JP2009242650A - Copper salt composition, resin composition using the same, infrared-absorbing film and optical member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a copper salt composition capable of obtaining an optical material which reduces the deterioration of transparency, discoloration and the like even at high temperatures and excels in heat resistance. <P>SOLUTION: The copper salt composition comprises: particles which are composed of a copper phosphonate formed from a phosphonic acid compound represented by formula (1) (wherein R<SP>1</SP>is an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, a (meth)acryloyloxyalkyl group or a (meth)acryloylpolyoxyalkyl group and these groups may each have a substituent) and a copper ion, and which have an average particle diameter of 0.005-0.3 μm; a polysiloxane component composed of a hydrolysate and/or a condensate of an alkoxysilane; a plasticizer; and a dispersant. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a copper salt composition, a resin composition using the same, an infrared absorption film, and an optical member.

  In addition to visible light, ultraviolet rays and infrared rays are included in sunlight rays that are incident from so-called opening portions such as windows in various buildings and vehicles. Infrared rays having a wavelength of 780 nm or more are also called heat rays, and cause the indoor temperature to rise by being incident from the opening. In order to solve this problem, in recent years, there has been a demand for a characteristic that shields heat rays while sufficiently taking in visible light, and suppresses an increase in indoor temperature while maintaining brightness.

  Metal ions can exhibit absorption characteristics with respect to light of a specific wavelength, and are applied to optical materials using the characteristics. Among these, copper ions are known to have good absorption characteristics for light in the near infrared region (hereinafter referred to as “near infrared light”) having a large thermal action. Specifically, near-infrared light is selectively absorbed by the electronic transition of the d-orbit of copper ions, and excellent near-infrared light absorption characteristics are exhibited. Therefore, attempts have been made to impart near-infrared light absorption characteristics by including copper ions in an interlayer film for laminated glass.

As an optical material using such characteristics of copper ions, for example, a material in which copper ions and phosphonic acid or phosphinic acid are contained in a solvent or resin is disclosed (Patent Document 1).
JP-A-2002-006101

  When the conventional optical material as described above is applied to an interlayer film or the like of laminated glass, it is often processed under a high temperature condition such as being exposed to a high temperature in extrusion sheet molding. Therefore, stability with respect to thermoforming at high temperatures is required. Patent Document 1 discloses that an optical material contains a phosphonic acid or a phosphinic acid to form a copper salt that hardly undergoes alteration such as decomposition even under high temperature conditions.

  However, optical materials using phosphonic acid copper salts, when exposed to high temperatures during thermoforming, do not cause deterioration of the copper salts themselves, but their transparency (visible light transmission) decreases when mixed with resin. In addition, it cannot always exhibit sufficient stability during thermoforming, such as yellowing. Moreover, since phosphonic acid copper salt does not melt | dissolve with respect to resin, when it mixes with resin as it is, there also existed a problem that transparency worsened.

  Therefore, the present invention has been made in view of such circumstances, and has excellent near-infrared light absorption characteristics and can exhibit high transparency and stability even when mixed with a resin and exposed to high temperatures. An object is to provide a copper salt composition. Another object of the present invention is to provide a resin composition containing the copper salt composition, and an infrared absorption film and a laminate using the resin composition.

  In order to achieve the above object, the present inventors have conducted intensive research, and as a result, when the phosphonic acid copper salt is mixed with a resin by making the phosphonic acid copper salt composition mixed with a specific compound, However, the inventors have found that sufficiently high transparency can be obtained and that excellent thermal stability can be obtained, and the present invention has been completed.

［式中、Ｒ^１は、アルキル基、シクロアルキル基、アルケニル基、アルキニル基、アリール基、アリル基、オキシアルキル基、ポリオキシアルキル基、オキシアリール基、ポリオキシアリール基、（メタ）アクリロイルオキシアルキル基又は（メタ）アクリロイルポリオキシアルキル基であり、これらの基における少なくとも一つの水素原子が、ハロゲン原子、オキシアルキル基、ポリオキシアルキル基、オキシアリール基、ポリオキシアリール基、アシル基、アルデヒド基、カルボキシル基、ヒドロキシル基、（メタ）アクリロイル基、（メタ）アクリロイルオキシアルキル基、（メタ）アクリロイルポリオキシアルキル基又はエステル基で置換されていてもよい。］］ That is, the copper salt composition of the present invention comprises a phosphonic acid copper salt formed from a phosphonic acid compound represented by the following general formula (1) and copper ions, and has an average particle size of 0.005 to 0.3 μm. It contains particles, a polysiloxane component comprising a hydrolyzate and / or condensate of alkoxysilane, a plasticizer, and a dispersant.

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, (meth) acryloyloxy An alkyl group or a (meth) acryloyl polyoxyalkyl group, and at least one hydrogen atom in these groups is a halogen atom, oxyalkyl group, polyoxyalkyl group, oxyaryl group, polyoxyaryl group, acyl group, aldehyde Group, carboxyl group, hydroxyl group, (meth) acryloyl group, (meth) acryloyloxyalkyl group, (meth) acryloyl polyoxyalkyl group or ester group may be substituted. ]]

  Since the phosphonic acid copper salt itself has high heat resistance as described above, it was difficult to cause deterioration or the like even at a high temperature. Thus, it has been found that copper phosphonate may promote the deterioration of the resin used for the optical material. That is, although deterioration of the phosphonic acid copper salt did not occur under high temperature conditions, the resin was deteriorated, resulting in a decrease in transparency and yellowing of the optical material.

  On the other hand, the copper salt composition of the present invention contains a phosphonic acid copper salt in the form of particles having a predetermined average particle diameter, and further contains a polysiloxane component in combination with the particles of the phosphonic acid copper salt. Therefore, it is possible to greatly suppress the deterioration of the resin due to the high temperature as described above, and as a result, higher heat resistance than conventional can be obtained. Although it is not always clear about such factors, it is difficult for the polysiloxane component to work with the resin by covering at least a part of the copper phosphonate, and the polysiloxane component causes the resin degradation reaction by the copper salt. It is conceivable to have characteristics that can be suppressed. And since the copper salt composition of this invention has these specific particle diameters and contains a plasticizer and a dispersing agent in combination, the effect | action with resin etc. is reduced. Nevertheless, the resin has high dispersibility. As a result, a decrease in transparency due to aggregation of the phosphonic acid copper salt or the like hardly occurs.

  The copper salt composition of the present invention can be mixed with a resin to form a resin composition. Since such a resin composition includes the copper salt composition of the present invention, it can absorb a wide range of light in the near-infrared region, and has excellent optical properties such as excellent visible light transmission, and high temperature. The infrared absorption film of the present invention having excellent heat resistance can be formed with little deterioration of the phosphonic acid copper salt itself and the resin even under the above. As such a resin, polyvinyl butyral (PVB) is preferable. PVB is suitable as a material for an intermediate film and the like because it is excellent in flexibility, adhesiveness, and shape stability against heat. Moreover, since the copper salt composition of this invention can be disperse | distributed especially favorably, it becomes easier to obtain high thermal stability and transparency by using PVB.

  And the laminated body of this invention provided with the infrared rays absorption layer which consists of a translucent board | substrate and the said infrared absorption film of this invention is excellent in absorptivity of a heat ray, and also this heat ray absorptivity and transparency over a long period under high temperature. It can be applied as a laminated glass with little deterioration in properties.

  According to the present invention, it is possible to provide a copper salt composition that has excellent near-infrared light absorption characteristics and can exhibit high transparency and stability even when it is mixed with a resin and exposed to high temperatures. . In addition to excellent optical properties, it is possible to provide a resin composition having high heat resistance, an infrared absorption film and a laminate using the resin composition.

  Hereinafter, preferred embodiments of the present invention will be described.

[Copper salt composition]
First, the copper salt composition of a preferred embodiment will be described.

  The copper salt composition of the present embodiment is a particle composed of a phosphonic acid copper salt formed by a phosphonic acid compound and copper ions and having an average particle diameter of 0.005 to 0.3 μm (hereinafter, “phosphonic acid copper salt particles”). And a polysiloxane component comprising a hydrolyzate and / or condensate of alkoxysilane, a plasticizer, and a dispersant.

  First, as the plasticizer, a known plasticizer used for adjusting the physical properties of the resin can be applied without particular limitation. By including a plasticizer, for example, the flexibility of the resin is improved, and when applied to an interlayer film or the like of laminated glass, impact absorbability and penetration resistance are improved. Examples of such plasticizers include known plasticizers such as phosphate ester plasticizers, phthalic acid plasticizers, fatty acid plasticizers, and glycol plasticizers. More specifically, for example, organic plasticizers such as monobasic organic acid esters and polybasic organic acid esters; phosphoric acid plasticizers such as organic phosphoric acid and organic phosphorous acid are preferably used. It is done. These plasticizers may be used alone or in combination of two or more, and are used properly in consideration of compatibility and the like depending on the type of resin to be contained in the resin composition described later.

  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 dispersant is a component that can be mixed with metal salt particles and the like to suppress aggregation of the particles. Examples of such a dispersant include polymer dispersants and phosphate ester dispersants. Among these, a polymer dispersant having a structure having an affinity for a copper salt, an organic solvent or a resin (particularly a thermoplastic resin) and having a high light transmittance in the visible light region is desirable.

  Specific examples of the polymer dispersant include a polyacrylate dispersant, a polyurethane dispersant, a polyether dispersant, a polyester dispersant, a polyester urethane dispersant, and the like. The polymer dispersant can be used in the liquid, solid or gel state at room temperature. On the other hand, examples of the phosphoric acid ester dispersant include polyoxyethylene alkyl ether phosphoric acid and its phosphate.

  The phosphonic acid copper salt particles are composed of a phosphonic acid copper salt. This phosphonic acid copper salt is formed from a copper ion and a phosphonic acid compound, and has, for example, a form of a copper salt (copper complex) in which a phosphonic acid compound is coordinated to a copper ion.

  The copper ion in the phosphonic acid copper salt is a divalent copper ion. This copper ion is mixed with a phosphonic acid compound in the form of a copper salt to form a phosphonic acid copper salt. Specific examples of this copper salt include copper acetate anhydrides of organic acids such as copper acetate, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate and copper citrate, hydration Or an hydrate or hydrate of copper salts of inorganic acids such as copper oxide, copper chloride, copper sulfate, copper nitrate, basic copper carbonate, or copper hydroxide. 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.

On the other hand, the phosphonic acid compound is, for example, a compound represented by the following general formula (1).

In the formula (1), the group represented by R ¹ includes an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxy group. An aryl group, a (meth) acryloyloxyalkyl group, or a (meth) acryloylpolyoxyalkyl group can be mentioned, and these groups preferably have 1 to 30 carbon atoms. In these groups, at least one hydrogen atom in the group is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde group, a carboxyl group, a hydroxyl group, It may be substituted with a (meth) acryloyl group, a (meth) acryloyloxyalkyl group, a (meth) acryloyl polyoxyalkyl group or an ester group.

As the phosphonic acid compound, alkylphosphonic acid in which the group represented by R ¹ is an alkyl group is preferable. A copper salt composition containing a phosphonic acid copper salt having an alkylphosphonic acid tends to exhibit excellent infrared absorption characteristics and heat resistance. Alkylphosphonic acids include ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid Tridecylphosphonic acid, tetradecylphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, octadecylphosphonic acid and the like. In addition, as a phosphonic acid compound, said thing may be used independently and may be used in combination of multiple types.

  In the phosphonic acid copper salt particles, the phosphonic acid compound is preferably contained in an amount of 0.5 to 3 mol, more preferably 0.8 to 2 mol, per mol of copper ions. When the amount of the phosphonic acid compound is 0.5 mol or less, the thermal stability of the copper salt itself is deteriorated. On the other hand, when 3 mol or more of a phosphonic acid compound is contained, there is a possibility that thermal deterioration of the resin is caused by an excess of the phosphonic acid compound when it is contained in the resin and thermoformed. That is, the phosphonic acid copper salt particles having the copper ion and the phosphonic acid compound in the above ratio show high infrared absorption characteristics and have excellent heat resistance.

  The phosphonic acid copper salt particles are particles formed from the copper ions and the phosphonic acid compound as described above, and the average particle diameter is 0.005 to 0.3 μm. When the average particle diameter of the phosphonic acid copper salt particles is less than 0.005 μm, the cohesive force is increased in the resin composition, and it is difficult to disperse in the resin. On the other hand, when it exceeds 0.3 μm, transparency in the case of a resin composition or the like is lowered. From the viewpoint of obtaining better transparency, the average particle diameter of the phosphonic acid copper salt particles is preferably 0.005 to 0.25 μm, and more preferably 0.01 to 0.2 μm. In addition, as an average particle diameter of phosphonic acid copper salt particle | grains, the value obtained by the measurement by a dynamic scattering method is applicable, for example. As an example, this measurement can be performed using N4plus manufactured by Beckman Coulter.

  The polysiloxane component is a hydrolyzate and / or condensate of alkoxysilane, preferably an alkoxysilane condensate. Here, the hydrolyzate or condensate of alkoxysilane is a product produced by hydrolyzing alkoxysilane molecules by heating alkoxysilane or the like, or a product produced by dehydration condensation between alkoxysilane molecules. It is a thing.

  The alkoxy silane that is the raw material of the polysiloxane component includes tetramethoxy silane, tetraethoxy silane, tetrabutoxy silane, methyl trimethoxy silane, methyl triethoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, butyl triethoxy silane, octyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxy Silicon compounds such as silane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, methyl silicate, ethyl Silicate, alkyl silicates such as methyl silicate, and the like. As alkoxysilane, these things can be included individually or in combination of multiple types.

  The suitable content rate of each component which comprises a copper salt composition is as follows. That is, first, the content of the plasticizer is preferably 1 to 150 parts by mass, more preferably 2 to 100 parts by mass, and 2 to 50 parts by mass with respect to 1 part by mass of the phosphonic acid copper salt particles. More preferably. When the content ratio of the phosphonic acid copper salt particles is less than the above, sufficient infrared absorption characteristics tend not to be obtained when a resin composition is used. On the other hand, when it is more than the above range, the transparency of the resin composition tends to decrease.

  Further, the content of the polysiloxane component is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 9 parts by mass with respect to 1 part by mass of the phosphonic acid copper salt particles, and 0.05 More preferably, it is -8 mass parts. When the content ratio of the polysiloxane component is less than the above, sufficient heat resistance tends to be not obtained when a resin composition is used. On the other hand, when the content is larger than the above range, the transparency of the resin may be lowered due to an excessive polysiloxane component when it is contained in the resin.

  Furthermore, the content ratio of the dispersant depends on the particle size of the phosphonic acid copper salt particles, but is preferably 0.2 parts by mass or more and less than 50 parts by mass with respect to 1 part by mass of the phosphonic acid copper salt particles. The amount is more preferably 0.5 parts by mass or more and less than 30 parts by mass, and further preferably 1 part by mass or more and less than 15 parts by mass. When the blending ratio of the dispersant is less than 0.2 parts by mass, for example, in the step of removing the organic solvent at the time of producing the phosphonic acid copper salt composition, the phosphonic acid copper salt particles are aggregated to disperse. It tends to be insufficient. In this case, for example, even if the phosphonic acid copper salt composition is added to the organic solvent and the dispersant is dissolved, a dispersion in which the phosphonic acid copper salt particles are uniformly dispersed in the organic solvent cannot be obtained. There is a risk that it may be difficult to produce the object. In addition, when the phosphonic acid copper salt composition is diluted and kneaded with a resin (thermoplastic resin) and molded into a sheet to obtain an infrared absorption film, the haze value may increase. On the other hand, when the blending ratio of the dispersant is 50 parts by mass or more, a large amount of the dispersant is contained in the infrared absorption film formed using the phosphonic acid copper salt composition. In particular, there is a possibility that the problem that the impact strength and toughness are lowered tends to occur.

  Such a copper salt composition can be obtained, for example, by the following method. That is, first, phosphonic acid copper salt particles are formed by a predetermined method, and then the phosphonic acid copper salt particles are mixed with a plasticizer and further dispersed in a predetermined solvent to obtain a copper salt dispersion. The solvent used here is not particularly limited as long as the phosphonic acid copper salt particles can be uniformly dispersed. For example, alcohols such as methanol and ethanol, ketones such as acetone, and aromatics such as toluene and xylene are preferable.

  Next, alkoxysilane and water are added to the obtained copper salt dispersion and stirred, and the alkoxysilane is hydrolyzed to produce a hydrolyzate and / or a dehydrated condensate. At this time, the concentration of the alkoxysilane varies depending on the type of the organic solvent to be dissolved, and thus suitable conditions are set as appropriate. When the amount of water to be added is large, the reaction rate increases. Therefore, in order to adjust the reaction rate, catalysts such as acids and amines, alkanolamines and the like may be used. Moreover, conditions may be set so that hydrolysis and condensation of the alkoxysilane are favorably generated by applying heat during the reaction. For example, the reaction temperature is preferably 10 to 100 ° C, more preferably 15 to 90 ° C.

  Then, from the mixture of the copper salt dispersion and the hydrolyzate or condensate of alkoxysilane generated by hydrolysis or condensation, the solvent used in the above preparation is removed by an evaporator or the like, and the preferred embodiment A copper salt composition is obtained. In addition, the manufacturing method of a copper salt composition is not limited above, You may change suitably.

[Resin composition]
Next, the resin composition of a preferred embodiment will be described.

  The resin composition of this embodiment contains the copper salt composition described above and a resin. As the resin to be combined with the copper salt composition, a resin that can favorably disperse the phosphonic acid copper salt and the polysiloxane component in the above-described copper salt composition and is excellent in the property of transmitting visible light is preferable. Examples of such resins include polyvinyl acetal resin, ethylene-vinyl acetate copolymer (EVA), (meth) acrylic resin, polyester resin, polyurethane resin, vinyl chloride resin, polyolefin resin, polycarbonate resin, norbornene resin, and the like. Can be mentioned.

  Among these resins, polyvinyl acetal resin is preferable, and polyvinyl butyral (PVB) is particularly preferable. These have excellent adhesion to a light-transmitting substrate in a laminate (laminated glass) described later, and are flexible and difficult to deform depending on temperature. For this reason, the shaping | 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 has a characteristic that the above-described copper salt composition is particularly easily dispersed. For this reason, according to the combination of the copper salt composition and the polyvinyl acetal resin, a laminated glass having excellent visible light permeability and durability can be obtained.

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

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

  Such a resin composition can be obtained by adding the above-described copper salt composition to these resins and stirring them. And the phosphonic acid copper salt particle | grains and polysiloxane component in a copper salt composition are uniformly disperse | distributed in resin by the plasticizer contained in a copper salt composition.

  The preferred content of each component in the resin composition is as follows. That is, the copper salt composition is preferably an amount such that the phosphonic acid copper salt particles in the copper salt composition are 0.05 to 30 parts by mass with respect to 100 parts by mass of the resin, and 0.1 to 20 parts by mass. It is more preferable that the amount is as follows. When this ratio is too smaller than the above, the ratio of the phosphonic acid copper salt decreases, and it may be difficult to obtain sufficient infrared absorption characteristics. On the other hand, even if it is too large, the amount of phosphonic acid copper salt particles may increase so that deterioration of the resin due to high temperature cannot be sufficiently suppressed.

  In addition to the resin and the copper salt composition, the resin composition may further contain other components in a range in which the optical characteristics and the heat resistance are not excessively lowered in accordance with required characteristics.

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

  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.

  The resin composition may further contain other additives in addition to the plasticizer and the adhesion modifier. Examples of such additives include components for adjusting the color tone, components for adjusting physical properties, components for stabilizing the resin composition, and a translucent substrate when forming a laminate described later. Ingredients for improving the adhesion to the surface. 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 stabilization 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.

[Optical member]
By using the resin composition described above, an optical member having excellent properties for blocking near infrared light can be obtained. Examples of such an optical member include first and second forms shown below.
1st form: The sheet-like molding obtained by processing a resin composition.
2nd form: The laminated body which has a translucent board | substrate and the infrared absorption layer comprised by the infrared absorption film which consists of a resin composition provided in the at least one side of 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 resin composition mentioned above, and specifically, a sheet and a film are mentioned. This sheet-like molded product exhibits high infrared absorption characteristics and is applied to various uses as an infrared absorption film. 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 second form is a laminate having a translucent substrate and an infrared absorption layer composed of an infrared absorption film made of a resin composition provided adjacent to the translucent substrate. is there.

  The light-transmitting substrate is a substrate that transmits visible light. For example, the light-transmitting substrate is a substrate that can transmit 50% or more of light having a wavelength of 550 nm. The material constituting the light-transmitting substrate is not particularly limited as long as it is a material having visible light permeability, and can be appropriately selected according to the use of the optical member. From the viewpoint of obtaining good hardness, heat resistance, chemical resistance, durability, etc., glass or plastic is preferably used. Examples of the glass include inorganic glass and organic glass. Examples of the plastic include polycarbonate, acrylonitrile-styrene copolymer, polymethyl methacrylate, vinyl chloride resin, polystyrene, polyester, polyolefin, norbornene resin and the like. When there are a plurality of light-transmitting substrates, each substrate may be composed of the same type of material or may be composed of different materials.

  Such a laminate is formed by, for example, forming a sheet or film (infrared absorbing film) similar to the optical member of the first embodiment described above, and then bonding these sheet and the light transmitting substrate together. Can be manufactured. As a method of laminating them, a means for bonding by pressurization or reduced pressure such as a press method, a multi-roll method, a decompression method, a means for adhesion by heating using an autoclave, or a combination of these is used. be able to.

  Moreover, as a manufacturing method of a laminated body, the method of forming an infrared rays 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-described resin composition is dispersed in an appropriate solvent to form a coating agent, and this solution is applied to a light-transmitting substrate, and then the solvent is evaporated, whereby the light-transmitting substrate is coated. Examples thereof include a method for forming a thin film, a covering or a thin layer made of a resin composition. The thin film formed in this way is called a coating. When an infrared absorption layer is formed using such a method, for the purpose of improving the flatness of the layer, various auxiliary agents such as a leveling agent and an antifoaming agent are added to the coating described above. You may add in an agent.

  The optical member of the second form, i.e., the laminate, is not limited to one having the above-described translucent substrate and one infrared absorption layer, and may have a plurality of these layers. Specifically, a substrate provided with a pair of translucent substrates and an intermediate film (infrared absorbing layer) made of the infrared absorbing film disposed between the translucent substrates is exemplified. Such a laminate is a so-called laminated glass.

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

  FIG. 1 is a diagram schematically showing a cross-sectional configuration of a laminated glass. A laminated glass 10 shown in FIG. 1 includes a pair of translucent substrates 1 and an intermediate film 2 (infrared absorbing layer) sandwiched between the pair of translucent substrates 1. The intermediate film 2 is an infrared absorption film made of the above resin composition, and the same light-transmitting substrate 1 as described above can be applied.

  In the laminated glass 10 having such a structure, for example, a sheet-like molded product (infrared absorbing film) made of the resin composition described above is sandwiched between a pair of translucent substrates, and this is pre-pressed between each layer. After the remaining air is removed, it can be manufactured by a method in which these are pressure bonded and brought into close contact with each other.

  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 the translucent substrate 1 and the sheet are overlapped is improved, and, for example, visible light permeability due to bubbles generated due to insufficient deaeration, etc. Can be prevented.

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

  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 has less visible light transmittance deterioration 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.

  Further, in recent years, another characteristic required for the laminated glass 10 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 characteristic capable of exhibiting a heat shielding property by absorbing 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. Note that the intermediate film 2 containing the oxide fine particles described above tends to have low visible light permeability, so the particle diameter of the oxide fine particles is regulated (Japanese Patent No. 271589, JP 2002). -293833), a method for improving dispersibility and maintaining good translucency may be applied. As a method for enhancing the dispersibility of the oxide fine particles as in the latter case, known fine particle dispersion techniques such as mechanically dispersing the fine particles and 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 / 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 exhibits the property of blocking near-infrared light, which is a heat ray, by the resin composition contained in the intermediate film absorbing light in the near-infrared light region. However, the laminated glass (laminate) of the present invention is a layer having a property of reflecting near infrared light in addition to the infrared absorption layer (reflection) for the purpose of further improving the near infrared light blocking property. It may further have a layer).

  FIG. 2 is a diagram schematically 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, an infrared absorption layer 22, a reflective layer 23, and a translucent substrate 21 in this order. The same thing as the thing in the laminated glass 10 mentioned above is applicable for the translucent board | substrate 21 and the infrared rays absorption layer 22. FIG.

  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 disposed on one surface side of the sheet to be the infrared absorption layer 22 so that the reflective layer 23 is in contact with the other surface side. Only the optical substrate 21 is disposed. And the laminated glass 20 can be obtained by crimping these.

  By the way, when the reflective layer 23 is formed between the translucent substrate 21 and the infrared absorption layer 22 in this way, the adhesiveness between the reflection layer 23 and the infrared absorption layer 22 may be lowered. 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 infrared absorption layer 22 and the reflection layer 23. By doing so, it is possible to improve the adhesion between the reflective layer 23 and the infrared absorption layer 22.

  As a means for improving the adhesive force, for example, when the resin component contained in the infrared absorption layer 22 is polyvinyl acetal, a layer made of polyvinyl acetal having a higher acetal degree than the infrared absorption layer 22 (special Kaihei 7-187726, JP-A-8-337446), a layer made of PVB having a predetermined ratio of acetoxy groups (JP-A-8-337445), a layer made of a predetermined silicone oil (JP-A-7- 314609 public information) and the like can be adopted.

  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 infrared absorption layer in the laminated glass as described above, and is made of, for example, a plurality of resins between the light-transmitting substrates. When the layers are formed, it may be in a form provided between these layers.

  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, an infrared absorption layer 32, a reflection layer 33, a resin layer 34, an infrared absorption layer 32, and a translucent substrate 31 in this order. In this laminated glass 30, the same thing as what was mentioned above is applicable as the translucent board | substrate 31, the infrared 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 addition, in the laminated glass 30 having such a structure, it is sufficient that at least one infrared absorption layer 32 is provided. For example, one of the infrared absorption layers 32 described above absorbs near infrared light. The layer which consists of a resin material which does not have the characteristic to do may be sufficient.

  In this way, by providing a reflection layer in addition to the infrared absorption layer (intermediate film), it is possible to give the laminated glass a more excellent property of blocking near-infrared light by the effect of both layers. it can. Moreover, if the method for improving the adhesion between the reflective layer and the infrared absorbing layer as described above is employed, a laminated glass having excellent strength in addition to the near infrared light blocking property can be obtained. Is also possible.

  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, an infrared absorption layer that is an intermediate film develops near-infrared light absorption characteristics. Heat rays in the optical 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.

  Also especially. The laminated glass having the above structure includes an intermediate film obtained by using a copper salt composition containing phosphonic acid copper salt particles and a polysiloxane component. And in this intermediate film, since deterioration of the phosphonate copper salt particles themselves and deterioration of the resin due to the phosphonate copper salt particles are greatly suppressed even at high temperatures, the laminated glass provided with such an intermediate film is a window material. Even when it is used for a long period of time and exposed to high temperatures, the infrared absorption characteristics and transparency can be maintained over a long period of time, and coloring due to long-term use is unlikely to occur.

  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 above-described embodiment has excellent near-infrared light blocking performance, building materials (construction) for taking in natural light such as sunlight and other external light (For example, window materials for automobiles, ships, aircraft or train (railway) vehicles, canopies for passages such as arcades, curtains, canopies for carports and garages, windows or walls for solariums) Window materials for show windows and showcases, tents or window materials, blinds, roofing materials for fixed and temporary housing, skylights and other window materials, coating materials for painted surfaces such as road signs, sunscreen materials such as parasols, etc. It can be suitably used for various members that need to be shielded from heat rays.

  EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples.

[Example 1]
(Preparation of copper salt composition)
First, a dispersion in which ethylphosphonic acid copper salt having an average particle diameter of 165 nm was dispersed in triethylene glycol bis-2-ethylhexanate was diluted with ethanol to obtain a copper salt dispersion. Next, tetraethoxylane (TEOS) was further added to the copper salt dispersion and stirred. Then, after further adding water to this mixed solution and stirring at 80 ° C. for 4 hours, ethanol is distilled off by a rotary evaporator to obtain a copper salt composition containing an ethylphosphonic acid copper salt and a polysiloxane component. It was.

(Formation of infrared absorption film)
Chloroform and polyvinyl butyral resin (PVB) were added to the copper salt composition obtained above and stirred. Then, this dispersion was poured into a vat to remove chloroform, and then dried under reduced pressure at 80 ° C. for 2 hours. The resin film thus obtained was put into a 0.76 mm thick mold and pressed at 120 ° C. for 3 minutes to prepare a sheet-like molded product (infrared absorbing film).

[Comparative Example 1]
An infrared absorption film was produced in the same manner as in Example 1 except that the copper salt composition was obtained without adding TEOS to the copper salt dispersion.

[Comparative Example 2]
A dispersion in which ethylphosphonic acid copper salt having an average primary particle size of 1.7 μm was dispersed in triethylene glycol bis-2-ethylhexanate (3GO) and polyvinyl butyral resin were kneaded with Brabender. The obtained resin composition was put into a 0.76 mm thick mold and pressed at 120 ° C. for 3 minutes to produce an infrared absorption film. When the haze of the obtained film was measured, it was as high as 69.9 and the transparency was extremely low. Therefore, heat resistance evaluation described later was not performed.

[Characteristic evaluation]
The infrared absorption films obtained in Example 1 and Comparative Example 1 were each subjected to a high temperature treatment that was pressed at 200 ° C. for 15 minutes.

  And about each infrared absorption film, the laminated glass was produced using the thing before performing a high temperature process, and the thing after performing a high temperature process, respectively. That is, each infrared absorption film is sandwiched between a pair of glass slides (length 76 mm × width 26 mm × thickness 1 mm), which are translucent substrates, and these are pressure-bonded in an autoclave at 130 ° C. and 1.5 MPa for 30 minutes. As a result, four types of laminated glass were obtained as the infrared absorption film of Example 1 or Comparative Example 1, respectively, before and after the high temperature treatment, as an intermediate film.

  And about each obtained laminated glass, spectral characteristics were measured using the spectrophotometer (the Shimadzu Corporation make, U-4000). The result of the laminated glass obtained using the infrared absorption film of Example 1 is shown in FIG. 5, and the result of the laminated glass obtained using the infrared absorption film of Comparative Example 1 is shown in FIG. In FIG.4 and FIG.5, the result at the time of using the infrared absorption film before and behind performing a high temperature process was shown collectively.

Further, based on the evaluation of the spectral characteristics described above, the yellow index (YI value) when the infrared absorption film before and after the high temperature treatment is used for the laminated glass including the infrared absorption film of Example 1 or Comparative Example 1. I asked for each. The YI value is calculated according to the following formula (A) based on the tristimulus values (X, Y, Z) of the XYZ color system obtained by a method based on JIS Z8701 by measurement using a spectrophotometer. can do.
YI value = (128X−106Z) / Y (A)

Then, a change in yellow index value (ΔYI value) in the case of using the infrared absorption film after the high temperature treatment with respect to the case of using the infrared absorption film before the high temperature treatment was obtained by the following formula (1). The obtained results are shown in Table 1.
ΔYI = YI ₁ (YI value after high temperature treatment) −YI ₀ (YI value before high temperature treatment) (1)

  4 and 5, the laminated glass provided with the infrared absorption film of Example 1 obtained using the copper salt composition corresponding to the present invention is the infrared absorption film of Comparative Examples 1 and 2 not corresponding to the present invention. It was confirmed that the change in spectral characteristics was small before and after the high-temperature treatment was performed on the infrared absorption film, in particular, the decrease in the transmittance of light in the visible region was small compared to the laminated glass provided with. Further, from Table 1, the laminated glass using the infrared absorption film of Example 1 has sufficient transparency because of its small haze, and also has a small ΔYI value compared to that of the comparative example. It was confirmed that yellowing due to high-temperature treatment hardly occurred. From the above results, it was found that the infrared absorption films of the examples were excellent in infrared absorption characteristics and transparency and had high heat resistance.

It is a figure which shows typically the cross-sectional structure of a laminated glass. 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. It is a figure which shows the spectral characteristics of the laminated glass obtained using the infrared rays absorption film of the comparative example 1. It is a figure which shows the spectral characteristics of the laminated glass obtained using the infrared rays absorption film of Example 1.

Explanation of symbols

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

Claims (5)

Particles composed of a phosphonic acid copper salt formed of a phosphonic acid compound represented by the following general formula (1) and copper ions, and having an average particle diameter of 0.005 to 0.3 μm;
A polysiloxane component comprising a hydrolyzate and / or condensate of alkoxysilane;
A plasticizer,
A dispersant,
The copper salt composition characterized by containing.

[Wherein, R ¹ represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, an allyl group, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, (meth) acryloyloxy An alkyl group or a (meth) acryloyl polyoxyalkyl group, and at least one hydrogen atom in these groups is a halogen atom, an oxyalkyl group, a polyoxyalkyl group, an oxyaryl group, a polyoxyaryl group, an acyl group, an aldehyde Group, carboxyl group, hydroxyl group, (meth) acryloyl group, (meth) acryloyloxyalkyl group, (meth) acryloyl polyoxyalkyl group or ester group may be substituted. ] Resin,
The copper salt composition according to claim 1 dispersed in the resin;
A resin composition comprising:   The resin composition according to claim 2, wherein the resin is polyvinyl butyral.   An infrared absorption film comprising the resin composition according to claim 3. A translucent substrate;
An infrared absorption layer comprising the infrared absorption film according to claim 4 disposed on the translucent substrate;
A laminate comprising:

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