JPWO2005111170A1 - Near infrared light absorbing material, near infrared light absorbing composition and laminate - Google Patents

Abstract

The present invention provides a laminated glass with a near-infrared light absorbing material capable of imparting not only the property of blocking near-infrared light but also excellent light resistance, a near-infrared light-absorbing composition containing the same, and An object of the present invention is to provide a laminate including a layer containing the near infrared light absorbing composition. A laminated glass 10 according to an embodiment of the present invention has a structure in which an intermediate film 2 is disposed between a pair of translucent substrates 1. This intermediate film 2 has (I): a phosphate ester compound having an alkenyl group having 12 to 24 carbon atoms, (II): an alkyl group, or a monovalent group having an ether bond and / or an ester bond. And (III): a near infrared light absorbing composition containing a copper ion-containing near infrared light absorbing material and a synthetic resin.

Description

  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 them.

  As an optical member for use in a window material or the like, a laminated glass having a structure in which an intermediate film made of polyvinyl acetal resin, acrylic resin, or the like is sandwiched between a pair of translucent substrates made of glass or the like is known. Such a laminated glass is frequently used because it has excellent properties such as high strength and high durability.

  In recent years, these laminated glasses have been required to have characteristics capable of blocking infrared rays or light rays having wavelengths in the vicinity thereof (hereinafter referred to as “near infrared light”). If laminated glass having such characteristics is applied to window materials, wall materials, and the like, for example, light having a wavelength in the above-described region in sunlight, that is, entry of heat rays into the room can be suppressed. Thereby, it becomes possible to keep the indoor environment comfortable by suppressing the temperature from becoming excessively high, and it is also possible to reduce the cost for cooling and the like.

As a laminated glass capable of blocking near-infrared light, one having a layer (near-infrared light absorbing layer) having a property of absorbing near-infrared light as an intermediate film is known (for example, Patent Documents). 1-3). Such an intermediate film can be formed by, 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.
JP 9-2111220 A Japanese Patent Laid-Open No. 7-101756 JP 2002-293583 A

  By the way, the laminated glass having the above-described configuration is required to have a property of being excellent in light resistance in addition to a property of blocking near infrared light. That is, it is desirable that the film has a characteristic that turbidity or the like hardly occurs 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, and therefore has extremely high practicality.

  The present invention has been made in view of such circumstances, and a near-infrared light absorbing material capable of imparting not only the property of blocking near-infrared light but also excellent light resistance to laminated glass, An object is to provide a near-infrared light-absorbing composition containing, and a laminate including a near-infrared light-absorbing layer containing these.

  In order to achieve the above object, as a result of intensive studies, the present inventors have a specific functional group as a phosphorus-containing compound in a near-infrared light-absorbing material containing a phosphorus atom-containing compound and copper ions. By using two or more kinds of compounds, it has been found that even when exposed to sunlight for a long time, the near-infrared light blocking property is less lowered, and an intermediate film having high translucency can be provided. The present invention has been reached.

［式中、Ｒ^１は炭素数１２〜２４のアルケニル基、Ｒ^２１は炭素数１〜１５の鎖状又は環状アルキル基、Ｒ^２２はエーテル結合及び／又はエステル結合を有する１価の有機基を示し、ｉ、ｊ及びｋはそれぞれ独立に１又は２である。］That is, the near infrared light absorbing material of the present invention contains (I), (II) and (III).
(I): Phosphate ester compound represented by the following general formula (1) (II): Phosphate ester compound represented by the following general formula (2a) and / or represented by the following general formula (2b) Phosphate ester compound (III): Copper ion

[Wherein, R ¹ represents an alkenyl group having 12 to 24 carbon atoms, R ²¹ represents a chain or cyclic alkyl group having 1 to 15 carbon atoms, and R ²² represents a monovalent organic group having an ether bond and / or an ester bond. I, j and k are each independently 1 or 2. ]

  Thus, the near-infrared light-absorbing material of the present invention has a phosphate ester compound having an alkenyl group having 12 to 24 carbon atoms and an alkyl group, or an ether bond and / or an ester bond as a phosphorus-containing compound. It contains in combination with a phosphate compound having a monovalent organic group. According to the near-infrared light-absorbing material containing the phosphoric acid ester compound in such a combination, an intermediate film of laminated glass that has not only high near-infrared light absorbability but also excellent light resistance can be obtained. This is because the near-infrared light absorbing material containing these phosphoric acid ester compounds can be easily dissolved and / or dispersed in the resin material, or decomposed into sunlight or the like. This is thought to be due to the difficulty of being made.

In the near-infrared light absorbing material of the present invention, R ¹ is preferably an oleyl group. The near-infrared light-absorbing material containing a phosphate ester compound having an oleyl group as the component (I) exhibits better near-infrared light absorption and light resistance when used in an interlayer film of laminated glass. obtain.

［式中、Ｒ^３１は炭素数２〜４のアルキレン基、Ｒ^３２は炭素数１〜１２のアルキル基又は炭素数２〜５のアシル基を示し、ｍは１〜６の整数である。］Also, in the near infrared absorbing material of the present invention, among the compounds of (II), phosphoric acid ester compound represented by the general formula (2b), as the group represented by R ^22, the following general formula It is preferable that it has a monovalent group represented by (3). If it carries out like this, the light resistance of the intermediate film of a laminated glass can further be improved.

[Wherein R ³¹ represents an alkylene group having 2 to 4 carbon atoms, R ³² represents an alkyl group having 1 to 12 carbon atoms or an acyl group having 2 to 5 carbon atoms, and m is an integer of 1 to 6. ]

In the near-infrared light-absorbing material of the present invention, (II) is a phosphate ester compound represented by the general formula (2a), and R ²¹ in the compound has 8 carbon atoms. It is more preferable that it is an alkyl group. By using a combination of such a phosphate ester compound and a phosphate ester compound having an oleyl group, it becomes possible to obtain a laminated glass having further excellent near-infrared light absorption characteristics and light resistance.

  Moreover, the near-infrared light absorbing composition of the present invention contains the near-infrared light absorbing material of the present invention and a synthetic resin. In such a near-infrared light-absorbing composition, as described above, the near-infrared light-absorbing material is well dissolved and / or dispersed in the synthetic resin (resin material). An interlayer film of laminated glass or the like hardly causes a change in translucency even when exposed to sunlight for a long time. Therefore, a laminated glass provided with such an intermediate film has excellent near-infrared light blocking characteristics and excellent light resistance.

  The present invention also provides a laminate comprising a translucent substrate and a near-infrared light absorbing layer comprising the near-infrared light-absorbing composition of the present invention provided on the translucent substrate. Such a laminate is provided with a near infrared light absorbing layer comprising the near infrared light absorbing composition of the present invention, so that it has not only excellent properties for blocking near infrared light but also light resistance. It has the property of being excellent. Moreover, if this laminated body is made into the structure which pinches | interposes a near-infrared-light absorption layer with a pair of translucent board | substrates, the laminated glass excellent in both a near-infrared-light cutoff characteristic and light resistance can be obtained.

  According to the present invention, a near-infrared light absorbing material capable of imparting not only the property of blocking near-infrared light but also excellent light resistance to laminated glass, and a near-infrared light-absorbing composition containing the same And it becomes possible to provide the laminated body provided with the near-infrared-light absorption layer containing these.

It is a figure which shows typically an example of the cross-section of the laminated glass which concerns on suitable embodiment. It is a figure which shows typically an example of the cross-section of the laminated glass which has a reflection layer. It is a figure which shows typically an example of the cross-section of the laminated glass which has a reflection layer between the some layers provided between the translucent board | substrates.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Translucent substrate, 2 ... Intermediate film, 10 ... Laminated glass, 20 ... Laminated glass, 21 ... Translucent substrate, 22 ... Near-infrared light absorption layer, 23 ... Reflective layer, 30 ... Laminated glass, 31 ... Translucent substrate, 32 ... near infrared light absorbing layer, 33 ... reflective layer, 34 ... resin layer.

  DESCRIPTION OF EXEMPLARY EMBODIMENTS Hereinafter, preferred embodiments of the invention will be described with reference to the drawings.

(Near infrared light absorbing material)
First, a near infrared light absorbing material according to a preferred embodiment will be described. The near-infrared light absorbing material contains the above (I), (II) and (III). The component (I) is a phosphate ester compound represented by the above general formula (1), and has an alkenyl group having 12 to 24 carbon atoms as the group represented by R ¹ . This alkenyl group has at least one unsaturated bond in the structure. The group represented by R ¹ is more preferably an alkenyl group having 14 to 24 carbon atoms, and further preferably an alkenyl group having 16 to 22 carbon atoms. For example, examples of the group represented by R ¹ include an oleyl group, trans-9-octadecenyl group, cis, cis-9,12-octadecenyl group, cis-9-tetradecenyl group, cis-11-tetradecenyl group, and cis-8. -Dodecenyl group, cis-13-docosenyl group, and the like. The phosphate ester compound represented by the general formula (1) may be a mixture of a phosphate monoester compound in which i is 1 and a phosphate diester in which i is 2.

Among them, the group represented by R ^1, oleyl group. Such a compound can be represented by the following general formula (4). In formula, i is synonymous with the above.

  The component (II) is a phosphate ester compound represented by the above general formula (2a) and / or a phosphate ester compound represented by the above general formula (2b). The near-infrared light-absorbing material may contain these compounds individually or in combination. Moreover, the phosphate ester compound represented by the general formula (2a) and the phosphate ester compound represented by the general formula (2b) include a phosphate monoester compound in which j or k is 1, j or k It may be a mixture with a phosphoric acid diester in which is 2.

Phosphoric acid ester compound represented by the general formula (2a) has an alkyl group as the group represented by R ^21. As an alkyl group, a C1-C15 alkyl group is preferable, a C4-C12 alkyl group is more preferable, and a C8 alkyl group is still 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. An ethylhexyl group is preferred.

The compound represented by the general formula (2b) has a monovalent organic group containing an ether bond and / or an ester bond as the group represented by R ²² . Such an organic group may have either an ether bond or an ester bond, or may have both.

Examples of the monovalent group having an ether bond include the group represented by the general formula (3). In the group represented by the general formula (3), R ³¹ is preferably an alkylene group having 2 to 3 carbon atoms. Moreover, m is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3. Further, in R ³² , the alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and the acyl group is preferably a (meth) acryl group. Here, the (meth) acryl group means an acryl group or a methacryl group.

Examples of the group represented by general formula (3) in which R ³² is an alkyl group include groups represented by the following chemical formulas (5a) to (5j).

In addition, among the groups represented by the general formula (3), examples of the group in which R ³² is an acyl group include groups represented by the following general formula (6). In the following formula, n is 5 or 6.

On the other hand, the monovalent group having an ester bond, which is a group represented by R ²² , includes a group having an ester group in the molecular chain and a (meth) acryl group at the terminal. Specific examples include groups represented by the following chemical formula (7).

The phosphoric acid ester compounds of (I) and (II) described above are, for example, (1) a hydroxyl compound (alcohol) having a hydroxyl group at the terminal of the structure represented by R ¹ , R ²¹ or R ²² A method of reacting phosphorus pentoxide, (2) a method of reacting the hydroxyl compound with phosphorus oxyhalide and then hydrolyzing, and (3) a reaction of the hydroxyl compound with phosphorus trihalide to phosphonate. After the compound is synthesized, the compound can be synthesized by a method of oxidizing the obtained phosphonate compound. Any of these reactions can be carried out without solvent or in the presence of a predetermined organic solvent. Moreover, the mixing ratio of a monoester body and a diester body is also controllable by selecting these methods suitably and also changing reaction conditions suitably.

  The component (III) is a divalent copper ion. Specific examples of copper salts for supplying copper ions include copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, and other organic acids. Salt anhydride, hydrate or hydrate, or copper salt anhydride, hydrate or hydrate, or copper hydroxide of inorganic acid such as copper chloride, copper sulfate, copper nitrate, basic copper carbonate, etc. Can be mentioned. Among these, copper acetate, copper acetate monohydrate, copper benzoate, copper hydroxide, and basic copper carbonate are preferably used. In addition, these copper salts which are copper ion sources may be used independently, and may be used in multiple combination.

  As described above, the near-infrared light absorbing material of the embodiment includes the components (I), (II), and (III) as essential components. In the material, (I), (II) And each component of (III) may exist merely as a mixture, and the phosphate ester compound of (I) and the phosphate ester compound of (II) react with a divalent copper ion to form a phosphate ester copper compound. It may be present in the state of forming.

  In the latter case, the phosphoric acid ester copper compound is preferably generated by an ionic bond and / or a coordinate bond between the phosphate group and the copper ion in each phosphoric ester compound. Such phosphate ester copper compounds may be prepared by mixing the phosphate esters of (I) and (II) and then reacting this mixture with copper ions. The phosphoric acid ester copper compound corresponding to each phosphoric ester compound is obtained by reacting with copper ions, and then prepared by mixing them.

  In the near-infrared light absorbing material, the content of the phosphate ester compound (I) is preferably 10% by mass or more based on the total amount of the phosphate ester compounds (I) and (II). More preferably, it is 15-99 mass%, and it is still more preferable that it is 20-90 mass%. When the content of the phosphoric acid ester compound of (I) is less than 10% by mass, the solubility and / or dispersibility of the near-infrared light absorbing material in the resin component tends to be reduced. The light resistance of the laminated glass used may be insufficient.

  Furthermore, the ratio of the content of the phosphate ester compound of copper ion and (I) and (II) is such that when these phosphate ester compounds have a hydroxyl group or a hydroxyl group-derived oxygen atom (hydroxyl group or oxygen atom ) / Cu in a molar ratio, preferably 1 to 6, more preferably 1 to 4, and even more preferably 1.5 to 2.5. If this ratio is less than 1, the solubility and / or dispersibility of the near-infrared light absorbing material is lowered, and the near-infrared light absorbing performance and translucency tend to be lowered. On the other hand, if it exceeds 6, the amount of hydroxyl groups that do not participate in coordination bonds or ionic bonds with copper ions becomes excessive, and the hygroscopicity tends to be too large.

  The near-infrared light absorbing material may contain metal ions other than copper ions. Examples of such other 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. Examples of rare earth metals include neodymium, praseodymium and holmium. Such rare earth metals have excellent absorption characteristics for light of a specific wavelength (wavelength near 580 nm or wavelength near 520 nm) due to the electronic transition of the f-orbital of rare earth ions, and these wavelength ranges are the maximum response wavelengths of the human eyeball photoreceptor cells. Therefore, antiglare property can be imparted to the above-mentioned material.

(Near infrared light absorbing composition)
A near-infrared light absorbing composition according to a preferred embodiment includes the above-described near-infrared light absorbing material and a synthetic resin, and the near-infrared light absorbing material is dissolved and / or dispersed in the synthetic resin. It is made. As the synthetic resin, a resin that is excellent in dispersibility of the near-infrared light absorbing material and excellent in the property of transmitting visible light is preferable. Examples of such synthetic resins include polyvinyl acetal resin, ethylene-vinyl acetate copolymer (EVA), (meth) acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, norbornene resin, and the like. Is mentioned.

  Among these synthetic resins, polyvinyl acetal resin is preferable, and polyvinyl butyral (PVB) is particularly preferable. Such a resin has not only excellent adhesion to a light-transmitting substrate in a laminate described later, but also has a characteristic that it is flexible and hardly deforms depending on temperature. For this reason, the shaping | molding process at the time of manufacturing a laminated body becomes easy by using polyvinyl acetal resin. Further, the obtained interlayer film has excellent transparency, weather resistance, adhesion to glass, and the like. Furthermore, the polyvinyl acetal resin also has a characteristic that the near-infrared light absorbing material described above is particularly easy to dissolve and / or disperse. For this reason, according to the combination of the near-infrared light absorbing material and the polyvinyl acetal resin, a laminated glass having excellent translucency and light resistance can be obtained.

  The polyvinyl acetal resin may be blended in an appropriate combination depending on the required physical properties, or may be a polyvinyl acetal resin obtained by acetalizing a combination of aldehydes during acetalization. The molecular weight, molecular weight distribution, and degree of acetalization of the polyvinyl acetal resin are not particularly limited, but the degree of acetalization is generally 40 to 85%, and the preferred lower limit is 60% and the upper limit is 75%.

  The polyvinyl acetal resin can be obtained by acetalizing a polyvinyl alcohol resin with an aldehyde. The polyvinyl alcohol resin is generally obtained by saponifying polyvinyl acetate, and a polyvinyl alcohol resin having a saponification degree of 80 to 99.8 mol% is generally used. The preferable lower limit of the viscosity average polymerization degree of the polyvinyl alcohol resin is 200, and the upper limit is 3000. The penetration resistance of the laminated glass obtained as it is less than 200 falls. When it exceeds 3000, the moldability of the resin film is deteriorated, and the rigidity of the resin film is excessively increased, so that the workability is deteriorated. A more preferred lower limit is 500 and an upper limit is 2000. The viscosity average polymerization degree and the saponification degree of the polyvinyl alcohol resin can be measured based on, for example, JIS K 6726 “Testing method for polyvinyl alcohol”.

  The aldehyde is not particularly limited, and examples thereof include aldehydes having 1 to 10 carbon atoms. More specifically, examples include n-butyraldehyde, isobutyraldehyde, n-valeraldehyde, 2-ethylbutylarte. Examples include hydride, n-hexyl aldehyde, n-octyl aldehyde, n-nonyl aldehyde, n-decyl aldehyde, 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 near-infrared light-absorbing composition having such a structure can be obtained by dissolving and / or dispersing the near-infrared light-absorbing material directly in the synthetic resin, or by absorbing the near-infrared light in the monomer of the synthetic resin. After the material is dissolved and / or dispersed, it can be prepared by a method of polymerizing the monomer.

  The former method is effective, for example, when the synthetic resin has thermoplasticity. Specifically, after the synthetic resin is heated and melted, the near infrared light absorbing material is kneaded, or after the synthetic resin is dissolved and / or dispersed in a solvent, the near infrared light absorbing material is added to the solution. After adding and mixing, it can be carried out by a method of removing the solvent.

  The latter method is effective when the synthetic resin has thermosetting properties. As a polymerization method, radical polymerization is generally used. In this case, a polymerization initiator may be further contained in a mixture comprising a near-infrared light absorbing material and a synthetic resin monomer. Such a polymerization reaction does not need to be performed immediately after the monomer and the near-infrared light absorbing material are mixed. For example, as described later, the polymerization reaction is performed after coating on a predetermined substrate. You can also.

  Furthermore, it is preferable that the near-infrared light-absorbing composition contains a plasticizer that is excellent in compatibility with the synthetic resin in addition to the above-mentioned near-infrared light-absorbing material and synthetic resin. When the plasticizer is contained, the solubility and / or dispersibility of the near-infrared light absorbing material in the synthetic resin is further enhanced, and the light resistance can be further improved. Examples of such plasticizers include known plasticizers that are used for intermediate films, such as phosphate ester plasticizers, phthalic acid plasticizers, fatty acid plasticizers, glycol-based plasticizers. A plasticizer etc. can be illustrated.

  More specifically, for example, organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are preferably used. It is done. These plasticizers may be used alone or in combination of two or more, and are used properly in consideration of compatibility or the like depending on the type of resin.

  Examples of monobasic organic acid esters include glycols such as triethylene glycol, tetraethylene glycol or tripropylene glycol, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptanoic acid, n-octanoic acid, 2- Examples thereof include glycol esters obtained by reaction with monobasic organic acids such as ethylhexanoic acid, pelargonic acid (n-nonyl acid) or decyl acid. More specifically, triethylene glycol di-2-ethylhexanoate (3GO), triethylene glycol di-2 ethyl butyrate (3GH), dihexyl adipate (DHA), tetraethylene glycol diheptanoate (4G7) , Tetraethylene glycol di-2-ethylhexanoate (4GO), triethylene glycol diheptanoate (3G7) and the like. Of these, 3GO, 3GH, 3G7 and the like are preferable.

  The polybasic organic acid ester is not particularly limited. For example, by reacting a polybasic organic acid such as adipic acid, sebacic acid or azelaic acid with a linear or branched alcohol having 4 to 8 carbon atoms. Examples are esters obtained. For example, dibutyl sebacate, dioctyl azelate, dibutyl carbitol adipate and the like are suitable.

  Examples of the organic phosphate plasticizer include tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphate, and the like.

  The plasticizer content in the composition is preferably 1 to 120 parts by mass, more preferably 1 to 100 parts by mass, and 2 to 80 parts by mass with respect to 100 parts by mass of the resin material. Is more preferable. When 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 ions and the phosphorus-containing compound may be reduced, and the translucency may be insufficient. On the other hand, when it exceeds 100 parts by mass, the resin material as the base material becomes too flexible, and for example, it tends to be difficult to use as an interlayer film in laminated glass.

  Moreover, the near-infrared light absorptive composition may contain the adhesive force regulator. In addition, an adhesive force regulator may be apply | coated to the surface of the intermediate film (near infrared light absorption layer) mentioned later. Examples of the adhesion modifier include alkali metal salts or alkaline earth metal salts of organic or inorganic acids, modified silicone oils, and the like. The organic acid is not particularly limited, and examples thereof include carboxylic acids such as octanoic acid, hexanoic acid, butyric acid, acetic acid, and formic acid. It does not specifically limit as said inorganic acid, For example, hydrochloric acid, nitric acid, etc. are mentioned. It does not specifically limit as said alkali metal salt and alkaline-earth metal salt, For example, salts, such as potassium, sodium, calcium, magnesium, are mentioned.

  Among the alkali metal salts or alkaline earth metal salts of the organic acid or inorganic acid, alkali metal salts and alkaline earth metal salts of organic acids having 2 to 16 carbon atoms are preferable, and more preferably 2 to 16 carbon atoms. Potassium salt and magnesium salt of carboxylic acid.

  Although it does not specifically limit as said C2-C16 carboxylic acid potassium salt and magnesium salt, For example, magnesium acetate, potassium acetate, magnesium propionate, potassium propionate, magnesium 2-ethylbutanoate, potassium 2-ethylbutanoate, Magnesium 2-ethylhexanoate, potassium 2-ethylhexanoate and the like are suitable. These may be used alone or in combination of two or more.

  The minimum with the preferable compounding quantity of the alkali metal salt or alkaline-earth metal salt of the said organic acid or inorganic acid is 0.001 weight part with respect to 100 weight part of resin, and an upper limit is 0.5 weight part. If it is less than 0.001 part by weight, the adhesive strength of the peripheral part may be lowered in a high humidity atmosphere. If it exceeds 0.5 parts by weight, the transparency of the film may be lost. A more preferred lower limit is 0.01 parts by weight and an upper limit is 0.2 parts by weight.

  Examples of the modified silicone oil include epoxy-modified silicone oil, ether-modified silicone oil, ester-modified silicone oil, amine-modified silicone oil, carboxyl-modified silicone oil, and the like. These may be used independently and 2 or more types may be used together. These modified silicone oils are generally obtained by reacting a compound to be modified with polysiloxane.

  The preferable lower limit of the molecular weight of the modified silicone oil is 800, and the upper limit is 5000. If it is less than 800, localization to the surface may be insufficient. If it exceeds 5000, the compatibility with the resin may be reduced, bleeding out to the surface of the film, and the adhesive force with the glass may be reduced. A more preferred lower limit is 1500 and an upper limit is 4000.

  The preferable lower limit of the blending amount of the modified silicone oil is 0.01 part by weight with respect to 100 parts by weight of the resin, and the upper limit is 0.2 part by weight. If it is less than 0.01 part by weight, the effect of preventing whitening due to moisture absorption may be insufficient. If the amount exceeds 0.2 parts by weight, the compatibility with the resin may decrease, and the adhesive force between the resin and glass may decrease due to bleeding out on the film surface. A more preferred lower limit is 0.03 parts by weight and an upper limit is 0.1 parts by weight.

  The near-infrared light-absorbing composition may contain other additives in addition to the plasticizer and the adhesion modifier. Examples of such additives include a component for adjusting the color tone, a component for adjusting physical properties, a component for stabilizing the polymer after polymerizing the polymerizable composition, and a laminate described later. Examples of the component for improving the adhesion to the light-transmitting substrate when the film is formed. In addition, additives such as an antioxidant, a surfactant, a flame retardant, an antistatic agent, and a moisture-resistant agent for preventing deterioration due to heat in the extruder may be added as necessary.

  For example, examples of the component for adjusting the color tone include dyes, pigments, and metal compounds. In addition, as components for adjusting physical properties, (meth) acrylic monomers having an α, β-unsaturated bond such as styrene, butadiene, vinyl acetate, oligomers excellent in compatibility with (meth) acrylic resins, Examples thereof include polymers.

  Furthermore, examples of the component for stabilizing the polymerizable composition include a light stabilizer, a heat stabilizer, an antioxidant, and an ultraviolet absorber. Furthermore, 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 coupling such as a silane coupling agent such as vinyl silane, acrylic silane, or epoxy silane is used. An agent can be illustrated.

  Examples of the ultraviolet light absorber include benzoate compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, oxalic acid anilide compounds, triazine compounds, and the like.

  More specifically, examples of the benzoate compound include 2,4-di-t-butylphenyl-3 ', 5'-di-t-butyl-4'-hydroxybenzoate. Examples of salicylate compounds include phenyl salicylate and pt-butylphenyl salicylate.

  Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2 ′, 4,4′-tetrahydrobenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2′-dihydroxy-4 , 4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone-5,5′-sodium disulfonate, 2,2′-dihydroxy-5-methoxybenzophenone, 2-hydroxy-4-methacryloyl Oxyethylbenzophenone, - benzoyloxy-2-hydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxy benzophenone.

  Examples of the benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzo. Triazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) ) Benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-butylphenyl) benzotriazole, 2- [2'-hydroxy-3 ' -(3 ", 4", 5 ", 6" -tetrahydrophthalimidomethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy -3 ', 5'-di-t-amylphenyl) benzotriazole, 2- (2'-hydroxy-5-t-octylphenyl) benzotriazole, 2- [2'-hydroxy-3', 5'-bis (Α, α-dimethoxybenzoyl) phenyl] benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] 2- (2′-hydroxy-5′-methacryloyloxyethylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, methyl-3- [ 3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol Like condensates of.

  Examples of cyanoacrylate compounds include ethyl-2-cyano-3,3-diphenyl acrylate and octyl-2-cyano-3,3-diphenyl acrylate. Examples of oxalic acid anilide compounds include 2-ethoxy-2 ′. -Ethyl oxalic acid bisanilide and 2-ethoxy-5-t-butyl-2'-ethyl oxalic acid bisanilide. Examples of the triazine-based compound include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol.

  Further, as the light stabilizer, a hindered amine light stabilizer (HALS) or a Ni compound can be applied. In particular, when the above-described ultraviolet light absorber and these light stabilizers are used in combination, the stability to light tends to be very good.

  More specifically, HALS includes bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1 -[2- [3- (3,5-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionyloxy ] -2,2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl- 1,3,8-triazaspiro [4,5] decane-2,4-dione, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-t -Butyl-4-hydroxybe Diyl) -2-n-butylmalonate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (2,2,6) , 6-Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, (Mixed 1,2,2,6,6-pentamethyl-4-piperidyl / tridecyl) -1,2,3 , 4-Butanetetracarboxylate, Mixed {1,2,2,6,6-pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8, 10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, Mixed {2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2 , 4,8,10-tetraoxaspiro (5,5) undecane] diethyl} -1,2,3,4-butanetetracarboxylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 1 , 2,2,6,6-pentamethyl-4-piperidyl methacrylate, poly [(6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl) ] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) iminol], dimethyl succinate polymer-with-4 - Droxy-2,2,6,6-tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2 , 2,6,6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine-1,3,5-triazine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethylpiperidyl) butylamine polycondensate, decane And diacid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester.

  Ni-based light stabilizers include [2,2′-thio-bis (4-t-octylphenolate)]-2-ethylhexylamine-nickel (II), nickel dibutyldithiocarbonate, [2,2 '-Thio-bis (4-t-octylphenolate)]-butylamine-nickel (II) and the like.

  The content of the near-infrared light-absorbing material in the near-infrared light-absorbing composition is preferably 0.5 to 45% by mass with respect to the total amount of the near-infrared light-absorbing composition, and 1 to 40 More preferably, it is 1 mass%, and it is still more preferable that it is 1-35 mass%. When the content of the near-infrared light absorbing material is less than 0.5% by mass, the near-infrared light blocking property of the laminated glass obtained using the composition tends to be lowered. On the other hand, when the content exceeds 45% by mass, the near-infrared light absorbing material is not sufficiently dissolved in the synthetic resin, and the translucency of the laminated glass obtained using the composition tends to be reduced. is there.

(Optical member)
By using the above-described near-infrared light absorbing composition, an optical member having excellent properties for blocking near-infrared light can be obtained. Examples of such an optical member include first and second forms shown below.
1st form: The sheet-like molding obtained by processing a near-infrared-light-absorbing composition.
2nd form: The laminated body which has a translucent board | substrate and the near-infrared-light absorption layer which consists of a near-infrared-light absorption composition provided adjacent to this translucent board | substrate.

  First, the first embodiment will be described. The optical member of the 1st form is a sheet-like molded product which consists of a near-infrared light absorptive composition mentioned above, and specifically, a sheet and a film are mentioned. Here, the sheet is a thin plate having a thickness exceeding 250 μm. The film is a thin film having a thickness of 5 to 250 μm. These sheets or films can be produced using a known sheet or film forming method. Examples of such sheet or film forming methods include melt extrusion molding, stretch molding, calendar molding, press molding, solution casting, and the like.

  Next, a 2nd form is demonstrated. The optical member of the 2nd form is a laminated body which has a translucent board | substrate and the near-infrared-light absorption layer which consists of a near-infrared-light absorption composition provided adjacent to this translucent board | substrate.

  The material which comprises a translucent board | substrate is not specifically limited if it is a translucent material which has visible-light transmissivity, According to the use of an optical member, it can select suitably. From the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, etc., glass or plastic is preferably used. Examples of the glass include inorganic glass and organic glass. Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin and the like. When there are a plurality of light-transmitting substrates, each substrate may be composed of the same type of material or may be composed of different materials.

  Such a laminate can be produced, for example, by forming a sheet or film similar to the optical member of the first embodiment described above, and then laminating the sheet and the translucent substrate. As a method for pasting them together, a means for bonding by pressurization or pressure reduction such as a press method, a multi-roll method, a decompression method, a means for adhesion by heating using an autoclave, or a combination of these is used. be able to.

  Moreover, as a manufacturing method of a laminated body, the method of forming a near-infrared-light absorption layer directly on a translucent base material other than the method of bonding together the sheet | seat formed previously can also be applied. As such a method, for example, the above-mentioned near-infrared light absorbing composition is dissolved and / or dispersed in an appropriate solvent to form a coating agent, and this solution is applied to a light-transmitting substrate, and then the solvent is evaporated. Can illustrate a method of forming a thin film, covering or thin layer comprising a near-infrared light absorbing composition on a translucent substrate. The thin film thus formed is called a coating. When forming a near-infrared light absorbing layer using such a method, for the purpose of improving the flatness of the layer, various auxiliary agents such as leveling agents and antifoaming agents are used as described above. You may add in the coating agent.

  Furthermore, as another method for directly forming a near infrared light absorbing layer on a translucent substrate, a composition in which a near infrared light absorbing material is dissolved and / or dispersed in a synthetic resin monomer is prepared. In addition, there may be mentioned a method in which a polymerization reaction of a monomer is caused on the surface of the base material after the composition is applied onto the translucent base material. In this case, a solvent may be further added to the composition.

  The optical member of the second form, i.e., the laminate, is not limited to one provided with the light-transmitting substrate and the near-infrared light absorbing layer as described above, and may include a plurality of these layers. Good. Specifically, what includes 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 mentioned. It is done. Such a laminate is a so-called laminated glass.

  Here, with reference to FIG. 1, the laminated glass of suitable embodiment is demonstrated.

  FIG. 1 is a diagram schematically illustrating 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 absorption 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 the same light-transmitting substrate 1 as described above can be applied.

  The laminated glass 10 having such a structure is obtained by, for example, sandwiching a sheet-like molded product made of the above-described near-infrared light absorbing composition between a pair of translucent substrates, and pre-pressing the sheet-like molded product to remain between the layers. After the removed air is removed, it can be manufactured by a method in which these are pressure-bonded to bring them into close contact.

  When the laminated glass 10 is produced by such a production method, the so-called blocking phenomenon in which the sheets are bonded to each other to form a lump at the time of storage does not occur on the intermediate film 2 or the film is removed in the pre-compression bonding. It is required to have good temper. When these requirements are satisfied, workability when superimposing the translucent substrate 1 and the sheet is improved, and, for example, translucency due to bubbles generated due to insufficient deaeration, etc. Decline can be prevented.

  Such a laminated glass 10 is required to have excellent translucency, that is, a property of transmitting light in the visible light region, in addition to the property of blocking near-infrared light. In order to obtain such excellent translucency, it is preferable that bubbles are not formed between the translucent substrate 1 and the intermediate film 2 as much as possible.

  As one of means for reducing bubbles in this way, a method using an intermediate film 2 having a large number of minute irregularities called emboss on the surface is known. According to the intermediate film 2 to which such embossing is applied, the degassing property in the above-described pre-compression bonding step or the like becomes extremely good. As a result, the laminated glass 10 is less subject to a decrease in translucency due to bubbles.

  Examples of such embossed forms include various uneven patterns composed of a large number of convex portions and a large number of concave portions with respect to these convex portions, and various types of grooves composed of a large number of convex strips and a large number of concave grooves corresponding to these convex strips. There are embossed shapes with various values for various shape factors such as uneven patterns, roughness, arrangement, size, etc.

  As these embossments, for example, those described in Japanese Patent Laid-Open No. 6-198809, the size of the convex portion is changed, and the size and arrangement thereof are defined, and those described in Japanese Patent Laid-Open No. 9-40444 are disclosed. Surface roughness of 20-50 μm, described in JP-A-9-295839, arranged so that the ridges intersect, or described in JP-A-2003-48762, The thing which formed the smaller convex part on the main convex part is mentioned. Also, as a method for embossing, Special Table 2003-528749 includes a method using a melt fracture generated during resin molding, Special Table 2002-505111, and Special Table 9-502755 include crosslinked PVB particles and nucleating agents. A method of using is proposed.

  In addition, another characteristic required for the laminated glass 10 in recent years is sound insulation. According to the laminated glass having excellent sound insulation, for example, when used for a window material, the influence of ambient noise and the like can be reduced, and the indoor environment can be further improved. In general, the sound insulation performance is shown as a transmission loss amount corresponding to a change in frequency, and the transmission loss amount is defined by JISA 4708 at a constant value according to the sound insulation grade at 500 Hz or more.

  However, the sound insulation performance of a glass plate generally used as a translucent substrate for laminated glass tends to be significantly reduced due to the coincidence effect in a frequency region centered on 2000 Hz. Here, the coincidence effect means that when a sound wave is incident on a glass plate, the transverse wave propagates through the glass plate due to the rigidity and inertia of the glass plate, and the transverse wave and the incident sound resonate. This is a phenomenon that occurs. Therefore, in general laminated glass, it is difficult to avoid a decrease in sound insulation performance due to such a coincidence effect in a frequency region centered on 2000 Hz, and improvement of this point is demanded.

  In this regard, it is known from the equal loudness curve that human hearing exhibits a very good sensitivity in the range of 1000 to 6000 Hz compared to other frequency regions. Therefore, it is important to improve the sound insulation performance to eliminate the drop in the sound insulation performance due to the coincidence effect. From this point of view, in order to improve the sound insulation performance of the laminated glass 10, it is necessary to alleviate the decrease in the sound insulation performance due to the coincidence effect and to prevent the minimum portion of the transmission loss caused by the coincidence effect.

  As a method for imparting sound insulation to the laminated glass 10, a method for increasing the mass of the laminated glass 10, a method for compounding the glass to be the translucent substrate 1, a method for subdividing the glass area, and a glass plate support There are ways to improve the means. In addition, the sound insulation performance depends on the dynamic viscoelasticity of the interlayer film 2, and in particular, it may be influenced by the loss tangent, which is the ratio of the storage elastic modulus and the loss elastic modulus. Moreover, the sound insulation performance of the laminated glass 10 can be enhanced.

  As means for controlling the value of loss tangent as the latter, for example, a method using a resin film having a specific degree of polymerization, a method for defining the resin structure as described in JP-A-4-2173443, Examples thereof include a method for defining the amount of plasticizer in the resin as described in JP-A-2001-220183. It is also known that the sound insulation performance of the laminated glass 10 can be enhanced over a wide temperature range by combining two or more different resins to form an intermediate film. For example, a method of blending a plurality of types of resins described in JP-A-2001-206742, and a method of laminating a plurality of types of resins described in JP-A-2001-206741 and JP-A-2001-226152. And a method described in Japanese Patent Application Laid-Open No. 2001-192243 for imparting a deflection to the amount of plasticizer in the intermediate film. By adopting these techniques and carrying out an appropriate combination of means such as modification of the resin structure, addition of a plasticizer, combination of two or more resins, etc., the loss tangent of the resin material on which the intermediate film 2 is to be formed The value, that is, the sound insulation property can be controlled.

  Furthermore, it is preferable that the laminated glass 10 further has a heat shielding property other than blocking near infrared light as described above. As described above, as a method for improving the heat shielding property of the laminated glass 10, the interlayer film 2 further contains a metal having a heat shielding function, oxide fine particles, metal boride, or the like, or a layer containing these is laminated glass. The method of introduce | transducing into this laminated structure is mentioned. As such a method, for example, JP 2001-206743 A, JP 2001-261383 A, JP 2001-302289 A, JP 2004-244613 A, WO 02/060988, etc. Can be applied.

Examples of the oxide fine particles that can improve the heat shielding property include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), and aluminum-doped zinc oxide (AZO). Further, as boride fine particles, YB ₆ , LaB ₆ , CeB ₆ , PrB ₆ , NdB ₆ , SmB ₆ , EuB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , HoB ₆ , ErB ₆ , TbB ₆ , TmB ₆ , TmB _{6 6} , boride fine particles such as ZrB ₆ , BaB ₆ , SrB ₆ , CaB _{6 and the} like. In addition, since the intermediate film 2 containing the oxide fine particles described above tends to have low translucency, the particle diameter of the oxide fine particles may be specified (Japanese Patent No. 271589, JP 2002-2002). No. 293583), a method for improving dispersibility and maintaining good translucency may be applied. As a method for enhancing the dispersibility of oxide fine particles as in the latter case, known fine particle dispersion techniques such as mechanically dispersing the fine particles or using a dispersant can be applied.

  In addition, as a method of improving the heat shielding property of the laminated glass, in addition to the method of containing the oxide fine particles and the like described above, for example, a method of containing a dye / pigment having an organic heat shielding function, or a heat shielding performance A method using a translucent substrate is also included. Examples of the former method of containing a dye / pigment having an organic heat-shielding function include methods described in JP-A-7-157344 and JP-A-319271. Specific examples of such dyes and pigments include phthalocyanine, anthraquinone, naphthoquinone, cyanine, naphthalocyanine, pyrrole, imonium, dithiol, and mercaptonaphthol dyes and pigments. .

  Examples of the light-transmitting substrate having the heat shielding performance of the latter include, for example, an Fe-containing glass (for example, green glass) described in JP-A No. 2001-151539, and JP-A No. 2001-261384. And a glass plate in which a metal and a metal oxide are laminated as described in Japanese Patent Laid-Open No. 2001-226148.

  As described above, the laminated glass of the above-described embodiment has a characteristic that the near-infrared light absorbing material included in the intermediate film absorbs light in the near-infrared light region, thereby blocking near-infrared light that is a heat ray. Although demonstrated, the laminated glass (laminate) of the present invention reflects near infrared light in addition to the near infrared light absorbing layer for the purpose of further improving near infrared light blocking characteristics. You may have further the layer (reflection layer) which has.

  FIG. 2 is a diagram schematically illustrating 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 same thing as in the laminated glass 10 mentioned above can be applied to the translucent substrate 21 and the near infrared light absorption layer 22.

  Examples of the reflective layer 23 include layers composed of metals and metal oxides. Specifically, for example, gold, silver, copper, tin, aluminum, nickel, palladium, silicon, chromium, titanium, indium, antimony Examples thereof include simple metals such as metals, alloys, mixtures, and oxides.

  The laminated glass 20 having such a reflective layer 23 can be manufactured, for example, as follows. That is, first, a substrate provided with a reflective layer 23 on one surface of a translucent substrate 21 is prepared. Here, as a method of forming the reflective layer 23 on the translucent substrate 21, a method of depositing a metal or a metal oxide on the translucent substrate 21, or the like can be given. Next, the translucent substrate 21 on which the reflective layer 23 is formed is arranged on one surface side of the sheet to be the near-infrared light absorbing layer 22 so that the reflective layer 23 is in contact with the other surface side. Only the translucent substrate 21 is disposed. And the laminated glass 20 can be obtained by crimping these.

  By the way, when the reflective layer 23 is formed between the translucent substrate 21 and the near-infrared light absorbing layer 22 in this way, the adhesion between the reflective layer 23 and the near-infrared light absorbing layer 22 is reduced. There is. In this case, for example, when the laminated glass 20 is broken, the translucent substrate 21 is easily peeled and scattered, which causes a problem in terms of safety. From the viewpoint of avoiding such a problem, for example, it is preferable to further provide a layer capable of improving the adhesive force between the near-infrared light absorbing layer 22 and the reflective layer 23. By doing so, it becomes possible to improve the adhesion between the reflective layer 23 and the near-infrared light absorbing layer 22.

  As a means for improving the adhesive force in this way, for example, when the resin component contained in the near infrared light absorption layer 22 is polyvinyl acetal, the polyvinyl acetal having a higher acetal degree than the near infrared light absorption layer 22 is used. Layer (Japanese Patent Laid-Open No. 7-187726, Japanese Patent Laid-Open No. 8-337446), a layer made of PVB having a predetermined ratio of acetoxy groups (Japanese Patent Laid-Open No. 8-337445), a layer made of predetermined silicon oil ( JP, 7-314609, A) can be employed.

  Further, as the reflective layer 23, in addition to the above-described layers containing metals and metal oxides, Special Tables Hei 09-506837, Special Tables 2000-506082, Special Tables 2000-506084, Special Tables 2004-525403, Special Tables. It is also possible to use a polymer multilayer film that reflects a specific wavelength by utilizing light interference, as shown in 2003-515754, JP-A-2002-231038, JP-T-2004-503402, and the like.

  Note that 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. For example, a plurality of resins are provided between the light-transmitting substrates. When the layer which consists of is formed, the form provided between these layers may be sufficient.

  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 translucent substrates. The laminated glass 30 has a structure including a translucent substrate 31, a near infrared light absorption layer 32, a reflection layer 33, a resin layer 34, a near infrared light absorption layer 32, and a translucent substrate 31 in this order. . In this laminated glass 30, the same thing as what was mentioned above is applicable as the translucent board | substrate 31, the near-infrared-light absorption layer 32, and the reflection layer 33. FIG. Moreover, what consists of a well-known resin material is applicable as the resin layer 34, For example, a polyethylene terephthalate, a polycarbonate, etc. are mentioned as such a resin material. In the laminated glass 30 having such a structure, at least one near-infrared light absorbing layer 32 only needs to be provided. For example, one of the above-described near-infrared light absorbing layers 32 has a near red color. It may be a layer made of a resin material having no external light absorption characteristics.

  Thus, by providing a reflection layer in addition to the near-infrared light absorbing layer (intermediate film), it is possible to give a more excellent near-infrared light blocking property to the laminated glass by the effect of both layers. it can. Moreover, if the method which improves the adhesiveness of a reflection layer and a near-infrared-light absorption layer as mentioned above is employ | adopted, in addition to such a near-infrared-light cutoff characteristic, the laminated glass which has the outstanding intensity | strength will be obtained. It is also possible.

  In a laminated body such as laminated glass having the above-described configuration, when light containing a heat ray component such as sunlight is incident, the near-infrared light absorption layer that is an intermediate film exhibits a near-infrared light absorption characteristic, thereby Heat rays in the outside light region (wavelength of about 700 to 1200 nm) are blocked. In general, light in this wavelength range tends to feel the irritating and exciting heat that burns the skin, but the light transmitted through the above-mentioned laminate is blocked by such near-infrared light. Therefore, it is mainly visible light. Therefore, if such a laminated body is used for a window material or the like, it is possible to suppress an increase in indoor or indoor temperature while efficiently capturing visible light.

  From the viewpoint of sufficiently capturing visible light, the laminated glass preferably has a haze of 50% or less, more preferably 40% or less, and even more preferably 35% or less. If it exceeds 50%, the translucency of the laminated glass tends to decrease, and the visible light intake tends to be insufficient.

  Thus, since the laminated body (laminated glass) of the present invention has excellent near-infrared light blocking performance, it is a building material (a building member) for taking in natural light such as sunlight or other external light. For example, window materials for automobiles, ships, aircraft or train (railway) vehicles, canopy materials for passages such as arcades, curtains, canopies for carports and garages, solarium windows or wall materials, show windows, Showcase window materials, tents or window materials, blinds, roofing materials such as stationary and temporary housing, skylights and other window materials, coating materials for painted surfaces such as road signs, sunshade materials such as parasols, and other heat shielding Can be suitably used for various members that require the above.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.
[Preparation of alkyl phosphate copper compound]

(Preparation Example 1)
As the phosphate ester compound, oleyl phosphate (an equimolar mixture of monoester and diester, manufactured by Tokyo Chemical Industry Co., Ltd .; hereinafter abbreviated as “OLP”) was used, and 63.1 g thereof was dissolved in 180 g of toluene. 20.0 g of copper acetate monohydrate was added to the resulting solution, and acetic acid was removed while the solution was refluxed. Then, toluene was distilled off from the reaction solution to obtain 80.4 g of a phosphate ester copper compound (oleyl phosphate ester copper compound; OLPC).

(Preparation Examples 2 to 7)
In the compound represented by the above general formula (2a) instead of OLP as the phosphate compound, a compound in which R ²¹ is a 2-ethylhexyl group (Preparation Example 2, manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as “2-EHP”) ”), 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 to obtain a copper phosphate ester compound. Table 1 shows the blending amounts of the raw material and copper acetate monohydrate and the yield of the obtained phosphate ester copper compound in each of the preparation examples.

(Preparation Examples 8-12)
First, as a phosphate compound, R ²² in the compound represented by the above general formula (2b) is a group represented by the above chemical formula (5a) (Preparation Example 8), and represented by the above chemical formula (5c). A group represented by the above chemical formula (5d) (preparation example 10), a group represented by the above chemical formula (5e) (preparation example 11), A group represented by the above chemical formula (5b) (Preparation Example 12) was synthesized.

  Here, the production of these phosphate ester compounds was performed as follows. That is, first, various alcohols having an oxyalkylene unit and a terminal structure corresponding to each phosphate compound were dissolved in toluene, and then cooled in an ice bath. Next, diphosphorus pentoxide was gradually added to each solution and stirred, and then heated at 100 ° C. for 2 hours to complete the reaction. Thereafter, toluene was distilled off from the reaction product to obtain a phosphate compound.

  After obtaining various phosphate ester compounds in this way, the obtained phosphate ester compound was added to toluene together with copper acetate monohydrate and stirred. Water and acetic acid were removed. And after completion | finish of reaction, after filtering the reaction liquid, the filtrate was concentrated and the phosphate ester copper compound was obtained.

  Table 2 summarizes the blending amounts and yields of each component used in the synthesis of the phosphoric ester compounds of Preparation Examples 8 to 12 and the synthesis of the phosphoric ester copper compound.

(Preparation Example 13)
As the phosphate ester compound, a compound in which R ²² in the compound represented by the general formula (2b) is a group represented by the chemical formula (7) was used, and 15.48 g thereof was dissolved in 60.18 g of toluene. . To the resulting solution, 5.01 g of copper acetate monohydrate was added, and acetic acid was removed while the solution was refluxed. And toluene was distilled off from the obtained solution, and 20.82 g of phosphate ester copper compounds were obtained.

(Preparation Example 14)
As the phosphoric ester compound, a compound represented by the above chemical formula (6) was used, and 21.40 g thereof was dissolved in 80.23 g of toluene. To the resulting solution, 5.01 g of copper acetate monohydrate was added, and acetic acid was removed while the solution was refluxed. And toluene was distilled off from the obtained solution, and 26.02 g of phosphate ester copper compounds were obtained.

(Preparation Examples 15-17)
First, as a phosphate compound, R ¹ in the compound represented by the general formula (1) is a 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-docosenyl group (group represented by the following chemical formula (8c)) (Preparation Example 17) was synthesized. These phosphate ester compounds were synthesized in the same manner as the phosphate ester compounds in Preparation Examples 8 to 12 above.

  Next, using the obtained phosphoric ester compound, a phosphoric ester copper compound was obtained in the same manner as in Preparation Examples 8-12. Table 3 summarizes the blending amounts and yields of each component used in the synthesis of the phosphoric ester compounds of Preparation Examples 15 to 17 and the synthesis of the phosphoric ester copper compound.

(Preparation Examples 18 to 21)
First, as the phosphate compound, R ¹ in the compound represented by the general formula (1) is a cis-3-hexenyl group (group represented by the following chemical formula (9a)) (Preparation Example 18). , A trans-octenyl group (a group represented by the following chemical formula (9b) (Preparation Example 19), a cis-3-octenyl group (a group represented by the following Chemical Formula (9c)) (Preparation Example 20) ) And a stearyl group (Preparation Example 21) were synthesized.

  Next, using the obtained phosphoric ester compound, a phosphoric ester copper compound was obtained in the same manner as in Preparation Examples 8-12. Table 4 summarizes the blending amounts and yields of each component used in the synthesis of the phosphoric ester compounds of Preparation Examples 18 to 21 and the synthesis of the phosphoric ester copper compound.

［近赤外光吸収性組成物の製造］

[Production of near-infrared light absorbing composition]

(Examples 1-16, Comparative Examples 1-8)
(I) Phosphate ester copper compounds obtained in Preparation Examples 1 and 15 to 21 and (II) Phosphate ester copper compounds obtained in Preparation Examples 2 to 14 are shown in Tables 5 and 6, respectively. To obtain a near infrared light absorbing material. Next, after dissolving 1 g of these near infrared light absorbing materials in 2 g of triethylene glycol-di-2-ethylhexanate as a plasticizer, 7 g of PVB (Eslec BH-3, manufactured by Sekisui Chemical Co., Ltd.) And a near infrared light absorbing composition was obtained. In Tables 5 and 6, in the columns (I) and (II), the numbers of the preparation examples of the phosphate ester copper compounds used in the respective examples are shown in parentheses.

(Examples 17 to 19)
First, (I) OLP and (II) 2-EHP were dissolved in toluene. Copper acetate monohydrate was added to the resulting solution, and the acetic acid was removed while refluxing the solution. Then, toluene was further removed to obtain a phosphate copper compound containing OLP and 2-EHP. In addition, the compounding quantity and yield of a raw material and copper acetate monohydrate were as showing in Table 7. In Table 7, in the columns of (I) and (II), the molar ratio between the two was written in parentheses.

  1 g of the obtained phosphoric acid ester copper compound was dissolved in 2 g of triethylene glycol-di-2-ethylhexanate, which is a plasticizer, and then mixed with 7 g of PVB (S-REC BH-3, manufactured by Sekisui Chemical Co., Ltd.). Thus, a near infrared light absorbing composition was obtained.

(Example 20)
The compound of (II) was replaced with 2-EHP in the same manner as in Example 17 except that in the compound represented by the general formula (2a), R ²¹ was a decyl group. An infrared light absorbing composition was obtained. In addition, the compounding quantity and yield of a raw material and copper acetate monohydrate were as showing in Table 7.

(Example 21)
First, a phosphate ester copper compound was prepared by the method shown below. That is, first, 158 g of OLP and 88.9 g of 2-EHP were dissolved in toluene. To the obtained solution was added 100 g of copper acetate monohydrate, and after removing the acetic acid while refluxing this solution, toluene was further removed to obtain 270 g of a phosphate ester copper compound containing OLP and 2-EHP. .

Next, 0.1 g of the obtained phosphoric ester copper compound, 5 g of 2-ethylhexyl methacrylate, 4 g of 2-ethylhexyl acrylate, 0.1 g of di-tert-butyl peroxide as a polymerization initiator, and a polymerization rate regulator Was mixed with 0.02 g of α-methylstyrene to obtain a near infrared light absorbing composition.
[Manufacture of laminated glass]

(Examples 22 to 41, Comparative Examples 9 to 16)
First, after the near-infrared light absorptive composition of Examples 1-20 and Comparative Examples 1-8 was pressed several times at 85 degreeC with a press machine (WF-50, the product made by Shinto Metal Industry Co., Ltd.), it was further 120 The sheet-like molded product having a thickness of 1.0 mm was obtained by pressing at several times.

  Subsequently, 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 1 mm to obtain a laminate. And this laminated body was crimped | bonded on conditions with a temperature of 130 degreeC and a pressure of 1.2 MPa in the autoclave, and the laminated glass of Examples 22-41 and Comparative Examples 10-18 was obtained. In addition, the case where the near-infrared light absorptive composition of Examples 1-20 is used for Examples 22-41, and the case where the gold-infrared-light absorptive composition of Comparative Examples 1-8 is used is Comparative Example 9. It corresponds to -16 respectively.

(Example 42)
First, two pairs of slide glasses having a length of 26 mm, a width of 76 mm, and a thickness of 1 mm were prepared and held in a state of being separated by 1 mm so as to face each other. Both side surfaces were sealed with a polyester tape except for the inlet. And after inject | pouring the near-infrared-light-absorbing composition of Example 21 from an injection port, the said injection port was block | closed with the polyester tape. Thereafter, the near-infrared light absorbing composition was polymerized and cured at 110 ° C. After cooling this, the polyester tape attached to the side surface was peeled off to obtain a laminated glass of Example 42.
[Evaluation of light resistance]

Using the laminated glasses of Examples 21 to 42 and Comparative Examples 9 to 16, light resistance was evaluated by the method shown below. That is, first, about each laminated glass immediately after manufacture, the turbidity (haze (0h)) was evaluated using a turbidity meter (NDH-1001DP, manufactured by Nippon Denshoku Industries Co., Ltd.) (method based on JISK 7136) ). Then, a xenon weather meter (Atlas C135, manufactured by Toyo Seiki Seisakusho; light source: xenon lamp, automatic irradiation intensity: 0.83 W / m ² , black panel temperature: 63 ° C.) is used for these laminated glasses. UV irradiation was performed for a period of time. Thereafter, the turbidity (haze (100 h)) of each laminated glass after irradiation with ultraviolet rays was measured in the same manner as described above. And the change (haze = haze (100h) -haze (0h)) of the laminated glass before and after irradiating an ultraviolet-ray was computed, and light resistance was evaluated based on this.

  Tables 8 and 9 collectively show the haze values and Δhaze values obtained before and after the ultraviolet irradiation. In addition, since the translucency change (deterioration) of a laminated glass is so small that the value of (DELTA) haze is small, it has shown that light resistance is high.

  From Table 8 and Table 9, since all the laminated glasses of Examples 22-42 using the combination of a specific phosphate ester compound have the haze value (0h and 100h) less than 50, translucency ( Since the transparency was excellent and the Δhaze value was less than 5, it was confirmed that even after ultraviolet irradiation, the decrease in translucency was extremely small and the light resistance was excellent.

  On the other hand, the laminated glasses of Comparative Examples 9 to 16 that did not use the phosphate ester compound in the above specific combination have a haze exceeding 50 and low translucency, and are unsuitable as window materials, or The Δhaze exceeded 5 and the light resistance was low.

  In particular, in the near-infrared light absorbing composition, the laminated glasses of Examples 22 to 34 and Examples 38 to 41 using the OLPC of Preparation Example 1 as (I) have a Δhaze value within ± 5. It was found to be extremely excellent in light resistance.

Claims (6)

A near-infrared light-absorbing material comprising (I), (II) and (III).
(I): Phosphate ester compound represented by the following general formula (1) (II): Phosphate ester compound represented by the following general formula (2a) and / or represented by the following general formula (2b) Phosphate ester compound (III): Copper ion

[Wherein, R ¹ represents an alkenyl group having 12 to 24 carbon atoms, R ²¹ represents a chain or cyclic alkyl group having 1 to 15 carbon atoms, and R ²² represents a monovalent organic group having an ether bond and / or an ester bond. I, j and k are each independently 1 or 2. ] The near-infrared light-absorbing material according to claim ^1, wherein R ¹ is an oleyl group. The near infrared light absorbing material according to claim 1, wherein R ²² is a monovalent group represented by the following general formula (3).

[Wherein R ³¹ represents an alkylene group having 2 to 4 carbon atoms, R ³² represents an alkyl group having 1 to 12 carbon atoms or an acyl group having 2 to 5 carbon atoms, and m is an integer of 1 to 6. ] Wherein (II), said a general formula (2a) phosphoric acid ester compound represented by the R ²¹ in the compound according to claim 1 or 2, wherein an alkyl group of 8 carbon atoms Near infrared light absorbing material. A near-infrared light-absorbing composition comprising the near-infrared light-absorbing material according to any one of claims 1 to 4 and a synthetic resin. A translucent substrate;
A near-infrared light-absorbing layer comprising the near-infrared light-absorbing composition according to claim 5 provided on the translucent substrate;
A laminate comprising:

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