WO2014119618A1 - Procédé pour la production d'un absorbant des infrarouges proches, absorbant des infrarouges proches et son utilisation - Google Patents

Procédé pour la production d'un absorbant des infrarouges proches, absorbant des infrarouges proches et son utilisation Download PDF

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Publication number
WO2014119618A1
WO2014119618A1 PCT/JP2014/051969 JP2014051969W WO2014119618A1 WO 2014119618 A1 WO2014119618 A1 WO 2014119618A1 JP 2014051969 W JP2014051969 W JP 2014051969W WO 2014119618 A1 WO2014119618 A1 WO 2014119618A1
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WIPO (PCT)
Prior art keywords
resin
solvent
copper
infrared absorber
complex
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PCT/JP2014/051969
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English (en)
Japanese (ja)
Inventor
巨樹 岩間
町田　克一
則之 荒川
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株式会社クレハ
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Priority to JP2014559718A priority Critical patent/JPWO2014119618A1/ja
Publication of WO2014119618A1 publication Critical patent/WO2014119618A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • 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
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • 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 method for producing a near-infrared absorber, a near-infrared absorber obtained by the production method, and uses thereof.
  • Metal ions are known to have unique spectral characteristics, such as exhibiting absorption characteristics with respect to light of a specific wavelength, and are applied to optical materials using these characteristics.
  • an optical material that can sufficiently exhibit the spectral characteristics peculiar to metal ions at least one of a predetermined phosphonic acid monoester compound, a predetermined phosphinic acid compound, a predetermined phosphoric acid diester compound, and a predetermined phosphoric acid monoester compound
  • An optical material comprising a compound, a predetermined phosphonic acid compound, and a metal ion such as a copper ion is known (for example, see Patent Document 1).
  • near-infrared In general, copper ions among metal ions are known to have excellent absorption characteristics of light in the near-infrared region (hereinafter also referred to as “near-infrared”), and optical materials containing copper ions are near-infrared absorbers. It was used as.
  • the near-infrared absorber together with a resin and apply it to a window material or the like.
  • the visible light transmittance hereinafter also referred to as transparency
  • the near-infrared absorber disclosed in Patent Document 2 has a small particle size, it is disclosed that an optical material using the near-infrared absorber is excellent in transparency and that the optical material is also excellent in heat resistance. Yes.
  • Patent Literature 2 a step of reacting a mixture containing a specific phosphonic acid compound and a specific phosphate ester compound with a copper salt in a first solvent to obtain a reaction mixture, and at least a first mixture from the reaction mixture.
  • the near-infrared absorber is manufactured by the manufacturing method which has the process of removing a solvent, and the mixing process of mixing the reaction mixture from which the 1st solvent was removed with the 2nd solvent.
  • Patent Document 2 in the step of obtaining the reaction mixture, by reacting the specific phosphonic acid compound with a copper salt in the presence of the specific phosphate ester compound, fine particulate copper phosphonate. Manufactures salt.
  • the present invention gradually The particle size of the resulting particulate phosphonic acid copper salt increases, and when the phosphonic acid copper salt having an increased particle size is used together with a resin, the transparency tends to deteriorate or the haze tends to increase. I found out.
  • the present inventors have reused the solvent used in reacting the phosphonic acid compound and the copper salt under specific conditions, together with the resin. It has been found that a near-infrared absorber having excellent transparency when used can be stably produced, and the present invention has been completed.
  • the method for producing a near-infrared absorber of the present invention comprises mixing a phosphonic acid compound represented by the following general formula (1), a phosphoric ester compound dispersant, and a copper salt in a solvent, Step A for obtaining a reaction mixture containing an infrared absorber, Step B for recovering a solvent from the reaction mixture, and Step C using the solvent recovered in Step B as a solvent for Step A,
  • the solvent used in is an organic solvent having a water content of 0 to 8.0% by mass.
  • 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 fluorine having 1 to 20 carbon atoms. Represents an alkyl group.
  • the organic solvent includes at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, N, N-dimethylformamide, and tetrahydrofuran, and at least selected from methanol and ethanol. More preferably, it contains one organic solvent.
  • the step B is preferably a step of recovering the solvent as a fraction by distilling the reaction mixture under reduced pressure.
  • the near-infrared absorber of this invention is obtained by the said manufacturing method.
  • the resin composition of this invention contains the said near-infrared absorber and resin.
  • the resin is at least one selected from polyvinyl acetal resin, ethylene-vinyl acetate copolymer, (meth) acrylic acid resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, and norbornene resin.
  • a resin is preferable, and a polyvinyl acetal resin or an ethylene-vinyl acetate copolymer is more preferable.
  • the interlayer film for laminated glass of the present invention is formed from the resin composition.
  • the laminated glass of the present invention has the interlayer film for laminated glass.
  • the manufacturing method of the near-infrared absorber of the present invention includes reusing a solvent used when reacting a phosphonic acid compound and a copper salt, and a solvent used when reacting a phosphonic acid compound and a copper salt.
  • a solvent used when reacting a phosphonic acid compound and a copper salt By setting the water content within a specific range, it is possible to stably produce a near infrared absorber that is excellent in transparency when used together with a resin.
  • the manufacturing method of the near-infrared absorber of this invention mixes the phosphonic acid compound represented by following General formula (1), a phosphate ester compound dispersing agent, and a copper salt in a solvent, and absorbs near-infrared rays.
  • Used in Step A including Step A for obtaining a reaction mixture containing an agent, Step B for recovering a solvent from the reaction mixture, and Step C using the solvent recovered in Step B as a solvent for Step A
  • the solvent to be used is an organic solvent having a water content of 0 to 8.0% by mass.
  • 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 fluorine having 1 to 20 carbon atoms. Represents an alkyl group.
  • Step A In the method for producing a near-infrared absorber of the present invention, first, a phosphonic acid compound represented by the general formula (1), a phosphate ester compound dispersant, and a copper salt are mixed in a solvent, The process A which obtains the reaction mixture containing an infrared absorber is performed.
  • the “phosphonic acid compound represented by the general formula (1)” is also referred to as “specific phosphonic acid compound”.
  • the near-infrared absorber obtained in step A is considered to have near-infrared absorption characteristics mainly due to the copper ions of the phosphonic acid copper salt obtained by the reaction between the specific phosphonic acid compound and the copper salt.
  • the phosphonic acid copper salt is considered to be maintained in a very fine state by the phosphate ester compound dispersant.
  • the copper phosphonate is represented by the following general formula (3).
  • the near-infrared absorber obtained in Step A is mainly coordinated with the specific phosphonic acid compound with respect to copper ions, and further the phosphate compound dispersant is present therearound.
  • the phosphate ester compound dispersant is coordinated with a part of the copper ions.
  • the copper ion in the near-infrared absorber is excellent in stability to heat or the like.
  • the resin composition containing the near-infrared absorber and the resin is thermoformed. Even when the resin is used, the resin is not affected by copper ions, and is less colored and excellent in transparency.
  • 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 fluorine having 1 to 20 carbon atoms. Represents an alkyl group.
  • R 11 in the general formulas (1) and (3) is hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl.
  • dodecyl group dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, perfluoroethyl group, perfluoropropyl group, perfluoro-n-butyl group, perfluorohexyl group, perfluorooctyl Group, perfluorodecyl group and the like.
  • the R 11 in the general formulas (1) and (3) is a group having a large number of carbon atoms or a group having a long molecular chain. Since dispersibility tends to decrease, R 11 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms.
  • the phosphate ester compound dispersant used in the present invention is not particularly limited as long as it is a phosphate ester compound used as a dispersant.
  • at least 1 sort (s) of phosphate ester compound selected from the phosphate ester compound represented by the following general formula (2b) is used.
  • R 21 , R 22 and R 23 are monovalent groups represented by — (CH 2 CH 2 O) n R 5 ; n is an integer of 2 to 65, 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. ]
  • R 21 , R 22 and R 23 is a monovalent group (polyoxyalkyl group) represented by — (CH 2 CH 2 O) n R 5 .
  • n is an integer of 2 to 65, preferably an integer of 4 to 65, more preferably 4 to 45, and particularly preferably an integer of 6 to 45.
  • n is less than 2
  • the molded product is produced using the near-infrared absorbent of the present invention together with a resin, the transparency of the molded product becomes insufficient.
  • n exceeds 65 the amount of the phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, 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 8 to 20 carbon atoms. Is more preferable, and 12 to 20 alkyl groups are particularly preferable.
  • R 5 is a group having less than 6 carbon atoms, the transparency of the molded article becomes insufficient. Further, if R 5 is a group having more than 25 carbon atoms, the amount of the phosphoric acid ester compound necessary for obtaining a molded article having sufficient transparency increases, resulting in high costs.
  • a phosphate ester compound represented by the general formula (2a) When obtaining a near-infrared absorber in the step A, it is preferable to use at least one of a phosphate ester compound represented by the general formula (2a) and a phosphate ester compound represented by the general formula (2b). However, it is more preferable to use both the phosphate compound represented by the general formula (2a) and the phosphate compound represented by the general formula (2b).
  • the phosphoric acid ester compound represented by the general formula (2a) and the phosphoric acid ester compound represented by the general formula (2b) because the molded article tends to be excellent in transparency and heat resistance.
  • the phosphate compound represented by the general formula (2a) is used, the phosphate compound represented by the general formula (2a)
  • the ratio of the phosphoric acid ester compound represented by the general formula (2b) is not particularly limited, but is usually 10:90 to 90:10 in molar ratio ((2a) :( 2b)).
  • a phosphate ester compound represented by the said General formula (2a) it may be used individually by 1 type, or 2 or more types may be used, As a phosphate ester compound represented by the said General formula (2b) May be used alone or in combination of two or more.
  • phosphate esters can be used as the phosphate ester compound dispersant.
  • examples of other phosphate esters include phosphate triesters, and these phosphate triesters may be used alone or together with the specific phosphate ester compound.
  • phosphate ester compound selected from the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b), commercially available phosphoric acid An ester compound can also be used.
  • the copper salt a copper salt capable of supplying divalent copper ions is usually used.
  • the copper salt what is necessary is just copper salts other than the phosphonic acid copper salt represented by the said General formula (3).
  • 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.
  • Salt, hydrate or hydrate of copper salt of organic acid 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.
  • copper salt you may use individually by 1 type, or may use 2 or more types.
  • the copper salt anhydrous copper acetate and copper acetate monohydrate are preferably used from the viewpoint of solubility and removal of by-products.
  • the near-infrared absorber obtained in the step A it is considered that the phosphonic acid copper salt obtained by reacting the specific phosphonic acid compound and the copper salt is present, and further, the phosphate ester compound dispersant is present therearound. It is also considered that there is a phosphonic acid copper salt in which a part of the specific phosphonic acid compound constituting the phosphonic acid copper salt is replaced with the phosphoric acid ester compound dispersant.
  • the amount of each component used in step A is as follows.
  • the specific phosphonic acid compound is preferably used in an amount of 5 mol or more, more preferably 8 to 100 mol, and particularly preferably 10 to 80 mol, per mol of the phosphate ester compound dispersant. If it is less than 5 mol, the near-infrared absorption characteristics of the molded article may deteriorate, or the heat resistance may decrease.
  • the specific phosphonic acid compound is preferably 0.4 mol or more, more preferably 0.5 to 1.5 mol, and more preferably 0.7 to 1 mol per mol of copper in the copper salt. Particularly preferred is 2 moles. Within the said range, since the transparency and heat resistance of a molded object are especially excellent, it is preferable.
  • step A as described above, the specific phosphonic acid compound, the phosphate ester compound dispersant, and the copper salt are mixed in a solvent to obtain a reaction mixture containing a near-infrared absorber.
  • the following reactions are considered to occur.
  • the specific phosphonic acid compound reacts with the copper salt mainly in the presence of the phosphate ester compound dispersant, and by the reaction, particulate copper phosphonate that does not dissolve in the solvent. A salt is formed. Since the phosphate ester compound dispersant can act as a good dispersant during the reaction, the phosphonic acid copper salt can maintain high dispersibility and suppress aggregation.
  • step A not only the reaction between the specific phosphonic acid compound and the copper salt, but also, for example, the phosphate ester compound dispersant and the copper salt may react.
  • the specific phosphonic acid compound, the specific phosphate ester compound, and a part of the copper salt may remain without reacting.
  • an organic solvent having a water content of 0 to 8.0% by mass is used as the solvent used in Step A.
  • the particle diameter of the obtained near-infrared absorber can be controlled to 10 to 150 nm, and a resin composition containing near-infrared fine particles and a resin is used. Even when a molded body is obtained, it is possible to produce a near-infrared absorber having low haze and excellent transparency.
  • the water content is preferably 0 to 4.0% by mass and preferably 0 to 2.5% by mass when the organic solvent is ethanol or modified ethanol from the viewpoint of preventing aggregation of near-infrared absorber particles.
  • the organic solvent is methanol, it is preferably 0 to 8.0% by mass, and more preferably 0 to 5.0% by mass.
  • the organic solvent preferably contains at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, N, N-dimethylformamide (DMF), and tetrahydrofuran (THF). Further, from the viewpoint of reactivity, it preferably contains at least one organic solvent selected from methanol, ethanol, THF, and DMF, and more preferably contains at least one organic solvent selected from methanol and ethanol. preferable. As said organic solvent, only these organic solvents may be contained and the other organic solvent may be included.
  • the organic solvent is at least one organic solvent selected from methanol, ethanol, isopropyl alcohol, n-butanol, DMF, and THF (preferably at least one selected from methanol, ethanol, THF, and DMF).
  • the organic solvent is usually 0 to 50 parts by mass, preferably 0 to 30 parts by mass with respect to 100 parts by mass of the organic solvent (more preferably at least one organic solvent selected from methanol and ethanol). May be included.
  • specific examples thereof include denatured ethanol containing ethanol and a small amount of other organic solvents.
  • the denatured ethanol contains 3 to 50 parts by mass, preferably 3 to 30 parts by mass of other organic solvents with respect to 100 parts by mass of ethanol.
  • Examples of the modified ethanol include methanol-modified ethanol, isopropyl alcohol-modified ethanol, and toluene-modified ethanol.
  • Step A is usually 0 to 80 ° C., preferably 10 to 60 ° C., more preferably room temperature to 60 ° C., particularly preferably 20 to 40 ° C., usually 0.5 to 60 hours, preferably Is carried out for 0.5 to 30 hours, more preferably 0.5 to 20 hours, particularly preferably 1 to 15 hours.
  • a reaction mixture containing a near infrared absorber is obtained.
  • the reaction mixture may contain a solvent, a by-product depending on the raw material used, an unreacted raw material, and the like.
  • Step B In the manufacturing method of the near-infrared absorber of this invention, the process B which collect
  • step A As a method for recovering the solvent from the reaction mixture obtained in step A, for example, a method in which the solid content in the reaction mixture is precipitated and the solvent is recovered as a supernatant, and the solvent is recovered as a fraction by distillation of the reaction mixture. The method of doing is mentioned.
  • Examples of the method for precipitating the solid content include a method for precipitating the solid content by allowing the reaction mixture to stand, and a method for precipitating the solid content by centrifuging the reaction mixture.
  • a method of recovering the solvent a method of recovering the solvent as a fraction by distilling the reaction mixture is preferable from the viewpoint that a general apparatus can be used.
  • step B is preferably a step of recovering the solvent as a fraction by distilling the reaction mixture under reduced pressure.
  • the vacuum distillation is usually performed at a pressure of 0.01 to 15 kPa.
  • the outflow temperature of the fraction varies depending on the type and pressure of the organic solvent, but is usually 30 to 150 ° C.
  • Step C In the manufacturing method of the near-infrared absorber of this invention, the process C which uses the solvent collect
  • the solvent recovered in step B is not particularly limited as a specific method for use in step A.
  • the recovered solvent may be reused in the next batch production, or in continuous production. You may reuse as a solvent.
  • the manufacturing method of the near-infrared absorber of the present invention is an excellent manufacturing method from the viewpoint of resource reduction and cost reduction because the solvent can be used repeatedly.
  • a solvent is repeatedly used, there exists a tendency for the water content of the solvent collect
  • the water content of the solvent recovered in step B exceeds the above range, or when it is desired to reduce the water content of the solvent, replace part or all of the recovered solvent with a new organic solvent having a low water content.
  • a treatment such as distillation or addition of a dehydrating agent may be performed before use in the step A.
  • a near-infrared absorber can be manufactured by the above-mentioned method.
  • Step B for recovering the solvent from the reaction mixture obtained in Step A is performed, and the reaction mixture from which the solvent obtained in Step B is recovered is the aforementioned. It is a near-infrared absorber containing the phosphonic acid copper salt.
  • the reaction mixture from which the solvent has been recovered may be used as it is as a near-infrared absorber, or may be used as a near-infrared absorber after further steps.
  • a step of dispersing the reaction mixture from which the solvent has been recovered in a dispersion medium and removing the dispersion medium may be performed.
  • the reaction mixture from which the solvent has been recovered may be dispersed in a dispersion medium and used as a near-infrared absorber dispersion for each application.
  • dispersion medium examples include toluene, xylene, methanol, tetrahydrofuran (THF), dimethylformamide (DMF), methylene chloride, chloroform, triethylene glycol bis (2-ethylhexanoate), and the like. May be used singly or in combination of two or more.
  • the near-infrared absorber of this invention is obtained by the manufacturing method of the above-mentioned near-infrared absorber. Since the near-infrared absorber of the present invention is obtained by the above production method and is excellent in transparency when used together with a resin, the resin composition comprising the near-infrared absorber and the resin can be used for various kinds of interlayer films for laminated glass, etc. It is possible to manufacture a molded object suitably.
  • the average particle size of the near infrared absorber of the present invention is preferably 10 to 150 nm, more preferably 20 to 140 nm.
  • the resin composition of this invention contains the above-mentioned near-infrared absorber and resin.
  • Examples of the method for producing the resin composition include a method of obtaining a resin composition by mixing a near-infrared absorber powder and a resin, and dispersing the obtained near-infrared absorber in the aforementioned dispersion medium. The liquid and the resin are mixed, and the dispersion medium is removed from the obtained mixture, thereby obtaining a resin composition, the dispersion liquid and the resin solution are mixed, and the dispersion medium and The method of obtaining a resin composition by removing a solvent is mentioned.
  • the removal method is not particularly limited, but is usually performed by drying such as drying under normal pressure or vacuum drying.
  • the molded object which consists of this resin composition
  • a molded body may be obtained by molding into a shape of, and after obtaining the resin composition as a master batch such as pellets, the master batch and the resin are used to perform various processes such as extrusion molding, cast molding, injection molding, etc.
  • a molded body such as an interlayer film for laminated glass may be obtained by a molding method.
  • the resin is not particularly limited as long as it can disperse the above-described near-infrared absorber.
  • the resin used in the present invention is selected from polyvinyl acetal resin, ethylene-vinyl acetate copolymer, (meth) acrylic acid resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, and norbornene resin. It is preferable that at least one type of resin can disperse the near-infrared absorber well and is excellent in visible light transmittance.
  • the resin used in the present invention is more preferably at least one resin selected from polyvinyl acetal resin or ethylene-vinyl acetate copolymer, polyvinyl butyral resin (PVB), or ethylene-vinyl acetate copolymer. Particularly preferred is at least one resin selected from coalescence.
  • polyvinyl acetal resin it is excellent in dispersibility of the above-mentioned near-infrared absorber, and, for example, when an interlayer film for laminated glass is produced using the resin composition of the present invention, it has excellent adhesion to glass or the like.
  • the resin composition is preferable because it is flexible and hardly deforms the near-infrared absorber due to a temperature change.
  • polyvinyl acetal resin it is preferable to use polyvinyl butyral resin (PVB) from the viewpoints of glass adhesion, dispersibility, transparency, heat resistance, light resistance, and the like.
  • the polyvinyl acetal resin may be a blend of two or more kinds 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%, with a preferred lower limit being 60% and an upper limit being 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. If it is less than 200, the penetration resistance of the resulting laminated glass may be lowered. When it exceeds 3000, the moldability of the resin composition may be deteriorated, and the rigidity of the resin composition is excessively increased, resulting in poor processability.
  • a more preferred lower limit is 500 and an upper limit is 2200.
  • 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 “Polyvinyl alcohol test method”.
  • 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.
  • the resin solution can be obtained by dissolving the aforementioned resin in a solvent.
  • the solvent is not particularly limited as long as it can dissolve the resin, and examples thereof include toluene, ethanol, methanol, methylene chloride, chloroform and the like.
  • the solvent one kind may be used alone, or two or more kinds may be used.
  • the resin composition of the present invention may contain a plasticizer.
  • the plasticizer is not particularly limited.
  • examples include tetraethylene glycol diheptanoate, dihexyl adipate, tributoxyethyl phosphate, and isodecylphenyl phosphate.
  • the resin composition of the present invention preferably contains 0.5 to 30 parts by mass, more preferably 1 to 25 parts by mass of a near infrared absorber per 100 parts by mass of the resin. If the amount is less than 0.5 parts by mass, sufficient near-infrared absorption characteristics may not be obtained. If the amount is more than 30 parts by mass, the heat resistance, light resistance, transparency, and adhesion to glass of the resin are greatly reduced. There is a risk.
  • the plasticizer is preferably contained in an amount of 10 to 60 parts by mass, more preferably 20 to 50 parts by mass, per 100 parts by mass of the resin.
  • the near-infrared absorber contained in the resin composition of the present invention is excellent in transparency when used with a resin, and is an intermediate for structural materials such as laminated glass because coloring during heating, that is, yellowing is suppressed. It can be suitably used as a membrane.
  • 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 added when manufacturing the resin composition of the present invention, or may be added when manufacturing the near-infrared absorber and the resin, respectively.
  • the resin composition of the present invention is usually used for applications where it is desired to absorb near infrared rays.
  • the resin film formed from the resin composition of the present invention has excellent near-infrared absorptivity and is suitable as an intermediate film for structural materials such as an interlayer film for laminated glass because coloring during heating, that is, yellowing is suppressed. Can be used.
  • 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.
  • solution B a solution prepared by dissolving 0.789 g of n-butylphosphonic acid in 20 g of the ethanol (water content 0.07% by mass).
  • the water content in ethanol was measured using a trace moisture measuring device AQ-2200 (manufactured by Hiranuma Sangyo).
  • a phosphonate copper complex toluene dispersion (1) 30 g was added to the blue-green solid, and ultrasonic irradiation was performed for 3 hours to prepare a phosphonate copper complex toluene dispersion (1).
  • the average particle size of the toluene dispersion (1) was measured and found to be 52 nm.
  • the particle size of the copper complex was measured using a particle size measuring device ELS-Z2 (manufactured by Otsuka Electronics Co., Ltd.), a quartz cell having a cell length of 10 mm as a cell, and toluene as a solvent for concentration adjustment, at a temperature of 25 ° C. The measurement was performed at 1 to 0.6 mol / L.
  • the laminated glass (1) is heated in an autoclave in a nitrogen atmosphere at a pressure of 1.5 MPa and 130 ° C. for 0.5 hours to obtain a haze measurement sample (1) in which slide glasses are arranged on both surfaces of the resin sheet. It was.
  • the haze of the haze measurement sample (1) was measured using Nippon Denshoku Industries NDH-2000 (D65 light source, single beam), the haze was 1.2.
  • the water content in methanol was measured using a trace moisture measuring device AQ-2200 (manufactured by Hiranuma Sangyo). Liquid B was added dropwise to liquid A in about 1.5 hours. This reaction solution was stirred at 20 ° C. for 12 hours to obtain a reaction mixture containing a phosphonic acid copper complex (6) which is a near infrared absorber.
  • the solvent was distilled off from the reaction mixture by performing the following solvent recovery operation.
  • 30 g of toluene was added to the reaction mixture from which the solvent had been distilled off (remainder), and the mixture was distilled off with an evaporator until a constant weight was obtained, whereby a 1.45 g (100% yield) pale pale white solid (copper phosphonate complex ( 6)) was obtained.
  • This dispersion was spread on a Teflon (registered trademark) vat and air-dried at 20 ° C. for 12 hours. Furthermore, it vacuum-dried at 40 degreeC for 5 hours, and 70 degreeC for 4 hours, the solvent was removed completely, and the PVB resin (6) in which the copper complex fine particle disperse
  • Teflon registered trademark
  • the haze of the haze measurement sample (c1) was 22.5.
  • the synthesis of the copper phosphonate complex (c1) corresponds to a comparative example because the methanol used has a high water content.

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Abstract

La présente invention concerne un procédé de production d'un absorbant des infrarouges proches pouvant produire, de manière stable, un absorbant des infrarouges proches qui présente une excellente transparence dans les cas où l'absorbant des infrarouges proches est utilisé avec une résine. Selon l'invention, un procédé pour la production d'un absorbant des infrarouges proches comprend : une étape A dans laquelle un composé d'acide phosphonique représenté par la formule générale (1), un dispersant de type composé d'ester d'acide phosphorique et un sel de cuivre sont mélangés dans un solvant, ce qui permet d'obtenir un mélange réactionnel qui contient un absorbant des infrarouges proches ; une étape B dans laquelle le solvant est récupéré du mélange réactionnel ; et une étape C dans laquelle le solvant récupéré dans l'étape B est utilisé comme solvant pour l'étape A. Le solvant utilisé dans l'étape A est un solvant organique présentant une teneur en humidité de 0-8,0 % en masse. Dans la formule, R1 représente un groupe monovalent représenté par -CH2CH2-R11 ; et R11 représente un atome d'hydrogène, un groupe alkyle comprenant 1-20 atomes de carbone ou un groupe alkyle fluoré comprenant 1-20 atomes de carbone.
PCT/JP2014/051969 2013-01-31 2014-01-29 Procédé pour la production d'un absorbant des infrarouges proches, absorbant des infrarouges proches et son utilisation WO2014119618A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015080184A1 (fr) * 2013-11-29 2015-06-04 株式会社クレハ Composition de résine et son utilisation
JP2019081896A (ja) * 2017-10-31 2019-05-30 コニカミノルタ株式会社 近赤外線吸収性組成物、近赤外線吸収性膜及び固体撮像素子用イメージセンサー
WO2022206714A1 (fr) * 2021-03-30 2022-10-06 浙江华帅特新材料科技有限公司 Dispersion absorbant les infrarouges, verre organique transparent thermo-isolant et procédé de fabrication associé

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011099038A (ja) * 2009-11-05 2011-05-19 Kureha Corp 近赤外線吸収剤及びその製造方法、並びに光学材料
JP2012087243A (ja) * 2010-10-21 2012-05-10 Kureha Corp 銅塩微粒子分散樹脂の製造方法、銅塩微粒子分散樹脂およびマスターバッチ
JP2012185385A (ja) * 2011-03-07 2012-09-27 Kureha Corp 近赤外線吸収剤分散液の製造方法
JP2012201865A (ja) * 2011-03-28 2012-10-22 Kureha Corp 銅塩微粒子分散樹脂の製造方法、および銅塩微粒子分散樹脂

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011099038A (ja) * 2009-11-05 2011-05-19 Kureha Corp 近赤外線吸収剤及びその製造方法、並びに光学材料
JP2012087243A (ja) * 2010-10-21 2012-05-10 Kureha Corp 銅塩微粒子分散樹脂の製造方法、銅塩微粒子分散樹脂およびマスターバッチ
JP2012185385A (ja) * 2011-03-07 2012-09-27 Kureha Corp 近赤外線吸収剤分散液の製造方法
JP2012201865A (ja) * 2011-03-28 2012-10-22 Kureha Corp 銅塩微粒子分散樹脂の製造方法、および銅塩微粒子分散樹脂

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015080184A1 (fr) * 2013-11-29 2015-06-04 株式会社クレハ Composition de résine et son utilisation
JP2019081896A (ja) * 2017-10-31 2019-05-30 コニカミノルタ株式会社 近赤外線吸収性組成物、近赤外線吸収性膜及び固体撮像素子用イメージセンサー
JP7099251B2 (ja) 2017-10-31 2022-07-12 コニカミノルタ株式会社 近赤外線吸収性組成物、近赤外線吸収性膜及び固体撮像素子用イメージセンサー
WO2022206714A1 (fr) * 2021-03-30 2022-10-06 浙江华帅特新材料科技有限公司 Dispersion absorbant les infrarouges, verre organique transparent thermo-isolant et procédé de fabrication associé

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