Resin composition and molded body

Abstract

To provide a resin composition which has such heat resistance as to withstand melting and kneading at or above 270°C and can form into a molding having good invisibility.SOLUTION: The resin composition is produced by melting and kneading a near-infrared absorbing dye (A) and a thermoplastic resin (B), where the near-infrared absorbing dye is a compound of at least one of the general formulas (1) and (2) in the figure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition containing a near-infrared absorbing dye, and a molded article. [Background technology]

[0002] In recent years, various applications of materials that absorb near-infrared rays (700 nm to 1000 nm) have been proposed, and there is a strong demand for materials with higher performance. Major applications include near-infrared cut filters, such as near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural near-infrared absorbing films for the purpose of selectively utilizing sunlight, recording media that utilize the heat absorbed by near-infrared rays, protective glasses, eyeglasses, sunglasses, heat-blocking films, electrophotographic photoreceptors, materials for laser welding, materials for laser marking, optical filters for semiconductor light-receiving elements that have the function of absorbing and cutting near-infrared rays, near-infrared cut filters for electronic devices, and near-infrared filters for photography.

[0003] Materials for these applications have been used by coating compositions containing near-infrared absorbing dyes and resins on glass substrates or resin substrates. However, in order to make these materials into thin films, the substrate itself may be blended with near-infrared absorbing dyes to form resin molded bodies (hereinafter referred to as molded bodies). The molded bodies must be formed by melting and kneading thermoplastic resins and near-infrared absorbing dyes at high temperatures, so the near-infrared absorbing dyes must be heat resistant.

[0004] Therefore, Patent Document 1 discloses a resin composition containing a diimonium compound as a near-infrared absorbing dye. Patent Document 2 discloses a resin composition containing a hexaboride as a near-infrared absorbing dye. Patent Document 3 discloses a resin composition containing a bipyrroloisoquinoline compound as a near-infrared absorbing dye. Patent Document 4 discloses a resin composition containing a phthalocyanine compound as a near-infrared absorbing dye. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2001-133624 A [Patent Document 2] JP 2003-227922 A [Patent Document 3] JP 2012-131862 A [Patent Document 4] JP 2013-88486 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, among the compounds used in conventional resin compositions, diimonium dyes have low heat resistance and cannot be used in moldings of thermoplastic resins with high melting or softening points (e.g., engineering plastics). In addition, hexaborides have a low absorption coefficient per unit weight, and the thickness of the molding must be increased, making them unsuitable for thin film formation. In addition, phthalocyanine compounds have heat resistance, but coatings using phthalocyanine compounds have a problem of low transparency and invisibility due to absorption due to a structure called the soret band in the visible light region. Bipyrroloisoquinoline compounds also have heat resistance, but have a problem of low invisibility. In addition, invisibility means a property of a near-infrared cut filter that absorbs near-infrared rays while showing little coloring in visible light, making it difficult to see that near-infrared rays are being absorbed by the naked eye. When invisibility is high, the absorption of visible light is low compared to the absorption of near-infrared rays, and coloring of visible light is reduced while the near-infrared rays are sufficiently absorbed.

[0007] The present invention relates to a resin composition which has heat resistance sufficient to withstand melt kneading at 270° C. or higher and which can be used to form a molded article having good invisibility. [Means for solving the problem]

[0008] The resin composition of the present invention is a melt-kneaded mixture of a near-infrared absorbing dye (A) which is at least one compound represented by the following general formula (1) and general formula (2), and a thermoplastic resin (B), The thermoplastic resin (B) includes a crystalline resin having a melting point of 200° C. or higher, or an amorphous resin having a glass transition temperature of 120° C. or higher.

[0009] [ka]

[0010] In general formula (1), X 101 ~X 110 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SONR 101 R 102 , -COOR 101 , -CONR 101 R 102 R represents a nitro group, a cyano group, or a halogen atom. 101 , R 102 each independently represents a hydrogen atom or an alkyl group which may have a substituent. 101 ~X 110 The substituents may be bonded to each other to form a ring. In the general formula (2), Q1, Q4, Q5 and Q8 each independently represent a carbon atom or a nitrogen atom. When Q1, Q4, Q5 or Q8 is a nitrogen atom, X 201 , X 204 , X 205 Or X 208 is not assumed to exist. R1 to R5 each independently represent a hydrogen atom, a sulfo group, or -SO3 - M + or a halogen atom. + represents an inorganic or organic cation. X 201 ~X 208each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR6R7, a sulfo group, -SO2NR8R9, -COOR 10 , -CONR 11 R 12 , a nitro group, a cyano group or a halogen atom. 201 ~X 208 may be bonded to each other to form a ring. R6~R 12 R and R each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. 9、 R 11 and R 12 may be bonded to each other to form a ring. Effect of the Invention

[0011] According to the present invention, the present invention has heat resistance capable of withstanding melt kneading at 270°C or higher, and is excellent. It is possible to provide a resin composition capable of forming a molded article having good invisibility, and the molded article. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The resin composition of the present invention is a melt-kneaded mixture of a near-infrared absorbing dye (A) which is at least one compound represented by the following general formula (1) and general formula (2), and a thermoplastic resin (B), The thermoplastic resin (B) includes a crystalline resin having a melting point of 200° C. or higher, or an amorphous resin having a glass transition temperature of 120° C. or higher.

[0013] [ka]

[0014] In general formula (1), X101 ~X 110 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SONR 101 R 102 , -COOR 101 , -CONR 101 R 102 R represents a nitro group, a cyano group, or a halogen atom. 101 , R 102 each independently represents a hydrogen atom or an alkyl group which may have a substituent. 101 ~X 110 The substituents may be bonded to each other to form a ring. In the general formula (2), Q1, Q4, Q5 and Q8 each independently represent a carbon atom or a nitrogen atom. When Q1, Q4, Q5 or Q8 is a nitrogen atom, X 201 , X 204 , X 205 Or X 208 is not assumed to exist. R1 to R5 each independently represent a hydrogen atom, a sulfo group, or -SO3 - M + or a halogen atom. + represents an inorganic or organic cation. X 201 ~X 208 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR6R7, a sulfo group, -SO2NR8R9, -COOR 10 , -CONR 11 R 12 , a nitro group, a cyano group or a halogen atom. 201 ~X 208 may be bonded to each other to form a ring. R6~R 12R and R each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. 9、 R 11 and R 12 may be bonded to each other to form a ring.

[0015] The near infrared absorbing dye (A) contained in the resin composition of the present specification is usually a cyanine dye having low heat resistance. The squarylium dye is included in the group of squarylium dyes, and is a compound of at least one of general formula (1) and general formula (2), and thus has heat resistance that can withstand melt kneading at 270°C or higher. It is preferable to produce a molded article using the resin composition of the present specification. The molded article can be used for various applications such as near-infrared absorbing films and near-infrared absorbing plates that block heat rays for energy saving, agricultural near-infrared absorbing films for the purpose of selectively utilizing sunlight, recording media that utilize the heat absorbed by near-infrared rays, protective glasses, spectacles, sunglasses, heat-blocking films, electrophotographic photoreceptors, materials for laser welding, materials for laser marking, optical filters for semiconductor light-receiving elements having the function of absorbing and cutting near-infrared rays, near-infrared cut filters for electronic devices, and near-infrared filters for photography, and does not deteriorate even in high-temperature environments or manufacturing processes. In addition, the molded article is preferably used as an optical filter.

[0016] <Near infrared absorbing dye (A)> The near infrared absorbing dye (A) is at least one of the compounds represented by the general formula (1) and the general formula (2). Generally, squarylium dyes included in cyanine dyes have low heat resistance, but at least one of the compounds represented by the general formula (1) and the general formula (2) has heat resistance sufficient to withstand melt kneading at 270°C or higher.

[0017] (Compound represented by general formula (1)) The compound represented by the general formula (1) is 101 ~X 110each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SONR 101 R 102 , -COOR 101 , -CONR 101 R 102 R represents a nitro group, a cyano group, or a halogen atom. 101 , R 102 each independently represents a hydrogen atom or an alkyl group which may have a substituent. 101 ~X 110 The substituents may be bonded to each other to form a ring.

[0018] X 101 ~X 110 In the above, examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, the methyl group, the ethyl group, and the n-propyl group are preferred from the viewpoints of imparting durability and the ease of synthesis, and the methyl group is particularly preferred.

[0019] X 101 ~X 110 In the above, examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, etc. Among these, the vinyl group and the allyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

[0020] X 101~X 110 In the above, examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group, etc. Among these, the phenyl group and the 4-methylphenyl group are preferred from the viewpoints of imparting durability and ease of synthesis.

[0021] X 101 ~X 110 In the above formula, examples of the "aralkyl group which may have a substituent" include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, etc. Among these, a benzyl group is preferred from the viewpoints of imparting durability and ease of synthesis.

[0022] X 101 ~X 110 In the above, examples of the "alkoxy group even if it has a substituent" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, etc. Among these, a methoxy group, an ethoxy group, and a trifluoromethoxy group are preferred from the viewpoints of imparting durability and ease of synthesis.

[0023] X 101 ~X 110 In the above, the "aryloxy group which may have a substituent" is, for example, a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, Examples of the phenyloxy group include a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, and a 4-nitrophenyloxy group. Among these, a phenoxy group and a naphthyloxy group are preferred from the viewpoints of durability and ease of synthesis.

[0024] X 101 ~X 110In the above, examples of the "substituted amino group" include a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an N,N-di(2-hydroxyethyl)amino group, a phenylamino group, a naphthylamino group, a 4-tert-butylphenylamino group, a diphenylamino group, an N-phenyl-N-ethylamino group, etc. Among these, the dimethylamino group and the diethylamino group are preferred from the viewpoints of imparting durability and ease of synthesis.

[0025] X 101 ~X 110 In the above formula, examples of the "halogen atom" include fluorine, bromine, chlorine, and iodine.

[0026] X 101 ~X 110 The substituents can be bonded to each other to form a ring. Examples of the ring include, but are not limited to, the following structures:

[0027] [ka]

[0028] R 101 , R 102 In the above, the "alkyl group which may have a substituent" is, for example, X1 to X 10 This has the same meaning as:

[0029] X 101 ~X 110 preferably contains an unsubstituted alkyl group, and X 103 , X 104 , X 107 and X 8108 At least one of X is preferably an unsubstituted alkyl group. 103 and X 107 is more preferably an unsubstituted alkyl group. A preferred unsubstituted alkyl group is, for example, a methyl group.

[0030] (Method for producing the compound represented by formula (1)) The compound represented by the general formula (1) can be synthesized, for example, by heating and refluxing 1,8-diaminonaphthalene and a cyclohexanone represented by the following general formula (3) in a solvent together with a catalyst to cause condensation, and then adding 3,4-dihydroxy-3-cyclobutene-1,2-dione represented by the following chemical formula (4) and further heating and refluxing to cause condensation. It goes without saying that the synthesis is not limited to the above method.

[0031] [ka]

[0032] (Compound represented by general formula (2)) In the compound represented by the general formula (2), Q1, Q4, Q5 and Q8 each independently represent a carbon atom or a nitrogen atom. When Q1, Q4, Q5 or Q8 is a nitrogen atom, X 201 , X 204 , X 205 Or X 108 has no substituents or atoms. R1 to R5 each independently represent a hydrogen atom, a sulfo group, or -SO3 - M + or a halogen atom. + represents an inorganic or organic cation. X 201 ~X 208 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR6R7, a sulfo group, -SO2NR8R9, -COOR 10 , -CONR 11 R 12 , a nitro group, a cyano group or a halogen atom. 201 ~X 208 may be bonded to each other to form a ring. R6~R 12each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridine group which may have a substituent. R6 and R7, R8 and R 9、 R 11 and R 12 may be bonded to each other to form a ring.

[0033] Q1, Q4, Q5 and Q8 are, for example, more preferably carbon atoms.

[0034] In R1 to R5, examples of the "halogen atom" include fluorine, bromine, chlorine, and iodine.

[0035] M in R1 to R5 + The "inorganic or organic cation" in the above can be, for example, any known cation without limitation, and in the case of an organic cation, it can be either a low molecular type or a high molecular type. Specific examples include metal atoms, ammonium compounds, pyridinium compounds, imidazolium compounds, phosphonium compounds, and sulfonium compounds. In the case of a high molecular type, for example, a "resin having a quaternary ammonium base" can be mentioned, but is not limited thereto. Among these, trivalent metal atoms, ammonium compounds, and resins having a quaternary ammonium base are preferred from the viewpoint of heat resistance.

[0036] From the viewpoint of imparting resistance, R1 to R5 are all hydrogen atoms, or four of R1 to R5 are hydrogen atoms and one is a sulfo group, -SO3 - M + Among these, it is particularly preferable that all of R1 to R5 are hydrogen atoms, or four of R1 to R5 are hydrogen atoms and one is a sulfo group or a halogen atom.

[0037] X 201 ~X 208In the above, examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, a methyl group and an ethyl group are preferred from the viewpoint of the difficulty of synthesis.

[0038] X 201 ~X 208 In the above, examples of the "alkenyl group which may have a substituent" include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, a 5-hexenyl group, etc. Among these, a vinyl group and an allyl group are preferred from the viewpoint of the difficulty of synthesis.

[0039] X 201 ~X 208 In the above, examples of the "aryl group which may have a substituent" include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, a 4-cyanophenyl group, etc. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoint of the ease of synthesis.

[0040] X 201 ~X 208 In the above, examples of the "aralkyl group which may have a substituent" include a benzyl group, a phenethyl group, a phenylpropyl group, a naphthylmethyl group, etc. Among these, a benzyl group is preferred from the viewpoint of the ease of synthesis.

[0041] X 201 ~X 208In the above, examples of the "alkoxy group even if it has a substituent" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and a 2-(diethylamino)ethoxy group. Among these, a methoxy group, an ethoxy group, a trifluoromethoxy group, a 2-(diethylamino)ethoxy group, and the like are particularly preferred. A toxyl group is preferred from the viewpoint of ease of synthesis.

[0042] X 201 ~X 208 In the above, the "aryloxy group which may have a substituent" is, for example, a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, Examples of the phenyloxy group include a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, and a 4-nitrophenyloxy group. Among these, a phenoxy group and a naphthyloxy group are preferred from the viewpoint of the ease of synthesis.

[0043] X 201 ~X 208 In the above formula, examples of the "halogen atom" include fluorine, bromine, chlorine, and iodine.

[0044] X 201 ~X 208 The substituents may be bonded to each other to form a ring. Preferred examples of the ring are shown below. However, the ring is not limited to these.

[0045] [ka]

[0046] X 201 ~X 208 From the viewpoints of dispersibility, storage stability, and ease of synthesis, it is particularly preferable that all of are hydrogen atoms.

[0047] R6~R12 In the above, examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an isobutyl group, a sec-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, etc. Among these, a methyl group and an ethyl group are preferred from the viewpoint of the difficulty of synthesis.

[0048] R6~R 12 In the above, the "aryl group which may have a substituent" is, for example, a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, Examples of the phenyl group include a phenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group. Among these, a phenyl group and a 4-methylphenyl group are preferred from the viewpoint of the ease of synthesis.

[0049] R6~R 12 In the above, examples of the "acyl group which may have a substituent" include an acetyl group, a propioyl group, a benzoyl group, an acrylyl group, a trifluoroacetyl group, etc. Among these, the acetyl group is preferred from the viewpoint of the ease of synthesis.

[0050] R6~R 12 In the above, examples of the "pyridinyl group which may have a substituent" include a 2-pyridinyl group, a 3-pyridinyl group, a 4-pyridinyl group, a 2-methyl-4-pyridinyl group, etc. Among these, the 4-pyridinyl group is preferred from the viewpoint of the ease of synthesis.

[0051] R6 and R7, R8 and R 9、 R 11 and R 12 The substituents may be bonded to each other to form a ring.

[0052] (Method for producing the compound represented by formula (2)) The compound represented by the general formula (2) can be explained, for example, by the following reaction diagram. First, 1,8-diaminonaphthalenes and fluorenones are condensed together with a catalyst in a solvent by heating under reflux, and then 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and further heated. It can be synthesized by refluxing and condensing. Note that at least one of R1 to R5 is SO3 - M + In this case, the hydrogen ion of the sulfo group of the dye substituted with a sulfo group is exchanged with the compound having the desired cation to form SO3 - M + It is needless to say that the synthesis is not limited to the above method.

[0053] [ka]

[0054] The content of the near infrared absorbing dye (A) is preferably from 0.001 to 5 mass %, and more preferably from 0.005 to 1 mass %, in 100 mass % of the resin composition.

[0055] <Thermoplastic resin (B)> The thermoplastic resin (B) is a crystalline resin having a melting point of 200°C or higher, or an amorphous resin having a glass transition temperature of 120°C or higher. The melting point of the crystalline resin is preferably 220°C or higher. The melting point is preferably 500°C or lower. The glass transition temperature of the amorphous resin is preferably 130°C or higher. The glass transition temperature is preferably 300°C or lower. Both the melting point and the glass transition temperature can be measured by a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

[0056] Examples of crystalline resins having a melting point of 200° C. or higher include polyamide resins, polyacetal resins, polyphenylene sulfide resins, and polyether ether ketone resins. Examples of amorphous resins having a glass transition temperature of 120° C. or higher include cycloolefin resins, polyetherimide resins, polyamideimide resins, polyethersulfone resins, polysulfone resins, polyarylate resins, polyphenylene ether resins, and polycarbonate resins.

[0057] (Polyamide resin) The polyamide resin is a crystalline resin, and can be synthesized, for example, by a dehydration condensation reaction between a carboxylic acid component and a compound (Am) having two or more amino groups.

[0058] Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The carboxylic acid component may be a compound having three or more carboxyl groups. The compound (Am) having two or more amino groups may be, for example, a known compound, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diamino alcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine. Commercially available polyamide resins include, for example, nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), nylon 610, and the like.

[0059] (Polycarbonate resin) Polycarbonate resin is an amorphous resin, and is synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or a carbonic acid diester. In the case of a synthesis reaction using phosgene, for example, an interfacial method is preferable. In the case of a synthesis reaction using a carbonic acid diester, a transesterification method in which the reaction is carried out in a molten state is preferable.

[0060] Examples of the aromatic dihydroxy compound include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane; bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, etc. Also, piperazine, dipiperidyl hydroquinone, resorcin, and 4,4'-dihydroxydiphenyls may be used in combination.

[0061] Examples of the carbonate precursor include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0062] The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, and more preferably 16,000 to 27,000. Note that the viscosity average molecular weight in this specification is a value converted from the solution viscosity measured at a temperature of 25° C. using methylene chloride as a solvent.

[0063] Commercially available polycarbonate resins include, for example, Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 23,000), and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 27,000).

[0064] (Cycloolefin resin) Cycloolefin resin is an amorphous resin having an alicyclic structure in the main chain and / or side chain. Examples of the alicyclic structure include norbornene polymer, monocyclic olefin polymer, cyclic conjugated diene polymer, vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. Among these, norbornene polymer is preferred because of its excellent moldability and transparency. Examples of norbornene monomer include bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.12,5]deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]deca-3-ene (common name: methanotetrahydrofluorene), tetracyclo[4.4.0.12,5.17,10]dodec-3-ene (common name: tetracyclododecene), and the like. Commercially available cycloolefin resins include, for example, Topas (manufactured by Polyplastics Co., Ltd.) and Apel (manufactured by Mitsui Chemicals, Inc.).

[0065] (Polyetherimide resin) Polyetherimide resin is an amorphous resin with a glass transition temperature of over 180°C, and has good transparency, high strength, high heat resistance, high elastic modulus and wide range of chemical resistance, which is why it is widely used in a variety of applications such as automobiles, telecommunications, aerospace, electrical / electronics, transportation and healthcare. One process for the production of polyetherimide resins is by polymerization of an alkali metal salt of a dihydroxy aromatic compound, such as bisphenol A disodium salt (BPA·Na2), with a bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be controlled in two ways. The first method is to use a molar excess of the bis(halophthalimide) relative to the alkali metal salt of the dihydroxy aromatic compound. The second method is to prepare the bis(halophthalic anhydride) in the presence of a monofunctional compound, such as phthalic anhydride, which forms an end-capping agent. The phthalic anhydride reacts with a portion of the organic diamine to form a monohalo-bis(phthalimide). The monohalo-bis(phthalimide) serves as an end-capping agent in the polymerization step by reaction with the phenoxide end groups in the growing polymer chain. An example of a commercially available polyetherimide resin is ULTEM (manufactured by Saudi Basic Industries Corporation).

[0066] The resin composition of the present invention may contain additives other than the near infrared absorbing dye (A) and the thermoplastic resin (B). Examples of additives include ultraviolet absorbers, light stabilizers, antioxidants, colorants, dispersants, etc. These additives may be compounds known in the art for use in molded articles.

[0067] The ultraviolet absorbing agent is used to impart ultraviolet resistance to the molded article. Examples of the ultraviolet absorbing agent include benzophenone-based, benzotriazole-based, triazine-based, and salicylic acid ester-based agents. The content of the ultraviolet absorbing agent is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

[0068] The light stabilizer is used to impart ultraviolet resistance to the molded product, and is preferably used in combination with an ultraviolet absorber. The light stabilizer is preferably, for example, a hindered amine light stabilizer. The content of the light stabilizer is preferably 0.01 to 5 mass% in 100 mass% of the resin composition.

[0069] The antioxidant is used to reduce the deterioration of the molded article when the molded article is exposed to natural or artificial light sources and becomes hot. The antioxidant is preferably, for example, a monophenol-based, bisphenol-based, polymeric phenol-based, sulfur-based, or phosphoric acid-based antioxidant. The content of the antioxidant is preferably 0.01 to 5% by mass in 100% by mass of the resin composition.

[0070] The dispersant is used to disperse the near infrared absorbing dye more uniformly in the molded product. For example, the dispersant is preferably a polyolefin wax, a fatty acid wax, a fatty acid ester wax, a partially saponified fatty acid ester wax, a saponified fatty acid wax, etc. The content of the dispersant is preferably 50 to 250 parts by mass relative to 100 parts by mass of the infrared absorbing dye (A).

[0071] <Preparation of Resin Composition> In the present specification, the method for producing a resin composition is a method for producing a resin composition in which a near infrared absorbing dye (A), which is at least one compound represented by general formula (1) and general formula (2), and a thermoplastic resin (B) are melt-kneaded at 270°C or higher, and the thermoplastic resin (B) is a crystalline resin having a melting point of 200°C or higher, or an amorphous resin having a glass transition temperature of 120°C or higher. It is preferable to cool the mixture after melt-kneading. The melt-kneading temperature is more preferably 300°C or higher. The upper limit of the melt-kneading temperature is not limited because it varies depending on the type of thermoplastic resin (B). If forced to give a higher limit, it is preferably 500°C or lower, and more preferably 450°C or lower. The upper limit must be lower than the sublimation temperature or decomposition temperature of the near infrared absorbing dye (A). Examples of the melt kneading device include a single screw kneading extruder, a twin screw kneading extruder, and a tandem type twin screw kneading extruder.

[0072] The resin composition is preferably prepared as a so-called master batch. When a master batch is prepared and then melt-kneaded with a diluent resin (thermoplastic resin (B)) to prepare a molded body, the near-infrared absorbing dye (A) can be easily dispersed uniformly in the molded body and the aggregation of the near-infrared absorbing dye (A) can be suppressed, compared with a molded body prepared without using a master batch. This improves the transparency of the molded body. The master batch is preferably prepared by forming the mixture into pellets using a pelletizer after the melt-kneading. When prepared as a master batch, the content of the near infrared absorbing dye (A) is preferably from 0.01 to 20 mass %, and more preferably from 0.05 to 2 mass %, in 100 mass % of the resin composition.

[0073] <Liquid masterbatch composition (E)> It is more preferable that the resin composition is prepared by preparing a liquid master batch composition (E) and then melt-kneading it together with a diluent resin (thermoplastic resin (B)) to prepare a molded article.

[0074] (Liquid resin (B)) The liquid resin (B) of the present invention plays the role of a dispersion medium for dispersing the near-infrared absorbing dye (A) in producing the liquid master batch composition (E). The liquid resin (B) preferably has a viscosity of 8,000 mPa·s or less at 25°C, more preferably 10 to 5,000 mPa·s, and even more preferably 100 to 3,000 mPa·s. A viscosity within the above range is preferable in terms of antistatic properties. In this specification, the viscosity is a value measured at 25°C using a B-type viscometer in accordance with JIS K7117-1:1999.

[0075] The content of the liquid resin (B) is preferably 50% by mass or more, more preferably 60 to 95% by mass, and even more preferably 70 to 90% by mass, based on 100% by mass of the liquid masterbatch composition (E). When the liquid resin (B) is contained in an appropriate amount, the fluidity can be maintained during the stirring and dispersion steps during production, the masterbatch production suitability is excellent, and the dispersibility is improved. In addition, the transparency of the molded product is also improved.

[0076] The number average molecular weight (Mn) of the liquid resin (B) is preferably from 100 to 3000, more preferably from 200 to 2000, further preferably from 500 to 1500, and particularly preferably from 1000 to 1500. An Mn of 200 or more is preferred in terms of suitability for film production and transparency, while an Mn of 2000 or less is preferred in terms of dispersibility and antistatic properties.

[0077] Examples of the liquid resin (B) include epoxy resins such as epoxidized soybean oil and epoxidized linseed oil, fatty acid polyester resins, polyalkylene glycol resins, polyether ester resins, and acetyl tributyl citrate. Among these, fatty acid polyester resins, polyalkylene glycol resins, polyether ester resins, and acetyl tributyl citrate are preferred because of their high heat resistance and excellent antistatic properties.

[0078] [Fatty acid polyester resin] It is a polyester resin which is a reaction product of an aliphatic polycarboxylic acid and a polyhydric alcohol.

[0079] The aliphatic polycarboxylic acid is an aliphatic carboxylic acid having two or more carboxyl groups. Examples of the aliphatic polycarboxylic acid include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, tricarballylic acid, 1,3,6-hexanetricarboxylic acid, and 1,3,5-hexanetricarboxylic acid.

[0080] The polyhydric alcohol is an alcohol having two or more hydroxyl groups. Examples of polyhydric alcohols include aliphatic glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-n-butyl-2-ethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-octadecanediol; and polyalkylene glycols such as diethylene glycol and dipropylene glycol.

[0081] The freezing point of the fatty acid polyester resin is preferably -5°C or lower, and more preferably -50°C to -10°C.

[0082] The commercially available fatty acid polyester resin is "ADEKA Cizer PN-170 (ADEKA Corporation) Examples of such resins include Adeka Cizer P-200 (manufactured by ADEKA Corporation, viscosity at 25°C 800 mPa s, freezing point -15°C, adipic acid polyester resin), Adeka Cizer P-200 (manufactured by ADEKA Corporation, viscosity at 25°C 2,600 mPa s, freezing point -20°C, adipic acid polyester resin), and Adeka Cizer PN-250 (manufactured by ADEKA Corporation, viscosity at 25°C 4,500 mPa s, freezing point -20°C, adipic acid polyester resin).

[0083] The fatty acid polyester resin may be prepared from a single raw material or a combination of two or more raw materials.

[0084] [Polyalkylene glycol resin] The polyalkylene glycol resin is preferably an alkylene glycol having a repeating unit having 1 to 6 carbon atoms, and from the viewpoint of compatibility and water absorption, more preferably a polyalkylene glycol resin having a repeating unit having 2 to 4 carbon atoms. Needless to say, resins other than those mentioned above can be used as long as they satisfy the predetermined viscosity characteristics.

[0085] Examples of polyalkylene glycol resins include polyethylene glycol, both of which have 2 carbon atoms in their repeating units, polytrimethylene glycol and polypropylene glycol, both of which have 3 carbon atoms in their repeating units, and polytetramethylene glycol and polybutylene glycol, both of which have 4 carbon atoms in their repeating units.

[0086] [Polyetherester resin] The polyether ester resin is a resin obtained by esterifying the above-mentioned aliphatic polycarboxylic acid and the above-mentioned alkylene glycol.

[0087] Commercially available polyether ester resins include Adeka Cizer RS-107 (manufactured by ADEKA Corporation, viscosity 20 mPa s at 25°C, freezing point -47°C, adipic acid ether ester resin) and Adeka Cizer RS-700 (manufactured by ADEKA Corporation, viscosity 30 mPa s at 25°C, freezing point -53°C, polyether ester resin).

[0088] The solidification point of the liquid resin (B) is preferably -5°C or lower, and more preferably -50°C to -10°C.

[0089] In general, it is preferable to prepare a masterbatch in which a molding resin composition containing a dye or a functional material is incorporated in a thermoplastic resin at a high concentration. When a masterbatch is prepared and then melt-kneaded with a diluent resin to prepare a molded body, the dye or functional material can be easily dispersed uniformly in the molded body and the aggregation of the dye or functional material can be suppressed compared to a molded body prepared without using a masterbatch. This improves the transparency of the molded body. The masterbatch is preferably prepared by molding into pellets using a pelletizer after the melt-kneading, and the masterbatch is usually solid. However, for applications requiring high transparency, such as optical filters, the above solid masterbatches may not have sufficient transparency, which is particularly noticeable when using engineering plastics that have low fluidity even at melting temperatures.

[0090] The liquid masterbatch composition (E) contains the liquid resin (B) and is in a liquid state. Therefore, the liquid masterbatch composition (E) has high fluidity during melt kneading in the production of a molded product. Since the near-infrared absorbing dye (A) is dispersed very uniformly in the liquid masterbatch composition (E), the obtained molded product has very high transparency. The content of the near infrared absorbing dye (A) in the liquid masterbatch composition (E) of the present invention is preferably from 1 to 30 mass %, more preferably from 2 to 20 mass %, based on 100 mass % of the liquid masterbatch composition.

[0091] (Resin-type dispersant (F)) The liquid masterbatch composition (E) preferably contains a resin-type dispersant (F). This allows the near-infrared absorbing dye (A) to be more uniformly dispersed in the liquid masterbatch composition, and the resulting molded product has higher transparency. In addition, the inclusion of the resin-type dispersant (F) improves the storage stability of the liquid masterbatch.

[0092] Examples of the resin-type dispersant (F) include polycarboxylates such as polyurethanes and polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, as well as oil-based dispersants, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0093] The resin-type dispersant (F) is preferably used in an amount of about 5 to 200% by mass relative to the near-infrared absorbing dye (A), and from the viewpoint of film-forming properties, more preferably about 10 to 100% by mass.

[0094] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or A manufactured by BYK Japan Co., Ltd. nti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 29000, 30000, 31000, 32000, 33000, 34000, 35000, 36000, 37000, 38000, 39000, 40000, 41000, 42000, 43000, 44000, 45000, 46000, 47000, 48000, 49000, 5000, 51000, 52000, 53000, 54000, 55000, 56000, 57000, 58000, 59000, 60000, 61000, 62000, 63000, 64000, 65000, 66000, 67000, 68000, 69000, 70000, 71000, 72000, 73000, 74000, 75000, 76000, 77 8000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by Chiba Japan , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0095] When the resin-type dispersant (F) is used by dissolving it in an organic solvent, it is preferable to add the liquid resin (C), and then heat the mixture under reduced pressure to distill off the solvent.

[0096] <Method for producing liquid masterbatch composition (E)> The liquid master batch (E) is obtained by stirring and mixing or dispersing a near infrared absorbing dye (A), which is at least one of the compounds represented by general formula (1) and general formula (2), a liquid resin (C), and a resin-type dispersant (D). The obtained liquid master batch composition (E) is melt-kneaded with a thermoplastic resin (B) at 270°C or higher to produce a resin composition. The thermoplastic resin (B) is preferably a crystalline resin with a melting point of 200°C or higher, or an amorphous resin with a glass transition temperature of 120°C or higher.

[0097] The dispersion treatment is carried out by finely dispersing the mixture using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0098] The molded article of the present specification is preferably produced by molding the resin composition. The molded article can be produced by molding the resin composition as it is. Alternatively, the molded article can be produced by preparing a master batch, melt-kneading it with a dilution resin (thermoplastic resin (B)), and then molding it. In this case, the mass ratio of the master batch (X) to the diluted resin (Y) is preferably X / Y=1 / 5 to 1 / 500. When the mass ratio is within this range, the molded product tends to have good optical properties. In particular, when a liquid masterbatch composition (E) is used as the masterbatch, it is more preferable that the liquid masterbatch composition (E) is contained in an amount of 0.1 to 5 mass% in 100 mass% of the resin composition (molded article).

[0099] <Application> The applications of the molded article are, for example, as follows.

[0100] (Heat absorbing material) The molded article of the present invention can be used as a heat ray absorbing material. Sunlight contains near infrared rays of 700 to 2000 nm, and among them, near infrared rays of 700 to 1000 nm are particularly strong. Near infrared rays have the property of increasing the temperature of a substance, and are called heat rays. Among them, by absorbing and blocking the particularly strong near infrared rays of 700 to 1000 nm, it is possible to suppress the temperature increase of a substance. Heat ray absorbing materials, when applied as molded films to windows of buildings and cars, have the effect of suppressing the rise in temperature inside rooms and cars caused by sunlight. The above films can also be used in agricultural vinyl greenhouses, and are effective in suppressing the rise in temperature inside the greenhouse. The same can be said for protective goggles, eyeglasses, and sunglasses, and they can be used to block heat rays.

[0101] (Optical recording media) The molded article of the present invention can be used as an optical recording medium. By irradiating the molded article with near infrared rays, the crystalline state of the dye changes, causing a phenomenon in which the refractive index of the resin molded article changes. This principle is used in recording media such as optical disks. The resin composition of the present invention can be used for the above-mentioned optical recording media.

[0102] (Laser welding materials / Laser marking materials) The molded article of the present invention can be used as a laser welding material or a laser marking material. When a molded body is irradiated with a laser with a wavelength that is absorbed by the near-infrared absorbing dye (A), the dye absorbs the laser light and generates heat, causing the resin to melt and carbonize. When the resin melts, it can be welded to other resins, and this principle is used in laser welding. Laser marking also uses the blackening caused by carbonization. In the case of laser welding, carbon or the like is usually added to the resin to perform welding, but in the case of near-infrared absorbing dyes, a phenomenon occurs in which transparent resins are melted together by adding the dye to the transparent resin and irradiating it with a near-infrared laser. This is because the resin is transparent even if it contains near-infrared absorbing dyes, as it does not absorb light in the visible range, and when irradiated with near-infrared light, it heats up and melts. Laser marking can also be used to mark transparent resins.

[0103] (Optical Filter) The molded article of the present invention can be used as an optical filter. For example, a digital camera recognizes color by decomposing the light received when capturing an image with red, green, and blue filters and sending it to a photodiode that converts the light into an electrical signal. However, a photodiode also reacts to near-infrared rays and converts them into electrical signals, so a filter that blocks them is necessary. The molded article can be used as a filter that blocks this near-infrared rays. However, if there is absorption in the visible region in addition to the near-infrared absorbing dye, it will have a negative effect on color recognition. Since the near-infrared absorbing dye (A) of the present invention has high invisibility, it has little negative effect on color recognition by the photodiode. In addition, LEDs with wavelengths of 850 nm, 900 nm, 940 nm, etc. have recently become widespread and are used for distance measurement and face recognition in automatic driving, and for light detection in various sensors. However, since light rays of all wavelengths, such as ultraviolet rays, visible light, and near-infrared rays, exist in the atmosphere, a filter that blocks light other than the wavelength to be detected is required. Therefore, by combining a near-infrared absorbing dye that absorbs light in the range of 700 to 1000 nm with a dye that absorbs visible light, an ultraviolet absorber, or the like, it is possible to transmit only light with a wavelength longer than the absorption wavelength of the near-infrared absorbing dye, and block light with a wavelength shorter than that. Examples of combinations of dyes and pigments include a near-infrared absorbing dye, a blue dye, a yellow dye, and a red dye. The preferred blue pigment is Pigment Blue 15:3, the preferred yellow pigment is Pigment Yellow 147, and the preferred red pigment is Solvent Red 52. EXAMPLES

[0104] The present invention will be described in more detail below. The present invention is not limited to the examples. In addition, "parts by mass" is expressed as "parts" and "% by mass" is expressed as "%". Examples 2, 13, 51 and 62 herein are for reference only.

[0105] <Method for producing near infrared absorbing dye (A)> (Production of near infrared absorbing dye (A1-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione were added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane was added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 61.9 parts of near-infrared absorbing dye (A1-1) (yield: 92%). As a result of mass analysis using a TOF-MS (time-of-flight mass spectrometer), it was identified as near-infrared absorbing dye (A1-1).

[0106] (Production of near infrared absorbing dye (A1-2)) Except for using 32.2 parts of 2,6-dimethylcyclohexanone instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye (A1-1), the same operation as in the production of near-infrared absorbing dye [A-1] was carried out to obtain 71.9 parts of near-infrared absorbing dye (A1-2) (yield: 97%). As a result of mass analysis by TOF-MS, it was identified as near-infrared absorbing dye (A1-2).

[0107] (Production of near infrared absorbing dye (A1-3)) Except for using 32.2 parts of 3,5-dimethylcyclohexanone instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye (A1-1), the same operation as in the production of near-infrared absorbing dye [A-1] was carried out to obtain 72.6 parts of near-infrared absorbing dye (A1-3) (yield: 98%). As a result of mass analysis by TOF-MS, it was identified as near-infrared absorbing dye (A1-3).

[0108] (Production of near infrared absorbing dye (A1-4)) Instead of 25.1 parts of cyclohexanone used in the production of the near-infrared absorbing dye (A1-1), 28.6 parts of 4-methylcyclohexanone were used, and the same operation as in the production of the near-infrared absorbing dye [A-1] was carried out to obtain 67.2 parts of near-infrared absorbing dye (A1-4) (yield: 95%). As a result of mass analysis by TOF-MS, it was identified as the near-infrared absorbing dye (A1-4).

[0109] (Production of near infrared absorbing dye (A1-5)) Except for using 39.4 parts of 3,5-diethylcyclohexanone instead of 25.1 parts of cyclohexanone used in the production of near-infrared absorbing dye (A1-1), the same operation as in the production of near-infrared absorbing dye (A1-1) was carried out to obtain 76.9 parts of near-infrared absorbing dye (A1-5) (yield: 95%). As a result of mass analysis by TOF-MS, it was identified as near-infrared absorbing dye (A1-5).

[0110] (Production of near infrared absorbing dye (A1-6)) The same procedure as in the production of the near infrared absorbing dye (A1-1) was carried out except that 28.1 parts of 2-norbornanone was used instead of 25.1 parts of cyclohexanone used in the production of the near infrared absorbing dye (A1-1), to obtain 64.6 parts of near infrared absorbing dye (A1-6) (yield: 92%). As a result of mass analysis by TOF-MS, it was identified as the near infrared absorbing dye (A1-6).

[0111] The structure of the near infrared absorbing dye synthesized as above is as follows.

[0112] [ka]

[0113] (Production of near infrared absorbing dye (A2-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 46.0 parts of 9-fluorenone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione were added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled, and 200 parts of hexane were added while stirring the resulting reaction mixture. The resulting black-brown precipitate was filtered off, washed with hexane, ethanol and acetone, and dried under reduced pressure to obtain 84.6 parts (yield: 97%) of near-infrared absorbing dye (A2-1). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as the near-infrared absorbing dye [A-1].

[0114] (Production of near infrared absorbing dye (A2-2)) Except for using 49.6 parts of 2-methyl-9-fluorenone instead of 46.0 parts of 9-fluorenone used in the production of near-infrared absorbing dye (A2-1), the same operation as in the production of near-infrared absorbing dye (A2-1) was carried out to obtain 86.7 parts of near-infrared absorbing dye [A2-2] (yield: 96%). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as near-infrared absorbing dye (A2-2).

[0115] (Production of near infrared absorbing dye (A2-3)) The same procedure as in the production of the near infrared absorbing dye (A2-1) was carried out except that 60.3 parts of 3,6-diethyl-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near infrared absorbing dye (A2-1), to obtain 95.0 parts of the near infrared absorbing dye (A2-3) (yield: 94%). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as the near infrared absorbing dye (A2-3).

[0116] (Production of near infrared absorbing dye (A2-4)) The same operation as in the production of the near infrared absorbing dye (A2-1) was carried out, except that 80.7 parts of 2,7-bis(trifluoromethyl)-9-fluorenone was used instead of 46.0 parts of 9-fluorenone used in the production of the near infrared absorbing dye (A2-1), to obtain 109.8 parts of the near infrared absorbing dye (A2-4) (yield: 91%). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as the near infrared absorbing dye (A2-4).

[0117] (Production of near infrared absorbing dye (A2-5)) Except for using 50.1 parts of 2-hydroxy-9-fluorenone instead of 46.0 parts of 9-fluorenone used in the production of near-infrared absorbing dye (A2-1), the same operation as in the production of near-infrared absorbing dye (A2-1) was carried out to obtain 83.9 parts of near-infrared absorbing dye (A2-5) (yield: 92%). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as near-infrared absorbing dye (A2-5).

[0118] (Production of near infrared absorbing dye (A2-6)) The same procedure as in the production of the near infrared absorbing dye (A2-1) was carried out except that 72.1 parts of 13H-benzo[g]indeno[2,1-b]quinoxalin-13-one was used instead of 46.0 parts of 9-fluorenone used in the production of the near infrared absorbing dye (A2-1), to obtain 107.1 parts of the near infrared absorbing dye (A2-6) (yield: 96%). As a result of mass analysis and elemental analysis by TOF-MS, it was identified as the near infrared absorbing dye (A2-6).

[0119] [ka]

[0120] <Thermoplastic resin (B)> (B-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264°C) (B-2) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265°C) (B-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Corporation, amorphous resin, glass transition temperature 145°C) (B-4) Topas 6013M-07 (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 142°C) (B-5) APEL (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135°C) (B-6) ULTEM (Polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217℃)

[0121] <Liquid resin (C)> (C-1): Uniol D-1200 (NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 1200, viscosity 200 mPa s) (C-2): PEG-400 (manufactured by Sanyo Chemical Industries, Ltd., polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 90 mPa s) (C-3): Uniol D-400 (NOF Corporation, polyalkylene glycol resin, polypropylene glycol resin, number average molecular weight 400, viscosity 100 mPa s) (C-4): Adeka Cizer RS-107 (ADEKA Corporation, ether ester resin, adipic acid ether ester resin, number average molecular weight 430, viscosity 20 mPa s) (C-5): Adeka Cizer PN-6810 (ADEKA Corporation, acetyl tributyl citrate, number average molecular weight 190, viscosity 43 mPa s) (C-6): Adeka Cizer PN-250 (ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 2100, viscosity 4,500 mPa s) (C-7): Adeka Cizer PN-350 (ADEKA Corporation, fatty acid polyester resin, adipic acid polyester resin, number average molecular weight 4500, viscosity 10,000 mPa s)

[0122] <Resin-type dispersant (F)> (Production of Resin-Type Dispersant Solution (F-1)) BYK-LPN6919 manufactured by BYK Japan, which has a non-volatile content of 60%, was mixed with the same amount of liquid resin (C-4) as BYK-LPN6919, heated to 100°C, reduced pressure, and the solvent was distilled off to obtain a basic resin-type dispersant solution (F-1) with a solid content of BYK-LPN6919 / liquid resin (C-4) = 1 / 1.

[0123] (Production of Resin-Type Dispersant Solution (F-2)) [Synthesis of ethylenically unsaturated monomer (b-5)] In a reaction vessel equipped with a stirrer and a thermometer, 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of tetrahydrofuran (THF) were charged and stirred at room temperature for 5 hours. After confirming that the reaction was complete by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following ethylenically unsaturated monomer (b-5) as a pale yellow transparent liquid (yield 82%). The obtained compound was identified by 1H-NMR.

[0124] Ethylenically unsaturated monomers (b-5) [ka]

[0125] [Synthesis of ethylenically unsaturated monomer (b-9)] In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of the ethylenically unsaturated monomer (b-5) obtained by the synthesis of the ethylenically unsaturated monomer (b-5) and 5 parts of ion-exchanged water were charged, and after stirring at room temperature, 8 parts of a 35% aqueous hydrochloric acid solution were added dropwise. The completion of the reaction was confirmed by amine value measurement, and 20 parts of an aqueous solution of the ethylenically unsaturated monomer (b-9) was obtained as a pale yellow transparent liquid. The obtained compound was identified by 1H-NMR.

[0126] Ethylenically unsaturated monomers (b-9) [ka]

[0127] In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the reaction system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of PGMAc (propylene glycol monomethyl ether acetate) were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 20 parts of PGMAc, 21.2 parts of ethylenically unsaturated monomer (b-5) as the second block monomer, and 27 parts of an aqueous solution of ethylenically unsaturated monomer (b-9) (non-volatile content 38%) were added to the reaction tank, and the mixture was stirred while maintaining the temperature at 110°C under a nitrogen atmosphere to continue the reaction. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a basic resin-type dispersant solution was obtained with an amine value per non-volatile content of 50 mgKOH / g, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass. Furthermore, a liquid resin (C-4) in an amount equal to the solid content of this resin-type dispersant solution was added, and the mixture was heated to 100°C and reduced pressure to distill off the PGMAc, thereby obtaining a resin-type dispersant solution (F-2) in which the solid content of the resin-type dispersant solution / liquid resin (C-4)=1 / 1.

[0128] Example 1 <Masterbatch manufacturing> One part of the near-infrared absorbing dye (A1-1) and 99 parts of the thermoplastic resin (B-1) were fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to produce a master batch (D-1).

[0129] <Film molding> 95 parts of the thermoplastic resin (B-1) as the diluted resin was mixed with 5 parts of the obtained master batch (D-1), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (X-1) having a thickness of 250 μm.

[0130] (Examples 2 to 22, Comparative Examples 1 to 3) The same procedure as in Example 1 was carried out except that the materials shown in Table 1 were used, and films (X-2) to (X-22) and (XY-1) to (XY-3) each having a thickness of 250 μm were molded. The following compounds were used.

[0131] (AY-1) Cyanine dye [ka]

[0132] (AY-2) Diimonium Dyes (N,N,N',N'-Tetrakis(p-diethylaminophenyl)-p-benzoquinone-bis(immonium) hexafluoroantimonate (AY-3) Phthalocyanine dye [ka]

[0133] Example 23 <Production of liquid masterbatch composition (E)> A liquid master batch composition (E-1) was prepared by kneading 10 parts of the near infrared absorbing dye (A1-1) and 90 parts of the liquid resin (C-1) with a two-roll mill.

[0134] <Film molding> 0.5 parts of the obtained liquid master batch composition (E-1) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (X-23) having a thickness of 250 μm.

[0135] (Examples 24 to 35) The same procedure as in Example 23 was carried out except that the materials shown in Table 1 were used, and films (X-24) to (X-35) each having a thickness of 250 μm were formed.

[0136] (Example 36) <Production of liquid masterbatch composition (E)> A liquid master batch composition (E-14) was prepared by dispersing 10 parts of the near infrared absorbing dye (A1-1), 20 parts of the resin-type dispersant (F-1), and 70 parts of the liquid resin (C-1) in a bead mill.

[0137] <Film molding> 0.5 parts of the obtained liquid master batch composition (E-14) was mixed with 99.5 parts of the thermoplastic resin (B-3) as the dilution resin, and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (X-36) having a thickness of 250 μm.

[0138] (Examples 37 to 49) The same procedure as in Example 36 was carried out except that the materials shown in Table 1 were used, and films (X-37) to (X-49) each having a thickness of 250 μm were formed.

[0139] [Table 1]

[0140] <Near infrared absorption> The absorption spectrum of the obtained film in the wavelength range of 700 to 1000 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation), and the near-infrared absorbing ability was evaluated according to the following criteria based on the absorbance at the maximum absorption wavelength. ○: The absorbance at the maximum absorption wavelength is 1.0 or more and less than 1.5. Good △: The absorbance at the maximum absorption wavelength is 0.5 or more and less than 1.0 (practical range) ×: The absorbance at the maximum absorption wavelength is less than 0.5, or 0.1 or more. Not practical. ××: The absorbance at the maximum absorption wavelength is less than 0.1. Not practical.

[0141] <Invisibility> Using the absorption spectrum in the wavelength range of 400 to 1000 nm obtained in the near-infrared absorption test, the invisibility was evaluated according to the following criteria based on the "average absorbance from 400 to 700 nm" when the absorbance at the maximum absorption wavelength of 700 to 1000 nm was normalized to 1. ○: Less than 0.05 △: 0.05 or more, less than 0.1 × : 0.1 or more

[0142] <Haze value> The haze value of the obtained film was measured using a haze meter (NDH4000, manufactured by Nippon Denshoku Industries Co., Ltd.) and evaluated according to the following criteria. ◎+: Less than 0.2 Very good ◎: 0.2 or more and less than 0.5 - Very good ○: 0.5 or more but less than 2 Good △: 2 or more but less than 5 Good × :5 or more Not practical

[0143] <Transparency> The transparency of the obtained film was evaluated visually. ○: No turbidity observed at all. △: Slight turbidity is observed. ×: Turbidity is clearly observed.

[0144] <Light resistance> A test film was prepared using the same procedure as for the near-infrared absorption evaluation, and placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and subjected to an irradiance of 47 mW / cm 2 , 30 The film was irradiated with broadband light of 0 to 800 nm and left for 24 hours. The test film was then taken out and the absorbance at the maximum absorption wavelength of the test film was measured, and the remaining ratio to the absorbance before the light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula. Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100 ○: Residual rate is 90% or more △: Residual rate is 85% or more but less than 90% ×: Residual rate is less than 85%.

[0145] <Heat absorption> The obtained test film was cut to 10 cm x 10 cm and a 50 W / m 2 A xenon lamp with an illuminance of 10 ... ○: 3℃ or higher △: 0.5℃ to less than 3℃ ×: Less than 0.5℃

[0146] <Laser welding> The obtained film was cut into two pieces measuring 10 cm x 2 cm, and the pieces were arranged so that the 10 cm x 1 cm portions overlapped each other, and the overlapping portions were irradiated with laser light using a semiconductor laser having a wavelength of 808 nm under conditions of a laser scanning speed of 1 cm / sec and a laser output of 30 W. As a result, it was confirmed that all of the films obtained in Examples 1 to 49 were welded.

[0147] <Laser marking> The obtained film was cut into two pieces measuring 4 cm x 1 cm, and the pieces were arranged so that the 1 cm x 1 cm portions overlapped each other, and the center of the overlapped portion was irradiated with laser light for one second using a semiconductor laser having a wavelength of 808 nm and a laser output of 30 W. As a result, it was confirmed that all of the films obtained in Examples 1 to 49 were blackened.

[0148] [Table 2]

[0149] In Comparative Examples 1 and 2, AY-1 and AY-2 did not show any absorbance at 700 to 1000 nm in the evaluation of near-infrared absorption, so no other tests were carried out. It is believed that they decomposed during melt kneading at 300°C.

[0150] <Near infrared transmission filter> (Example 50) <Masterbatch manufacturing> One part of near-infrared absorbing dye (A1-1), one part of Pigment Blue 15:3, one part of Pigment Yellow 147, one part of Solvent Red 52, and 96 parts of thermoplastic resin (B-1) were fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to prepare a master batch (DD-1).

[0151] <Film molding> 95 parts of the thermoplastic resin (B-1) as the dilution resin was mixed with 5 parts of the obtained master batch (DD-1), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (XX-1) having a thickness of 250 μm.

[0152] (Examples 51 to 71, Comparative Examples 4 to 6) The same procedure as in Example 1 was carried out except that the materials shown in Table 1 were used, and films (XX-2) to (X-22) and (XXY-1) to (XXY-3) each having a thickness of 250 μm were formed. (Example 72) <Production of liquid masterbatch composition (E)> A liquid master batch composition (EE-1) was prepared by kneading 2.5 parts of near-infrared absorbing dye (A1-1), 2.5 parts of Pigment Blue 15:3, 2.5 parts of Pigment Yellow 147, 2.5 parts of Solvent Red 52, and 90 parts of liquid resin (C-1) with a two-roll mill.

[0153] <Film molding> 98.0 parts of the thermoplastic resin (B-3) as the dilution resin was mixed with 2.0 parts of the obtained liquid master batch composition (E-1), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (XX-23) having a thickness of 250 μm.

[0154] (Examples 73 to 84) The same procedure as in Example 73 was carried out except that the materials shown in Table 1 were used, and films (XX-24) to (XX-35) each having a thickness of 250 μm were formed.

[0155] (Example 85) <Production of liquid masterbatch composition (E)> A liquid master batch composition (EE-14) was prepared by dispersing 2.5 parts of near-infrared absorbing dye (A1-1), 2.5 parts of Pigment Blue 15:3, 2.5 parts of Pigment Yellow 147, 2.5 parts of Solvent Red 52, a resin-type dispersant (F-1), and 80 parts of liquid resin (C-1) in a bead mill.

[0156] <Film molding> 98.0 parts of the thermoplastic resin (B-3) as the dilution resin was mixed with 2.0 parts of the obtained liquid master batch composition (EE-14), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (XX-36) having a thickness of 250 μm.

[0157] (Examples 86 to 98) The same procedure as in Example 85 was carried out except that the materials shown in Table 1 were used, to form films (XX-37) to (XX-49) each having a thickness of 250 μm.

[0158] [Table 3]

[0159] The obtained film was evaluated for suitability as a near-infrared filter. The filter function is, for example, whether it can transmit near-infrared rays and whether it can block light in other wavelength ranges. The transmittance at 900 nm and 940 nm, and the absorbance in the wavelength range of 400 to 800 nm were evaluated below.

[0160] <Absorption from 400 to 800 nm> The transmission spectrum of the obtained film was measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0161] <900nm transparency> The transmittance of the obtained film at 900 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). ○: 80% or more △: 40% or more but less than 80% ×: Less than 40%

[0162] <940nm transparency> The transmittance of the obtained film at 940 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). ○: 80% or more △: 40% or more but less than 80% ×: Less than 40%

[0163] <Transparency> The transparency of the obtained film was evaluated visually. ○: No turbidity observed at all. △: Slight turbidity is observed. ×: Turbidity is clearly observed.

[0164] <Haze value> The haze value of the obtained film was measured with a haze meter and evaluated according to the following criteria. ◎+: Less than 0.2 Very good ◎: 0.2 or more and less than 0.5 - Very good ○: 0.5 or more but less than 2 Good △: 2 or more but less than 5 Good × :5 or more Not practical

[0165] <Light resistance> The obtained film was subjected to a light resistance test using a light resistance tester (TOYOSEIKI "SUNTEST CP S+") and left for 24 hours. At this time, the test was performed with a broadband light of 300 to 800 nm at an irradiance of 47 mW / cm2. After that, the transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100, Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0166] [Table 4]

[0167] From the results of Tables 2 and 4, the near infrared absorbing dyes (A1-1 to A1-6) and (A2-1 to A2-6) absorb near infrared rays in the wavelength range of 700 to 800 nm and transmit near infrared rays of 900 nm and 940 nm. The films obtained in Examples 23 to 44 contain both the near infrared absorbing dye and a dye that absorbs visible light of 400 to 700 nm, so they absorb light in the entire range of 400 to 800 nm and transmit near infrared rays of 900 nm and 940 nm. Note that, although the results of Table 4 of Comparative Example 6 were good, invisibility was not obtained in Comparative Example 3, which used the same AY-3 as in Table 2.

Claims

1. A molding resin composition (excluding resin compositions to be molded to a thickness of 0.1 to 20 μm) which is a melt-kneaded mixture of a near-infrared absorbing dye (A) which is at least one compound represented by the following general formula (1) and general formula (2) and a thermoplastic resin (B), The thermoplastic resin (B) contains a crystalline resin having a melting point of 200° C. or higher, or an amorphous resin having a glass transition temperature of 120° C. or higher, The crystalline resin having a melting point of 200° C. or higher is a polyacetal resin, a polyphenylene sulfide resin, or a polyether ether ketone resin, The molding resin composition, wherein the amorphous resin having a glass transition temperature of 120° C. or higher is a cycloolefin resin, a polyetherimide resin, a polyamideimide resin, a polyethersulfone resin, a polysulfone resin, a polyarylate resin, a polyphenylene ether resin or a polycarbonate resin. 【Chemistry 1】 [In general formula (1), X １０１ ~X １１０ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ２ N.R. １０１ R １０２ , -COOR １０１ , -CONR １０１ R １０２ R represents a nitro group, a cyano group, or a halogen atom. １０１ , R １０２ each independently represents a hydrogen atom or an alkyl group which may have a substituent. １０１ ~X １１０ The substituents may be bonded to each other to form a ring. In general formula (2), Q １ , Q ４ , Q ５ and Q. ８ each independently represents a carbon atom or a nitrogen atom. １ , Q ４ , Q ５ Or Q ８ When is a nitrogen atom, X ２０１ , X ２０４ , X ２０５ Or X ２０８ is not assumed to exist. R １ ~R ５ each independently represents a hydrogen atom, a sulfo group, or —SO ３ － M ＋ or a halogen atom. ＋ represents an inorganic or organic cation. X ２０１ ~X ２０８ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR ６ R ７ , sulfo group, —SO ２ N.R. ８ R ９ , -COOR １０ , -CONR １１ R １２ , a nitro group, a cyano group or a halogen atom. ２０１ ~X ２０８ may be bonded to each other to form a ring. R ６ ~R １２ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. ６ and R ７ , R ８ and R ９、 R １１ and R １２ may be bonded to each other to form a ring.

2. 2. The molding resin composition according to claim 1, wherein the resin composition contains 0.001 to 5% by mass of the near infrared absorbing dye (A).

3. 3. The molding resin composition according to claim 1, comprising a melt-kneaded product of a liquid masterbatch composition (E) containing a near-infrared absorbing dye (A), which is at least one compound represented by general formula (1) or general formula (2), and a liquid resin (C) having a viscosity of less than 8,000 mPa·s at 25°C, and a thermoplastic resin (B).

4. 4. The molding resin composition according to claim 3, wherein the liquid masterbatch composition (E) further comprises a resin-type dispersant (F).

5. 5. The molding resin composition according to claim 3, comprising 50% by mass or more of the liquid resin (C) relative to 100% by mass of the liquid masterbatch composition (E).

6. The molding resin composition according to any one of claims 3 to 5, wherein the liquid resin (C) has a number average molecular weight of 200 to 2,000.

7. The molding resin composition according to any one of claims 3 to 6, wherein the liquid resin (C) is at least one selected from the group consisting of fatty acid polyester resins, polyalkylene glycol resins, and polyether ester resins.

8. The molding resin composition according to any one of claims 3 to 7, comprising 0.1 to 5 mass% of the liquid master batch composition (E) per 100 parts by weight of the resin composition.

9. A molded article obtained by molding the molding resin composition according to any one of claims 1 to 8.

10. A method for producing a molding resin composition (excluding resin compositions to be molded to a thickness of 0.1 to 20 μm) by melt-kneading a near-infrared absorbing dye (A), which is at least one compound represented by the following general formula (1) and general formula (2), and a thermoplastic resin (B) at 270° C. or higher, The thermoplastic resin (B) contains a crystalline resin having a melting point of 200° C. or higher, or an amorphous resin having a glass transition temperature of 120° C. or higher, The crystalline resin having a melting point of 200° C. or higher is a polyacetal resin, a polyphenylene sulfide resin, or a polyether ether ketone resin, The method for producing a molding resin composition, wherein the amorphous resin having a glass transition temperature of 120° C. or higher is a cycloolefin resin, a polyetherimide resin, a polyethersulfone resin, a polysulfone resin, a polyarylate resin, a polyphenylene ether resin or a polycarbonate resin. 【Chemistry 2】 [In general formula (1), X １０１ ~X １１０ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ２ N.R. １０１ R １０２ , -COOR １０１ , -CONR １０１ R １０２ R represents a nitro group, a cyano group, or a halogen atom. １０１ , R １０２ each independently represents a hydrogen atom or an alkyl group which may have a substituent. １０１ ~X １１０ The substituents may be bonded to each other to form a ring. In general formula (2), Q １ , Q ４ , Q ５ and Q. ８ each independently represents a carbon atom or a nitrogen atom. １ , Q ４ , Q ５ Or Q ８ When is a nitrogen atom, X ２０１ , X ２０４ , X ２０５ Or X ２０８ is not assumed to exist. R １ ~R ５ each independently represents a hydrogen atom, a sulfo group, or —SO ３ － M ＋ or a halogen atom. ＋ represents an inorganic or organic cation. X ２０１ ~X ２０８ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, an amino group, -NR ６ R ７ , sulfo group, —SO ２ N.R. ８ R ９ , -COOR １０ , -CONR １１ R １２ , a nitro group, a cyano group or a halogen atom. ２０１ ~X ２０８ may be bonded to each other to form a ring. R ６ ~R １２ R each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, or a pyridinyl group which may have a substituent. ６ and R ７ , R ８ and R ９、 R １１ and R １２ may be bonded to each other to form a ring.

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