WO2005111170A1 - 近赤外光吸収材料、近赤外光吸収性組成物及び積層体 - Google Patents
近赤外光吸収材料、近赤外光吸収性組成物及び積層体 Download PDFInfo
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- WO2005111170A1 WO2005111170A1 PCT/JP2005/008894 JP2005008894W WO2005111170A1 WO 2005111170 A1 WO2005111170 A1 WO 2005111170A1 JP 2005008894 W JP2005008894 W JP 2005008894W WO 2005111170 A1 WO2005111170 A1 WO 2005111170A1
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- infrared light
- group
- light absorbing
- laminated glass
- compound
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- 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
- B32B17/10009—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 number, the constitution or treatment of glass sheets
- B32B17/10036—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 number, the constitution or treatment of glass sheets comprising two outer glass sheets
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- 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
Definitions
- Near infrared light absorbing material near infrared light absorbing composition and laminate
- the present invention relates to a near-infrared light absorbing material, a near-infrared light absorbing composition containing the same, and a laminate having a near-infrared light absorbing layer containing the same.
- An optical member for use as a window material or the like has a structure in which an intermediate film having a force such as polybutylacetal resin / acrylic resin is sandwiched between a pair of light-transmitting substrates having a force such as glass.
- Raze glass is known.
- Such a laminated glass has excellent characteristics such as high strength and high durability, and is therefore frequently used.
- these laminated glasses have been required to have a property of blocking light having a wavelength in the infrared region or a region in the vicinity thereof (hereinafter, "near-infrared light"). If a laminated glass having such characteristics is applied to a window material, a wall material, or the like, it is possible to suppress, for example, rays of sunlight having a wavelength in the above-described region, that is, heat rays, from entering the room. As a result, it is possible to keep the room from becoming excessively hot and to maintain a comfortable indoor environment, and it is also possible to reduce the cost of power for cooling and the like.
- a laminated glass capable of blocking near-infrared light a laminated glass having a layer having a property of absorbing near-infrared light (near-infrared light absorbing layer) as an intermediate film is known (for example, see patent documents 1-3.
- Such an intermediate film can be formed of, for example, a composition in which a material having a property of absorbing near infrared light (near infrared light absorbing material) is dispersed in a resin material.
- Patent document 1 Japanese Patent Application Laid-Open No. 9-221220
- Patent Document 2 JP-A-7-101756
- Patent Document 3 JP-A-2002-293583
- laminated glass having the above-described configuration has almost no characteristic of blocking near-infrared light. It is required to have a characteristic of being excellent in light resistance and light resistance. That is, it is desirable that the interlayer film has such characteristics that it does not easily become turbid even when exposed to sunlight or the like for a long time. A laminated glass having such characteristics can maintain high translucency even when used for a long period of time, so that it is extremely practical.
- the present invention has been made in view of such circumstances, and has a near-infrared light absorption that can impart not only a property of blocking near-infrared light but also excellent light resistance to a laminated glass. It is an object of the present invention to provide a material, a near-infrared light absorbing composition containing the same, and a laminate including a near-infrared light absorbing layer containing the same.
- the present inventors have conducted intensive studies, and as a result, as a near-infrared light absorbing material containing a compound containing a phosphorus atom and copper ions, a phosphorous-containing compound was used.
- a near-infrared light absorbing material containing a compound containing a phosphorus atom and copper ions
- a phosphorous-containing compound was used.
- an intermediate film that has a small decrease in near-infrared light blocking characteristics even when exposed to sunlight or the like for a long time and has high translucency is provided.
- the inventors have found that the present invention can be used, and have reached the present invention.
- the near-infrared light absorbing material of the present invention is characterized by containing (1), ()), and (III).
- R 1 is an alkyl group having 12 to 24 carbon atoms
- R 21 is a linear or cyclic alkyl group having 1 to 15 carbon atoms
- R 22 is a monovalent organic compound having an ether bond and / or an ester bond.
- i and j and k are each independently 1 or 2.
- the near-infrared light-absorbing material of the present invention provides, as a phosphorus-containing conjugate, a phosphoric ester compound having an alkenyl group having 12 to 24 carbon atoms, an alkyl group, or an ether bond. And a combination of Z or a phosphate compound having a monovalent organic group having an ester bond.
- a phosphoric ester compound having an alkenyl group having 12 to 24 carbon atoms, an alkyl group, or an ether bond a combination of Z or a phosphate compound having a monovalent organic group having an ester bond.
- an interlayer film of a laminated glass having not only high near-infrared light absorption but also excellent light resistance can be obtained. become.
- the R 1 is a Oreiru group.
- the near-infrared light-absorbing material containing a phosphoric ester compound having an oleyl group as a component of (I) exhibits better near-infrared light absorption and light resistance when used for an interlayer film of laminated glass. I can do it.
- phosphoric acid Esuterui ⁇ compound represented by the general formula (2b) is a group represented by R 22 It is preferable that the compound has a monovalent group represented by the following general formula (3). This can further improve the light resistance of the interlayer film of the laminated glass.
- R dl is an alkylene group having 2 to 4 carbon atoms
- R is an alkyl group having 1 to 12 carbon atoms or carbon. It represents a primed 2-5 acyl group, and m is an integer of 1-6.
- (II) is a phosphoric acid ester conjugate represented by the general formula (2a), and More preferably, R 21 in is an alkyl group having 8 carbon atoms.
- the near-infrared light absorbing composition of the present invention is characterized by containing the near-infrared light absorbing material of the present invention and a synthetic resin.
- a near-infrared light-absorbing composition since the near-infrared light-absorbing material is well dissolved and Z or dispersed in the synthetic resin (resin material) as described above, An interlayer film of a laminated glass, which also has a strong composition power, hardly causes a change in translucency even when exposed to sunlight for a long time. Therefore, a laminated glass having such an interlayer film has excellent near-infrared light blocking characteristics and excellent light resistance.
- the present invention also provides a laminate comprising a light-transmitting substrate and a near-infrared light absorbing layer formed on the light-transmitting substrate and comprising the near-infrared light absorbing composition of the present invention.
- a laminate comprising a light-transmitting substrate and a near-infrared light absorbing layer formed on the light-transmitting substrate and comprising the near-infrared light absorbing composition of the present invention.
- a laminate is provided with a near-infrared light absorbing layer made of the above-mentioned near-infrared light absorbing composition of the present invention, it has not only excellent properties of blocking near-infrared light but also light resistance. It has the characteristic that it is also excellent.
- the laminated body is configured to sandwich the near-infrared light absorbing layer between a pair of translucent substrates, it is possible to obtain a laminated glass excellent in both near-infrared light blocking characteristics and light resistance. .
- a near-infrared light-absorbing material capable of imparting not only a property of blocking near-infrared light but also excellent light resistance to a laminated glass, and a near-infrared light including the same It is possible to provide an absorbent composition and a laminate including a near-infrared light absorbing layer containing these.
- FIG. 1 is a view schematically showing an example of a cross-sectional structure of a laminated glass according to a preferred embodiment.
- FIG. 2 is a view schematically showing an example of a cross-sectional structure of a laminated glass having a reflective layer.
- FIG. 3 is a diagram schematically illustrating an example of a cross-sectional structure of a laminated glass having a reflective layer between a plurality of layers provided between light-transmitting substrates.
- the near-infrared light absorbing material contains the above (1), (II) and (III).
- Component of (I) is a phosphoric acid Esuterui ⁇ compound represented by the general formula (1), Aruke of 12 to 24 carbon atoms as the group represented by R 1 - has a Le group. This alkenyl group has at least one unsaturated bond in the structure.
- the group represented by R 1, Aruke 16-22 more preferably fixture carbon atoms an alkenyl group having 14 to 24 carbon atoms - are more preferred Le group.
- the group represented by R 1 includes an oleyl group, a trans-9-octadecyl group, a cis, cis-9,12-octadecyl group, a cis-9-tetradecyl group, and a cis-11 —Tetradecyl group, cis-8-dodecyl group, cis-13-docosenyl group and the like.
- the phosphate compound represented by the general formula (1) may be a mixture of a phosphate monoester compound in which i is 1 and a phosphate ester in which i is 2.
- R 1 is preferably an oleyl group.
- Such a compound can be represented by the following general formula (4). Wherein i is as defined above.
- the component (II) is a phosphate ester compound represented by the above general formula (2a) and Z or It is a phosphoric acid ester conjugate represented by the general formula (2b).
- the near-infrared light-absorbing material may contain these compounds alone or in combination.
- the phosphoric acid ester conjugate represented by the above general formula (2a) and the phosphoric acid ester conjugate represented by the above general formula (2b) are each a phosphoric acid monoester liposide wherein j or k is 1. It may be a mixture of the compound and a phosphoric diester wherein j or k is 2.
- the phosphoric acid ester conjugate represented by the general formula (2a) has an alkyl group as a group represented by R 21 .
- the alkyl group an alkyl group having 1 to 15 carbon atoms is preferable, and an alkyl group having 8 carbon atoms is more preferable, and an alkyl group having 4 to 12 carbon atoms is more preferable. More specifically, examples of the alkyl group include an n-butyl group, an n-hexyl group, an n-octyl group, a 2-ethylhexyl group, an n-decyl group, and an n-dodecyl group. 2 An ethylhexyl group is preferred!
- the compound represented by the general formula (2b) has a monovalent organic group containing an ether bond and a Z or ester bond as a group represented by R 22 .
- Such an organic group may have one or both of an ether bond and an ester bond, or may have both.
- Examples of the monovalent group having an ether bond include a group represented by the above general formula (3).
- R 31 is preferably an alkylene group having 2 to 3 carbon atoms.
- m is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.
- R 32 is preferably an alkyl group having 1 to 10 carbon atoms as the alkyl group, more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a (meth) acryl group as the acyl group.
- the (meth) acryl group refers to an acryl group or a methacryl group.
- Examples of the group represented by the general formula (3) in which R 32 is an alkyl group include groups represented by the following chemical formulas (5a) to (3 ⁇ 4).
- the monovalent group having an ester bond which is a group represented by R 22 , has an ester group in a molecular chain and has a (meth) acryl group at a terminal.
- Specific examples include a group represented by the following chemical formula (7).
- the phosphoric acid ester conjugates of (I) and (II) described above include, for example, (1) R 21 or Is a method of reacting a hydroxylyl conjugate (alcohol) having a hydroxyl group at the terminal of the structure represented by with phosphorus pentoxide, (2) after reacting the hydroxylyl conjugate with the oxyhalogenide phosphorus (3) a method of synthesizing a phosphonate ester compound by reacting the above hydroxylate conjugate with trihalogenide phosphorus and then oxidizing the resulting phosphonate esteride conjugate. And the like. These reactions can be carried out without any solvent or in the presence of a predetermined organic solvent. The mixing ratio between the monoester and the diester can also be controlled by appropriately selecting these methods and changing the reaction conditions as appropriate.
- the component (III) is a divalent copper ion.
- copper salts for supplying copper ions include organic compounds such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetate, copper pyrophosphate, copper naphthenate, and copper citrate.
- Copper salt anhydrides, hydrates or hydrates of acids, or anhydrides, hydrates or hydrates of copper salts of inorganic acids such as copper chloride, copper sulfate, copper nitrate, basic copper carbonate, or Copper hydroxide is exemplified.
- 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 alone or in combination of two or more.
- the near-infrared light-absorbing material of the embodiment includes the components (I), (II), and (III) as essential components.
- Each of the components (II) and (III) may simply exist as a mixture, and the phosphate compound of (I) and the phosphate compound of (II) may be combined with a divalent copper ion. It may be present in a state where it has reacted to form a phosphate copper compound.
- the phosphate copper compound is formed by ionic bond and Z or coordinate bond between a phosphate group and copper ion in each phosphate ester conjugate.
- Such phosphate copper compounds may be prepared by mixing the phosphate esters (I) and (II) and then reacting the mixture with copper ions. It may be prepared by reacting the ligated product with copper ions to obtain a phosphoric acid ester copper compound corresponding to each phosphoric acid ligated product, and then mixing them.
- the content of the phosphoric acid ester conjugate of (I) is the total amount of the phosphoric acid ester conjugates of (I) and (II). respect, further preferably a more preferred device 20 to 90 weight 0/0 If it is preferred instrument 15 to 99 weight 0/0 If it is 10 mass% or more. If the content of the phosphate compound (I) is less than 10% by mass, the dissolution of the near-infrared light-absorbing material in the resin component and the Z or dispersibility tend to decrease. The light resistance of the laminated glass using such a material may be insufficient.
- the content ratio of the copper ion to the phosphoric acid ester conjugate of (I) and (II) is determined when the phosphoric acid ester compound has a hydroxyl group or an oxygen atom derived from a hydroxyl group.
- Total amount of hydroxyl group or oxygen atom It is preferable that ZCu has a molar ratio of preferably 1 to 6, more preferably 1 to 4, and still more preferably 1.5 to 2.5. If this ratio is less than 1, the dissolution and Z or dispersibility of the near-infrared light-absorbing material tend to decrease, and the near-infrared light absorbing performance and translucency tend to decrease. On the other hand, if it exceeds 6, the amount of hydroxyl groups not involved in coordination bond or ion bond with copper ion becomes excessive, and the hygroscopicity tends to be too large.
- the near infrared light absorbing material may contain a metal ion other than the copper ion.
- metal ions include ions of metals such as rare earth metals, sodium, potassium, lithium, calcium, strontium, iron, manganese, magnesium, nickel, chromium, indium, titanium, antimony, and tin.
- the rare earth metal include neodymium, praseodymium, and holmium. Strong rare earth metals have excellent absorption characteristics for light of a specific wavelength (around 580 nm or around 52 Onm) due to the electronic transition of the f-orbit of rare earth ions, and these wavelength ranges are the maximum of the photoreceptors of the human eye. Since the material matches the response wavelength, the above-described material can be provided with antiglare properties.
- the near-infrared light-absorbing composition contains the above-described near-infrared light-absorbing material and a synthetic resin. It is something that is scattered.
- the synthetic resin a resin having excellent dispersibility of the near-infrared light-absorbing material and an excellent property of transmitting visible light is preferable.
- fats include polybutyl acetal resin, ethylene-butyl acetate copolymer (EVA), (meth) acrylic resin, polyester resin, polyurethane resin, chloride resin, polyolefin resin, and polycarbonate. Resin, norbornene resin and the like.
- polyvinyl butyral is particularly preferred, in which polybutyl acetal resin is preferred.
- a resin is excellent in adhesiveness to a light-transmitting substrate in a laminate described later, is flexible, and has a property of being hardly deformed depending on temperature. For this reason, by using the polybutylacetal resin, the molding process at the time of manufacturing the laminate is facilitated. Further, the transparency, weather resistance, adhesion to glass, and the like of the obtained intermediate film are improved.
- the polyvinyl acetal resin also has the property of easily dissolving and Z or dispersing the above-mentioned near-infrared light absorbing material, in particular. Therefore, according to the combination of the near-infrared light absorbing material and the polybutyl acetal resin, a laminated glass having excellent light transmission and light resistance can be obtained.
- the polyvinyl acetal resin may be blended in an appropriate combination according to the required physical properties.
- the polyvinyl acetal obtained by combining the aldehyde with the aldehyde during acetalization may be used. ⁇ It may be fat.
- the molecular weight, molecular weight distribution, and acetal degree of the polybutylacetal resin are not particularly limited, the acetalization degree is generally 40 to 85%, and the preferable lower limit is 60% and the upper limit is 75%.
- the polybutyl acetal resin can be obtained by acetalizing a polybutyl alcohol resin with an aldehyde.
- the poly Bulle alcohol ⁇ is generally one obtained by Sani spoon the Po Li acetate Bulle, degree of oxidation from 80 to 99.8 mole 0/0 port Li Bulle alcohol ⁇ 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 resulting laminated glass will have low penetration resistance. If it exceeds 3,000, the moldability of the resin film becomes poor, and the elasticity of the resin film becomes too large, and the workability becomes poor.
- the lower limit is 500 and the upper limit is 2000.
- the viscosity average degree of polymerization and the degree of oxidation of the polyvinyl alcohol resin can be measured, for example, based on JIS K 6726 “Testing method for polybutyl alcohol”.
- the aldehyde is not particularly limited, and includes, for example, aldehydes having 1 to 10 carbon atoms, and more specifically, n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2 —Ethyl butyl aldehyde, n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, formaldehyde, aceto aldehyde, benzaldehyde and the like.
- n-butyraldehyde, n-hexylaldehyde, n-valeraldehyde and the like are preferable. More preferably, it is butyraldehyde having 4 carbon atoms.
- the near-infrared light-absorbing composition having such a structure can be obtained by directly dissolving and / or dispersing a near-infrared light-absorbing material in a synthetic resin, or by a method in which a near-infrared light-absorbing material is used in a monomer of a synthetic resin. After dissolving and dispersing or dispersing the infrared light absorbing material, it can be prepared by a method of polymerizing this monomer or the like.
- the former method is effective, for example, when the synthetic resin has thermoplasticity. Specifically, a method of kneading a near-infrared light absorbing material after heating and melting a synthetic resin, or dissolving and Z or dispersing a synthetic resin in a solvent, and then adding the near-infrared light absorbing material in this solution Is added and mixed, and then the solvent is removed.
- Radical polymerization is generally used as the polymerization method.
- a mixture of a near-infrared light absorbing material and a synthetic resin monomer may further contain a polymerization initiator. It is not necessary to carry out such a polymerization reaction immediately after mixing the monomer and the near-infrared light-absorbing material.For example, as described later, the polymerization reaction is carried out after coating on a predetermined base material. You can also.
- the near-infrared light absorbing composition preferably contains a plasticizer having excellent compatibility with the synthetic resin, in addition to the above-mentioned near-infrared light absorbing material and the synthetic resin.
- a plasticizer When a plasticizer is contained, the dissolution and the Z or dispersibility of the near-infrared light absorbing material in the synthetic resin are further enhanced, and the light resistance can be further improved.
- plasticizers which are commonly used for intermediate films, such as phosphate ester plasticizers, phthalic acid plasticizers, fatty acid plasticizers, and glycol plasticizers. Examples include a plasticizer.
- monobasic organic acid esters for example, monobasic organic acid esters, polybasic organic acid esters, etc.
- Organic plasticizers for example, phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are preferably used. These plasticizers may be used alone or two or more of them may be used in combination. Depending on the type of the resin, they are used in consideration of compatibility and the like.
- Examples of the monobasic organic acid ester include dalicol such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, and caproic acid.
- Dalicol system obtained by reaction with monobasic organic acids such as, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2-ethylhexanoic acid, pelargonic acid (n-nolic acid) or decylic acid Esters and the like. More specifically, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2-ethyl butyrate (3GH), dihexyl adipate (DHA), tetraethylene glycol diheptanoate (4G7), Examples thereof include ethylene glycol di-2-ethylhexanoate (4GO) and triethylene glycol diheptanoate (3G7). Of these, 3GO, 3GH, 3G7, etc. are preferred.
- the polybasic organic acid ester is not particularly limited.
- a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid and a linear or branched alcohol having 4 to 8 carbon atoms are used.
- the ester obtained by the reaction with For example, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are preferred.
- organic phosphate plasticizer examples include tributoxyshethyl phosphate, isodecyl phenyl phosphate, triisopropyl phosphate and the like.
- the content of the plasticizer in the composition is preferably 1 to 120 parts by mass relative to 100 parts by mass of the resin material 1 to: more preferably LOO parts by mass 2 More preferably, it is set to be 80 parts by mass. If the content of the plasticizer is less than 1 part by mass with respect to 100 parts by mass of the resin material, the solubility of the copper ion or phosphorus-containing conjugate decreases and the light transmittance becomes insufficient. There is a case. On the other hand, if it exceeds 100 parts by mass, the resin material as the base material tends to be too flexible, and for example, it tends to be difficult to use it as an interlayer in laminated glass.
- the near-infrared light-absorbing composition may also contain an adhesion regulator.
- the adhesive force adjuster may be applied to the surface of an intermediate film (near infrared light absorbing layer) described later.
- Contact Examples of the adhesion regulator include alkali metal salts or alkaline earth metal salts of organic acids or inorganic acids, and modified silicone oils.
- 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.
- the inorganic acid is not particularly limited, and examples thereof include hydrochloric acid and nitric acid.
- the above alkali metal salt and alkaline earth metal salt are not particularly limited, and examples thereof include salts of potassium, sodium, calcium, magnesium and the like.
- 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 Potassium salts and magnesium salts of carboxylic acids of the formulas 2 to 16;
- the potassium salt and magnesium salt of the carboxylic acid having 2 to 16 carbon atoms are not particularly limited.
- the preferred 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, and the upper limit is 0.5 part by weight based on 100 parts by weight of the resin. It is. If the amount is less than 0.001 parts by weight, the adhesive strength of the peripheral portion may be reduced in a high humidity atmosphere. If the amount 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.
- modified silicone oil examples include an epoxy-modified silicone oil, an ether-modified silicone oil, an ester-modified silicone oil, an amine-modified silicone oil, and a carboxyl-modified silicone oil. These may be used alone or in combination of two or more. These modified silicone oils are generally obtained by reacting a polysiloxane with a compound to be modified.
- the preferred lower limit of the molecular weight of the modified silicone oil is 800, and the upper limit is 5,000. If it is less than 800, localization on the surface may be insufficient. If it exceeds 5,000, the compatibility with the resin will be reduced, and it will bleed out to the film surface, and the adhesive strength with glass may be reduced. More preferably, the lower limit is 1500 and the upper limit is 4000. [0055] A preferred lower limit of the amount of the modified silicone oil is 0.01 parts by weight and an upper limit of 0.2 parts by weight based on 100 parts by weight of the resin. If the amount is less than 0.01 part by weight, the effect of preventing whitening due to moisture absorption may be insufficient.
- the compatibility with the resin may be reduced, and the resin may bleed out to the film surface and the adhesive strength between the resin and the glass may be reduced. More preferably, the lower limit is 0.03 parts by weight and the upper limit is 0.1 parts by weight.
- the near-infrared light-absorbing composition may contain other additives in addition to the above-mentioned plasticizer and adhesive force adjuster.
- additives include a component for adjusting color tone, a component for adjusting physical properties, a component for stabilizing a polymer after polymerizing the polymerizable composition, and a laminate described below. And the like for improving the adhesion to the light-transmitting substrate when forming the film.
- 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. .
- components for adjusting color tone include dyes, pigments, metal compounds, and the like.
- Components for adjusting physical properties include (meth) acrylic monomers having a, ⁇ unsaturated bonds, such as styrene, butadiene, and vinyl acetate, and oligomers having excellent compatibility with (meth) acrylic resins. Polymers and the like.
- Examples of the component for stabilizing the polymerizable composition include a light stabilizer, a heat stabilizer, an antioxidant, and an ultraviolet absorber. Further, as a component for improving the adhesion to the light-transmitting substrate, for example, when a glass substrate is used as the light-transmitting substrate, a silane coupling agent such as vinyl silane, acrylic silane, epoxy silane, or the like may be used. Coupling agents can be exemplified.
- Examples of the ultraviolet light absorber include a benzoate compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, a oxalic acid aldehyde compound, and a triazine compound.
- examples of the benzoate-based compound include 2,4-di-tert-butylphenyl 3 ', 5,1-di-t-butyl4,1-hydroxybenzoate and the like.
- examples of salicylate compounds include phenol salicylate and p-t-butyl phenol salicylate.
- benzophenone-based compound examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4methoxybenzophenone 5 snolephonic acid, and 2-hydroxy-14-n-o Cthyloxybenzophenone, 2-hydroxy-1-4-n-dodecyloxybenzophenone, 2,2 ', 4,4,1-tetrahydrobenzozophenone, bis (5-benzoyl-4-hydroxy-12-methoxyphenyl) methane 2,2,1-dihydroxy-1,4,4'dimethoxybenzophenone, 2,2'-dihydroxy-4,4'dimethoxybenzophenone-1,5,5,1-disulfonic acid sodium salt, 2,2'-dihydroxy 1-Methoxybenzophenone, 2-hydroxy-4-methacryloyloxyshethyl benzophenone, 4-Benzyloxy 2-hydroxybenzophenone, 2, 2 ', 4 , 4'-tetrahydroxy
- Benzotriazole compounds include 2- (2,1-hydroxy-15,1-methylphenyl) benzotriazole and 2- (2'-hydroxy-3'-t-butyl-5'methylphenyl) 5chloro Benzotriazole, 2- (2,1-Hydroxy-1,3,5,1-di-t-butyl) 5 Clo-Venzotriazole, 2- (2,1-Hydroxy-1,3,, 5,1-t-t) Butylphenyl-benzo) triazole, 2- (2,1-hydroxy-15-t-octylphenyl) benzotriazole, 2- (2-hydroxy-5t-butylphenyl) benzotriazole, 2- [2,1- Hydroxy-1,3,1- (3 ,,, 4 ", 5", 6,1, tetrahydrophthalimidomethyl) 5,1-methylphenyl] benzotriazole, 2- (2,1-hydroxy-1,3,, 5, Di-t-amylphenol-benzotriazole
- Examples of the cyanoacrylate-based compound include ethyl 2 cyano 3,3 diphenyl atalylate octyl-2 cyano 3, 3 diphenyl atalylate, and oxalic acid.
- -Lido compounds include bisethoxy-l-ethoxy 2'-ethyloxalic acid bis-lide 2-ethoxy-5-t-butyl-2 'ethyl oxalolic acid.
- Examples of the triazine-based compound include 2- (4,6 diphenyl-1,3,5 triazine-12-yl) 5-[(hexyl) oxy] phenol.
- a hindered amine light stabilizer HALS
- a Ni compound As the light stabilizer, a hindered amine light stabilizer (HALS) or a Ni compound can be applied.
- HALS hindered amine light stabilizer
- Ni compound a Ni compound
- the stability to light tends to be extremely good.
- HALS includes bis (2,2,6,6-tetramethyl-14piperidyl) sebacate, bis (1,2,6,6 pentamethyl-4-piperidyl) sebacate, 1 [ Two
- Ni-based light stabilizers include [2,2-thio-bis (4t-otatinolephenolate)]-1-2-ethylhexylamine-nickel (II), nickel dibutyl dithiocarbonate, 2,2-thio-bis (4-t-octylphenolate)]-butylamine-nickel ( ⁇ ).
- the content of the near-infrared light-absorbing material in the near-infrared light-absorbing composition is preferably 0.5 to 45% by mass based on the total amount of the near-infrared light-absorbing composition. Mashigashi More preferably 1 to 40% by mass, and still more preferably 1 to 35% by mass. If the content of the near-infrared light absorbing material is less than 0.5% by mass, the near-infrared light blocking properties of the laminated glass obtained using the composition tend to be reduced. On the other hand, if this content exceeds 45% by mass, the near-infrared light-absorbing material becomes difficult to dissolve sufficiently in the synthetic resin, and the light transmittance of the laminated glass obtained using the composition tends to decrease. It is in.
- optical members By using the above-described near-infrared light absorbing composition, an optical member having excellent properties of blocking near-infrared light can be obtained.
- Such optical members include the following first and second embodiments.
- First form A sheet-like molded product obtained by processing a near-infrared light absorbing composition.
- Second embodiment a laminate including a light-transmitting substrate and a near-infrared light absorbing layer made of a near-infrared light absorbing composition provided adjacent to the light-transmitting substrate.
- the optical member according to the first mode is a near-infrared light It is a sheet-like molded product made of the absorbent composition, and specific examples include a sheet and a film.
- the sheet is a thin plate having a thickness exceeding 250 m.
- the film is a thin film with a thickness of 5 to 250 m.
- These sheets or films can be produced using a known sheet or film forming method. Examples of such a sheet or film forming method include a melt extrusion molding method, a stretch molding method, a calendar molding method, a press molding method, a solution casting method and the like.
- the optical member of the second embodiment is a laminate having a light-transmitting substrate and a near-infrared light absorbing layer provided near the light-transmitting substrate and having a near-infrared light absorbing composition.
- the material forming the light-transmitting substrate is not particularly limited as long as it is a light-transmitting material having visible light transmittance, and can be appropriately selected according to the use of the optical member.
- glass and plastic are preferably used.
- the glass include inorganic glass and organic glass.
- the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, butyl chloride resin, polystyrene, polyester, polyolefin, and norbornene resin.
- each substrate may be made of the same type of material, or may be made of a different material.
- Such a laminated body is manufactured by, for example, forming a sheet-like film similar to the optical member of the first embodiment described above, and then bonding this sheet or the like to a light-transmitting substrate.
- a method for laminating these means for bonding by pressurization or decompression such as press method, multi-roll method, decompression method, means for bonding by heating using an autoclave or the like, or a combination of these Means can be used.
- a method for manufacturing a laminate a method of directly forming a near-infrared light absorbing layer on a light-transmitting substrate can be applied in addition to a method of laminating sheets formed in advance.
- the above-mentioned near-infrared light absorbing composition is dissolved and Z or dispersed in an appropriate solvent to form a coating agent, and after applying this solution to a light-transmitting substrate, the solvent is evaporated.
- a method of forming a thin film, coating, or thin layer comprising a near-infrared light absorbing composition on a translucent substrate can be exemplified.
- the thin film formed in this way is What is called.
- a dissolution aid such as various surfactants such as a leveling agent and an antifoaming agent is used in order to enhance the flatness of the layer. May be added to the above-mentioned coating agent.
- a near-infrared light absorbing material is dissolved and Z or dispersed in a synthetic resin monomer.
- a method of preparing a composition applying the composition on a light-transmitting substrate, and then causing a polymerization reaction of a monomer on the surface of the substrate.
- a solvent may be further added to the composition.
- the optical member of the second embodiment is not limited to the above-described one including the translucent substrate and the near-infrared light absorbing layer, but includes a plurality of these layers. There may be. Specifically, a substrate including a pair of light-transmitting substrates and an intermediate film (near-infrared light absorbing layer) made of the near-infrared light-absorbing composition disposed between the light-transmitting substrates is exemplified. Can be Such a laminate is what is called a laminated glass.
- FIG. 1 is a diagram schematically showing an example of a cross-sectional structure of a laminated glass.
- a laminated glass 10 shown in FIG. 1 includes a pair of translucent substrates 1 and an intermediate film 2 (near-infrared light absorbing layer) sandwiched between the pair of translucent substrates 1.
- the intermediate film 2 is made of the above-mentioned near-infrared light-absorbing composition, and as the light-transmitting substrate 1, the same one as described above can be applied.
- the laminated glass 10 having a strong structure is formed, for example, by sandwiching a sheet-shaped molded product made of the above-described near-infrared light-absorbing composition between a pair of light-transmitting substrates, and preliminarily pressing this. After removing the air remaining between the layers, it can be manufactured by a method in which they are completely bonded by pressure bonding.
- the intermediate film 2 does not have a so-called blocking phenomenon that the sheets are bonded to each other during storage to form a lump, It is required that the deaeration in the pressure bonding be good.
- workability when laminating the translucent substrate 1 and the sheet is improved, and the translucency due to bubbles generated due to insufficient degassing, for example, is improved. Decline Can be prevented.
- Such a laminated glass 10 is required to be excellent not only in the property of blocking near-infrared light but also in the property of translucency, that is, the property of transmitting light in the visible light region. In order to obtain such excellent translucency, it is preferable that there be no bubbles between the translucent substrate 1 and the intermediate film 2 as described above.
- Examples of the form of such embossing include, for example, various uneven patterns composed of a large number of convex portions and a large number of concave portions with respect to these convex portions, a large number of convex portions, and a large number of concave grooves for these convex portions.
- embossed shapes having various values for various shape factors such as various uneven patterns, roughness, arrangement, size, etc.
- embosses for example, those in which the size of a convex portion is changed, and its size and arrangement are specified, as described in JP-A-6-198809, are described in JP-A-9-40444.
- the surface roughness of 20 to 50 / ⁇ the one described in Japanese Patent Application Laid-Open No. 9-295839, in which the ridges are arranged so as to intersect, or the method disclosed in Japanese Patent Application Laid-Open No. 2003-48762.
- Japanese Patent Application Laid-Open Publication No. HEI 7-175 in which an even smaller projection is formed on the main projection.
- 2003-528749 discloses a method using melt flattening generated during resin molding
- Japanese Patent Application No. 2002-505211 discloses cross-linked PVB particles or molding.
- a method using a nucleating agent has been proposed.
- Another characteristic recently required of the laminated glass 10 is sound insulation.
- the laminated glass having excellent sound insulation properties for example, when the laminated glass is used as a window material, the influence of ambient noise and the like can be reduced, and the indoor environment can be further improved.
- the sound insulation performance is indicated as a transmission loss amount according to a change in frequency, and the transmission loss amount is specified in JISA 4708 at a constant value of 500 Hz or more, and according to the sound insulation class. .
- the sound insulation performance of a glass plate generally used as a translucent substrate of a laminated glass is significantly reduced due to the coincidence effect in a frequency region centered at 2000 Hz.
- the coincidence effect means that when a sound wave enters a glass plate, a 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. As a result, sound transmission occurs The phenomenon that occurs. Therefore, in a general laminated glass, in a frequency region centered on 2000 Hz, an improvement in this point, in which it is difficult to avoid a decrease in sound insulation performance due to a strong coincidence effect, is required.
- the sound insulation performance is affected by the dynamic viscoelasticity of the interlayer 2, and may be affected by the loss tangent which is the ratio of the storage elastic modulus to the loss elastic modulus.
- the sound insulation performance of the laminated glass 10 can be improved.
- the means for controlling the value of the loss tangent as in the latter for example, a method using a resin film having a specific polymerization degree, a resin as described in JP-A-4-2317443 And a method for defining the amount of plasticizer in the resin as described in JP-A-2001-220183.
- the sound insulation performance of the laminated glass 10 can be enhanced over a wide temperature range by forming an interlayer by combining two or more different resins.
- a method of blending a plurality of kinds of resins described in JP-A-2001-206742 a method of blending a plurality of kinds of resins described in JP-A-2001-206741 and JP-A-2001-226152.
- a lamination method a method described in Japanese Patent Application Laid-Open No. 2001-192243, and a method in which the amount of a plasticizer in an intermediate film is deviated, and the like are exemplified.
- the intermediate film 2 should be formed by adopting these techniques and appropriately combining means such as modifying the resin structure, adding a plasticizer, and combining two or more kinds of resins. It is possible to control the value of the loss tangent of the resin material, that is, the sound insulation.
- the laminated glass 10 further has a heat-shielding property other than blocking the near-infrared light as described above.
- a metal, an oxide fine particle, a metal boride, or the like having a heat shielding function is further contained in the intermediate film 2, or a layer containing these is combined.
- the applied method can be applied
- boride fine particles include YB, LaB, CeB, PrB, NdB, SmB, EuB, and GdB.
- the particle size of the oxide fine particles is regulated (Japanese Patent No. 271589; 2002-2933583), and a method for improving the dispersibility and maintaining good light transmission may be applied.
- a known fine particle dispersing technique such as mechanically dispersing the fine particles or using a dispersant can be applied.
- a method for improving the heat-shielding property of the laminated glass in addition to the above-described method for containing the oxidized fine particles and the like, for example, a method for containing a dye or pigment having an organic heat-shielding function, And a method using a light-transmitting substrate having heat-shielding performance.
- the former method of incorporating an organic dye / pigment having a heat-shielding function include the methods described in JP-A-7-157344 and JP-A-319271.
- dyes and pigments include phthalocyanine-based, anthraquinone-based, naphthoquinone-based, cyanine-based, naphthalocyanine-based, pyrrole-based, imo-pam-based, dithiol-based, and mercaptonaphthol-based dyes. 'Pigments.
- the light-transmitting substrate having the latter heat-shielding performance for example, Japanese Unexamined Patent Application Publication No. 2001-1 Fe-containing glass (eg, green glass) as described in 51539, metal as described in JP-A-2001-261384 and JP-A-2001-226148, metal oxide Glass plate on which objects are laminated.
- Japanese Unexamined Patent Application Publication No. 2001-1 Fe-containing glass eg, green glass
- metal as described in JP-A-2001-261384 and JP-A-2001-226148
- metal oxide Glass plate on which objects are laminated for example, Japanese Unexamined Patent Application Publication No. 2001-1 Fe-containing glass (eg, green glass) as described in 51539, metal as described in JP-A-2001-261384 and JP-A-2001-226148, metal oxide Glass plate on which objects are laminated.
- the near-infrared light-absorbing material contained in the intermediate film absorbs light in the near-infrared light region, thereby blocking near-infrared light that is a heat ray.
- the laminated glass (laminate) of the present invention exhibits near-infrared light absorption properties in addition to the near-infrared light absorbing layer, the laminated glass (laminate) of the present invention further improves near-infrared light blocking properties. It may further have a layer (reflection layer) having the property of reflecting light.
- 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, a near-infrared light absorbing layer 22, a reflective layer 23, and a translucent substrate 21 in this order.
- the translucent substrate 21 and the near-infrared light absorbing layer 22 those similar to those in the laminated glass 10 described above can be applied.
- Examples of the reflection layer 23 include a layer composed of a metal or a metal oxide. Specifically, for example, gold, silver, copper, tin, aluminum, nickel, palladium, silicon, chromium, titanium , Indium, antimony, and other metals, alloys, mixtures, and oxides.
- the laminated glass 20 having such a reflective layer 23 can be manufactured, for example, as follows. That is, first, a substrate in which the reflective layer 23 is provided on one surface of the translucent substrate 21 is prepared. Here, as a method of forming the reflective layer 23 on the translucent substrate 21, a method of vapor-depositing a metal or a metal oxide on the translucent substrate 21 or the like is used. Next, on one surface side of the sheet to be the near-infrared light absorbing layer 22, the light-transmitting substrate 21 on which the reflective layer 23 is formed is arranged so that the reflective layer 23 is in contact with the transparent substrate 21, and the other surface side Only the translucent substrate 21 is disposed. Then, by pressing these, the laminated glass 20 can be obtained.
- the adhesiveness between the reflective layer 23 and the near-infrared light absorbing layer 22 decreases. In some cases. In this case, for example, when the laminated glass 20 is broken, the translucent substrate 21 is easily peeled off and scattered, which causes a problem in terms of safety. From the viewpoint of avoiding a strong problem, for example, it is preferable to further provide a layer between the near-infrared light absorbing layer 22 and the reflective layer 23 that can improve the adhesive strength between them. By doing so, the adhesiveness between the reflective layer 23 and the near-infrared light absorbing layer 22 is improved. It can be improved.
- JP-A-09-506837, JP-T-2000-506082, JP-T-2000-5050684, JP-T-2004 Polymer multilayer films that reflect specific wavelengths using light interference, such as those shown in 525 403, Table 2003-515754, JP-A-2002-231038, Table 2004-505032, etc., can also be used. .
- the reflective layer is not necessarily provided between the light-transmitting substrate and the near-infrared light absorbing layer in the laminated glass as described above.
- a layer made of the above resin is formed, a form provided between these layers may be employed.
- 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 light-transmitting substrate 31, a near-infrared light absorbing layer 32, a reflective layer 33, a resin layer 34, a near-infrared light absorbing layer 32, and a light-transmitting substrate 31 in this order. ing.
- the same ones as described above can be applied as the light-transmitting substrate 31, the near-infrared light absorbing layer 32 and the reflecting layer 33.
- the resin layer 34 a material having a known resin material strength can be applied, and examples of such a resin material include polyethylene terephthalate and polycarbonate.
- a resin material include polyethylene terephthalate and polycarbonate.
- the laminated glass 30 having such a structure at least one layer of the near-infrared light absorbing layer 32 may be provided.
- the layer may be a resin material layer having no near-infrared light absorption characteristics.
- the effect of both layers can provide a further excellent near-infrared light blocking property for laminated glass. Can be granted it can. Further, if a method for improving the adhesiveness between the reflective layer and the near-infrared light absorbing layer as described above is employed, a laminated glass having excellent strength in addition to such near-infrared light blocking characteristics can be obtained. It is also possible to obtain.
- the laminated glass preferably has a haze of 50% or less, more preferably 40% or less, more preferably 35% or less. If the haze exceeds 50%, the transmissivity of the laminated glass tends to decrease, and the uptake of visible light tends to be insufficient.
- the laminated body (laminated glass) of the present invention has excellent near-infrared light blocking performance
- building materials building materials for taking in natural light such as sunlight and other external light
- Window materials for show windows and showcases tents or their window materials, blinds, roof materials for fixed housing and temporary housing, etc.
- skylights and other window materials covering materials for painted surfaces such as road signs, sunshades such as parasols It can be suitably used for materials and other members that need to block heat rays.
- oleyl phosphate (monoester and diester) 63. lg thereof was dissolved in 180 g of toluene by using an equimolar mixture of the toluene form, manufactured by Tokyo Chemical Industry; hereinafter, abbreviated as "OLP". 20. Og of copper acetate monohydrate was added to the obtained solution, and the solution was refluxed to remove acetic acid. Thereafter, toluene was distilled off from the reaction solution to obtain 80.4 g of a copper ester phosphate compound (oleyl phosphate ester copper compound; OLPC).
- phosphate ester compound a compound represented by the above general formula (2a), in which R 21 is a 2-ethylhexyl group instead of OLP (Preparation Example 2, manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter, ⁇ 2- ⁇ ]), n-butyl group (Preparation Example 3), methyl group (Preparation Example 4), octadecyl group (Preparation Example 5), hexadecyl group (Preparation Example) 6) or a diphenyl group (Preparation Example 7) was used in the same manner as in Preparation Example 1, except that a phosphoric acid copper ester conjugate was obtained.
- Table 1 shows the amounts of the raw materials and copper acetate monohydrate in each Preparation Example, and the yield of the obtained copper phosphate ester compound.
- Table 2 shows the amounts and the yields of the components used in the synthesis of the phosphoric acid ester conjugates and the phosphoric acid ester copper compounds of Preparation Examples 8 to 12.
- a compound in which R 22 in the compound represented by the above general formula (2b) is a group represented by the above chemical formula (7) was used, and 15.48 g thereof was dissolved in 60.18 g of toluene. . 5. Olg of copper acetate monohydrate was added to the resulting solution, and the solution was refluxed to remove acetic acid. Then, toluene was distilled off from the obtained solution to obtain 20.82 g of a phosphoric acid ester copper compound.
- a compound represented by the above formula (1) which is a R 1 trans-9-octadecenyl group (a group represented by the following chemical formula (8a)) (Preparation Example 15), cis , cis-9,12-octadecenyl group (group represented by the following chemical formula (8b)) (Preparation Example 16) and cis-13-docosel group (group represented by the following chemical formula (8c)) (Preparation Example 17) was synthesized.
- These phosphoric acid ester conjugates were synthesized in the same manner as the phosphoric acid ester conjugates in Preparation Examples 8 to 12 described above.
- a compound which is an R 11 S cis 3 hexenyl group (a group represented by the following chemical formula (9a)) in the compound represented by the above general formula (1) (Preparation Example 18)
- An otatenyl group (a group represented by the following chemical formula (9b) (Preparation Example 19)); a cis 3 otatenyl group (a group represented by the following chemical formula (9c)) (Preparation Example 20); and a stearyl group (Preparation Example 21) was synthesized.
- a phosphate copper compound was obtained in the same manner as in Preparation Example 812 above, using the obtained phosphate ester conjugate.
- Table 4 shows the amounts and the yields of the components used for the synthesis of the phosphate ester conjugate of Preparation Example 18 21 and the synthesis of the phosphate ester copper compound.
- the obtained phosphoric acid ester copper compound lg was dissolved in 2 g of triethylene glycol di-2-ethylhexanate as a plasticizer, and further dissolved in 7 g of PVB (Eslek BH-3, manufactured by Sekisui Chemical Co., Ltd.). By mixing, a near-infrared light absorbing composition was obtained.
- a compound of the formula (2a) was prepared in the same manner as in Example 17 except that, in place of 2-EHP, a compound represented by the general formula (2a) wherein R 21 was a decyl group was used as the compound (II). Thus, a near-infrared light absorbing composition was obtained.
- the amounts and yields of the raw materials and copper acetate monohydrate were as shown in Table 7.
- a phosphoric acid ester copper compound was prepared by the following method. That is, first, 158 g of OLP and 88.9 g of 2-EHP were dissolved in toluene. To the resulting solution was added lOOg of copper acetate monohydrate, acetic acid was removed while refluxing the solution, and then toluene was further removed to obtain 270 g of a copper phosphate ester compound containing OLP and 2-EHP. .
- the near-infrared light-absorbing compositions of Examples 1 to 20 and Comparative Examples 1 to 8 were pressed several times at 85 ° C by a press (WF-50, manufactured by Shinto Metal Industry Co., Ltd.), and then further pressed. By pressing at 120 ° C several times, a sheet-like molded product having a thickness of 1. Omm was obtained.
- the obtained sheet-like molded product was sandwiched between a pair of slide glasses having a length of 26 mm, a width of 76 mm, and a thickness of lmm to obtain a laminate.
- the laminated body was pressure-bonded in an autoclave at a temperature of 130 ° C. and a pressure of 1.2 MPa to obtain laminated glasses of Examples 22 to 41 and Comparative Examples 10 to 18.
- the cases using the near-infrared light-absorbing compositions of Examples 1 to 20 were compared with Examples 22 to 41, and the cases using the gold-infrared light-absorbing yarns of Comparative Examples 1 to 8 were compared. Examples 9 to 16 respectively apply.
- the haze values and ⁇ haze values before and after the irradiation of the ultraviolet rays are collectively shown in Tables 8 and 9.
- Example 22 5. 6. 8. 6 2. 9 Example 23 4. 5.5 5 0.5 Example 24 3. 6. 6. 3 2.5 Example 25 3. 7 7. 6 3. 9 Example 26 10 10.7 0.7 Example 27 34.6 31.3 -3.3 Example 28 1 2.2 1.2 Example 29 1.3 1.7 0.4 Example 30 2.6.2.2. -0.4 Example 31 3.8.2.1.6 -1.2 Example 32 1.3 5.4.4 4.1 Example 33 1.7 4.73 Example 34 3.9.3.10 .3 Example 35 3.4 2.9 -0.5 Example 36 3 7 4 Example 37 31.4 15.7 -15.7 Example 38 3.7 4 0.3 Example 39.5.7 2.5-3.2 Example 40 8. 1 7.1-1 Example 41 9.2 8.4 -0.8 Example 42 42 0.1 0.1 0.7 0.6 Laminated glass light resistance test
- the laminated glasses of Examples 22 to 42 using specific combinations of phosphoric acid ester conjugates had haze values (Oh and 100h) of less than 50. Excellent in light transmittance (transparency), and the force is ⁇ haze value of less than 5, so that even after irradiation with ultraviolet rays, the decrease in light transmittance is extremely small and the light resistance is excellent. It is certain that f * i3 ⁇ 4.
- the laminated glass of Comparative Examples 9 to 16 in which the phosphoric acid ester conjugate was used in the specific combination described above was unsuitable as a window material having a haze exceeding 50 and a low translucency. Or the ⁇ haze was more than 5 and the light resistance was low.
- the laminated glass of Examples 22 to 34 and Examples 38 to 41 using the OLPC of Preparation Example 1 as (I) had a ⁇ haze value of ⁇ 5. It was found to be extremely excellent in light resistance.
Abstract
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JP2006220872A (ja) * | 2005-02-09 | 2006-08-24 | Olympus Corp | 光学フィルタ、光学フィルタの製造方法および撮像装置 |
WO2007142095A1 (ja) * | 2006-05-31 | 2007-12-13 | Sekisui Chemical Co., Ltd. | 合わせガラス用中間膜及び合わせガラス |
JPWO2006035756A1 (ja) * | 2004-09-29 | 2008-05-15 | 株式会社クレハ | 近赤外光吸収材料及び積層体 |
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JP2015220026A (ja) * | 2014-05-15 | 2015-12-07 | 株式会社小糸製作所 | 車両用灯具 |
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 |
WO2019244589A1 (ja) * | 2018-06-19 | 2019-12-26 | 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 |
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