WO2012105150A1 - Composition de résine et son utilisation - Google Patents

Composition de résine et son utilisation Download PDF

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Publication number
WO2012105150A1
WO2012105150A1 PCT/JP2011/080415 JP2011080415W WO2012105150A1 WO 2012105150 A1 WO2012105150 A1 WO 2012105150A1 JP 2011080415 W JP2011080415 W JP 2011080415W WO 2012105150 A1 WO2012105150 A1 WO 2012105150A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
resin
copper salt
laminated glass
general formula
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PCT/JP2011/080415
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English (en)
Japanese (ja)
Inventor
町田　克一
留美 佐野
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株式会社クレハ
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Priority to JP2012555709A priority Critical patent/JP5766218B2/ja
Publication of WO2012105150A1 publication Critical patent/WO2012105150A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C09J123/0869—Acids or derivatives thereof
    • C09J123/0876—Neutralised polymers, i.e. ionomers
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10614—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer comprising particles for purposes other than dyeing
    • B32B17/10633—Infrared radiation absorbing or reflecting agents
    • 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
    • B32B17/10005—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 laminated safety glass or glazing
    • B32B17/1055—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10743—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 laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof

Definitions

  • the present invention relates to a resin composition and its use, and more particularly to a resin composition containing a polyvalent metal ionomer resin and a phosphonic acid copper salt and its use.
  • laminated glass is used in various applications such as vehicles such as automobiles, buildings, and solar cells.
  • an interlayer film for laminated glass a polyvinyl butyral resin film, an ionomer resin film, and the like are known.
  • ionomer resins have excellent strength and hardness compared to polyvinyl butyral resins, and are excellent in durability, transparency, and adhesiveness, and therefore can be suitably used as an intermediate film for structural materials such as laminated glass. is there.
  • the sun rays include ultraviolet rays, infrared rays and the like in addition to visible rays.
  • infrared rays infrared rays having a wavelength close to visible light are called near infrared rays.
  • Near-infrared rays are also called heat rays and are one of the causes of temperature rise inside vehicles and buildings.
  • Patent Document 1 a copper salt composition containing a phosphonic acid copper salt, a polysiloxane component, a plasticizer, and a dispersant is known (see, for example, Patent Document 1).
  • Patent Document 1 provides an infrared absorption film in which the resin composition containing the copper salt composition and the resin is excellent in visible light transmission and stability even when exposed to high temperatures. It is disclosed that it is possible.
  • Patent Document 1 discloses a polyvinyl acetal resin, an ethylene-vinyl acetate copolymer (EVA), a (meth) acrylic resin, a polyester resin, a polyurethane resin, a vinyl chloride resin, and a polyolefin as a resin mixed with a copper salt composition. Resins, polycarbonate resins, norbornene resins and the like are disclosed.
  • the present invention has been made in view of the above prior art, and an object of the present invention is to provide a resin composition excellent in near-infrared absorbing ability, which contains an ionomer resin and a copper phosphonate.
  • the inventors of the present invention have intensively studied in order to achieve the above-mentioned problems.
  • the present inventors mixed an ionomer resin and a phosphonic acid copper salt which is a near-infrared absorber, and depending on the type of the ionomer resin, the obtained resin composition is colored and inferior in near-infrared absorbing ability. I found out.
  • the inventors speculated that this cause is due to ion exchange between the metal ion contained in the ionomer resin and the copper ion contained in the near-infrared absorber.
  • the present inventors have further researched, and by using a polyvalent metal ionomer resin as the ionomer resin, it is possible to provide a resin composition having excellent visible light transmittance and excellent near-infrared absorption ability. As a result, the present invention was completed.
  • the resin composition of the present invention comprises a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the following general formula (1).
  • R 1 is a monovalent group represented by —CH 2 CH 2 —R 11
  • R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups.
  • the polyvalent metal is preferably a divalent metal, and more preferably at least one divalent metal selected from zinc, magnesium and calcium.
  • the resin composition of the present invention preferably contains 0.05 to 30 parts by mass of the phosphonic acid copper salt per 100 parts by mass of the polyvalent metal ionomer resin.
  • the resin film and the interlayer film for laminated glass of the present invention are formed from the resin composition.
  • the interlayer film for laminated glass of the present invention has a layer formed from the resin composition, and layers formed from other resin compositions on both sides of the layer, and is formed from the other resin composition. At least one of the layers is preferably an ultraviolet cut layer.
  • the laminated glass of the present invention has the glass interlayer film.
  • the resin composition of the present invention contains a specific polyvalent metal ionomer resin and a copper phosphonate, and has excellent visible light transmittance and near-infrared absorption ability. Moreover, the resin film formed from this resin composition can be suitably used as an interlayer film for laminated glass.
  • seat formed from the resin composition of Example 1 is shown.
  • seat formed from the resin composition of Example 2 is shown.
  • seat formed from the resin composition of the comparative example 1 is shown.
  • seat formed from the resin composition of the comparative example 2 is shown.
  • the resin composition of the present invention is characterized by containing a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer and a phosphonic acid copper salt represented by the general formula (1).
  • Polyvalent metal ionomer resin As the polyvalent metal ionomer resin used in the present invention, a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer can be used.
  • the resin composition of the present invention is made of an interlayer film formed from a resin composition obtained by using a polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer among ionomer resins. When manufactured, it is excellent in strength, hardness, durability, transparency and adhesiveness.
  • the polyvalent metal ionomer resin of the ethylene / unsaturated carboxylic acid copolymer is also simply referred to as a polyvalent metal ionomer resin.
  • the polyvalent metal ionomer resin used in the present invention is an ionomer resin obtained by neutralizing at least part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer with a divalent or higher metal ion.
  • the ethylene / unsaturated carboxylic acid copolymer is a copolymer having at least a structural unit derived from ethylene and a structural unit derived from unsaturated carboxylic acid, and may have a structural unit derived from another monomer.
  • Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, maleic acid and the like. Acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable.
  • Examples of the other monomer include 1-butene.
  • the ethylene / unsaturated carboxylic acid copolymer preferably has 75 to 99 mol% of structural units derived from ethylene, assuming that the total structural units of the copolymer are 100 mol%, and derived from unsaturated carboxylic acid. It is preferable to have 1 to 25 mol% of the structural unit.
  • the polyvalent metal ionomer resin of the ethylene / unsaturated carboxylic acid copolymer is an ionomer resin obtained by neutralizing or crosslinking at least a part of the carboxyl group of the ethylene / unsaturated carboxylic acid copolymer with a metal ion.
  • the neutralization degree of the carboxyl group is usually 1 to 90%, preferably 5 to 85%.
  • the ion source in the polyvalent metal ionomer resin used in the present invention may be a polyvalent metal, that is, a metal having a valence of 2 or more.
  • the polyvalent metal is preferably a divalent metal, more preferably at least one divalent metal selected from zinc, magnesium and calcium, and at least one divalent metal selected from zinc and magnesium. Particularly preferred is zinc.
  • the production method of the polyvalent metal ionomer resin used in the present invention is not particularly limited, and can be produced by a conventionally known production method.
  • radical copolymerization of ethylene and an unsaturated carboxylic acid under high temperature and high pressure to produce an ethylene / unsaturated carboxylic acid copolymer, the ethylene / unsaturated carboxylic acid copolymer, and the ion source A polyvalent metal ionomer resin of an ethylene / unsaturated carboxylic acid copolymer can be produced by reacting with a metal compound containing.
  • polyvalent metal ionomer resin used in the present invention a commercially available product may be used. 1650 or the like.
  • the resin composition of the present invention contains a phosphonic acid copper salt represented by the following general formula (1).
  • R 1 is a monovalent group represented by —CH 2 CH 2 —R 11
  • R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups.
  • R 11 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
  • R 11 hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group Tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group and the like are preferable.
  • a phosphonic acid copper salt represented by General formula (1) it may be used individually by 1 type, or 2 or more types may be used.
  • phosphonic acid copper salt represented by the general formula (1) is also simply referred to as “phosphonic acid copper salt”.
  • a copper salt containing a fluorine atom that is, a phosphonic acid copper salt in which R 11 is a fluorinated alkyl group having 1 to 20 carbon atoms is used as the phosphonic acid copper salt
  • a phosphonic acid with respect to the polyvalent metal ionomer resin is used.
  • the refractive index of the phosphonic acid copper salt is higher than that when R 11 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Can be lowered.
  • a copper phosphonate having a small difference in refractive index from the polyvalent metal ionomer resin the transparency of the resin composition of the present invention can be further improved.
  • the method for producing the phosphonic acid copper salt used in the present invention is not particularly limited, and for example, it can be produced by the following method.
  • a phosphonic acid compound represented by the following general formula (2) and a copper salt are mixed in a solvent in the presence of a dispersant as required, and a reaction mixture is prepared.
  • the method include a step of obtaining (hereinafter also referred to as a reaction step) and a step of obtaining a copper salt of phosphonic acid by removing a solvent in the reaction mixture (hereinafter also referred to as a solvent removal step).
  • R 1 is a monovalent group represented by —CH 2 CH 2 —R 11
  • R 11 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or 1 carbon atom. Represents -20 fluorinated alkyl groups.
  • the phosphonic acid compound represented by the general formula (2) those in which R 11 is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms are preferred.
  • Examples of the phosphonic acid compound represented by the general formula (2) include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, and decylphosphonic acid.
  • Examples thereof include alkylphosphonic acids such as acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, and octadecylphosphonic acid.
  • a phosphonic acid compound represented by General formula (2) it may be used individually by 1 type, or 2 or more types may be used.
  • the copper salt a copper salt capable of supplying divalent copper ions is usually used.
  • the copper salt include copper of organic acids such as anhydrous copper acetate, anhydrous copper formate, anhydrous copper stearate, anhydrous copper benzoate, anhydrous ethyl acetoacetate copper, anhydrous pyrophosphate, anhydrous naphthenic acid copper, and anhydrous copper citrate.
  • copper salt of inorganic acid such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, hydrate of copper salt of inorganic acid Or a hydrate
  • copper hydroxide is mentioned.
  • anhydrous copper acetate and copper acetate monohydrate are preferably used from the viewpoint of solubility and removal of by-products.
  • a dispersant may be used. It is preferable to use a dispersant because the dispersibility of the phosphonic acid copper salt represented by the general formula (1) is improved.
  • the dispersant include at least one phosphate ester compound selected from a phosphate ester compound represented by the general formula (3a) and a phosphate ester compound represented by the general formula (3b), the phosphoric acid Examples thereof include phosphoric acid (P—OH) in an ester compound, that is, a compound obtained by neutralizing a hydroxyl group with a base.
  • the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, and calcium hydroxide.
  • R 21 , R 22 and R 23 are monovalent groups represented by — (CH 2 CH 2 O) n R 5 , and n is 4 to 25 R 5 is an integer, and R 5 represents an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms. However, R 21 , R 22 and R 23 may be the same or different.
  • the n is more preferably an integer of 6 to 15. When n is less than 4, transparency may be insufficient when a laminated glass or the like is produced. On the other hand, when n exceeds 25, the amount of the phosphoric ester compound necessary for obtaining laminated glass having sufficient transparency tends to increase, resulting in high costs.
  • R 5 is an alkyl group having 6 to 25 carbon atoms or an alkylphenyl group having 6 to 25 carbon atoms, preferably an alkyl group having 6 to 25 carbon atoms, and preferably an alkyl group having 12 to 20 carbon atoms. Is more preferable.
  • R 5 is a group having less than 6 carbon atoms, transparency may be insufficient when a laminated glass or the like is produced. Further, if R 5 is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound required to obtain a laminated glass having sufficient transparency tends to increase, leading to high costs. .
  • the phosphoric acid ester compound represented by the general formula (3a) and the phosphoric acid ester compound represented by the general formula (3b) is used.
  • the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) are used, the phosphate ester compound represented by the general formula (3a) And the ratio of the phosphoric acid ester compound represented by the general formula (3b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((3a) :( 3b)).
  • a phosphate ester compound represented by the said general formula (3a) it may be used individually by 1 type, or 2 or more types may be used, and the phosphate ester compound represented by the said General formula (3b) May be used alone or in combination of two or more.
  • phosphate ester compound selected from the phosphate ester compound represented by the general formula (3a) and the phosphate ester compound represented by the general formula (3b) commercially available phosphoric acid Ester compounds such as DLP-8, DLP-10, DDP-8, DDP-10, TDP-8, TDP-10 (above, manufactured by Nikko Chemicals), Prisurf A219B, Prisurf A210B (above, No. 1) Ichikogaku Kagaku Co., Ltd.) can also be used.
  • the phosphoric acid in these phosphate ester compounds, ie, the compound which neutralized the hydroxyl group with the appropriate base can also be used.
  • the base used for neutralization include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide and the like.
  • the dispersant is at least one phosphate ester compound selected from a phosphate ester compound represented by the general formula (3a) and a phosphate ester compound represented by the general formula (3b), and / or
  • phosphoric acid in the phosphoric ester compound that is, a compound obtained by neutralizing a hydroxyl group with a base, it is preferably used in an amount of 0.02 to 0.40 mol per mol of the copper salt.
  • the reaction step is preferably carried out at room temperature to 60 ° C., more preferably 20 to 40 ° C., preferably for 0.5 to 50 hours, more preferably for 1 to 30 hours.
  • the phosphonic acid compound represented by the general formula (2) reacts with the copper salt, and fine phosphonic acid copper salt that does not dissolve in the solvent is generated by the reaction.
  • the reaction is good. Therefore, the phosphonic acid copper salt can maintain high dispersibility and suppress aggregation.
  • the reaction step not only the reaction between the phosphonic acid compound represented by the general formula (2) and the copper salt, but also, for example, the phosphate ester compound represented by the general formula (3a) and the general formula (3b) At least one type of phosphate ester compound selected from the phosphate ester compounds represented by) may react with a part of the copper salt. Further, a part of the raw material may remain without reacting.
  • the phosphonic acid copper salt is normally obtained as microparticles
  • the solvent removal step at least a part of the solvent is removed from the reaction mixture.
  • the liquid components in the reaction mixture may be removed together.
  • the temperature is usually room temperature to 230 ° C., preferably 60 to 200 ° C.
  • the drying may be performed under normal pressure or under reduced pressure. When drying under reduced pressure, there is a case where heating may not be performed or a temperature during drying may be low.
  • the drying time is usually 0.5 to 3 hours.
  • the solvent removal step there is a method of obtaining a phosphonic acid copper salt by heating at least a part of the solvent by heating the reaction mixture.
  • the heating conditions are usually room temperature to 70 ° C., preferably 40 to 60 ° C.
  • the solvent removal step may be performed under normal pressure or under reduced pressure. When the solvent removal step is performed under reduced pressure, heating may not be performed or the heating temperature may be low.
  • a step of removing the dispersion medium after the phosphonic acid copper salt is dispersed in the dispersion medium may be provided.
  • the copper phosphonate used in the present invention fine particles composed of a copper phosphonate having an average particle diameter of 1 to 1000 nm are usually used.
  • the average particle diameter is 1 to 1000 nm, a resin composition can be obtained in which fine particles composed of copper phosphonate are present unevenly.
  • the average particle diameter is more preferably 5 to 300 nm in order to ensure the transparency of the resin composition.
  • the resin composition of the present invention may be a composition containing the above-described polyvalent metal ionomer resin and a phosphonic acid copper salt. Usually, the above-mentioned polyvalent metal ionomer resin and a phosphonic acid copper salt are included.
  • the melt kneading can be performed using a known kneader such as a plastograph, a single screw extruder, a twin screw extruder, a Banbury mixer, and the like. The melt-kneading is usually performed in the range of 100 to 230 ° C.
  • the resin composition of the present invention preferably contains 0.05 to 30 parts by mass, more preferably 0.1 to 20 parts by mass of the phosphonic acid copper salt per 100 parts by mass of the polyvalent metal ionomer resin. . If the amount is less than 0.05 parts by mass, sufficient near infrared absorption characteristics may not be obtained. If the amount is more than 30 parts by mass, the transparency and adhesiveness of the resin may be significantly reduced.
  • the resin composition of the present invention is excellent in visible light transmittance and near-infrared absorbing ability, and since it contains a polyvalent metal ionomer resin as a resin, it is excellent in both strength and hardness, and in durability, transparency and adhesiveness. Since it is excellent, it can be suitably used as an intermediate film for structural materials such as laminated glass.
  • additives may be contained in the resin composition of the present invention.
  • the additive include a dispersant, an antioxidant, an ultraviolet absorber, and a light stabilizer. These additives may be kneaded together with the polyvalent metal ionomer resin and the phosphonic acid copper salt when the above-mentioned melt-kneading is performed. When producing the phosphonic acid copper salt, the polyvalent metal ionomer resin is produced. It may be added at the time.
  • the resin composition of the present invention can be used in various applications in which an ionomer resin is used, but is usually used in applications where it is desired to absorb near infrared rays.
  • the resin film formed from the resin composition of the present invention is excellent in visible light transmittance and near-infrared absorptivity, excellent in strength and hardness, and excellent in durability, transparency, and adhesiveness. It can be suitably used as an intermediate film for a structural material such as an intermediate film.
  • the resin film of the present invention may be formed only from the resin composition of the present invention, or may be a laminate having a layer formed from the resin composition of the present invention and other layers.
  • the interlayer film for laminated glass may be a resin film formed only from the resin composition of the present invention.
  • another resin is formed on both sides of the layer formed from the resin composition of the present invention.
  • An interlayer film for laminated glass having a layer formed from the composition may be used.
  • at least one layer of this layer is an ultraviolet-ray cut layer.
  • one layer is provided on each side of the layer formed from the resin composition of the present invention. The above layers may be provided.
  • the layer structure is preferably UV cut layer / layer formed from the resin composition of the present invention / UV cut layer.
  • an ultraviolet cut layer because the visible light transmittance of the laminated glass tends to be maintained over a long period of time. Moreover, when not providing an ultraviolet cut layer, the effect similar to the case where an ultraviolet cut layer is provided can be acquired by adding a ultraviolet absorber to the resin composition of this invention.
  • resin which comprises the layer formed from the said other resin composition ionomer resin from a viewpoint of adhesiveness with the layer formed from the resin composition of this invention, or adhesiveness with glass Is preferred.
  • the metal contained in the ionomer resin used in this case may be a polyvalent metal or a monovalent metal such as Na, Li, or K.
  • desired physical properties can be imparted to a layer formed from the other resin composition.
  • a composition containing an ultraviolet absorber is usually used as the other resin composition.
  • the laminated glass of the present invention has the interlayer film for laminated glass.
  • glass which comprises the laminated glass of this invention A conventionally well-known thing can be used.
  • Example 1 (Synthesis of copper ethylphosphonate) In a reaction vessel, 32.34 g of ethylphosphonic acid was dissolved in 500 ml of methanol, and 58.67 g of copper acetate monohydrate was added thereto, followed by heating under reflux for 4 hours to obtain a suspension.
  • Example 2 Zn salt of ethylene-methacrylic acid copolymer (ionomer in which 29% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Zn ion) was converted into ethylene-methacrylic acid.
  • Example 1 except that the copolymer was replaced with a Zn salt (an ionomer in which 13% of the carboxyl groups contained in the ethylene-methacrylic acid copolymer having 15 wt% methacrylic acid units were neutralized with Zn ions).
  • a resin composition (2) An ionomer in which 13% of the carboxyl groups contained in the ethylene-methacrylic acid copolymer having 15 wt% methacrylic acid units were neutralized with Zn ions.
  • Example 1 except that Na salt of copolymer (ionomer in which 54% of carboxyl groups contained in ethylene-methacrylic acid copolymer having 15% by weight of methacrylic acid unit were neutralized with Na ion) was replaced. To obtain a resin composition (c2).
  • the spectral transmittance of the sheet was measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).
  • FIG. 1 is a spectral transmittance of a sheet formed from the resin composition of Example 1
  • FIG. 2 is a spectral transmittance of a sheet formed from the resin composition of Example 2
  • FIG. 3 is a comparison.
  • FIG. 4 shows the spectral transmittance of a sheet formed from the resin composition of Example 1
  • FIG. 4 shows the spectral transmittance of the sheet formed from the resin composition of Comparative Example 2.
  • a sheet formed from a resin composition containing a polyvalent metal ionomer resin and a copper phosphonate has a broad absorption band in the near infrared region of 800 to 1200 nm.
  • a sheet formed from a resin composition containing a monovalent metal ionomer resin and a copper phosphonate has a weak absorption band in the vicinity of 600 to 1200 nm.
  • the sheet formed from the resin composition of the present invention is formed from a resin composition containing a monovalent metal ionomer resin and a copper phosphonate, while being excellent in visible light transmission and infrared absorption.
  • the sheet is inferior in visible light transmission and near infrared absorption.
  • Example 3 Preparation of UV cut layer sheet 100 parts by weight of an Na salt of an ethylene-methacrylic acid copolymer (an ionomer obtained by neutralizing 54% of carboxyl groups contained in an ethylene-methacrylic acid copolymer having 15 wt% of methacrylic acid units with Na ions), ultraviolet rays 2 parts by weight of 2- (2′-hydroxy-5′-octylphenyl) benzotriazole as an absorbent is supplied to a plastograph (manufactured by Brabender) and melt-kneaded for 15 minutes at 190 ° C. and a screw speed of 30 rpm. A resin composition (a) containing an ultraviolet absorber was obtained.
  • an Na salt of an ethylene-methacrylic acid copolymer an ionomer obtained by neutralizing 54% of carboxyl groups contained in an ethylene-methacrylic acid copolymer having 15 wt% of methacrylic acid units with Na ions
  • the resin composition (a) was preheated for 5 minutes with a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then heated and pressed at a pressure of 15 MPa for 5 minutes to obtain a thickness of 1 A sheet for UV cut layer of 0.0 mm was prepared.
  • a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then heated and pressed at a pressure of 15 MPa for 5 minutes to obtain a thickness of 1
  • a sheet for UV cut layer of 0.0 mm was prepared.
  • the resin composition (1) containing the ethylphosphonic acid copper salt obtained in Example 1 was preheated for 5 minutes with a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then at a pressure of 15 MPa. By heating and pressing for 5 minutes, a near-infrared absorbing layer sheet having a thickness of 0.75 mm was produced.
  • a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then at a pressure of 15 MPa.
  • the ultraviolet cut layer sheet was cut out using a scissors to prepare two 25 ⁇ 75 mm ultraviolet cut layer sheets.
  • the near-infrared absorbing layer sheet was cut out using a scissors to prepare a 25 ⁇ 75 mm near-infrared absorbing layer sheet.
  • the cut out UV cut layer sheet, near infrared absorbing layer sheet, and UV cut layer sheet were stacked in this order, and preheated for 5 minutes with a 150 ° C. press (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) Then, a resin sheet having a thickness of 2.7 mm was formed by heating and pressurizing at a pressure of 15 MPa for 5 minutes, in which an ultraviolet cut layer sheet, a near infrared absorption layer sheet, and an ultraviolet cut layer sheet were laminated in this order.
  • a 150 ° C. press (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.
  • a laminated resin sheet is placed on a glass plate (25 ⁇ 75 mm, thickness 1 mm) heated to 90 ° C., and a glass plate (25 ⁇ 75 mm, thickness 1 mm) heated to 90 ° C. is further used to use a roller.
  • a glass plate 25 ⁇ 75 mm, thickness 1 mm heated to 90 ° C. is further used to use a roller.
  • the glass set subjected to the temporary pressure bonding was subjected to heat pressure bonding at 130 ° C. and 15 MPa for 30 minutes using an autoclave to produce a laminated glass.
  • the layer structure of the obtained laminated glass is glass plate / ultraviolet cut layer / near infrared absorbing layer / ultraviolet cut layer / glass plate.
  • Example 4 (Preparation of near-infrared absorbing layer sheet)
  • the resin composition (1) containing the ethylphosphonic acid copper salt obtained in Example 1 was preheated for 5 minutes with a press machine (“WF-50”, manufactured by Shindo Metal Industry Co., Ltd.) at 150 ° C., and then at a pressure of 15 MPa.
  • a sheet for near infrared absorption layer having a thickness of 0.75 mm was produced by heating and pressing for 5 minutes.
  • the near-infrared absorbing layer sheet was cut out using a scissors to prepare a 25 ⁇ 75 mm near-infrared absorbing layer sheet.
  • the glass set subjected to the temporary pressure bonding was subjected to heat pressure bonding at 130 ° C. and 15 MPa for 30 minutes using an autoclave to produce a laminated glass.
  • the layer structure of the obtained laminated glass is glass plate / near infrared absorption layer / glass plate.
  • the light resistance test was conducted for 200 hours under the conditions of 180 W / m 2 (black panel temperature 63 ° C., humidity 50%, no rain) using a Super Xenon Weather Meter SX75 manufactured by Suga Test Instruments Co., Ltd. The results are shown in Table 1.
  • the visible light transmittance in Table 1 was calculated based on JIS R 3106 from spectral transmittance data measured using a spectrophotometer (U-4000, manufactured by Hitachi, Ltd.).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine pouvant être utilisée en tant que couche intermédiaire dans des matériaux résistants tels que le verre feuilleté. Ladite composition de résine contient une résine ionomère et du phosphonate de cuivre et présente de remarquables caractéristiques en matière d'absorption de l'énergie du rayonnement infra-rouge proche. Cette composition de résine contient donc une résine ionomère d'un métal polyvalent constituée d'un copolymère d'acide carboxylique insaturé/éthylène, et un phosphonate de cuivre de formule (1).
PCT/JP2011/080415 2011-02-02 2011-12-28 Composition de résine et son utilisation WO2012105150A1 (fr)

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WO2014171215A1 (fr) * 2013-04-16 2014-10-23 株式会社クレハ Composition de resine et son utilisation
WO2014175231A1 (fr) * 2013-04-26 2014-10-30 株式会社クレハ Composition de résine et son utilisation
WO2015080184A1 (fr) * 2013-11-29 2015-06-04 株式会社クレハ Composition de résine et son utilisation
WO2019054363A1 (fr) * 2017-09-14 2019-03-21 三井・デュポンポリケミカル株式会社 Composition de résine destinée à un film de couche intermédiaire de verre stratifié ou à un encapsulant de cellule solaire, film de couche intermédiaire de verre stratifié, verre stratifié, encapsulant de cellule solaire, et module de cellule solaire
WO2022270545A1 (fr) * 2021-06-23 2022-12-29 株式会社クラレ Composition de résine ionomère, feuille de résine et verre feuilleté
WO2022270540A1 (fr) * 2021-06-23 2022-12-29 株式会社クラレ Feuille de résine ayant une couche qui contient une composition de résine ionomère, et verre feuilleté

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JPH0753636A (ja) * 1993-06-30 1995-02-28 Du Pont Mitsui Polychem Co Ltd アイオノマー包装材料
JP2009024085A (ja) * 2007-07-19 2009-02-05 Du Pont Mitsui Polychem Co Ltd 紫外線吸収性ポリマー材料
WO2009123016A1 (fr) * 2008-03-31 2009-10-08 株式会社クレハ Composé phosphonate de cuivre et matière d'absorption du rayonnement infrarouge et stratifié contenant le composé phosphonate de cuivre
JP2010083805A (ja) * 2008-09-30 2010-04-15 Kureha Corp ホスホン酸、ホスホン酸銅化合物、樹脂組成物及び積層体

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JPH0753636A (ja) * 1993-06-30 1995-02-28 Du Pont Mitsui Polychem Co Ltd アイオノマー包装材料
JP2009024085A (ja) * 2007-07-19 2009-02-05 Du Pont Mitsui Polychem Co Ltd 紫外線吸収性ポリマー材料
WO2009123016A1 (fr) * 2008-03-31 2009-10-08 株式会社クレハ Composé phosphonate de cuivre et matière d'absorption du rayonnement infrarouge et stratifié contenant le composé phosphonate de cuivre
JP2010083805A (ja) * 2008-09-30 2010-04-15 Kureha Corp ホスホン酸、ホスホン酸銅化合物、樹脂組成物及び積層体

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WO2014171215A1 (fr) * 2013-04-16 2014-10-23 株式会社クレハ Composition de resine et son utilisation
WO2014175231A1 (fr) * 2013-04-26 2014-10-30 株式会社クレハ Composition de résine et son utilisation
WO2015080184A1 (fr) * 2013-11-29 2015-06-04 株式会社クレハ Composition de résine et son utilisation
WO2019054363A1 (fr) * 2017-09-14 2019-03-21 三井・デュポンポリケミカル株式会社 Composition de résine destinée à un film de couche intermédiaire de verre stratifié ou à un encapsulant de cellule solaire, film de couche intermédiaire de verre stratifié, verre stratifié, encapsulant de cellule solaire, et module de cellule solaire
CN111094435A (zh) * 2017-09-14 2020-05-01 三井—陶氏聚合化学株式会社 夹层玻璃中间膜或太阳能电池密封材料用树脂组合物、夹层玻璃中间膜、夹层玻璃、太阳能电池密封材料以及太阳能电池模块
JPWO2019054363A1 (ja) * 2017-09-14 2020-05-28 三井・ダウポリケミカル株式会社 合わせガラス中間膜または太陽電池封止材用樹脂組成物、合わせガラス中間膜、合わせガラス、太陽電池封止材および太陽電池モジュール
US11628651B2 (en) 2017-09-14 2023-04-18 Dow-Mitsui Polychemicals Co., Ltd. Resin composition for laminated glass interlayer film or solar cell encapsulant, laminated glass interlayer film, laminated glass, solar cell encapsulant, and solar cell module
JP7267200B2 (ja) 2017-09-14 2023-05-01 三井・ダウポリケミカル株式会社 合わせガラス中間膜または太陽電池封止材用樹脂組成物、合わせガラス中間膜、合わせガラス、太陽電池封止材および太陽電池モジュール
WO2022270545A1 (fr) * 2021-06-23 2022-12-29 株式会社クラレ Composition de résine ionomère, feuille de résine et verre feuilleté
WO2022270540A1 (fr) * 2021-06-23 2022-12-29 株式会社クラレ Feuille de résine ayant une couche qui contient une composition de résine ionomère, et verre feuilleté

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