WO2009123020A1 - Composition de sel de cuivre, composition de résine l'utilisant, film absorbant dans l'infrarouge et élément optique - Google Patents

Composition de sel de cuivre, composition de résine l'utilisant, film absorbant dans l'infrarouge et élément optique Download PDF

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WO2009123020A1
WO2009123020A1 PCT/JP2009/056171 JP2009056171W WO2009123020A1 WO 2009123020 A1 WO2009123020 A1 WO 2009123020A1 JP 2009056171 W JP2009056171 W JP 2009056171W WO 2009123020 A1 WO2009123020 A1 WO 2009123020A1
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group
copper salt
resin
copper
infrared absorption
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PCT/JP2009/056171
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English (en)
Japanese (ja)
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留美 佐野
正孝 上遠野
雄一 福島
克一 町田
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株式会社クレハ
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Publication of WO2009123020A1 publication Critical patent/WO2009123020A1/fr

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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • 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
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • 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
    • B32B17/10761—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 vinyl acetal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/06—Surface treatment of glass, not in the form of fibres or filaments, by coating with metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2

Definitions

  • the present invention relates to a copper salt composition, a resin composition using the same, an infrared absorption film, and an optical member.
  • ultraviolet rays and infrared rays are included in sunlight rays that are incident from so-called opening portions such as windows in various buildings and vehicles.
  • Infrared rays having a wavelength of 780 nm or more are also called heat rays, and cause the indoor temperature to rise by being incident from the opening.
  • heat rays In order to solve this problem, in recent years, there has been a demand for a characteristic that shields heat rays while sufficiently taking in visible light, and suppresses an increase in indoor temperature while maintaining brightness.
  • Metal ions can exhibit absorption characteristics with respect to light of a specific wavelength, and are applied to optical materials using the characteristics.
  • copper ions are known to have good absorption characteristics for light in the near infrared region (hereinafter referred to as “near infrared light”) having a large thermal action.
  • near-infrared light is selectively absorbed by the electronic transition of the d-orbit of copper ions, and excellent near-infrared light absorption characteristics are exhibited. Therefore, attempts have been made to impart near-infrared light absorption characteristics by including copper ions in an interlayer film for laminated glass.
  • Patent Document 1 JP-A-2002-006101
  • Patent Document 1 discloses that an optical material contains a phosphonic acid or a phosphinic acid to form a copper salt that hardly undergoes alteration such as decomposition even under high temperature conditions.
  • the present invention has been made in view of such circumstances, and has excellent near-infrared light absorption characteristics and can exhibit high transparency and stability even when mixed with a resin and exposed to high temperatures.
  • An object is to provide a copper salt composition.
  • Another object of the present invention is to provide a resin composition containing the copper salt composition, and an infrared absorption film and a laminate using the resin composition.
  • the present inventors have conducted intensive research, and as a result, when the phosphonic acid copper salt is mixed with a resin by making the phosphonic acid copper salt composition mixed with a specific compound, However, the inventors have found that sufficiently high transparency can be obtained and that excellent thermal stability can be obtained, and the present invention has been completed.
  • R 1 represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, (meth) acryloyloxy
  • An alkyl group or a (meth) acryloyl polyoxyalkyl group, and at least one hydrogen atom in these groups is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde Group, carboxyl group, hydroxyl group, (meth) acryloyl group, (meth) acryloyloxyalkyl group, (meth) acryloyl polyoxyalkyl group or ester group may be substituted.
  • a halogen atom an oxyalkyl
  • the phosphonic acid copper salt itself has high heat resistance as described above, it was difficult to cause deterioration or the like even at a high temperature.
  • copper phosphonate may promote the deterioration of the resin used for the optical material. That is, although deterioration of the phosphonic acid copper salt did not occur under high temperature conditions, the resin was deteriorated, resulting in a decrease in transparency and yellowing of the optical material.
  • the copper salt composition of the present invention contains a phosphonic acid copper salt in the form of particles having a predetermined average particle diameter, and further contains a polysiloxane component in combination with the particles of the phosphonic acid copper salt. Therefore, it is possible to greatly suppress the deterioration of the resin due to the high temperature as described above, and as a result, higher heat resistance than conventional can be obtained. Although it is not always clear about such factors, it is difficult for the polysiloxane component to work with the resin by covering at least a part of the copper phosphonate, and the polysiloxane component causes the resin degradation reaction by the copper salt. It is conceivable to have characteristics that can be suppressed.
  • the copper salt composition of this invention has these specific particle diameters and contains a plasticizer and a dispersing agent in combination, the effect
  • the laminated body of this invention provided with the infrared rays absorption layer which consists of a translucent board
  • a copper salt composition that has excellent near-infrared light absorption characteristics and can exhibit high transparency and stability even when it is mixed with a resin and exposed to high temperatures.
  • a resin composition having high heat resistance, an infrared absorption film and a laminate using the resin composition.
  • the copper salt composition of the present embodiment is a particle composed of a phosphonic acid copper salt formed of a phosphonic acid compound and copper ions and having an average particle size of 0.005 to 0.3 ⁇ m (hereinafter referred to as “phosphonic acid copper salt particles”). And a polysiloxane component comprising a hydrolyzate and / or condensate of alkoxysilane, a plasticizer, and a dispersant.
  • plasticizer a known plasticizer used for adjusting the physical properties of the resin can be applied without particular limitation.
  • a plasticizer for example, the flexibility of the resin is improved, and when applied to an interlayer film or the like of laminated glass, impact absorbability and penetration resistance are improved.
  • plasticizers include known plasticizers such as phosphate ester plasticizers, phthalic acid plasticizers, fatty acid plasticizers, and glycol plasticizers. More specifically, for example, organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are preferably used. It is done.
  • plasticizers may be used alone or in combination of two or more, and are used properly in consideration of compatibility and the like depending on the type of resin to be contained in the resin composition described later.
  • monobasic organic acid esters examples include glycols such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2- Examples thereof include glycol esters obtained by reaction with monobasic organic acids such as ethylhexanoic acid, pelargonic acid (n-nonyl acid) or decyl acid.
  • 3GO, 3GH, 3G7 and the like are preferable.
  • the polybasic organic acid ester is not particularly limited.
  • the polybasic organic acid ester is obtained by reacting a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid with a linear or branched alcohol having 4 to 8 carbon atoms.
  • esters obtained for example, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are suitable.
  • organic phosphate plasticizer examples include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.
  • the dispersant is a component that can be mixed with metal salt particles and the like to suppress aggregation of the particles.
  • examples of such a dispersant include polymer dispersants and phosphate ester dispersants.
  • a polymer dispersant having a structure having an affinity for a copper salt, an organic solvent or a resin (particularly a thermoplastic resin) and having a high light transmittance in the visible light region is desirable.
  • the phosphonic acid copper salt particles are composed of a phosphonic acid copper salt.
  • This phosphonic acid copper salt is formed from a copper ion and a phosphonic acid compound, and has, for example, a form of a copper salt (copper complex) in which a phosphonic acid compound is coordinated to a copper ion.
  • the copper ion in the phosphonic acid copper salt is a divalent copper ion.
  • This copper ion is mixed with a phosphonic acid compound in the form of a copper salt to form a phosphonic acid copper salt.
  • Specific examples of this copper salt include copper acetate anhydrides of organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate and copper citrate, hydration Or an hydrate or hydrate of copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, or copper hydroxide.
  • copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used.
  • these copper salts which are copper ion sources may be used independently, and may be used in multiple combination.
  • the phosphonic acid compound is, for example, a compound represented by the following general formula (1).
  • the group represented by R 1 includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxy group.
  • examples thereof include an aryl group, a (meth) acryloyloxyalkyl group, and a (meth) acryloylpolyoxyalkyl group, and these groups each preferably have 1 to 30 carbon atoms.
  • At least one hydrogen atom in the group is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group, It may be substituted with a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, a (meth) acryloyl polyoxyalkyl group or an ester group.
  • alkylphosphonic acid in which the group represented by R 1 is an alkyl group is preferable.
  • a copper salt composition containing a phosphonic acid copper salt having an alkylphosphonic acid tends to exhibit excellent infrared absorption characteristics and heat resistance.
  • Alkylphosphonic acids include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid Tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, octadecylphosphonic acid and the like.
  • a phosphonic acid compound said thing may be used independently and may be used in combination of multiple types.
  • the phosphonic acid compound is preferably contained in an amount of 0.5 to 3 mol, more preferably 0.8 to 2 mol, per mol of copper ions.
  • the amount of the phosphonic acid compound is 0.5 mol or less, the thermal stability of the copper salt itself is deteriorated.
  • 3 mol or more of a phosphonic acid compound is contained, there is a possibility that thermal deterioration of the resin is caused by an excess of the phosphonic acid compound when it is contained in the resin and thermoformed. That is, the phosphonic acid copper salt particles having the copper ion and the phosphonic acid compound in the above ratio show high infrared absorption characteristics and have excellent heat resistance.
  • the phosphonic acid copper salt particles are particles formed from the copper ions and the phosphonic acid compound as described above, and the average particle diameter is 0.005 to 0.3 ⁇ m.
  • the average particle diameter of the phosphonic acid copper salt particles is less than 0.005 ⁇ m, the cohesive force is increased in the resin composition, and it is difficult to disperse in the resin.
  • the average particle size of the phosphonic acid copper salt particles is preferably 0.005 to 0.25 ⁇ m, and more preferably 0.01 to 0.2 ⁇ m.
  • grains the value obtained by the measurement by a dynamic scattering method is applicable, for example. As an example, this measurement can be performed using N4plus manufactured by Beckman Coulter.
  • the polysiloxane component is a hydrolyzate and / or condensate of alkoxysilane, preferably an alkoxysilane condensate.
  • the hydrolyzate or condensate of alkoxysilane is a product produced by hydrolyzing alkoxysilane molecules by heating alkoxysilane or the like, or a product produced by dehydration condensation between alkoxysilane molecules. It is a thing.
  • the alkoxy silane that is the raw material of the polysiloxane component includes tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, butyl triethoxy silane, octyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -methacryloyloxypropyltrimethoxysilane, ⁇ -methacryloyloxypropyltriethoxy Silicon compounds such as silane, ⁇ -acryloyloxypropyltrimethoxysilane, ⁇ -acryloyloxypropyltrieth
  • the suitable content ratio of each component constituting the copper salt composition is as follows. That is, first, the content of the plasticizer is preferably 1 to 150 parts by mass, more preferably 2 to 100 parts by mass with respect to 1 part by mass of the phosphonic acid copper salt particles, and 2 to 50 parts by mass. More preferably. When the content ratio of the phosphonic acid copper salt particles is less than the above, sufficient infrared absorption characteristics tend not to be obtained when a resin composition is used. On the other hand, when it is more than the above range, the transparency of the resin composition tends to decrease.
  • the content of the polysiloxane component is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 9 parts by mass, with respect to 1 part by mass of the phosphonic acid copper salt particles, and 0.05 More preferably, it is ⁇ 8 parts by mass.
  • the content ratio of the polysiloxane component is less than the above, sufficient heat resistance tends to be not obtained when a resin composition is used.
  • the content is larger than the above range, the transparency of the resin may be lowered due to an excessive polysiloxane component when it is contained in the resin.
  • the content ratio of the dispersant depends on the particle size of the phosphonic acid copper salt particles, but is preferably 0.2 parts by mass or more and less than 50 parts by mass with respect to 1 part by mass of the phosphonic acid copper salt particles.
  • the amount is more preferably 0.5 parts by mass or more and less than 30 parts by mass, and further preferably 1 part by mass or more and less than 15 parts by mass.
  • the blending ratio of the dispersant is less than 0.2 parts by mass, for example, in the step of removing the organic solvent at the time of producing the phosphonic acid copper salt composition, the phosphonic acid copper salt particles are aggregated to disperse. It tends to be insufficient.
  • the phosphonic acid copper salt composition is added to the organic solvent and the dispersant is dissolved, a dispersion in which the phosphonic acid copper salt particles are uniformly dispersed in the organic solvent cannot be obtained. There is a risk that it may be difficult to produce the object.
  • the phosphonic acid copper salt composition is diluted and kneaded with a resin (thermoplastic resin) and molded into a sheet to obtain an infrared absorption film, the haze value may increase.
  • the blending ratio of the dispersant is 50 parts by mass or more, a large amount of the dispersant is contained in the infrared absorption film formed using the phosphonic acid copper salt composition. In particular, there is a possibility that the problem that the impact strength and toughness are lowered tends to occur.
  • Such a copper salt composition can be obtained, for example, by the following method. That is, first, phosphonic acid copper salt particles are formed by a predetermined method, and then the phosphonic acid copper salt particles are mixed with a plasticizer and further dispersed in a predetermined solvent to obtain a copper salt dispersion.
  • the solvent used here is not particularly limited as long as the phosphonic acid copper salt particles can be uniformly dispersed.
  • alcohols such as methanol and ethanol, ketones such as acetone, and aromatics such as toluene and xylene are preferable.
  • alkoxysilane and water are added to the obtained copper salt dispersion and stirred, and the alkoxysilane is hydrolyzed to produce a hydrolyzate and / or a dehydrated condensate.
  • the concentration of the alkoxysilane varies depending on the type of the organic solvent to be dissolved, and thus suitable conditions are set as appropriate.
  • catalysts such as acids and amines, alkanolamines and the like may be used.
  • conditions may be set so that hydrolysis and condensation of the alkoxysilane are favorably generated by applying heat during the reaction.
  • the reaction temperature is preferably 10 to 100 ° C., more preferably 15 to 90 ° C.
  • the solvent used in the above preparation is removed by an evaporator or the like, and the preferred embodiment A copper salt composition is obtained.
  • the manufacturing method of a copper salt composition is not limited above, You may change suitably.
  • the resin composition of this embodiment contains the above-described copper salt composition and a resin.
  • a resin that can favorably disperse the phosphonic acid copper salt and the polysiloxane component in the above-described copper salt composition and is excellent in the property of transmitting visible light is preferable.
  • resins include polyvinyl acetal resin, ethylene-vinyl acetate copolymer (EVA), (meth) acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, norbornene resin, and the like. Can be mentioned.
  • polyvinyl acetal resin is preferable, and polyvinyl butyral (PVB) is particularly preferable.
  • PVB polyvinyl butyral
  • These have excellent adhesion to a light-transmitting substrate in a laminate (laminated glass) described later, and are flexible and difficult to deform depending on temperature. For this reason, the shaping
  • the polyvinyl acetal resin has a characteristic that the above-described copper salt composition is particularly easily dispersed. For this reason, according to the combination of the copper salt composition and the polyvinyl acetal resin, a laminated glass having excellent visible light permeability and durability can be obtained.
  • the polyvinyl acetal resin may be blended in an appropriate combination depending on the required physical properties, or may be a polyvinyl acetal resin obtained by acetalizing a combination of aldehydes during acetalization.
  • the molecular weight, molecular weight distribution, and degree of acetalization of the polyvinyl acetal resin are not particularly limited, but the degree of acetalization is generally 40 to 85%, and the preferred lower limit is 60% and the upper limit is 75%.
  • the polyvinyl acetal resin can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde.
  • the polyvinyl alcohol resin is generally obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol resin having a saponification degree of 80 to 99.8 mol% is generally used.
  • the preferable lower limit of the viscosity average polymerization degree of the polyvinyl alcohol resin is 200, and the upper limit is 3000.
  • the penetration resistance of the laminated glass obtained as it is less than 200 falls. When it exceeds 3000, the moldability of the resin film is deteriorated, and the rigidity of the resin film is excessively increased, so that the workability is deteriorated.
  • a more preferred lower limit is 500 and an upper limit is 2000.
  • the viscosity average degree of polymerization and the degree of saponification of the polyvinyl alcohol resin can be measured based on, for example, JISK 6726 “Testing method for polyvinyl alcohol”.
  • the aldehyde is not particularly limited, and examples thereof include aldehydes having 1 to 10 carbon atoms, and more specifically, for example, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutylartaldehyde. N-hexylaldehyde, n-octylaldehyde, n-nonylaldehyde, n-decylaldehyde, formaldehyde, acetaldehyde, benzaldehyde and the like. Of these, n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable. More preferred is butyraldehyde having 4 carbon atoms.
  • Such a resin composition can be obtained by adding the above-described copper salt composition to these resins and stirring them. And the phosphonic acid copper salt particle
  • each component in the resin composition is as follows. That is, the copper salt composition is preferably in an amount such that the phosphonic acid copper salt particles in the copper salt composition are 0.05 to 30 parts by mass with respect to 100 parts by mass of the resin, and 0.1 to 20 parts by mass. It is more preferable that the amount is as follows. When this ratio is too smaller than the above, the ratio of the phosphonic acid copper salt decreases, and it may be difficult to obtain sufficient infrared absorption characteristics. On the other hand, even if it is too large, the amount of phosphonic acid copper salt particles may increase so that deterioration of the resin due to high temperature cannot be sufficiently suppressed.
  • the resin composition may further contain other components in a range in which the optical characteristics and the heat resistance are not excessively lowered according to the required characteristics.
  • the resin composition may contain an adhesion adjusting agent.
  • an adhesive force regulator may be apply
  • the adhesion adjusting agent include alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids.
  • the organic acid is not particularly limited, and examples thereof include carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid, and formic acid. It does not specifically limit as said inorganic acid, For example, hydrochloric acid, nitric acid, etc. are mentioned. It does not specifically limit as said alkali metal salt and alkaline-earth metal salt, For example, salts, such as potassium, sodium, calcium, magnesium, are mentioned.
  • alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids alkali metal salts and alkaline earth metal salts of organic acids having 2 to 16 carbon atoms are preferable, and more preferably 2 to 16 carbon atoms.
  • Potassium salt and magnesium salt of carboxylic acid are preferable, and more preferably 2 to 16 carbon atoms.
  • the potassium salt and magnesium salt of the carboxylic acid having 2 to 16 carbon atoms are not particularly limited.
  • magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, potassium 2-ethylbutanoate, Magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are preferred. These may be used alone or in combination of two or more.
  • the preferable lower limit of the amount of the alkali metal salt or alkaline earth metal salt of the organic acid or inorganic acid is 0.001 part by weight with respect to 100 parts by weight of the resin, and the upper limit is 0.5 part by weight. If it is less than 0.001 part by weight, the adhesive strength of the peripheral part may be lowered in a high humidity atmosphere. If it exceeds 0.5 parts by weight, the transparency of the film may be lost.
  • a more preferred lower limit is 0.01 parts by weight and an upper limit is 0.2 parts by weight.
  • the resin composition may further contain other additives in addition to the plasticizer and the adhesion modifier.
  • additives include components for adjusting the color tone, components for adjusting physical properties, components for stabilizing the resin composition, and a translucent substrate when forming a laminate described later.
  • Ingredients for improving the adhesion to the surface include additives such as an antioxidant, a surfactant, a flame retardant, an antistatic agent, and a moisture-resistant agent for preventing deterioration due to heat in the extruder may be added as necessary.
  • examples of the component for adjusting the color tone include dyes, pigments, and metal compounds.
  • Components for adjusting physical properties include (meth) acrylic monomers having an ⁇ , ⁇ -unsaturated bond such as styrene, butadiene and vinyl acetate, oligomers having excellent compatibility with (meth) acrylic resins, and the like. Examples thereof include polymers.
  • examples of the component for stabilization include a light stabilizer, a heat stabilizer, an antioxidant, and an ultraviolet absorber.
  • a coupling such as a silane coupling agent such as vinyl silane, acrylic silane, or epoxy silane is used. An agent can be illustrated.
  • ultraviolet light absorber examples include benzoate compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, oxalic anilide compounds, triazine compounds, and the like.
  • benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydrobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4 , 4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone-5,5'-sodium disulfonate, 2,2'-dihydroxy-5-methoxybenzophenone, 2-hydroxy-4-methacryloyl Oxyethylbenzophenone 4-benzoyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone.
  • benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzo Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-butylphenyl) benzotriazole, 2- [2'-hydroxy-3 ' -(3 ′′, 4 ′′, 5 ′′, 6 ′′ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2- (2′-hydro Cis-3 ', 5'-di-t-amylpheny
  • Examples of cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate.
  • Examples of oxalic acid anilide compounds include 2-ethoxy-2 ′. -Ethyl oxalic acid bisanilide and 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid bisanilide.
  • Examples of triazine compounds include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.
  • a hindered amine light stabilizer HALS
  • a Ni compound can be applied as the light stabilizer.
  • HALS hindered amine light stabilizer
  • the stability to light tends to be very good.
  • HALS includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl- 1,3,8-triazaspiro [4,5] decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t -Butyl-4-hydroxy Ndyl) -2-n-butyl
  • Ni-based light stabilizers include [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel (II), nickel dibutyldithiocarbonate, [2,2 '-Thio-bis (4-t-octylphenolate)]-butylamine-nickel (II) and the like.
  • optical member By using the resin composition described above, an optical member having excellent properties for blocking near infrared light can be obtained.
  • Examples of such an optical member include first and second forms shown below. 1st form: The sheet-like molding obtained by processing a resin composition. 2nd form: The laminated body which has a translucent board
  • the optical member of the 1st form is a sheet-like molded product which consists of a resin composition mentioned above, and specifically, a sheet and a film are mentioned.
  • This sheet-like molded product exhibits high infrared absorption characteristics and is applied to various uses as an infrared absorption film.
  • the sheet is a thin plate having a thickness exceeding 250 ⁇ m.
  • the film is a thin film having a thickness of 5 to 250 ⁇ m.
  • the optical member of the second form is a laminate having a translucent substrate and an infrared absorption layer composed of an infrared absorption film made of a resin composition provided adjacent to the translucent substrate. is there.
  • the light-transmitting substrate is a substrate having transparency to visible light, for example, a substrate capable of transmitting light having a wavelength of 550 nm by 50% or more.
  • the material constituting the light-transmitting substrate is not particularly limited as long as it is a material having visible light permeability, and can be appropriately selected according to the use of the optical member. From the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, etc., glass or plastic is preferably used. Examples of the glass include inorganic glass and organic glass. Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin and the like. When there are a plurality of light-transmitting substrates, each substrate may be composed of the same type of material or may be composed of different materials.
  • Such a laminate is formed by, for example, forming a sheet or film (infrared absorbing film) similar to the optical member of the first embodiment described above, and then bonding these sheet and the light transmitting substrate together.
  • a means for bonding by pressurization or reduced pressure such as a press method, a multi-roll method, a decompression method, a means for adhesion by heating using an autoclave, or a combination of these is used. be able to.
  • a method of directly forming an infrared absorption layer on a translucent substrate can be applied in addition to a method of pasting sheets formed in advance.
  • the above-described resin composition is dispersed in an appropriate solvent to form a coating agent, and this solution is applied to a light-transmitting substrate, and then the solvent is evaporated, whereby the light-transmitting substrate is coated.
  • Examples thereof include a method for forming a thin film, a covering or a thin layer made of a resin composition. The thin film formed in this way is called a coating.
  • various auxiliary agents such as a leveling agent and an antifoaming agent are added to the coating described above. You may add in an agent.
  • the optical member of the second form is not limited to one having the above-described light-transmitting substrate and one infrared absorption layer, but may have a plurality of these layers.
  • a substrate provided with a pair of translucent substrates and an intermediate film (infrared absorbing layer) made of the infrared absorbing film disposed between the translucent substrates is exemplified.
  • Such a laminate is a so-called laminated glass.
  • FIG. 1 is a diagram schematically showing a cross-sectional configuration of a laminated glass.
  • a laminated glass 10 shown in FIG. 1 includes a pair of translucent substrates 1 and an intermediate film 2 (infrared absorbing layer) sandwiched between the pair of translucent substrates 1.
  • the intermediate film 2 is an infrared absorption film made of the above resin composition, and the same light-transmitting substrate 1 as described above can be applied.
  • the so-called blocking phenomenon in which the sheets are bonded to each other to form a lump at the time of storage does not occur on the intermediate film 2 or the film is removed in the pre-compression bonding. It is required to have good temper. When these requirements are satisfied, workability when the translucent substrate 1 and the sheet are overlapped is improved, and, for example, visible light permeability due to bubbles generated due to insufficient deaeration, etc. Can be prevented.
  • the laminated glass 10 is required to have excellent properties of transmitting light in the visible light region in addition to the property of blocking near-infrared light. In order to obtain such excellent visible light transmittance, it is preferable that bubbles are not formed between the translucent substrate 1 and the intermediate film 2 as much as possible.
  • emboss on the surface As one of means for reducing bubbles in this manner, a method using an intermediate film 2 having a large number of minute irregularities called emboss on the surface is known. According to the intermediate film 2 to which such embossing is applied, the degassing property in the above-described pre-compression bonding step or the like becomes extremely good. As a result, the laminated glass 10 has less visible light transmittance deterioration due to bubbles.
  • embossed forms include various uneven patterns composed of a large number of convex portions and a large number of concave portions with respect to these convex portions, and various types of grooves composed of a large number of convex strips and a large number of concave grooves corresponding to these convex strips.
  • embossed shapes with various values for various shape factors such as uneven patterns, roughness, arrangement, size, etc.
  • JP-A-6-198809 in which the size of the convex portion is changed and the size and arrangement thereof are defined, and in JP-A-9-40444, Surface roughness of 20-50 ⁇ m, described in JP-A-9-295839, arranged so that ridges intersect, or described in JP-A-2003-48762, The thing which formed the smaller convex part on the main convex part is mentioned.
  • JP 2003-528749 A uses a melt fracture generated at the time of resin molding
  • JP 2002-505211, and JP 9-502755 JP include crosslinked PVB particles and nucleating agents. A method of using is proposed.
  • the sound insulation performance of a glass plate generally used as a translucent substrate for laminated glass tends to be remarkably lowered due to the coincidence effect in a frequency region centered on 2000 Hz.
  • the coincidence effect means that when a sound wave is incident on a glass plate, the transverse wave propagates through the glass plate due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs. Therefore, in general laminated glass, it is difficult to avoid a decrease in sound insulation performance due to such a coincidence effect in a frequency region centered on 2000 Hz, and improvement of this point is demanded.
  • the sound insulation performance depends on the dynamic viscoelasticity of the interlayer film 2, and in particular, it may be influenced by the loss tangent, which is the ratio of the storage elastic modulus and the loss elastic modulus. Moreover, the sound insulation performance of the laminated glass 10 can be enhanced.
  • the sound insulation performance of the laminated glass 10 can be enhanced over a wide temperature range by combining two or more different resins to form an intermediate film.
  • a method of blending a plurality of types of resins described in JP-A-2001-206742, and a method of laminating a plurality of types of resins described in JP-A-2001-206741 and JP-A-2001-226152 For example, a method of blending a plurality of types of resins described in JP-A-2001-206742, and a method of laminating a plurality of types of resins described in JP-A-2001-206741 and JP-A-2001-226152. And a method described in Japanese Patent Application Laid-Open No. 2001-192243 for imparting a deflection to the amount of plasticizer in the intermediate film.
  • the laminated glass 10 further has a characteristic that can exhibit a heat shielding property by absorbing near infrared light as described above.
  • the interlayer film 2 further contains a metal having a heat shielding function, oxide fine particles, metal boride, or the like, or a layer containing these is laminated glass.
  • transducing into this laminated structure is mentioned. As such a method, for example, JP 2001-206743 A, JP 2001-261383 A, JP 2001-302289 A, JP 2004-244613 A, WO 02/060988, etc. Can be applied.
  • oxide fine particles examples include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO).
  • boride fine particles YB 6 , LaB 6 , CeB 6 , PrB 6 , NdB 6 , SmB 6 , EuB 6 , GdB 6 , TbB 6 , DyB 6 , HoB 6 , ErB 6 , TbB 6 , TmB 6 , TmB 6 6 , boride fine particles such as ZrB 6 , BaB 6 , SrB 6 , CaB 6 and the like.
  • the intermediate film 2 containing the oxide fine particles described above tends to have low visible light transmittance, so that the particle diameter of the oxide fine particles is regulated (Japanese Patent No. 271589, JP 2002). No. 293583), a method for maintaining good translucency by enhancing dispersibility may be applied.
  • known fine particle dispersion techniques such as mechanically dispersing the fine particles or using a dispersant can be applied.
  • a method of improving the heat shielding property of the laminated glass in addition to the method of containing the oxide fine particles and the like described above, for example, a method of containing a dye / pigment having an organic heat shielding function, or a heat shielding performance A method using a translucent substrate is also included.
  • Examples of the former method of containing a dye / pigment having an organic heat-shielding function include methods described in JP-A-7-157344 and JP-A-319271.
  • dyes and pigments include phthalocyanine, anthraquinone, naphthoquinone, cyanine, naphthalocyanine, pyrrole, imonium, dithiol, and mercaptonaphthol dyes and pigments. .
  • Examples of the light-transmitting substrate having the heat shielding performance of the latter include, for example, Fe-containing glass (for example, green glass) described in JP-A-2001-151539, JP-A-2001-261384. And a glass plate in which a metal and a metal oxide are laminated as described in JP-A-2001-226148.
  • the laminated glass of the above-described embodiment exhibits the property of blocking near-infrared light, which is a heat ray, by the resin composition contained in the intermediate film absorbing light in the near-infrared light region.
  • the laminated glass (laminate) of the present invention is a layer having a property of reflecting near infrared light in addition to the infrared absorption layer (reflection) for the purpose of further improving the near infrared light blocking property. It may further have a layer).
  • FIG. 2 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer.
  • the laminated glass 20 has a structure including a translucent substrate 21, an infrared absorption layer 22, a reflective layer 23, and a translucent substrate 21 in this order.
  • the same thing as the thing in the laminated glass 10 mentioned above is applicable for the translucent board
  • substrate 21 and the infrared rays absorption layer 22 is applicable for the translucent board
  • Examples of the reflective layer 23 include layers composed of metals and metal oxides. Specifically, for example, gold, silver, copper, tin, aluminum, nickel, palladium, silicon, chromium, titanium, indium, antimony Examples thereof include simple metals such as metals, alloys, mixtures, and oxides.
  • the laminated glass 20 having such a reflective layer 23 can be manufactured as follows, for example. That is, first, a substrate provided with a reflective layer 23 on one surface of a translucent substrate 21 is prepared. Here, as a method of forming the reflective layer 23 on the translucent substrate 21, a method of depositing a metal or a metal oxide on the translucent substrate 21, or the like can be given. Next, the translucent substrate 21 on which the reflective layer 23 is formed is disposed on one surface side of the sheet to be the infrared absorption layer 22 so that the reflective layer 23 is in contact with the other surface side. Only the optical substrate 21 is disposed. And the laminated glass 20 can be obtained by crimping these.
  • the adhesion between the reflection layer 23 and the infrared absorption layer 22 may be lowered.
  • the translucent substrate 21 is easily peeled and scattered, which causes a problem in terms of safety.
  • the resin component contained in the infrared absorption layer 22 is polyvinyl acetal
  • a layer made of polyvinyl acetal having a higher acetal degree than the infrared absorption layer 22 special JP-A-7-187726, JP-A-8-337446
  • a layer made of PVB having an acetoxy group in a predetermined ratio JP-A-8-337445
  • a layer made of a predetermined silicone oil JP-A-7-374) 314609 public information
  • the reflective layer 23 includes JP 09-506837, JP 2000-506082, JP 2000-506084, 2004-525403, JP It is also possible to use a polymer multilayer film that reflects a specific wavelength by utilizing light interference, as shown in 2003-515754, JP-A-2002-231038, JP-T-2004-503402, and the like.
  • a reflection layer does not necessarily need to be provided between the translucent board
  • the layers When the layers are formed, it may be in a form provided between these layers.
  • FIG. 3 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer between a plurality of layers provided between translucent substrates.
  • the laminated glass 30 has a structure including a translucent substrate 31, an infrared absorption layer 32, a reflection layer 33, a resin layer 34, an infrared absorption layer 32, and a translucent substrate 31 in this order.
  • substrate 31, the infrared absorption layer 32, and the reflection layer 33 is applicable as the translucent board
  • the laminated glass 30 having such a structure it is sufficient that at least one infrared absorption layer 32 is provided.
  • one of the infrared absorption layers 32 described above absorbs near infrared light.
  • the layer which consists of a resin material which does not have the characteristic to do may be sufficient.
  • the laminated glass by providing a reflection layer in addition to the infrared absorption layer (intermediate film), it is possible to give the laminated glass a more excellent property of blocking near-infrared light by the effect of both layers. it can. Moreover, if the method for improving the adhesion between the reflective layer and the infrared absorbing layer as described above is employed, a laminated glass having excellent strength in addition to the near infrared light blocking property can be obtained. Is also possible.
  • a laminated body such as laminated glass having the above-described configuration
  • an infrared absorption layer that is an intermediate film develops near-infrared light absorption characteristics.
  • Heat rays in the light region (wavelength of about 700 to 1200 nm) are blocked.
  • light in this wavelength range tends to feel the irritating and exciting heat that burns the skin, but the light transmitted through the above-mentioned laminate is blocked by such near-infrared light. Therefore, it is mainly visible light. Therefore, if such a laminated body is used for a window material or the like, it is possible to suppress an increase in indoor or indoor temperature while efficiently capturing visible light.
  • the laminated glass having the above-described configuration includes an intermediate film obtained using a copper salt composition containing phosphonic acid copper salt particles and a polysiloxane component.
  • this intermediate film since deterioration of the phosphonate copper salt particles themselves and deterioration of the resin due to the phosphonate copper salt particles are greatly suppressed even at high temperatures, the laminated glass provided with such an intermediate film is a window material. Even when it is used for a long period of time and exposed to high temperatures, the infrared absorption characteristics and transparency can be maintained over a long period of time, and coloring due to long-term use is unlikely to occur.
  • the laminated glass preferably has a haze of 50% or less, more preferably 40% or less, and even more preferably 35% or less. If it exceeds 50%, the translucency of the laminated glass tends to decrease, and the visible light intake tends to be insufficient.
  • the laminated body (laminated glass) of the above-described embodiment has excellent near-infrared light blocking performance, building materials (construction) for taking in natural light such as sunlight and other external light (For example, window materials for automobiles, ships, aircraft or train (railway) vehicles, canopies for passages such as arcades, curtains, canopies for carports and garages, windows or walls for solariums) Window materials for show windows and showcases, tents or window materials, blinds, roofing materials for stationary and temporary housing, skylights and other window materials, coating materials for painted surfaces such as road signs, sunscreen materials such as parasols, etc. It can be suitably used for various members that need to be shielded from heat rays.
  • Example 1 (Preparation of copper salt composition) First, a dispersion in which ethylphosphonic acid copper salt having an average particle diameter of 165 nm was dispersed in triethylene glycol bis-2-ethylhexanate was diluted with ethanol to obtain a copper salt dispersion. Next, tetraethoxylane (TEOS) was further added to the copper salt dispersion and stirred. Then, after further adding water to this mixed solution and stirring at 80 ° C. for 4 hours, ethanol is distilled off by a rotary evaporator to obtain a copper salt composition containing an ethylphosphonic acid copper salt and a polysiloxane component. It was.
  • TEOS tetraethoxylane
  • Example 1 An infrared absorption film was produced in the same manner as in Example 1 except that the copper salt composition was obtained without adding TEOS to the copper salt dispersion.
  • Example 1 The infrared absorption films obtained in Example 1 and Comparative Example 1 were each subjected to a high temperature treatment that was pressed at 200 ° C. for 15 minutes.
  • each infrared absorption film was produced using the thing before performing high temperature processing, and the thing after performing high temperature processing, respectively. That is, each infrared absorbing film is sandwiched between a pair of glass slides (length 76 mm ⁇ width 26 mm ⁇ thickness 1 mm), which are translucent substrates, and these are pressure-bonded in an autoclave at 130 ° C. and 1.5 MPa for 30 minutes. As a result, four types of laminated glass were obtained as the infrared absorption film of Example 1 or Comparative Example 1, respectively, before and after the high temperature treatment as an intermediate film.
  • the YI value is calculated according to the following formula (A) based on the tristimulus values (X, Y, Z) of the XYZ color system obtained by a method based on JIS Z8701 by measurement using a spectrophotometer. can do.
  • YI value (128X ⁇ 106Z) / Y (A)
  • the laminated glass provided with the infrared absorption film of Example 1 obtained using the copper salt composition corresponding to the present invention is the infrared absorption film of Comparative Examples 1 and 2 not corresponding to the present invention. It was confirmed that the change in spectral characteristics was small before and after the high-temperature treatment was performed on the infrared absorption film, in particular, the decrease in the transmittance of light in the visible region was small compared to the laminated glass provided with. Further, from Table 1, the laminated glass using the infrared absorption film of Example 1 has sufficient transparency because of its small haze, and also has a small ⁇ YI value compared to that of the comparative example. It was confirmed that yellowing due to high-temperature treatment hardly occurred. From the above results, it was found that the infrared absorption films of the examples were excellent in infrared absorption characteristics and transparency and had high heat resistance.

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Abstract

L'invention porte sur une composition de sel de cuivre qui permet la formation d'un matériau optique qui a une excellente résistance à la chaleur, tout en présentant une suppression de la diminution de transparence ou d'une mauvaise coloration même à des températures élevées. La composition de sel de cuivre contient des particules ayant un diamètre moyen de particule de 0,005 à 0,3 μm et composées d'un phosphonate de cuivre qui est formé à partir d'un composé de l'acide phosphonique représenté par la formule générale (1) et des ions du cuivre, d'un composant polysiloxane composé d'un produit d'hydrolyse et/ou d'un produit de condensation d'un alcoxysilane, d'un plastifiant et d'un agent dispersant. [Dans la formule, R1 représente un groupe alkyle, un groupe cycloalkyle, un groupe alcényle, un groupe alcynyle, un groupe aryle, un groupe allyle, un groupe oxyalkyle, un groupe polyoxyalkyle, un groupe oxyaryle, un groupe polyoxyaryle, un groupe (méth)acryloyloxyalkyle ou un groupe (méth)acryloylpolyoxyalkyle, qui peuvent avoir un substituant].
PCT/JP2009/056171 2008-03-31 2009-03-26 Composition de sel de cuivre, composition de résine l'utilisant, film absorbant dans l'infrarouge et élément optique WO2009123020A1 (fr)

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