WO2013191029A1 - Porphyrazine dye, and application therefor - Google Patents
Porphyrazine dye, and application therefor Download PDFInfo
- Publication number
- WO2013191029A1 WO2013191029A1 PCT/JP2013/066031 JP2013066031W WO2013191029A1 WO 2013191029 A1 WO2013191029 A1 WO 2013191029A1 JP 2013066031 W JP2013066031 W JP 2013066031W WO 2013191029 A1 WO2013191029 A1 WO 2013191029A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- formula
- dye
- porphyrazine
- composition
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/006—Preparation of organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/008—Preparations of disperse dyes or solvent dyes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
Definitions
- the present invention relates to a novel porphyrazine dye that exhibits excellent absorption in a specific near-infrared region, has high transmittance in the visible light region, and does not impair the design properties, and uses thereof.
- Patent Document 1 a porphyrazine dye is disclosed as a heat ray shielding material excellent in transparency.
- the dye described in Patent Document 1 has high visible light transmittance and excellent heat ray shielding properties, but has a strong yellowish color and significantly impairs the design properties. It was difficult to use.
- the present invention has been made in view of the situation as described above, and an object of the present invention is to provide a porphyrazine dye having high visible light transmittance and excellent heat ray shielding properties. Another object of the present invention is to provide a porphyrazine coloring matter that suppresses yellowishness, has an improved utility value in the industry, without impairing the design properties in the fields of housing and automobiles, and a heat ray shielding composition containing the coloring matter.
- the present inventors have solved the above-mentioned problem by a specific porphyrazine dye represented by the following formula (1) or a dye-dispersed composition containing the same. And the present invention has been completed. That is, the present invention provides (1) a porphyrazine dye represented by the following formula (1):
- M represents a metal atom, a metal oxide, a metal hydroxide, a metal halide, or a hydrogen atom
- the rings A, B, and C are each independently represented by the following formulas (2) to (8)
- * in the above formulas (2) to (8) represents a bonding site
- X represents a lower alkyl group or a lower alkoxy group.
- Y represents a divalent crosslinking group
- Z represents a sulfonic acid group, a carboxy group, or a primary or secondary amino group.
- a and b are each 0 or more and 12 or less, and the sum of a and b is 0 or more and 12 or less]
- the porphyrazine dye according to (1), wherein the rings A, B, and C in the formula (1) are the formula (2), the formula (4), and the formula (8), respectively.
- porphyrazine coloring matter of the present invention as a heat ray shielding material, a high visible light transmittance and an excellent heat ray shielding property were obtained, and yellowishness could be suppressed.
- dye can be applied to the field
- the present invention relates to a porphyrazine dye of the above formula (1), wherein the dye is dispersed in various dispersion media to obtain a dye dispersion composition. Further, the heat-shielding metal fine particles can be contained in the dye dispersion composition. These compositions are characterized by being applicable to heat ray-shielding pressure-sensitive adhesive sheets.
- examples of the aromatic ring in the rings A to C represented by broken lines include one or two nitrogen atoms such as a benzene ring or a naphthalene ring, a pyridine ring, a pyrazine ring, and a pyridazine ring.
- nitrogen-containing heteroaromatic rings examples include nitrogen-containing heteroaromatic rings.
- the combination of a benzene ring, a pyridine ring, and a naphthalene ring is preferable, and the combination of a pyridine ring and a naphthalene ring is more preferable.
- the pyridine ring is most preferably the formula (4).
- M represents a hydrogen atom, a metal atom, a metal oxide, a metal hydroxide, or a metal halide.
- M is other than a hydrogen atom, the M means that the porphyrin ring in the formula (1) has a so-called central metal.
- M is a hydrogen atom, it means that the porphyrin ring has no central metal.
- metal atom in M include, for example, Li, Na, K, Mg, Ti, Zr, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Ru, Rh, Pd,
- Examples include Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Hg, Al, Ga, In, Si, Ge, Sn, Pb, Sb, and Bi.
- Examples of the metal oxide include VO and GeO.
- Examples of the metal hydroxide include Si (OH) 2 , Cr (OH) 2 , Sn (OH) 2 , AlOH, and the like.
- As the metal halide for example, SiCl 2, VCl, VCl 2 , VOCl, FeCl, GaCl, ZrCl, AlCl , and the like.
- metal atoms such as Fe, Co, Cu, Ni, Zn, Al, and V
- metal oxides such as VO
- metal hydroxides such as AlOH, and the like are preferable. More preferred are Cu and VO, with VO being most preferred.
- X in the formula (1) represents a lower alkyl group, a lower alkoxy group, an amino group, a nitro group, a halogen group, a hydroxy group, a carboxy group, a sulfonic acid group, or a sulfonamide group.
- “lower” means 1 to 4 carbon atoms.
- Y is a divalent bridging group, for example, an alkylene group having 1 to 3 carbon atoms, —CO 2 —, —SO 2 —, —SO 2 NH (CH 2 ) c— (where c represents 0 to 4). And an alkylene group having 1 to 3 carbon atoms, —SO 2 NH— in which c is 0 is preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable.
- Z is a sulfonic acid group, a carboxy group, a residue excluding at least one hydrogen on the nitrogen atom of the primary or secondary amino group, or an excluding at least one hydrogen on the nitrogen atom of the heterocyclic ring containing nitrogen.
- a carboxy group, a phthalimide group which may have a sulfonic acid group substituent, a piperazino group which may have a substituent, a piperidino group which may have a substituent, etc. A carboxy group, a sulfonic acid group and a phthalimide group which may have a substituent are preferable, and a phthalimide group which may have a substituent is preferable.
- Z is a phthalimide group that may have a substituent, a piperazino group that may have a substituent, or a piperidino group that may have a substituent
- the substituent may be a hydrogen atom or a lower alkyl group.
- a lower alkoxy group, a substituted amino group, a nitro group, a halogen group and a sulfonic acid group preferably a hydrogen atom or a halogen group.
- the substituted amino group is not particularly limited, and examples thereof include an amino group substituted with a lower alkyl group or a lower alkoxy group.
- “lower” means 1 to 4 carbon atoms
- the halogen group means Cl, Br, or I.
- a and b are each 0 or more and 12 or less, and the sum of a and b is 0 or more and 12 or less.
- a and b are each 0 or more and 4 or less, and the sum of a and b is 0 or more and 4 or less.
- the porphyrazine dye represented by the formula (1) can be synthesized according to a known method disclosed in, for example, International Publication Nos. 2010/143619 and 2010/013455.
- the porphyrazine dye represented by the formula (1) is a derivative of each of the formulas (2) to (7) used as a reaction raw material when the synthesis is performed by a known nitrile method or the Weiler method. It can also be synthesized by changing the blending ratio with the naphthalic acid derivative.
- the compound represented by the formula (1) obtained by the above method is a regioisomer of the substitution position of the nitrogen-containing heteroaromatic ring in rings A to C and the substitution position of the nitrogen atom of the nitrogen-containing heteroaromatic ring. It is also as described in the said well-known literature that it becomes a mixture.
- the compound represented by 18 can be synthesized according to known methods disclosed in, for example, Japanese Patent No. 25077786, International Publication No. 2010/013455, and Japanese Patent No. 3813750.
- a conventional method can be used as a method for dispersing the compound of the formula (1) in a dispersion medium. That is, the compound of the formula (1) and a dispersion medium are mixed in a predetermined ratio, and a dispersant, a surfactant, etc. are added as necessary, and a dispersing device such as a sand mill, attritor, ball mill, homogenizer, roll mill, bead mill, etc. Can be dispersed. Among these, a bead mill is preferable. Further, in the pulverization of the pigment in the bead mill, it is preferable to use beads having a small diameter, and to process under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. It is preferred to remove the beads.
- the dispersion medium used for dispersion is not particularly limited, in the present invention, it refers to water, an organic solvent, an adhesive composition, and the like. These dispersion media may be mixed and used as a mixture.
- the organic solvent include hydrocarbon solvents (toluene, xylene, hexane, cyclohexane, n-heptane, etc.), alcohol solvents (methanol, ethanol, isopropyl alcohol, butanol, t-butanol, benzyl alcohol, etc.), ketone solvents.
- the dispersion medium is an acrylic pressure-sensitive adhesive composition
- the acrylic copolymer-based adhesive resin can be usually produced by copolymerization of a main monomer having a low glass transition point and a comonomer having a high glass transition point when formed into a polymer.
- the monomer used as the raw material for the acrylic copolymer-based pressure-sensitive adhesive resin is an alkyl acrylate ester having a low glass transition point and a C 2 to C 14 alkyl group or a C 4 to C 16 meta alkyl group.
- Acrylic acid alkyl ester and a monomer having a glass transition point higher than them and copolymerizable therewith are used.
- acrylic acid alkyl ester monomer having a low glass transition point when converted into a polymer examples include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methoxyethyl acrylate, n-butyl acrylate, isobutyl acrylate, and secondary acrylic acid Examples include butyl, 2-ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, isononyl acrylate, isostearyl acrylate, and the like.
- Examples of the methacrylic acid alkyl ester monomer having a low glass transition point when converted into a polymer include 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-lauryl methacrylate.
- copolymerizable monomer examples include vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, and the like.
- Amide, methylol acrylamide, dimethylacrylamide, glycidyl methacrylate, maleic anhydride and the like are also used.
- the acrylic adhesive composition preferably has a weight average molecular weight of 100,000 to 1,200,000. More preferably, it is 200,000 to 800,000.
- the degree of crosslinking of the polymer material constituting the pressure-sensitive adhesive composition varies depending on various conditions such as the type and composition of the polymer material, and is not particularly limited, but a plasticizer may be added to the polymer material as necessary.
- a plasticizer esters such as phthalic acid ester, trimellitic acid ester, pyromellitic acid ester, adipic acid ester, sebacic acid ester, phosphoric acid triester or glycol ester, process oil, liquid polyether, liquid polyterpene, Other liquid resin etc. are mentioned, Among these, 1 type or 2 types or more can be mixed and used. It is preferable that such a plasticizer has good compatibility with the pressure-sensitive adhesive composition.
- various additives such as a ultraviolet absorber or antioxidant, can be added to an adhesive composition other than the said plasticizer as needed, for example.
- the weight ratio of the compound of the formula (1) to the dispersion medium when dispersing is preferably 3 to 500 of the dispersion medium with respect to 1 of the compound of the formula (1), more preferably 15 to 100 of the dispersion medium. Most preferably, the dispersion medium is 20 to 50.
- Dispersants include fatty acid salts (soap), ⁇ -sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salt, dialkyldimethylammonium chloride, alkylpyridinium chloride, alkylcarboxyl betaine, sulfobetatai Low molecular amphoteric compounds such as lecithin, formalin condensate of n
- Typical examples are polymeric water-based dispersants such as polyacrylic acid partial alkyl esters and polyalkylene polyamines, and polymer cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers.
- polymeric water-based dispersants such as polyacrylic acid partial alkyl esters and polyalkylene polyamines
- polymer cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers.
- those having a structure other than the ones exemplified here are not excluded.
- Florene DOPA-15B Florene DOPA-17 (manufactured by Kyoeisha Chemical Co., Ltd.), Solplus AX5, Solplus TX5, Solsperse 9000, Solsperse 12000, Solsperse 17000, Solsperse 20000, Solsperse 21000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000, Solsperse 32000, Solsperse 35100, Solsperse 54000, Sol Six 250, (manufactured by Nippon Lubrizol Corporation), EFKA4008, EFKA4009, EFKA4010, EFKA4015, EFKA4046, EFKA4047, EFKA4060, EFKA7440E, EFKA7440E , EFKA4400, EFKA4401, EFKA4402, EFKA4403, EFKA4300, EFKA4330, EFKA4340, EF
- the heat ray-shielding metal fine particles used have small absorption of visible light and have good absorption characteristics from the near infrared part to the far infrared part. Is suitable.
- the electroconductive metal oxide which has a plasma wavelength in a near-infrared region is mentioned. Specific examples include tin oxide, indium oxide, zinc oxide, tungsten oxide, chromium oxide, and molybdenum oxide. Of these, tin oxide, indium oxide, and zinc oxide that absorb less light in the visible light region are preferable.
- the third component in order to improve the electrical conductivity of these oxides.
- Sb, V, Nb, Ta, etc. are selected for tin oxide, Zn, Al, Sn, Sb, Ga, Ge, etc. are selected for indium oxide, and zinc oxide is used.
- Al, Ga, In, Sn, Sb, Nb or the like is selected.
- heat ray shielding metal fine particles or near infrared absorbing dyes are used as main ingredients of the acrylic adhesive composition.
- the desired heat ray-shielding dye-dispersed composition can be obtained by dispersing in a monomer and then polymerizing it.
- a dispersion of heat ray blocking metal fine particles is prepared in advance by a known method (Japanese Patent Application No. 2011-203869), mixed with a monomer together with a composition in which a near infrared absorbing dye is dispersed in an organic solvent, and then the monomer is polymerized.
- the target dye-dispersed composition can be obtained.
- An even more convenient method is to directly mix a previously prepared dispersion of heat-shielding metal fine particles into a composition in which the pigment of formula (1) is dispersed in a dispersion medium that is an acrylic adhesive composition. It is also possible to obtain a dye dispersion composition.
- the dispersion medium is not particularly limited as to the coating method of the pigment dispersion composition using the organic solvent, the adhesive composition or a mixture thereof, or the pigment dispersion composition containing the heat ray-shielding metal fine particles, but a comma coater and a bar coater.
- a spin coater, a spray coater, a roll coater, a gravure coater, a knife coater or other various coating apparatuses can be used.
- the dispersion ratio of the heat ray shielding metal fine particles and the compound of the formula (1) to the acrylic adhesive composition is determined by the coating thickness of the adhesive layer and the shielding performance.
- the optical performance of the film coated with the dye-dispersed composition should be high in visible light transmittance and low in solar radiation transmittance. Therefore, the optical performance is determined.
- the coating thickness of the pressure-sensitive adhesive layer is usually 10 to 50 ⁇ m in consideration of the followability to the adherend surface, adhesive strength and economy, but the fine particles that give the above-mentioned heat ray shielding properties within this range
- the amount of (heat ray blocking metal fine particles + the compound of the above formula (1)): resin solid content 3: 97 to 1: 1 (weight ratio) is preferable.
- Example 1 (Compound Example No. 1) A composition obtained by adding 3.0 parts of phthalic anhydride, 11.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 part of ammonium molybdate and 3.5 parts of vanadyl chloride (V) to 120 parts of sulfolane. Was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 20.3 parts of a wet cake.
- V vanadyl chloride
- the obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 18.9 parts of a wet cake.
- the obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 16.1 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. 12.3 parts of 1 were obtained.
- the maximum absorption wavelength of this compound in concentrated sulfuric acid was 943 nm.
- Example 2 (Compound Example No. 2) In the same manner as in Example 1 except that 3.0 parts of phthalic anhydride in Example 1 is changed to 5.9 parts and 11.9 parts of naphthalic anhydride is changed to 7.9 parts. 12.1 parts of 2 were obtained.
- the maximum absorption wavelength of this compound in concentrated sulfuric acid was 951, 882, and 815 nm.
- Example 3 (Compound Example No. 9) To 120 parts of sulfolane, 3.3 parts of 3,4-pyridinedicarboxylic acid, 7.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 part of ammonium molybdate and 3.5 parts of vanadyl chloride (V) were obtained. The composition was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 200 parts of DMF at 80 ° C. to obtain 20.3 parts of a wet cake.
- DMF N, N-dimethylformamide
- the obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours.
- the precipitated solid was separated by filtration and washed with 200 parts of water to obtain 40.1 parts of a wet cake.
- the obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours.
- the precipitated solid was separated by filtration and washed with 7.9 parts of water to obtain 35.2 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. 10.8 parts of 9 were obtained.
- the maximum absorption wavelength of this compound in concentrated sulfuric acid was 933 nm.
- Example 4 (Compound Example No. 10) In the same manner as in Example 3 except that 3.3 parts of 3,4-pyridinedicarboxylic acid in Example 3 were changed to 6.7 parts and 11.9 parts of naphthalic anhydride were changed to 7.9 parts. Example No. 11.4 parts of 10 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 939, 804, and 711 nm.
- Example 5 (Compound Example No. 3) In 40 parts of polyphosphoric acid (116%), the compound No. obtained in Example 1 was obtained. 3.4 parts of 1, 4.9 parts of phthalimide and 1.0 part of paraformaldehyde were added, and the resulting composition was heated to 140 ° C. and reacted at the same temperature for 6 hours. After completion of the reaction, the reaction solution was cooled to 60 ° C. and 100 parts of water was added. The precipitated solid was separated by filtration and washed with water to obtain 34.0 parts of a wet cake. The obtained wet cake was added to 100 parts of a 10% aqueous potassium hydroxide solution, and the resulting composition was reacted at 50 ° C. for 2 hours.
- the precipitated solid was separated by filtration and washed with water to obtain 29 parts of a wet cake.
- the obtained wet cake was added to 100 parts of DMF, and the obtained composition was reacted at 25 ° C.
- the precipitated solid was separated by filtration and washed with water to obtain 13.3 parts of a wet cake.
- the obtained wet cake was dried at 80 ° C. 6.5 parts of 3 were obtained.
- the maximum absorption wavelength of this compound in concentrated sulfuric acid was 949 nm.
- Example 6 (Compound Example No. 11) In Example 5, the compound No. 1 obtained in Example 1 was used. 1 to 3.4 parts of compound No. 1 obtained in Example 4. Compound No. 10 was changed in the same manner as in Example 5 except for changing to 3.1 parts of No. 10. 5.7 parts of 11 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 940 nm.
- Example 7 (Dye dispersion composition 1) To 7 ml of toluene, 0.21 g of the compound of the formula (4) obtained in Example 1 and 0.21 g of the dispersant DisperBYK140 were added, and zirconia beads were further added as crushing beads. Dispersion treatment was performed using a film mix model 30-25, manufactured by Primics Co., Ltd. The obtained dispersion was centrifuged using a centrifuge (Hitachi Koki Co., Ltd., himac CR18) to obtain a pigment dispersion composition 1.
- Examples 8 to 10 (pigment dispersion compositions 2, 3, and 4)
- Dye dispersion compositions 2 to 4 were obtained in the same manner as in Example 7, except that the dye in Example 7 was replaced with the compound obtained in Example 2, 3, or 5.
- this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 ⁇ m) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 ⁇ m) was prepared by covering with a film (one side treated with silicone) (3801, manufactured by Lintec Corporation, thickness: 38 ⁇ m).
- Examples 14 to 16 Dye-dispersed composition coated sheets (thickness: 15 ⁇ m) 2-4 in the same manner as in Example 13, except that the dye-dispersed composition obtained in Example 7 was replaced with the dye-dispersed composition obtained in Examples 8-10. Got.
- a dye dispersion composition was prepared in the same manner as in Example 7 except that the compound represented by the formula (2) described in Patent Document 1 was used instead of the dye obtained in Example 1, and the dye dispersion composition was obtained in Example 7.
- a dye-dispersed composition-coated sheet was prepared in the same manner as in Example 13 except that this dye-dispersed composition was used instead of the dye-dispersed composition.
- Example 17 Evaluation of dye-dispersed composition-coated sheet
- the composition coated sheets prepared in Examples 13 to 16 and Comparative Example 1 were evaluated. The test method and the evaluation method of the results are described below.
- Tts Total solar energy
- Tts Total solar energy
- Solar Transmission is a measure of how much the thermal energy from the sun penetrates the target material, and was calculated by a calculation formula defined in ISO13837. The smaller the calculated numerical value, the smaller the total solar radiation energy, and the higher the heat ray shielding property.
- Production Example 1 (heat ray shielding metal fine particle dispersion) To 70 parts of toluene, 11.2 parts of indium tin oxide, 7.0 parts of acetylacetone, and 1.75 parts of dispersant DisperBYK140 are added, and zirconia beads are further added as crushing beads. Dispersion treatment was performed with Mix 30-25, manufactured by Primics Co., Ltd. Further, the obtained dispersion (heat ray blocking metal fine particle dispersion) was subjected to centrifugal treatment using a centrifuge (Hitachi Koki Co., Ltd. himac CR18).
- this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 ⁇ m) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 ⁇ m) was prepared by covering with a film (one side of which was subjected to silicone treatment) (3801 thickness: 38 ⁇ m, manufactured by Lintec Corporation).
- Comparative Example 2 A dye-dispersed composition-coated sheet (thickness) containing heat ray-shielding metal fine particles in the same manner as in Example 18 except that the dye-dispersed composition prepared in Comparative Example 1 was used instead of the dye-dispersed liquid obtained in Example 7. : 15 ⁇ m).
- Example 19 The sheets obtained in Example 18 and Comparative Example 2 were evaluated in the same manner as in Example 17. The results are summarized in Table 3.
- Example 19 As shown in Table 3, even when a dye dispersion composition obtained by mixing a heat ray shielding fine metal particle dispersion in a composition in which the porphyrazine dye of (1) was dispersed in a dispersion medium was used, Example 19 Similarly to the evaluation results shown in Fig. 2, the b * value is smaller than that of the dye dispersion composition using the dye represented by the formula (2) described in Patent Document 1, and the presence or absence of heat ray shielding metal fine particles is affected. As a result, it was found that the yellow color was greatly reduced.
- the present invention provides a near-infrared-absorbing dye as a heat ray-shielding material that has excellent heat ray shielding ability, little yellowness, and good design properties. Further, the obtained near-infrared absorbing dye can be applied to a heat ray shielding material for a window glass of a house or an automobile, and is extremely valuable in practical use.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
この熱線遮蔽性材料を住宅や自動車の窓ガラスへ付与する場合、視認性確保の点から可視光透過率が高いこと、また、省エネルギーや地球環境問題の観点から熱線遮蔽能力が高いこと、屋外使用でも耐えられる高耐久性が望まれている。また、意匠性の点から、出来るだけ無色透明、若しくは着色が薄いことが望ましいとされている。
特許文献1では、透明性に優れた熱線遮蔽性材料としてポルフィラジン色素が開示されている。しかし、本発明者らの検討の結果、特許文献1に記載の色素は、可視光透過率が高く、熱線遮蔽性も優れていたが、黄色味が強く、意匠性を著しく損なっており、産業上使用し難いものであった。 From the viewpoint of energy saving and global environmental problems in recent years, it is required to reduce the load on air conditioning equipment. For example, in the field of houses and automobiles, there is a heat ray shielding glass in which a heat ray shielding material capable of shielding heat rays from sunlight is applied to the window glass, and it is known that it is effective in suppressing temperature rise in the room or in the car. A near-infrared absorbing dye is used as the heat ray shielding material.
When this heat ray shielding material is applied to window glass of houses and automobiles, it has high visible light transmittance from the viewpoint of ensuring visibility, high heat ray shielding ability from the viewpoint of energy saving and global environmental problems, outdoor use However, high durability that can withstand is desired. Further, from the viewpoint of design properties, it is desirable that it is as colorless and transparent as possible or lightly colored.
In Patent Document 1, a porphyrazine dye is disclosed as a heat ray shielding material excellent in transparency. However, as a result of the study by the present inventors, the dye described in Patent Document 1 has high visible light transmittance and excellent heat ray shielding properties, but has a strong yellowish color and significantly impairs the design properties. It was difficult to use.
即ち、本発明は
(1)下記式(1)で表されるポルフィラジン色素 As a result of intensive studies, the present inventors have solved the above-mentioned problem by a specific porphyrazine dye represented by the following formula (1) or a dye-dispersed composition containing the same. And the present invention has been completed.
That is, the present invention provides (1) a porphyrazine dye represented by the following formula (1):
(2)式(1)中の環A、B、Cがそれぞれ式(2)、式(4)または式(8)である(1)に記載のポルフィラジン色素、
(3)式(1)中の環A、B、Cがそれぞれ式(4)または式(8)である(1)に記載のポルフィラジン色素、
(4)式(1)中のMはVOまたはCuである(3)に記載のポルフィラジン色素、
(5)式(1)中、Yは炭素数1~3のアルキレン基であり、Zは置換基を有してもよいフタルイミド基又は置換基を有してもよいピペラジノ基である(4)に記載のポルフィラジン色素、
(6)下記式(9)で表されるポルフィラジン色素
(2) The porphyrazine dye according to (1), wherein the rings A, B, and C in the formula (1) are the formula (2), the formula (4), and the formula (8), respectively.
(3) The porphyrazine dye according to (1), wherein rings A, B, and C in formula (1) are each formula (4) or formula (8),
(4) The porphyrazine dye according to (3), wherein M in the formula (1) is VO or Cu,
(5) In the formula (1), Y is an alkylene group having 1 to 3 carbon atoms, and Z is a phthalimide group which may have a substituent or a piperazino group which may have a substituent (4) Porphyrazine dyes as described in
(6) Porphyrazine dye represented by the following formula (9)
(7)(1)~(6)の何れか一項に記載のポルフィラジン色素を分散媒中に分散することを特徴とする色素分散組成物、
(8)分散媒がアクリル系粘着組成物であることを特徴とする(7)に記載の色素分散組成物、
(9)(8)に記載の色素分散組成物を塗布してなるシート、
(10)(8)に記載の色素分散組成物に熱線遮蔽性金属微粒子を含有することを特徴とする色素分散組成物、
(11)(10)に記載の熱線遮蔽性金属微粒子が酸化スズ、酸化インジウムまたは酸化亜鉛のいずれかである色素分散組成物、
(12)(11)に記載の色素分散組成物を塗布してなるシート、
に関する。
(7) A dye dispersion composition, wherein the porphyrazine dye according to any one of (1) to (6) is dispersed in a dispersion medium,
(8) The pigment dispersion composition according to (7), wherein the dispersion medium is an acrylic pressure-sensitive adhesive composition,
(9) A sheet formed by applying the pigment dispersion composition according to (8),
(10) A dye dispersion composition comprising heat-shielding metal fine particles in the dye dispersion composition according to (8),
(11) A dye dispersion composition in which the heat ray shielding metal fine particles according to (10) are any one of tin oxide, indium oxide, and zinc oxide,
(12) A sheet formed by applying the dye dispersion composition according to (11),
About.
下記の例は、本発明の色素を具体的に説明するために代表的な色素を示すものであり、本発明は下記の例に限定されるものではない。また、環A乃至Cの含窒素複素芳香環が前記式(2)、(3)及び(5)である場合、窒素原子の位置異性体が存在し、色素合成の際には異性体の混合物として得られる。これら異性体の単離は困難であり、また分析による異性体の特定も困難である。このため、通常は混合物のまま使用する。本発明の色素は、このような混合物をも含むものである。本明細書においては、これらの異性体等を区別することなく、構造式で表示される場合は、便宜的に代表的な1つの構造式を記載する。 Specific examples of rings A to C, X, Y, and Z and the numbers of a and b in the porphyrazine coloring matter of the present invention represented by the formula (1) are shown in Table 1 below.
The following examples show representative dyes for specifically explaining the dyes of the present invention, and the present invention is not limited to the following examples. In addition, when the nitrogen-containing heteroaromatic rings of rings A to C are represented by the above formulas (2), (3) and (5), there are positional isomers of nitrogen atoms, and a mixture of isomers during dye synthesis. As obtained. Isolation of these isomers is difficult, and it is difficult to identify isomers by analysis. For this reason, it is usually used as a mixture. The pigment | dye of this invention also contains such a mixture. In this specification, when it is expressed by a structural formula without distinguishing these isomers, a typical structural formula is described for convenience.
前記式(1)で表されるポルフィラジン色素は、例えば、国際公開第2010/143619号パンフレット及び国際公開第2010/013455号パンフレットに開示された公知の方法に準じて合成することができる。また、式(1)で表されるポルフィラジン色素は、公知の二トリル法、又はワイラー法にて合成を行う際に、反応原料として使用する前記式(2)乃至(7)それぞれの誘導体と、ナフタル酸誘導体との配合比率を変化させることによっても合成することが出来る。なお、上記方法によって得られる前記式(1)で表される化合物は、環A乃至Cにおける含窒素複素芳香環の置換位置、及び含窒素複素芳香環の窒素原子の置換位置に関する位置異性体の混合物となることも、上記公知文献に記載の通りである。
表1中の化合物No.3やNo.18で示される化合物は、例えば、特許第2507786号パンフレット、国際公開2010/013455号パンフレット及び特許第3813750号パンフレットに開示された公知の方法に準じて合成することが出来る。 A method for producing the porphyrazine coloring matter of the present invention represented by the formula (1) will be described.
The porphyrazine dye represented by the formula (1) can be synthesized according to a known method disclosed in, for example, International Publication Nos. 2010/143619 and 2010/013455. The porphyrazine dye represented by the formula (1) is a derivative of each of the formulas (2) to (7) used as a reaction raw material when the synthesis is performed by a known nitrile method or the Weiler method. It can also be synthesized by changing the blending ratio with the naphthalic acid derivative. In addition, the compound represented by the formula (1) obtained by the above method is a regioisomer of the substitution position of the nitrogen-containing heteroaromatic ring in rings A to C and the substitution position of the nitrogen atom of the nitrogen-containing heteroaromatic ring. It is also as described in the said well-known literature that it becomes a mixture.
Compound No. 1 in Table 1 3 or No. The compound represented by 18 can be synthesized according to known methods disclosed in, for example, Japanese Patent No. 25077786, International Publication No. 2010/013455, and Japanese Patent No. 3813750.
分散剤としては、脂肪酸塩(石けん)、α-スルホ脂肪酸エステル塩(MES)、アルキルベンゼンスルホン酸塩(ABS)、直鎖アルキルベンゼンスルホン酸塩(LAS)、アルキル硫酸塩(AS)、アルキルエーテル硫酸エステル塩(AES)、アルキル硫酸トリエタノールといった低分子陰イオン性(アニオン性)化合物、脂肪酸エタノールアミド、ポリオキシエチレンアルキルエーテル(AE)、ポリオキシエチレンアルキルフェニルエーテル(APE)、ソルビトール、ソルビタンといった低分子非イオン系化合物、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウムクロリド、アルキルピリジニウムクロリド、といった低分子陽イオン性(カチオン性)化合物、アルキルカルボキシルベタイン、スルホベタイン、レシチンといった低分子両性系化合物や、ナフタレンスルホン酸塩のホルマリン縮合物、ポリスチレンスルホン酸塩、ポリアクリル酸塩、ビニル化合物とカルボン酸系単量体の共重合体塩、カルボキシメチルセルロース、ポリビニルアルコールなどに代表される高分子水系分散剤、ポリアクリル酸部分アルキルエステル、ポリアルキレンポリアミンといった高分子非水系分散剤、ポリエチレンイミン、アミノアルキルメタクリレート共重合体といった高分子カチオン系分散剤が代表的なものであるが、本発明の粒子に好適に適用されるものであれば、ここに例示したような形態のもの以外の構造を有するものを排除しない。 The weight ratio of the compound of the formula (1) to the dispersion medium when dispersing is preferably 3 to 500 of the dispersion medium with respect to 1 of the compound of the formula (1), more preferably 15 to 100 of the dispersion medium. Most preferably, the dispersion medium is 20 to 50.
Dispersants include fatty acid salts (soap), α-sulfo fatty acid ester salts (MES), alkylbenzene sulfonates (ABS), linear alkylbenzene sulfonates (LAS), alkyl sulfates (AS), alkyl ether sulfates Low molecular weight anionic (anionic) compounds such as salt (AES) and alkyl sulfate triethanol, fatty acid ethanolamide, polyoxyethylene alkyl ether (AE), polyoxyethylene alkylphenyl ether (APE), sorbitol, sorbitan Nonionic compounds, low molecular weight cationic (cationic) compounds such as alkyltrimethylammonium salt, dialkyldimethylammonium chloride, alkylpyridinium chloride, alkylcarboxyl betaine, sulfobetatai Low molecular amphoteric compounds such as lecithin, formalin condensate of naphthalene sulfonate, polystyrene sulfonate, polyacrylate, copolymer salt of vinyl compound and carboxylic acid monomer, carboxymethyl cellulose, polyvinyl alcohol, etc. Typical examples are polymeric water-based dispersants such as polyacrylic acid partial alkyl esters and polyalkylene polyamines, and polymer cationic dispersants such as polyethyleneimine and aminoalkyl methacrylate copolymers. However, as long as it is suitably applied to the particles of the present invention, those having a structure other than the ones exemplified here are not excluded.
スルホラン120部にフタル酸無水物3.0部、ナフタル酸無水物11.9部、尿素29部、モリブデン酸アンモニウム0.40部及び塩化バナジル(V)3.5部加え、得られた組成物を200℃まで昇温し、同温度で11時間反応させた。反応終了後反応液を65℃まで冷却し、N,N-ジメチルホルムアミド(DMF)100部加え、析出固体をろ過分離した。得られた固体をDMF50部で洗浄し、ウェットケーキ20.3部得た。得られたウェットケーキをDMF100部に加え、得られた組成物を80℃に昇温し、同温度で2時間撹拌した。析出固体をろ過分離し、水200部で洗浄しウェットケーキを18.9部得た。得られたウェットケーキを水150部に加え、得られた組成物を90℃に昇温し、同温度で2時間撹拌した。析出固体をろ過分離し、水200部で洗浄してウェットケーキ16.1部を得た。得られたウェットケーキを80℃で乾燥し、前記化合物例No.1を12.3部得た。この化合物の濃硫酸中の極大吸収波長は943nmであった。 Example 1 (Compound Example No. 1)
A composition obtained by adding 3.0 parts of phthalic anhydride, 11.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 part of ammonium molybdate and 3.5 parts of vanadyl chloride (V) to 120 parts of sulfolane. Was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 50 parts of DMF to obtain 20.3 parts of a wet cake. The obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 18.9 parts of a wet cake. The obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 16.1 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 12.3 parts of 1 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 943 nm.
実施例1中のフタル酸無水物3.0部を5.9部に、ナフタル酸無水物11.9部を7.9部にする以外は実施例1と同様にして、前記化合物例No.2を12.1部得た。この化合物の濃硫酸中の極大吸収波長は951、882、815nmであった。 Example 2 (Compound Example No. 2)
In the same manner as in Example 1 except that 3.0 parts of phthalic anhydride in Example 1 is changed to 5.9 parts and 11.9 parts of naphthalic anhydride is changed to 7.9 parts. 12.1 parts of 2 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 951, 882, and 815 nm.
スルホラン120部に3,4-ピリジンジカルボン酸3.3部、ナフタル酸無水物7.9部、尿素29部、モリブデン酸アンモニウム0.40部及び塩化バナジル(V)3.5部加え、得られた組成物を200℃まで昇温し、同温度で11時間反応させた。反応終了後反応液を65℃まで冷却し、N,N-ジメチルホルムアミド(DMF)100部加え、析出固体をろ過分離した。得られた固体を80℃のDMF200部で洗浄し、ウェットケーキ20.3部得た。得られたウェットケーキをDMF100部に加え、得られた組成物を80℃に昇温し、同温度で2時間撹拌した。析出固体をろ過分離し、水200部で洗浄しウェットケーキを40.1部得た。得られたウェットケーキを水150部に加え、得られた組成物を90℃に昇温し、同温度で2時間撹拌した。析出固体をろ過分離し、水7.9部で洗浄してウェットケーキ35.2部を得た。得られたウェットケーキを80℃で乾燥し、前記化合物例No.9を10.8部得た。この化合物の濃硫酸中の極大吸収波長は933nmであった。 Example 3 (Compound Example No. 9)
To 120 parts of sulfolane, 3.3 parts of 3,4-pyridinedicarboxylic acid, 7.9 parts of naphthalic anhydride, 29 parts of urea, 0.40 part of ammonium molybdate and 3.5 parts of vanadyl chloride (V) were obtained. The composition was heated to 200 ° C. and reacted at the same temperature for 11 hours. After completion of the reaction, the reaction solution was cooled to 65 ° C., 100 parts of N, N-dimethylformamide (DMF) was added, and the precipitated solid was separated by filtration. The obtained solid was washed with 200 parts of DMF at 80 ° C. to obtain 20.3 parts of a wet cake. The obtained wet cake was added to 100 parts of DMF, and the resulting composition was heated to 80 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 200 parts of water to obtain 40.1 parts of a wet cake. The obtained wet cake was added to 150 parts of water, and the resulting composition was heated to 90 ° C. and stirred at the same temperature for 2 hours. The precipitated solid was separated by filtration and washed with 7.9 parts of water to obtain 35.2 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 10.8 parts of 9 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 933 nm.
実施例3中の3,4-ピリジンジカルボン酸3.3部を6.7部に、ナフタル酸無水物11.9部を7.9部にする以外は実施例3と同様にして、前記化合物例No.10を11.4部得た。この化合物の濃硫酸中の極大吸収波長は939、804、711nmであった。 Example 4 (Compound Example No. 10)
In the same manner as in Example 3 except that 3.3 parts of 3,4-pyridinedicarboxylic acid in Example 3 were changed to 6.7 parts and 11.9 parts of naphthalic anhydride were changed to 7.9 parts. Example No. 11.4 parts of 10 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 939, 804, and 711 nm.
ポリリン酸(116%)40部中に、実施例1で得られた化合物No.1を3.4部、フタルイミド4.9部、パラホルムアルデヒド1.0部加え、得られた組成物を140℃に昇温し、同温度で6時間反応させた。反応終了後、反応液を60℃まで冷却し、水100部を加えた。析出固体をろ過分離、水洗してウェットケーキを34.0部得た。
得られたウェットケーキを10%水酸化カリウム水溶液100部に加え、得られた組成物を50℃で2時間反応させた。析出固体をろ過分離し、水洗してウェットケーキ29部を得た。
得られたウェットケーキをDMF100部に加え、得られた組成物を25℃で反応させた。析出固体をろ過分離し、水洗してウェットケーキを13.3部得た。得られたウェットケーキを80℃で乾燥し、化合物No.3を6.5部得た。この化合物の濃硫酸中の極大吸収波長は949nmであった。 Example 5 (Compound Example No. 3)
In 40 parts of polyphosphoric acid (116%), the compound No. obtained in Example 1 was obtained. 3.4 parts of 1, 4.9 parts of phthalimide and 1.0 part of paraformaldehyde were added, and the resulting composition was heated to 140 ° C. and reacted at the same temperature for 6 hours. After completion of the reaction, the reaction solution was cooled to 60 ° C. and 100 parts of water was added. The precipitated solid was separated by filtration and washed with water to obtain 34.0 parts of a wet cake.
The obtained wet cake was added to 100 parts of a 10% aqueous potassium hydroxide solution, and the resulting composition was reacted at 50 ° C. for 2 hours. The precipitated solid was separated by filtration and washed with water to obtain 29 parts of a wet cake.
The obtained wet cake was added to 100 parts of DMF, and the obtained composition was reacted at 25 ° C. The precipitated solid was separated by filtration and washed with water to obtain 13.3 parts of a wet cake. The obtained wet cake was dried at 80 ° C. 6.5 parts of 3 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 949 nm.
実施例5中、実施例1で得られた化合物No.1の3.4部を実施例4で得られた化合物No.10の3.1部に替える以外は実施例5と同様にして化合物No.11を5.7部得た。この化合物の濃硫酸中の極大吸収波長は940nmであった。 Example 6 (Compound Example No. 11)
In Example 5, the compound No. 1 obtained in Example 1 was used. 1 to 3.4 parts of compound No. 1 obtained in Example 4. Compound No. 10 was changed in the same manner as in Example 5 except for changing to 3.1 parts of No. 10. 5.7 parts of 11 were obtained. The maximum absorption wavelength of this compound in concentrated sulfuric acid was 940 nm.
トルエン7mlに、実施例1で得た前記式(4)の化合物0.21g、分散剤DisperBYK140を0.21g加え、さらに解砕ビーズとしてジルコニアビーズを加え、バッチ式ビーズミリング装置(T.K.フィルミックス30-25型、プライミクス(株)製)にて分散処理を行った。得られた分散体を、遠心分離機(日立工機株式会社
himac CR18)を用いて遠心処理を行うことにより、色素分散組成物1を得た。 Example 7 (Dye dispersion composition 1)
To 7 ml of toluene, 0.21 g of the compound of the formula (4) obtained in Example 1 and 0.21 g of the dispersant DisperBYK140 were added, and zirconia beads were further added as crushing beads. Dispersion treatment was performed using a film mix model 30-25, manufactured by Primics Co., Ltd. The obtained dispersion was centrifuged using a centrifuge (Hitachi Koki Co., Ltd., himac CR18) to obtain a pigment dispersion composition 1.
実施例7中の色素を実施例2、3、又は5で得られた化合物に替える以外は実施例7と同様にして、色素分散組成物2~4を得た。 Examples 8 to 10 (pigment dispersion compositions 2, 3, and 4)
Dye dispersion compositions 2 to 4 were obtained in the same manner as in Example 7, except that the dye in Example 7 was replaced with the compound obtained in Example 2, 3, or 5.
アクリル酸n-ブチル291gとアクリル酸9gをトルエン366gに溶解し、アゾビスイソブチロニトリル0.15gを添加して、窒素気流下において70℃で6時間重合してアクリル樹脂共重合体(重量平均分子量:Mw=32万)を得た。この共重合体をトルエンで希釈し、固形分率29.36%、粘度2700mPasのアクリル系粘着組成物を得た。 Synthesis example 1 (acrylic adhesive composition)
291 g of n-butyl acrylate and 9 g of acrylic acid were dissolved in 366 g of toluene, 0.15 g of azobisisobutyronitrile was added, and polymerization was performed at 70 ° C. for 6 hours under a nitrogen stream to obtain an acrylic resin copolymer (weight) Average molecular weight: Mw = 320,000) was obtained. This copolymer was diluted with toluene to obtain an acrylic pressure-sensitive adhesive composition having a solid content of 29.36% and a viscosity of 2700 mPas.
実施例13
合成例1で得たアクリル系粘着組成物 100重量部(アクリル酸ブチル:アクリル酸=97:3)、実施例7で得た色素分散組成物2 8.1重量部を均一になるように混合溶解し、色素分散組成物を得た。また、これを離型シートのポリエステルフィルム(片面側にシリコーン処理を施したもの)(リンテック社製 3811 厚さ:38μm)上にコンマコーターで塗布して塗膜を乾燥し、離型シートのポリエステルフィルム(片面側にシリコーン処理を施したもの)(リンテック社製 3801 厚さ:38μm)で覆うことにより色素分散組成物塗布シート(厚さ:15μm)を作製した。 Preparation Example 13 of Dye Dispersion Composition in which Dispersion Medium is Mixture of Organic Solvent and Acrylic Adhesive Composition and Composition-Coated Sheet
100 parts by weight of the acrylic adhesive composition obtained in Synthesis Example 1 (butyl acrylate: acrylic acid = 97: 3) and 8.1 parts by weight of the pigment dispersion composition 2 obtained in Example 7 were mixed so as to be uniform. It melt | dissolved and the pigment dispersion composition was obtained. Also, this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 μm) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared by covering with a film (one side treated with silicone) (3801, manufactured by Lintec Corporation, thickness: 38 μm).
実施例7で得た色素分散組成物を実施例8~10で得られた色素分散組成物に替える以外は実施例13と同様にして色素分散組成物塗布シート(厚さ:15μm)2~4を得た。 Examples 14 to 16
Dye-dispersed composition coated sheets (thickness: 15 μm) 2-4 in the same manner as in Example 13, except that the dye-dispersed composition obtained in Example 7 was replaced with the dye-dispersed composition obtained in Examples 8-10. Got.
実施例1で得られた色素の代わりに特許文献1に記載の式(2)で示される化合物を用いた以外実施例7と同様にして色素分散組成物を作製し、実施例7で得た色素分散組成物の代わりにこの色素分散組成物を用いた以外実施例13と同様にして色素分散組成物塗布シート(厚さ:15μm)を作製した。 Comparative Example 1
A dye dispersion composition was prepared in the same manner as in Example 7 except that the compound represented by the formula (2) described in Patent Document 1 was used instead of the dye obtained in Example 1, and the dye dispersion composition was obtained in Example 7. A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared in the same manner as in Example 13 except that this dye-dispersed composition was used instead of the dye-dispersed composition.
実施例13~16、比較例1で作成した組成物塗布シートの評価を行った。試験方法及び結果の評価方法を以下に記載する。 Example 17 (Evaluation of dye-dispersed composition-coated sheet)
The composition coated sheets prepared in Examples 13 to 16 and Comparative Example 1 were evaluated. The test method and the evaluation method of the results are described below.
上記で得られた組成物塗布シートの透過スペクトルを、分光光度計(島津製作所製
UV-3150)を用いて測定し、透過率を算出した。 (A) Calculation of transmittance of composition-coated sheet The transmittance spectrum of the composition-coated sheet obtained above was measured using a spectrophotometer (UV-3150, manufactured by Shimadzu Corporation), and the transmittance was calculated.
全日射エネルギー(Tts;Total
Solar Transmittance)は太陽からの熱的エネルギーが、対象となる材料をどの程度透過するかという尺度であり、ISO13837に定義されている計算式にて算出した。算出された数値が小さいほど全日射エネルギーが小さいことを示し、熱線遮蔽性が高いことを示す。 (B) Calculation of total solar energy (Tts) Total solar energy (Tts; Total
(Solar Transmission) is a measure of how much the thermal energy from the sun penetrates the target material, and was calculated by a calculation formula defined in ISO13837. The smaller the calculated numerical value, the smaller the total solar radiation energy, and the higher the heat ray shielding property.
CIE1976(L*a*b*)表色系のb*値は測定対象物の黄色の色相を表す数値であり、数値が大きいほど黄色味が強くなり、数値が小さいほど黄色味が弱くなる。このb*値は(a)で得られた透過スペクトルより算出した。 (C) Calculation of b * value of CIE 1976 (L * a * b *) color system The b * value of CIE 1976 (L * a * b *) color system is a numerical value representing the yellow hue of the measurement object. The larger the value, the stronger the yellowness, and the smaller the value, the weaker the yellowness. This b * value was calculated from the transmission spectrum obtained in (a).
トルエン70部に、酸化インジウムスズ11.2部、アセチルアセトン7.0部、分散剤DisperBYK140を1.75部加え、さらに解砕ビーズとしてジルコニアビーズを加えてバッチ式ビーズミリング装置(T.K.フィルミックス30-25型、プライミクス(株)製)にて分散処理をおこなった。また、得られた分散体(熱線遮断性金属微粒子分散液)を、遠心分離機(日立工機株式会社
himac CR18)を用いて遠心処理を行った。 Production Example 1 (heat ray shielding metal fine particle dispersion)
To 70 parts of toluene, 11.2 parts of indium tin oxide, 7.0 parts of acetylacetone, and 1.75 parts of dispersant DisperBYK140 are added, and zirconia beads are further added as crushing beads. Dispersion treatment was performed with Mix 30-25, manufactured by Primics Co., Ltd. Further, the obtained dispersion (heat ray blocking metal fine particle dispersion) was subjected to centrifugal treatment using a centrifuge (Hitachi Koki Co., Ltd. himac CR18).
実施例18
合成例1で得たアクリル系粘着剤A 100重量部(アクリル酸ブチル:アクリル酸=97:3)、製造例1で得たスズ含有酸化インジウム(ITO)のトルエン分散液 144部、実施例7で得た色素分散液 14.7部を均一になるように混合溶解し、熱線遮蔽性粘着組成物を得た。また、これを離型シートのポリエステルフィルム(片面側にシリコーン処理を施したもの)(リンテック社製 3811 厚さ:38μm)上にコンマコーターで塗布して塗膜を乾燥し、離型シートのポリエステルフィルム(片面側にシリコーン処理を施したもの)(リンテック社製 3801 厚さ:38μm)で覆うことにより、色素分散組成物塗布シート(厚さ:15μm)を作製した。 Production Example 18 of Dye Dispersion Composition Using Organic Solvent, Adhesive Composition or Mixture thereof as Dispersion Medium, or Dye Dispersion Composition Coating Sheet of Dye Dispersion Composition Containing Heat Ray Shielding Metal Fine Particles in These
100 parts by weight of acrylic adhesive A obtained in Synthesis Example 1 (butyl acrylate: acrylic acid = 97: 3), 144 parts of a toluene dispersion of tin-containing indium oxide (ITO) obtained in Production Example 1, Example 7 14.7 parts of the pigment dispersion obtained in 1 above were mixed and dissolved so as to be uniform, and a heat ray shielding adhesive composition was obtained. Also, this was coated on a release sheet polyester film (one side treated with silicone) (Lintec 3811 thickness: 38 μm) with a comma coater, the coating film was dried, and the release sheet polyester A dye-dispersed composition-coated sheet (thickness: 15 μm) was prepared by covering with a film (one side of which was subjected to silicone treatment) (3801 thickness: 38 μm, manufactured by Lintec Corporation).
実施例7で得た色素分散液の代わりに比較例1で作製した色素分散組成物を用いた以外実施例18と同様にして熱線遮蔽性金属微粒子を含有した色素分散組成物塗布シート(厚さ:15μm)を作製した。 Comparative Example 2
A dye-dispersed composition-coated sheet (thickness) containing heat ray-shielding metal fine particles in the same manner as in Example 18 except that the dye-dispersed composition prepared in Comparative Example 1 was used instead of the dye-dispersed liquid obtained in Example 7. : 15 μm).
実施例18、比較例2で得られたシートを実施例17と同様にして評価を行った。その結果を表3にまとめた。 Example 19
The sheets obtained in Example 18 and Comparative Example 2 were evaluated in the same manner as in Example 17. The results are summarized in Table 3.
Claims (12)
- 下記式(1)で表されるポルフィラジン色素
- 式(1)中の環A、B、Cがそれぞれ式(2)、式(4)または式(8)である請求項1に記載のポルフィラジン色素。 The porphyrazine dye according to claim 1, wherein the rings A, B, and C in the formula (1) are each the formula (2), the formula (4), or the formula (8).
- 式(1)中の環A、B、Cがそれぞれ式(4)または式(8)である請求項1に記載のポルフィラジン色素。 The porphyrazine coloring matter according to claim 1, wherein the rings A, B and C in the formula (1) are each the formula (4) or the formula (8).
- 式(1)中のMはVOまたはCuである請求項3に記載のポルフィラジン色素。 The porphyrazine coloring matter according to claim 3, wherein M in the formula (1) is VO or Cu.
- 式(1)中、Yは炭素数1~3のアルキレン基であり、Zは置換基を有してもよいフタルイミド基又は置換基を有してもよいピペラジノ基である請求項4に記載のポルフィラジン色素。 The formula (1), wherein Y is an alkylene group having 1 to 3 carbon atoms, and Z is a phthalimide group which may have a substituent or a piperazino group which may have a substituent. Porphyrazine pigment.
- 請求項1~6の何れか一項に記載のポルフィラジン色素を分散媒中に分散することを特徴とする色素分散組成物。 A dye dispersion composition, wherein the porphyrazine dye according to any one of claims 1 to 6 is dispersed in a dispersion medium.
- 分散媒がアクリル系粘着組成物であることを特徴とする請求項7に記載の色素分散組成物。 The dye dispersion composition according to claim 7, wherein the dispersion medium is an acrylic pressure-sensitive adhesive composition.
- 請求項8に記載の色素分散組成物を塗布してなるシート。 The sheet | seat formed by apply | coating the pigment dispersion composition of Claim 8.
- 請求項8に記載の色素分散組成物に熱線遮蔽性金属微粒子を含有することを特徴とする色素分散組成物。 A dye dispersion composition comprising heat-shielding metal fine particles in the dye dispersion composition according to claim 8.
- 請求項10に記載の熱線遮蔽性金属微粒子が酸化スズ、酸化インジウムまたは酸化亜鉛のいずれかである色素分散組成物。 A dye dispersion composition, wherein the heat ray shielding metal fine particles according to claim 10 are any of tin oxide, indium oxide and zinc oxide.
- 請求項11に記載の色素分散組成物を塗布してなるシート。 The sheet | seat formed by apply | coating the pigment dispersion composition of Claim 11.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20147031501A KR20150023250A (en) | 2012-06-18 | 2013-06-11 | Porphyrazine dye, and application therefor |
JP2014521335A JP6181053B2 (en) | 2012-06-18 | 2013-06-11 | Porphyrazine dye and use thereof |
CN201380031619.2A CN104395409B (en) | 2012-06-18 | 2013-06-11 | Porphyrazine pigment and application thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012136550 | 2012-06-18 | ||
JP2012-136550 | 2012-06-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013191029A1 true WO2013191029A1 (en) | 2013-12-27 |
Family
ID=49768629
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/066031 WO2013191029A1 (en) | 2012-06-18 | 2013-06-11 | Porphyrazine dye, and application therefor |
Country Status (6)
Country | Link |
---|---|
JP (1) | JP6181053B2 (en) |
KR (1) | KR20150023250A (en) |
CN (2) | CN104395409B (en) |
HK (1) | HK1222407A1 (en) |
TW (1) | TWI601791B (en) |
WO (1) | WO2013191029A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022045235A1 (en) * | 2020-08-27 | 2022-03-03 | ||
JPWO2022045236A1 (en) * | 2020-08-27 | 2022-03-03 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4061654A (en) * | 1971-07-02 | 1977-12-06 | Polaroid Corporation | Novel tetrazaporphins |
JPS63139789A (en) * | 1986-12-02 | 1988-06-11 | Mitsui Toatsu Chem Inc | Optical recording medium |
JPH08281860A (en) * | 1995-04-11 | 1996-10-29 | Sumitomo Osaka Cement Co Ltd | Heat ray shielding film |
JPH09263717A (en) * | 1996-01-25 | 1997-10-07 | Mitsui Toatsu Chem Inc | Water-base coating material containing near-infrared absorber dispersed therein and its use |
US5763189A (en) * | 1993-09-24 | 1998-06-09 | Biosite Diagnostics Incorporated | Fluorescence energy transfer and intramolecular energy transfer in particles using novel compounds |
WO2012017873A1 (en) * | 2010-08-03 | 2012-02-09 | 富士フイルム株式会社 | Metal complex dye, photoelectric conversion element and photoelectrochemical cell |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH658771A5 (en) * | 1984-05-28 | 1986-12-15 | Ciba Geigy Ag | AZAPHTHALOCYANINE AND THEIR USE AS PHOTOACTIVATORS. |
JP3813750B2 (en) * | 1998-08-27 | 2006-08-23 | 大日精化工業株式会社 | Color filter manufacturing method and color filter |
CN100415715C (en) * | 2003-02-11 | 2008-09-03 | 杜锡光 | Super-phthalocyanine compound with six isoindole structure subunits in laver oxazine cycle and its synthesis and use |
JP4659403B2 (en) * | 2004-07-15 | 2011-03-30 | 富士フイルム株式会社 | Phthalocyanine compound, ink, ink jet recording method, and image forming method |
US7470315B2 (en) * | 2005-07-05 | 2008-12-30 | Silverbrook Research Pty Ltd | Red-shifted water dispersible napthalocyanine dyes |
US20070272918A1 (en) * | 2006-05-25 | 2007-11-29 | Barry Rand | Organic photosensitive devices using subphthalocyanine compounds |
TW201011076A (en) * | 2008-08-01 | 2010-03-16 | Nippon Kayaku Kk | Hydrosoluble naphthalocyanine pigment and aqueous ink composition containing the same |
JP2012025938A (en) * | 2010-06-21 | 2012-02-09 | Nippon Kayaku Co Ltd | Porphyrazine pigment, ink composition, recording method, and colored body |
JP2013256548A (en) * | 2010-10-14 | 2013-12-26 | Nippon Kayaku Co Ltd | Porphyrazine dye, method for producing the same, ink composition, and colored body |
-
2013
- 2013-06-11 KR KR20147031501A patent/KR20150023250A/en not_active Application Discontinuation
- 2013-06-11 WO PCT/JP2013/066031 patent/WO2013191029A1/en active Application Filing
- 2013-06-11 CN CN201380031619.2A patent/CN104395409B/en not_active Expired - Fee Related
- 2013-06-11 JP JP2014521335A patent/JP6181053B2/en active Active
- 2013-06-11 CN CN201610004096.8A patent/CN105733293B/en not_active Expired - Fee Related
- 2013-06-17 TW TW102121427A patent/TWI601791B/en not_active IP Right Cessation
-
2016
- 2016-09-09 HK HK16110731.5A patent/HK1222407A1/en not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4061654A (en) * | 1971-07-02 | 1977-12-06 | Polaroid Corporation | Novel tetrazaporphins |
JPS63139789A (en) * | 1986-12-02 | 1988-06-11 | Mitsui Toatsu Chem Inc | Optical recording medium |
US5763189A (en) * | 1993-09-24 | 1998-06-09 | Biosite Diagnostics Incorporated | Fluorescence energy transfer and intramolecular energy transfer in particles using novel compounds |
JPH08281860A (en) * | 1995-04-11 | 1996-10-29 | Sumitomo Osaka Cement Co Ltd | Heat ray shielding film |
JPH09263717A (en) * | 1996-01-25 | 1997-10-07 | Mitsui Toatsu Chem Inc | Water-base coating material containing near-infrared absorber dispersed therein and its use |
WO2012017873A1 (en) * | 2010-08-03 | 2012-02-09 | 富士フイルム株式会社 | Metal complex dye, photoelectric conversion element and photoelectrochemical cell |
Non-Patent Citations (2)
Title |
---|
"Figurel (structure4)", J. PHYS. CHEM. A, vol. 101, no. 35, 1997, pages 6202 - 6213 * |
"Figurel, NcPc3, Tablel-2, Experimental section", J. PHYS. CHEM. A, vol. 110, no. 10, 2006, pages 3533 - 3545 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPWO2022045235A1 (en) * | 2020-08-27 | 2022-03-03 | ||
WO2022045235A1 (en) * | 2020-08-27 | 2022-03-03 | Dic株式会社 | Phthalocyanine composition |
JPWO2022045236A1 (en) * | 2020-08-27 | 2022-03-03 | ||
JP7168126B2 (en) | 2020-08-27 | 2022-11-09 | Dic株式会社 | Method for producing phthalocyanine |
JP7205670B2 (en) | 2020-08-27 | 2023-01-17 | Dic株式会社 | Phthalocyanine composition |
CN115989285A (en) * | 2020-08-27 | 2023-04-18 | Dic株式会社 | Method for producing phthalocyanine |
CN115989284A (en) * | 2020-08-27 | 2023-04-18 | Dic株式会社 | Phthalocyanine compositions |
Also Published As
Publication number | Publication date |
---|---|
CN104395409A (en) | 2015-03-04 |
TW201402709A (en) | 2014-01-16 |
JPWO2013191029A1 (en) | 2016-05-26 |
KR20150023250A (en) | 2015-03-05 |
TWI601791B (en) | 2017-10-11 |
JP6181053B2 (en) | 2017-08-16 |
CN105733293A (en) | 2016-07-06 |
HK1222407A1 (en) | 2017-06-30 |
CN104395409B (en) | 2016-08-24 |
CN105733293B (en) | 2017-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6328812B2 (en) | Heat ray shielding adhesive composition, heat ray shielding transparent adhesive sheet and method for producing the same | |
JP5063345B2 (en) | Near-infrared absorbing dye-containing adhesive | |
WO2014077166A1 (en) | Optical filter | |
JP2007016198A (en) | Near infrared adsorbing adhesive film and optical filter using the same | |
JP6181053B2 (en) | Porphyrazine dye and use thereof | |
KR102489841B1 (en) | Pressure-sensitive adhesive layer, near-infrared ray absorption film, bonding structure, laminate, pressure-sensitive adhesive composition and method for producing the same | |
WO2014208484A1 (en) | Tetraphenylnaphthalocyanine compound, method for producing same, and use of same | |
JP6607396B2 (en) | Near-infrared absorbing pressure-sensitive adhesive composition, production method thereof, and near-infrared absorbing pressure-sensitive adhesive film | |
JP2015001649A (en) | Optical filter | |
JP2015059154A (en) | Shielding material and composition thereof | |
JP6194250B2 (en) | Heat ray shielding adhesive composition and heat ray shielding adhesive sheet | |
JP2013129701A (en) | Pressure-sensitive adhesive composition, pressure-sensitive adhesive film, and optical filter | |
JP7128804B2 (en) | Naphthalocyanine compound, production method and use thereof | |
CN103842463B (en) | Heat ray shielding adhesive composition and heat ray shielding bonding sheet | |
JP2014021131A (en) | Near-infrared absorption resin composition and near-infrared absorption film | |
WO2015152057A1 (en) | Ultraviolet ray absorber dispersion | |
WO2013162017A1 (en) | Phthalocyanine compound, mixture of phthalocyanine compounds, and heat-ray absorbing material using same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13806064 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2014521335 Country of ref document: JP Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 20147031501 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13806064 Country of ref document: EP Kind code of ref document: A1 |