Composite and heat-ray absorbing film

Abstract

To provide a composite and a heat-ray absorbing film, having excellent heat-ray absorption properties without using raw materials with high environmental load.SOLUTION: One embodiment of the present invention is a composite containing an amorphous sulfated polysaccharide and a polythiophene.SELECTED DRAWING: None

Description

Technical Field

[0001] The present disclosure 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 of infrared light or longer, and since these lights have a high thermal effect, they are called heat rays. Window materials that require transparency and are used in office buildings, automobiles, etc. generally transmit heat rays well, and it is known that the temperature inside a room or a vehicle rises as a result.

[0003] Therefore, for the purpose of energy conservation, it has been studied to impart a function of reflecting or absorbing heat rays to window materials. As a means of imparting a function (heat ray shielding property) of reflecting or absorbing heat rays to window materials, for example, a method of attaching an infrared absorbing film containing indium tin oxide (ITO) fine particles, antimony-doped 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 eagerly desired. In addition, in order to enhance the heat ray shielding property, when the addition amount of inorganic fine particles having a heat ray shielding property is increased to lower the solar transmittance, the transmittance of visible light also becomes low. Conversely, when the transmittance of visible light is increased to take in outside light, there is a problem that the solar transmittance increases and the heat ray shielding property decreases.

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

[0006]

Chemical Formula

Prior Art Documents

Patent Documents

[0007]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] According to the studies by the present inventors, the heat ray absorber disclosed in Patent Document 1 has insufficient near-infrared absorption ability for light in the range of, for example, 800 to 1800 nm, and the heat ray absorption characteristics (the absorbance of near-infrared light divided by the absorbance of visible light) are insufficient.

[0009] Therefore, an object of the present disclosure is to provide a composite and a heat ray absorption film that have excellent heat ray absorption characteristics without using raw materials with a high environmental load.

Means for Solving the Problems

[0010] The present inventors conducted intensive studies to solve the above problems and found that a composite containing an amorphous sulfated polysaccharide and polythiophene is a composite having excellent heat ray absorption characteristics without using raw materials with a high environmental load, leading to the present disclosure.

[0011] Examples of the embodiments of the present disclosure are described as follows.

[0012] [1] A composite containing an amorphous sulfated polysaccharide and polythiophene. [2] The complex according to [1], wherein the amorphous sulfated polysaccharide is at least one amorphous sulfated polysaccharide selected from carrageenan, sacran, laminaran sulfate, fucoidan, chondroitin sulfate, porphyran, funoran, dermatan sulfate, and heparin. [3] The complex according to [1] or [2], wherein the amorphous sulfated polysaccharide is at least one carrageenan selected from lambda-carrageenan, kappa-carrageenan, and iota-carrageenan. [4] The complex according to any one of [1] to [3], wherein 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).

Chemical formula

Chemical formula

[10] The complex according to any one of [1] to [9], wherein the viscosity of the aqueous dispersion containing 2 wt% of the complex, measured at 20 °C and a rotational speed of 6.0 rpm, is 100 mPa·s or more and 5000 mPa·s or less.

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

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

[11] .

[13] The heat ray absorbing film according to

[12] , wherein the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm is 4.5 or more.

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

[12] or

[13] .

Advantages of the Invention

[0013] According to the present disclosure, it is possible to provide a complex having excellent heat ray absorption characteristics and a heat ray absorbing film without using raw materials with a high environmental load.

Embodiments for Carrying Out the Invention

[0014] Hereinafter, the complex, the aqueous dispersion, the heat ray absorbing film, and the laminate of the present embodiment will be described in detail.

[0015] One aspect of the present embodiment is a composite comprising 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. Further, the composite of the present embodiment can increase the solid content concentration in an aqueous dispersion having a comparable viscosity compared to a composite comprising sulfated microcrystalline cellulose fibers and polythiophene. Therefore, when producing a heat ray absorption film having a comparable dry film thickness, the aqueous dispersion prepared from the composite of the present embodiment can have a thinner coating film thickness and can significantly shorten the drying time compared to a composite comprising sulfated microcrystalline cellulose fibers and polythiophene. Further, when coating with a comparable coating film thickness, the film thickness of the heat ray absorption film can be increased by using the aqueous dispersion prepared from the composite of the present embodiment compared to a composite comprising sulfated microcrystalline cellulose fibers and polythiophene.

[0016] Hereinafter, the present embodiment will be described in detail.

[0017] (Amorphous sulfated polysaccharide) The composite and the aqueous dispersion of the present embodiment contain an amorphous sulfated polysaccharide. Among the sulfated polysaccharides, the amorphous sulfated polysaccharide does not include those showing crystallinity such as sulfated cellulose. In the present disclosure, amorphous means that the cellulose I crystallinity calculated by the following formula 1 is less than 5% based on the measurement result of the diffraction intensity by an X-ray diffractometer. Cellulose I crystallinity (%) = [(I 200 - I am ) / I 200 × 100 … Formula 1 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°.

[0018] The amorphous sulfated polysaccharides are not particularly limited, and examples thereof include at least one amorphous sulfated polysaccharide selected from carrageenan, sacran, laminaran sulfate, fucoidan, chondroitin sulfate, porphyran, funoran, dermatan sulfate, and heparin. As the amorphous sulfated polysaccharide, at least one amorphous sulfated polysaccharide selected from carrageenan, sacran, and funoran is preferable, and carrageenan is more preferable. These amorphous sulfated polysaccharides are preferable because they can stabilize the dispersion of polythiophene.

[0019] In a preferred embodiment, the amorphous sulfated polysaccharide is at least one carrageenan selected from lambda-carrageenan, kappa-carrageenan, and iota-carrageenan. Carrageenan is a polysaccharide that is naturally extracted mainly from red algae. Carrageenan has a structure in which D-galactose is alternately linked by α-1,3 bonds or β-1,4 bonds. Carrageenan is classified into three types: kappa (κ), iota (ι), and lambda (λ) according to the number of sulfate groups and the presence or absence of anhydro bonds, and any of these can be used. For carrageenan, for example, commercially available products can be used, and the commercially available ones can be used as they are, or purified ones can be used.

[0020] Preferably, the carrageenan is at least one carrageenan selected from iota-carrageenan and kappa-carrageenan, and more preferably iota-carrageenan.

[0021] In one preferred embodiment, 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).

[0022]

Chemical formula

[0023]

Chemical formula

[0024] In general formulas (1) and (2), at least one of the Rs in parentheses is a group represented by the above general formula (3). The proportion of the group represented by the above general formula (3) is not particularly limited, but it is preferable that the amount of the substituent of the group represented by general formula (3) (also referred to as a sulfate group) is within the range described later.)

[0025] In general formulas (1) and (2), n represents the number of repetitions in parentheses, in other words, 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. Within the above range, it is preferable because the viscosity during water dispersion is appropriate.)

[0026] In general formula (3), X is a hydroxy group or -O - (M m+ ) 1 / m where M m+ includes metal ions, ammonium ions, etc. When m is 2 or 3, that is, when M m+ is a polyvalent cation, M m+ forms an ionic bond with two or three -SO3 - . As M m+ , when m is 1 and M m+ is M +One preferred embodiment is that it is a monovalent cation.

[0027] Examples of metal ions include alkali metal ions, alkaline earth metal ions, transition metal ions, and other metal ions.

[0028] Here, examples of alkali metal ions include lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), rubidium ion (Rb + ), cesium ion (Cs + ), etc. Examples of alkaline earth metal ions include calcium ion (Ca 2+ ), strontium ion (Sr 2+ ), etc. Examples of transition metal ions include iron ion, nickel ion, palladium ion, copper ion, silver ion, etc. Examples of other metal ions include beryllium ion, magnesium ion, zinc ion, aluminum ion, etc.

[0029] Examples of ammonium ions include not only NH4 + , but also ammonium ions derived from various amines in which one or more hydrogen atoms of NH4 + are replaced by organic groups. Examples of ammonium ions include, for example, NH4 + , quaternary ammonium cations, alkanolamine ions, pyridinium ions, etc.

[0030] 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.

[0031] In the general formula (3), X is a hydroxy group or -O - M +is preferably, a hydroxy group, or -O - Na + is particularly preferred.

[0032] X in the group represented by the general formula (3) may be only one kind, or may be two or more kinds.

[0033] The amount of substituents of the sulfate ester 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, it is preferable because the dispersion of polythiophene can be promoted.

[0034] The amount of substituents of the sulfate ester 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.

[0035] The number of constituent monosaccharides of the amorphous sulfated polysaccharide is not particularly limited, but 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. In addition, since the above-mentioned carrageenan and general formulas (1) and (2) have a disaccharide as a constituent unit, 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, for example, the method described in the examples.

[0036] (Polythiophene) The composite and the aqueous dispersion of the present embodiment contain polythiophene. Polythiophene usually has a monomer unit having a thiophene skeleton. The monomer unit means a constituent unit derived from a monomer that constitutes polythiophene, and means a repeating unit of polythiophene. Polythiophene preferably has a monomer unit (repeating unit) represented by the following general formula (4).

[0037] [Chemical formula] (In general formula (4), R 7 and R 8 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an alkoxy group having 1 to 8 carbon atoms, or R 7 and R 8 are linked to represent a dioxoalkylene group having 1 to 8 carbon atoms, an aromatic ring, or an alicyclic ring having 3 to 7 members, and n represents the number of repetitions in parentheses.)

[0038] In general formula (4), when R 7 and R 8 are alkyl groups having 1 to 8 carbon atoms, they may be either linear or branched. Note that the alkyl group preferably has 1 to 6 carbon atoms.

[0039] In general formula (4), when R 7 and R 8 are alkoxy groups having 1 to 8 carbon atoms, they may be either linear or branched. Note that the alkoxy group preferably has 1 to 6 carbon atoms.

[0040] When R 7 and R 8 are linked to form a dioxoalkylene group having 1 to 8 carbon atoms, the number of carbon atoms of the dioxoalkylene group is preferably 1 to 6 carbon atoms, more preferably 2 to 4 carbon atoms.

[0041] When R 7 and R 8 are linked to form an aromatic ring, for example, together with the carbon atom to which R 7 and R 8 are attached, a benzene ring may be formed.

[0042] When R 7 and R 8 are linked to form an alicyclic ring having 3 to 7 members, the alicyclic ring is preferably a 4 to 7 membered ring, more preferably a 5 to 6 membered ring.

[0043] The number of repeating units represented by the general formula (4) that form polythiophene, that is, the value of n, is not particularly limited, and examples thereof include 2 to 50. As the number of these repeating units increases, the properties such as the heat insulation property of polythiophene tend to improve.

[0044] The monomer (thiophene) constituting the repeating unit represented by the general formula (4) is represented by the following general formula (5).

[0045] [Chemical formula] (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 linked to represent a dioxyalkylene group having 1 to 8 carbon atoms, an aromatic ring, or an alicyclic ring having 3 to 7 members.)

[0046] As the thiophene represented by the general formula (5), preferably, 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; a 3,4-disubstituted thiophene in which a dioxyalkylene group having 1 to 8 carbon atoms is formed at the 3-position and 4-position of the thiophene skeleton can be mentioned. More specifically, 3,4-dialkylthiophene, 3,4-dialkoxythiophene, 3,4-alkylenedioxythiophene, etc. can be mentioned. Among these, 3,4-alkylenedioxythiophene is preferable.

[0047] Examples of the thiophene represented by the general formula (5) include 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, and the like. Among these, 3,4-ethylenedioxythiophene (hereinafter sometimes abbreviated as EDOT) is preferred.

[0048] Specific examples of the polythiophene represented by the general formula (4) include 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), and the like. Among these, poly(3,4-ethylenedioxythiophene), which is also abbreviated as PEDOT, is preferred.

[0049] (Composite) The composite of this embodiment is a composite containing an amorphous sulfated polysaccharide and a polythiophene. The composite of this 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 the polythiophene constituting the composite of this embodiment is not particularly limited, but 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 the polythiophene can be measured by the method described in the examples.

[0050] The complex has an absorbance at 500 nm of a 0.01 wt% aqueous dispersion containing the complex of 0.010 or more and 0.200 or less, and an absorbance at 1800 nm of 0.200 or more and 1.200 or less, and usually the absorbance at 500 nm is less than the absorbance at 1800 nm. It is preferable that the absorbance at 500 nm of a 0.01 wt% aqueous dispersion containing the complex 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, and 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 complex having such characteristics is excellent in heat ray absorption properties, the complex can be used as a heat ray absorber, a heat ray absorption film, or the like.

[0051] It is preferable that the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm of a 0.01 wt% aqueous dispersion containing the complex is 4.5 or more, more preferably 5.0 or more, and particularly preferably 5.5 or more. The value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm is preferably higher because the heat ray absorption characteristics are more excellent, and there is no particular limitation on the upper limit, but it is usually 8.0 or less. The complex having such characteristics is particularly excellent in heat ray absorption properties and is preferable.

[0052] Compared with a composite containing sulfated microcrystalline cellulose fibers and polythiophene, the composite of the present embodiment can increase the solid content concentration in an aqueous dispersion having the same degree of viscosity. 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 a 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 reduced and the drying time can be significantly shortened. Further, when coating with the same coating film thickness, by using the aqueous dispersion prepared from the composite of the present embodiment, compared with a composite containing sulfated microcrystalline cellulose fibers and polythiophene, the film thickness of the heat ray absorbing film can be increased.

[0053] The composite may contain components other than the amorphous sulfated polysaccharide and polythiophene, such as additives. The additive may be an inorganic additive or an organic additive.

[0054] Examples of the inorganic additive include inorganic fine particles. Examples of the inorganic fine particles include silica, mica, talc, clay, carbon, carbonates (e.g., calcium carbonate, magnesium carbonate), oxides (e.g., aluminum oxide, titanium oxide, zinc oxide, iron oxide), ceramics (e.g., ferrite), or fine particles of a mixture thereof. The inorganic fine particles may be contained in the composite, for example, in an amount within the range of 0.09 to 5% by mass.

[0055] The composite may contain a functional compound as an organic additive. Examples of the functional compound include a dye, a UV absorber, an antioxidant, an antistatic agent, and a surfactant. The organic additive may be contained in the composite, for example, in an amount within the range of 0.09 to 5% by mass.

[0056] The composite is usually solid. A dispersion of the composite in a dispersion medium is referred to as a dispersion of the composite, and a dispersion in water is referred to as an aqueous dispersion of the composite.

[0057] (Method for producing the composite) The composite can be obtained, for example, by polymerizing thiophene in the co - presence of an amorphous sulfated polysaccharide and thiophene to produce polythiophene. In one embodiment, the amorphous sulfated polysaccharide is doped into polythiophene by the polymerization of the thiophene.

[0058] Specifically, the composite can be produced by oxidative polymerization of the thiophene represented by the general formula (5) in the presence of an amorphous sulfated polysaccharide, a solvent and an oxidizing agent. For example, to a dispersion (such as an aqueous dispersion) prepared by previously dispersing an amorphous sulfated polysaccharide in a dispersion medium, the thiophene represented by the general formula (5) and an oxidizing agent are added, and the thiophene is polymerized to produce polythiophene, whereby the composite can be obtained in a state where the composite is dispersed in the dispersion medium. In the obtained composite, the bonding mode between polythiophene and the amorphous sulfated polysaccharide is not intended to be limitedly interpreted, but it is considered that the composite is formed in a state where the anions of the amorphous sulfated polysaccharide are doped into the polythiophene generated by the polymerization reaction.

[0059] In the production of the composite, the amounts of the thiophene represented by the general formula (5) and the amorphous sulfated polysaccharide used as raw material compounds may be adjusted so that the above - mentioned composite can be obtained.

[0060] As the oxidizing agent (which may be referred to as a polymerization initiator) used in the production of the composite, there is no particular limitation as long as it can oxidatively polymerize thiophene represented by the general formula (5). For example, peroxydisulfuric acid, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, inorganic ferric salts, organic ferric salts, hydrogen peroxide, potassium permanganate, potassium dichromate, alkali metal perborates, iron(III) sulfate, iron(III) chloride, etc. can be mentioned. Among these, peroxydisulfuric acid, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate, iron(III) sulfate, and iron(III) chloride are preferred. These oxidizing agents may be used alone or in combination of two or more.

[0061] In the production of the composite, the amount of the oxidizing agent used is not particularly limited. For example, in the range of 0.1 equivalent to 5 equivalents, more preferably in the range of 0.3 equivalent to 2 equivalents, per mole of thiophene represented by the general formula (5) is preferred.

[0062] When producing the composite, when the amount of the monosaccharide constituting the amorphous sulfated polysaccharide is 1 mole, the amount of thiophene is preferably in the range of 0.2 to 5 moles, more preferably in the range of 0.4 to 2.0 moles.

[0063] In the production of the composite (polymerization of polythiophene (e.g., PEDOT)), the concentration of the polymerization initiator with respect to thiophene (e.g., EDOT) can be, for example, in the range of 5 mol% to 92.5 mol%, or in the range of 5.7 mol% to 92.5 mol%. It is preferable to set the concentration of the polymerization initiator in the range of 11.6 mol% to 46.2 mol% because the near-infrared light absorption characteristics can be further improved. When the polymerization initiator is insufficient, the polymerization of polythiophene (e.g., PEDOT) becomes difficult to proceed. When there is too much polymerization initiator, the degree of polymerization of polythiophene (e.g., PEDOT) tends to be small. And it is considered that polymers (polythiophene) outside the system of amorphous sulfated polysaccharides with a very small degree of polymerization are produced.

[0064] Regarding the dispersion medium used in the production of the composite, any medium capable of performing the polymerization reaction of thiophene may be used. Specifically, an aqueous solvent is exemplified, and preferably water is mentioned. Further, as the solvent, an aqueous solvent in which a lower alcohol such as methanol or ethanol, or a polar organic solvent such as acetone or acetonitrile is mixed with water may be used. These solvents may be used alone or in combination of two or more.

[0065] In the production of the composite, the amount of the solvent used is not particularly limited. For example, in the range of 1000 ml to 50000 ml, preferably in the range of 10000 ml to 40000 ml, per mole of thiophene represented by the general formula (5) is preferable.

[0066] Regarding the reaction time and reaction temperature in the production of the composite, they may be appropriately set according to the type of thiophene and amorphous sulfated polysaccharide used as the raw material compound, the type of oxidizing agent, etc. The reaction temperature in the production of the composite is preferably in the range of 5°C to 90°C, more preferably in the range of 10°C to 80°C. The reaction time in the production of the composite is preferably in the range of 1 hour to 96 hours, more preferably in the range of 5 hours to 48 hours.

[0067] As described above, in the presence of an amorphous sulfated polysaccharide, by polymerizing the thiophene represented by the general formula (5), a dispersion solution of the composite can be obtained. The composite may be obtained as the state of the dispersion liquid obtained after the reaction (dispersion liquid of the composite). After the dispersion liquid of the composite is purified and additives are added as necessary, it may be coated on a substrate and dried to obtain a film-like composite (for example, a heat ray absorbing film), or the composite may be separated and purified as necessary to obtain a solid (for example, powder)-like composite. The solid (for example, powder)-like composite may be used as an additive for a heat ray absorbing film, or a film-like composite (for example, a heat ray absorbing film) may be produced by secondary processing.

[0068] (aqueous dispersion) The aqueous dispersion of one embodiment contains an amorphous sulfated polysaccharide, polythiophene, and water. Further, the aqueous dispersion of another embodiment contains an amorphous sulfated polysaccharide, polythiophene, and at least one resin selected from a water-soluble resin and an aqueous emulsion resin, and water.

[0069] (Heat ray absorption film) The heat ray absorption film of this embodiment contains the above-mentioned composite. In one embodiment, the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm of the heat ray absorption film is 4.5 or more, preferably 5.0 or more, and 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 it is, and although there is no particular limitation on the upper limit thereof, it is usually 8.0 or less.

[0070] The heat ray absorption film only needs to contain the above-mentioned amorphous sulfated polysaccharide and polythiophene derived from the composite, and other components may be contained. Examples of other components include the above-mentioned additives and other polymers.

[0071] In one embodiment, by adding the composite to a polymer, a heat ray absorbing film having excellent heat ray absorbing characteristics derived from the composite can be obtained. Examples of the polymer that is the matrix of the heat ray absorbing film include vinyl acetate-polyvinyl alcohol copolymer, polypropylene glycol, polyethylene glycol, polyvinyl alcohol, polyvinyl alcohol-ethylene copolymer, polyvinyl alcohol-butenediol copolymer, polyethylene-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, polyalkyl (alkyl group having 1 to 18 carbon atoms) (meth)acrylate, 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, hydroxyalkylene (alkylene 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, phenol resin, siloxane polymer, silsesquioxane, and the like.

[0072] The thickness of the heat ray absorbing film is not particularly limited, and is, for example, 1 to 10000 μm, preferably 10 to 1000 μm, and more preferably 10 to 100 μm. Among the heat ray absorbing films, those having a small thickness, for example, those having a thickness of 0.1 to 10 μm, may sometimes be referred to as heat ray absorbing films, but in the present disclosure, the heat ray absorbing film is included in the heat ray absorbing film.

[0073] The manufacturing method of the heat ray absorbing film is not particularly limited, and for example, it can be obtained by a method of applying a dispersion of the composite on a substrate and drying it. The method of applying the dispersion of the composite on the substrate is not particularly limited, and examples thereof include methods by coating such as spray coating method, spin coating method, air knife coating method, curtain coating method, blade coating method, dip coating method, casting method, two-roll coating method, gate roll press method, roll coating method, bar coating method, die coating method, gravure method, mist method, etc.; wet processes such as methods by patterning such as printing and inkjet. Among these, the spin coating method and the casting method are preferred.

[0074] The drying method is not particularly limited, and examples thereof include natural drying, heat drying, freeze drying, vacuum drying, hot air drying, hot press drying, infrared drying, supercritical drying, etc. The drying temperature is appropriately set according to the drying method. For example, a range of 50°C to 250°C is preferred, more preferably a range of 60°C to 150°C. The drying temperature is even more preferably in the range of 80°C to 120°C. By setting the drying temperature to 250°C or lower, it is possible to suppress the deterioration of the heat ray absorption characteristics of the composite during drying. Also, by setting the drying temperature higher, the drying time and the quality of the coating film during drying can be improved.

[0075] Examples of the substrate include a glass plate, a plastic sheet, a plastic film, etc. Examples of the plastic include polyester, polyethylene, polypropylene, polystyrene, polyimide, poly(meth)acrylate, polyamide, polyethylene terephthalate, polyethylene naphthalate, epoxy resin, chlorine-based resin, silicon-based resin, phenol resin, and those blended with these.

[0076] The laminate of the present embodiment is a laminate in which an adhesive layer and a release layer are laminated on one side of the above-described heat ray absorbing film. By laminating the adhesive layer and the release layer on one side of the heat ray absorbing film, it is possible to easily peel off the release layer during use and attach the heat ray absorbing film to a substrate or the like via the adhesive layer. There are no particular restrictions on the adhesive layer and the release layer, and for example, conventionally known ones can be appropriately used.

[0077] (Paint) The composite is usually in a solid state, but a dispersion of the composite can be used as a paint (for example, a heat insulating paint). That is, the paint of the present embodiment is a paint containing the above-described composite. In one embodiment, a paint containing the above-described composite and a dispersion medium (for example, water) can be mentioned. As another embodiment, a paint containing the above-described composite, at least one resin selected from a water-soluble resin and an aqueous emulsion resin, and a dispersion medium (for example, water) can be mentioned.

[0078] For example, by coating a substrate such as a glass plate with a paint, a laminate in which a composition containing the composite is coated on the substrate may be obtained.

Examples

[0079] Hereinafter, the present embodiment will be described with reference to examples, but the present disclosure is not limited to these examples.

[0080] In the examples, the following sulfated polysaccharides were used. Lambda-carrageenan: manufactured by Tokyo Chemical Industry Kappa-carrageenan: manufactured by Tokyo Chemical Industry Iota-carrageenan-1: manufactured by Tokyo Chemical Industry Iota-carrageenan-2: TS Gel SV manufactured by Taisho Technos

[0081] <Calculation of the number of constituent monosaccharides of carrageenan> Weighed 0.5 g of carrageenan and 500 g of ion-exchanged water, dispersed them at 60 °C for 1 hour, and then filtered through a 0.45 μm membrane filter to obtain a measurement solution. 20 μl of this solution was injected into a gel permeation chromatography measurement device (manufactured by Waters, Acquity UPLC H-Class Bio) to measure the number average molecular weight. Standard pullulan was used as the molecular weight standard. 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, which is the constituent unit of carrageenan.

[0082] [Synthesis Example 1] 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, stirred them for about 30 seconds using a magnetic stirrer at room temperature of 23 °C to prepare a defibrated solution.

[0083] Next, 5.0 g of softwood kraft pulp NBKP (manufactured by Nippon Paper Industries) was added to the defibrated solution, and the mixture was further stirred at room temperature of 23 °C for 120 minutes to carry out a sulfuric acid esterification reaction. After stirring, 250 ml of distilled water was added to the defibrated 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. Thereafter, the supernatant was removed by centrifugation to obtain a solid content.

[0084] Furthermore, 1350 ml of distilled water and 1350 ml of ethanol were added to the solid content and stirred until uniformly dispersed, and then the supernatant was removed by centrifugation to obtain a solid content. The same procedure was repeated for a total of 6 washings. The centrifugation speed in each operation was 12000 rpm, and the centrifugation time was 50 minutes. After washing by centrifugation, distilled water was added to the solid content and diluted until the total weight reached 1000 g to obtain a non-uniform mixture containing sulfuric acid esterified microcrystalline cellulose fibers and water.

[0085] Next, a 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 sulfated microcrystalline cellulose fibers were uniformly dispersed. Subsequently, 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 body of sulfated microcrystalline cellulose fibers.

[0086] Subsequently, 5 g of the dried body of sulfated microcrystalline cellulose fibers was treated for 3 minutes with a dry grinder (Wonder Blender WB1, manufactured by Osaka Chemical Co., Ltd.) to obtain Sample No. 1, which is a powder of sulfated microcrystalline cellulose fibers.

[0087] [Synthesis Example 2] 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 cooled to 10°C. 3.6 ml of chlorosulfonic acid was added dropwise to the DMF containing softwood kraft pulp NBKP over 60 minutes under a nitrogen atmosphere, and the mixture was stirred for 1 hour to obtain a reaction solution.

[0088] The reaction solution was poured into 5000 ml of a saturated sodium acetate solution for reprecipitation, and then the supernatant was removed by centrifugation to obtain a solid content. The solid content was washed once with a saturated ethanol solution of sodium acetate and then washed with ethanol until the supernatant became neutral. Thereafter, the supernatant was removed by centrifugation to obtain a solid content, distilled water was added to the solid content, and it was diluted until the total weight reached 1000 g to obtain a heterogeneous mixture containing sulfated microcrystalline cellulose fibers and water.

[0089] Next, a 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 sulfated microcrystalline cellulose fibers were uniformly dispersed. Subsequently, 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 body of sulfated microcrystalline cellulose fibers.

[0090] Subsequently, 5 g of the dried sulfuric acid esterified microcrystalline cellulose fibers were treated with a dry grinder (Wonder Blender WB1, manufactured by Osaka Chemical Co., Ltd.) for 3 minutes to obtain Sample No. 2, which is sulfuric acid esterified microcrystalline cellulose fiber powder.

[0091] <Calculation of the number of constituent monosaccharides of sulfuric acid esterified nanocellulose> 0.12 g of the solid content of the sulfuric acid esterified microcrystalline cellulose fiber powder was dissolved in 63.0 g of 0.5 M copper ethylenediamine solution and kept at 25 °C. Then, using a Cannon-Fenske viscometer tube, the flow-down time of the sulfuric acid esterified microcrystalline cellulose fiber / copper ethylenediamine solution was measured to measure the viscosity.

[0092] Regarding the viscosity of this sulfuric acid esterified microcrystalline cellulose fiber / copper ethylenediamine solution as η and the viscosity of the 0.5 M copper ethylenediamine solution as η0, the average degree of polymerization was calculated by the following formula. Limiting viscosity [η] = (η / η0) / {c(1 + A×η / η0)} (Here, c is the concentration of the sulfuric acid esterified microcrystalline cellulose fiber (g / dL) at the time of viscosity measurement, and A is a specific value depending on the type of solution. In the case of a 0.5 M copper ethylenediamine solution, A = 0.28.) Average degree of polymerization DP = [η] / aK (K and a are values determined by the type of polymer and the solvent used. In the case of cellulose dissolved in copper ethylenediamine, K = 5.7×10 -3 , a = 1.) The sulfuric acid esterified microcrystalline cellulose fiber was regarded as the average degree of polymerization and the number of constituent monosaccharides.

[0093] <Quantification of the amount of introduced sulfuric acid ester groups> Using the combustion absorption-IC method, the sulfur content due to carrageenan or sulfated microcrystalline cellulose fibers was quantified. Specifically, dry carrageenan or sulfated microcrystalline cellulose fiber powder (0.01 g) was placed on a magnetic board and burned in an oxygen atmosphere (flow rate: 1.5 L / min) in a circular furnace (1350 °C), and the generated gas components were absorbed into 3% hydrogen peroxide solution (20 ml). The resulting absorption solution was made up to 100 ml with pure water, and the sulfate ion concentration (mass%) of the diluted solution was measured by ion chromatography. Based on the measurement results, the sulfur introduction amount (mmol / g) due to sulfate ester groups per 1 g of carrageenan or sulfated microcrystalline cellulose fiber powder was calculated.

[0094] <Measurement method of crystallinity> Using an X-ray diffraction (XRD) apparatus (manufactured by Rigaku Corporation: SMARTLAB-9KW), I 200 : From the diffraction intensity of the lattice plane (200 plane) and I am : the diffraction intensity of the amorphous part, the crystallinity was calculated using the following formula 1. Cellulose I crystallinity (%) = [((I 200 - I am ) / I 200 × 100... Formula 1 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°.

[0095] <Measurement method of viscosity> 100 g of a 1 wt% aqueous dispersion of carrageenan or sulfated nanocellulose was defoamed with a defoaming device (manufactured by Shin-Kee, Foam Removing Rintaro ARE-310) for 10 seconds and allowed to stand for 24 hours. Subsequently, using a viscosity and viscoelasticity measuring device (manufactured by Thermo Fisher Scientific K.K., HAAKE MARS40), viscosity measurement was performed at a rotational speed of 6.0 rpm and a set temperature of 20 °C, and the viscosity at the 10-minute point after the start of measurement (after the start of rotation) was recorded.

[0096] The analysis results of each carrageenan and the sulfated microcrystalline cellulose fiber (S-CNF) obtained in the synthesis example are shown in Table 1.

[0097] [Table 1]

[0098] (Synthesis of PEDOT / Carrageenan or PEDOT / S-CNF) [Examples 1 - 4, Comparative Examples 1 - 2] Ion exchange was performed on 0.375 g each of lambda-carrageenan, kappa-carrageenan, iota-carrageenan-1, iota-carrageenan-2, and the sulfated microcrystalline cellulose fiber of Synthesis Example 1 or 2 to prepare 37.5 g of a 1.0 wt% aqueous dispersion. 0.332 g of 3,4-ethylenedioxythiophene (EDOT) was added thereto, 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 peroxydisulfate were added, and the mixture was stirred at room temperature for 24 hours. After stirring, dialysis was performed using a dialysis membrane for 72 hours or more to obtain an aqueous dispersion of a composite of poly(3,4-ethylenedioxythiophene) PEDOT / carrageenan or PEDOT / sulfated microcrystalline cellulose fiber.

[0099] (Change in EDOT amount) [Example 5] An aqueous dispersion of a PEDOT / carrageenan composite was obtained in the same manner as in Example 3 (using iota-carrageenan-1), except that the charged amount of EDOT was changed from 0.332 g to 0.266 g.

[0100] [Example 6] An aqueous dispersion of a PEDOT / carrageenan composite was obtained in the same manner as in Example 3 (using iota-carrageenan-1), except that the charged amount of EDOT was changed from 0.332 g to 0.199 g.

[0101] (Analysis of PEDOT / Carrageenan or PEDOT / S-CNF) <Method for Measuring Absorbance> The aqueous dispersions of the PEDOT / carrageenan or PEDOT / sulfate esterified microfibrillated 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, the absorbance was measured every 1 nm in the wavelength range of 200 nm to 1800 nm. The absorbance at 500 nm obtained was defined as the "absorbance of visible light", and the absorbance at 1800 nm was defined 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.

[0102] <Quantification of Carrageenan Content> 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 in an autoclave at 120 °C for 60 minutes. After adding 1 mL of galactosamine hydrochloride as an internal standard thereto, 20 μL was aliquoted, 80 μL of 0.5 mol / L aqueous sodium hydroxide 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. Thereafter, 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 with a touch mixer for 30 seconds or more, centrifugation was performed to remove the supernatant. 2 mL of toluene was added to the lower layer, and washing was performed by stirring, centrifugation, and removal of the supernatant, and the filtered product through a membrane filter was injected into HPLC (high performance liquid chromatography method, apparatus: manufactured by Thermo Fisher Scientific, Ultimate 3000 HPLC) at 5 μL to quantify the galactose component. From the galactose concentration after hydrolysis, the ratios (mass ratios) of PEDOT and carrageenan in the PEDOT / carrageenan composite were determined. The PEDOT / S-CNF composite was treated in the same manner to determine the glucose concentration, and the ratios (mass ratios) of PEDOT and S-CNF in the PEDOT / S-CNF composite were determined.

[0103]

Table 2

[0104] (Preparation of PEDOT / Carrageenan Film or PEDOT / S-CNF Film) [Examples 7 - 10, Comparative Examples 3 - 6] The aqueous dispersions of the composites of PEDOT / carrageenan or PEDOT / sulfate esterified microcrystalline cellulose fibers obtained in Examples 1 - 4 and Comparative Examples 1 and 2 were dried by an evaporator and then redispersed in water to adjust the solid content concentration of the dried product so that the viscosity (rotation speed 6.0 rpm, set temperature 20 °C) became about 1200 mPa·s, and an aqueous dispersion was prepared. To 100 g of this aqueous dispersion, 0.1 g of octylphenol ethoxylate (manufactured by Nacalai Tesque, Triton X - 100) was added as a surfactant, and the coating liquid was prepared by stirring well.

[0105] The coating liquid was applied to a polyester film (manufactured by Toray, Lumirror (registered trademark) T60) by appropriately setting the gap of the doctor blade so as to obtain the coating film thickness shown in Table 3. After coating, drying was carried out at 80 °C until the coating liquid was dried to obtain a heat ray absorbing film.

[0106] (Analysis of Heat Ray Absorbing Film) <Measurement Method of Film Thickness> The film thickness of the obtained heat ray absorbing film was measured using a 3D measurement laser microscope (manufactured by Olympus, OLS5100).

[0107] <Measurement Method of Absorbance> The obtained heat ray absorbing film was measured for absorbance every 1 nm in the wavelength range of 200 nm to 1800 nm using a near-infrared spectrophotometer manufactured by Agilent Technologies, Inc. The absorbance at 500 nm obtained was regarded as the "absorbance of visible light", and the absorbance at 1800 nm was regarded 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.

[0108] (Viscosity of Aqueous Dispersion Containing 2 wt% Composite) The aqueous dispersions of the composites of PEDOT / carrageenan or PEDOT / sulfuric acid esterified microcrystalline cellulose fibers obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were dried by an evaporator, and then the composites (dried products) were redispersed in water to prepare an aqueous dispersion containing 2 wt% of the composites. For the aqueous dispersion containing 2 wt% of the composites, the viscosity (rotation speed 6.0 rpm, set temperature 20 °C) was measured.

[0109] [Table 3]

[0110] [Table 4]

[0111] The composite of the present embodiment can increase the solid content concentration in an aqueous dispersion having a similar viscosity as compared with the comparative example. Therefore, when manufacturing a heat ray absorption film having a similar dry film thickness, the coating film thickness can be made thinner as compared with Comparative Examples 3 and 4, so the drying time can be significantly shortened. Further, when coating with a similar coating film thickness, the film thickness of the heat ray absorption film can be made thicker as compared with Comparative Examples 5 and 6.

[0112] [Example 11] (Preparation of PEDOT / carrageenan - water - soluble resin film) 91.7 g of butanediol 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.

[0113] 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.

[0114] The coating liquid was applied to a polyester film (manufactured by Toray Industries, Inc., Lumirror (registered trademark) T60) with a doctor blade set at a gap of 155 μm. After coating, it was dried at 80°C for 30 minutes to obtain a water-soluble resin heat ray absorption film.

[0115] [Example 12] (Preparation of PEDOT / Carrageenan - Aqueous Emulsion Resin Film) 7.1 g of the aqueous dispersion of the PEDOT / carrageenan composite obtained in Example 9 was added while stirring well to 14.1 g of urethane acrylate (manufactured by Daicel - Ornex Co., Ltd., UCECOAT 7200, solid content concentration 65 wt%). 0.49 g of a photoinitiator (manufactured by BASF, IRGACURE 1173) and 0.10 g of a surface conditioner (manufactured by Nissin Chemical Industry Co., Ltd., Surfynol 104E) were added and stirred well to prepare an aqueous emulsion resin coating liquid.

[0116] The coating liquid was applied to a polyester film (manufactured by Toray Industries, Inc., Lumirror (registered trademark) T60) with a doctor blade set at a gap of 110 μm. After coating, it was dried at 80°C for 10 minutes. Next, it was irradiated with an ultraviolet irradiation device (manufactured by Eye Graphics Co., Ltd., Eye Gratage ECS - 401GX type) at an illuminance of 200 mW·cm 2 , and an integrated light quantity of 800 mJ / cm 2 to be cured, obtaining a water-soluble resin heat ray absorption film.

[0117]

Table 5

[0118] It was confirmed that the composite of this embodiment is excellent in heat ray absorption characteristics in both the state of the aqueous dispersion and the film.

[0119] The upper limit value and / or lower limit value of the numerical range described in this specification can respectively be arbitrarily combined to define a preferred range. For example, the upper limit value and lower limit value of the numerical range can be arbitrarily combined to define a preferred range, the upper limit values of the numerical range can be arbitrarily combined to define a preferred range, and also the lower limit values of the numerical range can be arbitrarily combined to define a preferred range. Further, in the present application, the numerical range represented by the symbol "~" includes each of the numerical values described before and after the symbol "~" as the lower limit value and the upper limit value.

[0120] As described above in detail for this embodiment, the specific configuration is not limited to this embodiment, and even if there are design changes within the scope not departing from the gist of the present disclosure, they are included in the present disclosure.

Claims

1. A complex comprising an amorphous sulfated polysaccharide and polythiophene.

2. The complex according to claim 1, wherein the amorphous sulfated polysaccharide is at least one amorphous sulfated polysaccharide selected from carrageenan, sacran, laminaran sulfate, fucoidan, chondroitin sulfate, porphyran, funoran, dermatan sulfate, and heparin.

3. The complex according to claim 1, wherein the amorphous sulfated polysaccharide is at least one carrageenan selected from lambda-carrageenan, kappa-carrageenan, and iota-carrageenan.

4. The complex according to claim 1, wherein 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). 【Chemical 1】 (In general formulas (1) and (2), R is independently a hydrogen atom or a group represented by the following general formula (3), provided that at least one of the Rs in parentheses is a group represented by the following general formula (3), and n represents the number of repetitions in parentheses.) 【Chemical 2】 (In general formula (3), X is a hydroxy group or -O － (M ｍ＋ ) １／ｍ wherein m is an integer of 1 or more and 3 or less, M ｍ+ is an m-valent cation, and the wavy line is a bonding site with other atoms.)

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

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

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

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

9. The complex according to claim 1, wherein the value obtained by dividing the absorbance at 1800 nm by the absorbance at 500 nm of an aqueous dispersion containing 0.01 wt% of the complex is 4.5 or more, the absorbance at 500 nm 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.

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

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.

12. A heat ray absorbing film comprising the complex according to claim 1.

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

14. A laminate in which an adhesive layer and a release layer are laminated on one side of the heat ray absorption film according to claim 12.

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