JP2006241410A - Thermoplastic resin composition and application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition enabling melt molding, facilitating the molding, produced at a low production cost, exhibiting little absorption of visual light and large absorption of near infrared light, and maintaining the sufficient near infrared absorption function over wide temperature and moisture ranges; and to provide a molded article and a product such as an optical component comprising the composition. <P>SOLUTION: The thermoplastic resin composition contains a thermoplastic resin and a coloring matter, and has ≥80% maximum value of light transmittance at 1 mm optical path length and 400-700 nm wavelength, and ≤10% maximum value of the light transmittance at 1 mm optical path length and 700-1,000 nm wavelength, ≤5% rate of change of the maximum values of the light transmittance at 400-700 nm wavelength before and after the heating test of standing the resin still at 250°C for 30 min, and ≤10% maximum value of the light transmittance at 700-1,000 nm wavelength after the heating test. The molded article such as an optical lens comprises the resin composition. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition that is excellent in visible light transmittance, easy to mold, and has a sufficient near-infrared absorption function over a wide range of temperature and humidity, and an optical component such as an optical lens formed from the resin composition, and the same It is related with the optical lens unit containing.

  In an imaging apparatus using an imaging element such as a CCD or CMOS image sensor such as a digital camera, the imaging element has sensitivity not only in the visible region but also in the near-infrared region of a longer wavelength. Therefore, in order to obtain an image without distortion, it is necessary to incorporate a component that absorbs near-infrared light in the optical path from the subject to the image sensor (for example, in the lens unit).

  For such parts, as a requirement for improving the performance of the imaging device, the molding is easy, the manufacturing cost is low, the visible light absorption is low, the near infrared light absorption is large, and the durability is high. Is required.

  As such a component that absorbs near infrared rays, conventionally, a glass or resin plate coated with a near infrared absorption film or a near infrared reflection film, or a resin containing a substance having a near infrared blocking effect has been used. It was.

  For example, Patent Document 1 discloses optical components such as a camera photometric filter and a visibility correction filter by cast polymerization of an acrylic monomer composition mainly composed of a specific phosphate ester compound and a copper salt. Is described. However, this method can be applied only to a specific acrylic resin and requires a very long time for molding.

  As a resin molding method that can be efficiently performed in a short time, melt molding using a thermoplastic resin as a material can be considered. However, in the case of a thermoplastic resin containing a dye that absorbs near-infrared rays, the heat imposed during melt molding often reduces the near-infrared absorbing ability of the dye or increases the absorption of visible light, At present, it is difficult to find anything that can withstand the practical use of optical components.

JP-A-6-345877

  Based on the above background, the object of the present invention is to enable melt molding, easy molding, low production cost, low visible light absorption, large near infrared light absorption, and wide temperature and humidity range. An object of the present invention is to provide a resin composition and a molded body that maintain a sufficient near-infrared absorbing function, and products such as optical components made of these.

According to the invention:
[1] Contains a thermoplastic resin and a pigment, has a maximum light transmittance of 80% or more at an optical path length of 1 mm and a wavelength of 400 nm to 700 nm, and a light transmittance at an optical path length of 1 mm and a wavelength of 700 nm to 1000 nm. Is a thermoplastic resin composition having a maximum value of 10% or less, and in a heating test that is allowed to stand at 250 ° C. for 30 minutes, the rate of change before and after the heating test of the maximum value of light transmittance at a wavelength of 400 to 700 nm Is 5% or less, and the maximum value of the light transmittance at a wavelength of 700 to 1000 nm after the heating test is 10% or less.
[2] The resin composition according to [1], wherein the dye is a copper complex containing a phosphate group-containing compound and a copper atom.
[3] The resin composition according to [2], wherein the phosphate group-containing compound is represented by the formula (1):
Formula (1): PO (OH) _n {(-O-) _p -R ¹ } _3-n
(In the formula, R ¹ represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group , or an alicyclic group. These may have a ring-setting group. The substituent includes an alkyl group, an aryl group, Any one of an aralkyl group, an alkenyl group and an alicyclic group, p is 0 or 1, n is 1 or 2. (-O-) _p -R ^{1 When} there are a plurality of groups, they are the same or Different groups).
[4] The resin according to [2] or [3], wherein the total of C═O bond units and C—O—C bond units for one copper atom in the copper complex is 3 units or less. Composition.
[5] A molded article comprising the resin composition according to any one of [1] to [4];
[6] The molded article according to [5], which is an optical component;
[7] A molded article according to [6], which is an optical lens; and [8] an optical lens unit for an imaging device including the optical lens according to [7].

The resin composition and the molded product of the present invention have optical properties such that they absorb less visible light and can cut light in the near-infrared region efficiently, and can be melt-molded, so molding is very easy. In addition, the optical characteristics can be maintained stably for a long time under high temperature and high humidity.
In addition, since the optical component and optical lens of the present invention are made of the resin composition of the present invention, they are lighter, easier to mold, have higher impact resistance, and have better near-infrared absorption than glass products. Can be stably maintained, and is useful as a component of an apparatus such as an optical lens unit for an imaging apparatus.

  The resin composition of the present invention contains a thermoplastic resin and a pigment.

(Thermoplastic resin composition)
Examples of the thermoplastic resin include linear polyolefin, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyimide, polyacrylate, polyester sulfone, and alicyclic structure-containing polymer. From the viewpoints of long-term stability under high humidity and excellent optical properties, polycarbonate, polyacrylate, polyester sulfone, alicyclic structure-containing polymer resin, etc. are preferable. Polycarbonate, polyacrylate, alicyclic structure-containing polymer resin are preferable. Polymers are more preferred, and alicyclic structure-containing polymers are particularly preferred from the viewpoints of long-term stability under high temperature and high humidity and excellent optical properties.

  The alicyclic structure-containing polymer is a polymer containing an alicyclic structure in the repeating unit of the polymer. Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. Among these alicyclic structures, a cycloalkane structure is preferable if the purpose is to improve the thermal stability of a molded product obtained from the resin composition according to the present invention. Carbon number which forms an alicyclic structure is 4-30 normally, Preferably, it is 5-20, More preferably, it is 5-15. When the carbon number is within this range, a molded product having excellent heat resistance and flexibility can be obtained. This alicyclic structure may be present in either the main chain or the side chain of the polymer.

  There is no restriction | limiting in the content rate of the repeating unit containing an alicyclic structure in an alicyclic structure containing polymer, Although it selects suitably according to the property, physical property, etc. of the resin composition obtained, Usually, 50 mass% As mentioned above, Preferably it is 70 mass% or more, More preferably, it is 90 mass% or more, and an upper limit can be 100 mass%. When the content ratio of this repeating unit is too small, the heat resistance of the resulting resin composition may be lowered. In addition, the alicyclic structure containing polymer used for this invention may contain repeating units other than the repeating unit containing an alicyclic structure. Specific examples of the alicyclic structure-containing polymer include (1) a norbornene polymer, (2) a monocyclic olefin polymer, (3) a cyclic conjugated diene polymer, and (4) a vinyl alicyclic ring. And hydrocarbon hydrocarbon polymers. Among these, norbornene polymers are preferable from the viewpoints of heat resistance and mechanical strength.

  Examples of the norbornene-based polymer include a ring-opening polymer of a norbornene-based monomer, a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization, and these ring-opening polymers or ring-opening copolymers. Examples thereof include hydrides of polymers, addition polymers of norbornene monomers, and addition copolymers of norbornene monomers and other monomers capable of addition copolymerization therewith.

  Among these polymers and copolymers, a hydride of a ring-opening (co) polymer of a norbornene monomer is particularly preferable from the viewpoint of the heat resistance and mechanical strength of the resulting resin composition.

Examples of the norbornene-based monomer include bicyclo [2.2.1] hept-2-ene (common name: norbornene) and derivatives thereof (having substituents in the ring, the same shall apply hereinafter), tricyclo [5.2. 1.0 ^2,6] deca-3,8-diene (trivial name: dicyclopentadiene) and their derivatives, tetracyclo [9.2.1.0 ^2,10, 0 ^3,8] tetradeca-3,5, 7,12-tetraene (common name: metatetrahydrofluorene) and its derivatives, tetracyclo [6.2.1.1 ^3,6 . ^0,7 ] dodec-4-ene (common name: tetracyclododecene) and its derivatives.

  Examples of the substituent include an alkyl group having 1 to 12 carbon atoms, an alkylene group, a vinyl group, a phenyl group, and a biphenyl group. The norbornene-based monomer may have one or two or more of these substituents.

As the norbornene-based monomer having these substituents, 9-methyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methylidene-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethylidene-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-phenyltetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9- (biphenyl) -phenyltetracyclo [6.2.1 ^3,6 . ^0,7 ] dodec-4-ene and the like. These norbornene monomers may be used alone or in combination of two or more.

  Other monomers capable of ring-opening copolymerization with the norbornene-based monomer include cyclohexene, cycloheptene, cyclooctene and other monocyclic olefin monomers or cyclic diolefins having 5 to 20 carbon atoms, preferably 5 to 10 carbon atoms. A mer can be exemplified. A ring-opening polymer of a norbornene-based monomer and a ring-opening copolymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization in the presence of a known ring-opening polymerization catalyst in a solvent or It can be obtained by polymerization without solvent and usually at a polymerization temperature of −50 ° C. to 100 ° C. and a polymerization pressure of 0.01 to 5 MPa. The polymerization time may be appropriately adjusted according to the polymerization conversion rate of the monomer used.

  The solvent for the polymerization reaction can be used without limitation as long as it dissolves the polymer to be produced and does not inhibit the polymerization reaction. For example, aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, nitromethane and nitrobenzene , Nitrogen-containing hydrocarbons such as acetonitrile, ethers such as diethyl ether, tetrahydrofuran and dioxane, ketones such as acetone, ethyl methyl ketone and cyclohexanone, esters such as methyl acetate, ethyl propionate and methyl benzoate, chloroform, And halogenated hydrocarbons such as dichloromethane and trichlorobenzene. Among these, aromatic hydrocarbons, alicyclic hydrocarbons, ethers, ketones or esters are preferable. The amount of the solvent is appropriately adjusted in such a range that the monomer concentration in the polymerization reaction solution is 1 to 50% by mass, preferably 2 to 45% by mass, more preferably 5 to 40% by mass.

  Hydrogenated ring-opening polymers of norbornene monomers and hydrides of ring-opening copolymers of norbornene monomers with other monomers capable of ring-opening copolymerization are those of these ring-opening polymers or ring-opening copolymers. A known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to the reaction solution, and hydrogen is usually added to the reaction system at −10 to + 250 ° C., preferably 0 to 200 ° C., usually 0.01 to 10 MPa, preferably Is introduced at a pressure of 0.05 to 8 MPa, and is usually obtained by reacting for 0.1 to 50 hours. The hydrogenation rate is preferably 90% or more and more preferably 99% or more for the carbon-carbon unsaturated bond of the main chain.

  Examples of the other monomer capable of addition copolymerization with the norbornene-based monomer include, for example, a monocyclic olefin having 4 to 20 carbon atoms or a cyclic conjugated diene, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5- Non-conjugated dienes having 5 to 20 carbon atoms such as methyl-1,4-hexadiene, 1,7-octadiene and derivatives thereof, vinyl cycloalkenes such as vinylcyclohexene, vinyl alicyclics such as vinylcycloalkanes such as vinylcyclohexane Carbon such as hydrocarbon compounds, ethylene, propylene, 1-butene, 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and their derivatives Examples thereof include ethylene or α-olefin having a number of 2 to 20. Among these monomers, α-olefins, particularly ethylene is preferable. These monomers can be used alone or in combination of two or more.

  The addition polymer of the norbornene-based monomer and the addition copolymer of the norbornene-based monomer and another monomer that can be addition-copolymerized with the norbornene-based monomer are -50 ° C in a solvent in the presence of a known addition polymerization catalyst. It can be obtained by polymerization at a polymerization temperature of -100 ° C and a polymerization pressure of 0.01-5 MPa. The polymerization time may be appropriately adjusted according to the polymerization conversion rate of the monomer. As the solvent for the polymerization reaction, the same solvent as in the above ring-opening polymerization is used.

  In addition copolymerization of a norbornene monomer and another monomer copolymerizable therewith, in the resulting addition copolymer, a structural unit derived from the norbornene monomer and another monomer capable of addition copolymerization The amount of each monomer used is selected so that the ratio with the structural unit derived from is in the range of 50:50 to 99: 1, more preferably 70:30 to 97: 3, by mass ratio.

  Examples of the monocyclic olefin polymer include addition polymers of cyclic olefin monomers having a single ring such as cyclohexene, cycloheptene, and cyclooctene.

  Examples of the cyclic conjugated diene polymer include 1,2- or 1,4-addition polymers of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene, and hydrides thereof.

  Examples of the vinyl alicyclic hydrocarbon polymer include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and hydrides thereof, and vinyl aromatic hydrocarbon monomers such as styrene and α-methylstyrene. Hydride obtained by hydrogenating an aromatic moiety contained in a polymer obtained by polymerizing a vinyl, a cycloaliphatic hydrocarbon monomer or a vinyl aromatic hydrocarbon monomer, and the vinyl aromatic hydrocarbon monomer. Examples thereof include random copolymers with other polymerizable monomers, copolymers such as block copolymers, and hydrides of aromatic rings thereof. Examples of the block copolymer include diblock, triblock or higher multiblock, and gradient block copolymer.

  The alicyclic structure polymer suitably used in the present invention may have a polar group. However, since the molded body is preferably substantially hydrophobic, the content of the acceptable polar group in the alicyclic structure-containing polymer is preferably 0.8 mmol / g or less, more preferably 0.5 mmol. / G or less.

  Examples of the polar group include a hetero atom or an atomic group having a hetero atom, and examples of the hetero atom include an oxygen atom, a nitrogen atom, and a halogen atom. Among these heteroatoms, an oxygen atom and a nitrogen atom are preferable from the viewpoint of dispersibility and compatibility with the dye. Specific examples of the polar group include hydroxyl, carboxyl, oxy, epoxy, glycidyl, oxycarbonyl, carbonyloxy, carbonyl, amino, ester, halogen, cyano, and amide groups. , An imide group, a sulfonyl group, and a carbonyloxycarbonyl group. Among these, a carboxyl group, an oxycarbonyl group, a carbonyloxy group, a carbonyl group, an amide group, an imide group, and a carbonyloxycarbonyl group are preferable from the viewpoints of dispersibility and compatibility with the dye.

As the norbornene-based monomer having a polar group, 9-methoxycarbonyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-methyl-9-methoxycarbonyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-cyanotetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-diethylaminotetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-N, N′-dimethylaminocarbonyltetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, 9-ethyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene, N-methyl-bicyclo [2.2.1] hept-5-ene-2,3-carboximide, 9-phenylsulfonyltetracyclo [6.2.1 ^{3, 6} ． 0 ^2,7 ] dodec-4-ene, bicyclo [2.2.1] hept-5-ene-2-carboxaldehyde, bicyclo [2.2.1] hept-5-ene-2-carboxylic acid, bicyclo [2.2.1] hept-5-ene-2,3-carboxylic acid anhydride and the like.

  In the present invention, the mass average molecular weight (Mw) of the thermoplastic resin is preferably 500 to 500,000, more preferably 1,000 to 200,000, and particularly preferably 2,000 to 100,000. When the mass average molecular weight (Mw) of the thermoplastic resin is within this range, the mechanical strength and the moldability are highly balanced and suitable. The molecular weight can be measured using gel permeation chromatography (GPC).

  In the present invention, the glass transition temperature (Tg) of the thermoplastic resin used is usually 80 ° C. or higher, preferably 130 to 250 ° C. When the glass transition temperature of the thermoplastic resin is within this range, the polymer can withstand use at high temperatures and exhibit excellent durability without causing thermal deformation, stress concentration, and the like. The glass transition temperature can be measured by differential scanning calorimetry (DSC) according to JIS K7121.

(Dye)
The resin composition of the present invention contains a pigment in addition to the thermoplastic resin.

  In the present invention, the dye is a dye that gives the resin composition a light transmittance of 80% or more at a wavelength of 400 to 700 nm and a light transmittance of 10% or less at a wavelength of 700 to 1000 nm. Further, when the dye is subjected to a heating test in which the resin composition of the present invention is allowed to stand at 250 ° C. for 30 minutes, the change rate of the maximum value of the light transmittance at a wavelength of 400 to 700 nm before and after the heating test is 5 %, And the maximum light transmittance at a wavelength of 700 to 1000 nm after the heating test can be 10% or less.

  Specific examples of the dye include cyanine-based near infrared absorbers, pyrylium-based infrared absorbers, squarylium-based near-infrared absorbers, croconium-based infrared absorbers, azulenium-based near-infrared absorbers, naphthoquinone-based near-infrared absorbers, anthraquinone-based near-infrared absorbers. Infrared absorbers, indophenol-based near infrared absorbers, azo-based near infrared absorbers and the like can be mentioned. Further, phthalocyanine-based near-infrared absorbers, dithiol metal complex-based near-infrared absorbers, thiol nickel complex chromium / cobalt complex (Japanese Patent Publication No. 60-42269), chromium, cobalt complex salt (Japanese Patent Publication No. 60-42269) and copper Examples thereof include metal complexes such as complexes. Among these, a divalent copper complex is preferable because it efficiently absorbs near infrared rays from the transition of the ligand field.

  As the copper complex, a copper complex containing a phosphate group-containing compound and a copper atom (hereinafter simply referred to as “copper phosphate complex”) efficiently absorbs near infrared rays and efficiently transmits visible light. Therefore, it is preferable.

(Phosphate group-containing compound)
The phosphate group-containing compound constituting the copper phosphate complex is a component for forming a coordination bond or an ionic bond with a copper ion to disperse the copper ion in the resin. This phosphoric acid group-containing compound may be used alone or in combination of two or more.

As the phosphoric acid group-containing compound, a compound represented by the following formula (1) (hereinafter sometimes referred to as a phosphoric acid group-containing compound (1)) can be used:
Formula (1): PO (OH) _n {(-O-) _p -R ¹ } _3-n

In formula (1), R ¹ represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alicyclic group. These may have a substituent group. Such a substituent is any one of an alkyl group, an aryl group, an aralkyl group, an alkenyl group, and an alicyclic group. p is 0 or 1, and n is 1 or 2. In Formula (1), when there are a plurality of (—O—) _p —R ¹ groups, these are the same or different groups. Specifically, when n = 1, two (—O—) _p —R ¹ groups exist in the formula (1), but these may be the same structure or different structures. By appropriately selecting this group, it is possible to balance the compatibility with the thermoplastic resin, optical properties, and durability.

Examples of the substituent include linear, branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, and an octyl group; a phenyl group, Aryl groups such as tolyl group, dimethylphenyl group, 2,4,6-trimethylphenyl group and naphthyl group; aralkyl groups such as benzyl group, phenethyl group and naphthylmethyl group; vinyl group, propenyl group, butenyl group and octenyl group A monocyclic alicyclic group such as cyclopropane group, cyclobutane group, cyclopentane group, cyclohexane group, cycloheptane group, cyclooctane group; adamantane group, noradamantane group, norbornane group, norbornene group, dicyclopentadiene And polycyclic alicyclic groups such as a group. These may further have a substituent.
By appropriately selecting R ^{1 in the} formula (1), it is possible to balance the compatibility with the thermoplastic resin, optical characteristics, and durability.

  By appropriately selecting the structure of the phosphoric acid group-containing compound such as the phosphoric acid group-containing compound (1) and the ratio of the phosphoric acid group-containing compound and the copper atom, the copper phosphate complex has C = The sum total of O bond units and C—O—C bond units may be a specific number or less. When such a copper phosphate complex is used, a resin composition capable of particularly well maintaining the absorption characteristics under high temperature conditions such as melt molding conditions can be obtained, which is particularly preferable. Specifically, the total of C═O bond units and C—O—C bond units for one copper atom is preferably 3 units or less, more preferably 2 units or less, and even more preferably 1 unit or less. Discoloration when heat of 150 ° C. or higher is applied can be avoided, and a resin composition having excellent near infrared absorption ability can be obtained.

  The phosphate group-containing compound may be a low-molecular compound, an oligomer or a polymer, and preferably has a mass average molecular weight (Mw) of 100 to 500,000.

Although the preparation method of the phosphate group containing compound of this invention is not specifically limited, Specifically, it can synthesize | combine by making alcohol and various phosphorus compounds react. More specifically, it can be synthesized by any of the following methods (I) to (III). In the following methods (I) to (III), as the alcohol, a compound represented by the formula R ¹ —OH can be used. Examples of R ¹ include those similar to R ^{1 of the} compound represented by the formula (1) shown above.

Method (I): Method of reacting alcohol and phosphorus pentoxide in an appropriate organic solvent In this method, the organic solvent used for the reaction of alcohol and phosphorus pentoxide is an organic that does not react with phosphorus pentoxide. A solvent is mentioned. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, petroleum spirit; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene; diethyl ether, diisopropyl ether, dibutyl ether And ether solvents such as tetrahydrofuran; ketone solvents such as acetone, methyl ethyl ketone, and dibutyl ketone. Among these, toluene, xylene, and ether solvents are preferable.

  The reaction conditions between the alcohol and phosphorus pentoxide are such that the reaction temperature is 0 to 100 ° C., preferably 40 to 80 ° C., and the reaction time is 1 to 24 hours, preferably 4 to 9 hours.

  In method (I), a phosphate group-containing compound having a desired structure can be prepared by appropriately adjusting the ratio of alcohol to be subjected to the reaction and phosphorus pentoxide. For example, when the alcohol is monovalent, by using the alcohol and phosphorus pentoxide in a molar ratio of 3: 1, a phosphoric acid group-containing compound (hereinafter simply referred to as “the number n of hydroxyl groups” in formula (1) is 2). A mixture of “mono group-containing”) and a phosphoric acid ester compound (hereinafter simply referred to as “di-group-containing”) having a hydroxyl group number n of 1 in formula (1). Obtainable.

  Further, by selecting the ratio of alcohol to phosphorus pentoxide and the reaction conditions, the ratio of mono group content to di group content can be adjusted in a range where the molar ratio is 99: 1 to 40:60.

Method (II): Method in which alcohol and phosphorus oxyhalide are reacted in an appropriate organic solvent, and the resulting product is hydrolyzed by adding water. In this method, phosphorus oxyhalide is used as phosphorus oxychloride. Phosphorus and phosphorus oxybromide are preferably used, and phosphorus oxychloride is particularly preferable.

  Moreover, as an organic solvent used for reaction of alcohol and phosphorus oxyhalide, the organic solvent which does not react with phosphorus oxyhalide is mentioned. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, petroleum spirit; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene; diethyl ether, diisopropyl ether, dibutyl ether And ether solvents such as toluene, xylene, and ether solvents are preferable.

  The reaction conditions between the alcohol and phosphorus oxyhalide can be a reaction temperature of 0 to 110 ° C., preferably 40 to 80 ° C., and a reaction time of 1 to 20 hours, preferably 2 to 8 hours.

  Addition of water to the product obtained by the above reaction can be achieved by simply pouring excess water into the reaction mixture after completion of the reaction.

In the method (II), for example, by using alcohol and phosphorus oxyhalide in a molar ratio of 1: 1, it is possible to obtain a mono group. Also, reaction catalysts such as Lewis acid catalyst such as titanium tetrachloride (TiCl ₄ ), magnesium chloride (MgCl ₂ ), aluminum chloride (AlCl ₃ ), amines such as triethylamine and tributylamine, and hydrochloric acid scavengers such as pyridine. By using it, the mixture of mono group containing and di group containing can be obtained, and the ratio can be adjusted in the range from which molar ratio becomes 99: 1 to 1:99.

Method (III): A method of synthesizing a phosphonic acid group-containing compound by reacting an alcohol with phosphorus trihalide in an appropriate organic solvent, and then oxidizing the obtained phosphonic acid group-containing compound. In this case, phosphorus trichloride is preferably phosphorus trichloride or phosphorus tribromide, and phosphorus trichloride is particularly preferable.

  Moreover, as an organic solvent used for reaction of alcohol and phosphorus trihalide, the organic solvent which does not react with phosphorus trihalide is mentioned. For example, hydrocarbon solvents such as hexane, cyclohexane, heptane, octane, benzene, toluene, xylene, petroleum spirit; halogenated hydrocarbon solvents such as chloroform, carbon tetrachloride, dichloroethane, chlorobenzene; diethyl ether, diisopropyl ether, dibutyl ether And ether solvents such as hexane and heptane are preferable.

  The reaction conditions between the alcohol and phosphorus trihalide can be a reaction temperature of 0 to 90 ° C., preferably 40 to 75 ° C., and a reaction time of 1 to 10 hours, preferably 2 to 5 hours.

  As a means for oxidizing the phosphonic acid group-containing compound obtained by the above reaction, a phosphorohalolidate compound is synthesized by reacting the phosphonic acid group-containing compound with a halogen such as chlorine gas. Means for hydrolyzing the compound can be utilized. Here, the reaction temperature between the phosphonic acid group-containing compound and the halogen is preferably 0 to 40 ° C, particularly preferably 5 to 25 ° C.

  Moreover, before oxidizing a phosphonic acid group containing compound, the said phosphonic acid group containing compound can also be distilled and refine | purified.

In this method (III), for example, by using alcohol and phosphorus trihalide in a molar ratio of 3: 1, the digroup content can be obtained with high purity.
Also, by selecting the ratio of alcohol to phosphorus trihalide and the reaction conditions, a mixture of mono group-containing and di-group containing can be obtained, and the ratio of the molar ratio is 99: 1 to 1:99. It can be adjusted within the range.

(Preparation of copper phosphate complex)
The copper phosphate complex can be prepared by reacting the phosphate group-containing compound with a copper compound.

  Various types of copper compounds can be used. Specific examples include copper acetate, copper chloride, copper formate, copper stearate, copper benzoate, copper ethyl acetoacetate, copper pyrophosphate, copper naphthenate, copper citrate, copper sulfate, copper nitrate, copper carbonate, etc. Although a hydrate is mentioned, if a divalent copper ion can be supplied, it will not be limited only to these copper compounds.

  These compounding ratios when the phosphoric acid group-containing compound and the copper compound are reacted are such that the phosphoric acid group is usually 0.1 to 10 mol, preferably 0.5 to 6 mol, relative to 1 mol of the copper atom. Can do. When this ratio is 0.5 mol or more, copper atoms can be uniformly dispersed in the resin. Moreover, when this ratio exceeds 10 mol, since the ratio of the phosphate group which does not participate in the coordinate bond or ionic bond with a copper atom becomes excessive, the resin composition obtained by adding the said pigment | dye May be highly hygroscopic.

  The reaction between the phosphoric acid group-containing compound and the copper compound can be carried out by bringing them into contact under appropriate conditions. Specifically, (i) a method of mixing a phosphate group-containing compound and a copper compound and reacting both, (ii) a method of reacting a phosphate group-containing compound and a copper compound in an appropriate organic solvent, (Iii) The phosphate group-containing compound and the copper compound are reacted by bringing an organic solvent layer containing the phosphate group-containing compound into the organic solvent and an aqueous layer in which the copper compound is dissolved. Method, etc.

  Regarding the reaction conditions between the phosphate group-containing compound and the copper compound, the reaction temperature is 0 to 150 ° C., preferably 40 to 100 ° C., and the reaction time is 0.5 in any of the above methods (i) to (iii). 10 hours, preferably 1 to 7 hours. As a typical method for determining the end point of the copper phosphate complex formation reaction, the spectral transmission spectrum of the solution containing the copper phosphate complex is observed, and when the fluctuation of the spectral transmission spectrum is substantially eliminated, the end point of the reaction is determined. The method of judging.

  The organic solvent used in the method (ii) is not particularly limited as long as it can dissolve the specific phosphoric acid ester compound used. For example, aromatic hydrocarbons such as benzene, toluene and xylene; Alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; Glycol ethers such as methyl cellosolve and ethyl cellosolve; Ethers such as diethyl ether, diisopropyl ether and dibutyl ether; Ketones such as acetone and methyl ethyl ketone; Esters such as ethyl acetate Hexane, kerosene, petroleum ether and the like. Moreover, the organic solvent which has polymerizability, such as (meth) acrylic acid esters, such as (meth) acrylate, aromatic vinyl compounds, such as styrene and (alpha) -methylstyrene, can also be used. Of these, toluene is preferred.

  The organic solvent used in the method (iii) is not particularly limited as long as it is insoluble or hardly soluble in water and can dissolve the specific phosphoric acid ester compound used. ), Organic hydrocarbons exemplified in the method are aromatic hydrocarbons, ethers, esters, hexane, kerosene, (meth) acrylic acid esters, aromatic vinyl compounds, etc., preferably toluene. It is.

  In the reaction between the phosphate group-containing compound and the copper compound, the acid component is liberated. Since such an acid component may cause a decrease in moisture resistance and thermal stability of the resin composition, it is preferably removed as necessary.

  When the copper phosphate complex is produced by the method of (i) or (ii) above, the acid component is removed, for example, from the reaction mixture after completion of the reaction between the phosphate group-containing compound and the copper compound. This can be done by removing the components and organic solvent by distillation.

  Moreover, when manufacturing a copper phosphate complex by the method of said (iii), a copper phosphate complex can be obtained, removing an acid component, for example by performing the said manufacture in the following procedures: That is, water After neutralizing by adding an alkali to an organic solvent layer in which a phosphate group-containing compound is contained in an insoluble or hardly soluble organic solvent, this organic solvent layer is contacted with an aqueous layer in which a copper compound is dissolved Thus, the acid component can be removed by reacting the phosphate group-containing compound with the copper compound and then separating the organic solvent layer and the aqueous layer.

  Here, examples of the alkali include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonia and the like. According to such a method, a water-soluble salt is formed by the acid component and alkali released from the copper compound, and the salt is transferred to the aqueous layer, and the produced copper phosphate complex is formed in the organic solvent layer. Therefore, the acid component can be removed by separating the water layer and the organic solvent layer.

(Mixture and molding of thermoplastic resin and pigment)
In the resin composition of the present invention, the blending ratio when the thermoplastic resin and the pigment are blended is not particularly limited, and can be blended so as to satisfy characteristics such as specific light transmittance described later. . In particular, when a copper complex is used as the pigment, the content ratio is usually 0.1 to 50 parts by mass, preferably 0.1 to 40 parts by mass, more preferably 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin. It can be 0.1-30 mass parts. By setting this ratio to 0.1 parts by mass or more, the wavelength light in the near infrared region can be efficiently absorbed. On the other hand, by setting it to 50 parts by mass or less, the copper complex is uniformly distributed in the thermoplastic resin. It is easy to obtain a resin composition having excellent visible light transmittance.

  The resin composition of the present invention may optionally contain other optional components such as antioxidants, heat stabilizers, light stabilizers, weathering stabilizers, UV absorbers, lubricants, plasticizers, colorants, antistatic agents, etc. Various additives.

  As a method of blending the pigment and other optional components as required in the thermoplastic resin, a method in which the pigment is sufficiently dispersed in the thermoplastic resin can be appropriately selected. For example, there are a method of kneading the resin temperature in a molten state with a mixer, a twin-screw kneader or the like, a method of dissolving and dispersing in an appropriate solvent and removing the solvent by a solidification method, a casting method, or a direct drying method.

  Simultaneously with or after the operation of blending the dye, the resin composition can be further molded to obtain the molded article or optical component of the present invention. Such a molding method is not particularly limited. Depending on the purpose, injection molding, blow molding, injection blow molding, rotational molding, vacuum molding, extrusion molding, calendar molding, solution casting, etc. It can be a body. Of these various molding methods, the method of melting and molding a resin composition is particularly preferable because it can be processed into various shapes in a short time.

(Physical properties of resin composition)
In the resin composition of the present invention, the maximum value of the light transmittance in the wavelength range of 400 to 700 nm at an optical path length of 1 mm is 80% or more, and the light transmittance in the wavelength range of 700 to 1000 nm at an optical path length of 1 mm. The maximum value is 10% or less.

  When the maximum value of the light transmittance in the wavelength range of 400 to 700 nm is less than 80%, the transparency is not sufficient and it may not be practical when used as an optical material. Moreover, when the maximum value of the light transmittance in the wavelength range of 700 to 1000 nm exceeds 10%, the near infrared absorption ability is insufficient.

  Here, the optical path length generally refers to nL when a light beam passes through a medium having a refractive index n by a distance L. Moreover, the maximum value of the light transmittance in a specific wavelength range means the highest value among the values indicated when the light transmittance is measured over the entire wavelength range.

  As the light transmittance of the resin composition of the present invention, it is possible to employ a measured value for an optical path length of 1 mm of a plate obtained by molding the resin composition. The light transmittance is measured with a spectrophotometer (manufactured by JASCO Corporation: “UV-visible-near-infrared spectrophotometer V-570”) by continuously changing the wavelength in the range of 400 to 1000 nm. This can be achieved by determining the maximum light transmittance in the range of 700 nm and the maximum light transmittance in the range of 700 to 1000 nm.

  Further, the resin composition of the present invention is a heating test that is allowed to stand at 250 ° C. for 30 minutes, the change rate before and after the heating test of the maximum value of the light transmittance at a wavelength of 400 to 700 nm is within 5% and is heated. The maximum value of light transmittance at a wavelength of 700 to 1000 nm after the test is 10% or less.

In a heating test that is allowed to stand at 250 ° C. for 30 minutes, when the rate of change of the maximum light transmittance at a wavelength of 400 to 700 nm before and after the heating test is 5% or more, a molded product is obtained when the resin composition is melt-molded. The transparency of the is reduced. When the maximum value of the light transmittance at a wavelength of 700 to 1000 nm after the heating test exceeds 10%, the near-infrared absorbing ability of the molded article does not appear when the resin composition is melt-molded. This means that the dye may be altered by heat, and when the resin composition is melt-molded, the desired near-infrared absorbing ability is not expressed.
The change rate of the maximum value of the light transmittance at a wavelength of 400 to 700 nm before and after the heating test that is allowed to stand at 250 ° C. for 30 minutes can be obtained from the following formula.
Rate of change (%) = | T ₀ −T ₁ | / T ₀ × 100
In the above formula, T ₀ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm in a room temperature environment, and T ₁ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm after standing at 250 ° C. for 30 minutes. Represents.

  In the resin composition of the present invention, in a heating test that is allowed to stand at 250 ° C. for 30 minutes, the rate of change of the maximum light transmittance at a wavelength of 400 to 700 nm before and after the heating test is within 4%, and the heating test It is preferable that the maximum value of the light transmittance at a later wavelength of 700 to 1000 nm is 8% or less.

(Use)
The resin composition of the present invention can exhibit excellent characteristics such as the above-described absorption characteristics for specific wavelength light, molding processability, and stability in a high-temperature and high-humidity environment. Accordingly, the resin composition of the present invention and the molded product of the present invention comprising the resin composition of the present invention can be in various forms, and can be used in various applications as various functional materials or in combination with various functional materials. It can be used suitably.

  Specifically, for example, the molded article of the present invention has various forms such as a coat, a sheet, a disk, a fiber, a film, a prism, a lens, a column, a plate, and a film. Can do. Alternatively, the resin composition of the present invention can be used as an adhesive or an adhesive without being molded into a specific shape.

  Furthermore, various functional materials include coating materials (agents), hard coat materials (agents), bandpass functional materials such as low-pass filters, diffraction grating materials, electromagnetic shielding materials for removing EMI, birefringent plates, colorants, light Stabilizer, antioxidant, ultraviolet absorber, crystal, antistatic agent, thermal stabilizer, mold release agent, polymerization regulator, other optical materials, antireflection material (antireflection coating material), depolarizing plate, conductive layer And composite functional materials in combination with the above.

  Examples of the use of the resin composition of the present invention and the molded article of the present invention include window materials, agricultural coating materials, lighting fixtures, CCD lid materials, display front plates such as PDP front plates, display front filters, goggles, It is suitably used for optical components such as lenses such as glasses lenses or imaging element lenses, optical fibers, optical switches, optical filters, optical low-pass filters, visibility correction filters, photometric filters, and imaging filters.

  The optical component and the optical lens of the present invention are composed of the resin composition of the present invention. The optical lens unit for an image sensor according to the present invention includes the optical lens according to the present invention. The optical lens unit for an image sensor of the present invention can be a lens unit for an image sensor such as a CCD or a CMOS.

  In the optical lens unit for an image pickup device of the present invention, since the included optical lens also has a function as an infrared absorption filter, the near-infrared absorption filter required in the conventional product can be omitted, and the size can be reduced by reducing the number of components. Benefits such as cost reduction and price reduction can be obtained.

  Moreover, the optical component and the optical lens of the present invention can be easily manufactured in a free shape in a short time by melt molding. Therefore, the optical component and the optical lens of the present invention, and the optical lens unit for an image pickup device of the present invention including the optical component are further advantageous in terms of cost reduction.

  The optical component of the present invention can also be used as a near-infrared absorbing filter for a lens unit for an image sensor such as a CCD or CMOS. Since the optical component of the present invention can be lighter and more durable than a conventional glass filter, a unit that is less likely to be damaged by an impact such as dropping can be provided.

  The optical component of the present invention can be used as a cover material for an image sensor such as a CCD or CMOS. If the cover is provided on the image sensor, the apparatus can be reduced in size by omitting the near-infrared absorption filter.

  Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto. In the following description, “parts” and “%” represent mass ratios unless otherwise specified.

In the following examples and comparative examples, the test methods were as follows.
(1) Visible light transmittance and near-infrared absorption ability Using a flat plate having a thickness of 1 mm, a spectrophotometer (manufactured by JASCO Corporation: “UV-visible near-infrared spectrophotometer V-570”) has a wavelength of 400 to 1200 nm. The spectroscopic spectrum was measured. The measurement results of this test in the following examples and comparative examples are shown in the column “under normal temperature” in Table 1 below. If the maximum value of light transmittance at a wavelength of 400 to 700 nm is 80% or more, transparency is excellent in the visible light region, and excellent if the maximum value of light transmittance at a wavelength of 700 nm to 1000 nm is 10% or less. Evaluated as having infrared absorbing ability.
(2) Durability at 250 ° C. Using a flat plate with a thickness of 1 mm, the sample was allowed to stand in a high temperature environment at 250 ° C. for 30 minutes, then taken out and again measured for a spectrum at a wavelength of 400 to 1200 nm in a normal temperature environment. The maximum value of visible light transmittance at a wavelength of 400 to 700 nm after exposure to a high temperature environment was determined, and the rate of change was determined by comparison with the maximum value of visible light transmittance determined in (1). Moreover, the maximum value of the light transmittance in wavelength 700-1000nm after exposure to a high temperature environment was calculated | required. The measurement results of this test in the following Examples and Comparative Examples are shown in the column “After 250 ° C. Heat Test” in Table 1 below. Those having a change rate of the maximum transmittance in the visible light region within 5% and a maximum light transmittance in the range of 700 to 1000 nm of 10% or less are evaluated as having excellent durability.
In addition, the change rate of the maximum value of the light transmittance in wavelength 400-700nm before and behind the heat test which leaves still for 30 minutes at 250 degreeC was calculated | required from the following formula | equation.
Rate of change (%) = | T ₀ −T ₁ | / T ₀ × 100
In the above formula, T ₀ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm in a room temperature environment, and T ₁ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm after standing at 250 ° C. for 30 minutes. Represents.
(3) High-temperature and high-humidity durability Using a flat plate with a thickness of 1 mm, the sample was transferred to a high-temperature and high-humidity environment (80 ° C., relative humidity 90%) formed in a thermostatic bath, left for 1000 hours, then taken out and again at normal temperature. A spectral spectrum having a wavelength of 400 to 1200 nm was measured in a wet environment. The maximum value of visible light transmittance at a wavelength of 400 to 700 nm after exposure to a high temperature and high humidity environment was determined, and the rate of change was determined by comparison with the maximum value of visible light transmittance determined in (1). Moreover, the maximum value of the light transmittance in wavelength 700-1000nm after exposure to a high temperature, high humidity environment was calculated | required. The measurement results of this test in the following Examples and Comparative Examples are shown in the column “After High Temperature and High Humidity” in Table 1 below. Those having a change rate of the maximum transmittance in the visible light region within 5% and a maximum light transmittance in the range of 700 to 1000 nm of 10% or less are evaluated as having excellent durability.
The rate of change of the maximum value of the light transmittance at a wavelength of 400 to 700 nm before and after the high temperature and high humidity test can be obtained from the following equation.
Rate of change (%) = | T ₀ −T ₂ | / T ₀ × 100
In the above formula, T ₀ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm in a room temperature environment, and T ₂ represents the maximum value of light transmittance at a wavelength of 400 to 700 nm after the high temperature and high humidity test.

(Production Example 1: Production of thermoplastic resin (a))
500 parts of dehydrated cyclohexane, 0.82 part of 1-hexene (molecular weight regulator), 0.15 part of dibutyl ether (ring-opening polymerization catalyst system component) and 0.3 part of triisobutylaluminum (ring-opening polymerization catalyst system component) Into a reactor under a nitrogen atmosphere, mixed at room temperature and kept at 45 ° C., while maintaining 9-methyl-tetracyclo [6.2.1 ^3,6 . 0 ^2,7 ] dodec-4-ene (hereinafter abbreviated as “MTCD”) and 40 parts of a 0.7 mass% toluene solution (ring-opening polymerization catalyst system component) of tungsten hexachloride in 2 hours. It was continuously added over the course of polymerization. To the obtained polymerization solution, 1.06 part of butyl glycidyl ether and 0.52 part of isopropyl alcohol were added to inactivate the polymerization catalyst to stop the polymerization reaction, thereby obtaining a polymerization reaction solution containing an MTCD ring-opening polymer.

  Next, 270 parts of cyclohexane is added to 100 parts of the obtained polymerization reaction solution, and further 5 parts of nickel-alumina catalyst (manufactured by JGC Chemical Co., Ltd .: hydrogenation catalyst) is added, pressurized to 5 MPa with hydrogen, and stirred to 200 ° C. The mixture was heated and reacted for 4 hours to obtain a reaction solution containing 20% MTCD ring-opening polymer hydride. The resulting reaction solution was filtered to remove the hydrogenation catalyst, and then the antioxidant was added to the filtrate at a ratio of 0.1 part to 100 parts of the polymer (Irganox 1010, manufactured by Ciba Specialty Chemicals). Was added and dissolved. Subsequently, using a cylindrical concentrating dryer (manufactured by Hitachi, Ltd.), cyclohexane and other volatile components were removed at 270 ° C. and 1 kPa or less, then extruded into a strand having a diameter of 3 mm by an extruder, and after cooling, Cut with a length of 3 mm to produce an antioxidant-containing pellet of thermoplastic resin (a) (MTCD ring-opening polymer hydride) (hereinafter sometimes referred to as “thermoplastic resin (a) pellet”). did.

  The thermoplastic resin (a) (MTCD ring-opening polymer hydride) had a mass average molecular weight (Mw) of 40,000, a hydrogenation rate of 99.9%, and a glass transition temperature (Tg) of 148 ° C.

(Production Example 2-1: Production of phosphate group-containing compound)
96.5 parts of cyclohexanemethanol was dissolved in 200 parts of dimethoxyethane, and while cooling to 10 ° C. or less, 40 parts of diphosphorus pentoxide was added little by little, and the whole amount was stirred and added, and stirring was continued for 3 hours. Subsequently, it stirred and mixed at 60 degreeC for 3 hours.

After confirming the completion of the reaction by TLC (thin layer chromatography), dimethoxyethane and unreacted cyclohexanemethanol were distilled off under reduced pressure to obtain 124 parts of a colorless transparent viscous oily phosphate group-containing compound. . When obtained was measured infrared spectrum of the phosphoric acid group-containing compound, 1014 cm ^-1 derived from PO, peaks were observed in 1010 cm ^-1. Moreover, when the molecular weight was measured by GPC, the mass average molecular weight (Mw) of the obtained phosphate group-containing compound was 239.

(Production Example 3-1: Production of copper phosphate complex)
After 10 parts of the phosphate group-containing compound (having a cyclohexyl group) obtained in Production Example 2-1 was dissolved in 30 parts of toluene, 3.4 parts of copper acetate monohydrate was added and stirred, and the mixture (3 -1) was obtained. The mixture was heated to 110 ° C. for 2 hours at room temperature and refluxed for 4 hours. The end point of the reaction was determined by observing the spectral transmission spectrum of the reaction solution and determining that the end point of the reaction was when the fluctuation of the spectral transmission spectrum was substantially eliminated. Acetic acid and toluene were removed from the reaction solution under reduced pressure to obtain a copper phosphate complex. Analysis by gas chromatography revealed that the mono- and di-group contents of the phosphoric acid group-containing compound were almost the same, so that the obtained copper phosphate complex had 2 phosphoric acid groups per 1 mol of copper atoms. Contained 1 mole. As a result of analyzing the obtained copper phosphate complex by X-band ESR (Electron Spin Resonance), it was observed that there was almost no binuclear body of copper ions, and copper ions were present in an isolated state. It was found that the structure of the copper complex was a 6-coordinate octahedral structure. It can be seen from the amount of phosphoric acid group relative to the copper atom that the cyclohexyl group is 2-coordinated during 6-coordination. Therefore, this copper phosphate complex contained two cyclohexyl rings for one copper atom. When obtained was measured infrared spectra of copper phosphate complex, since no peaks observed due to C-O-C near peaks 1000 cm ^-1 due to C = O near 1725 cm ^-1, C It can be seen that there are no ═O and C—O—C bond units.

(Production Example 3-2: Production of Copper Phosphate Complex)
After dissolving 10 parts of butoxyethyl phosphoric acid (JP-506H, manufactured by Johoku Chemical Co., Ltd.) with 30 parts of toluene, 3.4 parts of copper acetate monohydrate was added and stirred to obtain a mixture (3-2). . A copper phosphate complex was obtained in the same manner as in Production Example 3-1, except that this was used instead of the mixture (3-1). As a result of analyzing the obtained copper phosphate complex by X-band ESR (Electron Spin Resonance), it was observed that there was almost no binuclear body of copper ions, and copper ions were present in an isolated state. It was found that the structure of the copper complex was a 6-coordinate octahedral structure. When analyzed by gas chromatography, the obtained copper phosphate complex is a mixture containing 51.2% of the mono group component, 47.6% of the di group component, and 1.2% of the phosphate component. Was confirmed. Since the molar ratio of the phosphoric acid group-containing compound and the copper compound is 2.1 mol, and the mono group component and the di group component are almost the same amount, the C—O—C bond unit per one copper atom is It can be said that it is 1.5 on average. It has a structure in which two bidentate coordination groups of the phosphate group are hexacoordinated and hexacoordinated, and two moles of water are coordinated in the axial position.

(Production Example 3-3: Production of copper phosphate complex)
30 parts of toluene with 1 part of (2-hydroxymethyl) methacrylate phosphoric acid (JPA-514, manufactured by Johoku Chemical Co., Ltd.) and 9 parts of the phosphate group-containing compound (having a cyclohexyl group) obtained in Production Example 2-1. After dissolution, 4.9 parts of copper benzoate was added and stirred to obtain a mixture (3-3). A copper phosphate complex was obtained in the same manner as in Production Example 3-1, except that this was used instead of the mixture (3-1). As a result of analyzing the obtained copper phosphate complex by X-band ESR (Electron Spin Resonance), it was observed that there was almost no binuclear body of copper ions, and copper ions were present in an isolated state. It was found that the structure of the copper complex was a 6-coordinate octahedral structure. As a result of analysis by gas chromatography, the ratio of the mono group component and the di group component was almost the same, so the phosphate group was calculated to be 6 mol per 1 mol of the copper atom, of which C═O bond unit and C— Since a methacryloyl group having an average of three O—C bond units is one coordinate and the remaining five coordinates are phosphate compounds containing a cyclohexyl group, a C═O bond unit per one copper atom and The average number of C—O—C bond units was calculated as 3 in total.

(Production Example 3-4: Production of copper phosphate complex)
After dissolving 5 parts of (2-hydroxymethyl) methacrylate phosphoric acid (JPA-514, Johoku Chemical Co., Ltd.) and 5 parts of butoxyethyl phosphoric acid (JP-506H, Johoku Chemical Co., Ltd.) with 30 parts of toluene, copper acetate 3.4 parts of monohydrate was added and stirred to obtain a mixture (3-4). A copper phosphate complex was obtained in the same manner as in Production Example 3-1, except that this was used instead of the mixture (3-1). As a result of analysis of the obtained copper phosphate complex by X-band ESR (Electron Spin Resonance), it was observed that almost no dinuclear copper ions were present, and copper ions were present in an isolated state. It was found that the structure of the copper complex was a 6-coordinate octahedral structure. When analyzed by gas chromatography, the ratio of the mono group component to the di group component was almost the same. The molar ratio of the phosphoric acid group-containing compound and the copper compound is 2.1 mol, and the mono group component and the di group component are almost the same amount. Therefore, the C = O bond unit and the C- It can be said that the average number of O—C bond units is 4.5. It has a structure in which two bidentate coordination groups of the phosphate group are hexacoordinated and hexacoordinated, and two moles of water are coordinated in the axial position.

(Production Example 3-5: Production of copper phosphate complex)
After dissolving 10 parts of (2-hydroxymethyl) methacrylate phosphoric acid (JPA-514, Johoku Chemical Co., Ltd.) with 30 parts of toluene, 3.4 parts of copper acetate monohydrate was added and stirred, and the mixture (3- 5) obtained. A copper phosphate complex was obtained in the same manner as in Production Example 3-1, except that this was used instead of the mixture (3-1). As a result of analysis of the obtained copper phosphate complex by X-band ESR (Electron Spin Resonance), it was observed that almost no dinuclear copper ions were present, and copper ions were present in an isolated state. It was found that the structure of the copper complex was a 6-coordinate octahedral structure. As a result of analysis by gas chromatography, the ratio of the mono group component and the di group component was almost the same, so that the phosphate group can be calculated to be 2.0 mol per 1 mol of the copper atom. The average number of C═O bond units and C—O—C bond units per copper atom is calculated to be 6 on average.

Example 1
After mixing 100 parts of the thermoplastic resin (a) pellets produced in Production Example 1 and 5 parts of the copper phosphate complex obtained in Production Example 3-1, a twin-screw extrusion kneader (TEM-) having a diameter of 35 mm. 35B, manufactured by Toshiba Machine Co., Ltd.) and kneaded at a resin temperature of 200 ° C. and pelletized with a pelletizer to obtain a pelletized resin composition.

  The obtained resin composition pellets were hot-pressed at a resin temperature of 200 ° C. and molded into a 1 mm × 100 mm × 60 mm plate to obtain a molded body. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability by the test methods described above. The results are shown in Table 1. The number of C═O bond units and C—O—C bond units is zero, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 2.6%, and the light transmittance at wavelengths of 700 nm to 1000 nm. The maximum value of the rate was 4.9%.

(Example 2)
Except having used the complex obtained by manufacture example 3-2 instead of the copper phosphate complex obtained by manufacture example 3-1, the pellet of a resin composition was obtained by operating like Example 1, Next, a molded body was obtained. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability by the test methods described above. The results are shown in Table 1. The average number of C═O bond units and C—O—C bond units is 1.5, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 3.9%, and the wavelength is 700 nm to 1000 nm. The maximum value of the light transmittance was 6.4%.

(Example 3)
Except for using the complex obtained in Production Example 3-3 instead of the copper phosphate complex obtained in Production Example 3-1, a resin composition pellet was obtained by operating in the same manner as in Example 1. Next, a molded body was obtained. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability. The results are shown in Table 1. There are three C═O bond units and three C—O—C bond units, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 4.4%, and the light transmittance at wavelengths of 700 nm to 1000 nm. The maximum value of the rate was 8.6%.

Example 4
Resin composition by operating in the same manner as in Example 1 except that methyl methacrylate resin (Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd., refractive index 1.49) was used instead of the thermoplastic resin (a) pellet. Pellets were obtained, and then a molded body was obtained. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability. The results are shown in Table 1. The number of C═O bond units and C—O—C bond units is zero, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 2.8%, and the light transmittance at wavelengths of 700 nm to 1000 nm. The maximum value of the rate was 5.8%.

(Example 5)
Instead of the thermoplastic resin (a) pellet, polycarbonate resin (Panlite L-1225, manufactured by Teijin Chemicals Ltd., refractive index 1.59) is used, and instead of the copper phosphate complex obtained in Production Example 3-1. A pellet of the resin composition was obtained by the same operation as in Example 1 except that the complex obtained in Production Example 3-2 was used. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability. The results are shown in Table 1. The number of C═O bond units and C—O—C bond units is 1.5, and the change rate of the transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 3.8% at a wavelength of 700 nm to 1000 nm. The maximum value of light transmittance was 7.9%.

(Comparative Example 1)
A pellet of the resin composition was obtained by operating in the same manner as in Example 1 except that the complex obtained in Production Example 3-4 was used instead of the copper phosphate complex obtained in Production Example 3-1. Then, a molded body was obtained. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability. The results are shown in Table 1. The number of C═O bond units and C—O—C bond units is 4.5, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 11.5%, and the wavelength is 700 nm to 1000 nm. The maximum value of light transmittance was 38.8%.

(Comparative Example 2)
Instead of the thermoplastic resin (a) pellets, methyl methacrylate resin (Acrypet VH, manufactured by Mitsubishi Rayon Co., Ltd., refractive index 1.49) was used instead of the copper phosphate complex obtained in Production Example 3-1. Except having used the complex obtained by manufacture example 3-5, the pellet of the resin composition was obtained by operating like Example 1, and the molded object was then obtained. The molded body was tested for visible light transmittance, near infrared absorption ability, 250 ° C. durability, and high temperature and high humidity durability. The results are shown in Table 1. There are 6 C═O bond units and 6 C—O—C bond units, the rate of change in transmittance at 400 to 700 nm before and after the 250 ° C. durability test is 39.8%, and the light transmittance at wavelengths of 700 nm to 1000 nm. The maximum value of the rate was 51.3%.

Claims (8)

  It contains a thermoplastic resin and a pigment, and the maximum value of light transmittance at an optical path length of 1 mm and a wavelength of 400 nm to 700 nm is 80% or more, and the maximum value of light transmittance at an optical path length of 1 mm and a wavelength of 700 nm to 1000 nm. Is a thermoplastic resin composition having a ratio of 10% or less, and in a heating test that is allowed to stand at 250 ° C. for 30 minutes, the rate of change of the maximum light transmittance at a wavelength of 400 to 700 nm before and after the heating test is 5%. And a maximum value of light transmittance at a wavelength of 700 to 1000 nm after the heating test is 10% or less.   The resin composition according to claim 1, wherein the dye is a copper complex containing a phosphate group-containing compound and a copper atom. The resin composition according to claim 2, wherein the phosphoric acid group-containing compound is represented by the formula (1):
Formula (1): PO (OH) _n {(-O-) _p -R ¹ } _3-n
(In the formula, R ¹ represents an alkyl group, an aryl group, an aralkyl group, an alkenyl group, or an alicyclic group. These may have a ring-setting group. The substituent includes an alkyl group, an aryl group, Any one of an aralkyl group, an alkenyl group and an alicyclic group, p is 0 or 1, n is 1 or 2. (-O-) _p -R ^{1 When} there are a plurality of groups, they are the same or Different groups).   4. The resin composition according to claim 2, wherein the total of C═O bond units and C—O—C bond units for one copper atom in the copper complex is 3 units or less. 5.   The molded object which consists of a resin composition of any one of Claims 1-4.   The molded article according to claim 5, which is an optical component.   The molded article according to claim 6, which is an optical lens.   An optical lens unit for an image pickup apparatus including the optical lens according to claim 7.