JP6007428B2 - Phthalocyanine compound and synthesis method thereof, near-infrared absorbing dye and near-infrared absorbing material - Google Patents

Description

  The present invention relates to a phthalocyanine compound that can absorb light of a specific wavelength.

  Conventionally, compounds capable of absorbing light in the near infrared region of 800 to 1000 nm have been required, and various phthalocyanine compounds have been proposed so far (see, for example, Patent Document 1). These phthalocyanine compounds have been suitably used for, for example, plasma displays (PDP) and heat ray cut films.

  The light emitting part of the plasma display is composed of a phosphor in which R (red), G (green), and B (blue) emit light and a cell in which neon gas containing 10% to 50% of xenon as a discharge gas is enclosed. When energy is applied to the cell by the discharge from the electrode, the enclosed discharge gas generates ultraviolet rays of 147 nm based on excited xenon and 173 nm based on excimer emission. These ultraviolet rays excite each phosphor of R, G, and B to emit light, whereby a color image is displayed.

  However, in the light component emitted from the PDP luminous body, in addition to RGB light emission, there is strong near-infrared light in the vicinity of 823 nm, 882 nm, 961 nm, and 980 nm based on the transition of xenon mixed in the discharge gas. These light components cause malfunctions in devices such as a remote control of a home appliance such as a television, a video deck, and an air conditioner and a wireless microphone. Therefore, in the PDP, an optical filter using a near-infrared absorbing dye is used to cut off absorption of these near-infrared light. The above phthalocyanine compounds have been applied to this optical filter.

  On the other hand, in order to cut the heat rays (infrared rays) from sunlight, in recent years, a heat ray cut film has been widely applied to the glass surface of vehicles such as automobiles and railways, buildings such as houses and buildings. Yes. In such a film, inorganic fine particles such as antimony-doped tin oxide (ATO) and tin-doped indium oxide (ITO) are used as a heat ray absorbent. These are excellent in heat ray shielding rate and visible light transmittance, but poor in heat ray shielding rate in the near infrared region of 800 to 1000 nm. In order to realize a heat ray cut film with a higher heat ray shielding rate, it is considered effective to use an organic dye having absorption in this wavelength region, and the above phthalocyanine compound is also applied to the heat ray cut film. It is believed that it can be applied.

JP 2011-12167 A

  An object of the present invention is to provide a phthalocyanine compound that has a wide absorption in the near-infrared region of 800 to 1000 nm and can contribute to the production of higher quality PDP and heat ray cut film in order to be applied to the above-described applications. It is said.

In order to achieve such an object, the present invention provides the following means (1) to ( 5 ).

(1): it has the formula where R ₁ to R ₄ in the following chemical formula 1 'are respectively represented by the following Table A, the half value width der Ru phthalocyanine compound or 80nm absorption maxima of 750~1050nm in the measurement of the transmission spectrum .

(2): General formula 'represented by the chemical formula 2' following chemical formula 2 of the phthalocyanine compound according to R ₅ to R ₈ are phthalonitrile compounds respectively represented by the following Table B in the the raw material (1) How to synthesize .

( 3 ): In a solution comprising the phthalocyanine compound according to (1) , wherein the concentration of the phthalocyanine compound is adjusted so that the minimum value of 750 to 1050 nm is 5 to 6% in the measurement of the transmission spectrum. A near-infrared absorbing dye having a visible light transmittance of 65% or more.

( 4 ): The phthalocyanine compound and the resin according to (1) are included , and the compounding amount of the phthalocyanine compound is 0.0005 to 20 parts by mass with respect to 100 parts by mass of the resin, and 800 to 1000 nm. A near infrared absorbing material that absorbs near infrared rays.

( 5 ): Near-infrared absorber as described in ( 4 ) used as a heat ray shielding material.

  According to the present invention, a phthalocyanine compound, a near-infrared absorbing dye, and a near-infrared absorbing material that have a wide absorption in the near-infrared region of 800 to 1000 nm and can contribute to the production of higher quality PDPs and heat ray cut films. Can be provided.

Explanatory drawing which concerns on 2nd embodiment of this invention. The graph which shows the light absorbency of the compound which concerns on the same embodiment and the synthesis example 1. The graph which shows the light absorbency of the compound which concerns on the same embodiment and the synthesis example 2. The graph which shows the light absorbency of the compound which concerns on the same embodiment and the synthesis example 3. FIG. The graph which shows the light absorbency of the compound which concerns on the same embodiment and the synthesis example 4. FIG. The graph which shows the light absorbency of the compound which concerns on the same embodiment and the synthesis example 5. FIG. The graph which shows the light absorbency of the compound which concerns on the embodiment and the synthesis example 6. FIG. The graph which shows the light absorbency of the compound which concerns on the embodiment and the synthesis example 7. The graph which shows the light absorbency of the compound which concerns on the embodiment and the synthesis example 8. The graph which shows the light absorbency of the compound which concerns on the same embodiment, an Example, and Comparative Examples 1-3.

<First embodiment>
Hereinafter, a first embodiment of the present invention will be described.

  (1): Chemical formula 1:

（式中Ｙ１〜Ｙ８は、それぞれ独立して炭素原子数１〜１０個のアルキル基、炭素原子数１〜１０個のアルコキシ基、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素数４〜６個の環状アルキルアミノ基、モルホリル基、ニトロ基、シアノ基、トリフルオロメチル基、水素原子、ハロゲン原子、カルボキシル基又はエステル基を表し；ｍは１〜５の整数を表し；Ｘは酸素原子又は硫黄原子を表し；Ｚ１〜Ｚ８はＸが酸素原子の場合、それぞれ独立して水素原子、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基、置換基Ａを有していてもよいフェニルオキシ基又は置換基Ｂを有していてもよいフェニルチオ基を表し、少なくとも４個は炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基であるか、或いはＺ１〜Ｚ８はＸが硫黄原子の場合、それぞれ独立して水素原子、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基又は置換基Ｂを有していてもよいフェニルチオ基を表し、少なくとも４個は置換基Ｂを有していてもよいフェニルチオ基を表すか又は炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基を表し；置換基Ａ及びＢは、それぞれ独立して炭素原子数１〜１０個のアルキル基、炭素原子数１〜１０個のアルコキシ基、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基、モルホリル基、ニトロ基、シアノ基、トリフルオロメチル基、水素原子、ハロゲン原子、カルボキシル基又はエステル基を表し；Ｍは水素原子、２価の金属原子、３価あるいは４価の置換金属又はオキシ金属を表す。）で示されるフタロシアニン化合物又は
化学式２：

Wherein Y1 to Y8 are each independently a monoalkylamino group having an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. , A dialkylamino group having an alkyl group having 1 to 10 carbon atoms, a cyclic alkylamino group having 4 to 6 carbon atoms, morpholyl group, nitro group, cyano group, trifluoromethyl group, hydrogen atom, halogen atom, carboxyl M represents an integer of 1 to 5; X represents an oxygen atom or a sulfur atom; and Z1 to Z8 each independently represents a hydrogen atom or a carbon number of 1 to 3 when X is an oxygen atom. A dialkylamino group having 10 alkyl groups, a cyclic alkylamino group having 4 to 6 carbon atoms, a phenyloxy group optionally having substituent A, or a substituent B Or a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, or a cyclic alkylamino group having 4 to 6 carbon atoms, or Z1 to Z8, wherein X is sulfur In the case of atoms, each independently a hydrogen atom, a monoalkylamino group having an alkyl group having 1 to 10 carbon atoms, a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, or 4 to 6 carbon atoms Represents one cyclic alkylamino group or a phenylthio group which may have a substituent B, at least four represent a phenylthio group which may have a substituent B, or 1 to 10 carbon atoms. A monoalkylamino group having an alkyl group, a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, and a cyclic alkylamino group having 4 to 6 carbon atoms Substituents A and B are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 10 carbon atoms, Dialkylamino group having an alkyl group having 1 to 10 carbon atoms, cyclic alkylamino group having 4 to 6 carbon atoms, morpholyl group, nitro group, cyano group, trifluoromethyl group, hydrogen atom, halogen atom, carboxyl M represents a hydrogen atom, a divalent metal atom, a trivalent or tetravalent substituted metal or an oxy metal) or a chemical formula 2:

（Ｙ９及びＹ１０は、それぞれ独立して炭素原子数１〜１０個のアルキル基、炭素原子数１〜１０個のアルコキシ基、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基、モルホリル基、ニトロ基、シアノ基、トリフルオロメチル基、水素原子、ハロゲン原子、カルボキシル基又はエステル基を表し；ｍは１〜５の整数を表し；Ｘは酸素原子又は硫黄原子を表し；Ｚ９及びＺ１０はＸが酸素原子の場合、それぞれ独立して水素原子、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基、置換基Ａを有していてもよいフェニルオキシ基又は置換基Ｂを有していてもよいフェニルチオ基を表し、少なくとも１個は炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基であるか、或いはＺ９及びＺ１０はＸが硫黄原子の場合、それぞれ独立して水素原子、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基又は置換基Ｂを有していてもよいフェニルチオ基を表し、少なくとも１個は置換基Ｂを有していてもよいフェニルチオ基を表すか又は炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基を表し；置換基Ａ及びＢは、それぞれ独立して炭素原子数１〜１０個のアルキル基、炭素原子数１〜１０個のアルコキシ基、炭素原子数１〜１０個のアルキル基を有するモノアルキルアミノ基、炭素原子数１〜１０個のアルキル基を有するジアルキルアミノ基、炭素原子数４〜６個の環状アルキルアミノ基、モルホリル基、ニトロ基、シアノ基、トリフルオロメチル基、水素原子、ハロゲン原子、カルボキシル基又はエステル基を表す。）で示されるフタロニトリル化合物を原料とするフタロシアニン化合物である。

(Y9 and Y10 are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a monoalkylamino group having an alkyl group having 1 to 10 carbon atoms, carbon Dialkylamino group having an alkyl group having 1 to 10 atoms, cyclic alkylamino group having 4 to 6 carbon atoms, morpholyl group, nitro group, cyano group, trifluoromethyl group, hydrogen atom, halogen atom, carboxyl group Or an ester group; m represents an integer of 1 to 5; X represents an oxygen atom or a sulfur atom; and Z9 and Z10 each independently represents a hydrogen atom or a carbon number of 1 to 10 when X is an oxygen atom. A dialkylamino group having one alkyl group, a cyclic alkylamino group having 4 to 6 carbon atoms, a phenyloxy group optionally having substituent A, or substituent B An optionally substituted phenylthio group, wherein at least one is a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, a cyclic alkylamino group having 4 to 6 carbon atoms, or Z9 and Z10 are X Each independently represents a hydrogen atom, a monoalkylamino group having an alkyl group having 1 to 10 carbon atoms, a dialkylamino group having an alkyl group having 1 to 10 carbon atoms, or 4 carbon atoms. Represents a phenylthio group optionally having 6 cyclic alkylamino groups or a substituent B, and at least one represents a phenylthio group optionally having a substituent B, or has 1 to 10 carbon atoms Monoalkylamino groups having 1 alkyl group, dialkylamino groups having 1 to 10 carbon atoms, and cyclic alkylamines having 4 to 6 carbon atoms. The substituents A and B each independently have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Monoalkylamino group, dialkylamino group having an alkyl group having 1 to 10 carbon atoms, cyclic alkylamino group having 4 to 6 carbon atoms, morpholyl group, nitro group, cyano group, trifluoromethyl group, hydrogen atom Represents a halogen atom, a carboxyl group, or an ester group).

  Hereinafter, the phthalocyanine compound represented by Formula 1 will be described.

  First, in the chemical formula 1, Y1 to Y8 may be the same or different, and when m is 2 or more, that is, when there are a plurality of Y1 to Y8, they are the same or different. May be.

  Z1 to Z8 and the substituents A and B may be the same or different.

  The “alkyl group having 1 to 10 carbon atoms” in the above chemical formulas 1 and 2 is a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, n-pentyl group, n-hexyl group, cyclohexyl group, An n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, a cyclohexylmethyl group, a 2-ethylhexyl group, and the like can be given.

  “The alkoxy group having 1 to 10 carbon atoms” in the above chemical formulas 1 and 2 is a linear, branched or cyclic alkoxy group having 1 to 10 carbon atoms. Specifically, methyloxy group, ethyloxy group, propyloxy group, isopropyloxy group, butyloxy group, sec-butyloxy group, tert-butyloxy group, isobutyloxy group, amyloxy group, isoamyloxy group, tert-amyloxy group, hexyl Examples thereof include an oxy group, a cyclohexyloxy group, a heptyloxy group, an isoheptyloxy group, a tert-heptyloxy group, an n-octyloxy group, an isooctyloxy group, a tert-octyloxy group, and a 2-ethylhexyloxy group. .

  The “dialkylamino group having an alkyl group having 1 to 10 carbon atoms” and the “monoalkylamino group having an alkyl group having 1 to 10 carbon atoms” in the above chemical formulas 1 and 2 are exemplified above. Such a dialkylamino group and monoalkylamino group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.

  Specific examples of the “cyclic alkylamino group having 4 to 6 carbon atoms” in the chemical formulas 1 and 2 include a pyrrolidino group, a piperidino group, and a homopiperidino group.

  In the above chemical formulas 1 and 3, “M” represents “a hydrogen atom, a divalent metal atom, a trivalent or tetravalent substituted metal or an oxymetal”. , Copper, nickel, palladium, cobalt and zinc. Moreover, as a most preferable thing, vanadyl or copper can be mentioned.

  And it is more preferable if at least four of Z1 to Z8 represent a dimethylamino group or a monobutylamino group.

  In addition, the phthalocyanine compound of the present invention preferably has a half width of an absorption maximum of 750 to 1050 nm in a transmission spectrum measurement of 80 nm or more.

  And in order to ensure the applicability to a filter, the near-infrared absorption dye which concerns on this invention has said phthalocyanine compound, and the minimum value of 750-1050 nm is 5-6 in the measurement of a transmission spectrum. %, The visible light transmittance is 65% or more in a solution in which the concentration of the phthalocyanine compound is adjusted to be%. And the near-infrared absorbing material according to the present invention comprises the phthalocyanine compound and a resin in order to take advantage of the characteristics of the phthalocyanine compound that can suitably absorb near infrared rays, and the blending amount of the phthalocyanine compound is It is 0.0005-20 mass parts with respect to 100 mass parts of said resin, and absorbs near infrared rays of 800-1000 nm, It is characterized by the above-mentioned.

  In addition, when the near-infrared absorbing material according to the present invention uses the phthalocyanine compounds having a plurality of different values of λmax, the range of 750 nm to 1050 nm is all included in the range of the half-value width of any phthalocyanine compound. Is preferred.

  And such a near-infrared absorber can be effectively applied not only as said filter but as a heat ray shielding material.

  In the phthalocyanine compound described above, for example, in the phthalocyanine skeleton represented by the following chemical formula (general formula) 3, R1, R4 at the α-position, R2, R3 at the β-position, and the central metal M are shown in Tables 1 to 10 below. Compound No. 1-No. The compound shown as 93 can be mentioned as an example.

＜第二実施形態＞
次に、上記第１実施形態にて記したフタロシアニン色素を用いてなるプラズマディスプレイ用フィルタ２をプラズマディスプレイＰＤに好適に適用した態様について詳述する。なお、本実施形態は、本発明をプラズマディスプレイＰＤに適用した一例を示したものであり、本発明を何ら限定するものではない。

<Second embodiment>
Next, an embodiment in which the plasma display filter 2 using the phthalocyanine dye described in the first embodiment is suitably applied to the plasma display PD will be described in detail. In addition, this embodiment shows an example in which the present invention is applied to the plasma display PD, and does not limit the present invention.

  The plasma display filter 2 according to the present invention is obtained by suitably applying the display filter 1 according to the first embodiment to a plasma display PD. That is, as shown in FIG. 1, the plasma display PD according to the present invention includes at least a plasma display main body PD1 for displaying an image and a plasma display filter 2 provided on the screen of the plasma display PD. It is a characteristic.

  Hereinafter, an example of the configuration of the plasma display PD and the plasma display filter 2 will be described with reference to the drawings.

  As shown in FIG. 1, the plasma display filter 2 is provided on the outside air side, and is provided on the plasma display PD side with a functional transparent layer 21 having antireflection and / or antiglare properties, and adheres to the screen. And a polymer film 23 provided as a substrate between the functional transparent layer 21 and the transparent adhesive layer 22. In addition, at least one of the functional transparent layer 21, the polymer film 23, and the transparent adhesive layer 22 contains the near-infrared absorbing dye NR made of the phthalocyanine compound according to the above embodiment. It is. In other words, at least one of the functional transparent layer 21, the polymer film 23, and the transparent adhesive layer 22 includes the phthalocyanine compound NR, thereby forming the plasma display filter 2 according to the first embodiment. It is what. In addition, as shown in the drawing, specifically, a polymer film 24 for increasing the thickness capable of containing the near-infrared absorbing dye NR may be further provided.

  Hereinafter, the plasma display filter 2 will be described.

  The plasma display filter 2 has a visible light transmittance of 30 to 85% as a whole.

  As described above, the functional transparent layer 21 is provided on the outside air side and has antireflection properties and / or antiglare properties. Specifically, one or more of hard coat properties, antireflection properties, antiglare properties, antistatic properties, antifouling properties, gas barrier properties, and UV protection properties, depending on the installation method on the display and the required functions It has the function of The visible light reflectance of the surface of the functional transparent layer 21 having antireflection properties is desirably 2% or less, preferably 1.3% or less, and more preferably 0.8% or less.

  As described above, the transparent adhesive layer 22 can be suitably attached to the plasma display main body PD1 by having adhesiveness.

  As described above, the polymer film 23 or the polymer film 24 for raising the bulk is provided as a substrate between the functional transparent layer 21 and the transparent adhesive layer 22, and the functional transparent layer 21 and the transparent adhesive are provided. Various existing materials and thicknesses can be adopted as long as the layer 22 can be favorably supported and has transparency.

  Therefore, as described above, the plasma display filter 2 according to the present embodiment includes the near-infrared absorbing dye NR for efficiently cutting near-infrared rays in the vicinity of 800 to 1000 nm emitted from the plasma display PD.

  The near-infrared absorbing dye NR is represented by the following chemical formula 4 to chemical formula 11, and the compound No. The compound example 3, the compound example 66, the compound example 67, the compound example 77, the compound example 79, and the compound example 91 to the compound phthalocyanine compound shown as the compound 93, and the minimum of 750 to 1050 nm in the measurement of the transmission spectrum. In the solution in which the concentration of the phthalocyanine compound is adjusted so that the value is 5 to 6%, the visible light transmittance is 65% or more.

これら化合物例３、化合物例６７、化合物例７７、及び化合物例７９として示されるフタロシアニン化合物の吸光度を図２及び図４〜図６にグラフとして示す。同図に示すように、本実施形態に係るフタロシアニン化合物は８７５、９１０、９６２、９７５ｎｍに吸収の幅が広いピークをそれぞれ有している。そのため、近赤外吸収色素ＮＲはこれらのうち１種のみでも有効であるが、４つの化合物を組み合わせて用いることにより、８００〜１０００ｎｍの近赤外線をより有効に吸収し得る。なお化合物例６６のフタロシアニン化合物は図３に示すように８９４ｎｍに幅広い吸収のピークを有している。化合物例９１のフタロシアニン化合物は図７に示すように８３０ｎｍに幅広い吸収のピークを有している。化合物例９２のフタロシアニン化合物は図８に示すように８１９ｎｍに幅広い吸収のピークを有している。化合物例９３のフタロシアニン化合物は図９に示すように９２４ｎｍに幅広い吸収のピークを有している。よってこれら化合物例６６及び化合物例９１〜化合物例９３も組み合わせて用いることにより、８００〜１０００ｎｍの近赤外線をより有効に吸収し得る。

The absorbances of the phthalocyanine compounds shown as Compound Example 3, Compound Example 67, Compound Example 77, and Compound Example 79 are shown as graphs in FIGS. 2 and 4 to 6. As shown in the figure, the phthalocyanine compound according to this embodiment has peaks with a wide absorption range at 875, 910, 962, and 975 nm, respectively. Therefore, the near-infrared absorbing dye NR is effective even with only one of these, but by using a combination of four compounds, the near-infrared light of 800 to 1000 nm can be more effectively absorbed. The phthalocyanine compound of Compound Example 66 has a broad absorption peak at 894 nm as shown in FIG. The phthalocyanine compound of Compound Example 91 has a broad absorption peak at 830 nm as shown in FIG. The phthalocyanine compound of Compound Example 92 has a broad absorption peak at 819 nm as shown in FIG. The phthalocyanine compound of Compound Example 93 has a broad absorption peak at 924 nm as shown in FIG. Therefore, by using these Compound Example 66 and Compound Example 91 to Compound Example 93 in combination, near infrared rays of 800 to 1000 nm can be absorbed more effectively.

  And the filter 2 for plasma displays which concerns on this embodiment has these phthalocyanine compounds and resin, and the compounding quantity of the said phthalocyanine compound is 0.0005-20 mass parts with respect to 100 mass parts of said resin, 800 It corresponds to the near-infrared absorbing material according to the present invention, characterized by absorbing near-infrared light of ˜1000 nm.

  By adopting the configuration as described above, the plasma display filter 2 according to the present embodiment also realizes the characteristic that the transmittance minimum at a wavelength of 800 to 1100 nm is 20% or less. For this reason, it is possible to prevent malfunctions of the peripheral electronic devices without adversely affecting the wavelengths used by the remote control, transmission optical communication, and the like.

  In addition, in order to prevent the pigment contained in the electromagnetic wave shielding body from being radiated from the display or being deteriorated by the ultraviolet rays included in the external light, the functional transparent layer 21 may have an ultraviolet cut property. . For example, a functional transparent layer 21 having an antireflection film composed of an inorganic thin film single layer or a multilayer that absorbs ultraviolet rays, a base material that forms a functional transparent film containing an ultraviolet absorber, or a hard coat film. is there. The type and concentration of the ultraviolet absorber are not particularly limited.

Further, at least one layer of the transparent adhesive layer 22 may contain an ultraviolet absorber.
It is important that the UV-cutting member is disposed between the surface on which the UV light is incident and the layer containing the dye, and the UV-cutting property varies depending on the durability of the dye and is not particularly limited.

  For example, as a modification to the above embodiment, the phthalocyanine compound and the resin described above are included, and the blending amount of the phthalocyanine compound is 0.0005 to 20 parts by mass with respect to 100 parts by mass of the resin. The heat ray shielding material characterized by absorbing near infrared rays of 800 to 1000 nm can be mentioned as an example of the near infrared absorbing material according to the present invention. Specifically, the said heat ray shielding material is affixed on the glass surface of buildings, such as vehicles, such as a motor vehicle and a railroad, a house, a building, and an antimony dope tin oxide (ATO) other than the said phthalocyanine compound. Inorganic fine particles such as tin-doped indium oxide (ITO) are used as heat ray absorbents. If it is such a thing, the performance which shields a heat | fever will be improved further by absorbing near infrared rays more than the conventional thing.

  Although the embodiment of the present invention has been described above, the specific configuration of each unit is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.

  For example, in the above embodiment, among the examples illustrated in the table, an embodiment using only a part of the compounds is disclosed, but of course, other compounds exemplified in the table or compounds not exemplified in the table are used. It may be. In addition, the specific composition of the resin used for the ultraviolet absorber and the specific mode of the pigment used in addition to the phthalocyanine compound are not limited to those of the above embodiment, but various modes including the existing ones Can be applied.

  In addition, the specific configuration of each part is not limited to the above embodiment, and various modifications can be made without departing from the spirit of the present invention.

Hereinafter, examples of the present invention, specifically, synthesis examples 1 to 8 in which the above phthalocyanine compound was synthesized will be described, but the present invention is not limited to the examples. For convenience of description in this specification, the description of the synthesis example 6 will be described after the description of the synthesis example 7.
<Synthesis Example 1>
A reaction flask equipped with a stirrer, thermometer, and Dimroth condenser was charged with 35.2 g of the compound represented by the following chemical formula 12, 4.40 g of formamide, 11.0 g of potassium tert-butoxide, and 90 ml of 1-hexanol, and the temperature was raised to 100 ° C. At this temperature, 4.40 g of vanadium trichloride was added. Next, the temperature was raised to 145 ° C. while allowing tert-butanol to flow out of the reaction system, and the mixture was stirred at this temperature for 8 hours. After allowing to cool, the reaction compound was diluted with 350 ml of methanol, and the precipitated dye was collected by filtration, washed with methanol, and dried at 100 ° C. to obtain a crude dye. This was purified by silica gel chromatography using a toluene developing solvent to obtain 14.5 g of a phthalocyanine compound of Compound Example 3 shown in FIG. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 875 nm, and the molar extinction coefficient was 1.14 × 10 ⁵ l / mol · cm.

＜合成実施例２＞
上記合成実施例１の化学式１２で示される化合物を下記化学式１３で示される化合物とした以外は同様にして、図３及び上記化学式５に示した化合物例６６のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは８９４ｎｍ、モル吸光係数は、１．１０×１０⁵ｌ／ｍｏｌ・ｃｍであった。

<Synthesis Example 2>
A phthalocyanine compound of Compound Example 66 shown in FIG. 3 and Chemical Formula 5 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 1 was changed to the compound represented by Chemical Formula 13 below. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 894 nm, and the molar extinction coefficient was 1.10 × 10 ⁵ l / mol · cm.

＜合成実施例３＞
上記合成実施例１の化学式１２で示される化合物を下記化学式１４で示される化合物とした以外は同様にして、図４及び上記化学式６に示した化合物例６７のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは９１０ｎｍ、モル吸光係数は、１．０７×１０⁵ｌ／ｍｏｌ・ｃｍであった。

<Synthesis Example 3>
A phthalocyanine compound of Compound Example 67 shown in FIG. 4 and Chemical Formula 6 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 1 was changed to the compound represented by Chemical Formula 14 below. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 910 nm, and the molar extinction coefficient was 1.07 × 10 ⁵ l / mol · cm.

＜合成実施例４＞
上記合成実施例１の化学式１２で示される化合物を下記化学式１５で示される化合物とした以外は同様にして、図５及び上記化学式７に示した化合物例７７のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは９６２ｎｍ、モル吸光係数は、１．３５×１０⁵1／ｍｏｌ・ｃｍであった。

<Synthesis Example 4>
A phthalocyanine compound of Compound Example 77 shown in FIG. 5 and Chemical Formula 7 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 1 was changed to the compound represented by Chemical Formula 15 below. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 962 nm, and the molar extinction coefficient was 1.35 × 10 ⁵ 1 / mol · cm.

また当該化合物例７７に係るフタロシアニン化合物は、特に青色を呈する４００ｎｍ付近の吸光度が顕著に低いという特性も合わせ持っており、当該特性により、例えばディスプレイのバックライトとしての青色の光を有効に透過し得るものと考えられる。
＜合成実施例５＞
上記合成実施例１の化学式１２で示される化合物を下記化学式１６で示される化合物とした以外は同様にして、図６及び上記化学式８に示した化合物例７９のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは９７５ｎｍ、モル吸光係数は、９．２４×１０⁴ｌ／ｍｏｌ・ｃｍであった。

In addition, the phthalocyanine compound according to Compound Example 77 also has a characteristic that the absorbance in the vicinity of 400 nm, which exhibits a blue color, is particularly low, and effectively transmits, for example, blue light as a backlight of a display. It is thought to get.
<Synthesis Example 5>
A phthalocyanine compound of Compound Example 79 shown in FIG. 6 and Chemical Formula 8 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 1 was changed to the compound represented by Chemical Formula 16 below. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 975 nm, and the molar extinction coefficient was 9.24 × 10 ⁴ l / mol · cm.

＜合成実施例７＞
攪拌機、温度計、ジムロート冷却管を付した反応フラスコに上記化学式１２で示される化合物１０．６g、１−ヘキサノール４０ｍｌ 、ＤＢＵ４．２６gを仕込み、１００℃に昇温し、ここに塩化銅（Ｉ）０．７９ｇを投入した。反応温度を１４０℃で１５時間反応し、放冷後トルエン２０ｍｌを加えた。反応液をメタノール１５０ｍｌで希釈し析出色素を濾集して、トルエン２０ｍｌに溶かし、メタノール１００ｍｌを加え固体を析出させた。濾集し１００℃で乾燥させ粗製色素を得た。これをトルエン展開溶媒としたシリカゲルクロマトグラフィーで精製して図８及び上記化学式１０に示した化合物例９２を５．３ｇ得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは８１９ｎｍ、モル吸光係数は、１．２１×１０⁵ｌ／ｍｏｌ・ｃｍであった。
＜合成実施例６＞
上記合成実施例７の化学式１２で示される化合物を上記化学式１３で示される化合物とした以外は同様にして、図７及び上記化学式９に示した化合物例９１のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは８３０ｎｍ、モル吸光係数は、１．３３×１０⁵ｌ／ｍｏｌ・ｃｍであった。
＜合成実施例８＞
上記合成実施例１の化学式１２で示される化合物を下記化学式１７で示される化合物とした以外は同様にして、図９及び上記化学式１１に示した化合物例９３のフタロシアニン化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは９２４ｎｍ、モル吸光係数は、１．２８×１０⁵ｌ／ｍｏｌ・ｃｍであった。

<Synthesis Example 7>
A reaction flask equipped with a stirrer, a thermometer, and a Dimroth condenser was charged with 10.6 g of the compound represented by the above chemical formula 12, 40 ml of 1-hexanol and 4.26 g of DBU, and the temperature was raised to 100 ° C., where copper (I) chloride was added. 0.79 g was charged. The reaction was conducted at 140 ° C. for 15 hours, and after cooling, 20 ml of toluene was added. The reaction solution was diluted with 150 ml of methanol, and the precipitated pigment was collected by filtration, dissolved in 20 ml of toluene, and 100 ml of methanol was added to precipitate a solid. It was collected by filtration and dried at 100 ° C. to obtain a crude pigment. This was purified by silica gel chromatography using a toluene developing solvent to obtain 5.3 g of Compound Example 92 shown in FIG. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 819 nm, and the molar extinction coefficient was 1.21 × 10 ⁵ l / mol · cm.
<Synthesis Example 6>
The phthalocyanine compound of Compound Example 91 shown in FIG. 7 and Chemical Formula 9 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 7 was changed to the compound represented by Chemical Formula 13. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 830 nm, and the molar extinction coefficient was 1.33 × 10 ⁵ l / mol · cm.
<Synthesis Example 8>
A phthalocyanine compound of Compound Example 93 shown in FIG. 9 and Chemical Formula 11 was obtained in the same manner except that the compound represented by Chemical Formula 12 of Synthesis Example 1 was changed to the compound represented by Chemical Formula 17 below. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 924 nm, and the molar extinction coefficient was 1.28 × 10 ⁵ l / mol · cm.

＜比較例１＞
特開２００７−５６１０５に記載の実施例２の合成法に従って下記化学式１８で示される化合物から下記化学式１９で示される公知の化合物を得た。クロロホルム溶液中で分光特性を測定した結果、λｍａｘは９０４ｎｍであった。

<Comparative Example 1>
According to the synthesis method of Example 2 described in JP-A-2007-56105, a known compound represented by the following chemical formula 19 was obtained from a compound represented by the following chemical formula 18. As a result of measuring the spectral characteristics in a chloroform solution, λmax was 904 nm.

＜比較例２＞
攪拌機、温度計、ジムロート冷却器を付した反応フラスコに下記化学式２０で示される化合物１．２ｇ、ホルムアミド０．１２ｇ、カリウムtert−ブトキシド０．３１ｇ、及び１−ヘキサノール１５ｍｌを仕込み、１１０℃に昇温し、この温度で三塩化バナジウム０．１２ｇを投入した。次いでtert−ブタノールを反応系外に流出させながら１４５℃まで昇温し、この温度で４時間攪拌した。放冷後、反応化合物をメタノール１２０ｍｌで希釈し、析出色素をろ集、メタノールで洗浄、１００℃で乾燥して粗製色素を得た。これをトルエン展開溶媒としたシリカゲルクロマトグラフィーで精製して、下記化学式２１で示される公知の化合物を０．３ｇ得た。λｍａｘは９６５ｎｍであった。

<Comparative example 2>
A reaction flask equipped with a stirrer, thermometer and Dimroth condenser was charged with 1.2 g of the compound represented by the following chemical formula 20, 0.12 g of formamide, 0.31 g of potassium tert-butoxide and 15 ml of 1-hexanol, and the temperature was raised to 110 ° C. At this temperature, 0.12 g of vanadium trichloride was added. Next, the temperature was raised to 145 ° C. while allowing tert-butanol to flow out of the reaction system, and the mixture was stirred at this temperature for 4 hours. After allowing to cool, the reaction compound was diluted with 120 ml of methanol, and the precipitated dye was collected by filtration, washed with methanol, and dried at 100 ° C. to obtain a crude dye. This was purified by silica gel chromatography using a toluene developing solvent to obtain 0.3 g of a known compound represented by the following chemical formula 21. λmax was 965 nm.

＜比較例３＞
特開２０１１−１２１６７に記載の実施例１の合成法に従って下記化学式２２で示される化合物から下記化学式２３で示される公知の化合物を得た。λｍａｘは８３６ｎｍであった。

<Comparative Example 3>
A known compound represented by the following chemical formula 23 was obtained from a compound represented by the following chemical formula 22 according to the synthesis method of Example 1 described in JP2011-12167A. λmax was 836 nm.

上記合成実施例２、合成実施例５及び合成実施例７に係る化合物について分光特性を測定した結果と、比較例１〜比較例３で合成した化合物について分光特性を測定した結果を図１０に示す。

FIG. 10 shows the results of measuring the spectral characteristics of the compounds according to Synthesis Example 2, Synthesis Example 5 and Synthesis Example 7, and the results of measuring the spectral characteristics of the compounds synthesized in Comparative Examples 1 to 3. .

  Table 11 shows the λmax and the half-value width for the compounds synthesized in Synthesis Examples 1 to 3, 5, 7 and Synthesis Example 8 and Comparative Examples 1 to 3.

以上のように、これら各合成例に係るフタロシアニン化合物は、８００〜１０００ｎｍの近赤外線をそれぞれ各比較例よりも有効に幅広く吸収し得るとともに、可視光に該当する波長の光を透過し易いという特性も併せ備えている。これらのことから、本発明に係るフタロシアニン化合物は、近赤外吸収色素及び近赤外吸収材として、好適に適用し得ることが明らかとなった。

As described above, the phthalocyanine compound according to each of these synthesis examples can absorb near infrared rays of 800 to 1000 nm more effectively than each comparative example, and easily transmits light having a wavelength corresponding to visible light. Is also provided. From these facts, it was revealed that the phthalocyanine compound according to the present invention can be suitably applied as a near infrared absorbing dye and a near infrared absorbing material.

  The present invention can be used as a phthalocyanine compound, a near infrared absorbing dye, and a near infrared absorbing material that absorb near infrared rays of 800 to 1000 nm.

  NR ... Near infrared absorbing dye

Claims (5)

It has the formula where R ₁ to R ₄ in the following chemical formula 1 'are respectively represented by the following Table A, the half value width der Ru phthalocyanine compound or 80nm absorption maxima of 750~1050nm in the measurement of the transmission spectrum.

The general formula is represented by the following chemical formula 2 ', and R in the chemical formula 2' _Five ~ R ₈ The method for synthesizing the phthalocyanine compound according to claim 1, using phthalonitrile compounds shown in Table B below as raw materials.

In a solution comprising the phthalocyanine compound according to claim 1, wherein the concentration of the phthalocyanine compound is adjusted so that the minimum value of 750 to 1050 nm is 5 to 6% in the measurement of the transmission spectrum. A near-infrared absorbing dye characterized in that the rate is 65% or more . It comprises the phthalocyanine compound according to claim 1 and a resin, and the blending amount of the phthalocyanine compound is 0.0005 to 20 parts by mass with respect to 100 parts by mass of the resin, and absorbs near infrared rays of 800 to 1000 nm. A near-infrared absorbing material characterized by The near-infrared absorbing material according to claim 4, which is used as a heat ray shielding material .

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