EP0346772A1

Composition for preparing a near IR absorbing material, and mouldings containing this composition or material.

Abstract

The invention relates to a composition for the preparation of a material which is absorbent in the near IR and contains at least one thiourea compound and at least one copper and/or lead compound. When this composition is heated, a material is obtained which absorbs near- IR light. The composition according to the invention and the material according to the invention can therefore be used to produce mouldings which absorb in the near IR and can therefore be used for the production of optical materials.

EP0346772A1, drawing sheet 1 — Sheet 1 of 13

Term

Term ended

Projected expiry passed 9 June 2009, 17.3 years ago.

11 claims: 2 independent, 9 dependent

1
Masse zur Herstellung eines im nahen IR absorbierenden Materials, die mindestens eine Thioharnstoffverbindung der allgemeinen Formel (I) und mindestens eine Kupfer- und/oder Bleiverbindung enthält:(worin R₁, R₂ und R₃ jeweils ein Wasserstoffatom, eine Alkyl-, Cycloalkyl-, Aryl-, Aralkyl-, Alkenylgruppe, oder einen einwertigen 5- oder 6-gliedrigen Ring bedeuten, wobei jede Gruppe durch mindestens einen Substituenten substituiert sein kann, oder R₁ und R₂ oder R₂ und R₃ gemeinsam einen Ring bilden können).
2
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Kupferverbindung eine Kupferverbindung der Formel (II) (R - X) n Cu (II) ist, worin R ein Wasserstoffatom, eine Alkyl-, Cycloalkyl-Aryl-, Aralkylgruppe oder einen einwertigen 5- oder 6-gliedrigen Ring bedeutet, wobei jede Gruppe durch mindestens einen Substituenten substituiert sein kann, X für -COO, -SO₄, -SO₃, -PO₄, oder -O steht und n eine ganze Zahl von 1 bis 4 ist.
3
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Kupferverbindung Kupferacetylacetonat ist.
4
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Kupferverbindung Chlorophyll-Kupfer oder Chlorophyllin-Kupfer oder Kupferhydroxid ist.
5
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Bleiverbindung eine Bleiverbindung der Formel (III) (R - X) n Pb (III) ist, worin R ein Wasserstoffatom, eine Alkyl-, Cycloalkyl-Aryl-, Aralkylgruppe, oder ein heterocyclischer Rest ist, (wobei jede Gruppe oder der Rest durch mindestens einen Substituenten substituiert sein kann), X für -COO, -SO₄, -SO₃, -PO₄, oder -O steht und n eine ganze Zahl von 1 bis 4 ist.
6
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Bleiverbindung Bleiacetylacetonat ist.
7
Masse nach Anspruch 1, dadurch gekennzeichnet, daß die Bleiverbindung Chlorophyll-Blei oder Chlorophyllin-Blei oder Bleihydroxid ist.
8
Im nahen IR absorbierendes Material erhältlich durch Hitzebehandlung der Masse nach einem der Ansprüche 1 bis 7.
9
Im nahen IR absorbierender Formkörper, dadurch gekennzeichnet, daß er die Masse nach einem der Ansprüche 1 bis 7 umfaßt.
10
Im nahen IR absorbierender Formkörper, erhältlich durch Hitzebehandlung des Formkörpers nach Anspruch 9.
11
Im nahen IR absorbierender Formkörper, dadurch gekennzeichnet, daß er das im nahen IR absorbierende Material nach Anspruch 8 umfaßt.

Independent claims11

101 paragraphs, as filed

0001This invention relates to a near-IR absorbent mass which contains at least one thiourea compound and at least one compound from the group of copper compounds and lead compounds, and a near-IR absorbent material, and to a shaped body which contains this mass or this material.

0002The materials absorbing in the near IR have been specially developed in recent years. These materials are widely used in practice, for example as light-sensitive materials in which a semiconductor laser with a wavelength in the near IR range, etc. is used as a light source; as information recording materials such as optical recording disks; as optical materials such as filters and films for the near IR, etc; that is, light-heat conversion recording materials in combination with the heat-sensitive materials.

0003As known near infrared absorbing materials, a chromium-cobalt complex is described in Japanese Patent Publication No. 42269/1985; a thiol-nickel complex in JO-LS No. 21294/1985; an anthraquinone derivative in JO-LS No. 115958/1986; a new squarylium compound with a maximum wavelength of 700-800 nm in JO-LS No. 218551/1986. In "In the near IR absorbing dye" (Kagakukogyo 43, May 1959) nitroso compounds, their metal complexes, polymethine dyes (cyanine dyes), thiol-cobalt complexes, thiol-platinum complexes, thio-palladium complexes, phthalocyanine dyes, triarylmethane dyes, diimmonium dyes, immononium thonone dyes, immononium dyes, immonon and the like.

0004The previous organic type materials absorbing in the near IR have the disadvantages that the durability is inferior; that is, the initial properties deteriorate under the influence of environmental conditions or over time. On the other hand, the complex-type materials absorbing in the near IR have superior durability, but they have the disadvantages that because of the absorption of the visible light, the materials are highly colored, which means that the materials are only used to a limited extent. Each material has an absorption maximum at a certain wavelength, but has almost no absorption capacity at other wavelengths. In the case of a recording material in which the above material is used and, for example, a laser light with a wavelength in the near IR is used as the light source, it is necessary that the laser wavelength match the absorption maximum of the material. Because the laser wavelength and the absorption material wavelength are limited, the combination possibilities in which the laser wavelength and the absorption material wavelength match are very small. Furthermore, such combinations are practically non-existent, taking into account the absorbency, durability, color, cost, etc. of the recording material. These materials are therefore used only to a limited extent.

0005The invention is based on the first object of providing a near IR absorbing material with less coloration, high durability and uniform absorption in the near IR range of 700-2000 nm wavelength. The invention is based on the second object of creating a mass from which a material which absorbs in the near IR can be easily produced.

0006The third object of the invention is to create a shaped body which contains a material which absorbs in the near IR or a mass which absorbs in the near IR.

0007According to the invention, this object is achieved as follows. The mass absorbing in the near IR according to the invention contains both at least one thiourea compound from the group of the general formula (I)<chemistry id="chem0001" num="0001"><img file="EP0346772A1_D0001.tif" /></chemistry> (wherein R₁, R₂ and R₃ each represent a hydrogen atom, an alkyl, cycloalkyl, aryl, aralkyl alkenyl group, or monovalent radical of a 5 or 6-membered ring, where each group can be substituted by at least one substituent, or R₁ and R₂ or R₂ and R₃ together can form a ring) as well as at least one compound from the group of copper and / or lead compounds.

0008The near IR absorbing material according to the invention comprises the reaction product obtained by the heat treatment of the composition according to the invention. The shaped body according to the invention comprises the mass according to the invention or the material according to the invention.

0009The choice of the thiourea compounds of the general formula (I) according to the invention is not particularly restricted, for example the following can be used:<chemistry id="chem0002" num="0002"><img file="EP0346772A1_D0002.tif" /></chemistry><chemistry id="chem0003" num="0003"><img file="EP0346772A1_D0003.tif" /></chemistry><chemistry id="chem0004" num="0004"><img file="EP0346772A1_D0004.tif" /></chemistry><chemistry id="chem0005" num="0005"><img file="EP0346772A1_D0005.tif" /></chemistry><chemistry id="chem0006" num="0006"><img file="EP0346772A1_D0006.tif" /></chemistry><chemistry id="chem0007" num="0007"><img file="EP0346772A1_D0007.tif" /></chemistry>

0010The copper compound according to the invention is a copper compound of the formula (II) (R - X) <sub>n</sub> C u (II) wherein R is a hydrogen atom, an alkyl, cycloalkyl, aryl, aralkyl group or a heterocyclic radical (where each group or the radical can be substituted by at least one substituent), X -COO, -SO₄, -SO₃, -PO₄, or -O means n is an integer from 1 to 4.

0011The choice of the copper compounds of the general formula (II) according to the invention is not particularly restricted, for example use the following: Copper stearate, copper palmitate, copper oleate, copper behenate, copper laurate, copper caprate, copper capronate, copper valerianate, copper isolactate, copper lactate, copper propionate, copper acetate, copper format, copper hydroxide, copper benzoate, copper o-toluylate, copper m-toluylate, copper p-toluylate p-tert-butyl benzoate, copper o-chlorobenzoate, copper m-chlorobenzoate, copper p-chlorobenzoate, copper dichlorobenzoate, copper trichloro benzoate, copper p-bromobenzoate, copper p-iodobenzoate, Copper-p-phenylbenzoate, copper-p-benzoylbenzoate, copper-p-nitrobenzoate, copper anthranilate, copper-p-aminobenzoate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper pimelate, copper suberate, copper azelate, copper phthalate, copper sebacate, copper sebacate, copper sebate Copper naphthalene carbonate, copper tartar, copper diphenylamine-2-carboxylate, copper 4-cyclohexyl lactate, copper diethyldithiocarbamate, copper gluconate, diethoxy copper, di-isopropoxy copper, Di-n-butoxy copper, copper octylate, copper alkylbenzenesulfonate, copper p-toluenesulfonate, copper naphthalenesulfonate, copper naphthylamine sulfonate, copper n-dodecylbenzenesulfonate, copper dodecylsulfate, copper-2,5-dimethylbenzenesulfonate, copper-2-carbomethylsulfonate, copper-2-carboxylate naphthyl phosphate, copper stearyl phosphate, copper lauryl phosphate, copper di-2-ethylhexyl phosphate, copper isodecyl phosphate, and the like.

0012The lead compound according to the invention is a lead compound of the formula (III) (R - X)<sub>n</sub> Pb (III) wherein R is a hydrogen atom, an alkyl, cycloalkyl, aryl, aralkyl group or a heterocyclic radical (where each group or the radical can be substituted by at least one substituent), X -COO, -SO₄, -SO₃, -PO₄, or -O means n is an integer from 1 to 4.

0013The choice of the lead compounds of the general formula (II) according to the invention is not particularly restricted, for example use the following: Lead stearate, lead palmitate, lead leatate, lead behenate, lead laurate, lead caprate, lead capronate, lead allianate, lead isolate, lead lactate, lead propionate, lead acetate, lead formate, lead hydroxide, lead benzate, lead-o-toluylate, lead-m-toluylate, lead p-tert-butyl benzoate, lead o-chlorobenzoate, lead m-chlorobenzoate, lead p-chlorobenzoate, lead dichlorobenzoate, lead richlor benzoate, lead p-bromobenzoate, lead p-iodobenzoate, lead p-phenyl benzoate, lead o-benzoyl benzoate, lead p-nitrobenzoate, Lead thranilate, lead p-aminobenzoate, lead oxalate, lead mononate, lead succinate, lead glutarate, lead adipate, lead pimelate, lead tuberate, lead acelate, lead sebacinate, lead phthalate, lead monoesterphthalate, lead naphthenate, lead naphthalene carbonate, lead diphenyl ether, 4 Lead gluconate, diethoxy lead, di-isopropoxy lead, di-n-butoxy lead, lead octylate, lead alkylbenzenesulfonate, lead p-toluenesulfonate, lead naphthalenesulfonate, Lead naphthylamine sulfonate, lead n-dodecylbenzenesulfonate, lead dodecyl sulfate, lead 2,5-dimethylbenzenesulfonate, lead 2-carbomethoxy-5-methylbenzenesulfonate, lead α-naphthylphosphate, lead arylphosphate, lead ilaurylphosphate, lead-ilaurylphosphate, lead-ilauryl-phosphate, 2-lead-ethyl-phosphate, b-lead-ethyl-phosphate-2-phosphate .

0014In formulas I, II and III, alkyl, alkenyl, alkoxy etc. can be straight-chain or branched. alkyl is preferably C₁-C₃₀-alkyl, in particular C₁-C₂₅-alkyl. Examples are methyl, ethyl, n- and i-propyl, butyl, stearyl or behenyl.

0015Cycloalkyl is preferably cyclopentyl or cyclohexyl.

0016Aryl is preferably phenyl or naphthyl, aralkyl is preferably phenyl-C₁-C₄-alkyl, such as benzyl or phenylethyl.

0017Alkenyl is preferably C₂-C₆ alkenyl, especially C₂-C₄ alkenyl.

0018The heterocyclic radicals are preferably 5- or 6-membered rings with one or more oxygen, sulfur or nitrogen heteroatoms, such as thiazolyl, thienyl, furyl, pyrrolidinyl, pyrrolyl, morpholinyl, piperazinyl, piperidinyl or pyridinyl. If R₁ and R₂ or R₂ and R₃ together form a ring, they are preferably ethylene, propylene or butylene.

0019Preferred substituents of the radicals present in the formulas I, II and III are straight-chain or branched C₁-C₁₈-alkyl (such as methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, dodecyl etc.), C₁-C₄ alkoxy, hydroxy, halogen (F, Cl, Br, J), nitro, amino, phenyl, cyclopentyl, cyclohexyl, benzoyl, acetyl.

0020Either the above thiourea compound or the above copper or lead compound hardly absorbs near IR light or only a certain wavelength. Heat treatment of the thiourea compound or the copper or lead compound has no effect on absorption in the near IR. But the mixture of this thiourea compound and this copper and / or lead compound absorbs near IR light strongly and evenly after its heat treatment.

0021Without heat treatment, the mixture of a thiourea compound of the general formula (I) and at least one compound from the group of the compounds of the general formula (II), the compounds of the general formula (III), copper and lead acetylacetonates, chlorophyll copper and lead and chlorophyllin copper and lead almost no near IR light.

0022If the mass according to the invention or the shaped bodies containing this mass are treated completely or partially (in sections) by supplying thermal energy, the heated part strongly absorbs the near IR light. The heated part does not pick up light in the visible wavelength range and produces a latent image (a pattern created by heating).

0023Therefore, using the above phenomenon, one can produce a detector for the pattern generated by heating and in combination with a suitable developing device, a recording paper.

0024Because the material of the present invention, which is obtained by the heat treatment of the composition containing a mixture of a thiourea compound and a copper and / or lead compound, strongly absorbs the light in the near IR range, it can be used in the manufacture of a near IR light detector and in the manufacture of the means for the laser beam recording system.

0025The strength of the absorption in the near IR can be adjusted by the type and the mixing ratio of thiourea compound and copper and / or lead compound, heating temperature and time, etc.

0026The composition according to the invention is produced by mixing the thiourea compound and the copper and / or lead compound in a suitable mixing ratio, or by combining the thiourea compound, the copper and / or lead compound, a binder, cellulose, wood pulp, thermoplastic resin powder, etc. and optionally additives such as dyes, etc. are mixed.

0027Furthermore, the composition according to the invention can be prepared by dissolving the mixture of all raw materials in a suitable solvent or a suitable dispersion, or by dissolving all raw materials except for binder, dye, etc. in a solvent in which binder, colorant, etc. are dispersed or dissolved.

0028The mass can be, for example, a coating mass, filler, etc. The mixing ratio, the mass content in the molded body and the addition amount of other substances are determined such that the thiourea compound and the copper and / or lead compound are brought into contact as solids or as a melt or as a mixture of solid and melt when heated.

0029The molded article according to the invention comprises a composition according to the invention which contains the thiourea compound and the copper and / or lead compound, or a material which absorbs in the near IR and is obtained by the heat treatment of the composition according to the invention. The process for producing this shaped body is carried out by:<ul id="ul0001" list-style="none"><li>(a) forming a mixture of the shaped body raw materials and the composition according to the invention or the near IR absorbing material according to the invention, or</li><li>(b) applying or impregnating a dipserged sludge of the composition according to the invention or of the material according to the invention onto the shaped body raw material by means of an atomizing, coating or printing machine.</li></ul>

0030The shaped body is produced by producing a film, a sheet or a rod from cellulose, wood pulp, fiber, thermoplastic resin, etc. in a known manner, for example by weaving, sheet formation, heat-forming, etc., and optionally further treating it.

0031The heat process for achieving absorption ability in the near IR is not particularly limited. All heat processes which involve the transfer of thermal energy for the purpose of achieving the absorption capacity in the near IR due to the reaction of the thiourea compound according to the invention with the copper or lead compound according to the invention can be used according to the invention. The heating can be carried out, for example, with the aid of an electric heating device, induction heating device, film extruder, etc., thermal head, semiconductor laser, IR lamp and the like.

0032The heat treatment is carried out under any atmosphere, for example an air atmosphere, an inert gas atmosphere, etc., usually under an air atmosphere.

0033The heating temperature is usually 40-400 ° C, preferably 50-350 ° C. The heating time is in the range of a few milliseconds to a few ten minutes.

0034Uniform mixing by means of a mixer, for example a whisk, by stirring and swiveling is preferred because this leads to uniform heat transfer and a high reaction rate because of the increasing frequency of contact between the materials.

0035The mixing ratio of thiourea compound, copper and / or lead compound differs depending on the type of these compounds, but 0.01-50 parts by weight, preferably 0.1-10 parts by weight of the thiourea compound, based on 1 part by weight of the Copper and / or lead compound are generally used.

0036As mentioned above, the mixture takes from the thiourea compound of the general formula (I) and from at least one compound from the group of copper and lead hydroxide, copper compound of the general formula (II), lead compound of the general formula (III), copper and lead acetylacetonate , Chlorophyll copper and lead, and chlorophyllin copper and lead after heat treatment near IR light evenly over the entire range of 700 - 2000 nm. The reason for the above fact is not clear.

0037As can be seen from the following examples and comparative examples, neither the thiourea compound nor the above copper and / or lead compound absorbs near IR light strongly and uniformly over the entire range of 700-2000 nm after heat treatment. The mixture of the thiourea compound of the general formula (I) and the above copper and / or lead compound without heat treatment likewise does not strongly and uniformly absorb near IR light. Therefore, it is believed that when the mixture is heat treated, a reaction occurs between the thiourea compound represented by the general formula (I) and the above copper and / or lead compound, thereby forming a complex.

0038The invention is illustrated by the following examples. As an abbreviation for parts by weight, "parts" is used.

[Example 1]

0039The thiourea compounds and copper compounds of Nos. 1, 3 and 5 of Table 1 were wet-ground in an attritor to a particle size of approximately 3 μ. <tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution A</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Thiourea compound of No. 1, 3 or 5</entry><entry namest="col2" nameend="col2" align="right">20th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">30th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">total</entry><entry namest="col2" nameend="col2" align="right">100 Parts</entry></row></tbody></tgroup><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution B</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Copper connection of No. 1, 3 or 5</entry><entry namest="col2" nameend="col2" align="right">20th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">30th Parts</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">total</entry><entry namest="col2" nameend="col2" align="right">100 Parts</entry></row></tbody></tgroup></table></tables>

004050 Parts of solution A and 50 parts of solution B were mixed together to prepare a coating composition.

0041This coating composition was applied in a coating amount of 5 g / m² on a high-quality paper with a weight of 60 g / m² by means of the Meyerbar device and dried. A recording sheet was obtained. All of the recording sheets obtained are white to pale blue, and turn pale green when they are touched with a metal plate from a surface temperature of 150 ° C for 5 seconds. For each colored part, the absorption values of the near IR light at 800, 900, 1000, 1500 and 2000 nm wavelength are on average more than 80% and are therefore high.

0042The heat sensitive printing was carried out by a heat sensitive bar code printer (BW-100T, manufactured by Mekano System Co., Ltd.). In each case, a pale green bar code pattern was printed on each of the sheets.

0043This pattern is readable by a bar code slip reader (MS-Ba-Dec 230, manufactured by Mekano System Co., Ltd.) using the light of a semiconductor laser as a reading light source.

Example 2

0044Based on the combination No. 1-23 in Table 1, 5 parts of a thiourea compound and 5 parts of a copper compound were mixed in a porcelain crucible. 10 parts of the mixture were heat-treated in an electric furnace at 150 ° C for 15 seconds.

0045The pale-colored powder product obtained was fixed in a certain thickness on high-quality paper.

0046The reflectance of the surface was measured with the spectrophotometer (UVID EC-590, manufactured by Japan Spectroscopic Co., Ltd.) with respect to the reflection spectrum of the near IR range in the wavelength range of 800 - 2500 nm.

0047The absorbance in the near IR is shown as the average value of the absorption values, this absorption value being the difference between 100% and the reflectance at the wavelengths of 800, 900, 1000, 1500 and 2000 nm. Here ⓞ shows an average value of at least 80%, ○ an average value of at least 60%, Δ an average value of at least 30%, and X an average value of less than 30%.

0048The material with an average value of at least 30% means a near IR absorbing material according to the invention. The near IR absorption capabilities of the materials according to the invention in Nos. 1-23 of Table 1 show an average value of at least 60%.

Comparative Example 1

0049Each of the thiourea compounds or copper compounds in Table 2 was heat-treated under the same conditions as in Example 2 and applied to the preparation of the product. The near IR reflection spectrum of a product obtained was measured, and the near IR absorbance was evaluated in the same manner as in Example 2. All absorption capabilities in the near IR are less than 30%, as can be seen from Table 2.

0050The change in the absorption capacity in the near IR in the separate heat treatment of the individual components, the mixture without heat treatment, and the mixture of a thiourea compound according to the invention and a copper compound according to the invention after heat treatment is illustrated in FIG. 1. In Figure 1, 1,3-diphenylthiourea is used as the thiourea compound and copper p-chlorobenzoate is used as the copper compound.

0051No. 1 and No. 4 of Comparative Example 1 (separate heat treatment) No. 1 of Example 1 (mixture without heat treatment) and No. 1 of Example 2 (heat treatment of the mixture) are in the range of 800 with respect to the near IR reflection spectra - 2000 nm compared.

0052From Figure 1 it can be seen that the absorption capacity of the heated mixture of 1,3-diphenylthiourea and copper p-chlorobenzoate (at No. 1 of Example 2) in the near IR is considerably higher than that of the separately heated components or than that of Mixture without heat treatment; that is, the near IR absorbance of No. 1 of Example 2 is more than 90% in the whole measurement wavelength range.

Example 3

0053The following compositions were prepared with each of the thiourea compounds and copper compounds of Nos. 24-32 of Table 3: <tables id="tabl0002" num="0002"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution A</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Thiourea compound</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">25th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">125 Parts</entry></row></tbody></tgroup><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution B</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Copper connection</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">25th Parts</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">125 Parts</entry></row></tbody></tgroup></table></tables>

0054The solutions of the above compositions were individually milled to a particle size of 1 micron in an attritor. The solutions were mixed together in the ratio shown in Table 3 to obtain a coating composition. The coating composition obtained was applied in a coating amount of 3.0 g / m² (solid content) to a high-class paper of 50 g / m² and dried to obtain a recording sheet.

0055This recording sheet was pressed for 5 seconds under a pressure of 10 g / m 2 against a plate heated to 150 ° C. (heat-treated). A near IR absorbing recording sheet was obtained.

0056The absorptivity of the obtained recording sheet was measured in the same manner as in Example 2, and the background color of the coating surface and the resistance of the IR absorptivity to heat, moisture, and light were determined as follows, and the results are summarized in Table 3.

[Remarks]

Background color

0057The reflectance of the coating surface after the heat treatment is measured with a Macbeth density meter (RD-914, use of the amber filter).

Heat resistance

0058One sheet is left in the oven at 60 ° C for 24 hours. Then the IR reflectance of the sheet is measured with a spectrophotometer (at a wavelength of 1000 nm).

0059Resistance to heat is evaluated as a residual percentage of near IR absorption by the following formula.<maths id="math0001" num=""><img file="EP0346772A1_D0008.tif" /></maths>

Resistance to humidity

0060A sheet is left at 40 ° C and 90% relative humidity. After 24 hours, the IR reflectance of the sheet is measured with a spectrophotometer (at a wavelength of 1000 nm). Resistance to air humidity is assessed as a residual percentage of the near IR absorption capacity using the following formula.<maths id="math0002" num=""><img file="EP0346772A1_D0009.tif" /></maths>

Lightfastness

0061A sheet is irradiated with the light of a fade-o-meter for 6 hours. The sheet's IR reflectance is measured with a spectrophotometer (at a wavelength of 1000 nm). The resistance to light is evaluated as a residual percentage of the near IR absorption capacity using the following formula.<maths id="math0003" num=""><img file="EP0346772A1_D0010.tif" /></maths>

Comparative Example 2

0062The dispersion A containing the thiourea compound or the dispersion B containing the copper compound used in Example 3 was separately applied in the same manner as in Example 3, dried, and then heat-treated to prepare a product. The near IR absorption capacity of the product was measured.

0063In the sheets on which a mixture of the thiourea compound and the copper compound of the invention were applied and which had been dried, heat treatment leads to a sheet with a high absorption capacity in the near IR, as can be seen from Table 3. This high IR absorption capacity is almost not reduced under the influence of heat, moisture and light and it is surprisingly stable against handling and changing environmental conditions. The surface of this sheet turns a little gray, but the sheet does not experience any striking changes in color. The sheet on which either the thiourea compound or the copper compound was applied and dried had no near-IR absorption ability when heat-treated, and therefore the stability of the IR-absorption ability during storage was not checked. <tables id="tabl0003" num="0003"><table frame="all"><title>Table 1</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Copper connection</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Near IR absorption ability</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Number 1</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 2</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.3</entry><entry namest="col2" nameend="col2" align="left">1,3-diethylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.4</entry><entry namest="col2" nameend="col2" align="left">1,3-dimethylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.5</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 6</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper stearate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.7</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper behenate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.8</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-nitrobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.9</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea + 1,3-dichlorothiourea</entry><entry namest="col3" nameend="col3" align="left">Copper m-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">(0.5:0.5):1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.10</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-bromobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.11</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper benzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.12</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper o-benzoyl benzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.13</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Chlorophyll copper</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.14</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper gluconate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.15</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper 4-cyclohexyl lactate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.16</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper n-dodecylbenzenesulfonate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.17</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper naphthalene sulfonate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.18</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper α-naphthyl phosphate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.19</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper stearate + copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:(0.5:0.5)</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.20</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper stearyl phosphate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.21</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper acetate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.22</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper succinate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No.23</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper glutarate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row></tbody></tgroup></table></tables><tables id="tabl0004" num="0004"><table frame="all"><title>Table 2</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Copper connection</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Near IR absorption ability</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Number 1</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 2</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.3</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.4</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.5</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Copper behenate</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No. 6</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Copper stearate</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></tbody></tgroup></table></tables><tables id="tabl0005" num="0005"><table frame="all"><title>Table 3</title><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Copper connection</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Background color</entry><entry namest="col6" nameend="col6" align="center">Near IR absorption ability</entry><entry namest="col7" nameend="col9" align="center"><u style="single">Resistance to</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" align="center">heat</entry><entry namest="col8" nameend="col8" align="center">humidity</entry><entry namest="col9" nameend="col9" align="center">light</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">No.24</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.26</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">98</entry><entry namest="col8" nameend="col8" align="right">95</entry><entry namest="col9" nameend="col9" align="right">97</entry></row><row><entry namest="col1" nameend="col1" align="left">No.25</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.27</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">97</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">96</entry></row><row><entry namest="col1" nameend="col1" align="left">No.26</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.25</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">96</entry><entry namest="col8" nameend="col8" align="right">93</entry><entry namest="col9" nameend="col9" align="right">95</entry></row><row><entry namest="col1" nameend="col1" align="left">No.27</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.24</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">98</entry><entry namest="col8" nameend="col8" align="right">96</entry><entry namest="col9" nameend="col9" align="right">98</entry></row><row><entry namest="col1" nameend="col1" align="left">No.28</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.25</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">97</entry><entry namest="col8" nameend="col8" align="right">96</entry><entry namest="col9" nameend="col9" align="right">97</entry></row><row><entry namest="col1" nameend="col1" align="left">No.29</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.22</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">96</entry><entry namest="col8" nameend="col8" align="right">95</entry><entry namest="col9" nameend="col9" align="right">95</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 30</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.27</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">95</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">96</entry></row><row><entry namest="col1" nameend="col1" align="left">No.31</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.28</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">94</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">93</entry></row><row><entry namest="col1" nameend="col1" align="left">No.32</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.26</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">95</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">92</entry></row><row><entry namest="col1" nameend="col1" align="left">No.8</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.08</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row><entry namest="col1" nameend="col1" align="left">No.9</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Copper p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.29</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row><entry namest="col1" nameend="col1" align="left">No.10</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.08</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No.11</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.08</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></tbody></tgroup></table></tables>

Example 4

0064Each of the thiourea compounds and the lead compounds described in Nos. 1, 3 and 5 of Table 4 was wet milled in a attritor to a particle size of approximately 3 microns. <tables id="tabl0006" num="0006"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution A</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Thiourea compound of No. 1, 3 or 5</entry><entry namest="col2" nameend="col2" align="right">20th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">30th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">total</entry><entry namest="col2" nameend="col2" align="right">100 Parts</entry></row></tbody></tgroup><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution B</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Lead compound of No. 1, 3 or 5</entry><entry namest="col2" nameend="col2" align="right">20th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">30th Parts</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">total</entry><entry namest="col2" nameend="col2" align="right">100 Parts</entry></row></tbody></tgroup></table></tables>

006550 Parts of solution A and 50 parts of solution B were mixed together to prepare a coating composition.

0066This coating composition was applied in a coating amount of 5 g / m² on a high-quality paper with a weight of 60 g / m² by means of the Meyerbar device and dried. A recording sheet was obtained. All of the recording sheets obtained are white to pale blue, and turn pale green when they are touched with a metal plate from a surface temperature of 150 ° C for 5 seconds. For each colored part, the absorption values of the near IR light at 800, 900, 1000, 1500 and 2000 nm wavelength are on average more than 80% and are therefore high.

0067The heat sensitive printing was carried out by a heat sensitive bar code printer (BW-100T, manufactured by Mekano System Co., Ltd.). In each case, a pale green bar code pattern was printed on each of the sheets.

0068This pattern is readable by a bar code reader (MS-Ba-Dec 230, manufactured by Mekano System Co., Ltd.), in which the light of a semiconductor laser was used as a reading light source.

Example 5

0069Based on the combinations No. 1 - 23 in Table 4, 5 parts of a thiourea compound and 5 parts of a lead compound were mixed in a porcelain crucible. 10 parts of the mixture were heat-treated in an electric furnace at 150 ° C for 15 minutes.

0070The pale-colored powder product obtained was fixed in a certain thickness on high-quality paper.

0071The reflectance of the surface was measured in the same manner as in Example 2.

0072The near IR absorbance is shown in the same manner as in Example 2. The near IR absorption capabilities of the materials according to the invention in Nos. 1-23 of Table 4 show an average value of at least 60%.

Comparative Example 3

0073Each of the thiourea compounds or each of the lead compounds in Table 5 was heat-treated under the same conditions as in Example 5 and applied to the production of the product. The near IR reflection spectrum of a product obtained was measured, and the near IR absorbance was evaluated in the same manner as in Example 5. All absorption capabilities in the near IR are less than 30%, as can be seen from Table 5.

0074The change in the absorption capacity in the near IR in the separate heat treatment of the individual components, the mixture without heat treatment, and the mixture of a thiourea compound according to the invention and a lead compound according to the invention after heat treatment is illustrated in FIG. 2. In Figure 2, 1,3-diphenylthiourea is used as the thiourea compound and lead p-chlorobenzoate is used as the lead compound. No. 1 and No. 4th of Comparative Example 3 (separate heat treatment) No. 1 of Example 4 (mixture without heat treatment) and No. 1 of Example 5 (heat treatment of the mixture) are compared with respect to the near IR reflection spectra in the range of 800-2000 nm.

0075From Figure 2 it can be seen that the absorption capacity of No. 1 of Example 5 in the near IR in the heated mixture of 1,3-diphenylthiourea and lead-p-chlorobenzoate is considerably higher than that of the separately heated components or than that of the mixture without Heat treatment; that is, the near IR absorptivity of No. 1 of Example 5 is more than 90% in the whole measurement wavelength range.

Example 6

0076The following compositions were prepared with each of the thiourea compounds and lead compounds of Nos. 24-32 of Table 6. <tables id="tabl0007" num="0007"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution A</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Thiourea compound</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">25th Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">125 Parts</entry></row></tbody></tgroup><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><thead valign="top"><row><entry namest="col1" nameend="col2" align="left">Solution B</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Lead compound</entry><entry namest="col2" nameend="col2" align="right">50 Parts</entry></row><row><entry namest="col1" nameend="col1" align="left">10% aqueous solution of polyvinyl alcohol</entry><entry namest="col2" nameend="col2" align="right">25th Parts</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">water</entry><entry namest="col2" nameend="col2" align="right">125 Parts</entry></row></tbody></tgroup></table></tables>

0077The solutions of the above compositions were individually milled to a particle size of 1 micron in an attritor. The solutions were mixed together in the ratio shown in Table 6 to obtain a coating composition. The coating composition obtained was applied in a coating amount of 3.0 g / m² (solid content) to a high-class paper of 50 g / m² and dried to obtain a recording sheet.

0078This recording sheet was pressed for 5 seconds under a pressure of 10 g / m 2 against a plate heated to 150 ° C. (heat-treated). A near IR absorbing recording sheet was obtained.

0079The absorptivity of the obtained recording sheet, the background color of the coating surface and the resistance of the IR absorptivity to heat, moisture, and light were determined in the same manner as in Example 3, and the results are summarized in Table 6.

Comparative Example 4

0080The dispersion A containing the thiourea compound or the dispersion B containing the lead compound used in Example 6 was separately applied in the same manner as in Example 6, dried, and then heat-treated to prepare a product. The near IR absorption capacity of the product was measured.

0081In the sheets on which a mixture of the thiourea compound and the lead compound of the invention were applied and which had been dried, heat treatment leads to a sheet with a high absorption capacity in the near IR, as can be seen from Table 6. This high IR absorption capacity is almost not reduced under the influence of heat, moisture and light and it is surprisingly stable against handling and changing environmental conditions. The surface of this sheet turns a little gray, but the sheet does not experience any striking changes in color. The sheet on which either the thiourea compound or the lead compound was applied and which was dried did not have near IR absorbency in the heat treatment, and therefore the stability of the

0082IR absorption capacity not tested during storage. <tables id="tabl0008" num="0008"><table frame="all"><title>Table 4</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Lead compound</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Near IR absorption ability</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Number 1</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 2</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.3</entry><entry namest="col2" nameend="col2" align="left">1,3-diethylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.4</entry><entry namest="col2" nameend="col2" align="left">1,3-dimethylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.5</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 6</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Pencil stearate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.7</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Bleibehenat</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.8</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-nitrobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.9</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea + 1,3-dichlorothiourea</entry><entry namest="col3" nameend="col3" align="left">Lead m-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">(0.5:0.5):1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.10</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-bromobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">ⓞ</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.11</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Stay benzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.12</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead o-benzoyl benzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.13</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Chlorophyll lead</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.14</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead gluconate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.15</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead 4-cyclohexyl lactate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.16</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead n-dodecylbenzenesulfonate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.17</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead naphthalene sulfonate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.18</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead α-naphthyl phosphate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.19</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead stearate + lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:(0.5:0.5)</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.20</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead aryl phosphate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.21</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead acetate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.22</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead succinate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No.23</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead glutarate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="right">○</entry><entry namest="col6" nameend="col6" align="left">Heat treatment</entry></row></tbody></tgroup></table></tables><tables id="tabl0009" num="0009"><table frame="all"><title>Table 5</title><tgroup cols="6" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="26.25mm" /><colspec colnum="2" colname="col2" colwidth="26.25mm" /><colspec colnum="3" colname="col3" colwidth="26.25mm" /><colspec colnum="4" colname="col4" colwidth="26.25mm" /><colspec colnum="5" colname="col5" colwidth="26.25mm" /><colspec colnum="6" colname="col6" colwidth="26.25mm" /><thead valign="top"><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Lead compound</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Near IR absorption ability</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">Number 1</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 2</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.3</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.4</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row><entry namest="col1" nameend="col1" align="left">No.5</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Bleibehenat</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No. 6</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Pencil stearate</entry><entry namest="col4" nameend="col4" align="right">O: 1</entry><entry namest="col5" nameend="col5" align="right">X</entry><entry namest="col6" nameend="col6" align="center">Heat treatment</entry></row></tbody></tgroup></table></tables><tables id="tabl0010" num="0010"><table frame="all"><title>Table 6</title><tgroup cols="9" colsep="1" rowsep="1"><colspec colnum="1" colname="col1" colwidth="17.50mm" /><colspec colnum="2" colname="col2" colwidth="17.50mm" /><colspec colnum="3" colname="col3" colwidth="17.50mm" /><colspec colnum="4" colname="col4" colwidth="17.50mm" /><colspec colnum="5" colname="col5" colwidth="17.50mm" /><colspec colnum="6" colname="col6" colwidth="17.50mm" /><colspec colnum="7" colname="col7" colwidth="17.50mm" /><colspec colnum="8" colname="col8" colwidth="17.50mm" /><colspec colnum="9" colname="col9" colwidth="17.50mm" /><thead valign="top"><row rowsep="0"><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" align="center">Thiourea compound</entry><entry namest="col3" nameend="col3" align="center">Lead compound</entry><entry namest="col4" nameend="col4" align="center">mixing ratio</entry><entry namest="col5" nameend="col5" align="center">Background color</entry><entry namest="col6" nameend="col6" align="center">Near IR absorption ability</entry><entry namest="col7" nameend="col9" align="center"><u style="single">Resistance to</u></entry></row><row><entry namest="col1" nameend="col1" /><entry namest="col2" nameend="col2" /><entry namest="col3" nameend="col3" /><entry namest="col4" nameend="col4" /><entry namest="col5" nameend="col5" /><entry namest="col6" nameend="col6" /><entry namest="col7" nameend="col7" align="center">heat</entry><entry namest="col8" nameend="col8" align="center">humidity</entry><entry namest="col9" nameend="col9" align="center">light</entry></row></thead><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">No.24</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.27</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">99</entry><entry namest="col8" nameend="col8" align="right">96</entry><entry namest="col9" nameend="col9" align="right">98</entry></row><row><entry namest="col1" nameend="col1" align="left">No.25</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.28</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">98</entry><entry namest="col8" nameend="col8" align="right">95</entry><entry namest="col9" nameend="col9" align="right">96</entry></row><row><entry namest="col1" nameend="col1" align="left">No.26</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.27</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">97</entry><entry namest="col8" nameend="col8" align="right">93</entry><entry namest="col9" nameend="col9" align="right">96</entry></row><row><entry namest="col1" nameend="col1" align="left">No.27</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.25</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">98</entry><entry namest="col8" nameend="col8" align="right">95</entry><entry namest="col9" nameend="col9" align="right">98</entry></row><row><entry namest="col1" nameend="col1" align="left">No.28</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.24</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">96</entry><entry namest="col8" nameend="col8" align="right">96</entry><entry namest="col9" nameend="col9" align="right">97</entry></row><row><entry namest="col1" nameend="col1" align="left">No.29</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.23</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">97</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">95</entry></row><row><entry namest="col1" nameend="col1" align="left">No. 30</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.28</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">95</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">94</entry></row><row><entry namest="col1" nameend="col1" align="left">No.31</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0.5:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.29</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">94</entry><entry namest="col8" nameend="col8" align="right">93</entry><entry namest="col9" nameend="col9" align="right">93</entry></row><row><entry namest="col1" nameend="col1" align="left">No.32</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">1:0.5</entry><entry namest="col5" nameend="col5" align="char" char=".">0.28</entry><entry namest="col6" nameend="col6" align="right">ⓞ</entry><entry namest="col7" nameend="col7" align="right">94</entry><entry namest="col8" nameend="col8" align="right">94</entry><entry namest="col9" nameend="col9" align="right">91</entry></row><row><entry namest="col1" nameend="col1" align="left">No.8</entry><entry namest="col2" nameend="col2" align="left">1,3-diphenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.08</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row><entry namest="col1" nameend="col1" align="left">No.9</entry><entry namest="col2" nameend="col2" align="center">-</entry><entry namest="col3" nameend="col3" align="left">Lead p-chlorobenzoate</entry><entry namest="col4" nameend="col4" align="right">0:1</entry><entry namest="col5" nameend="col5" align="char" char=".">0.30</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row><entry namest="col1" nameend="col1" align="left">No.10</entry><entry namest="col2" nameend="col2" align="left">1,3-di-m-chlorophenylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.08</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">No.11</entry><entry namest="col2" nameend="col2" align="left">1,3-dilaurylthiourea</entry><entry namest="col3" nameend="col3" align="center">-</entry><entry namest="col4" nameend="col4" align="right">1:0</entry><entry namest="col5" nameend="col5" align="char" char=".">0.07</entry><entry namest="col6" nameend="col6" align="right">X</entry><entry namest="col7" nameend="col7" /><entry namest="col8" nameend="col8" /><entry namest="col9" nameend="col9" /></row></tbody></tgroup></table></tables>

0083The near IR absorbing mass according to the invention and the sheet containing this mass are almost colorless, and the heated part immediately has a near IR absorption capacity. The heat treatment of the composition according to the invention, of the sheet containing the composition according to the invention, or of the sheet containing this heat-treated composition leads to the strong absorption capacity in the very near IR range of 800-2000 nm. Because of the above near IR absorption capacity, the products according to the invention can be used as optical materials such as a thermal detector; Filters for light in the near IR range; Recording material; Material to repel or isolate heat rays; Heat collector; Sensor for IR detectors and the like can be used.

0084The mass according to the invention or the material obtained by its heat treatment is only slightly discolored despite the presence of metal. Therefore, the shaped bodies (film, sheet, etc.) containing this mass or material have a superior appearance.

0085Any absorbency of the near IR absorbent mass of the present invention, the near IR absorbent material of the present invention, and the molded article containing this mass or material has superior stability against the change in environmental conditions with time, which does not deteriorate.

0086Furthermore, the near IR absorbing mass according to the invention can only be produced by mixing the components, and the near IR absorbing material according to the invention can only be produced by heating this mixture. The production of the molded body, which contains the composition according to the invention or the material according to the invention, does not require a new agent. Therefore, this invention is suitable for industrial production.

Every citation, both ways

Citations
Document	Relation	Office	Category	Cited during
US5723075A	Cited by	United States of America	–	Search report
EP0611754A1	Cited by	European Patent Office (EPO)	–	Search report
GB1202881A	Cites	United Kingdom	A	Search report
CHEMICAL ABSTRACTS, Band 86, Nr. 18, 2. Mai 1977, Seite 662, Zusammenfassung Nr. 131138z, Columbus, Ohio, US; JP-A-76 141 639 (MITA INDUSTRIAL CO., LTD) 02-06-1975	Non-patent	–	–	Search report

8 members in 5 offices

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Priority claims
Document	Office	Kind	Date
14526288	Japan	A	1988-06-13
14526288	Japan	–	1988-06-13
23207588	Japan	A	1988-09-16
23207588	Japan	–	1988-09-16
JP19880145262	–	–	–
JP19880232075	–	–	–
14526288	–	–	–
23207588	–	–	–

Members8

Family members, oldest first
Document	Office	Kind
EP0346772A1This record	European Patent Office (EPO)	A1	1989-12-20
JPH023493A	Japan	A	1990-01-09
JPH0280486A	Japan	A	1990-03-20
US5236633A	United States of America	A	1993-08-17
CA1334624C	Canada	C	1995-03-07
EP0346772B1	European Patent Office (EPO)	B1	1996-02-28
DE58909609D1	Germany	D1	1996-04-04
JP2505859B2	Japan	B2	1996-06-12

33 legal events, as 3 offices reported them to INPADOC

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	Event	Code	Office
2007-12-31	Be: lapsedLapsedBERE	BERE	EP
2006-03-31	Notification of lapseLapsedST	ST	FR
2006-03-01	Gb: european patent ceased through non-payment of renewal feeCeasedGBPC	GBPC	EP
2006-02-28	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2006-01-03	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2005-06-30	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2005-06-09	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2005-06-09	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
2004-08-12	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2004-06-17	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2004-06-09	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2004-06-08	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
2002-01-01	European patent in force as of 2002-01-01IF02	IF02	GB
2000-02-28	Se: european patent has lapsedLapsedEUG	EUG	EP
1999-06-29	Lapsed in a contracting state [announced via postgrant information from national office to epo]LapsedPG25	PG25	EP
1998-06-16	Annual fee paid to national office [announced via postgrant information from national office to epo]GrantedPGFP	PGFP	EP
1997-02-19	No opposition filedOpposition26N	26N	EP
1997-01-03	No opposition filed within time limitOppositionORIGINAL CODE: 0009261PLBE	PLBE	EP
1997-01-03	Information on the status of an ep patent application or granted ep patentGrantedSTATUS: NO OPPOSITION FILED WITHIN TIME LIMITSTAA	STAA	EP
1996-05-27	It: translation for a ep patent filedITF	ITF	EP
1996-05-27	It: translation for a ep patent filedITF	ITF	EP
1996-04-05	Fr: translation filedET	ET	EP
1996-04-04	Corresponds to:REF	REF	EP
1996-03-27	Gb: translation of ep patent filed (gb section 77(6)(a)/1977)GBT	GBT	EP
1996-02-28	Designated contracting statesAK	AK	EP
1996-01-12	(expected) grantORIGINAL CODE: 0009210GRAA	GRAA	EP
1996-01-05	Despatch of communication of intention to grant a patentORIGINAL CODE: EPIDOS IGRAGRAH	GRAH	EP
1993-10-20	Party data changed (applicant data changed or rights of an application transferred)RAP1	RAP1	EP
1993-03-26	Notification of lapseLapsedST	ST	FR
1992-09-23	First examination report despatched17Q	17Q	EP
1990-04-11	Request for examination filed17P	17P	EP
1989-12-20	Designated contracting statesAK	AK	EP
1989-11-04	Public reference made under article 153(3) epc to a published international application that has entered the european phaseORIGINAL CODE: 0009012PUAI	PUAI	EP

Composition for preparing a near IR absorbing material, and mouldings containing this composition or material.

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