形成し得る酸無水物としては、無水マレイン酸、無水シトラコン酸、無水イタコン酸、無水２，３－ジメチルマレイン酸、無水５－ノルボルネン－２，３－ジカルボン酸、無水アリルコハク酸、無水２－フェニルマレイン酸、無水ｃｉｓ－アコニット酸などのエチレン性不飽和カルボン酸無水物が挙げられる。中でも、工業的入手の容易さの観点から、酸無水物としては、無水マレイン酸、無水イタコン酸、無水５－ノルボルネン－２，３－ジカルボン酸を用いることが好ましく、樹脂シートの接着性および透明性を更に良好に両立する観点から、無水マレイン酸および無水イタコン酸を用いることがより好ましい。なお、これらは、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。 [Acid anhydride group-containing structural unit]
Examples of the acid anhydride that can form an acid anhydride group-containing structural unit 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. Among these, from the viewpoint of industrial availability, 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.
　そして、ブロック共重合体［Ｃ”］中の酸無水物基含有構造単位の含有割合は、特に限定されないが、ブロック共重合体［Ｃ”］全体を１００質量％とした場合に、０．０１質量％以上であることが好ましく、０．１質量％以上であることがより好ましく、０．３質量％以上であることが更に好ましく、９質量％以下であることが好ましく、６．５質量％以下であることがより好ましく、３．８質量％以下であることが更に好ましい。ブロック共重合体［Ｃ”］中の酸無水物基含有構造単位の含有割合が０．０１質量％以上であれば、得られる樹脂シートの透明性を更に高めることができる。一方、ブロック共重合体［Ｃ”］中の酸無水物基含有構造単位の含有割合が９質量％以下であれば、得られる樹脂シートの低吸水性を高めることができる。 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. When 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. When 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.
［重合体ブロック［Ａ”］］
　重合体ブロック［Ａ”］に好適に含まれる芳香族ビニル化合物に由来する構造単位を形成し得る芳香族ビニル化合物としては、酸無水物基含有ブロック共重合体の「重合体ブロック［Ａ］」の項で上述したものと同じものが挙げられる。また、重合体ブロック［Ａ”］は芳香族ビニル化合物に由来する構造単位以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、鎖状共役ジエン化合物に由来する構造単位であってもよい。また、その他の構造単位は、「重合体ブロック［Ａ］」の項で上述した鎖状オレフィンおよび環状オレフィンから形成されてもよく、上述した酸無水物から形成されてもよい。
　そして、ブロック共重合体［Ｃ”］中の重合体ブロック［Ａ”］の数も、上述した酸無水物基含有ブロック共重合体中の重合体ブロック［Ａ］の数と同じ範囲内で調整することができる。
　なお、ブロック共重合体［Ｃ”］が重合体ブロック［Ａ”］を複数有する場合は、複数の重合体ブロック［Ａ”］中の構造単位の組成は同一であっても異なっていてもよい。 [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.
In the case where 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. .
［重合体ブロック［Ｂ”］］
　重合体ブロック［Ｂ”］に好適に含まれる鎖状共役ジエン化合物に由来する構造単位を形成し得る鎖状共役ジエン化合物としては、酸無水物基含有ブロック共重合体の「重合体ブロック［Ｂ］」の項で上述したものと同じものが挙げられる。また、重合体ブロック［Ｂ”］は鎖状共役ジエン化合物に由来する構造単位以外の構造単位を含んでいてもよく、そのようなその他の構造単位は、芳香族ビニル化合物に由来する構造単位であってもよい。また、その他の構造単位は、「重合体ブロック［Ａ］」の項で上述した鎖状オレフィンおよび環状オレフィンから形成されてもよく、上述した酸無水物から形成されてもよい。
　そして、ブロック共重合体［Ｃ”］中の重合体ブロック［Ｂ”］の数も、上述した酸無水物基含有ブロック共重合体中の重合体ブロック［Ｂ］の数と同じ範囲内で調整することができる。
　なお、ブロック共重合体［Ｃ”］が重合体ブロック［Ｂ”］を複数有する場合は、複数の重合体ブロック［Ｂ”］中の構造単位の組成は同一であっても異なっていてもよい。 [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.
In addition, when 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. .
［質量分率］
　ここで、芳香族ビニル化合物に由来する構造単位がブロック共重合体［Ｃ”］全体に占める質量分率をｗＡ”とし、鎖状共役ジエン化合物に由来する構造単位がブロック共重合体［Ｃ”］全体に占める質量分率をｗＢ”としたときの、ｗＡ”とｗＢ”との比（ｗＡ”／ｗＢ”）は、上述した酸無水物基含有ブロック共重合体におけるｗＡとｗＢとの比（ｗＡ／ｗＢ）の範囲と同じ範囲で調整することができる。
　なお、ブロック共重合体［Ｃ”］におけるｗＡ”とｗＢ”との比（ｗＡ”／ｗＢ”）は、当該ブロック共重合体［Ｃ”］を水素化して得られる酸無水物基含有水素化物［Ｅ”］（酸無水物基含有ブロック共重合体）におけるｗＡとｗＢとの比（ｗＡ／ｗＢ）と一致する。 [Mass fraction]
Here, 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 of wA ″ to wB ″ (wA ″ / wB ″) when the mass fraction of the whole is wB ″ is the ratio of wA to wB in the above-mentioned acid anhydride group-containing block copolymer. Adjustment can be made in the same range as the range of (wA / wB).
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).
［構造単位比Ｓ”］
　ブロック共重合体［Ｃ”］は、上述した鎖状共役ジエン化合物がイソプレンである場合、イソプレンに由来する構造単位のうち、１，２－付加重合のみに由来する構造単位がブロック共重合体［Ｃ”］全体に占める質量分率をｗＰ”とし、３，４－付加重合のみに由来する構造単位がブロック共重合体［Ｃ”］全体に占める質量分率をｗＱ”とし、１，４－付加重合のみに由来する構造単位がブロック共重合体［Ｃ”］全体に占める質量分率をｗＲ”としたときの、下記式：
　構造単位比Ｓ”＝（ｗＰ”＋ｗＱ”）／（ｗＰ”＋ｗＱ”＋ｗＲ”）
で表わされる構造単位比Ｓ”の値は、０．３以上であることが好ましく、０．４以上であることがより好ましく、０．５以上であることが更に好ましく、０．５５以上であることが一層好ましく、０．６５以下であることが好ましい。上記構造単位比Ｓ”の値が上記所定の範囲内であれば、酸無水物基含有ブロック共重合体を含む樹脂組成物を用いて形成された樹脂シートは、優れた遮音性を発揮することができる。
　なお、上記構造単位比Ｓ”の値は、本明細書の実施例に記載された構造単位比Ｓ’の算出方法と同様の方法により求めることができる。
　また、ブロック共重合体［Ｃ”］における構造単位比Ｓ”は、当該ブロック共重合体［Ｃ”］を水素化して得られる酸無水物基含有水素化物［Ｅ”］（酸無水物基含有ブロック共重合体）における構造単位比Ｓと一致する。
　そして、上記構造単位比Ｓ”の値は、「ブロック共重合体［Ｃ］および［Ｃ’］」の項で上述したランダム化剤を用いることによって制御することができ、ランダム化剤の使用量も当該項で上述した範囲内で調整することができる。 [Structural unit ratio S "]
When the above-mentioned chain conjugated diene compound is isoprene, 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 ″. When the mass fraction of the structural unit derived only from addition polymerization in the entire block copolymer [C ″] is wR ″, the following formula:
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.
［ブロック構造］
　ブロック共重合体［Ｃ”］のブロックの構造は、鎖状型ブロックでもラジアル型ブロックでも良いが、機械的強度の観点から、鎖状型ブロックであるものが好ましい。また、ブロック共重合体［Ｃ”］は、重合体ブロック［Ｂ”］の両端に重合体ブロック［Ａ”］が結合した構造（すなわち、Ａ”－Ｂ”－Ａ”の順に並んだ構造）を少なくとも１箇所有することが好ましい。
　そして、ブロック共重合体［Ｃ”］の特に好ましい構造としては、重合体ブロック［Ｂ”］の両端に重合体ブロック［Ａ”］が結合してなるトリブロック共重合体（Ａ”－Ｂ”－Ａ”）、および、重合体ブロック［Ａ”］の両端に重合体ブロック［Ｂ”］が結合し、さらに、該２つの重合体ブロック［Ｂ”］の他端にそれぞれ重合体ブロック［Ａ”］が結合してなるペンタブロック共重合体（Ａ”－Ｂ”－Ａ”－Ｂ”－Ａ”）が挙げられ、トリブロック共重合体（Ａ”－Ｂ”－Ａ”）が最も好ましい。 [Block structure]
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 ″]. -A ") and the polymer block [B"] are bonded to both ends of the polymer block [A "], and the polymer block [A" is connected to the other end of the two polymer blocks [B "]. ”] Is a pentablock copolymer (A ″ -B ″ -A ″ -B ″ -A ″), and a triblock copolymer (A ″ -B ″ -A ″) is most preferable. .
［調製方法］
　ブロック共重合体［Ｃ”］の調製方法は特に限定されず、例えば、リビングアニオン重合を用いて、芳香族ビニル化合物および酸無水物を含有する組成物（Ａ）と、鎖状共役ジエン化合物および酸無水物を含有する組成物（Ｂ）とを交互に重合させることで、ブロック共重合体［Ｃ”］を調製することができる。 [Preparation method]
The method for preparing the block copolymer [C ″] is not particularly limited. For example, 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.
＜＜水素化＞＞
　ブロック共重合体［Ｃ］、ブロック共重合体［Ｃ’］の酸無水物変性体（即ち、酸無水物変性体［Ｄ’］）、およびブロック共重合体［Ｃ”］中の不飽和結合を水素化する方法（水素化方法）としては特に限定されず、既知の方法を採用することができるが、水素化率を高くしつつ、重合体鎖切断反応を抑制しうる水素化方法が好ましい。このような水素化方法としては、例えば、国際公開第２０１１／０９６３８９号、国際公開第２０１２／０４３７０８号などに記載された方法を挙げることができる。また、得られる樹脂シートの耐候性および耐熱性を高める観点から、上記ブロック共重合体または酸無水物変性体における鎖状共役ジエン化合物に由来する構造単位中の不飽和結合のみを選択的に水素化する方法を用いることが好ましい。このような水素化方法としては、例えば、特開２０１５－７８０９０号公報などに記載された方法を挙げることができる。
　なお、上述した方法で得られる水素化物は、通常、水素化触媒および／または重合触媒などを除去した後、水素化物を含む反応溶液から回収して得られる。回収された水素化物の形態は限定されるものではないが、例えばペレット形状とすることができる。 << Hydrogenation >>
Block copolymer [C], acid anhydride modified product of block copolymer [C ′] (ie, acid anhydride modified product [D ′]), and unsaturated bond in block copolymer [C ″] The method for hydrogenating (hydrogenation method) 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. Further, 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. As 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. Although the form of the collect | recovered hydride is not limited, For example, it can be set as a pellet shape.
［水素化率］
　そして、水素化により得られる水素化物の水素化率は、９０％以上であることが好ましく、９７％以上であることがより好ましく、９９％以上であることが更に好ましい。水素化率が９０％以上であれば、得られる樹脂シートの耐候性を十分に高く確保できる。
　なお、水素化率は、本明細書の実施例に記載の方法により測定することができる。 [Hydrogenation rate]
And 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.
＜＜酸無水物変性＞＞
　酸無水物変性は通常、ブロック共重合体［Ｃ］の水素化物（即ち、水素化物［Ｄ］）またはブロック共重合体［Ｃ’］と、エチレン性不飽和カルボン酸無水物とを、過酸化物の存在下で反応（酸無水物変性）させて、水素化物［Ｄ］またはブロック共重合体［Ｃ’］に酸無水物基を導入することにより行なわれる。 << Acid anhydride modification >>
In the 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 ′].
［エチレン性不飽和カルボン酸無水物］
　酸無水物変性に用い得るエチレン性不飽和カルボン酸無水物としては、水素化物［Ｄ］またはブロック共重合体［Ｃ’］と反応（例えば、グラフト重合）して、当該水素化物またはブロック共重合体に酸無水物基を導入し得るものであれば、特に限定されない。このようなエチレン性不飽和カルボン酸無水物としては、例えば、ブロック共重合体［Ｃ”］の項で上述したものを用いることができる。
　なお、導入される酸無水物基は、使用するエチレン性不飽和カルボン酸無水物に対応する。
　エチレン性不飽和カルボン酸無水物の使用量は、水素化物［Ｄ］またはブロック共重合体［Ｃ’］１００質量部に対して、０．０１質量部以上であることが好ましく、０．１質量部以上であることが好ましく、０．３質量部以上であることがより好ましく、通常１０質量部以下であり、７質量部以下であることが好ましく、４質量部以下であることがより好ましい。エチレン性不飽和カルボン酸無水物の使用量が０．０１質量部以上であれば、得られる樹脂シートの透明性を更に高めることができる。一方、エチレン性不飽和カルボン酸無水物の使用量が１０質量部以下であれば、得られる樹脂シートの低吸水性を高めることができる。 [Ethylenically unsaturated carboxylic acid anhydride]
Examples of the ethylenically unsaturated carboxylic acid anhydride that can be used for acid anhydride modification include reaction with hydride [D] or block copolymer [C ′] (for example, graft polymerization), and the hydride or block copolymer. There is no particular limitation as long as an acid anhydride group can be introduced into the coalescence. As such 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.
［過酸化物］
　酸無水物変性に用いる過酸化物としては、１分間半減期温度が１７０℃以上１９０℃以下のものが好ましく使用され、例えば、ｔ－ブチルクミルパーオキサイド、ジクミルパーオキサイド、ジ－ｔ－ヘキシルパーオキサイド、２，５－ジメチル－２，５－ジ－（ｔ－ブチルパーオキシ）ヘキサン、ジ－ｔ－ブチルパーオキサイド、ジ－（２－ｔ－ブチルパーオキシイソプロピル）ベンゼンなどの有機過酸化物が挙げられる。これらは、１種類を単独で用いてもよく、２種類以上を任意の比率で組み合わせて用いてもよい。
　過酸化物の使用量は、水素化物［Ｄ］またはブロック共重合体［Ｃ’］１００質量部に対して、通常０．０５質量部以上であり、好ましくは０．１質量部以上であり、より好ましくは０．２質量部以上であり、通常２質量部以下であり、好ましくは１質量部以下であり、より好ましくは０．５質量部以下である。 [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. For example, t-butylcumyl peroxide, dicumyl peroxide, di-t-hexyl 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.
［反応方法］
　水素化物［Ｄ］またはブロック共重合体［Ｃ’］とエチレン性不飽和カルボン酸無水物とを過酸化物の存在下で反応させる方法は特に限定されないが、例えば、これらの成分を二軸押出機にて混練することにより、当該水素化物または重合体に酸無水物基を導入することができる。混練温度は、通常１８０℃以上であり、好ましくは１８５℃以上であり、より好ましくは１９０℃以上であり、通常２２０℃以下であり、好ましくは２１０℃以下であり、より好ましくは２００℃以下である。混練時間は、通常０．１分以上であり、好ましくは０．２分以上であり、より好ましくは０．３分以上であり、通常１０分以下であり、好ましくは５分以下であり、より好ましくは２分以下である。このような混練温度、混練時間となるように適宜設定して、連続的に混練、押し出しをすればよい。 [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. By kneading with a machine, 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 | mixing and extrusion continuously, setting suitably so that it may become such kneading | mixing temperature and kneading | mixing time.
［酸無水物基の導入量］
　上述のようにして酸無水物変性を行うことにより水素化物［Ｄ］またはブロック共重合体［Ｃ’］に導入される酸無水物基の量は、水素化物［Ｄ］またはブロック共重合体［Ｃ’］１００質量部当たり、０．０１質量部以上であることが好ましく、０．１質量部以上であることがより好ましく、０．３質量部以上であることが更に好ましく、１０質量部以下であることが好ましく、７質量部以下であることがより好ましく、４質量部以下であることが更に好ましい。酸無水物基の導入量が、当該水素化物またはブロック共重合体１００質量部当たり０．０１質量部以上であれば、得られる樹脂シートの透明性を更に高めることができる。一方、酸無水物基の導入量が、当該水素化物またはブロック共重合体１００質量部当たり１０質量部以下であれば、得られる樹脂シートの低吸水性を高めることができる。
　なお、本発明において、水素化物［Ｄ］またはブロック共重合体［Ｃ’］１００部当たりに導入される酸無水物基の量は、当該水素化物またはブロック共重合体から得られた酸無水物変性体をフーリエ変換型赤外分光光度計（ＦＴ－ＩＲ）により測定し、得られたＩＲスペクトルにおける酸無水物基に由来する１７９０ｃｍ－１のピーク強度から算出することができる。 [Introduction amount of acid anhydride group]
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. If 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.
In the present invention, 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.
（樹脂組成物）
　本発明の樹脂組成物は、上述した酸無水物基含有ブロック共重合体と、金属酸化物の微粒子、金属ホウ化物の微粒子、および近赤外線吸収色素からなる群から選択される少なくとも１種の添加剤（Ｘ）とを含み、任意にその他の成分を更に含んでいてもよい。上述した酸無水物基含有ブロック共重合体と、添加剤（Ｘ）とを含む樹脂組成物を用いれば、優れた接着性および透明性を両立し得ると共に、優れた遮熱性を発揮し得る樹脂シートを得ることができる。 (Resin composition)
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.
　ここで、本発明の樹脂組成物の調製方法は特に限定されることはなく、例えば、酸無水物基含有ブロック共重合体を主成分として含有するペレットに、添加剤（Ｘ）等を添加し、既知の混合機で混合することにより調製することができる。なお、上記ペレット中の酸無水物基含有ブロック共重合体の含有量は、好ましくは９０質量％以上であり、より好ましくは９５質量％以上であり、更に好ましくは９９質量％以上である。 Here, the method for preparing the resin composition of the present invention is not particularly limited. For example, 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.
＜添加剤（Ｘ）＞
　添加剤（Ｘ）は、金属酸化物の微粒子、金属ホウ化物の微粒子、および近赤外線吸収色素からなる群から選択される少なくとも１種の添加剤であり、樹脂シートに優れた遮熱性を付与し得る成分である。 <Additive (X)>
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.
＜金属酸化物の微粒子＞
　金属酸化物の微粒子としては、酸化錫、アルミニウムドープ酸化錫、インジウムドープ酸化錫、アンチモンドープ酸化錫等の錫酸化物の微粒子；酸化亜鉛、アルミニウムドープ酸化亜鉛、インジウムドープ酸化亜鉛、ガリウムドープ酸化亜鉛、錫ドープ酸化亜鉛、珪素ドープ酸化亜鉛等の亜鉛酸化物の微粒子；酸化チタン、ニオブドープ酸化チタン等のチタン酸化物の微粒子；酸化タングステン、ナトリウムドープ酸化タングステン、セシウムドープ酸化タングステン、タリウムドープ酸化タングステン、ルビジウムドープ酸化タングステン等のタングステン酸化物の微粒子；酸化インジウム、錫ドープ酸化インジウム等のインジウム酸化物の微粒子；等が挙げられる。中でも、樹脂シートの遮熱性を更に高める観点から、金属酸化物の微粒子として、セシウムドープ酸化タングステンの微粒子を用いることが好ましい。
　これらの金属酸化物の微粒子は、１種を単独で、または２種以上を組み合わせて使用することができる。 <Metal oxide fine particles>
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. Among these, from the viewpoint of further improving the heat shielding property of the resin sheet, it is preferable to use 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.
　ここで、金属酸化物の微粒子の平均粒子径は、通常０．００１μｍ以上であり、好ましくは０．００５μｍ以上であり、より好ましくは０．０１μｍ以上であり、通常０．２μｍ以下であり、好ましくは０．１５μｍ以下であり、より好ましくは０．１μｍ以下である。金属酸化物の微粒子の平均粒子径が０．００１μｍ以上であれば、樹脂シートは更に優れた遮熱性を発揮することができる。一方、金属酸化物の微粒子の平均粒子径が０．２μｍ以下であれば、樹脂シートの透明性を十分に高く確保することができる。
　なお、本発明において、「平均粒子径」は、ＪＩＳ Ｚ８８２５に準拠し、レーザー回折法により体積平均粒子径として測定することができる。 Here, the average particle size of the metal oxide fine particles is usually 0.001 μm or more, preferably 0.005 μm or more, more preferably 0.01 μm or more, and usually 0.2 μm or less. Is 0.15 μm or less, more preferably 0.1 μm or less. If the average particle diameter of the metal oxide fine particles is 0.001 μm 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 μm or less, the transparency of the resin sheet can be secured sufficiently high.
In the present invention, the “average particle diameter” can be measured as a volume average particle diameter by a laser diffraction method in accordance with JIS Z8825.
　また、樹脂組成物中の金属酸化物の微粒子の含有量は、酸無水物基含有ブロック共重合体１００質量部に対して、通常０．００１質量部以上であり、好ましくは０．００２質量部以上であり、より好ましくは０．００５質量部以上であり、更に好ましくは０．２５質量部以上であり、一層好ましくは０．５質量部以上であり、通常２．０質量部以下であり、好ましくは１．５質量部以下であり、より好ましくは１．２５質量部以下である。樹脂組成物中の金属酸化物の微粒子の含有量が酸無水物基含有ブロック共重合体１００質量部に対して０．００１質量部以上であれば、樹脂シートは更に優れた遮熱性を発揮することができる。一方、樹脂組成物中の金属酸化物の微粒子の含有量が酸無水物基含有ブロック共重合体１００質量部に対して２．０質量部以下であれば、樹脂シートの透明性を十分に高く確保することができる。 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. When 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. On the other hand, if 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.
＜金属ホウ化物の微粒子＞
　金属ホウ化物の微粒子としては、ホウ化ランタン（六ホウ化ランタン、ＬａＢ６）、ホウ化セリウム（ＣｅＢ６）、ホウ化タングステン（Ｗ２Ｂ５）等の微粒子が挙げられる。中でも、樹脂シートの遮熱性を更に高める観点から、金属ホウ化物の微粒子として、ホウ化ランタンの微粒子を用いることが好ましい。
　これらの金属ホウ化物の微粒子は、１種を単独で、または２種以上を組み合わせて使用することができる。
　なお、金属ホウ化物の微粒子の平均粒子径は、通常０．００１μｍ以上であり、好ましくは０．００５μｍ以上であり、より好ましくは０．０１μｍ以上であり、通常０．２μｍ以下であり、好ましくは０．１５μｍ以下であり、より好ましくは０．１μｍ以下である。金属ホウ化物の微粒子の平均粒子径が０．００１μｍ以上であれば、樹脂シートは更に優れた遮熱性を発揮することができる。一方、金属ホウ化物の微粒子の平均粒子径が０．１５μｍ以下であれば、樹脂シートの透明性を十分に高く確保することができる。 <Fine particles of metal boride>
Examples of the metal boride fine particles include fine particles of lanthanum boride (lanthanum hexaboride, LaB 6 ), cerium boride (CeB 6 ), tungsten boride (W 2 B 5 ), and the like. Among these, from the viewpoint of further improving the heat shielding property of the resin sheet, it is preferable to use fine particles of lanthanum boride as the fine particles of the metal boride.
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 μm or more, preferably 0.005 μm or more, more preferably 0.01 μm or more, and usually 0.2 μm or less, preferably It is 0.15 μm or less, more preferably 0.1 μm or less. If the average particle diameter of the metal boride fine particles is 0.001 μm 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 μm or less, the transparency of the resin sheet can be secured sufficiently high.
　また、樹脂組成物中の金属ホウ化物の微粒子の含有量は、酸無水物基含有ブロック共重合体１００質量部に対して、通常０．００１質量部以上であり、好ましくは０．００２質量部以上であり、より好ましくは０．００５質量部以上であり、通常１．０質量部以下であり、好ましくは０．５質量部以下であり、より好ましくは０．３質量部以下であり、更に好ましくは０．２質量部以下である。樹脂組成物中の金属ホウ化物の微粒子の含有量が酸無水物基含有ブロック共重合体１００質量部に対して０．００１質量部以上であれば、樹脂シートは更に優れた遮熱性を発揮することができる。一方、樹脂組成物中の金属ホウ化物の微粒子の含有量が酸無水物基含有ブロック共重合体１００質量部に対して１．０質量部以下であれば、樹脂シートの透明性を十分に高く確保することができる。 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. On the other hand, if 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.
＜近赤外線吸収色素＞
　近赤外線吸収色素は、８００ｎｍ以上２０００ｎｍ以下の波長の範囲内のいずれかの領域の赤外線を遮蔽する機能を有するものである。
　ここで、「８００ｎｍ以上２０００ｎｍ以下の波長の範囲内のいずれかの領域の赤外線を遮蔽する機能を有する」とは、「近赤外線吸収色素が、８００ｎｍ以上２０００ｎｍ以下の波長の範囲内のいずれかの領域において、赤外線を吸収して、結果として赤外線が通過するのを遮断する機能を有する」という意味である。近赤外線吸収色素は、８００ｎｍ以上２０００ｎｍ以下の波長の範囲内のいずれかの領域において、最大吸収波長を有するものであっても、８００ｎｍ以上２０００ｎｍ以下の波長の範囲外のいずれかの領域において、最大吸収波長を有するものであってもよい。 <Near-infrared absorbing dye>
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.
Here, “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.
　近赤外線吸収色素としては、例えば、フタロシアニン化合物、ナフタトシアニン化合物、ポリメチン化合物、ジフェニルメタン化合物、アントラキノン化合物、ペンタジエン化合物、アゾメチン化合物などが挙げられる。 Examples of the near-infrared absorbing dye include phthalocyanine compounds, naphthatocyanine compounds, polymethine compounds, diphenylmethane compounds, anthraquinone compounds, pentadiene compounds, and azomethine compounds.
　また、樹脂組成物中の近赤外線吸収色素の含有量は、酸無水物基含有ブロック共重合体１００質量部に対して、通常０．００１質量部以上であり、好ましくは０．００２質量部以上であり、より好ましくは０．００５質量部以上であり、通常１．０質量部以下であり、好ましくは０．７質量部以下であり、より好ましくは０．５質量部以下である。樹脂組成物中の近赤外線吸収色素の含有量が酸無水物基含有ブロック共重合体１００質量部に対して０．００１質量部以上であれば、樹脂シートは更に優れた遮熱性を発揮することができる。一方、樹脂組成物中の近赤外線吸収色素の含有量が酸無水物基含有ブロック共重合体１００質量部に対して１．０質量部以下であれば、樹脂シートの透明性を十分に高く確保することができる。 Further, 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. On the other hand, if the content of the near-infrared absorbing pigment 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 do.
＜その他の成分＞
　本発明の樹脂組成物は、所望の効果が得られる範囲内で、上述した酸無水物基含有ブロック共重合体および添加剤（Ｘ）以外のその他の成分を含んでいてもよい。ここで、その他の成分には、酸無水物基含有ブロック共重合体の調製時に使用されたことにより樹脂組成物中に残存する添加剤等も含まれるものとする。
　その他の成分としては、例えば、粘着剤、紫外線吸収剤、光安定剤、酸化防止剤等が挙げられる。なお、酸化防止剤としては、例えば、ペンタエリスリトール・テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］などのフェノール系酸化防止剤を用いることができる。 <Other ingredients>
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. Here, 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.
Examples of other components include an adhesive, an ultraviolet absorber, a light stabilizer, and an antioxidant. As the antioxidant, for example, a phenolic antioxidant such as pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] can be used.
（樹脂シート）
　本発明の樹脂シートは、上述した樹脂組成物からなる樹脂層を少なくとも１層含むことを特徴とする。上述した樹脂組成物からなる樹脂層を少なくとも１層含む樹脂シートであれば、優れた接着性および透明性を両立することができる。したがって、本発明の樹脂シートは、合わせガラスの中間膜として好適に使用することができる。
　本発明の樹脂シートは、上述した樹脂組成物からなる樹脂層を少なくとも１層含む限り、特に限定されることなく、例えば、上述した樹脂組成物を成形して得られる樹脂層のみで構成された単層シートまたは多層シートであってもよいし、当該樹脂層と、当該樹脂層以外の機能層とを積層してなる積層シートであってもよい。なお、樹脂シートが上述した樹脂組成物からなる樹脂層を複数備える場合、当該樹脂層は同一の樹脂組成物によって形成されていてもよいし、互いに異なる樹脂組成物によって形成されていてもよい。 (Resin sheet)
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. For example, 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 | stacking the said resin layer and functional layers other than the said resin layer may be sufficient. In addition, when a resin sheet is provided with two or more resin layers which consist of the resin composition mentioned above, the said resin layer may be formed with the same resin composition, and may be formed with a mutually different resin composition.
　ここで、樹脂組成物を成形して樹脂層（単層シート）を作製する方法としては、特に限定されることはなく、例えば、溶融押出し成形法、カレンダー成形法、インフレーション成形、などを挙げることができる。
　溶融押出し成形法により樹脂層（単層シート）を作製する場合、樹脂組成物の温度およびダイを、１４０℃以上とすることが好ましく、１５０℃以上とすることがより好ましく、１６０℃以上とすることが特に好ましく、２２０℃以下とすることが好ましく、２１０℃以下とすることがより好ましく、２００℃以下とすることが特に好ましい。樹脂組成物およびダイの温度を１４０℃以上とすることにより、流動性が悪化するのを防止して、樹脂層（単層シート）の表面にゆず肌やダイライン等の不良を生じるのを防止すると共に、押出し速度を上げて、工業的に有利に成形することができ、樹脂組成物およびダイの温度を２２０℃以下とすることにより、流動性が高くなり過ぎるのを防止して、均等な厚さの樹脂層（単層シート）を成形することができる。 Here, 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.
When a resin layer (single layer sheet) is produced by a melt extrusion molding method, 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. By setting the temperature of the resin composition and the die to 140 ° C. or more, 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. At the same time, the extrusion speed can be increased and the molding can be advantageously carried out industrially. By setting the temperature of the resin composition and the die to 220 ° C. or less, the fluidity is prevented from becoming too high, and the uniform thickness is obtained. The resin layer (single layer sheet) can be formed.
　樹脂層（単層シート）の厚みは、特に制限はなく、例えば、０．０１ｍｍ以上であることが好ましく、０．０５ｍｍ以上であることがより好ましく、０．１ｍｍ以上であることが好ましく、３．０ｍｍ以下であることが好ましく、２．５ｍｍ以下であることがより好ましく、２．０ｍｍであることが特に好ましい。
　樹脂層（単層シート）の厚みを０．０１ｍｍ以上とすることにより、樹脂層（単層シート）にシワが発生するのを防止することができ、樹脂層（単層シート）の厚みを３．０ｍｍ以下とすることにより、樹脂層（単層シート）の透明性を十分に高く確保することができる。 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.
By setting the thickness of the resin layer (single layer sheet) to 0.01 mm or more, wrinkles can be prevented from occurring in the resin layer (single layer sheet), and 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.
　上述した樹脂層と、当該樹脂層以外の機能層とを積層してなる積層シートを作製する場合、機能層としては、例えば、接着層を用いることができる。
　そして、積層シートを製造する方法としては、特に限定されることはなく、例えば、（ｉ）樹脂層と接着層とを熱プレス等の加熱手段で貼り合わせる方法、（ｉｉ）樹脂層に接着剤組成物を噴霧、塗布し、溶剤を除去する方法、（ｉｉｉ）樹脂層を接着剤組成物にディッピングし、溶剤を除去する方法、（ｉｖ）樹脂層を押出し成形しながら、予め準備した接着層を樹脂層の少なくとも１面以上にラミネートする方法、（ｖ）樹脂層と接着層とを溶融成形時に共押出し成形する方法などの公知の方法を用いることができる。 When producing a laminated sheet formed by laminating the above-described resin layer and a functional layer other than the resin layer, for example, 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.
　ここで、接着層の形成に用いられる接着剤組成物としては、特に限定されることはなく、樹脂層および被着材との接着性が良好な公知の接着剤を含むものを使用することができる。
　例えば、被着材がガラスの場合に好適な接着剤としては、例えば、スチレン等の芳香族ビニル化合物に由来する構造単位を主成分とする重合体ブロックと、イソプレン等の鎖状共役ジエン化合物を主成分とする重合体ブロックとからなるブロック共重合体の水素化物のアルコキシシラン変性体／酸無水物変性体；等が挙げられる。なお、上記ブロック共重合体の水素化物の酸無水物変性体は、本発明の酸無水物基含有ブロック共重合体には該当しないものとする。そして、上述した接着剤の中でも、透明性および防湿性の観点から、スチレン等の芳香族ビニル化合物を主成分とする重合体ブロックと、イソプレン、等の鎖状共役ジエン化合物を主成分とする重合体ブロックとからなるブロック共重合体の水素化物のアルコキシシラン変性体を用いることが好ましい。 Here, 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.
For example, as an adhesive suitable when the adherend is glass, for example, 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. Examples include hydrides of block copolymers composed of a polymer block as a main component, and alkoxysilane-modified / acid anhydride-modified products of hydrides. In addition, 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. Among the adhesives described above, from the viewpoint of transparency and moisture resistance, 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.
　接着層の厚みは、特に限定されることはなく、０．０２ｍｍ以上であることが好ましく、０．０５ｍｍ以上であることがより好ましく、０．１ｍｍ以上であることが更に好ましく、５ｍｍ以下であることが好ましく、３ｍｍ以下であることがより好ましく、１ｍｍ以下であることが更に好ましい。接着層の厚みを０．０２ｍｍ以上とすることにより、樹脂シートおよび被着材に対して十分な接着力を有する接着層を得ることができる。また、接着層の厚みを５ｍｍ以下とすることにより、樹脂シートの透明性を十分に高く確保することができる。 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. By setting the thickness of the adhesive layer to 0.02 mm or more, it is possible to obtain an adhesive layer having sufficient adhesive force with respect to the resin sheet and the adherend. Moreover, the transparency of the resin sheet can be secured sufficiently high by setting the thickness of the adhesive layer to 5 mm or less.
　なお、積層シートが樹脂層の両面に接着層を備える場合、樹脂層の両面に配置された２枚の接着層は同一の接着剤組成物によって形成されていても、互いに異なる接着剤組成物によって形成されていてもよい。 In addition, when a laminated sheet is provided with an adhesive layer on both surfaces of a resin layer, even if two adhesive layers arranged on both surfaces of the resin layer are formed of the same adhesive composition, It may be formed.
（合わせガラス）
　本発明の合わせガラスは、上述した樹脂シートを少なくとも１枚備えることを特徴とする。本発明の合わせガラスは、上述したように、優れた接着性および透明性を両立し得る樹脂シートを備えるため、例えば、建築物の窓ガラス、屋根用ガラス、部屋用遮熱壁材、自動車のフロントガラス、サイドガラス、リアガラス、サンルーフ用ガラス、並びに、鉄道車両および船舶用の窓ガラス、などとして有用である。 (Laminated glass)
The laminated glass of the present invention comprises at least one resin sheet as described above. As described above, the laminated glass of the present invention includes a resin sheet that can achieve both excellent adhesiveness and transparency. For example, 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.
　そして、本発明の合わせガラスは、上述した樹脂シートを少なくとも１枚備える限り、特に限定されることはないが、通常、上述した樹脂シートを２枚のガラス板の間に介在させて一体化した積層体である。ここで、ガラス板と樹脂シートとの間には接着用シートが介在していてもよい。なお、接着用シートは、「樹脂シート」の項で上述した接着剤組成物を用いて既知の方法により形成することができる。 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. Here, 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”.
＜製造方法＞
　合わせガラスを製造する方法としては、特に制限はなく、（ｉ）オートクレーブを使用する方法、（ｉｉ）真空ラミネータを使用する方法、などが挙げられる。例えば、第１のガラス板／接着用シート／樹脂シート／接着用シート／第２のガラス板の順に重ね、減圧可能な耐熱性の樹脂製袋に入れて脱気後、（ｉ）オートクレーブを使用して、加熱加圧下で接着させて合わせガラスを製造する方法、（ｉｉ）真空ラミネータを使用して、加熱下で真空圧着して接着させる方法、などがある。
　オートクレーブを使用する場合、加熱温度は、１００℃以上であることが好ましく、１５０℃以下であることが好ましく、加熱時間は１５分以上６０分以下が好ましく、また、圧力（ゲージ圧）は、０．３ＭＰａ以上であることが好ましく、１．１ＭＰａ以下であることが好ましい。一方、真空ラミネータを使用する場合、加熱温度は、１３０℃以上であることが好ましく、１７０℃以下であることが好ましく、また、圧力は、０．０１ＭＰａ以上であることが好ましく、０．１ＭＰａ以下であることが好ましい。 <Manufacturing method>
There is no restriction | limiting in particular as a method of manufacturing a laminated glass, (i) The method of using an autoclave, (ii) The method of using a vacuum laminator, etc. are mentioned. For example, first glass plate / adhesive sheet / resin sheet / adhesive sheet / second glass plate are stacked in this order, placed in a heat-resistant resin bag that can be decompressed, degassed, and (i) using an autoclave Then, there are a method of producing a laminated glass by bonding under heating and pressure, and (ii) a method of using a vacuum laminator to adhere by vacuum pressure bonding under heating.
When using an autoclave, the heating temperature is preferably 100 ° C. or more, preferably 150 ° C. or less, the heating time is preferably 15 minutes or more and 60 minutes or less, and the pressure (gauge pressure) is 0. .3 MPa or more is preferable, and 1.1 MPa or less is preferable. On the other hand, when a vacuum laminator is used, 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
＜＜ガラス板＞＞
　使用するガラス板の厚みとしては、特に制限はないが、通常、０．５ｍｍ以上１０ｍｍ以下程度である。また、ガラス板として、厚みが０．０５ｍｍ以上０．５ｍｍ以下程度の極薄ガラス板を使用することもできる。また、例えば、厚み２．１ｍｍのガラス板／厚み２．４ｍｍの成形体（例えば、樹脂シートからなる中間膜）／厚み０．５ｍｍの薄膜ガラス板の３層構成となるような、異なる厚みのガラス板を使用することもできる。 << Glass plate >>
Although there is no restriction | limiting in particular as thickness of the glass plate to be used, Usually, it is about 0.5 mm or more and 10 mm or less. Moreover, an ultra-thin glass plate having a thickness of about 0.05 mm or more and 0.5 mm or less can be used as the glass plate. In addition, for example, a three-layer structure of a glass plate having a thickness of 2.1 mm / a molded body having a thickness of 2.4 mm (for example, an intermediate film made of a resin sheet) / a thin glass plate having a thickness of 0.5 mm, A glass plate can also be used.
　ガラス板の材質としては、特に制限はなく、例えば、アルミノ珪酸ガラス、アルミノ硼珪酸ガラス、ウランガラス、カリガラス、珪酸ガラス、結晶化ガラス、ゲルマニウムガラス、石英ガラス、ソーダガラス、鉛ガラス、バリウム硼珪酸ガラス、硼珪酸ガラス、などが挙げられる。 The material of the glass plate is not particularly limited. For example, 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.
　なお、合わせガラスに用いる２枚以上のガラス板同士は、厚みや材質等が互いに同一であっても、相異なっていてもよい。 It should be noted that the two or more glass plates used for the laminated glass may be the same or different in thickness and material.
＜光線透過率＞
　ここで、本発明の合わせガラスは、８００ｎｍ以上２０００ｎｍ以下の波長の範囲内に光線透過率が５０％以下の領域を有することが好ましい。８００ｎｍ以上２０００ｎｍ以下の波長の範囲内に光線透過率が５０％以下の領域を有する合わせガラスであれば、優れた遮熱性を発揮し得る。
　さらに、本発明の合わせガラスは、５００ｎｍの波長での光線透過率が６０％以上であることが好ましい。５００ｎｍの波長での光線透過率が６０％以上である合わせガラスであれば、更に優れた透明性を発揮し得る。 <Light transmittance>
Here, 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.
　以下に、本発明を実施例および比較例によりさらに詳細に説明するが、本発明は、以下の実施例のみに限定されるものではない。なお、「部」および「％」は特に断りのない限り、質量基準である。また、複数種類の化合物を共重合して調製される重合体において、ある化合物に由来する構造単位の当該重合体全体に占める質量分率は、別に断らない限り、通常は、その重合体の調製時に重合する全化合物の総質量に占める当該ある化合物の質量の比率(仕込み比)と一致する。
　本実施例における測定および評価は、以下の方法によって行なった。 EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited only to the following examples. “Part” and “%” are based on mass unless otherwise specified. In addition, in a polymer prepared by copolymerizing a plurality of types of compounds, the mass fraction of the structural unit derived from a certain compound in the entire polymer is usually the preparation of the polymer unless otherwise specified. It coincides with the mass ratio (preparation ratio) of the certain compound to the total mass of all the compounds that are sometimes polymerized.
Measurement and evaluation in this example were performed by the following methods.
＜構造単位比Ｓ’＞
　ブロック共重合体における構造単位比Ｓ’は、ブロック共重合体の１Ｈ－ＮＭＲスペクトル（測定溶媒：重クロロホルム、測定機器：ＢＲＵＫＥＲ社製「ＡＶＡＮＣＥ　５００」）に基づいて算出した。具体的には、取得された１Ｈ－ＮＭＲスペクトルにおいて、ポリマー主鎖にある炭素－炭素不飽和結合部の炭素に結合した１Ｈのピーク面積を、１，２－付加重合のみに由来する構造単位がブロック共重合体全体に占める質量分率ｗＰ’と、３，４－付加重合のみに由来する構造単位がブロック共重合体全体に占める質量分率ｗＱ’との合計（ｗＰ’＋ｗＱ’）に相当する値とし、ポリマー側鎖にある炭素－炭素不飽和結合部の炭素に結合した１Ｈのピーク面積を、１，４－付加重合のみに由来する構造単位がブロック共重合体全体に占める質量分率ｗＲ’に相当する値とすることで、両者の値の比率から、構造単位比Ｓ’［＝（ｗＰ’＋ｗＱ’）／（ｗＰ’＋ｗＱ’＋ｗＲ’）］の値を算出した。 <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. Sum of mass fraction wP ′ whose units occupy the entire block copolymer and mass fraction wQ ′ occupying the entire block copolymer of structural units derived only from 3,4-addition polymerization (wP ′ + wQ ′) The structural unit derived solely from 1,4-addition polymerization accounts for the peak area of 1 H bonded to the carbon of the carbon-carbon unsaturated bond part in the polymer side chain in the entire block copolymer. By setting the value corresponding to the mass fraction wR ′, the value of the structural unit ratio S ′ [= (wP ′ + wQ ′) / (wP ′ + wQ ′ + wR ′)] was calculated from the ratio of both values.
＜水素化率＞
　各製造例における水素化反応に用いるブロック共重合体と、水素化反応により得られる水素化物とについて、溶媒として重クロロホルムを用いた１Ｈ－ＮＭＲ測定を行い、ブロック共重合体の主鎖、側鎖および芳香環に存在した全不飽和結合のうち消失した不飽和結合の割合を算出することで、ブロック共重合体水素化物の水素化率を求めた。 <Hydrogenation rate>
The block copolymer used for the hydrogenation reaction in each production example and the hydride obtained by the hydrogenation reaction were subjected to 1 H-NMR measurement using deuterated chloroform as a solvent, and the main chain and side of the block copolymer were measured. The hydrogenation rate of the block copolymer hydride was determined by calculating the proportion of unsaturated bonds that had disappeared among all unsaturated bonds present in the chain and aromatic ring.
＜重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）＞
　酸無水物基変性水素化物（酸無水物基含有ブロック共重合体）の重量平均分子量（Ｍｗ）は、テトラヒドロフラン（ＴＨＦ）を溶離液とするゲルパーミエーションクロマトグラフィー（ＧＰＣ）による、標準ポリスチレン換算値として求めた。ＧＰＣは３８℃において測定した。測定装置としては、東ソー社製「ＨＬＣ８０２０ＧＰＣ」を用いた。
　さらに上記と同様にして、数平均分子量（Ｍｎ）を測定した後、酸無水物基変性水素化物の分子量分布（Ｍｗ／Ｍｎ）を求めた。 <Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)>
The weight average molecular weight (Mw) of the acid anhydride group-modified hydride (an acid anhydride group-containing block copolymer) 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.
＜全光線透過率＞
　合わせガラスの全光線透過率の測定は、積分球式分光光度計（日本分光社製「Ｖ－６７０」）を使用して、３００ｎｍ以上２５００ｎｍ以下の波長の範囲内で測定した。 <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.
＜遮音性＞
　樹脂シートから長さ３００ｍｍ、幅２５ｍｍの試験片を切り出し、長さ３００ｍｍ、幅２５ｍｍ、厚さ１．２ｍｍの２枚のソーダガラス板の間に当該試験片１枚を挟持させて、遮音性評価用の合わせガラス試験片を作製した。当該合わせガラスについて、ＪＩＳ　Ｋ７３９１に基づき、振動減衰試験装置（リオン社製「ＳＡ－０２」）を使用して、中央加振法により周波数に対応した損失係数を測定した。ここで求めた損失係数と、合わせガラスの共振周波数との比から、周波数に対応した音響透過損失を求めることにより、合わせガラスが備える樹脂シートの遮音性を評価した。
　樹脂シートの遮音性は、周波数２０００～４０００Ｈｚの範囲において、音響透過損失の値が３５ｄＢを下回る領域が無い場合はＡ（良好）とし、音響透過損失の値が３５ｄＢを下回る領域が有る場合はＢ（不良）として評価した。 <Sound insulation>
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).
＜透明性＞
　樹脂シートの透明性は、合わせガラスのヘイズを測定することにより評価した。合わせガラスのヘイズは、ヘイズメータ（日本電色工業社製「ＮＤＨ７０００ＳＰ」）を用いて測定した。合わせガラスのヘイズの値が小さいほど、合わせガラスの備える樹脂シートの透明性は良好であるといえる。そして、樹脂シートの透明性は以下の基準により評価した。
　Ａ：合わせガラスのヘイズが１未満である。
　Ｂ：合わせガラスのヘイズが１以上３以下である。
　Ｃ：合わせガラスのヘイズが３超である。 <Transparency>
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. And the transparency of the resin sheet was evaluated according to the following criteria.
A: The haze of the laminated glass is less than 1.
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.
＜接着性＞
＜＜ソーダガラス板に対する接着性＞＞
　厚さ１．１ｍｍ、縦１００ｍｍ、横１００ｍｍの１枚のソーダガラス板と、当該ソーダガラス板と同じ縦および横の長さで切り出した１枚の樹脂シートとを重ね合わせて作製した樹脂シート／ソーダガラス板の積層物を、ＮＹ（ナイロン）／ＰＰ（ポリプロピレン）製の厚さ７５μｍの袋に入れ、袋の開口部の中央部を２００ｍｍ幅残して両側をヒートシーラーでヒートシールした後、密封パック器（パナソニック社製「ＢＨ－９５１」）を使用して、袋内を脱気しながら開口部をヒートシールして積層物を密封包装し、その後、密封包装した積層物をオートクレーブに入れて、３０分間、温度１００℃、圧力０．８ＭＰａで加熱加圧し、接着性評価用試験片を作製した。当該試験片を、試験法ＪＩＳ　Ｋ６８５４－２に準拠して、１８０°はく離試験を行うことにより、当該試験片が備える樹脂シートの接着性を評価した。樹脂シートのソーダガラス板に対する接着性は、当該試験片の接着力が１０Ｎ以上である場合にＡ（良好）、当該試験片の接着力が１０Ｎ未満である場合にＢ（不良）として評価した。
＜＜アクリル樹脂板に対する接着性＞＞
　厚さ１．１ｍｍ、縦１００ｍｍ、横１００ｍｍのソーダガラス板に代えて、厚さ１ｍｍ、縦５０ｍｍ、横１００ｍｍのアクリル樹脂板を用いたこと以外は、上述したソーダガラス板に対する接着性の評価と同様にして、樹脂シートのアクリル樹脂板に対する接着性を評価した。 <Adhesiveness>
<< 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 μm 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. , 30 minutes, heated and pressurized at a temperature of 100 ° C. and a pressure of 0.8 MPa to produce a 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.
（製造例１）
＜ブロック共重合体［Ｃ１］の調製＞
　攪拌装置を備え、内部が充分に窒素置換された反応器に、脱水シクロヘキサン２７０部、ランダム化剤としてのエチレングリコールジブチルエーテル０．５３部を入れ、さらに、重合開始剤としてのｎ－ブチルリチウム（１５％シクロヘキサン溶液）０．４７部を加えた。全容を６０℃で攪拌しながら、芳香族ビニル化合物としての脱水スチレン１２．５部を４０分間に亘って連続的に反応器内に添加した。添加終了後、さらに６０℃で２０分間全容を攪拌した。反応液をガスクロマトグラフィーにより測定したところ、この時点での重合転化率は９９．５％であった。 (Production Example 1)
<Preparation of block copolymer [C1]>
A reactor equipped with a stirrer and sufficiently purged with nitrogen inside was charged with 270 parts of dehydrated cyclohexane and 0.53 part of ethylene glycol dibutyl ether as a randomizing agent, and n-butyllithium ( 0.47 part of 15% cyclohexane solution) was added. While stirring the whole volume at 60 ° C., 12.5 parts of dehydrated styrene as an aromatic vinyl compound was continuously added into the reactor over 40 minutes. After completion of the addition, the whole volume was further stirred at 60 ° C. for 20 minutes. When the reaction solution was measured by gas chromatography, the polymerization conversion rate at this point was 99.5%.
　次に、鎖状共役ジエン化合物としての脱水イソプレン７５．０部を、反応液に１００分間に亘って連続的に添加し、添加終了後そのまま２０分間攪拌を続けた。この時点での重合転化率は９９．５％であった。
　その後、更に、芳香族ビニル化合物としての脱水スチレン１２．５部を、６０分間に亘って連続的に添加し、添加終了後そのまま全容を３０分間攪拌した。この時点での重合転化率はほぼ１００％であった。 Next, 75.0 parts of dehydrated isoprene as a chain conjugated diene compound was continuously added to the reaction solution over 100 minutes, and stirring was continued for 20 minutes after the addition was completed. The polymerization conversion rate at this time was 99.5%.
Thereafter, 12.5 parts of dehydrated styrene as an aromatic vinyl compound was continuously added over 60 minutes, and the whole volume was stirred as it was after completion of the addition for 30 minutes. The polymerization conversion rate at this point was almost 100%.
　ここで、反応液に重合停止剤としてのイソプロピルアルコール０．５部を加えて反応を停止させた。得られたブロック共重合体［Ｃ１］の構造単位比Ｓ’は０．５８であった。 Here, 0.5 part of isopropyl alcohol as a polymerization terminator was added to the reaction solution to stop the reaction. The structural unit ratio S ′ of the obtained block copolymer [C1] was 0.58.
＜水素化物［Ｄ１］の製造＞
　次に、上記重合体溶液を、攪拌装置を備えた耐圧反応器に移送し、水素化触媒として珪藻土担持型ニッケル触媒（日揮触媒化成社製、製品名「Ｅ２２Ｕ」、ニッケル担持量６０％）７．０部、および脱水シクロヘキサン８０部を添加して混合した。反応器内部を水素ガスで置換し、さらに溶液を攪拌しながら水素を供給し、温度１９０℃、圧力４．５ＭＰａにて６時間水素化反応を行なった。 <Production of hydride [D1]>
Next, the polymer solution is transferred to a pressure-resistant reactor equipped with a stirrer, and a diatomaceous earth supported nickel catalyst (product name “E22U”, nickel supported amount 60%, manufactured by JGC Catalysts & Chemicals Co., Ltd.) as a hydrogenation catalyst 7 0.0 parts and 80 parts of dehydrated cyclohexane were added and mixed. The inside of the reactor was replaced with hydrogen gas, and hydrogen was supplied while stirring the solution. A hydrogenation reaction was performed at a temperature of 190 ° C. and a pressure of 4.5 MPa for 6 hours.
　水素化反応終了後、反応溶液をろ過して水素化触媒を除去した後、ろ液に、フェノール系酸化防止剤であるペンタエリスリトール・テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］（コーヨ化学研究所社製「Ｓｏｎｇｎｏｘ（登録商標）１０１０」）０．１部を溶解したキシレン溶液１．０部を添加して溶解させた。
　次いで、上記溶液を、円筒型濃縮乾燥器（日立製作所社製「コントロ」）を用いて、温度２６０℃、圧力０．００１ＭＰａ以下で、溶液から溶媒であるシクロヘキサン、キシレン及びその他の揮発成分を除去した。連続して溶融ポリマーをダイからストランド状に押出し、冷却後、ペレタイザーにより水素化物［Ｄ１］のペレット９３部を得た。得られたペレット状の水素化物［Ｄ１］の水素化率はほぼ１００％であった。 After completion of the hydrogenation reaction, 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.
Next, 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%.
（製造例２）
　芳香族ビニル化合物としての脱水スチレンの添加量を、１２．５部を２回の合計２５部から、７．５部を２回の合計１５部に変更し、鎖状共役ジエン化合物としての脱水イソプレンの添加量を、７５部から８５部に変更したこと以外は、製造例１のブロック共重合体［Ｃ１］の調製と同様にして、ブロック共重合体［Ｃ２］を調製した。なお、ブロック共重合体［Ｃ２］の構造単位比Ｓ’は０．５５であった。
　次いで、ブロック共重合体［Ｃ２］を含む重合体溶液を用いて、製造例１の水素化物［Ｄ１］の製造と同様にして、水素化物［Ｄ２］を得た。得られたペレット状の水素化物［Ｄ２］の水素化率はほぼ１００％であった。 (Production Example 2)
The addition amount of dehydrated styrene as the aromatic vinyl compound was changed from 25 parts in total for 12.5 parts to 15 parts in total for 7.5 parts, and dehydrated isoprene as a chain conjugated diene compound. The block copolymer [C2] was prepared in the same manner as the preparation of the block copolymer [C1] in Production Example 1 except that the amount of addition was changed from 75 parts to 85 parts. The structural unit ratio S ′ of the block copolymer [C2] was 0.55.
Subsequently, using the polymer solution containing the block copolymer [C2], a hydride [D2] was obtained in the same manner as in the production of the hydride [D1] of Production Example 1. The hydrogenation rate of the obtained pellet-like hydride [D2] was almost 100%.
（製造例３）
　攪拌装置を備え、内部が充分に窒素置換された反応器に、脱水シクロヘキサン５５０部、芳香族ビニル化合物としての脱水スチレン２５部、ランダム化剤としてのジ－ｎ－ブチルエーテル（ジブチルエーテル）０．４７５部を入れ、６０℃で撹拌しながらさらに、重合開始剤としてのｎ－ブチルリチウム（１５％シクロヘキサン溶液）０．９部を加えた。添加終了後、そのままさらに６５℃で６０分間全容を攪拌した。反応液をガスクロマトグラフィーにより測定したところ、この時点での重合転化率は９９．９％であった。
　次に、鎖状共役ジエン化合物としての脱水イソプレン５０．０部を加え、添加終了後そのまま４０分間攪拌を続けた。この時点での重合転化率は９９．６％であった。
　その後、更に、芳香族ビニル化合物としての脱水スチレン２５部を加え、添加終了後そのまま全容を６０分間攪拌した。この時点での重合転化率はほぼ１００％であった。 (Production Example 3)
In a reactor equipped with a stirrer and sufficiently purged with nitrogen inside, 550 parts of dehydrated cyclohexane, 25 parts of dehydrated styrene as an aromatic vinyl compound, 0.475 of di-n-butyl ether (dibutyl ether) as a randomizing agent While stirring at 60 ° C., 0.9 part of n-butyllithium (15% cyclohexane solution) as a polymerization initiator was further added. After completion of the addition, the whole volume was further stirred at 65 ° C. for 60 minutes. When the reaction solution was measured by gas chromatography, the polymerization conversion rate at this point was 99.9%.
Next, 50.0 parts of dehydrated isoprene as a chain conjugated diene compound was added, and stirring was continued for 40 minutes as it was after completion of the addition. The polymerization conversion rate at this point was 99.6%.
Thereafter, 25 parts of dehydrated styrene as an aromatic vinyl compound was further added, and the whole volume was stirred as it was for 60 minutes after the addition was completed. The polymerization conversion rate at this point was almost 100%.
　ここで、反応液に重合停止剤としてのメタノール２．０部を加えて反応を停止させた。得られたブロック共重合体［Ｃ３］の構造単位比Ｓ’は０．０８であった。 Here, 2.0 parts of methanol as a polymerization terminator was added to the reaction solution to stop the reaction. The structural unit ratio S ′ of the obtained block copolymer [C3] was 0.08.
　次いで、ブロック共重合体［Ｃ３］を含む重合体溶液を用いて、製造例１の水素化物［Ｄ１］の製造と同様にして、水素化物［Ｄ３］を得た。得られたペレット状の水素化物［Ｄ３］の水素化率はほぼ１００％であった。 Subsequently, using a polymer solution containing the block copolymer [C3], 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%.
（製造例４）
　ランダム化剤を、エチレングリコールジブチルエーテル０．５３部からジ－ｎ－ブチルエーテル（ジブチルエーテル）０．４７５部に変更したこと以外は、製造例１のブロック共重合体［Ｃ１］の調製と同様にして、ブロック共重合体［Ｃ４］を調製した。なお、ブロック共重合体［Ｃ４］の構造単位比Ｓ’は０．０８であった。
　次いで、ブロック共重合体［Ｃ４］を含む重合体溶液を用いて、製造例１の水素化物［Ｄ１］の製造と同様にして、水素化物［Ｄ４］を得た。得られたペレット状の水素化物［Ｄ４］の水素化率はほぼ１００％であった。 (Production Example 4)
Except that the randomizing agent was changed from 0.53 part of ethylene glycol dibutyl ether to 0.475 part of di-n-butyl ether (dibutyl ether), it was the same as the preparation of the block copolymer [C1] in Production Example 1. Thus, a block copolymer [C4] was prepared. The structural unit ratio S ′ of the block copolymer [C4] was 0.08.
Subsequently, using the polymer solution containing the block copolymer [C4], a hydride [D4] was obtained in the same manner as in the production of the hydride [D1] of Production Example 1. The hydrogenation rate of the obtained pellet-like hydride [D4] was almost 100%.
（実施例１）
＜酸無水物変性水素化物［Ｅ１］の製造＞
　製造例１で得られた水素化物［Ｄ１］のペレット１００部に対して、エチレン性不飽和カルボン酸無水物としての無水マレイン酸２．０部および２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン（日油社製「パーヘキサ（登録商標）２５Ｂ」、１分間半減期：１７９．８℃）０．２部を添加した。この混合物を、二軸押出機（東芝機械社製「ＴＥＭ－３７Ｂ」）を用いて、樹脂温度２００℃、滞留時間６０～７０秒で混練し、ストランド状に押出し、空冷した後、ペレタイザーによりカッティングし、酸無水物変性水素化物［Ｅ１］のペレット９６部を得た。 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.
　得られた酸無水物変性水素化物［Ｅ１］のペレット１０部をシクロヘキサン１００部に溶解した後、脱水アセトン４００部中に注いで、酸無水物変性水素化物［Ｅ１］を凝固させ、精製した。凝固物を分離し、２５℃で真空乾燥して、酸無水物変性水素化物［Ｅ１］のクラム９．０部を単離した。
　得られた酸無水物変性水素化物［Ｅ１］のクラムを用いて、ＦＴ－ＩＲスペクトルを測定したところ、酸無水物基に由来する１７９０ｃｍ－１のピークが観察され、当該ピーク強度から、水素化物［Ｄ１］１００部に対して、無水マレイン酸０．１８部が結合したことが確認された。 Ten parts of the obtained acid anhydride-modified hydride [E1] pellets were dissolved in 100 parts of cyclohexane, and then poured into 400 parts of dehydrated acetone to solidify and purify the acid anhydride-modified hydride [E1]. The coagulum was separated and vacuum dried at 25 ° C. to isolate 9.0 parts of crumb of acid anhydride-modified hydride [E1].
When FT-IR spectrum was measured using crumb of the obtained acid anhydride-modified hydride [E1], a peak at 1790 cm −1 derived from the acid anhydride group was observed, and from the peak intensity, hydride was observed. It was confirmed that 0.18 parts of maleic anhydride was bonded to 100 parts of [D1].
　また、得られた酸無水物変性水素化物［Ｅ１］について、重量平均分子量（Ｍｗ）および分子量分布（Ｍｗ／Ｍｎ）を求めたところ、重量平均分子量（Ｍｗ）は７５，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．５９であった。 Moreover, when the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were calculated | required about the obtained acid anhydride modified hydride [E1], the weight average molecular weight (Mw) was 75,000 and molecular weight distribution ( Mw / Mn) was 1.59.
＜樹脂シートの作製＞
　そして、得られた酸無水物変性水素化物［Ｅ１］のペレット１００部に対し、添加剤（Ｘ）としてのセシウムドープ酸化タングステン（以下、「ＣＷＯ」と称することがある。；住友金属鉱山社製「ＹＭＤＳ－８７４」、平均粒子径：５５ｎｍ）０．５部を加え、ミキサーにて混合した。この混合物を、幅４００ｍｍのＴダイを備えた二軸押出機（東芝機械社製「ＴＥＭ－３７Ｂ」）を用いて、溶融樹脂温度２００℃、Ｔダイ温度２００℃の条件にて押出成形し、酸無水物変性水素化物［Ｅ１］に添加剤（Ｘ）としてのＣＷＯを配合した樹脂組成物［Ｅ１Ｃ１］からなる樹脂シート［Ｅ１Ｓ１］（厚さ：７６０μｍ）を作製した。
　そして、得られた樹脂シートの遮音性および接着性を評価した。結果を表１に示す。 <Production of resin sheet>
And with respect to 100 parts of pellets of the obtained acid anhydride modified hydride [E1], cesium-doped tungsten oxide (hereinafter referred to as “CWO”) as additive (X) may be referred to as Sumitomo Metal Mining Co., Ltd. 0.5 parts of “YMDS-874” (average particle size: 55 nm) was added and mixed with a mixer. 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 μm) 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.
＜合わせガラスの作製＞
　得られた樹脂シート［Ｅ１Ｓ１］から、縦２９０ｍｍ、横２９０ｍｍの試験片を切り出した。
　また、別途、国際公開第２０１２／０４３７０８号に記載の方法に従って作製した、ブロック共重合体（スチレン由来の構造単位／イソプレン由来の構造単位の含有割合：５０／５０（質量比））の水素化物のアルコキシシラン変性体（アルコキシシリル基含有量：１．８％、重量平均分子量（Ｍｗ）：３９，０００）からなる厚さ１００μｍの接着用シートから、縦３００ｍｍ、横３００ｍｍのシートを切り出した。
　次いで、上記樹脂シート［Ｅ１Ｓ１］の試験片と、接着用シートとを、厚さ１．１ｍｍ、縦３００ｍｍ、横３００ｍｍの２枚のソーダガラス板の間に、ソーダガラス板／接着用シート／樹脂シート［Ｅ１Ｓ１］／接着用シート／ソーダガラス板の順に重ねて積層物とした。樹脂シート［Ｅ１Ｓ１］は接着用シートの中央部に配置し、合わせガラスにした場合に、樹脂シート［Ｅ１Ｓ１］の端部が全周に亘って接着用シートの端部より内側に位置し、接着用シート内に封入されるようにした。
　この積層物を、ＮＹ（ナイロン）／ＰＰ（ポリプロピレン）製の厚さ７５μｍの袋に入れ、袋の開口部の中央部を２００ｍｍ幅残して両側をヒートシーラーでヒートシールした後、密封パック器（パナソニック社製「ＢＨ－９５１」）を使用して、袋内を脱気しながら開口部をヒートシールして積層物を密封包装した。
　その後、密封包装した積層物をオートクレーブに入れて、３０分間、温度１４０℃、圧力０．８ＭＰａで加熱加圧し、合わせガラス［Ｅ１Ｇ１］を作製した。 <Production of laminated glass>
A test piece having a length of 290 mm and a width of 290 mm was cut out from the obtained resin sheet [E1S1].
In addition, 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 μm consisting of a modified alkoxysilane (alkoxysilyl group content: 1.8%, weight average molecular weight (Mw): 39,000).
Next, 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. When 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 μm 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. Using “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.
After that, 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].
　そして、得られた合わせガラス［Ｅ１Ｇ１］の全光線透過率および透明性を測定および評価した。結果を表１に示す。 And the total light transmittance and transparency of the obtained laminated glass [E1G1] were measured and evaluated. The results are shown in Table 1.
（実施例２～４）
　添加剤（Ｘ）としてのＣＷＯの添加量を、酸無水物変性水素化物［Ｅ１］のペレット１００部に対して０．５部から０．２５部、１．２５部、および２部にそれぞれ変更した樹脂組成物［Ｅ１Ｃ２］、［Ｅ１Ｃ３］、および［Ｅ１Ｃ４］を用いたこと以外は、実施例１と同様にして、樹脂シート［Ｅ１Ｓ２］、［Ｅ１Ｓ３］、および［Ｅ１Ｓ４］（各厚さ：７６０μｍ）を作製した。
　次いで、樹脂シート［Ｅ１Ｓ２］、［Ｅ１Ｓ３］、および［Ｅ１Ｓ４］をそれぞれ用いたこと以外は実施例１と同様にして、合わせガラス［Ｅ１Ｇ２］、［Ｅ１Ｇ３］、および［Ｅ１Ｇ４］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (Examples 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 μm).
Next, 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.
（実施例５）
　製造例１で得られた水素化物［Ｄ１］のペレット１００部に対して、エチレン性不飽和カルボン酸無水物として、無水マレイン酸２．０部に代えて、無水イタコン酸２．０部を添加したこと以外は、実施例１と同様にして、酸無水物変性水素化物［Ｅ２］のペレット９６部を取得し、同様の項目について測定を行なったところ、重量平均分子量（Ｍｗ）は７５，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．５９であった。なお、実施例１と同様の方法で測定したところ、水素化物［Ｄ１］１００部に対して、無水イタコン酸０．１７部が結合したことが確認された。
　次いで、酸無水物変性水素化物［Ｅ１］に代えて、酸無水物変性水素化物[Ｅ２]を使用したこと以外は、実施例１と同様にして、酸無水物変性水素化物［Ｅ２］に添加剤（Ｘ）としてのＣＷＯを配合した樹脂組成物［Ｅ２Ｃ１］からなる樹脂シート［Ｅ２Ｓ１］（厚さ：７６０μｍ）、を作製した。さらに、樹脂シート［Ｅ１Ｓ１］に代えて、樹脂シート［Ｅ２Ｓ１］を用いたこと以外は実施例１と同様にして、合わせガラス［Ｅ２Ｇ１］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (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].
Next, 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 μm) made of a resin composition [E2C1] containing CWO as the agent (X) was produced. Further, 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.
（実施例６）
　添加剤（Ｘ）として、セシウムドープ酸化タングステン（ＣＷＯ）０．５部に代えて、六ホウ化ランタン（住友金属鉱山社製「ＫＨＤＳ－０６」、平均粒子径：４０ｎｍ）０．２部を添加した樹脂組成物［Ｅ１Ｃ５］を用いたこと以外は、実施例１と同様にして、樹脂シート［Ｅ１Ｓ５］（厚さ：７６０μｍ）を作製した。
　次いで、樹脂シート［Ｅ１Ｓ５］を用いたこと以外は実施例１と同様にして、合わせガラス［Ｅ１Ｇ５］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (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) A resin sheet [E1S5] (thickness: 760 μm) was produced in the same manner as in Example 1 except that the resin composition [E1C5] was used.
Next, 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.
（実施例７および８）
　製造例１で得られた水素化物［Ｄ１］のペレット１００部に代えて、製造例２で得られた水素化物［Ｄ２］、および製造例４で得られた水素化物［Ｄ４］をそれぞれ使用したこと以外は、実施例１と同様にして、酸無水物変性水素化物［Ｅ３］および［Ｅ４］のペレットをそれぞれ９６部取得し、同様の項目について測定を行なったところ、酸無水物変性水素化物［Ｅ３］については、重量平均分子量（Ｍｗ）は７４，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．６１であり、酸無水物変性水素化物［Ｅ４］については、重量平均分子量（Ｍｗ）は７５，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．５９であった。なお、実施例１と同様の方法で測定したところ、酸無水物変性水素化物［Ｅ３］では、水素化物［Ｄ２］１００部に対して、無水マレイン酸０．１８部が結合し、酸無水物変性水素化物［Ｅ４］では、水素化物［Ｄ４］１００部に対して、無水マレイン酸０．１７部が結合したことが確認された。
　次いで、酸無水物変性水素化物［Ｅ１］に代えて、酸無水物変性水素化物[Ｅ３]および［Ｅ４］をそれぞれ使用したこと以外は、実施例１と同様にして、樹脂組成物［Ｅ３Ｃ１］からなる樹脂シート［Ｅ３Ｓ１］（厚さ：７６０μｍ）、および樹脂組成物［Ｅ４Ｃ１］からなる樹脂シート［Ｅ４Ｓ１］（厚さ：７６０μｍ）を作製した。さらに、樹脂シート［Ｅ１Ｓ１］に代えて、樹脂シート［Ｅ３Ｓ１］および［Ｅ４Ｓ１］をそれぞれ用いたこと以外は実施例１と同様にして、合わせガラス［Ｅ３Ｇ１］および［Ｅ４Ｇ１］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (Examples 7 and 8)
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. For [E3], the weight average molecular weight (Mw) is 74,000 and the molecular weight distribution (Mw / Mn) is 1.61, and for 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].
Next, in the same manner as in Example 1 except that acid anhydride-modified hydrides [E3] and [E4] were used in place of acid anhydride-modified hydride [E1], resin composition [E3C1] Resin sheet [E3S1] (thickness: 760 μm) made of and resin sheet [E4S1] (thickness: 760 μm) made of the resin composition [E4C1]. Further, laminated glass [E3G1] and [E4G1] are produced in the same manner as in Example 1 except that the resin sheets [E3S1] and [E4S1] are used in place of the resin sheet [E1S1]. Items were measured and evaluated. The results are shown in Table 1.
（比較例１）
　製造例１で得られた水素化物［Ｄ１］のペレット１００部に代えて、製造例３で得られた水素化物［Ｄ３］を使用したこと以外は、実施例１と同様にして、酸無水物変性水素化物［Ｅ５］のペレット９６部を取得し、同様の項目について測定を行なったところ、重量平均分子量（Ｍｗ）は４４，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．２０であった。なお、実施例１と同様の方法で測定したところ、水素化物［Ｄ３］１００部に対して、無水マレイン酸１．７部が結合したことが確認された。
　次いで、酸無水物変性水素化物［Ｅ１］に代えて、酸無水物変性水素化物[Ｅ５]を使用したこと以外は、実施例１と同様にして、酸無水物変性水素化物［Ｅ５］に添加剤（Ｘ）としてのＣＷＯを配合した樹脂組成物［Ｅ５Ｃ１］からなる樹脂シート［Ｅ５Ｓ１］（厚さ：７６０μｍ）を作製した。さらに、樹脂シート［Ｅ１Ｓ１］に代えて、樹脂シート［Ｅ５Ｓ１］を用いたこと以外は実施例１と同様にして、合わせガラス［Ｅ５Ｇ１］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (Comparative Example 1)
In the same manner as in Example 1, except that the hydride [D3] obtained in Production Example 3 was used in place of 100 parts of the hydride [D1] pellet obtained in Production Example 1, acid anhydride was used. 96 parts of the modified hydride [E5] pellets were obtained and measured for the same items. The weight average molecular weight (Mw) was 44,000 and the molecular weight distribution (Mw / Mn) was 1.20. . In addition, when measured by the same method as in Example 1, it was confirmed that 1.7 parts of maleic anhydride was bonded to 100 parts of hydride [D3].
Subsequently, it was added to the acid anhydride-modified hydride [E5] in the same manner as in Example 1 except that the acid anhydride-modified hydride [E5] was used instead of the acid anhydride-modified hydride [E1]. A resin sheet [E5S1] (thickness: 760 μm) made of a resin composition [E5C1] containing CWO as the agent (X) was produced. Further, a laminated glass [E5G1] was produced in the same manner as in Example 1 except that the resin sheet [E5S1] was used instead of the resin sheet [E1S1], and the same items were measured and evaluated. The results are shown in Table 1.
（比較例２）
　酸無水物変性水素化物［Ｅ１］に代えて、酸無水物変性をしていない水素化物[Ｄ１]を使用したこと以外は、実施例１と同様にして、水素化物［Ｄ１］に添加剤（Ｘ）としてのＣＷＯを配合した樹脂組成物［Ｄ１Ｃ１］からなる樹脂シート［Ｄ１Ｓ１］（厚さ：７６０μｍ）を作製した。なお、水素化物［Ｄ１］の重量平均分子量（Ｍｗ）は７５，０００で、分子量分布（Ｍｗ／Ｍｎ）は１．５９であった。そして、樹脂シート［Ｅ１Ｓ１］に代えて、樹脂シート［Ｄ１Ｓ１］を用いたこと以外は実施例１と同様にして、合わせガラス［Ｄ１Ｇ１］を作製し、同様の項目について測定および評価を行なった。結果を表１に示す。 (Comparative Example 2)
In the same manner as in Example 1 except that the hydride [D1] not modified with acid anhydride was used instead of the acid anhydride-modified hydride [E1], an additive ( A resin sheet [D1S1] (thickness: 760 μm) made of a resin composition [D1C1] containing CWO as X) was prepared. The hydride [D1] had a weight average molecular weight (Mw) of 75,000 and a molecular weight distribution (Mw / Mn) of 1.59. And it replaced with resin sheet [E1S1] and produced laminated glass [D1G1] like Example 1 except having used resin sheet [D1S1], and measured and evaluated about the same item. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１より、所定の構造単位［ａ１］および／または［ａ２］を主成分として含有する重合体ブロック[Ａ]と、所定の構造単位［ｂ１］および／または［ｂ２］を主成分として含有する[Ｂ]とを所定の質量分率で有し、且つ、前記構造単位［ａ２］および［ｂ２］の少なくとも一方を含有する酸無水物基含有ブロック共重合体を用いた実施例１～８の樹脂シートは、優れた接着性および透明性を両立し得ることが分かる。
　一方、重合体ブロック[Ａ]と重合体ブロック[Ｂ]との質量分率が所定の範囲外である酸無水物基含有ブロック共重合体を用いた比較例１の樹脂シートは、透明性は良好であるものの、接着性に劣ることが分かる。
　さらに、酸無水物基を含有しないブロック共重合体を用いた比較例２の樹脂シートは、接着性および透明性のいずれにも劣ることが分かる。 From Table 1, 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. Of [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]. It can be seen that the resin sheet can achieve both excellent adhesion and transparency.
On the other hand, 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.
　本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを提供可能な酸無水物基含有ブロック共重合体、および樹脂組成物を提供することができる。そして、本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを提供することができる。さらに、本発明によれば、優れた接着性および透明性を両立し得る樹脂シートを備える合わせガラスを提供することができる。 According to the present invention, it is possible to provide 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. And according to this invention, the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided. Furthermore, according to this invention, a laminated glass provided with the resin sheet which can make the outstanding adhesiveness and transparency compatible can be provided.

Claims (10)

  1. 　酸無水物基を含有するブロック共重合体であり、
    　芳香族ビニル化合物に由来する構造単位［ａ１］、および／または芳香族ビニル化合物に由来する構造中の不飽和結合の少なくとも一部を水素化してなる構造単位［ａ２］を主成分として含有する重合体ブロック［Ａ］と、
    　鎖状共役ジエン化合物に由来する構造単位［ｂ１］、および／または鎖状共役ジエン化合物に由来する構造中の不飽和結合を水素化してなる構造単位［ｂ２］を主成分として含有する重合体ブロック［Ｂ］と、を有し、
    　前記構造単位［ａ１］および［ａ２］が前記ブロック共重合体全体に占める質量分率をｗＡとし、前記構造単位［ｂ１］および［ｂ２］が前記ブロック共重合体全体に占める質量分率をｗＢとしたときの、ｗＡとｗＢとの比（ｗＡ／ｗＢ）が５／９５以上２９／７１以下であり、
    　前記構造単位［ａ２］および［ｂ２］の少なくとも一方を含有する、酸無水物基含有ブロック共重合体。     A block copolymer containing an acid anhydride group,
    Heavy component containing, as a main component, a structural unit [a1] derived from an aromatic vinyl compound and / or a structural unit [a2] obtained by hydrogenating at least a part of unsaturated bonds in the structure derived from an aromatic vinyl compound. Combined block [A],
    A polymer block containing as a main component a structural unit [b1] derived from a chain conjugated diene compound and / or a structural unit [b2] obtained by hydrogenating an unsaturated bond in the structure derived from a chain conjugated diene compound [B]
    The mass fraction of the structural units [a1] and [a2] occupying the entire block copolymer is wA, and the mass fraction of the structural units [b1] and [b2] occupying the entire block copolymer is wB. The ratio of wA to wB (wA / wB) is 5/95 or more and 29/71 or less,
    An acid anhydride group-containing block copolymer containing at least one of the structural units [a2] and [b2].
  2. 　前記酸無水物基が無水マレイン酸基および／または無水イタコン酸基を含む、請求項１に記載の酸無水物基含有ブロック共重合体。 The acid anhydride group-containing block copolymer according to claim 1, wherein the acid anhydride group includes a maleic anhydride group and / or an itaconic anhydride group.
  3. 　前記鎖状共役ジエン化合物がイソプレンであり、
    　イソプレンに由来する構造単位、およびイソプレンに由来する構造中の不飽和結合を水素化してなる構造単位のうち、１，２－付加重合のみに由来する構造単位と、１，２－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＰとし、３，４－付加重合のみに由来する構造単位と、３，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＱとし、１，４－付加重合のみに由来する構造単位と、１，４－付加重合のみに由来する構造中の不飽和結合を水素化してなる構造単位とが前記ブロック共重合体全体に占める質量分率をｗＲとしたときの、下記式：
    　構造単位比Ｓ＝（ｗＰ＋ｗＱ）／（ｗＰ＋ｗＱ＋ｗＲ）
    で表わされる構造単位比Ｓの値が０．３以上である、請求項１または２に記載の酸無水物基含有ブロック共重合体。     The chain conjugated diene compound is isoprene;
    Of structural units derived from isoprene and structural units obtained by hydrogenating unsaturated bonds in structures derived from isoprene, structural units derived only from 1,2-addition polymerization and 1,2-addition polymerization only The structural unit obtained by hydrogenating unsaturated bonds in the structure derived from wP represents the mass fraction of the entire block copolymer, and the structural unit derived only from 3,4-addition polymerization; The structural unit derived from hydrogenation of the unsaturated bond in the structure derived only from addition polymerization is represented by wQ as the mass fraction of the entire block copolymer, and the structural unit derived only from 1,4-addition polymerization; When the weight fraction of the structural unit formed by hydrogenating unsaturated bonds in the structure derived solely from 1,4-addition polymerization in the block copolymer is wR, the following formula:
    Structural unit ratio S = (wP + wQ) / (wP + wQ + wR)
    The acid anhydride group-containing block copolymer according to claim 1 or 2, wherein the value of the structural unit ratio S represented by
  4. 　請求項１～３のいずれかに記載の酸無水物基含有ブロック共重合体と、
    　金属酸化物の微粒子、金属ホウ化物の微粒子、および近赤外線吸収色素からなる群から選択される少なくとも１種の添加剤（Ｘ）とを含む、樹脂組成物。     An acid anhydride group-containing block copolymer according to any one of claims 1 to 3,
    A resin composition comprising: metal oxide fine particles, metal boride fine particles, and at least one additive (X) selected from the group consisting of near-infrared absorbing dyes.
  5. 　前記添加剤（Ｘ）が金属酸化物の微粒子を含み、
    　前記金属酸化物がセシウムドープ酸化タングステンを含む、請求項４に記載の樹脂組成物。     The additive (X) contains metal oxide fine particles,
    The resin composition according to claim 4, wherein the metal oxide includes cesium-doped tungsten oxide.
  6. 　前記添加剤（Ｘ）が金属ホウ化物の微粒子を含み、
    　前記金属ホウ化物がホウ化ランタンを含む、請求項４または５に記載の樹脂組成物。     The additive (X) includes fine particles of metal boride,
    The resin composition according to claim 4 or 5, wherein the metal boride contains lanthanum boride.
  7. 　請求項４～６のいずれかに記載の樹脂組成物からなる樹脂層を少なくとも１層含む、樹脂シート。 A resin sheet comprising at least one resin layer comprising the resin composition according to any one of claims 4 to 6.
  8. 　請求項７に記載の樹脂シートを少なくとも１枚備える、合わせガラス。 Laminated glass comprising at least one resin sheet according to claim 7.
  9. 　８００ｎｍ以上２０００ｎｍ以下の波長の範囲内に光線透過率が５０％以下の領域を有する、請求項８に記載の合わせガラス。 The laminated glass according to claim 8, which has a region having a light transmittance of 50% or less within a wavelength range of 800 nm to 2000 nm.
  10. 　５００ｎｍの波長での光線透過率が６０％以上である、請求項９に記載の合わせガラス。 The laminated glass according to claim 9, wherein the light transmittance at a wavelength of 500 nm is 60% or more.
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