JP5561936B2 - Solar control laminate - Google Patents

Description

  The present invention relates to the field of devices that reduce the transmission of radiation, and more particularly to devices that reduce the transmission of infrared radiation.

  Glass laminated products or “safety glass” have contributed to society for almost a century. Safety glass is characterized by high impact resistance and penetration resistance, and is further characterized by minimal scattering of glass fragments and fragments when crushed. These laminates typically consist of a sandwich structure of polymer film or sheet intermediate layers present between two glass plates or glass panels. One or both of the glass plates can be replaced with an optically clear rigid or non-rigid polymer sheet, such as a sheet of polycarbonate material or polyester film. Safety glass has been further developed to include three or more layers of glass and / or polymer sheets joined together with two or more intermediate layers.

  In addition to the well-known safety glass commonly used in automobile windshields, glass laminates are incorporated as windows in trains, airplanes, ships, and almost any other vehicle. Recently, designers have incorporated more glass surfaces into their buildings, so the architectural use of safety glass is also expanding rapidly.

  Society continues to demand additional functionality other than optical and decorative performance and safety characteristics for laminated glass products. One desirable goal is to reduce energy consumption in structures such as automobiles or buildings by developing solar control glazing. Since the near-infrared spectrum is not perceived by the human naked eye, one typical method is to develop a glass laminate that prevents some of the solar energy from the near-infrared spectrum from entering the structure. Met. For example, in a structure fitted with a solar control window that blocks a portion of the near infrared spectrum without reducing or distorting the transmission of the visible light spectrum, the energy consumed by air conditioning can be reduced. .

  Solar control of the glass laminate can be achieved by modifying the glass or polymer interlayer, adding additional solar control layers, or a combination of these methods. One form of solar control laminate glass includes a metallized substrate film, such as a polyester film having a conductive aluminum or silver metal layer. In general, a metallized film reflects light of an appropriate wavelength, thereby obtaining appropriate solar control characteristics. Metallized films are generally manufactured by vacuum deposition or sputtering methods that require high vacuum equipment and a precise atmosphere control system. In addition to infrared light, metallized films also reflect certain radio wavelengths, so radio, television, global positioning system (GPS), automatic toll collection, keyless entry, communication system, automatic garage opener, automatic cash automatic It interferes with the function of similar systems commonly used in depositors, radio frequency identification (RFID), and other structures that may be protected by automobiles or solar control laminated glass. This disturbance occurs directly because the metal layer is continuous and therefore conductive.

  A more recent trend is to use metal-containing nanoparticles that absorb rather than reflect infrared light. In order to maintain the clarity and transparency of the substrate, these materials ideally have a nominal particle size of less than about 200 nanometers (nm). Since these materials do not form a conductive film, the operation of devices that transmit and receive radiation placed inside structures protected by this type of solar control glazing is not disturbed. However, when these nanoparticles are added into the polymer interlayer, the manufacturing method of these laminates is necessarily complicated.

  Infrared-absorbing phthalocyanines and phthalocyanine-based materials are known for use in optical information recording media that are optionally used in combination with a binder resin that may contain polyvinyl butyral. Recent examples of patents in the art include US Pat. Nos. 6,057,075, 6,197,472, 6,576,396, No. 197,464, No. 6,207,334, No. 6,238,833, No. 6,376,143, No. 6,465,142 And US Pat. No. 6,489,072.

  An alkoxy-substituted phthalocyanine compound is also used as an infrared absorbing material in an optical information recording medium optionally used in combination with a binder resin. For example, U.S. Pat. Nos. 4,769,307, 5,296,162, 5,409,634, 5,358,833, and 5 No. 4,446,142, No. 5,646,273, No. 5,750,229, No. 5,594,128, No. 5,663,326. No. 6,726,755; and European Patent Application No. 0 373 643.

  Various solar control devices including organic infrared absorbing materials such as phthalocyanine compounds are also well known. For example, Avecia Corp. (Wilmington, DE) sells crotch phthalocyanine compounds as infrared absorbers for incorporation into glazing materials such as glass, plastic, and film coatings. Examples of glass laminate interlayer compositions containing phthalocyanines include US Pat. Nos. 5,830,568, 6,315,848, 6,329,061; and See U.S. Patent 6,579,608; U.S. Patent Application Publication No. 2004/0241458; and WO 2002/070254.

  Infrared absorbing naphthalocyanine materials are also generally disclosed for use in optical information recording media that may contain a binder resin. For example, U.S. Pat. Nos. 4,492,750, 4,529,688, 4,769,307, 4,886,721, No. 2,021,563, No. 4,927,735, No. 4,960,538, No. 5,282,894, No. 5,446,142. No. 5,484,685, No. 6,197,851, No. 6,210,848, No. 6,641,965, No. 5, 039,600 specification. And US Pat. No. 5,229,859. Certain naphthalocyanine materials dispersed in a binder resin that may contain polyvinyl butyral have been disclosed in the art. For example, U.S. Pat. No. 4,766,054 describes an optical recording medium containing certain naphthalocyanine dyes.

  However, phthalocyanine-type and naphthalocyanine-type infrared absorbers are often relatively poor solar control agents because of their dark colors. In other words, many phthalocyanines and naphthalocyanines have a considerable amount of absorption at visible wavelengths.

  Accordingly, it remains desirable to provide a new solar control laminate that reduces transmission of infrared energy and provides more sufficient transmission of visible light and high frequencies.

  The present invention provides a composition consisting essentially of an infrared-absorbing phthalocyanine compound or naphthalocyanine compound and a plasticizer.

  The present invention also provides a solar control composition comprising an infrared absorbing phthalocyanine compound or naphthalocyanine compound and a resin having an elastic modulus of 20,000 psi (138 MPa) to 1000 psi (7 MPa). Preferably, the resin has a modulus of 15,000 psi (104 MPa) to 1000 psi (7 MPa) and comprises polyvinyl butyral or ethylene-co-vinyl acetate.

  The present invention further provides a solar control laminate comprising an infrared absorbing phthalocyanine compound or naphthalocyanine compound and a resin having an elastic modulus of 20,000 psi (138 MPa) to 1000 psi (7 MPa). Preferably, the resin has a modulus of 15,000 psi (104 MPa) to 1000 psi (7 MPa) and comprises polyvinyl butyral or ethylene-co-vinyl acetate.

The present invention is a solar control laminate including a solar control layer composed of polyvinyl butyral or ethylene-co-vinyl acetate and an infrared-absorbing phthalocyanine compound or a concentrate of naphthalocyanine compound, and includes a simulation method A. When the laminate was simulated using the simulation, the visible light transmittance simulation value T _vis-sim was 0.65 <T _vis-sim <0.75, and the solar light transmittance simulation value T _sol-sim was If a phthalocyanine compound <become as _{(0.932 (T vis-sim)} -0.146) , and when the naphthalocyanine compound _{<(0.481 (T vis-sim} ) -0.166), the layer thickness Further provided is a solar control laminate having solar transmittance and visible light transmittance.

  Further provided is a method of reducing infrared transmission into the interior of a structure having an external window. The method includes creating a solar control laminate of the present invention and inserting the solar control laminate into an external window of the structure.

  Except where limited to special cases, the definitions herein apply to terms used throughout this specification.

  As used herein, the term “solar control” means reducing the intensity of radiation of any wavelength emitted by the sun. Preferably, in the present invention, the intensity of the infrared or near-infrared wavelength decreases, and the intensity of the visible wavelength does not change substantially. Under these conditions, heat transmission is reduced while at the same time visual transparency is maintained and the appearance of the colored object is not substantially distorted.

  As used herein, the terms “finite amount” and “finite value” mean an amount or value greater than zero.

  As used herein, the term “about” means that amounts, sizes, formulas, parameters, and other quantities and characteristics are not strict, need not be strict, tolerance, conversion rate, rounding Means that it can be approximated and / or increased or decreased as desired, reflecting measurement errors, etc., and other factors known to those skilled in the art. In general, an amount, size, formulation, parameter, or other quantity or characteristic is “about” or “approximately” whether or not so stated.

  As used herein, the term “or” is inclusive, and more specifically, the phrase “A or B” means “A, B, or both A and B”. . In this specification, the exclusive “or” is expressed by a term such as “any one of A or B” and “one of A or B”.

  Where materials, methods, or machines are described herein with the term “well known to those skilled in the art”, or with synonymous words or phrases, the terms are prior art materials, methods, and machines as of the filing of this application. Is included in the description herein. Also included are materials, methods, and machines that are not currently prior art, but will become recognized in the art as being suitable for similar purposes.

  Unless otherwise limited, all percentage values, parts, ratios, etc. used herein are on a weight basis.

  Finally, unless stated otherwise, the ranges described herein include the endpoints of the ranges. Further, if an amount, concentration, or other value or parameter is given as a range, one or more preferred ranges, or a list of upper preferred values and lower preferred values, this may be any upper limit value or Explicitly disclosing all ranges formed from any set of upper preferred values and any lower or lower preferred values, regardless of whether such sets are disclosed separately; Should be understood as.

  In one aspect, the present invention provides a composition consisting essentially of a plasticizer and a phthalocyanine compound or naphthalocyanine compound. This composition is useful as a precursor for a solar control layer containing a phthalocyanine compound or naphthalocyanine compound and a resin, which will be described in more detail below.

  As used herein, the term “phthalocyanine compound” means phthalocyanine and its ions, metal phthalocyanines, phthalocyanine derivatives, and their ions, and metallized phthalocyanine derivatives. As used herein, the term “phthalocyanine derivative” means any compound having a phthalocyanine nucleus. In other words, as the phthalocyanine derivative, a molecule containing a tetrabenzo [b, g, l, q] -5,10,15,20-tetraazaporphyrin moiety, which is the 1-position, 2-position, 3-position of the phthalocyanine moiety, Any of the peripheral hydrogen atoms bonded to the carbon atom at the 4th, 8th, 9th, 10th, 11th, 15th, 16th, 17th, 18th, 22nd, 23rd, 24th or 25th position Instead, any molecule having any number of peripheral substituents is included. When two or more peripheral substituents are present, these peripheral substituents may be the same or different.

  As used herein, the term “naphthalocyanine compound” means naphthalocyanine and its ions, metal naphthalocyanines, naphthalocyanine derivatives and their ions, and metallated naphthalocyanine derivatives. As used herein, the term “naphthalocyanine derivative” means any compound having a naphthalocyanine nucleus. In other words, the naphthalocyanine derivative includes a molecule containing a tetranaphthalo [b, g, l, q] -5,10,15,20-tetraazaporphyrin moiety and a peripheral hydrogen bonded to a carbon atom of the naphthalocyanine moiety. Any molecule having any number of peripheral substituents in place of any of the atoms is included. When two or more peripheral substituents are present, these peripheral substituents may be the same or different.

  Suitable phthalocyanine compounds and naphthalocyanine compounds for use in the present invention include any infrared-absorbing phthalocyanine compound or naphthalocyanine compound. Some suitable phthalocyanine and naphthalocyanine compounds can function as dyes, i.e., they become soluble in the plasticizer composition. Alternatively, others can function as pigments, i.e., they become insoluble in the plasticizer composition.

  Suitable phthalocyanine and naphthalocyanine compounds can be metallized, for example, monovalent metals such as sodium, potassium, and lithium; copper, zinc, iron, cobalt, nickel, ruthenium, rhodium, palladium, platinum, manganese, Divalent metals such as tin, vanadium, and calcium; or can be metallized using trivalent metals, tetravalent metals, or metals with higher valences.

In general, except for those containing divalent metals, the charge of any metallized phthalocyanine or naphthalocyanine compound is due to an appropriately charged cation or anion that often coordinates axially to the metal ion. Balanced. Examples of suitable ions include, but are not limited to, halogen anions, metal ions, hydroxide anions, oxide anions (O ²⁻ ), alkoxide anions, and the like. Preferred examples of the metal phthalocyanine compound and metal naphthalocyanine compound include DAl ³⁺ Cl ⁻ , DAl ³⁺ Br ⁻ , DIn ³⁺ Cl ⁻ , DIn ³⁺ Br ⁻ , DIn ³⁺ I ⁻ , DSi ⁴⁺ (Cl ^−). ) ₂ , DSi ⁴⁺ (Br ⁻ ) ₂ , DSi ⁴⁺ (F ⁻ ) ₂ , DSn ⁴⁺ (Cl ⁻ ) ₂ , DSn ⁴⁺ (Br ⁻ ) ₂ , DSn ⁴⁺ (F ⁻ ) ₂ , DGe ^{4 +} (Cl ⁻ ) ₂ , DGe ⁴⁺ (Br ⁻ ) ₂ , DGe ⁴⁺ (F ⁻ ) ₂ , DSi ⁴⁺ (OH ⁻ ) ₂ , DSn ⁴⁺ (OH ⁻ ) ₂ , DGe ⁴⁺ (OH ⁻ ) ₂ , DV ⁴⁺ O ²⁻ , and DTi ⁴⁺ O ^2−, where “D” is a divalent anion of phthalocyanine or naphthalocyanine or a disubstituted anion of phthalocyanine or naphthalocyanine substituted at the periphery. It means a charged anion. Preferably, in the case of phthalocyanine compounds, the metal comprises copper (II), nickel (II), or a mixture of copper (II) and nickel (II). Preferably, in the case of naphthalocyanine compounds, the metal is copper (II), nickel (II), silicon (IV), or a mixture of two or more of copper (II), nickel (II), and silicon (IV) including.

  Most preferably, the phthalocyanine compounds and naphthalocyanine compounds of the present invention are not metallized.

  Phthalocyanine derivatives and naphthalocyanine derivatives are preferred. Preferably, in the case of phthalocyanine derivatives, one hydrogen atom of each of the four peripheral benzo rings is substituted symmetrically or asymmetrically. Also preferably, the phthalocyanine derivative may be substituted at the 1-position, 4-position, 8-position, 11-position, 15-position, 18-position, 22-position, and 25-position, or substituted at all 16 peripheral carbon positions. May be. Preferably, in the case of naphthalocyanine derivatives, one or two hydrogen atoms of each of the four peripheral naphthalo rings are substituted symmetrically or asymmetrically. Also preferably, the naphthalocyanine derivative may be substituted at all 24 peripheral carbon positions.

  Suitable substituents for the phthalocyanine derivative or naphthalocyanine derivative include halogen, alkyl groups, alkoxyalkyl groups, alkoxyl groups, aryloxy groups, and partially halogenated or perhalogenated alkyl groups. The alkyl substituent may be linear or branched. Specific examples of preferred alkyl substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, neopentyl group, isopentyl group, neopentyl group. 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl Group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropylbutyl group , 1-t-butyl-2-methylpropyl group, n-nonyl group, and mixtures thereof. Specific examples of the alkoxyalkyl substituent include methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxy. An ethyl group, a diethoxyethyl group, and mixtures thereof are mentioned. Specific examples of the partially halogenated or perhalogenated alkyl substituent include chloromethyl group, 2,2,2-trichloromethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro- Examples include 2-propyl groups and mixtures thereof. Specific examples of aryloxy substituents include phenoxy, 4-tert-butylphenyloxy group, 4-cumylphenoxy group, naphthyloxy group, and mixtures thereof.

  More preferably, the phthalocyanine compound or naphthalocyanine compound of the present invention comprises an alkoxy-substituted phthalocyanine or an alkoxy-substituted naphthalocyanine. Tetrasubstituted and octasubstituted alkoxyphthalocyanine compounds or tetrasubstituted and octasubstituted alkoxynaphthalocyanine compounds are preferred. Examples of preferred alkoxyl groups include methoxyl, ethoxyl, n-propoxyl, isopropoxyl, n-butoxyl, isobutoxyl, sec-butoxyl, tert-butoxyl, n-pentoxyl, isopentoxyl, neopentoxyl, 1,2-dimethyl Propoxyl, n-hexyloxyl, isohexyloxyl, neohexyloxyl, cyclohexyloxyl, heptyloxyl, 1,3-dimethylbutoxyl, 1-isopropylpropoxyl, 1,2-dimethylbutoxyl, 1,4-dimethylpent Xyl, 2-methyl-1-isopropylpropoxyl, 1-ethyl-3-methylbutoxyl, 2-ethylhexoxyl, 3-methyl-1-isopropylbutoxyl, 2-methyl-1-isopropylbutoxyl, 1 -T- Chill-methyl propoxyl, n- octyl oxyl, n- Noniruokishiru, n- decyloxyl, and mixtures thereof. A butoxyl group is preferred.

  Specific examples of preferred phthalocyanine compounds include aluminum 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine triethylsiloxide; copper (II) 1,4,8,11, 15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; 8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; zinc 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; copper (II ) 2,3,9,10,16,17,23,24-octakis (octyloxy) -29H, 31H-phthalocyan 2,3,9,10,16,17,23,24-octakis (octyloxy) -29H, 31H-phthalocyanine; silicon 2,3,9,10,16,17,23,24-octakis (octyl) Oxy) -29H, 31H-phthalocyanine dihydroxide; zinc 2,3,9,10,16,17,23,24-octakis (octyloxy) -29H, 31H-phthalocyanine; and mixtures thereof.

  Even more preferably, the phthalocyanine compound of the present invention comprises an n-butoxyl substituted phthalocyanine compound. Again, tetra- and octa-substituted alkoxy phthalocyanine compounds are preferred. Specific examples of preferred butoxyl phthalocyanine compounds include aluminum 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine triethylsiloxide; copper (II) 1,4,8, 11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; 4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; zinc 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine; and A mixture thereof may be mentioned.

  Specific examples of preferable naphthalocyanine compounds include, for example, aluminum 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine triethylsiloxide, copper (II) 5,9, 14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, nickel (II) 5,9,14,18,23,27,32,36-octabutoxy-2,3-na Phthalocyanine, 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine, zinc 5,9,14,18,23,27,32,36-octabutoxy-2, 3-Naphthalocyanine, and mixtures thereof.

Alternatively, preferred phthalocyanine and naphthalocyanine compounds can be identified experimentally by showing a favorable balance of optical properties. A transmission spectrum is obtained for a film containing a phthalocyanine compound and a naphthalocyanine compound, or a laminate comprising such a film. Solar transmittance, which is the transmittance of all light in the solar spectrum, by processing the transmission spectrum of a given film or using the measured transmission spectrum of a given laminate in the simulation program described below. (T _sol-sim ) and the transmittance of light in the visible light spectrum weighted by the sensitivity of the naked eye to a simulated glass / resin / glass laminate containing a resin interlayer with a processed transmission spectrum The visible light transmittance (T _vis-sim ) is calculated. Preferred phthalocyanine compounds in polyvinyl butyral or ethylene-co-vinyl acetate such that T _vis-sim is between 0.65 and 0.75, using T _vis-sim and glass and resin parameters The concentration of naphthalocyanine compound is calculated. Preferred phthalocyanine compounds give a T _{sol-sim of} less than (0.932T _vis-sim -0.146). More preferred phthalocyanine compounds yield T _sol-sim less than (0.964 T _vis-sim −0.192), and even more preferred phthalocyanine compounds produce T _sol less than (1.086 T _vis-sim −0.305). _-sim is obtained. Preferred naphthalocyanine compounds yield T _{sol-sim of} less than (0.481 T _vis-sim -0.166).

  Another analysis can also define preferred phthalocyanine or naphthalocyanine compounds. For example, the phthalocyanine compound or naphthalocyanine compound of the present invention and the calculated concentration thereof can be adjusted to obtain any desired visible light transmittance. More specifically, in the case of an automobile windshield, a visible light transmittance of 0.75 or more is generally required. However, architectural laminates can have a much lower visible light transmission, such as 0.50 or less.

  Preferably, the amount of phthalocyanine compound or naphthalocyanine compound in the plasticizer, based on the total weight of the phthalocyanine / plasticizer or naphthalocyanine / plasticizer composition, is about 0.0001 to about 10% by weight, more preferably About 0.001 to about 5% by weight, more preferably about 0.001 to about 1% by weight, more preferably about 0.01 to about 0.1% by weight.

  Suitable plasticizers for the compositions of the present invention can include any known in the art. Preferred plasticizers are well known in the art, for example, U.S. Pat. Nos. 3,841,890, 4,144,217, 4,276,351, No. 4,335,036, US Pat. No. 4,902,464, US Pat. No. 5,013,779, and WO 96/28504. Commonly used plasticizers are polybasic acids or esters of polyhydric alcohols. Preferred plasticizers are diesters obtained by reaction of triethylene glycol or tetraethylene glycol with aliphatic carboxylic acids having 6 to 10 carbon atoms; sebacic acid and aliphatics having 1 to 18 carbon atoms. Diesters obtained by reaction with alcohols; oligoethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, dihexyl adipate, dioctyl adipate, a mixture of heptyl adipate and nonyl adipate, sebacine Polymer plasticizers such as dibutyl acid, tributoxyethyl phosphate, isodecylphenyl phosphate, triisopropyl phosphite, oil-modified sebaside alkyd, and the phosphate and adipate Compounds, and mixtures of adipates and alkyl benzyl phosphate, and mixtures thereof. More preferred plasticizers are triethylene glycol di-2-ethylhexanoate, tetraethylene glycol di-n-heptanoate, dibutyl sebacate, and mixtures thereof. The most preferred plasticizers are triethylene glycol di-2-ethylhexanoate and tetraethylene glycol di-n-heptanoate. One type of plasticizer can be used, or a mixture of a plurality of plasticizers can be used. For convenience, when describing the composition of the present invention, a mixture of a plurality of plasticizers may be referred to herein as a “plasticizer”. That is, as used herein, the singular form of the term “plasticizer” can represent either the use of one type of plasticizer or the use of a mixture of two or more types of plasticizers.

  In the formulation of the composition of the present invention, processing aids, glidants, lubricants, pigments, dyes, flame retardants, impact modifiers, nucleating agents for increasing crystallinity, anti-blocking agents such as silica, Includes heat stabilizers, UV absorbers, UV stabilizers, dispersants, surfactants, chelating agents, coupling agents, adhesives, primers, crosslinking agents, curing agents, pH adjusting agents, antifoaming agents, and wetting agents And may be convenient. The specific types of these additives, their amounts, and the method of incorporating the additives into the composition of the present invention can be selected by methods well known in the art.

  The present invention further provides a solar control composition comprising an infrared absorbing phthalocyanine compound or naphthalocyanine compound and a resin. Preferably, the resin comprises polyvinyl butyral or ethylene-co-vinyl acetate. In the present specification, this solar control composition may be referred to as a “matrix composition”.

  The solar control composition of the present invention comprises a resin having an elastic modulus of 20,000 psi (138 MPa) to 1000 psi (7 MPa), preferably 15,000 psi (104 MPa) to 1000 psi (7 MPa). Examples of matrix resins include: poly (ethylene-co-vinyl acetate); ethyl acrylic acetate (EM); ethyl methacrylate (EMAC); metallocene catalyzed polyethylene; plasticized poly (vinyl chloride); ISD resins described in US Pat. Nos. 5,624,763 and 5,464,659; polyurethanes; for example, US Pat. Nos. 4,382,996 and 5, No. 773,102, etc., and is sound-insulating modified poly (vinyl chloride) commercially available from Sekisui Company; plasticized poly (vinyl butyral); for example, described in JP-A No. 05-138840 Sound insulation modified poly (vinyl butyral), and The combination of these, and the like. The elastic modulus of each of these materials is described in US Pat. No. 6,432,522. Preferably, the matrix resin of the present invention comprises an ethylene vinyl acetate copolymer or polyvinyl butyral.

  The solar control composition of the present invention also contains at least one phthalocyanine compound or naphthalocyanine compound. When the solar control composition is used as an infrared cutoff filter, the amount of phthalocyanine compound is about 0.01 to about 80 weight percent, preferably about 0.01 to about 80, based on the total weight of the solar control composition. 10 weight percent; more preferably from about 0.01 to about 5 weight percent. When the solar control composition is used as an infrared cut-off filter, the amount of naphthalocyanine compound is about 0.01 to about 50 weight percent, preferably about 0.01 to about 50 weight percent, based on the total weight of the solar control composition. About 10 percent by weight; more preferably about 0.01 to about 5 percent by weight. When the solar control composition is prepared as a concentrate, the amount of phthalocyanine compound in the solar control composition is about 30 to about 80 weight percent, preferably about 30 to about 50 weight percent, based on the total weight of the composition. More preferably from about 35 to about 45 weight percent. When the solar control composition is prepared as a concentrate, the amount of naphthalocyanine compound in the solar control composition is about 30 to about 50 weight percent, more preferably about 35 to about 50, based on the total weight of the composition. 45 weight percent.

  The matrix composition of the present invention can also include one or more plasticizers. Dispersant, surfactant, chelating agent, coupling agent, UV absorber, hindered amine light stabilizer (HALS), processing aid, glidant, lubricant, pigment, dye, flame retardant, impact modifier, crystal Nucleating agent to increase the degree of conversion, anti-blocking agent such as silica, heat stabilizer, UV stabilizer, adhesive, primer, crosslinking agent, curing agent, pH adjuster, antifoaming agent, inorganic infrared absorber, organic Infrared absorber and wetting agent. Suitable amounts of these additives and methods for incorporating these additives into the polymer composition are available to those skilled in the art. See, for example, “Modern Plastics Encyclopedia”, McGraw-Hill, New York, NY 1995.

  The solar control composition of the present invention can be produced by any suitable method. Preferably, the phthalocyanine compound or naphthalocyanine compound is dispersed in the resin by high shear mixing the molten resin with the phthalocyanine compound or naphthalocyanine compound and other optional ingredients. This high shear mixing can be performed by a static mixer, a rubber mill, a Brabender mixer, a single screw extruder, a twin screw extruder, a heated or non-heated two-roll mill, and the like. The resin and / or matrix composition can be dried before any drying step. The matrix composition can then be mixed as a dry blend with additional phthalocyanine or naphthalocyanine compounds, as well as other optional ingredients, typically referred to as a “pellet blend”. Alternatively, the resin and the phthalocyanine or naphthalocyanine compound can be fed simultaneously via two different feeders. Alternatively, the phthalocyanine compound or naphthalocyanine compound can be dissolved, dispersed, or suspended in a solvent or plasticizer to form a concentrate. This concentrate is then added to the resin by a powerful melt mixing process. Generally, the melt processing temperature of the resin is in the range of about 50 ° C to about 300 ° C. The exact processing conditions vary depending on the individual resin. The amount of resin and concentrate is selected so that the final concentration of phthalocyanine or naphthalocyanine compound in the solar control composition provides the desired reduction in solar radiation transmission.

  The amount of phthalocyanine or naphthalocyanine compound in the matrix resin affects the efficiency of the process of reducing the phthalocyanine particles or naphthalocyanine particles to a usable size. For optimal transparency, the particles are preferably approximately nanoparticles. As is well known, the melt viscosity of polymer / particle blends generally increases with increasing volume concentration of particles. Therefore, the volume concentration of the particles needs to be in a range where a high melt viscosity sufficient to apply a large shear stress during the mixing process can be obtained. By this shear stress, crude phthalocyanine particles or naphthalocyanine particles are deagglomerated to primary particles. Conversely, the maximum concentration obtainable with particles in the resin is limited by the maximum melt viscosity that can be processed with the selected equipment.

  The present invention further provides a molded article comprising the solar control composition of the present invention. The molded article of the present invention is preferably a coating, a film, a multilayer film, a sheet, or a multilayer sheet.

  Preferably, the molded article of the present invention is a solar control layer. The solar control layer of the present invention may be a coating, film, sheet, multilayer film, or multilayer sheet. Although the difference between a film and a sheet is the thickness, there is no industry standard that defines the thickness at which the film becomes a sheet. For purposes of this invention, the film has a thickness of about 10 mils (0.25 mm) or less. Preferably, the film has a thickness of about 0.5 mil (0.012 mm) to about 10 mil (0.25 mm). More preferably, the film has a thickness of about 1 mil (0.025 mm) to about 5 mils (0.13 mm). For automotive applications, the film thickness may be preferably in the range of about 1 mil (0.025 mm) to about 4 mils (0.1 mm). For purposes of this invention, the sheet has a thickness greater than about 10 mils (0.25 mm). Preferably, the sheet has a thickness of about 15 mils (0.38 mm) or greater. More preferably, the sheet has a thickness of about 30 mils (0.75 mm) or greater.

  Preferred polymer resins for use in the film include poly (ethylene terephthalate), polycarbonate, polypropylene, polyethylene, polypropylene, cyclic polyolefin, norbornene polymer, polystyrene, syndiotactic polystyrene, styrene-acrylate copolymer, acrylonitrile-styrene copolymer, poly ( Ethylene naphthalate), polyethersulfone, polysulfone, nylon, poly (urethane), acrylic, cellulose acetate, cellulose triacetate, vinyl chloride polymer, polyvinyl fluoride, polyvinylidene fluoride, poly (vinyl butyral), ethylene-co-vinyl acetate Etc. Preferably, the film of the present invention is a biaxially stretched poly (ethylene terephthalate) film.

  Preferred polymer resins for use in the sheet include polymers having an elastic modulus of independently selected 20,000 psi (138 MPa) to 1000 psi (7 MPa). More preferably, the sheet of the present invention comprises an independently selected polymer having a modulus of elasticity between 15,000 psi (104 MPa) and 1000 psi (7 MPa). Preferred examples of matrix materials and polymer resins used in the sheet include, for example, poly (ethylene-co-vinyl acetate) compositions; ethyl acrylate acetate; ethyl methacrylate; metallocene catalyzed polyethylene; Poly (vinyl chloride); ISD resin; Polyurethane; Sound insulation modified poly (vinyl chloride) such as those commercially available from Sekisui Company; Plasticized poly (vinyl butyral) composition; Sound insulation modified poly (vinyl acetal) composition Products, sound insulation modified poly (vinyl butyral) compositions; and combinations thereof.

  Preferably, the solar control layer of the present invention is transparent to visible light. Also preferably, the melt processing temperature of the film and sheet compositions of the present invention is from about 50 ° C to about 300 ° C, more preferably from about 100 ° C to about 250 ° C. Since the films and sheet compositions of the present invention generally have excellent thermal stability, they can be processed at high temperatures sufficient to reduce the effective melt viscosity.

  In the case of sheets, poly (vinyl butyral) is a more preferred polymer resin. Preferred poly (vinyl butyral) resins range from about 30,000 to about 600,000 daltons, preferably from about 45,000 to about 300,000, as measured by size exclusion chromatography using small angle laser light scattering. Having a weight average molecular weight in the range of 000 daltons, more preferably in the range of about 200,000 to 300,000 daltons. Preferred poly (vinyl butyral) materials are about 5 to about 30 percent, preferably about 11 to about 25 percent, and more preferably about 15 to about 22 percent hydroxyl by weight, calculated as polyvinyl alcohol (PVOH). Contains groups. Further, preferred poly (vinyl butyral) materials contain from about 0 to about 10 percent, preferably from about 0 to about 3 percent of residual ester groups, typically acetate groups, calculated as polyvinyl esters, with the balance being Butyraldehyde acetal. Poly (vinyl butyral) can also contain relatively small amounts of acetal groups other than butyral, such as 2-ethylhexanal, as described in US Pat. No. 5,137,954. The poly (vinyl butyral) resin can be made by aqueous or solvent acetalization or by any other suitable means.

  Preferably, the poly (vinyl butyral) contains at least one plasticizer. The total amount of plasticizer depends on the individual poly (vinyl butyral) resin and the properties desired. Commonly used plasticizers are polybasic acids or esters of polyhydric alcohols.

  Poly (ethylene-co-vinyl acetate) resin is also a more preferred polymer resin for sheets. Suitable poly (ethylene-co-vinyl acetate) resins include Bridgestone Corporation, Exxon Corporation, Specialized Technologies Resources, Inc. , And E. I. du Pont de Nemours & Co. ("DuPont") (Wilmington, DE).

  Poly (ethylene-co-vinyl acetate) resins include other non-volatile materials such as, for example, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, and mixtures thereof. Saturated comonomers can be incorporated. Any of the foregoing plasticizers can be used with the poly (ethylene-co-vinyl acetate) resin.

  In order to control adhesive bonding between the glass rigid layer and the polymer film or sheet of the present invention, an adhesion control agent can be included in the film or sheet containing poly (vinyl butyral). The adhesion modifier is generally an alkali or alkaline earth metal salt of an organic or inorganic acid.

  The solar control layer of the present invention can include one or more of the aforementioned additives for use in the solar control composition of the present invention. These layers may also contain other additives that will be recognized by those skilled in the art as being suitable.

  The solar control layer of the present invention can be made by any suitable means. Certain preferred means are described in detail below. The compositions of the present invention (phthalocyanine or naphthalocyanine / plasticizer composition and solar control composition) can be used as intermediates in the production of solar control layers. For example, the solar control composition can be added as a concentrate to the pellet blend with the resin as a concentrate to form a solar control sheet. Other uses of the composition of the present invention to form the solar control layer of the present invention will be apparent to those skilled in the art.

  Thin films can be produced, for example, by dip coating as described in US Pat. No. 4,372,311, compression molding as described in US Pat. No. 4,427,614, US Pat. It can be formed by melt extrusion as described in US Pat. No. 4,880,592, melt blow as described in US Pat. No. 5,525,281, or other suitable methods. The polymer sheet can be formed by extrusion molding, calendering, solution casting, injection molding or the like. One skilled in the art will be able to determine the appropriate process parameters based on the composition of the polymer and the method used to form the sheet or film.

  However, preferably, the solar control film of the present invention is formed by solution casting or extrusion, and the solar control sheet of the present invention is formed by extrusion. Extrusion is particularly preferred when forming “endless” products such as films and sheets that appear in continuous lengths.

  The solar control layer of the present invention includes a multilayer stack having two or more layers. Multi-layer film and sheet structures are any suitable, for example, coextrusion, blown film, dip coating, solution coating, blade, paddle, air knife, printing, Dahlgren, gravure printing, powder coating, spraying, or other technical methods It can be formed by any means. The individual layers can be joined together, such as by heat, adhesives, and / or tie layers. Preferably, the multilayer film is produced by an extrusion casting method.

  The sheet and film of the present invention can have a smooth surface. Preferably, however, the sheet used as an intermediate layer in the laminate has at least one roughened surface so that most of the air can be efficiently removed from between the multiple surfaces of the laminate during the lamination process. Have

  The solar control layer of the present invention can comprise a film or sheet coated with one or both sides of the composition of the present invention. This coating can be performed by applying a coating solution or the like. The term “coating solution” refers to one or more polymer solutions, one or more polymer precursor solutions, one or more emulsion polymers, or a mixture of one or more polymer solutions, polymer precursor solutions, or emulsion polymers. The phthalocyanine compound or naphthalocyanine compound dissolved, dispersed or suspended therein is contained therein.

  The coating solution can include one or more solvents that dissolve, partially dissolve, disperse, or suspend the binder. The solvent or solvent mixture is responsible for the solubility of the matrix resin, the surface tension of the resulting coating solution, and the evaporation rate of the coating solution, the polarity and surface characteristics of the phthalocyanine compound used, and any dispersants and other additives. It is selected taking into account such properties as the chemical properties, the viscosity of the coating, and the compatibility of the surface tension of the coating with its surface energy film material. The solvent or solvent mixture should also be chemically inert to the binder material.

  Alternatively, the solvent can be partially or completely replaced with a plasticizer. Suitable plasticizers are described in detail above. Next, the coating solution, suspension or dispersion based on the plasticizer can be treated in the same manner as the coating solution based on the solvent.

  The thickness of the coating depends to some extent on the amount of solvent in the coating solution, and the amount of phthalocyanine compound or naphthalocyanine compound in the coating solution depends on the amount of binder and solvent in the coating solution, and the amount of phthalocyanine compound or solvent in the coating. It depends greatly on the desired amount of phthalocyanine compound.

  To prepare the coating solution, the phthalocyanine compound or naphthalocyanine compound is uniformly dispersed throughout the polymer solution by mixing the phthalocyanine compound or naphthalocyanine compound, matrix resin, optional additives, and solvent. Alternatively, as described in WO 01/00404 and US Pat. No. 5,487,939, the concentrate is mixed by kneading together the matrix resin and the phthalocyanine compound or naphthalocyanine compound. Can be formed and then added to the solvent. Regardless of the method of forming the coating solution, the phthalocyanine compound or naphthalocyanine compound can be deagglomerated by ball milling, roll milling, sand grinder grinding, paint shaker, kneader, dissolver, ultrasonic disperser or the like. .

  Alternatively, the phthalocyanine-containing or naphthalocyanine-containing coating may be an actinic radiation curable coating comprising one or more radiation curable monomers and / or oligomers. Suitable radiation curable matrix materials are described, for example, in US Pat. No. 5,504,133.

  Alternatively, the phthalocyanine-containing or naphthalocyanine-containing coating can include a photocationic curable matrix material as described in US Pat. No. 6,191,884. Generally, the photocationic curable matrix material comprises an epoxide material and / or a vinyl ether material.

  Alternatively, the phthalocyanine-containing or naphthalocyanine-containing coating composition can be cured by a heating process. If an effect based on the heating process is desired, it is preferable to incorporate a suitable radical polymerization initiator such as azobisisobutyronitrile into the coating composition instead of the photoinitiator. Examples of preferable thermosetting binders include thermosetting resins such as melamine resins, polyurethane resins, silicone resins, silicone-modified resins, and mixtures thereof.

  Preferably, the thickness of the dried coating is 10 mils (0.25 mm) or less, more preferably between about 0.1 mil (0.0025 mm) and about 5 mils (0.13 mm). Thicker coatings with a thickness of about 20 mils (0.50 mm) or greater can also be formed.

  The polymer film or sheet of the present invention can be coated by any suitable coating method. Extrusion is a particularly preferred method of coating polymer films and sheets. Melt extrusion of a coating onto a substrate can be performed, for example, in US Pat. Nos. 5,294,483, 5,475,080, 5,611,859, and 5 No. 7,795,320, No. 6,183,814, and No. 6,197,380. Alternatively, the solar control film can be formed by casting a coating solution onto a polymer film or sheet and drying. In general, solution casting provides a more stable coating thickness than melt extrusion.

  One preferred method of forming the solar control layer is transfer printing. Suitable transfer printing methods generally comprise coating a solar control composition onto a peelable substrate such as a coated paper or polyester film. After drying or curing, the coating, i.e. the solar control layer, is contacted with the surface of the polymer substrate or rigid sheet and then transferred from the peelable substrate onto the substrate. If necessary, the uncoated surface of the peelable substrate can be heated to promote peeling of the coating and adhesion to the substrate. General information on transfer printing is described in EP 0 576 419.

  Preferably, one or both sides of the solar control layer are treated to improve adhesion. Virtually any adhesive or primer is suitable for use in the present invention. If an adhesive or primer is used, one skilled in the art will be able to determine the appropriate coating thickness and process parameters based on the composition of the solar control layer, adhesive or primer, and the coating process.

  The solar control layer of the present invention has a hard coat layer formed from an ultraviolet (UV) curable resin on one or both sides to protect the outer polymer layer from abrasion, abrasion, and similar damage. You can also. Any suitable hardcoat formulation can be used. One preferred hard coat is described in US Pat. No. 4,027,073.

  The present invention also provides a solar control laminate comprising the solar control layer of the present invention. In addition, the solar control laminate can include at least one additional layer that can be a film, sheet, or coating on the film or sheet. This additional layer may be a solar control layer or a solar control film. If the additional layer is a sheet, it may be a rigid or flexible sheet. In certain preferred embodiments, the solar control laminate includes one or more rigid sheets, a solar control layer, and at least one additional layer.

  Preferred films for use as the additional film layer include stretched and unstretched polyester films, polycarbonate films, polyurethane films, and polyvinyl chloride films. Preferably, the additional film layer is biaxially oriented poly (ethylene terephthalate). Preferred sheets for use as the additional sheet layer include polyvinyl butyral compositions, sound insulating polyvinyl acetal compositions, sound insulating polyvinyl butyral compositions, ethylene vinyl acetate compositions, thermoplastic polyurethane compositions, polyvinyl chloride copolymer compositions, And ethylene acid copolymer compositions, and sheets comprising ionomers derived therefrom.

  One preferred rigid sheet is glass. As used herein, the term “glass” includes special glass that can include window glass, thick glass, silicate glass, flat glass, float glass, colored glass, components that control solar heating, and the like. Glass coated with a sputter metal such as silver, for example, glass coated with antimony tin oxide (ATO) and / or indium tin oxide (ITO), E glass, Solex ™ glass (PPG Industries (Pittsburgh, PA)), as well as Toroglass ™. One typical glass type is 90 mil thick annealed glazing, which is preferably oriented with the tin side of the glass towards the intermediate layer to achieve optimal adhesion. Alternatively, the rigid sheet may be a rigid polymer sheet such as, for example, polycarbonate, acrylic, polyacrylate, cyclic polyolefin, metallocene catalyzed polystyrene, and mixtures or combinations thereof. Preferably, the rigid sheet is transparent. However, when transparency or clarity is not required in the solar control laminate, a metal or ceramic plate can be used as the rigid sheet.

  The additional layer can impart additional properties such as acoustic barrier properties, or can have a functional coating containing an organic infrared absorber or reflective agent. In applications where conductivity is not a drawback, the functional coating may be a sputtered metal layer.

  Preferred solar control laminates are one solar control layer and one polymer film; one solar control layer and one polymer sheet; one solar control layer and two polymer sheets; one solar control layer and one polymer film , And one or two polymer sheets.

  Preferred solar control laminates of the present invention also include a structure comprising an adjacent layer as follows: polymer film / solar control layer; polymer sheet / solar control layer; rigid sheet / solar control layer; rigid sheet / polymer sheet / solar Control layer; first rigid sheet / polymer sheet / solar control layer / additional polymer sheet / second rigid sheet; rigid sheet / polymer sheet / solar control layer / additional polymer sheet / addition film; rigid sheet / additional polymer sheet / Additional film / polymer sheet / solar control layer; rigid sheet / polymer sheet / solar control layer / second polymer sheet / addition film / third polymer sheet / second rigid sheet; and first rigid sheet DOO / polymer sheet / solar control layer / additional polymeric sheet / second rigid sheet / second additional polymeric sheet / additional film / third additional polymeric sheet / third rigid sheet. In each of the above embodiments, “/” indicates an adjacent layer. Further, the second layer of any film or sheet may be the same as or different from the first layer of the film or sheet. Similarly, the third layer may be the same as or different from the first and second layers of the film or sheet, and so on. Furthermore, in certain preferred embodiments of the present invention, adjacent layers are laminated directly to one another so that they are adjacent and more preferably bordered.

  Any suitable method can be used to produce the solar control laminate of the present invention. Those skilled in the art recognize that different methods and conditions may be desirable depending on the composition of the layers in the solar control laminate and whether a rigid or flexible laminate is desired.

For example, the polymer sheet and solar control film can be bonded together and / or bonded to one or more additional layers in a nip roll process. Additional layers, along with the film or sheet of the present invention, are fed into one or more calender roll nips, in which medium pressure is applied to the two layers, resulting in a weakly bonded laminate. . Generally, the bonding pressure is in the range of about 10 psi (0.7 kg / cm ² ) to about 75 psi (5.3 kg / cm ² ), preferably the pressure is about 25 psi (1.8 kg / cm ² ) to about 30 psi. It is in the range of (2.1 kg / cm ² ). Typical line speeds are in the range of about 5 feet (1.5 meters) per minute to about 30 feet (9.2 meters). This nip roll method can be performed using moderate heating supplied by an oven, a heated roll or the like, or can be performed without using it. When heated, the polymer surface should reach a temperature sufficient to promote temporary fusing, ie, a temperature sufficient to make the surface of the polymer sheet or film tacky. Suitable surface temperatures for the preferred polymer films and sheets of the present invention are in the range of about 50 ° C. to about 120 ° C., preferably the surface temperature is about 65 ° C. After fusing, the laminate can be passed over one or more cooling rolls to provide sufficient strength to the laminate and prevent sticking when rolled up for storage. In order to achieve this objective, cooling of the process water is generally sufficient.

  In another exemplary procedure for manufacturing a solar control laminate, an intermediate layer comprising the solar control laminate of the present invention, such as an intermediate layer having a polymer sheet / solar control film / polymer sheet structure, Placing between the glass plates forms a glass / interlayer / glass pre-press assembly. Preferably, these glass plates have been washed and dried. Pre-press using a vacuum bag (see, eg, US Pat. No. 3,311,517), a vacuum ring, or another device capable of maintaining a vacuum of about 27-28 inches (689-711 mmHg) Remove air from between the layers of the assembly. The pre-press assembly is sealed under vacuum and then placed in an autoclave and heated under pressure. In order of increasing preference, the temperature in the autoclave is about 130 ° C to about 180 ° C, about 120 ° C to about 160 ° C, about 135 ° C to about 160 ° C, or about 145 ° C to about 155 ° C. The pressure in the autoclave is preferably about 200 psi (15 bar). In a more preferred order, the pre-press assembly is heated in the autoclave for about 10 to about 50 minutes, about 20 to about 45 minutes, about 20 to about 40 minutes, or about 25 to about 35 minutes. After this heating and pressurization cycle, the air in the autoclave is cooled without adding additional gas to maintain the pressure in the autoclave. After cooling for about 20 minutes, excess air pressure is released and the laminate is removed from the autoclave.

  Alternatively, the solar control laminate can be produced using a nip roll method. In one such method, the glass / interlayer / glass assembly is heated in an oven between about 80 ° C. and about 120 ° C., preferably between about 90 ° C. and about 100 ° C. for about 30 minutes. To do. The heated glass / interlayer / glass assembly is then passed through a set of nip rolls to expel air in the gap between the glass and the intermediate layer. At this point, the end of the structure is sealed to form a pre-press assembly, which can be processed under vacuum in an autoclave as described above to produce a solar control laminate.

  The solar control laminate can also be produced by a method that does not use an autoclave. Some suitable methods that do not use an autoclave are described in U.S. Pat. Nos. 3,234,062, 3,852,136, 4,341,576, No. 385,951, No. 4,398,979, No. 5,536,347, No. 5,853,516, No. 6,342,116 No. 5,415,909, U.S. Patent Application Publication No. 2004/0182493, European Patent No. 1 235 683B1, and International Publication No. 91/01880 and International Publication No. 03 / 057478A1. It is described in the issue pamphlet. In general, methods that do not use an autoclave include heating the pre-press assembly and using vacuum, pressure, or both. For example, the pre-press assembly can be passed through a heated oven and nip roll.

  For use in construction and transportation vehicles, one preferred glass laminate is a single intermediate comprising two glass layers and a solar control laminate of the present invention laminated directly to both glass layers. With layers. Preferably, the intermediate layer also includes a second polymer sheet, each polymer sheet being in contact with one glass layer. In these applications, the glass laminate preferably has an overall thickness of about 3 mm to about 30 mm. The interlayer typically has a thickness of about 0.38 mm to about 4.6 mm, and each glass layer is typically at least 1 mm thick. Includes glass / intermediate layer / glass / intermediate layer / glass 5 layer laminate, glass / intermediate layer / glass / intermediate layer / glass / intermediate layer / glass 7 layer laminate, and additional intermediate layer / glass assembly A multilayer solar control laminate such as a laminate is also preferred.

Examples and Comparative Experiments The examples are provided for illustrative purposes only and are not intended to limit the scope of the invention in any way.

Elastic Modulus All elastic moduli are measured according to ASTM D 638-03 (2003).

Room Temperature As used herein, the term “room temperature” means a temperature of 21 ° C. ± 5 ° C.

Standard solution of phthalocyanine compound To a mixture of N, N-dimethylformamide (12.00 g ± 0.02 g) and methanol (4.00 g ± 0.05 g), add a phthalocyanine compound (about 2.0 mg unless otherwise specified). It was. Where noted, this solution contained dichloromethane in addition to or instead of methanol. The mixture was stirred at room temperature until the phthalocyanine compound did not dissolve. If solids remained, they were removed by decantation. Polyvinyl butyral (Mowital ™ B30T, 4.00 g ± 0.02 g, Kuraray Co., Ltd., Osaka, Japan) was added to the resulting solution, and the solution was stirred at room temperature until the polyvinyl butyral was dissolved.

Standard Stabilization Solution At room temperature, Tinuvin ™ 571 (0.40 g, CAS 23328-52-2, Ciba Specialty Chemicals, Basel, Switzerland), bis (1-octyloxy-2,2,6,6-) sebacate Tetramethyl-4-piperidyl) (0.40 g, CAS 129757-67-1, Tinuban ™ 123 from Ciba Specialty Chemicals), 4- (1,1,3,3-tetramethylbutyl) phenol (0.08 g) , CAS 140-66-9), N, N-dimethylformamide, (120.00 g), and methanol (40.00 g) were prepared standard stabilizing solutions.

Standard procedure for forming a phthalocyanine-containing layer or a naphthalocyanine-containing layer on a polyester film A standard solution of a phthalocyanine compound or a solution of a naphthalocyanine compound is equilibrated at room temperature, Casted. The two films were cast using a 6 inch Gardiner blade, with the first film having a 10 mil blade gap and the second film having a 20 mil blade gap. The drawdown thicknesses of the two resulting films are described as “10 mil” and “20 mil”, respectively, and the two films are described as “10 mil film” and “20 mil film”, respectively. These two cast films were dried overnight at room temperature and ambient humidity and then heated in an oven at 75 ° C. for 30 minutes before being tested for solar control properties. Where noted, some films were heated on a hot plate at 70 ° C. to 90 ° C. for 5 or 10 minutes before or after heating in the oven.

Standard Transfer Printing Procedure The coated surface of a coated polyester film prepared by the standard procedure described above was applied to a Butacite (R) polyvinyl butyral sheet (2.5 inches x 6 inches (6.4 cm x 15.2 cm) x 30 mils thick). (0.76 mm) (available from DuPont)). An iron preheated to 100 ° C. was placed on the uncoated side of the polyester film and pressure was applied by hand. After 1 minute, the iron was removed, and the polyester release film was released to obtain a Butacite (registered trademark) sheet coated with a phthalocyanine compound-containing layer.

Standard Procedure for Lamination A pre-press assembly in which all layers in the laminate are cut to the same size and stacked in the desired order is placed in a vacuum bag and heated at 90-100 ° C. for 30 minutes, Remove any air contained between the layers of the press assembly. The pre-press assembly is heated in an air autoclave at 135 ° C. for 30 minutes at a pressure of 200 psig (14.3 bar). The air is then cooled without adding additional gas, thereby reducing the pressure in the autoclave. After cooling for 20 minutes, when the air temperature is less than about 50 ° C., excess pressure is evacuated and the laminate is removed from the autoclave.

Standard Procedure for Plaque Preparation First, two standard solutions were prepared. Solution I consists of 92.8% by weight plasticizer triethylene glycol bis (2-ethylhexanoate), 3% by weight Tinuvin ™ 571, 3% by weight Tinuvin ™ 123, and 1.2% by weight. % Octylphenol. Solution II contained 88.5 wt% water, 5.3 wt% potassium acetate, and 6.2 wt% magnesium acetate. Polyvinyl butyral (144.2 g) was then added to the plasticizer triethylene glycol bis (2-ethylhexanoate) (15.8 g ± 0.1 g), an aliquot of solution I (40.0 g), and solution II. Aliquots (1.25 mL). When a phthalocyanine compound was included in the plaque, the compound was added as a 1 wt% solution in the plasticizer and the total amount of neat plasticizer and phthalocyanine solution was maintained at 15.8 g ± 0.1 g.

  The polyvinyl butyral mixture was fed to a Brabender extruder (extruder head 25: 1 L / d single screw, screw diameter 0.75 inch, screw speed 40 rpm). The temperature profile was: feed zone 110 ° C .; section 1 190 ° C .; section 2 190 ° C .; die plate 190 ° C. The resulting blended mixture was collected, cooled and subsequently pressed to provide a 3 inch x 3 inch x 30 mil (76 mm x 76 mm x 0.75 mm) and 2.5 inch x 6 inch x 30 mil ( A plaque having a size of 63 mm × 152 mm × 0.75 mm was prepared. The melt press cycle included a 3 minute heating step at a pressure of 6000 psi, a 2 minute maintenance at 12,000 psi, and a 4 minute cooling at 12,000 psi, with a maximum press temperature of 180 ° C.

Solar Control Properties of Films The following methods were used to calculate solar and visible light transmission values for the simulated laminates. A Varian Cary 5000 uv / vis / nir spectrometer was used to determine the transmission spectrum of the phthalocyanine-containing or naphthalocyanine-containing layer supported on a polyethylene terephthalate film. One of the resulting spectra is processed to compensate for the reflectivity from the front and back surfaces due to a refractive index mismatch with air, thereby between two material layers having a refractive index that matches the sample. The transmission spectrum of the film obtained when the film was sandwiched was simulated. Next, using the compensated spectrum as an intermediate layer material, International Glazing Database No. Input into Lawrence Berkeley National Laboratory's Optics Software Package Version 5.1 (Maintenance Pack 2) with 14.0 installed.

Simulation method A
In Method A, a 6 mm thick general clear glass (clear_6.dat) (from outboard light to inboard light), the compensated interlayer data obtained above, The laminate was used using a 15 mil thick Butacite® NC010 layer (15 PVB6.dup) and a 3 mm thick transparent glass 3 mm inboard light (clear_3.dat). Simulated. The following examples were prepared laminate was simulated using sequentially phthalocyanine or naphthalocyanine-containing layers having described in the "number-th power" in the spectral data. Next, the transmission and reflection spectra of the simulated laminate are simulated by the software using method W5_NFRC_2003, and the visible light transmittance (T _vis-sim ) and sunlight transmittance (T _sol-sim ) are simulated. Calculate Spectral data of the simulated laminate was saved and subsequently imported into Lawrence Berkeley National Laboratory's Window 5.2 Software version 5.2.12. The T _vis-sim and T _sol-sim calculated for the film are summarized in Table 1.

Simulation method B
Method B is the same as Method A, except that the simulated laminate did not contain 6 mm thick common transparent glass (clear — 6.dat). The T _vis-sim and T _sol-sim calculated for the film are summarized in Table 1.

Solar Control Properties of Laminates According to ASTM test methods E424 and E308, and ISO test methods 9050: 2003 and 13837 procedures, using a Perkin Elmer Lambda 19 spectrophotometer (PerkinElmer, Inc. (Wellesley, Mass.)) The spectrum was determined. These measurements were used directly as described immediately above to calculate simulated transmission. Table 2 summarizes T _vis-sim and T _sol-sim calculated for the laminate.

Comparative experiment CE1
A coated polyester film was standardized using a standard solution of aluminum hydroxide phthalocyanine (0.0020 g, hydroxy (29H, 31H-phthalocyaninato) aluminum, CAS 18155-23-2, dye content about 85%). It was produced by.

Comparative experiment CE2
A coated polyester film was made according to standard procedures using a standard solution of nickel (II) phthalocyanine tetrasulfonic acid tetrasodium salt (0.0021 g, CAS 27835-99-0).

Comparative experiment CE3
A coated polyester film was made by standard procedures using a standard solution of gallium (III) phthalocyanine (0.0021 g, CAS 63371-84-6, dye content about 75%).

Comparative experiment CE4
A coated polyester film was made by standard procedures using a standard solution of gallium (III) phthalocyanine (0.0080 g, CAS 63371-84-6, dye content about 75%). Dichloromethane (4.00 g) was used instead of methanol.

Comparative experiment CE5
A coated polyester film was made according to standard procedures using a standard solution of zinc phthalocyanine (0.0020 g, CAS 14320-04-8, dye content about 97%). The 10 mil film was dried at room temperature overnight, then heated on a hot plate at 90 ° C. for 5 minutes, followed by heating in an oven at 75 ° C. for 0.50 hours. The 20 mil film was dried overnight at room temperature and heated in an oven at 75 ° C. for 0.50 hours, followed by heating on a hot plate at 80 ° C. for 10 minutes.

Comparative experiment CE6
Coating using a standard solution of Green Pigment 7 deagglomerated concentrate (0.0050 g, 40 wt% Green Pigment 7 based on the total weight of the concentrate) in Mowital ™ B30T polyvinyl butyral A coated polyester film was prepared by standard procedures. The 20 mil film was dried at room temperature overnight, then heated in an oven at 75 ° C. overnight, followed by heating at 80 ° C. for 10 minutes.

Comparative experiment CE7
Use standard solution of Blue Pigment 15: 4 deagglomerated concentrate (0.0050 g, 40 wt% Blue Pigment 15: 4 based on total weight of concentrate) in Mowital ™ B30T polyvinyl butyral A coated polyester film was then prepared according to standard procedures.

Comparative experiment CE8
A coated polyester film was made according to standard procedures using a standard solution of tetrakis (4-cumylphenoxy) phthalocyanine (0.0080 g, CAS 83484-76-8). Dichloromethane (4.02 g) was used instead of methanol.

Comparative experiment CE9
A coated polyester film was made according to standard procedures using a standard solution of manganese (II) phthalocyanine (0.0202 g, CAS 14325-24-7).

Comparative experiment CE10
A coated polyester film was made according to standard procedures using a standard solution of manganese (II) phthalocyanine (0.0081 g, CAS 14325-24-7). Dichloromethane (4.04 g) was used instead of methanol.

Comparative experiment CE11
A coated polyester film was made according to standard procedures using a standard solution of manganese (III) chloride phthalocyanine (0.0080 g, CAS 53432-32-9).

Comparative experiment CE12
A coated polyester film was made by standard procedures using a standard solution of aluminum chloride phthalocyanine (0.0161 g, CAS 14154-42-8).

Comparative experiment CE13
A coated polyester film was made by standard procedures using a standard solution of aluminum chloride phthalocyanine (0.0081 g, CAS 14154-42-8). Dichloromethane (4.03 g) was used instead of methanol.

Comparative experiment CE14
Coated polyester films were made by standard procedures using a standard solution of Pro-jet ™ 800 W (0.0081 g, Avecia, Inc., Wilmington, DE).

Comparative experiment CE15
Coated polyester films were made according to standard procedures using a standard solution of Pro-jet ™ 800 NP (0.0081 g, Avecia, Inc., Wilmington, DE).

Comparative experiment CE16
A coated polyester film was made according to standard procedures using a standard solution of Excolor ™ IR-10A (0.0080 g, Nippon Shokubai Company, Osaka, Japan).

Comparative experiment CE17
A coated polyester film was made according to standard procedures using a standard solution of Excolor ™ IR-12 (0.0081 g, Nippon Shokubai Company, Osaka, Japan).

Comparative experiment CE18
Coated polyester films were made according to standard procedures using a standard solution of Excolor ™ IR-14, (0.0081 g, Nippon Shokubai Company, Osaka, Japan).

Comparative experiment CE19
A coated polyester film was made according to standard procedures using a standard solution of Excolor ™ TX-EX-906B (0.0082 g, Nippon Shokubai Company, Osaka, Japan).

Comparative experiment CE20
A coated polyester film was prepared according to standard procedures using a standard solution of Excolor ™ TX-EX-910B (0.0080 g, Nippon Shokubai Company, Osaka, Japan).

Reference Example E1
A coated polyester film was made by standard procedures using a standard solution of OPM-868 (0.0081 g, Toyo Ink Manufacturing Company, Tokyo, Japan).

Reference Example E2
A solution of OPM-868 (0.0160 g, Toyo Ink Manufacturing Company, Tokyo, Japan) was prepared by adding OPM-868 to an aliquot (16.0893 g) of the standard stabilizing solution. After OPM-868 was dissolved, polyvinyl butyral (3.9823 g, Mowital (TM) B30T) was added and the mixture was stirred at room temperature until the polyvinyl butyral was dissolved.

  Using this OPM-868 solution, a coated polyester film was made according to standard procedures.

Reference Example E3
A coated polyester film was made according to standard procedures using a standard solution of OPM-249 (0.0080 g, Toyo Ink Manufacturing Company, Tokyo, Japan).

Reference Example E4
A solution of OPM-249 (0.0161 g, Toyo Ink Manufacturing Company, Tokyo, Japan) was prepared by adding OPM-868 to an aliquot (16.0900 g) of the standard stabilizing solution. After OPM-249 was dissolved, polyvinyl butyral (3.9857 g, Mowital ™ B30T) was added and the mixture was stirred at room temperature until the polyvinyl butyral was dissolved.

  Using this OPM-249 solution, a coated polyester film was made by standard procedures.

Comparative experiment CE21
A coated polyester film was made according to standard procedures using a standard solution of YKR-3080 (0.0081 g, Yamamoto Chemicals, Inc., Osaka, Japan).

Comparative experiment CE22
A coated polyester film was made according to standard procedures using a standard solution of YKR-3080 (0.0081 g, Yamamoto Chemicals, Inc., Osaka, Japan). Dichloromethane (4.03 g) was used instead of methanol.

Reference Example E5
A coated polyester film was made according to standard procedures using a standard solution of YKR-3020 (0.0079 g, Yamamoto Chemicals, Inc., Osaka, Japan).

Reference Example E6
A coated polyester film was made by standard procedures using a standard solution of YKR-3020 (0.0081 g, Yamamoto Chemicals, Inc., Osaka). Dichloromethane (4.03 g) was used instead of methanol.

Comparative experiment CE23
The Butacite® sheet was conditioned overnight at 23% relative humidity and a temperature of 72 ° F. In order, an annealed clear float glass sheet layer, a conditioned Butacite® sheet layer, and an annealed second clear float glass sheet layer (size of each layer is 6 inches × 2.5 inches (15.2 cm × 6 4 cm); glass layer thickness 2.5 mm; Butacite® sheet thickness 30 mil (0.75 mm)) / glass-conditioned Butacite® sheet / glass pre-press assembly, Lamination was done by standard lamination procedures.

Example E7
Polyester film coated with a standard solution of 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine, (0.0060 grams, CAS 116453-73-7) Was made by standard procedures.

Example E8
The coated 10 mil film of Example E7 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures.

  The transfer printed Butacite® sheet was conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, an annealed clear float glass plate layer, a transfer printed and conditioned Butacite® sheet layer, and a second annealed clear float glass plate layer (size of each layer is 6 inches x 2.5 inches (15. 2 cm × 6.4 cm); glass layer thickness 2.5 mm; butacite® sheet thickness 30 mil (0.75 mm)) / transfer printed and conditioned butacite® sheet / glass The pre-press assembly was laminated by standard lamination procedures.

Example E9
The coated 20 mil film of Example E7 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. This transfer printed Butacite (R) sheet was conditioned as described in Example E8 and used to glass / transfer printed and conditioned Butacite (R) using the procedure described in Example E8. Trademark) sheet / glass laminate was prepared.

Example E10
Preparation of a solution of 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine, (0.0060 grams, CAS 116453-73-7) By adding to an aliquot (16.0888 g) of the crystallization solution. After the phthalocyanine compound was dissolved, polyvinyl butyral (3.9036 g, Mowital ™ B30T) was added and the mixture was stirred at room temperature until the polyvinyl butyral was dissolved.

  Using this phthalocyanine solution, a coated polyester film was prepared by standard procedures.

Example E11
The coated 20 mil film of Example E10 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer-printed Butacite® sheets were conditioned as described in Example E8 and used to glass / transfer-printed and conditioned Butacite® using the procedure described in Example E8. ) A sheet / glass laminate was prepared.

Example E12
Using a standard solution of copper (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine, (0.0080 grams, CAS 107227-88-3) A coated polyester film was prepared by standard procedures.

Example E13
The coated 10 mil film of Example E12 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer-printed Butacite® sheets were conditioned as described in Example E8 and used to glass / transfer-printed and conditioned Butacite® using the procedure described in Example E8. ) A sheet / glass laminate was prepared.

Example E14
The coated 20 mil film of Example E12 was transfer printed onto a Butacite® polyvinyl butyral sheet according to standard transfer printing procedures. Transfer-printed Butacite® sheets were conditioned as described in Example E8 and used to glass / transfer-printed and conditioned Butacite® using the procedure described in Example E8. ) A sheet / glass laminate was prepared.

Example E15
Preparation of a solution of copper (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0080 grams, CAS 107227-88-3) was prepared using the above phthalocyanine compound. Was added to an aliquot (16.0888 g) of the standard stabilizing solution. After the phthalocyanine compound was dissolved, polyvinyl butyral (3.9877 g, Mowital ™ B30T) was added and the mixture was stirred at room temperature until the polyvinyl butyral was dissolved.

  Using this phthalocyanine solution, a coated polyester film was prepared by standard procedures.

Example E16
The coated 20 mil film of Example E15 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. A transfer printed Butacite (R) sheet was conditioned as described in Example E8 and used to glass / transfer print and condition the Butacite (R) using the procedure described in Example E8. A sheet / glass laminate was prepared.

Comparative experiment CE24
Two Butacite® sheets were conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, an annealed transparent float glass plate layer, a first conditioned Butacite® sheet layer, a second conditioned Butacite® sheet layer, and an annealed second transparent float glass plate layer (each layer The size of the glass is 6 inches × 2.5 inches (15.2 cm × 6.4 cm)); glass layer thickness 2.5 mm; Butacite® sheet thickness 15 mil (0.38 mm)) The conditioned Butacite® sheet / conditioned Butacite® sheet / glass pre-press assembly was laminated by standard lamination procedures.

Example E17
The coated 10 mil film of Example E10 was transfer printed onto two Butacite (R) polyvinyl butyral sheets by standard transfer printing procedures. Transfer-printed Butacite (R) sheets were conditioned as described in comparative experiment CE24, and they were used to perform glass / transfer-printed and conditioned Butacite (R) using the procedure described in comparative experiment CE24. (Trademark) sheet / transfer printed and conditioned Butacite (R) sheet / glass laminate. The coated surfaces of the transfer printed Butacite (R) sheet were brought into contact with each other.

Example E18
Coating using a standard solution of copper (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine, (0.0020 g, CAS 107227-88-3) A coated polyester film was prepared by standard procedures.

Example E19
The coated 20 mil film of Example E18 was transfer printed onto two Butacite (R) polyvinyl butyral sheets by standard transfer printing procedures. Transfer-printed Butacite (R) sheets were conditioned as described in comparative experiment CE24, and they were used to perform glass / transfer-printed and conditioned Butacite (R) using the procedure described in comparative experiment CE24. (Trademark) sheet / transfer printed and conditioned Butacite (R) sheet / glass laminate. The coated surfaces of the transfer printed Butacite (R) sheet were brought into contact with each other.

Example E20
Coating using a standard solution of nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0020 grams, CAS 155773-71-0) A coated polyester film was prepared by standard procedures. The resulting film was dried overnight at room temperature, heated on a hot plate at 90 ° C. for 10 minutes, and then heated in an oven at 75 ° C. for 0.5 hour.

Example E21
The coated 20 mil film of Example E20 was transfer printed onto two Butacite (R) polyvinyl butyral sheets by standard transfer printing procedures. Transfer-printed Butacite (R) sheets were conditioned as described in comparative experiment CE24, and they were used to perform glass / transfer-printed and conditioned Butacite (R) using the procedure described in comparative experiment CE24. (Trademark) sheet / transfer printed and conditioned Butacite (R) sheet / glass laminate. The coated surfaces of the transfer printed Butacite (R) sheet were brought into contact with each other.

Example E22
Preparation of a solution of nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0080 grams, CAS 155773-71-0) Was added to an aliquot (16.0090 g) of the standard stabilization solution. After the phthalocyanine compound was dissolved, polyvinyl butyral (3.9025 g, Mowital ™ B30T) was added and the mixture was stirred at room temperature until the polyvinyl butyral was dissolved.

  Using this phthalocyanine solution, a coated polyester film was prepared by standard procedures.

Example E23
The coated 20 mil film of Example E22 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer-printed Butacite® sheets were conditioned as described in comparative experiment CE24, and used to glass / transfer-printed and conditioned Butacite® using the procedure described in comparative experiment CE24. (Trademark) sheet / transfer printed and conditioned Butacite (R) sheet / glass laminate. The coated surfaces of the transfer printed Butacite (R) sheet were brought into contact with each other.

Comparative experiment CE25
Butacite® sheets and uncoated biaxially stretched poly (ethylene terephthalate) films were conditioned overnight at 23% relative humidity and a temperature of 72 ° F. In order, annealed clear float glass plate layer, conditioned Butacite® sheet layer, conditioned uncoated poly (ethylene terephthalate) film, Teflon® film, and annealed second transparent float glass Glass / conditioned consisting of plate layers (size of each layer 3 inches × 3 inches (7.6 cm × 7.6 cm); glass layer thickness 3 mm; Butacite® sheet thickness 30 mil (75 mm)) The Butacite® sheet / conditioned biaxially stretched poly (ethylene terephthalate) film / Teflon® film / glass pre-press assembly was laminated by standard lamination procedures. The Teflon® film and the second glass layer were removed to give a glass / conditioned Butacite® / conditioned biaxially oriented poly (ethylene terephthalate) film laminate.

Example E24
The coated 10 mil film of Example E18 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer printed Butacite (R) sheet and uncoated biaxially oriented poly (ethylene terephthalate) film are conditioned and used as described in comparative experiment CE25, using the procedure described in comparative experiment CE25 A glass / transfer printed and conditioned Butacite® sheet / conditioned biaxially oriented poly (ethylene terephthalate) film laminate was prepared.

Example E25
The coated 10 mil film of Example E22 was transfer printed onto a Butacite® polyvinyl butyral sheet according to standard transfer printing procedures. Transfer-printed Butacite (R) sheets and uncoated biaxially oriented poly (ethylene terephthalate) films were conditioned and used as described in comparative experiment CE25, using the procedure described in comparative experiment CE25. Used to make a glass / transfer printed and conditioned Butacite® sheet / conditioned biaxially oriented poly (ethylene terephthalate) film laminate.

Comparative experiment CE26
Butacite (R) sheets and uncoated biaxially oriented poly (ethylene terephthalate) films were conditioned and used as described in comparative experiment CE25, using the procedure described in comparative experiment CE25 A green glass / conditioned Butacite® / conditioned biaxially oriented poly (ethylene terephthalate) film laminate was prepared. The only difference was that a Solex ™ green glass plate was used instead of the first annealed clear float glass plate.

Example E26
The coated 10 mil film of Example E20 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer-printed Butacite (R) sheets and uncoated biaxially stretched poly (ethylene terephthalate) film are conditioned and used as described in comparative experiment CE26, using the procedure described in comparative experiment CE26 A green glass / transfer printed and conditioned Butacite® sheet / conditioned biaxially stretched poly (ethylene terephthalate) film laminate was prepared.

Example E27
Preparation of a solution of 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0020 g, CAS 116453-73-7), the above phthalocyanine compound was triethylene glycol bis By adding to (2-ethylhexanoate) plasticizer (1.5002 g, CAS 94-28-0). The mixture was stirred at room temperature. The phthalocyanine compound was soluble and formed a green solution.

Example E28
Preparation of a solution of copper (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0020 g, CAS 107227-88-3) By adding to triethylene glycol bis (2-ethylhexanoate) plasticizer (1.5044 g, CAS 94-28-0). The mixture was stirred at room temperature. The phthalocyanine compound was soluble and formed a green solution.

Example E29
Preparation of a solution of nickel (II) 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0021 g, CAS 155773-71-0) By adding to triethylene glycol bis (2-ethylhexanoate) plasticizer (1.5041 g, CAS 94-28-0). The mixture was stirred at room temperature. The phthalocyanine compound was soluble and formed a green solution.

Comparative experiment CE27
Control plaques containing no phthalocyanine compound were made by standard procedures for plaque preparation.

Example E30
According to standard procedures for plaque preparation, 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (CAS 116453-) in plasticizer instead of 3.0 g of neat plasticizer. Plaques were made using 3.0 g of a 1 wt% solution of 73-7).

Example E31
According to the standard procedure for plaque preparation, 5.0 g of 1 wt% solution of 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine instead of 5.0 g of neat plasticizer (CAS 116453-73-7; plaques were made using 5.0 g of a 1 wt% solution in plasticizer.

Comparative experiment CE28
A 3 inch × 3 inch × 30 mil (7.6 cm × 7.6 cm × 0.75 mm) plaque made in Comparative Experiment CE27 was conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In turn, an annealed clear float glass plate layer, a conditioned polyvinyl butyral plaque layer, and a second annealed clear float glass plate layer (size of each layer is 3 inches x 3 inches (7.6 cm x 7.6 cm); glass A glass / conditioned polyvinyl butyral plaque / glass pre-press assembly consisting of a layer thickness of 2.3 mm) was laminated by standard lamination procedures.

Example E32
A 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E30 was conditioned and used as described in comparative experiment CE28. Glass / conditioned polyvinyl butyral plaque / glass laminates were made using the procedure described in CE28.

Example E33
A 3 inch × 3 inch × 30 mil (7.6 cm × 7.6 cm × 0.75 mm) plaque made in Example E31 was conditioned and used as described in comparative experiment CE28. Glass / conditioned polyvinyl butyral plaque / glass laminates were made using the procedure described in CE28.

Comparative experiment CE29
A comparative experiment CE28 glass / conditioned polyvinyl butyral plaque / glass laminate was made again, except that the plaques used and the dimensions of all glass layers were 2.5 inches x 6 inches (63 mm x 152 mm). .

Comparative experiment CE30
Comparative Experiment CE29 Glass / conditioned polyvinyl butyral plaque / glass laminate was made again.

Comparative experiment CE31
The glass / conditioned polyvinyl butyral plaque / glass laminates of comparative experiments CE29 and CE30 were again made.

Example E34
The glass / conditioned polyvinyl butyral plaque / glass laminate of Example E32, except that the dimensions of the plaque used and all glass layers were 2.5 inches x 6 inches (6.3 cm x 15.2 cm) Was made again.

Example E35
The glass / conditioned polyvinyl butyral plaque / glass laminate of Example E34 was again made.

Example E36
The glass / conditioned polyvinyl butyral plaque / glass laminates of Examples E34 and E35 were made again.

Example E37
The glass / conditioned polyvinyl butyral plaque / glass laminate of Example E33, except that the dimensions of the plaques used and all glass layers were 2.5 "x 6" (6.3 cm x 15.2 cm). Was made again.

Example E38
The glass / conditioned polyvinyl butyral plaque / glass laminate of Example E37 was again made.

Example E39
The glass / conditioned polyvinyl butyral plaque / glass laminates of Examples E37 and E38 were again made.

Comparative experiment CE32
Two 3 inch × 3 inch × 30 mil (7.6 cm × 7.6 cm × 0.75 mm) plaques made in Comparative Experiment CE27 were conditioned overnight at a temperature of 72 ° F. and 23% relative humidity. In turn, an annealed clear float glass plate layer, two conditioned polyvinyl butyral plaques, and a second annealed clear float glass plate layer (each layer has dimensions of 3 inches x 3 inches (7.6 cm x 7.6 cm); A glass / conditioned polyvinyl butyral plaque / conditioned polyvinyl butyral plaque / glass pre-press assembly consisting of a glass layer thickness of 2.3 mm) was laminated by standard lamination procedures.

Example E40
Two 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaques made in Example E30 were conditioned and used as described in comparative experiment CE32. The procedure described in Comparative Experiment CE32 was used to make a glass / conditioned polyvinyl butyral plaque / conditioned polyvinyl butyral plaque / glass laminate.

Example E41
Two 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaques made in Example E31 were conditioned and used as described in comparative experiment CE32. The procedure described in Comparative Experiment CE32 was used to make a glass / conditioned polyvinyl butyral plaque / conditioned polyvinyl butyral plaque / glass laminate.

Comparative experiment CE33
Comparative Experiment CE27 3 inch × 3 inch × 30 mil (7.6 cm × 7.6 cm × 0.75 mm) plaques were conditioned overnight at a temperature of 72 ° F. and 23% relative humidity. Conditioned overnight at a temperature of 72 ° F. and 23% relative humidity. In turn, a Solex ™ green glass plate layer, a conditioned polyvinyl butyral plaque layer, and an annealed clear float glass plate layer (size of each layer is 3 inches x 3 inches (7.6 cm x 7.6 cm); A green glass / conditioned polyvinyl butyral plaque / glass pre-press assembly consisting of 2.3 mm thick) was laminated by standard lamination procedures.

Example E42
A 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E30 was conditioned and used as described in comparative experiment CE33. A green glass / conditioned polyvinyl butyral plaque / glass laminate was made using the procedure described in CE33.

Example E43
A 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque prepared in Example E31 was conditioned and used as described in comparative experiment CE33. A green glass / conditioned polyvinyl butyral plaque / glass laminate was made using the procedure described in CE33.

Comparative experiment CE34
A 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Comparative Example CE27 and an uncoated biaxially oriented poly (ethylene terephthalate) film with 23% relative humidity and Conditioned overnight at a temperature of 72 ° F. In order, an annealed transparent float glass plate layer, a conditioned Butacite® sheet layer, a conditioned uncoated poly (ethylene terephthalate) film, a Teflon® film, and an annealed second transparent float glass plate Glass / conditioned polyvinyl butyral plaque / conditioned biaxially stretched poly (ethylene terephthalate) film / layers (size of each layer is 3 inches × 3 inches (7.6 cm × 7.6 cm); glass layer thickness 3 mm) / A Teflon® film / glass pre-press assembly was laminated by standard lamination procedures. The glass / conditioned polyvinyl butyral plaque / conditioned biaxially stretched poly (ethylene terephthalate) film laminate was obtained by removing the Teflon® film and the second glass layer.

Example E44
The 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E30 and an uncoated biaxially oriented poly (ethylene terephthalate) film are described in Comparative Experiment CE34. They were conditioned and used to make glass / conditioned polyvinyl butyral plaque / conditioned biaxially oriented poly (ethylene terephthalate) film laminates using the procedure described in Comparative Experiment CE34.

Example E45
The 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E31 and an uncoated biaxially oriented poly (ethylene terephthalate) film are described in Comparative Experiment CE34. They were conditioned and used to make glass / conditioned polyvinyl butyral plaque / conditioned biaxially oriented poly (ethylene terephthalate) film laminates using the procedure described in Comparative Experiment CE34.

Comparative experiment CE35
A 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Comparative Example CE27 and an uncoated biaxially oriented poly (ethylene terephthalate) film are described in Comparative Experiment CE34. They were conditioned and used to make green glass / conditioned polyvinyl butyral plaque / conditioned biaxially stretched poly (ethylene terephthalate) film laminates using the procedure described in Comparative Experiment CE34. The only difference was that a Solex ™ green glass plate was used instead of the first annealed clear float glass plate.

Example E46
The 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E30 and an uncoated biaxially oriented poly (ethylene terephthalate) film are described in Comparative Experiment CE35. They were conditioned and used to make green glass / conditioned polyvinyl butyral plaque / conditioned biaxially stretched poly (ethylene terephthalate) film laminates using the procedure described in Comparative Experiment CE35.

Example E47
The 3 inch x 3 inch x 30 mil (7.6 cm x 7.6 cm x 0.75 mm) plaque made in Example E31 and an uncoated biaxially oriented poly (ethylene terephthalate) film are described in Comparative Experiment CE35. They were conditioned and used to make green glass / conditioned polyvinyl butyral plaque / conditioned biaxially stretched poly (ethylene terephthalate) film laminates using the procedure described in Comparative Experiment CE35.

Reference Example E48
The coated 10 mil film of Reference Example E2 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. A transfer printed Butacite (R) sheet was conditioned as described in Example E8 and used to glass / transfer print and condition the Butacite (R) using the procedure described in Example E8. A sheet / glass laminate was prepared.

Reference Example E49
The laminate of Reference Example E48 was produced again.

Reference Example E50
The coated 10 mil film of Reference Example E2 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. A transfer printed Butacite (R) sheet was conditioned as described in Example E8 and used to glass / transfer print and condition the Butacite (R) using the procedure described in Example E8. A sheet / glass laminate was prepared.

Reference Example E51
The laminate of Reference Example 50 was produced again.

Reference Example E52
The coated 20 mil film of Reference Example E1 was transfer printed onto a 6 inch × 3 inch × 15 mil (15.2 cm × 7.6 cm × 0.38 mm) Butacite® polyvinyl butyral sheet by standard transfer printing procedures. . The transfer printed sheet is then folded so that the coating surface is in contact to form a double layer, thereby providing a 3 inch having a Butacite® sheet / coating / coating / Buactite® sheet structure. A x3 inch (7.6 cm x 7.6 cm) double Butacite (R) layer was formed.

  This double Butacite® layer was conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. An annealed clear float glass plate layer, a conditioned double Butacite (R) layer, and an annealed second clear float glass plate layer (size of each layer is 3 inches x 3 inches (7.6 cm x 7.6 cm); A glass / conditioned double Butacite® layer / glass pre-press assembly consisting of a glass layer thickness of 3 mm) was laminated by standard lamination procedures.

Reference Example E53
The coated 20 mil film of Reference Example E3 was transfer printed onto a 6 inch × 3 inch × 15 mil (15.2 cm × 7.6 cm × 0.38 mm) Butacite® polyvinyl butyral sheet by standard transfer printing procedures. . The transfer printed sheet is then folded so that the coating surface is in contact to form a double layer, thereby having a Butacite® sheet / coating / coating // Buactite® sheet structure 3 An inch x 3 inch (7.6 cm x 7.6 cm) double Butacite (R) layer was formed.

  This dual Butacite® layer was conditioned and used as described in Example E52 and using the procedure described in Example E52, the glass / conditioned dual Butacite® layer was used. ) A layer / glass laminate was prepared.

Reference Example E54
The coated 10 mil film of Reference Example E1 was transfer printed onto a 6 inch × 3 inch × 15 mil (15.2 cm × 7.6 cm × 0.38 mm) Butacite® polyvinyl butyral sheet by standard transfer printing procedures. . The transfer printed sheet is then folded so that the coating surface is in contact to form a double layer, thereby having a Butacite® sheet / coating / coating // Buactite® sheet structure 3 An inch x 3 inch (7.6 cm x 7.6 cm) double Butacite (R) layer was formed.

  This double Butacite® layer was conditioned and used as described in Example E52 and using the procedure described in Example E52, green glass / conditioned double Butacite® (Trademark) layer / glass laminate was produced. The only difference was that a Solex ™ green glass plate was used instead of the first annealed clear float glass plate.

Reference Example E55
The coated 10 mil film of Reference Example E3 was transfer printed onto a 6 inch × 3 inch × 15 mil (15.2 cm × 7.6 cm × 0.38 mm) Butacite® polyvinyl butyral sheet by standard transfer printing procedures. . The transfer printed sheet is then folded so that the coating surface is in contact to form a double layer, thereby having a Butacite® sheet / coating / coating // Buactite® sheet structure 3 An inch x 3 inch (7.6 cm x 7.6 cm) double Butacite (R) layer was formed.

  This dual Butacite® layer was conditioned and used as described in Example E52, and a green glass / conditioned double Butacite® using the procedure described in Example E52. ) A layer / glass laminate was prepared. The only difference was that a Solex ™ green glass plate was used instead of the first annealed clear float glass plate.

Reference Example E56
The coated 10 mil film of Reference Example E6 was transfer printed onto a 4 inch × 4 inch × 30 mil (10.2 cm × 10.2 cm × 0.38 mm) Butacite® polyvinyl butyral sheet by standard transfer printing procedures. .

  This transfer printed Butacite (R) sheet was conditioned and used as described in Example E8, and using the procedure described in Example E8, glass / transfer printed and conditioned Butacite (R) Trademark) sheet / glass laminate was prepared. The only difference was that all layers were 4 inches x 4 inches (10.2 cm x 10.2 cm) and the glass layer thickness was 3 mm.

Comparative experiment CE36
Two Butacite® sheets and a biaxially oriented poly (ethylene terephthalate) film were conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, annealed clear float glass plate layer, first conditioned Butacite® sheet layer, conditioned biaxially oriented poly (ethylene terephthalate) film, second conditioned Butacite® sheet layer and annealed Second transparent float glass plate layer (size of each layer is 6 inches × 2.5 inches (15.2 cm × 6.4 cm); glass layer thickness 2.5 mm; Butacite® sheet thickness 15 Mill (0.38 mm)) / conditioned Butacite® sheet / conditioned biaxially oriented poly (ethylene terephthalate) film / conditioned Butacite® sheet / glass pre-press assembly The solid was laminated by standard lamination procedures.

Comparative experiment CE37
N, N-dimethylformamide by mixing a deagglomerated concentrate of Blue Pigment 15: 4 (0.061 grams, 40% by weight of Blue Pigment 15: 4 based on total composition) at room temperature. Dissolved in a mixture of (18.01 grams) and methanol (6.00 grams). Mowital ™ B30T polyvinyl butyral (5.9457 grams) was added and stirred until a solution was formed.

  Using this solution and a flame-treated biaxially stretched polyester film, a coated biaxially stretched polyester film was prepared according to standard procedures.

Comparative experiment CE38
Two Butacite® sheets and a 20 mil coated biaxially stretched polyester film from Comparative Experiment CE37 were conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, an annealed clear float glass sheet layer, a first conditioned Butacite® sheet layer, a conditioned coated biaxially oriented polyester film, a second conditioned Butacite® sheet layer, and an annealed A second transparent float glass plate layer (size of each layer is 4 inches × 4 inches (10.2 cm × 10.2 cm); glass layer thickness 2.5 mm; Butacite® sheet thickness 15 mil (0 .38 mm)) / conditioned butadiene sheet / conditioned biaxially oriented polyester film with coating / conditioned conditioned sheet / glass pre-press assembly Were laminated according to standard lamination procedures.

Comparative experiment CE39
A laminate of Comparative Example CE26 was produced again.

Reference Example E57
The Butacite® sheet and the coated polyester film 2 of Reference Example E2 (drawdown thickness 10 mil) were conditioned overnight at 23% relative humidity and a temperature of 72 ° F. These Butacite (R) sheets and coated polyester films were conditioned as described in Comparative Experiment CE26, and they were used to produce green glass / conditioned Butacite using the procedure described in Comparative Experiment CE26. A (registered trademark) sheet / conditioned polyester film laminate with coating was prepared.

Example E58
Preparation of a solution of 1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine, (0.0090 grams, CAS 116453-73-7) by mixing at room temperature The above phthalocyanine compound was added to a mixture of N, N-dimethylformamide (18.01 grams) and methanol (6.00 grams). Mowital ™ B30T polyvinyl butyral (5.9786 grams) was added and stirred until a solution was formed.

  Using this solution and a flame-treated biaxially stretched poly (ethylene terephthalate) film, a coated biaxially stretched poly (ethylene terephthalate) film was prepared by standard procedures. The coated film was dried at room temperature overnight and then heated in an oven at 75 ° C. for 30 minutes.

Example E59
Two Butacite® sheets and the 10 mil coated biaxially oriented poly (ethylene terephthalate) film of Example E58 were conditioned and used as described in comparative experiment CE38, and used in comparative experiment CE38. The glass / conditioned Butacite® sheet / conditioned coated biaxially oriented poly (ethylene terephthalate) film / conditioned Butacite® sheet / glass laminate was made using the procedure described in.

Example E60
The only difference was that the laminate of Example E59 was made again and the 20 mil coated biaxially stretched poly (ethylene terephthalate) film of Example E58 was used.

Example E61
1,4,8,11,15,18,22,25-octabutoxy-29H, 31H-phthalocyanine (0.0090 g, CAS 116453-73-7) and Mowital ™ B30T in standard stabilizing solution ( A coated polyester film was made according to standard procedures using 24.1328 g). This polyester was flame treated and biaxially stretched. The film was dried at room temperature overnight and then heated in an oven at 75 ° C. for 30 minutes.

Example E62
The Butacite® sheet, and the 20 mil coated polyester film of Example E61 were conditioned and used as described in comparative experiment CE25, using the procedure described in comparative experiment CE25. A glass / conditioned Butacite® sheet / conditioned polyester film laminate with coating was prepared.

Example E63
Butacite® sheet, SentryGlas® Plus ethylene / methacrylic acid copolymer sheet (available from DuPont), and the coated 20 mil polyester film of Example E61 at a temperature of 72 ° F. and a relative humidity of 23% overnight. Conditioned. In order, an annealed transparent float glass plate layer, a conditioned Butacite® sheet layer, a conditioned coated polyester film, a conditioned SentryGlas® Plus sheet layer, and an annealed second transparent float glass plate layer (Dimensions of each layer are 2 inches × 4 inches (5.6 cm × 10.2 cm); glass layer thickness 2.5 mm; Butacite® sheet and SentryGlas® Pl sheet thickness 15 mil (0 38mm)) / conditioned Butacite (R) sheet / conditioned polyester film with coating / conditioned SentryGlas (registered) TM Plus sheet / glass pre-press assembly was laminated by standard lamination procedures.

Example E64
Two Butacite® sheets and the coated 10 mil film of Example E15 were conditioned and used as described in comparative experiment CE38, using the procedure described in comparative experiment CE38, Glass / conditioned Butacite® sheet / conditioned coated polyester film / conditioned Butacite® sheet / glass laminate was prepared. The only difference was that the dimensions of each layer were 6 inches x 2.5 inches (15.2 cm x 6.4 cm).

Reference Example E65
Preparation of a mixture of 2,3-naphthalocyanine (0.0081 grams, CAS 23627-89-6, dye content about 95 percent), add the naphthalocyanine compound to dichloromethane (4.00 grams) and mix at room temperature Went by. To this mixture was added N, N-dimethylformamide (12.00 grams). A small amount of insoluble material was removed. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9982 grams, Kuraray Corporation) and the resulting mixture was mixed at room temperature until a solution was formed.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Reference Example E66
A coated 10 mil film of Reference Example E65 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. The only difference was that the Butacite® sheet was 2 inches × 2 inches (5.1 cm × 5.1 cm) × 15 mils thick (0.38 mm).

  The transfer printed Butacite® sheet and Butacite® sheet were conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, annealed transparent float glass plate layer, transfer-printed and conditioned Butacite® sheet layer, conditioned Butacite® sheet layer (transfer-printed Butacite® sheet coating surface is Butacite® Trademarked sheet surface) and an annealed second transparent float glass plate layer (each layer dimension is 2 inches × 2 inches (5.1 cm × 5.1 cm); glass layer thickness 2.3 mm) A glass / transfer-printed and conditioned Butacite® sheet / conditioned Butacite® sheet / glass pre-press assembly consisting of: 15 cm (0.38 mm) of Butacite® sheet thickness; Standard laminate Laminated by the procedure.

Reference Example E67
Two Butacite® sheets and a coated 20 mil poly (ethylene terephthalate) film made in Reference Example E65 were conditioned overnight at a temperature of 72 ° F. and a relative humidity of 23%. In order, annealed clear float glass plate layer, first conditioned Butacite® sheet layer, conditioned coated poly (ethylene terephthalate) film of Reference Example E65, second conditioned Butacite® sheet Layer and annealed second transparent float glass plate layer (size of each layer is 2 inches x 2 inches (5.1 cm x 5.1 cm); glass layer thickness 2.3 mm; Butacite (R) sheet thickness 15 mil (0.38 mm)) / conditioned Butacite® sheet / conditioned coated poly (ethylene terephthalate) film / conditioned Butacite® shi The sheet / glass pre-press assembly was laminated by standard lamination procedures.

Reference Example E68
Preparation of a mixture of 2,3-naphthalocyanine (0.0080 grams, CAS 23627-89-6, dye content about 95 percent) was added to the above naphthalocyanine compound in dichloromethane (4.02 grams) and mixed at room temperature Went by. An aliquot (16.0955 grams) of a standard stabilizing solution was added to the mixture. A small amount of insoluble material was removed. To the resulting mixture was added Mowital ™ B30T polyvinyl butyral (3.9287 grams, Kuraray Corporation) and the resulting mixture was mixed until a solution was formed at room temperature.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Reference Example E69
A coated 10 mil film of Reference Example E68 was transfer printed onto a Butacite (R) polyvinyl butyral sheet using standard transfer printing procedures, and a Butacite (R) polyvinyl butyral sheet (2 inches x 2 inches (5.1 cm x 5.1 cm)). The only difference was that the transfer printed Butacite® sheet was conditioned and used as described in Example E8, using the procedure described in Example E8. Glass / transfer printed and conditioned Butacite® sheet / glass laminates were prepared, each layer having dimensions of 2 inches × 2 inches (5.1 cm × 5.1 cm) and a glass layer thickness of 2 The only difference was that it was 3 mm.

Reference Example E70
The Butacite® sheet and the coated 20 mil poly (ethylene terephthalate) film of Reference Example E68 were conditioned and used as described in Comparative Experiment CE25, using the procedure described in Comparative Experiment CE25. A glass / conditioned Butacite® sheet / conditioned poly (ethylene terephthalate) film laminate with coating was prepared. The coated side of the conditioned coated poly (ethylene terephthalate) film was contacted with a conditioned Butacite® sheet. The only difference was that the dimensions of each layer were 2 inches x 2 inches (5.1 cm x 5.1 cm) and the glass layer thickness was 2.3 mm.

Example E71
Of nickel (II) 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (0.0080 grams, CAS 155773-70-9, dye content about 98 percent) The solution was prepared by adding the naphthalocyanine compound to dichloromethane (16.00 grams) and mixing at room temperature. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9929 grams, Kuraray Corporation) and dichloromethane (5.17 grams). 0.50 hours prior to film casting, additional dichloromethane (4.15 grams) was added to the solution and the resulting solution was mixed at room temperature until casting.

  Using this naphthalocyanine compound solution, a 10 mil coated poly (ethylene terephthalate) film was made according to standard procedures.

Example E72
The coated 10 mil film of Example E71 was transfer printed onto a Butacite® polyvinyl butyral sheet by standard transfer printing procedures. Transfer-printed Butacite® sheets and uncoated poly (ethylene terephthalate) films were conditioned and used as described in comparative experiment CE25, using the procedure described in comparative experiment CE25. Glass / transfer printed and conditioned Butacite® sheet / conditioned poly (ethylene terephthalate) film laminate was prepared. The only difference was that the dimensions of each layer were 2 inches x 2 inches (5.1 cm x 5.1 cm) and the glass layer thickness was 2.3 mm.

Example E73
The Butacite® sheet and the 10 mil coated poly (ethylene terephthalate) film made in Example E71 were conditioned and used as described in comparative experiment CE25 and used as described in comparative experiment CE25. The procedure was used to make a green glass / conditioned Butacite® / biaxially oriented poly (ethylene terephthalate) film laminate. The coated side of the conditioned coated poly (ethylene terephthalate) film was contacted with a conditioned Butacite® sheet. A Solex ™ green glass plate was used in place of the first annealed clear float glass plate, each layer had dimensions of 2 inches × 2 inches (5.1 cm × 5.1 cm), and the annealed float glass layer The only difference was that the thickness was 2.3 mm.

Reference Example E74
Preparation of a mixture of silicon 2,3-naphthalocyanine bis (trihexylsilyloxide) (0.0081 grams, CAS 92396-88-8), the above naphthalocyanine compound was converted to N, N-dimethylformamide (12.00 grams) This was done by adding to a mixture of and methanol (4.00 grams) and mixing at room temperature until dissolved. A small amount of insoluble material was removed. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9904 grams, Kuraray Corporation) and the resulting mixture was mixed until a solution was formed at room temperature.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Reference Example E75
Preparation of a solution of silicon 2,3-naphthalocyanine bis (trihexylsilyloxide) (0.0080 grams, CAS 92396-88-8) was added to the above naphthalocyanine compound in dichloromethane (4.00 grams) at room temperature. This was done by mixing. To this solution was added N, N-dimethylformamide (12.01 grams) and mixed at room temperature. A small amount of insoluble material was removed. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9904 grams, Kuraray Corporation) and the resulting mixture was mixed until a solution was formed at room temperature.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Reference Example E76
Preparation of a mixture of silicon 2,3-naphthalocyanine dioctyl oxide (0.0081 grams, CAS 92941-50-9), the above naphthalocyanine compound with N, N-dimethylformamide (12.01 grams) and methanol (4. 01 gram) and mixed at room temperature until dissolved. A small amount of insoluble material was removed. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9940 grams, Kuraray Corporation) and the resulting mixture was mixed until a solution was formed at room temperature.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Reference Example E77
Preparation of a mixture of silicon 2,3-naphthalocyanine dioctyl oxide (0.0080 grams, CAS 92941-50-9) is performed by adding the naphthalocyanine compound to dichloromethane (4.13 grams) and mixing at room temperature. It was. To this mixture was added N, N-dimethylformamide (12.02 grams) and mixed at room temperature. A small amount of insoluble material was removed. To the resulting solution was added Mowital ™ B30T polyvinyl butyral (3.9976 grams, Kuraray Corporation) and the resulting mixture was mixed until a solution was formed at room temperature.

  Using this naphthalocyanine compound solution, a coated poly (ethylene terephthalate) film was prepared by standard procedures.

Table 1
Film data

^*注：記号のない試料番号は、ソーラーコントロール特性をシミュレーション方法Ａにより計算したフィルムを示している。記号「（Ｂ）」を有する試料番号は、ソーラーコントロール特性をシミュレーション方法Ｂにより計算したフィルムを意味する。 (Table 1 continued)

^* Note: Sample numbers without symbols indicate films whose solar control characteristics were calculated by simulation method A. The sample number having the symbol “(B)” means a film whose solar control characteristics are calculated by the simulation method B.

Table 2
Laminate data

^*注：「ａ」は、フィルムドローダウン厚さが１０ミルであることを意味し；「ｂ」は、フィルムドローダウン厚さが２０ミルであることを意味する。 (Table 2 continued)

^* Note: “a” means film drawdown thickness is 10 mils; “b” means film drawdown thickness is 20 mils.

Although some preferred embodiments of the present invention have been described and illustrated in detail above, it is not intended that the present invention be limited to such embodiments. Various changes may be made without departing from the scope and spirit of the invention as set forth in the claims.
Next, a preferred embodiment of the present invention will be shown.
1. An infrared absorbing phthalocyanine compound or a composition consisting essentially of a naphthalocyanine compound and a plasticizer, wherein the plasticizer contains one or more esters of a polybasic acid or a polyhydric alcohol, and the phthalocyanine compound or The composition wherein the naphthalocyanine compound is present in an amount of about 0.0001 to about 10% by weight, based on the total weight of the composition.
2. 2. The composition according to 1 above, which is a solution and the phthalocyanine compound or naphthalocyanine compound is an alkoxy-substituted phthalocyanine compound or naphthalocyanine compound, or a butoxy-substituted phthalocyanine compound or naphthalocyanine compound.
3. A solar control composition comprising an infrared-absorbing phthalocyanine compound or naphthalocyanine compound, and a resin having an elastic modulus of 20,000 psi (138 MPa) to 1000 psi (7 MPa).
4). 4. The solar control composition as described in 3 above, wherein the resin comprises polyvinyl butyral or ethylene-co-vinyl acetate.
5). A molded article comprising an infrared-absorbing phthalocyanine compound or naphthalocyanine compound and polyvinyl butyral or ethylene-co-vinyl acetate and in the form of a coating, film, multilayer film, sheet, or multilayer sheet.
6). A solar control laminate comprising an infrared-absorbing phthalocyanine compound or naphthalocyanine compound and polyvinyl butyral or ethylene-co-vinyl acetate.
7). A solar control laminate comprising a solar control layer comprising polyvinyl butyral or ethylene-co-vinyl acetate and an infrared-absorbing phthalocyanine compound or a concentrate of naphthalocyanine compound, said method using simulation method A When the laminate is simulated, the simulation value T _{vis-sim of} visible light transmittance is 0.65 <T _vis-sim <0.75, and the simulation value T _{sol-sim of} sunlight transmittance is a phthalocyanine compound. In the case of <(0.932 (T _vis-sim ) −0.146), the case of naphthalocyanine compound <(0.481 (T _vis-sim ) −0.166) A solar control laminate having solar transmittance and visible light transmittance.
8). 8. The solar control laminate according to 7, wherein the phthalocyanine compound or naphthalocyanine compound is an alkoxy-substituted phthalocyanine compound or naphthalocyanine compound, or a butoxy-substituted phthalocyanine compound or naphthalocyanine compound.
9. Polymer sheet / solar control layer, rigid sheet / solar control layer, rigid sheet / polymer sheet / solar control layer, first rigid sheet / polymer sheet / solar control layer / additional polymer sheet / second rigid sheet, rigid sheet / Polymer sheet / first solar control layer / additional polymer sheet / addition film, rigid sheet / additional polymer sheet / additional film / polymer sheet / solar control layer, and first rigid sheet / polymer sheet / solar control layer / additional polymer Sheet / second rigid sheet / second additional polymer sheet / addition film / third additional polymer sheet / third rigid sheet, having a structure selected from the group consisting of “/” means an adjacent layer The solar controller The “second” layer of the film or sheet may be the same or different from the first layer of the film or sheet, and the “third” layer may be a film or sheet. The solar control laminate according to 7, wherein the layer may be the same as or different from the first and second layers of the film or sheet.
10. A method for reducing the transmission of infrared rays into the interior of a structure having an external window,
a. Creating a solar control laminate as described in 7 above;
b. Inserting the solar control laminate into the external window of the structure.
11. 11. The method according to 10 above, wherein the structure is a building or a vehicle, and the phthalocyanine compound or naphthalocyanine compound is an alkoxy-substituted phthalocyanine compound or naphthalocyanine compound, or a butoxy-substituted phthalocyanine compound or naphthalocyanine compound. .

Claims (5)

An infrared absorbing alkoxy substituted phthalocyanine compound or alkoxy-substituted naphthalocyanine compounds, polyvinyl butyral or ethylene - co - vinyl acetate and a composition comprising a plasticizer, wherein the plasticizer is a polybasic acid or polyhydric alcohol A composition for glass laminates, wherein the phthalocyanine compound or naphthalocyanine compound is present in an amount of 0.0001 to 10% by weight, based on the total weight of the composition. It possesses an infrared-absorbing alkoxy substituted phthalocyanine compound or alkoxy-substituted naphthalocyanine compounds, 20,000 psi and (138MPa) ~1000psi elastic modulus (7 MPa) (measured according to ASTM D 638-03 (2003)), polyvinyl butyral Or the solar control composition for glass laminated bodies containing resin containing ethylene-co-vinyl acetate .   Molding for glass laminates comprising an infrared absorbing alkoxy-substituted phthalocyanine compound or alkoxy-substituted naphthalocyanine compound and polyvinyl butyral or ethylene-co-vinyl acetate and in the form of a film, multilayer film, sheet, or multilayer sheet Goods.   A solar control glass laminate comprising an infrared-absorbing alkoxy-substituted phthalocyanine compound or an alkoxy-substituted naphthalocyanine compound and polyvinyl butyral or ethylene-co-vinyl acetate. A method for reducing the transmission of infrared rays into the interior of a structure having an external window,
a. Creating a solar control glass laminate according to claim 4 ;
b. Inserting the solar control laminate into the external window of the structure.