Composite and heat ray absorbing film

Abstract

The purpose of the present invention is to provide a composite and a heat-ray-absorbing film which have excellent heat-ray-absorbing characteristics without using a raw material having a high environmental burden. One of the embodiments is a complex comprising an amorphous sulfated polysaccharide and a polythiophene.

Description

Technical Field

[0001] The present invention relates to a composite and a heat ray absorbing film. Background Art

[0002] Approximately 40% of the radiant energy of sunlight is light in the wavelength region above infrared rays, and these lights have a high thermal effect, so they are called heat rays. It is known that window materials that require transparency and are used in office buildings, automobiles, etc. generally transmit heat rays well, so the temperature inside the room and inside the vehicle rises.

[0003] Therefore, in order to save energy, consideration is given to imparting a function of reflecting or absorbing heat rays to the window material. As a means of imparting a function of reflecting or absorbing heat rays (heat ray shielding property) to the window material, for example, a method of pasting an infrared absorbing film containing indium tin oxide (ITO) fine particles, antimony tin oxide (ATO) fine particles, cesium tungstate, etc. to window glass has been proposed.

[0004] Both antimony and cesium are toxic, and indium is a rare metal, so the cost is high, and alternative materials for these materials are urgently needed. In addition, when the addition amount of inorganic fine particles having a heat ray shielding property is increased to improve the heat ray shielding property and the solar transmittance is lowered, the visible light transmittance is also lowered in the same way. On the other hand, when the visible light transmittance is increased to allow external light to enter, there is a problem that the solar transmittance is increased and the heat ray shielding property is lowered.

[0005] For example, there is known a heat ray absorbing material containing: sulfated cellulose nanocrystals represented by the following Chemical Formula 1 obtained from fibrous cellulose having a fiber width in the range of 3 nm to 1500 nm, and polythiophene doped with the sulfated cellulose nanocrystals (for example, refer to Patent Document 1).

[0006] [Chemical Formula 1]

[0007]

[0008] R represented by Chemical Formula 1 1 ~R 6 each independently represents a hydrogen atom, a sulfonic acid group or an alkylsulfonic acid group having 1 to 6 carbon atoms, and at least one of R 1 ~R 6 is a sulfonic acid group or an alkylsulfonic acid group having 1 to 6 carbon atoms. In addition, n in Chemical Formula 1 represents the repetition in parentheses.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-111747 Summary of the Invention

[0012] Technical Problem to be Solved by the Invention

[0013] According to the research of the present inventors, among the heat ray absorbing materials disclosed in Patent Document 1, for example, the near-infrared absorption ability of light at 800 to 1800 nm is insufficient, and the heat ray absorption characteristics (obtained by dividing the absorbance of near-infrared light by the absorbance of visible light) are insufficient.

[0014] Therefore, an object of the present invention is to provide a composite and a heat ray absorbing film that do not use raw materials with a high environmental load and have excellent heat ray absorption characteristics.

[0015] Technical Means for Solving the Problem

[0016] The present inventors conducted in-depth research to solve the above problems and found a composite containing an amorphous sulfated polysaccharide and polythiophene, which does not use raw materials with a high environmental load and has excellent heat ray absorption characteristics, thus completing the present invention.

[0017] Examples of the present embodiment are as follows.

[0018] [1] A composite comprising an amorphous sulfated polysaccharide and polythiophene.

[0019] [2] The composite according to [1], wherein

[0020] the amorphous sulfated polysaccharide is at least one amorphous sulfated polysaccharide selected from carrageenan, SACRAN, rhamnan sulfate, fucoidan, chondroitin sulfate, porphyran, gloiopeltis polysaccharide, dermatan sulfate, and heparin.

[0021] [3] The composite according to [1] or [2], wherein

[0022] the amorphous sulfated polysaccharide is at least one carrageenan selected from λ-carrageenan, κ-carrageenan, and ι-carrageenan.

[0023] [4] The composite according to any one of [1] to [3], wherein

[0024] the amorphous sulfated polysaccharide is at least one sulfated polysaccharide selected from the sulfated polysaccharide represented by the following general formula (1) and the sulfated polysaccharide represented by the following general formula (2),

[0025] [Chemical Formula 2]

[0026]

[0027]

[0028] (In the general formulae (1) and (2), R is independently a hydrogen atom or a group represented by the following general formula (3), wherein at least one R in the brackets is a group represented by the following general formula (3), and n represents the number of repetitions in the brackets.)

[0029] [Chemical formula 3]

[0030]

[0031] (In general formula (3), X is hydroxyl or -O - (M m+ ) 1 / m , m is an integer greater than or equal to 1 and less than or equal to 3, M m+ It is an m-valent cation, and the wavy line is the bonding site with other atoms.)

[0032] [5] The complex according to any one of [1] to [4], wherein

[0033] The amount of substituents of sulfate groups in the amorphous sulfated polysaccharide is 2.0 mmol / g or more and 6.0 mmol / g or less.

[0034] [6] The complex according to any one of [1] to [5], wherein

[0035] The number of constituent monosaccharides of the amorphous sulfated polysaccharide is 200 or more.

[0036] [7] The complex according to any one of [1] to [6], wherein

[0037] The amorphous sulfated polysaccharide is iota-carrageenan.

[0038] [8] The complex according to any one of [1] to [7], wherein

[0039] The value obtained by dividing the absorbance at 1800 nm of the aqueous dispersion containing the composite at a content of 0.01 wt % by the absorbance at 500 nm is 4.5 or more.

[0040] [9] The complex according to any one of [1] to [8], wherein

[0041] The absorbance at 1800 nm of an aqueous dispersion containing the composite at 0.01 wt % is divided by the absorbance at 500 nm and is 4.5 or more. The absorbance at 500 nm is 0.010 or more and 0.200 or less. The absorbance at 1800 nm is 0.200 or more and 1.200 or less.

[0042]

[10] The complex according to any one of [1] to [9], wherein

[0043] The viscosity of the aqueous dispersion containing the complex at a content of 2 wt% as measured at a rotational speed of 6.0 rpm and 20°C is 100 mPa·s or more and 5000 mPa·s or less.

[0044]

[11] An aqueous dispersion comprising: an amorphous sulfated polysaccharide; polythiophene; at least one resin selected from a water-soluble resin and an aqueous emulsion resin; and water.

[0045]

[12] A heat ray absorbing film comprising the complex according to any one of [1] to

[11] .

[0046]

[13] The heat ray absorbing film according to

[12] , wherein

[0047] The value obtained by dividing the absorbance of the heat ray absorbing film at 1800 nm by the absorbance at 500 nm is 4.5 or more.

[0048]

[14] A laminate having an adhesive layer and a release layer laminated on one side of the heat ray absorbing film according to

[12] or

[13] .

[0049] Effects of the Invention

[0050] According to the present invention, it is possible to provide a complex and a heat ray absorbing film that do not use raw materials with a high environmental load and have excellent heat ray absorption characteristics. Detailed Description of Embodiments

[0051] Hereinafter, the complex, the aqueous dispersion, the heat ray absorbing film, and the laminate of the present embodiment will be described in detail.

[0052] One aspect of the present embodiment is a complex comprising an amorphous sulfated polysaccharide and polythiophene. The complex of the present embodiment does not use raw materials with a high environmental load and has excellent heat ray absorption characteristics. In addition, in the complex of the present embodiment, compared with a complex containing sulfated microcrystalline cellulose fibers and polythiophene, the solid content concentration in an aqueous dispersion having the same degree of viscosity can be increased. Therefore, when manufacturing a heat ray absorbing film having the same degree of dry film thickness, compared with a complex containing sulfated microcrystalline cellulose fibers and polythiophene, the aqueous dispersion prepared from the complex of the present embodiment can reduce the coating film thickness and can significantly shorten the drying time. Further, when coating with the same degree of coating film thickness, compared with a complex containing sulfated microcrystalline cellulose fibers and polythiophene, the film thickness of the heat ray absorbing film can be increased by using the aqueous dispersion prepared from the complex of the present embodiment.

[0053] Hereinafter, the present embodiment will be described in detail.

[0054] (Amorphous sulfated polysaccharide)

[0055] The complex and the aqueous dispersion of this embodiment contain an amorphous sulfated polysaccharide. Regarding the amorphous sulfated polysaccharide, it does not include polysaccharides showing crystallinity among sulfated polysaccharides such as sulfated cellulose. It should be noted that in the present invention, amorphous means that based on the measurement result of the diffraction intensity by an X-ray diffractometer, the crystallinity of cellulose I type calculated by the following mathematical formula 1 is less than 5%.

[0056] Crystallinity of cellulose I type (%) = [(I 200 - I am ) / I 200 × 100... Mathematical formula 1

[0057] Here, I 200 represents the X-ray diffraction intensity at 2θ = 22.6°, and I am represents the X-ray diffraction intensity at 2θ = 18.5°.

[0058] The amorphous sulfated polysaccharide is not particularly limited. For example, at least one amorphous sulfated polysaccharide selected from carrageenan, SACRAN, rhamnan sulfate, fucoidan, chondroitin sulfate, porphyran, gloiopeltis polysaccharide, dermatan sulfate, and heparin can be mentioned. As the amorphous sulfated polysaccharide, at least one amorphous sulfated polysaccharide selected from carrageenan, SACRAN, and gloiopeltis polysaccharide is preferable, and carrageenan is more preferable. These amorphous sulfated polysaccharides can stabilize the dispersion of polythiophene, so they are preferable.

[0059] As a preferable mode, the amorphous sulfated polysaccharide is at least one carrageenan selected from λ-carrageenan, κ-carrageenan, and ι-carrageenan. Carrageenan is a polysaccharide mainly extracted from natural red algae. Carrageenan has a structure in which D-galactose is bonded by alternately repeating α-1,3 bonds or β-1,4 bonds. Carrageenan is classified into three types, κ (kappa), ι (iota), and λ (lambda), according to the number of sulfate groups and the presence or absence of anhydro bonds, and any one can be used. Carrageenan can be, for example, a commercially available product, and the commercially available product can be used as it is, or a purified substance can be used.

[0060] As carrageenan, at least one carrageenan selected from ι-carrageenan and κ-carrageenan is preferable, and ι-carrageenan is more preferable.

[0061] One of the preferable modes of the amorphous sulfated polysaccharide is a sulfated polysaccharide which is at least one selected from the sulfated polysaccharide represented by the following general formula (1) and the sulfated polysaccharide represented by the following general formula (2).

[0062] [Chemical Formula 4]

[0063]

[0064]

[0065] (In general formulas (1) and (2), R is independently a hydrogen atom or a group represented by the following general formula (3). Among them, at least one R in the parentheses is a group represented by the following general formula (3), and n represents the number of repetitions in the parentheses.)

[0066] [Chemical Formula 5]

[0067]

[0068] (In general formula (3), X is a hydroxyl group or -O - (M m+ ) 1 / m , m is an integer of 1 or more and 3 or less, M m+ is an m-valent cation, and the wavy line is the bonding site with other atoms.)

[0069] In general formulas (1) and (2), at least one R in the parentheses is the group represented by the general formula (3). The proportion of the group represented by the general formula (3) is not particularly limited, and the amount of the substituent of the group represented by the general formula (3) (also referred to as a sulfate group) is preferably within the following range.)

[0070] In general formulas (1) and (2), n represents the number of repetitions in the parentheses. In other words, n represents the degree of polymerization. n is, for example, 100 or more, preferably 100 or more and 10,000 or less, more preferably 300 or more and 5,000 or less, and particularly preferably 500 or more and 2,000 or less. In the case within the above range, the viscosity during water dispersion is appropriate, so it is preferred.)

[0071] In general formula (3), X is a hydroxyl group or -O - (M m+ ) 1 / m . As M m+ , metal ions, ammonium ions, etc. can be cited. When m is 2 or 3, that is, when M m+ is a polyvalent cation, an ionic bond is formed between M m+ and two or three -SO3 - . As M m+ , when m is 1 and M m+ is M + (monovalent cation) is one of the preferred modes.)

[0072] Examples of the metal ion include alkali metal ions, alkaline earth metal ions, transition metal ions, and other metal ions.

[0073] Here, examples of the alkali metal ions include lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), cesium ion (Cs + ), etc. Examples of the alkaline earth metal ions include calcium ion (Ca 2+ ), strontium ion (Sr 2+ ), etc. Examples of the transition metal ions include iron ion, nickel ion, palladium ion, copper ion, silver ion, etc. Examples of the other metal ions include beryllium ion, magnesium ion, zinc ion, aluminum ion, etc.

[0074] Examples of the ammonium ion include not only NH4 + , but also ammonium ions derived from various amine sources in which one or more hydrogen atoms of NH4 + are optionally substituted with organic groups. Examples of the ammonium ion include NH4 + , quaternary ammonium cations, alkanolamine ions, pyridinium ions, etc.

[0075] As M m+ , from the viewpoint of the viscosity of the aqueous dispersion, sodium ion, potassium ion, calcium ion, or quaternary ammonium cation is preferred, sodium ion, potassium ion, or calcium ion is more preferred, and sodium ion (Na + ) is particularly preferred.

[0076] In the general formula (3), X is preferably a hydroxyl group or -O - M + , and particularly preferably a hydroxyl group or -O - Na + .

[0077] As X having the group represented by the general formula (3), there may be one kind or two or more kinds.

[0078] The amount of the substituent of the sulfate group of the amorphous sulfated polysaccharide is preferably 2.0 mmol / g or more and 6.0 mmol / g or less, more preferably 2.0 mmol / g or more and 4.0 mmol / g or less, and particularly preferably 2.5 mmol / g or more and 3.5 mmol / g or less. Within the above range, the dispersion of polythiophene can be promoted, so it is preferred.

[0079] The amount of the substituent of the sulfate group can be determined by, for example, the combustion absorption-ion chromatography (IC) method (combustion absorption-IC method, combustion IC method) described in the examples.

[0080] The number of constituent monosaccharides of the amorphous sulfated polysaccharide is not particularly limited, and is, for example, 200 or more, preferably 200 or more and 20,000 or less, more preferably 600 or more and 10,000 or less, and still more preferably 1,000 or more and 4,000 or less. It should be noted that the carrageenan and the constituent units of the general formulas (1) and (2) are disaccharides, so twice the degree of polymerization corresponds to the number of constituent monosaccharides. The number of constituent monosaccharides of the amorphous sulfated polysaccharide can be determined by the method described in the examples, for example.

[0081] (Polythiophene)

[0082] The composite and the aqueous dispersion of the present embodiment contain polythiophene. Polythiophene generally has a monomer unit containing a thiophene skeleton. It should be noted that the monomer unit refers to the constituent unit derived from the monomer that constitutes polythiophene, and is the repeating unit of polythiophene. As polythiophene, it preferably has a monomer unit (repeating unit) represented by the following general formula (4).

[0083] [Chemical formula 6]

[0084]

[0085] (In the general formula (4), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or R 7 and R 8 are connected and represent a dialkylene oxide group having 1 to 8 carbon atoms, an aromatic ring or an alicyclic ring having 3 to 7 members. n represents the number of repetitions in the parentheses.)

[0086] In the general formula (4), when R 7 and R 8 are alkyl groups having 1 to 8 carbon atoms, they can be either linear or branched. It should be noted that as the alkyl group, it is preferably an alkyl group having 1 to 6 carbon atoms.

[0087] In the general formula (4), when R 7 and R 8 are alkoxy groups having 1 to 8 carbon atoms, they can be either linear or branched. It should be noted that as the alkoxy group, it is preferably an alkoxy group having 1 to 6 carbon atoms.

[0088] When R 7 and R 8 are connected to form a dialkylene oxide group having 1 to 8 carbon atoms, the number of carbon atoms of the dialkylene oxide group is preferably 1 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms.

[0089] When R 7 and R 8When forming an aromatic ring by connection, for example, R 7 and R 8 can form a benzene ring together with the carbon atom to which they are bonded.

[0090] R 7 and R 8 When forming an alicyclic ring with 3 to 7 ring members by connection, as the alicyclic ring, a 4- to 7-membered ring is preferred, and a 5- to 6-membered ring is more preferred.

[0091] There is no particular limitation on the number of repeating units represented by the general formula (4) for forming polythiophene, that is, the value of n. For example, 2 to 50 can be cited. As the number of the repeating units increases, there is a tendency to improve properties such as the heat insulation property of polythiophene.

[0092] The monomer (thiophene) constituting the repeating unit represented by the general formula (4) is as shown in the following general formula (5).

[0093] [Chemical formula 7]

[0094]

[0095] (In the general formula (5), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or R 7 and R 8 are connected and represent a dialkyleneoxy group having 1 to 8 carbon atoms, an aromatic ring or an alicyclic ring having 3 to 7 ring members.)

[0096] As the thiophene represented by the general formula (5), a compound in which an alkyl group having 1 to 8 carbon atoms and / or an alkoxy group having 1 to 8 carbon atoms are independently substituted at the 3-position and 4-position of the thiophene skeleton is preferred; 3,4-disubstituted thiophenes in which a dialkyleneoxy group having 1 to 8 carbon atoms is formed at the 3-position and 4-position of the thiophene skeleton can be cited. More specifically, 3,4-dialkylthiophenes, 3,4-dialkoxythiophenes, 3,4-alkylenedioxythiophenes, etc. can be cited. Among them, 3,4-alkylenedioxythiophene is preferred.

[0097] As the thiophene represented by the general formula (5), for example, 3,4-dihexylthiophene, 3,4-diethylthiophene, 3,4-dipropylthiophene, 3,4-dimethoxythiophene, 3,4-diethoxythiophene, 3,4-dipropoxythiophene, 3,4-dibutoxythiophene, 3,4-methylenedioxythiophene, 3,4-ethylenedioxythiophene, 3,4-propylenedioxythiophene, etc. can be cited. Among them, 3,4-ethylenedioxythiophene (hereinafter sometimes simply referred to as EDOT) is preferred.

[0098] As specific examples of the polythiophene represented by the general formula (4), for example, poly(3,4-dihexylthiophene), poly(3,4-diethylthiophene), poly(3,4-dipropylthiophene), poly(3,4-dimethoxythiophene), poly(3,4-diethoxythiophene), poly(3,4-dipropoxythiophene), poly(3,4-dibutoxythiophene), poly(3,4-methylenedioxythiophene), poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), etc. can be cited. Among them, poly(3,4-ethylenedioxythiophene) abbreviated as PEDOT is preferred.

[0099] (Composite)

[0100] The composite of the present embodiment is a composite containing an amorphous sulfated polysaccharide and polythiophene. The composite of the present embodiment does not use raw materials with a high environmental load and has excellent heat ray absorption characteristics. The mass ratio of the amorphous sulfated polysaccharide to polythiophene constituting the composite of the present embodiment is not particularly limited, and the amorphous sulfated polysaccharide / polythiophene (mass ratio) is preferably 60 / 40 to 90 / 10, more preferably 50 / 50 to 85 / 15, and particularly preferably 60 / 40 to 80 / 20. The mass ratio of the amorphous sulfated polysaccharide to polythiophene can be measured by the method described in the examples.

[0101] Regarding the composite, the absorbance at 500 nm of the aqueous dispersion containing 0.01 wt% of the composite is 0.010 or more and 0.200 or less, and the absorbance at 1800 nm is 0.200 or more and 1.200 or less. Usually, the absorbance at 500 nm is smaller than the absorbance at 1800 nm. Preferably, the absorbance at 500 nm of the aqueous dispersion containing 0.01 wt% of the composite is 0.020 or more and 0.150 or less, and the absorbance at 1800 nm is 0.250 or more and 1.000 or less. More preferably, the absorbance at 500 nm is 0.040 or more and 0.100 or less, and the absorbance at 1800 nm is 0.300 or more and 0.800 or less. Since the composite having such characteristics has excellent heat ray absorption properties, the composite can be used as a heat ray absorber, a heat ray absorption film, etc.

[0102] Regarding the composite, the value obtained by dividing the absorbance at 1800 nm of the aqueous dispersion containing the composite at a content of 0.01 wt% by the absorbance at 500 nm is preferably 4.5 or more, more preferably 5.0 or more, and particularly preferably 5.5 or more. The higher the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm, the more excellent the heat ray absorption characteristics, so it is preferred. There is no particular limitation as the upper limit, and it is usually 8.0 or less. The composite having such characteristics is particularly excellent in heat ray absorption properties, so it is preferred.

[0103] In the composite of the present embodiment, compared with the composite containing sulfated microcrystalline cellulose fibers and polythiophene, the solid content concentration in the aqueous dispersion having the same viscosity can be increased. In one embodiment, the viscosity of the aqueous dispersion containing 2 wt% of the composite, measured at a rotational speed of 6.0 rpm and 20 °C, is preferably 100 mPa·s or more and 5000 mPa·s or less, more preferably 200 mPa·s or more and 2000 mPa·s or less, and particularly preferably 300 mPa·s or more and 1000 mPa·s or less. When manufacturing a heat ray absorbing film having the same dry film thickness, compared with the composite containing sulfated microcrystalline cellulose fibers and polythiophene, the aqueous dispersion prepared from the composite of the present embodiment can increase the solid content concentration, so that the coating film thickness can be thinned and the drying time can be significantly shortened. In addition, when coating with the same coating film thickness, compared with the composite containing sulfated microcrystalline cellulose fibers and polythiophene, the film thickness of the heat ray absorbing film can be increased by using the aqueous dispersion prepared from the composite of the present embodiment.

[0104] The composite may contain components other than amorphous sulfated polysaccharides and polythiophene, such as additives. As the additive, it may be an inorganic additive or an organic additive.

[0105] As the inorganic additive, for example, inorganic fine particles can be cited. As examples of the inorganic fine particles, fine particles of silica, mica, talc, clay, carbon, carbonates (such as calcium carbonate, magnesium carbonate), oxides (such as alumina, titanium oxide, zinc oxide, iron oxide), ceramics (such as ferrite) or mixtures thereof can be cited. The inorganic fine particles may be contained in the composite in an amount in the range of 0.09 to 5% by mass, for example.

[0106] The composite may contain a functional compound as an organic additive. As the functional compound, pigments, UV absorbers, antioxidants, antistatic agents, and surfactants can be cited. The organic additive may be contained in the composite in an amount in the range of 0.09 to 5% by mass, for example.

[0107] The composite is usually solid. The substance obtained by dispersing the composite in a dispersion medium is denoted as the dispersion of the composite, and the substance obtained by dispersing it in water is denoted as the aqueous dispersion of the composite.

[0108] (Method for manufacturing the composite)

[0109] The composite is obtained by polymerizing thiophene to form polythiophene in the coexistence of, for example, amorphous sulfated polysaccharides and thiophene. In one embodiment, the amorphous sulfated polysaccharides are doped into the polythiophene by the polymerization of the thiophene.

[0110] Specifically, the complex can be produced by oxidatively polymerizing the thiophene represented by the general formula (5) in the presence of an amorphous sulfated polysaccharide, a solvent, and an oxidizing agent. For example, the thiophene represented by the general formula (5) and an oxidizing agent can be added to a dispersion (e.g., an aqueous dispersion) prepared by previously dispersing an amorphous sulfated polysaccharide in a dispersion medium, and the thiophene is polymerized to form polythiophene, and the complex is obtained in a state where the complex is dispersed in the dispersion medium. In the obtained complex, the binding mode of polythiophene and the amorphous sulfated polysaccharide is not desired to be interpreted in a limited manner, and it is considered that the complex is formed in a state where the anions of the amorphous sulfated polysaccharide are doped in the polythiophene obtained by the polymerization reaction.

[0111] In the production of the complex, the amounts of the thiophene represented by the general formula (5) and the amorphous sulfated polysaccharide used as raw material compounds may be adjusted in such a manner that the above-described complex can be obtained.

[0112] The oxidizing agent (sometimes referred to as a polymerization initiator) used in the production of the complex is not particularly limited as long as it can oxidatively polymerize the thiophene represented by the general formula (5). Examples thereof include persulfuric acid, sodium persulfate, potassium persulfate, ammonium persulfate, inorganic iron oxide salts, organic iron oxide salts, hydrogen peroxide, potassium permanganate, potassium dichromate, alkaline perborate, iron(III) sulfate, iron(III) chloride, and the like. Among them, persulfuric acid, sodium persulfate, potassium persulfate, ammonium persulfate, iron(III) sulfate, and iron(III) chloride are preferred. These oxidizing agents may be used alone or in combination of two or more.

[0113] In the production of the complex, the amount of the oxidizing agent used is not particularly limited. For example, per 1 mole of the thiophene represented by the general formula (5), it is preferably in the range of 0.1 equivalent to 5 equivalents, and more preferably in the range of 0.3 equivalent to 2 equivalents.

[0114] When producing the complex, when the amount of the monosaccharide constituting the amorphous sulfated polysaccharide is 1 mole, the amount of the thiophene is preferably in the range of 0.2 to 5 moles, and more preferably in the range of 0.4 to 2.0 moles.

[0115] In the production of the composite (polymerization of polythiophene (e.g., PEDOT)), the concentration of the polymerization initiator relative to thiophene (e.g., EDOT) can be in the range of, for example, 5 mol% to 92.5 mol% or 5.7 mol% to 92.5 mol%. From the aspect of being able to further improve the near-infrared light absorption characteristics, it is preferred that the concentration of the polymerization initiator be in the range of 11.6 mol% to 46.2 mol%. It should be noted that when the polymerization initiator is insufficient, the polymerization of polythiophene (e.g., PEDOT) is difficult, and when the polymerization initiator is excessive, the degree of polymerization of polythiophene (e.g., PEDOT) tends to become smaller. And it is considered that for the polymer (polythiophene) outside the system of the amorphous sulfated polysaccharide, a polymer with a very small degree of polymerization is formed.

[0116] For the dispersion medium used in the production of the composite, as long as the polymerization reaction of thiophene can be carried out. Specifically, an aqueous solvent can be mentioned, and preferably water can be mentioned. In addition, for the said solvent, an aqueous solvent obtained by mixing a lower alcohol such as methanol and ethanol, a polar organic solvent such as acetone and acetonitrile with water can be used. These solvents can be used alone in 1 kind, or can be used in combination of 2 or more kinds.

[0117] In the production of the composite, there is no particular limitation on the amount of use of the said solvent. For example, per 1 mole of thiophene represented by the general formula (5), it is preferably in the range of 1000 ml to 50000 ml, and more preferably in the range of 10000 ml to 40000 ml.

[0118] For the reaction time and reaction temperature in the production of the composite, they can be appropriately set according to the types of thiophene, amorphous sulfated polysaccharide, oxidant, etc. used as raw material compounds. The reaction temperature in the production of the composite is, for example, preferably in the range of 5 °C to 90 °C, and more preferably in the range of 10 °C to 80 °C. The reaction time in the production of the composite is, for example, preferably in the range of 1 hour to 96 hours, and more preferably in the range of 5 hours to 48 hours.

[0119] As described above, by polymerizing the thiophene represented by the general formula (5) in the presence of the amorphous sulfated polysaccharide, a dispersion solution of the composite is obtained. For the composite, it can be obtained in the state of the obtained dispersion liquid (dispersion liquid of the composite) after the reaction, or can be obtained as a film-like composite (e.g., heat ray absorption film) by coating on a substrate and drying after purifying the dispersion liquid of the composite and adding additives as needed, or can be obtained as a solid (e.g., powder-like) composite by separating and purifying the composite as needed. The solid (e.g., powder-like) composite can be used as an additive for a heat ray absorption film, or a film-like composite (e.g., heat ray absorption film) can be manufactured by secondary processing.

[0120] (aqueous dispersion)

[0121] An aqueous dispersion according to one embodiment contains an amorphous sulfated polysaccharide, a polythiophene, and water. Further, an aqueous dispersion according to another embodiment contains an amorphous sulfated polysaccharide, a polythiophene, at least one resin selected from a water-soluble resin and an aqueous emulsion resin, and water.

[0122] (infrared ray absorbing film)

[0123] The infrared ray absorbing film according to the present embodiment contains the complex. In the case of the infrared ray absorbing film, in one embodiment, the value obtained by dividing the absorbance at 1800 nm of the infrared ray absorbing film by the absorbance at 500 nm is 4.5 or more, preferably 5.0 or more, more preferably 5.5 or more. Further, the higher the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm, the more preferable, and there is no particular limitation on the upper limit thereof, and it is usually 8.0 or less.

[0124] The infrared ray absorbing film only needs to contain the amorphous sulfated polysaccharide and the polythiophene derived from the complex, and may also contain other components. Examples of the other components include the additives and other polymers.

[0125] In one embodiment, an infrared ray absorbing film having excellent infrared ray absorption characteristics derived from the complex can be obtained by adding the complex to a polymer. Examples of the polymer as the matrix of the infrared ray absorbing film include vinyl acetate-polyvinyl alcohol copolymer, polypropylene glycol, polyethylene glycol, polyvinyl alcohol, ethylene-vinyl alcohol copolymer, butanediol-vinyl alcohol copolymer, ethylene-vinyl acetate copolymer, cellulose monoalkylate (alkyl group having 1 to 18 carbon atoms), cellulose dialkylate (alkyl group having 1 to 18 carbon atoms), cellulose trialkylate (alkyl group having 1 to 18 carbon atoms), polyethylene, polypropylene, polystyrene, poly(alkyl methacrylate) (alkyl group having 1 to 18 carbon atoms), sodium carboxymethyl cellulose, cellulose alkyl ether (alkyl group having 1 to 18 carbon atoms), polyethylene terephthalate, polyethylene naphthalate, polyacrylamide and its derivatives, poly(meth)acrylic acid, polyvinyl chloride, cellulose, starch, gelatin, pullulan, dextran, hydroxyalkyl (alkylidene group having 1 to 18 carbon atoms) (meth)acrylate, polyurethane, nylon-6,6, nylon-6, nylon-6,10, polyvinyl alkylal (alkyl group having 1 to 18 carbon atoms), polyimide, syndiotactic 1,2-polybutadiene, 1,4-polybutadiene, polyisoprene, polystyrene-butadiene copolymer, ABS resin, phenolic resin, silicone polymer, silsesquioxane, etc.

[0126] The thickness of the heat ray absorption film is not particularly limited, for example, it is 1 to 10,000 μm, preferably 10 to 1,000 μm, more preferably 10 to 100 μm. It should be noted that among the heat ray absorption films, a thinner film in terms of thickness, for example, a film with a thickness of 0.1 to 10 μm, is sometimes also referred to as a heat ray absorption thin film. In the present invention, the heat ray absorption film includes the heat ray absorption thin film.

[0127] The method for manufacturing the heat ray absorption film is not particularly limited. For example, it can be obtained by coating a dispersion of the composite on a substrate and drying it. The method for coating the dispersion of the composite on the substrate is not particularly limited. For example, coating-based methods such as spraying method, spin coating method, air knife coating method, curtain coating method, doctor blade coating method, dip coating method, casting method, double roll coating method, gate roll press method, roll coating method, bar coating method, die coating method, gravure printing method, spraying method, etc.; wet methods such as printing, inkjet, etc. based on patterning methods. Among them, the spin coating method and the casting method are preferred.

[0128] The drying method is not particularly limited. For example, natural drying, heat drying, freeze drying, vacuum drying, hot air drying, hot press drying, infrared drying, supercritical drying, etc. can be cited. The drying temperature can be appropriately set according to the drying method. For example, it is preferably in the range of 50°C to 250°C, more preferably in the range of 60°C to 150°C. The drying temperature is further preferably in the range of 80°C to 120°C. By setting the drying temperature below 250°C, the reduction of the heat ray absorption characteristics of the composite during drying can be suppressed. In addition, by setting a higher drying temperature, the drying time and the coating film quality during drying can be improved.

[0129] As the substrate, for example, a glass plate, a plastic sheet, a plastic film, etc. can be cited. As the plastic, polyester, polyethylene, polypropylene, polystyrene, polyimide, poly(meth)acrylate, polyamide, polyethylene terephthalate, polyethylene naphthalate, epoxy resin, chlorine-based resin, silicone-based resin, phenolic resin, and their mixtures, etc. can be cited.

[0130] In the laminate of the present embodiment, an adhesive layer and a release layer are laminated on one side of the heat ray absorption film. By laminating the adhesive layer and the release layer on one side of the heat ray absorption film, the release layer can be easily peeled off during use, and the heat ray absorption film can be attached to a substrate or the like through the adhesive layer. The adhesive layer and the release layer are not particularly limited. For example, those conventionally known can be appropriately used.

[0131] (Coating)

[0132] The complex is usually in a solid state, and a dispersion of the complex can also be used as a coating material (e.g., a heat-insulating coating). That is, the coating material of the present embodiment is a coating material containing the complex. In one embodiment, a coating material containing the complex and a dispersion medium (e.g., water) can be cited. As another embodiment, a coating material containing the complex, at least one resin selected from water-soluble resins and aqueous emulsion resins, and a dispersion medium (e.g., water) can be cited.

[0133] For example, a laminate can be obtained by coating a coating material onto a substrate such as a glass plate and applying a composition containing the complex on the substrate.

[0134] [Examples]

[0135] Hereinafter, examples are given to illustrate the present embodiment, and the present invention is not limited to these examples.

[0136] The following sulfated polysaccharides were used in the examples.

[0137] λ-carrageenan: manufactured by Tokyo Chemical Industry

[0138] κ-carrageenan: manufactured by Tokyo Chemical Industry

[0139] ι-carrageenan-1: manufactured by Tokyo Chemical Industry

[0140] ι-carrageenan-2: TS gel SV manufactured by TAISHO TECHNOS

[0141] [Calculation of the number of constituent monosaccharides of carrageenan]

[0142] Weigh 0.5 g of carrageenan and 500 g of ion-exchanged water, disperse at 60 °C for 1 hour, and then filter with a 0.45 μm membrane filter to obtain a measurement solution. Inject 20 μl of this into a gel permeation chromatography measurement device (manufactured by Waters, AcquityUPLC H-Class Bio) to measure the number-average molecular weight. As the molecular weight standard, standard pullulan was used. The number of constituent monosaccharides was calculated by doubling the value obtained by dividing the number-average molecular weight by the molecular weight of the dimer that is the constituent unit of carrageenan.

[0143] [Synthesis Example 1]

[0144] Put 150 g of DMSO, 16.5 g of acetic anhydride, and 3.2 g of 98% sulfuric acid into a 300 ml sample bottle, and stir with a magnetic stirrer at room temperature of 23 °C for about 30 seconds to prepare a fibrillation solution.

[0145] Next, 5.0 g of softwood kraft pulp NBKP (manufactured by Nippon Paper Industries Co., Ltd.) was added to the fibrillation solution, and the solution was further stirred at room temperature of 23 °C for 120 minutes to carry out a sulfation reaction. After stirring, 250 ml of distilled water was added to the fibrillation solution containing cellulose to stop the reaction, and then a 10 mass% aqueous sodium hydroxide solution was added until the pH reached 7 to neutralize the reaction solution. Then, the supernatant was removed by centrifugation to obtain a solid component.

[0146] Furthermore, 1350 ml of distilled water and 1350 ml of ethanol were added to the solid component and stirred until uniformly dispersed, and then the supernatant was removed by centrifugation to obtain a solid component. The same procedure was repeated for a total of 6 times. It should be noted that the centrifugation speed in each operation was 12,000 rpm and the centrifugation time was 50 minutes. After washing by centrifugation, distilled water was added to the solid component and diluted to a total weight of 1000 g to obtain a non-uniform mixture containing sulfated microcrystalline cellulose fibers and water.

[0147] Next, the non-uniform mixture was stirred for 3 minutes using a mixer (G5200, manufactured by Biolomix) to obtain 1000 g of an aqueous dispersion in which 0.5 mass% of sulfated microcrystalline cellulose fibers was uniformly dispersed. Then, the obtained aqueous dispersion of sulfated microcrystalline cellulose fibers was dried for 72 hours using a freeze dryer (FDU-2110, manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a dried product of sulfated microcrystalline cellulose fibers.

[0148] Next, a sample No. 1 of sulfated microcrystalline cellulose fiber powder was obtained by treating 5 g of the dried product of sulfated microcrystalline cellulose fibers with a dry pulverizer (Wonder Blender WB1, manufactured by OSAKA CHEMICAL) for 3 minutes.

[0149] [Synthesis Example 2]

[0150] 5.0 g of softwood kraft pulp NBKP (manufactured by Nippon Paper Industries Co., Ltd.) was added to 500 ml of N,N-dimethylformamide (DMF), and the mixture was cooled to 10 °C. 3.6 ml of chlorosulfonic acid was added dropwise to the DMF containing softwood kraft pulp NBKP in a nitrogen atmosphere over 60 minutes, and the mixture was stirred for 1 hour to obtain a reaction solution.

[0151] The reaction solution was poured into 5000 ml of a saturated sodium acetate solution, and after reprecipitation, the supernatant was removed by centrifugation to obtain a solid component. After washing the solid component once with a saturated ethanol solution of sodium acetate, it was washed with ethanol until the supernatant became neutral. Then, the supernatant was removed by centrifugation to obtain a solid component, and distilled water was added to the solid component and diluted to a total weight of 1000 g to obtain a heterogeneous mixture containing sulfuric acid esterified microcrystalline cellulose fibers and water.

[0152] Next, the heterogeneous mixture was stirred for 3 minutes using a mixer (G5200, manufactured by Biolomix) to obtain 1000 g of an aqueous dispersion in which 0.5% by mass of sulfuric acid esterified microcrystalline cellulose fibers were uniformly dispersed. Then, the obtained aqueous dispersion of sulfuric acid esterified microcrystalline cellulose fibers was dried for 72 hours using a freeze dryer (FDU-2110, manufactured by Tokyo Rika Kikai Co., Ltd.) to obtain a dried product of sulfuric acid esterified microcrystalline cellulose fibers.

[0153] Next, 5 g of the dried product of sulfuric acid esterified microcrystalline cellulose fibers was treated for 3 minutes using a dry pulverizer (Wonder Blender WB1, manufactured by OSAKA CHEMICAL) to obtain Sample No. 2 as a powder of sulfuric acid esterified microcrystalline cellulose fibers.

[0154] <Calculation of the number of constituent monosaccharides of sulfuric acid esterified nanocellulose>

[0155] 0.12 g of the solid component of the sulfuric acid esterified microcrystalline cellulose fiber powder was dissolved in 63.0 g of a 0.5 M cuprammonium ethylenediamine solution, and after incubation at 25 °C, the viscosity was measured by measuring the flow-down time of the sulfuric acid esterified microcrystalline cellulose fiber - cuprammonium ethylenediamine solution using a Cannon-Fenske kinematic viscometer tube.

[0156] Let the viscosity of the sulfuric acid esterified microcrystalline cellulose fiber - cuprammonium ethylenediamine solution be η, and the viscosity of the 0.5 M cuprammonium ethylenediamine solution be η0. The average degree of polymerization was calculated by the following calculation formula.

[0157] Limiting viscosity [η] = (η / η0) / {c(1 + A×η / η0)}

[0158] (where c is the concentration of sulfuric acid esterified microcrystalline cellulose fibers (g / dL) at the time of viscosity measurement, and A is an inherent value based on the type of solution. In the case of a 0.5 M cuprammonium ethylenediamine solution, A = 0.28.)

[0159] Average degree of polymerization DP = [η] / aK

[0160] (K and a are values determined by the type of polymer and the solvent used. In the case of cellulose dissolved in cuprammonium ethylenediamine, K = 5.7×10-3 , a = 1.)

[0161] Regarding the sulfated microcrystalline cellulose fiber, the average degree of polymerization is taken as the number of constituent monosaccharides.

[0162] <Quantification of the amount of sulfate group introduced>

[0163] Using the combustion absorption-IC method, the sulfur content rate derived from carrageenan or sulfated microcrystalline cellulose fiber was quantified. Specifically, the dried carrageenan or sulfated microcrystalline cellulose fiber powder (0.01 g) was placed on a magnetic plate and burned in an oxygen atmosphere (flow rate: 1.5 L / minute) in a ring furnace (1350 °C). The generated gas components were absorbed by 3% hydrogen peroxide water (20 ml). The obtained absorption solution was made up to 100 ml with pure water, and the sulfate ion concentration (mass%) was measured by ion chromatography of the dilution solution. Based on the measurement results, the sulfur introduction amount (mmol / g) of the sulfate group derived from each 1 g of carrageenan or sulfated microcrystalline cellulose fiber powder was calculated.

[0164] <Method for measuring crystallinity>

[0165] Using an X-ray diffraction (XRD) device (manufactured by Rigaku Corporation: SMARTLAB-9KW), from I 200 : the diffraction intensity of the lattice plane (200 plane) and I am : the measurement results of the diffraction intensity of the amorphous part, using the following mathematical formula 1, the crystallinity was calculated.

[0166] Cellulose I crystallinity (%) = [(I 200 -I am ) / I 200 ×100…Mathematical formula 1

[0167] Here, I 200 represents the X-ray diffraction intensity at 2θ = 22.6°, and I am represents the X-ray diffraction intensity at 2θ = 18.5°.

[0168] <Method for measuring viscosity>

[0169] A 100 g of 1 wt% aqueous dispersion of carrageenan or sulfated nanocellulose was defoamed for 10 seconds by a defoaming device (manufactured by THINKY, Awatori Rentaro ARE-310) and allowed to stand for 24 hours. Then, using a viscosity and viscoelasticity measuring device (manufactured by THERMO FISHER SCIENTIFIC Co., Ltd., HAAKE MARS40), viscosity measurement was carried out at a rotational speed of 6.0 rpm and a set temperature of 20 °C, and the viscosity at 10 minutes after the start of measurement (after the start of rotation) was recorded.

[0170] The analysis results of each carrageenan and the sulfated microcrystalline cellulose fiber (S-CNF) obtained through the synthesis examples are shown in Table 1.

[0171] [Table 1]

[0172]

[0173] (Synthesis of PEDOT / Carrageenan or PEDOT / S-CNF)

[0174] [Examples 1 to 4, Comparative Examples 1 to 2]

[0175] To 0.375 g of λ-carrageenan, κ-carrageenan, ι-carrageenan-1, ι-carrageenan-2, and the sulfated microcrystalline cellulose fiber of Synthesis Example 1 or 2, ion-exchanged water was added respectively to prepare 37.5 g of a 1.0 wt% aqueous dispersion. To this, 0.332 g of 3,4-ethylenedioxythiophene (EDOT) was added, and internal ultrasonic waves were irradiated for 1 minute to disperse EDOT. Next, 2.0 g of concentrated hydrochloric acid, 1.0 g of an aqueous solution of iron(III) chloride hexahydrate at 0.48 g / L, and 0.14 g of potassium persulfate were added, and the mixture was stirred at room temperature for 24 hours. After stirring, dialysis was performed through a dialysis membrane for 72 hours or more to obtain an aqueous dispersion of a complex of poly(3,4-ethylenedioxythiophene) PEDOT / carrageenan or PEDOT / sulfated microcrystalline cellulose fiber.

[0176] (Change in the amount of EDOT)

[0177] [Example 5]

[0178] Except that the input amount of EDOT was changed from 0.332 g to 0.266 g, the same procedure as in Example 3 (using ι-carrageenan-1) was carried out to obtain an aqueous dispersion of a PEDOT / carrageenan complex.

[0179] [Example 6]

[0180] Except that the input amount of EDOT was changed from 0.332 g to 0.199 g, the same procedure as in Example 3 (using ι-carrageenan-1) was carried out to obtain an aqueous dispersion of a PEDOT / carrageenan complex.

[0181] (Analysis of PEDOT / Carrageenan or PEDOT / S-CNF)

[0182] >[Method for measuring absorbance]

[0183] The aqueous dispersions of the PEDOT / carrageenan or PEDOT / sulfated microcrystalline cellulose fiber composites obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were diluted to 0.01 wt%, and using a near-infrared spectrophotometer manufactured by AGILENT TECHNOLOGIES, Ltd., the absorbance was measured at each 1 nm in the wavelength range of 200 nm to 1800 nm. The absorbance at 500 nm obtained was taken as the "absorbance of visible light", and the absorbance at 1800 nm was taken as the "absorbance of near-infrared light" for evaluation. The value obtained by dividing the absorbance value at 1800 nm by the absorbance value at 500 nm was evaluated as the heat ray absorption property.

[0184] <Quantification of carrageenan content>

[0185] The aqueous dispersion of the obtained PEDOT / carrageenan composite was diluted to 0.1 wt%, and 50 mL was collected. 5 mL of 1 mol / L sulfuric acid was added thereto, and it was heated at 120 °C for 60 minutes in an autoclave. After adding 1 mL of galactosamine hydrochloride as an internal standard thereto, 20 μL was separated, 80 μL of 0.5 mol / L sodium hydroxide aqueous solution and 100 μL of PMP (1-phenyl-3-methyl-5-pyrazolone) solution were added, and it was heated at 60 °C for 30 minutes. Then, 1 mL of ion-exchanged water, 50 μL of 0.5 mol / L sulfuric acid, and 2 mL of toluene were added, and after stirring for 30 seconds or more with a touch mixer, centrifugation was performed to remove the supernatant. 2 mL of toluene was added to the lower layer, stirring, centrifugation, and washing based on removal of the supernatant were performed, and 5 μL of the liquid filtered through a membrane filter was injected into HPLC (high-speed chromatography, apparatus: manufactured by Thermo Fisher Scientific, Ultimate3000 HPLC) to quantify the galactose component. From the concentration of hydrolyzed galactose, the ratio (mass ratio) of PEDOT and carrageenan in the PEDOT / carrageenan composite was determined. The PEDOT / S-CNF composite was treated in the same manner to obtain the glucose concentration, and the ratio (mass ratio) of PEDOT and S-CNF in the PEDOT / S-CNF composite was determined.

[0186] [Table 2]

[0187]

[0188] (Preparation of PEDOT / carrageenan film or PEDOT / S-CNF film) [Examples 7 to 10, Comparative Examples 3 to 6]

[0189] After drying and solidifying the aqueous dispersions of the PEDOT / carrageenan or PEDOT / sulfated microcrystalline cellulose fiber composites obtained in Examples 1 to 4 and Comparative Examples 1 and 2 through an evaporator, the composites were redispersed in water and the solid content concentration of the dry solids was adjusted to make the viscosity (rotation speed 6.0 rpm, set temperature 20 °C) about 1200 mPa·s, thereby preparing an aqueous dispersion. By adding 0.1 g of octylphenol ethoxylate (manufactured by NACALAITESQUE, Triton X-100) as a surfactant to 100 g of this aqueous dispersion and stirring well, a coating liquid was prepared.

[0190] The gap of the doctor blade was appropriately set, and the coating liquid was coated onto a polyester film (manufactured by TORAY, LUMIRROR (registered trademark) T60) so as to achieve the coating film thickness described in Table 3, and then dried at 80 °C until the coating liquid was dry, obtaining a heat ray absorbing film.

[0191] (Analysis of the heat ray absorbing film)

[0192] (Method for measuring the film thickness)

[0193] The film thickness of the obtained heat ray absorbing film was measured using a 3D measuring laser microscope (manufactured by OLYMPUS, OLS5100).

[0194] (Method for measuring the absorbance)

[0195] For the obtained heat ray absorbing film, using a near-infrared spectrophotometer manufactured by AGILENT TECHNOLOGIES, the absorbance was measured every 1 nm in the wavelength range of 200 nm to 1800 nm. The absorbance at 500 nm obtained was taken as the "absorbance of visible light", and the absorbance at 1800 nm was taken as the "absorbance of near-infrared light" for evaluation. The value obtained by dividing the absorbance value at 1800 nm by the absorbance value at 500 nm was evaluated as the heat ray absorption characteristic.

[0196] (Viscosity of the aqueous dispersion containing 2 wt% of the composite)

[0197] After drying and solidifying the aqueous dispersions of the PEDOT / carrageenan or PEDOT / sulfated microcrystalline cellulose fiber composites obtained in Examples 1 to 4 and Comparative Examples 1 and 2 through an evaporator, the composites (dry solids) were redispersed in water to prepare an aqueous dispersion containing 2 wt% of the composite. For the aqueous dispersion containing 2 wt% of the composite, the viscosity (rotation speed 6.0 rpm, set temperature 20 °C) was measured.

[0198] [Table 3]

[0199]

[0200] [Table 4]

[0201]

[0202] Compared with the comparative examples, the composite of this embodiment can increase the solid content concentration in the aqueous dispersion having the same viscosity. Therefore, when manufacturing a heat ray absorbing film having the same dry film thickness, compared with Comparative Examples 3 and 4, the coating film thickness can be made thinner, so the drying time can be significantly shortened. In addition, when coating with the same coating film thickness, compared with Comparative Examples 5 and 6, the film thickness of the heat ray absorbing film can be made thicker.

[0203] [Example 11]

[0204] (Preparation of PEDOT / carrageenan - water - soluble resin film)

[0205] 91.7 g of butylene glycol vinyl alcohol copolymer (manufactured by MITSUBISHI CHEMICAL Corporation, Nichigo G - Polymer TM ) and 569.1 g of water were stirred in a 1000 mL container at 40 °C for 12 hours to prepare a 13.9 wt% resin aqueous solution.

[0206] Next, 0.018 g of octylphenol ethoxylate (manufactured by NACALAI TESQUE, Triton X - 100) was added as a surfactant to 20.0 g of the aqueous dispersion of the PEDOT / carrageenan composite obtained in Example 9, and then 66.1 g of the 13.9 wt% resin aqueous solution was added and stirred well to prepare a water - soluble resin coating solution.

[0207] The doctor blade was set to a gap of 155 μm, and the coating solution was coated onto a polyester film (manufactured by TORAY, LUMIRROR (registered trademark) T60), and then dried at 80 °C for 30 minutes to obtain a water - soluble resin heat ray absorbing film.

[0208] [Example 12]

[0209] (Preparation of PEDOT / carrageenan - water - based emulsion resin film)

[0210] 7.1 g of the aqueous dispersion of the PEDOT / carrageenan composite obtained in Example 9 was added to 14.1 g of urethane acrylate (manufactured by DAICEL·ALLNEX Co., Ltd., UCECOAT 7200, solid content concentration 65 wt%), and stirred well. 0.49 g of a photoinitiator (manufactured by BASF, IRGACURE 1173) and 0.10 g of a surface modifier (manufactured by Nissin Chemical Industry Co., Ltd., SURFYNOL 104E) were added, and stirred well to prepare an aqueous emulsion resin coating solution.

[0211] The doctor blade was set to a gap of 110 μm, and the coating solution was coated onto a polyester film (manufactured by TORAY, LUMIRROR (registered trademark) T60), and then dried at 80 °C for 10 minutes. Next, it was irradiated with a UV irradiation device (manufactured by EYE GRAPHICS Co., Ltd., EyeGrandage ECS-401GX type) at an illuminance of 200 mW·cm 2 , and a cumulative light amount of 800 mJ / cm 2 to cure it, and a water-soluble resin heat ray absorption film was obtained.

[0212] [Table 5]

[0213]

[0214] The composite of this embodiment was confirmed to have excellent heat ray absorption characteristics in either the aqueous dispersion or the film state.

[0215] The upper limit value and / or the lower limit value of the numerical range described in this specification can be arbitrarily combined to define a preferred range. For example, a preferred range can be defined by arbitrarily combining the upper limit value and the lower limit value of the numerical range, a preferred range can be defined by arbitrarily combining the upper limit values of the numerical range, and a preferred range can be defined by arbitrarily combining the lower limit values of the numerical range. In addition, in this application, the numerical ranges represented by the symbol "~" respectively include the numerical values described before and after the symbol "~" as the lower limit value and the upper limit value.

[0216] As described above, this embodiment has been described in detail. The specific configuration is not limited to the above embodiment, and there are design changes within the scope not departing from the gist of the present invention, and the present invention includes these design changes.

Claims

1. A complex comprising: Amorphous sulfated polysaccharides, and Polythiophene.

2. The composite according to claim 1, wherein The amorphous sulfated polysaccharide is at least one amorphous sulfated polysaccharide selected from the group consisting of carrageenan, SACRAN, rhamnan sulfate, fucoidan, chondroitin sulfate, porphyran, haran, dermatan sulfate, and heparin.

3. The composite according to claim 1, wherein: The non-crystalline sulfated polysaccharide is at least one carrageenan selected from the group consisting of λ-carrageenan, κ-carrageenan and ι-carrageenan.

4. The composite according to claim 1, wherein The amorphous sulfated polysaccharide is at least one sulfated polysaccharide selected from the group consisting of a sulfated polysaccharide represented by the following general formula (1) and a sulfated polysaccharide represented by the following general formula (2). [Chemical formula 1] In the general formulae (1) and (2), R is independently a hydrogen atom or a group represented by the following general formula (3), wherein at least one R in the brackets is a group represented by the following general formula (3), and n represents the number of repetitions in the brackets. [Chemical formula 2] In the general formula (3), X is a hydroxyl group or -O - (M m+ ) 1 / m , m is an integer greater than or equal to 1 and less than or equal to 3, M m+ It is an m-valent cation, and the wavy line is the bonding site with other atoms.

5. The composite according to claim 1, wherein: The amount of substituents of sulfate groups in the amorphous sulfated polysaccharide is 2.0 mmol / g or more and 6.0 mmol / g or less.

6. The composite according to claim 1, wherein The number of constituent monosaccharides of the amorphous sulfated polysaccharide is 200 or more.

7. The composite according to claim 1, wherein: The amorphous sulfated polysaccharide is iota-carrageenan.

8. The composite according to claim 1, wherein: The value obtained by dividing the absorbance at 1800 nm of the aqueous dispersion containing the composite at a content of 0.01 wt % by the absorbance at 500 nm is 4.5 or more.

9. The composite according to claim 1, wherein: The absorbance at 1800 nm of an aqueous dispersion containing the composite at 0.01 wt % is divided by the absorbance at 500 nm and is 4.5 or more. The absorbance at 500 nm is 0.010 or more and 0.200 or less. The absorbance at 1800 nm is 0.200 or more and 1.200 or less.

10. The composite according to claim 1, wherein: The viscosity of an aqueous dispersion containing the composite at a content of 2 wt % measured at a rotation speed of 6.0 rpm and 20° C. is 100 mPa·s or more and 5000 mPa·s or less.

11. An aqueous dispersion comprising: Amorphous sulfated polysaccharides; Polythiophene; At least one resin selected from the group consisting of a water-soluble resin and an aqueous emulsion resin; and water. 12 . A heat ray absorbing film comprising the composite according to claim 1 .

13. The heat ray absorbing film according to claim 12, wherein The value obtained by dividing the absorbance at 1800 nm of the heat ray absorbing film by the absorbance at 500 nm is 4.5 or more.

14. A laminate comprising a pressure-sensitive adhesive layer and a release layer laminated on one side of the heat ray absorbing film according to claim 12.

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