Molded product and method for producing molded product

Abstract

To provide a molded product containing phycocyanin and a method for producing a molded product.SOLUTION: The present invention provides a molded product obtained by molding a resin composition containing a colorant, where the colorant contains phycocyanin. The phycocyanin may be phycocyanin derived from blue-green algae of the Spirulina genus, LINABLUE G1 (product name, manufactured by DIC LIFETEC Co., Ltd.), or water-insolubilized (laked) phycocyanin.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a molded article and a method for producing the molded article. [Background technology]

[0002] Traditionally, coloring materials such as dyes and pigments have been widely used to impart color to various applications such as inks, paints, cosmetics, molded products, etc. Among these, synthetic colorants such as Blue No. 1 and Yellow No. 5 have also been used for food applications. In recent years, there has been a strong tendency to avoid synthetic colorants due to concerns about their carcinogenicity, and expectations are growing for natural dyes, which are thought to be safer. Recently, there is an increasing demand for natural materials not only for food applications as described above but also for industrial applications, and there is a demand for the use of natural dyes as colorants for packaging and cushioning materials. When packaging paper or cushioning materials colored with industrial dyes are used as food containers, problems have arisen such as the color bleeding or fading of the dye components due to water such as rainwater, which can contaminate food that has come into contact with the paper or cushioning materials.

[0003] For example, phycocyanin, an algae pigment, is a natural blue pigment. Phycocyanin is a protein-bound pigment that is known to be able to be extracted from cyanobacteria such as spirulina. Phycocyanin is a pigment that exhibits a vivid blue color, and there are high expectations in the market for it as a sustainable pigment.

[0004] Patent Document 1 describes an acidic aqueous coloring material solution that contains phycocyanin (A), a polycarboxylic acid (B) containing one or more hydroxyl groups, and at least one nonionic emulsifier (C) having an HLB of 15 or more selected from the group consisting of sucrose esters and polyglycerol esters, and discloses that the aqueous coloring material solution is used in foods and beverages, pharmaceuticals such as tablets, and cosmetics. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2020 / 129745 Summary of the Invention [Problem to be solved by the invention]

[0006] However, research into the incorporation of phycocyanin into molded products has not been carried out sufficiently, and there has been a problem in that its usefulness has not been fully elucidated or utilized.

[0007] Therefore, the problem to be solved by the present invention is to provide a molded article containing phycocyanin and a method for producing the molded article. [Means for solving the problem]

[0008] As a result of intensive research, the present inventors have found that the above problems can be solved by molding a resin composition containing phycocyanin by various methods.

[0009] That is, the present invention provides the following inventions. [1] A molded article obtained by molding a resin composition containing a colorant, wherein the colorant contains phycocyanin.

[0010] [2] The molded article according to [1], wherein the phycocyanin is derived from cyanobacteria of the genus Spirulina.

[0011] [3] The molded article according to [1] or [2], wherein the phycocyanin is Linablue G1 (trade name, manufactured by DIC Lifetech Co., Ltd.).

[0012] [4] The molded article according to any one of [1] to [3], wherein the colorant contains phycocyanin insoluble in water (laked).

[0013] [5] The molded article according to any one of [1] to [3], wherein the colorant is a composite of phycocyanin and a silica structure.

[0014] [6] The molded article according to [5], wherein the silica structure is a two-phase continuous silica structure consisting of a phase mainly composed of silica, the chemical bonds of which are Q4 bonds, and an air phase.

[0015] [7] The molded article according to [1], wherein the resin composition contains a resin produced using a compound derived from a biomass resource.

[0016] [8] The molded article according to [7], wherein the compound derived from a biomass resource is a diol compound.

[0017] [9] The molded article according to [1], wherein the resin composition contains an active energy ray-curable compound.

[0018]

[10] The molded article according to [1], wherein the resin composition contains a thermosetting resin or a thermoplastic resin.

[0019]

[11] A molded article of [1] further containing filler, inorganic fibers, or organic fibers.

[0020]

[12] A molded product of any of [1] to

[11] , which is used for automobile body exteriors, plastics for building materials, steel sheets for building materials, housing equipment, or daily necessities.

[0021]

[13] Any of the molded products [1] to

[12] molded by compression molding, injection molding, extrusion molding, casting molding, foam molding, or optical stereolithography.

[0022]

[14] A step 1 of coating a resin substrate with the resin composition to obtain a coated product; Step 2: obtaining a laminate having a cured material layer by irradiating the coated material with active energy rays or heating the coated material; and a step 3 of bending the obtained laminate. Effect of the Invention

[0023] According to the molded article and the manufacturing method of the molded article of the present invention, a molded article containing phycocyanin can be obtained. Since the molded article has a color characteristic of phycocyanin, it is expected that the molded article will affect human sensibility and reduce the burden on living organisms and the environment compared to molded articles using only synthetic pigments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0024] <Molded products> The molded article of the present invention is produced by molding a resin composition containing a colorant.

[0025] [Coloring agent] The colorant used in the present invention contains phycocyanin. Phycocyanin used in the present invention is a water-soluble pigment protein known as a photosynthetic pigment that exhibits a blue color. Phycocyanin is also known by other names such as blue-green algae, phycocyan, and algae green algae. Phycocyanin is a pigment protein having allophycocyanin, phycocyanobilin, and C-phycocyanin as chromophores, and is known to be contained in spirulina, blue-green algae, red algae, cryptophytes, and the like.

[0026] The raw material for phycocyanin is not particularly limited, but can be one obtained from biological materials such as algae containing phycocyanin, such as spirulina, blue-green algae, red algae, and cryptophyte, and preferably phycocyanin obtained from blue-green algae, and more preferably phycocyanin obtained from spirulina.

[0027] Spirulina used as a raw material for phycocyanin is a unicellular algae belonging to the order Oscillatory, Cyanobacteria, and examples thereof include Spirulina geitlerii, Spirulina platensis, Spirulina maxima, Spirulina mayer, Spirulina laxissima, Spirulina aldaria, etc. The origin of the spirulina in the present invention is not particularly limited, and natural products and artificially cultured products can be used as appropriate.

[0028] The phycocyanin used in the present invention can be obtained by extracting the above-mentioned spirulina, blue-green algae, red algae, cryptophyte algae, etc. The method for extracting phycocyanin is not particularly limited as long as it is a method that can obtain phycocyanin, and known methods such as crushing, extraction, squeezing, centrifugation, and supercritical extraction can be used alone or in combination. In addition, known extraction methods such as the methods described in JP-A-2003-342489 and JP-A-4677250 can be used.

[0029] The extraction solvent used to extract phycocyanin may be one or a combination of two or more selected from water or organic solvents, and examples of these extraction solvents include water, alcohols such as ethanol and methanol, and various organic solvents such as hexane and pentane, and preferably water, ethanol, and mixtures thereof. In addition, when extracting with these extraction solvents, various additives may be added to the extent that the effects of the present invention are not impaired in order to increase the extraction efficiency.

[0030] The amount of the extraction solvent used to extract phycocyanin is preferably about 1 to 1000 times, more preferably about 5 to 200 times, the amount of the raw algae such as spirulina. The extraction method is not particularly limited, but it is usually sufficient to use a method ranging from room temperature to the boiling point of the solvent under normal pressure, and the extraction operation may be performed once or multiple times. When extracting phycocyanin multiple times, fresh extraction solvent can be added to the residue after extraction again and the extraction operation can be performed, or the extraction solvent can be brought into contact with the extraction raw material multiple times. If necessary, further purification treatment such as centrifugation or filtration can be added, and the mixture can be concentrated and dried by a vacuum concentration device such as an evaporator or by removing the solvent by heating.

[0031] The phycocyanin used in the examples of the present invention is a commercially available product mixed with a stabilizer, Linablue G1 (manufactured by DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%). As described in JP-A-11-299450, trehalose is used to increase thermal stability, and citric acid is used as a pH adjuster.

[0032] The colorant may contain phycocyanin insoluble in water (laked).

[0033] The colorant may be a composite of phycocyanin and a silica structure.

[0034] The silica structure may be a two-phase continuous silica structure consisting of a phase mainly composed of silica in which the chemical bonds are Q4 bonds, and an air phase.

[0035] The fact that the chemical bond of silica is composed of Q4 bonds means that it does not substantially have silanol groups. The silanol group is a functional group that is hydrophilic and has a high affinity for water. For this reason, for example, when a water-soluble dye is used in combination with a silica compound having a silanol group, the silica compound adsorbs or absorbs water, which makes the dye more likely to come off the silica, and as a result, it is thought that this may cause bleeding. On the other hand, it is difficult for silica composed of highly hydrophobic Q4 bonds to adsorb water-soluble dyes to its surface. In this situation, the specific structure of phycocyanin can interact with the two-phase cocontinuous silica structure of the present application, and as a result, a complex of phycocyanin and a two-phase cocontinuous silica structure can be prepared in a simple manner, and this can be used as a water-insoluble dye. This is the present invention.

[0036] The two-phase co-continuous silica structure is not particularly limited as long as it is substantially free of silanol groups as described above and the air phase and the silica phase are co-continuous.

[0037] A simple method for obtaining such a two-phase bicontinuous silica structure is to use silica obtained by an existing silica synthesis method as a precursor raw material, utilize the affinity between a metal oxide that exhibits high-temperature sublimation and silica, and infiltrate the vapor of the metal oxide near the silanol groups, where the silica is scraped off, the chemical bonds of the silica are converted into Q4 bonds, and hollow tunnels are formed from the outer surface of the structure to the entire interior, making the two phases of silica and air continuous with each other.

[0038] [Resin composition] The resin composition used in the present invention may contain a resin produced using a compound derived from a biomass resource.

[0039] Examples of the compounds derived from biomass resources include diol compounds, propylene, ethylene, monoethylene glycol, terephthalic acid, sebacic acid, hexamethylenediamine, isosorbide, hydroxyalkanoic acid, lactic acid, amino acids such as aspartic acid, succinimide, etc. Resins can be obtained by chemically synthesizing, fermenting, etc., these compounds.

[0040] The resin composition used in the present invention may contain a thermosetting resin or a thermoplastic resin (hereinafter simply referred to as a synthetic resin). A thermosetting resin is a resin that has the property of becoming substantially insoluble and infusible when cured by means of heating, radiation, catalysts, etc. Specific examples of thermosetting resins include phenolic resins, urea resins, melamine resins, benzoguanamine resins, alkyd resins, unsaturated polyester resins, vinyl ester resins, diallyl terephthalate resins, epoxy resins, silicone resins, urethane resins, furan resins, ketone resins, xylene resins, thermosetting polyimide resins, benzoxazine resins, active ester resins, aniline resins, cyanate ester resins, and styrene-maleic anhydride (SMA) resins. These thermosetting resins can be used alone or in combination of two or more.

[0041] Thermoplastic resin refers to a resin that can be melt molded by heating. Specific examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more.

[0042] The resin composition used in the present invention may contain an active energy ray-curable compound. The active energy ray-curable compound may be a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate.

[0043] Examples of monofunctional (meth)acrylates include alkyl (meth)acrylates having an alkyl group having 1 to 22 carbon atoms, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and lauryl (meth)acrylate; cycloalkyl (meth)acrylates, such as cyclohexyl (meth)acrylate and isobornyl (meth)acrylate; and ω-alkoxyalkyl (meth)acrylates, such as 2-methoxyethyl (meth)acrylate and 4-methoxybutyl (meth)acrylate. Examples of such hydroxyethyl (meth)acrylate include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, caprolactone-modified hydroxy(meth)acrylate (for example, trade name "Placcel" manufactured by Daicel Chemical Industries, Ltd.), polycarbonate-modified hydroxy(meth)acrylate, mono(meth)acrylate of polyester diol obtained from phthalic acid and propylene glycol, mono(meth)acrylate of polyester diol obtained from succinic acid and propylene glycol, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, and (meth)acrylic acid adducts of various epoxy esters.

[0044] Examples of polyfunctional (meth)acrylates having difunctionality from 2 to 5 include dihydric alcohol di(meth)acrylates such as 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and tripropylene glycol di(meth)acrylate; Polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, di(meth)acrylate of tris(2-hydroxyethyl)isocyanurate, di(meth)acrylate of diol obtained by adding 4 moles or more of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol, di(meth)acrylate of diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A, Di(meth)acrylates of diols obtained by adding ethylene oxide or propylene oxide to the isocyanurate, di(meth)acrylates or tri(meth)acrylates obtained by reacting 1 mole of tris(2-hydroxyethyl)isocyanurate with 2 to 3 moles of acrylic acid, trimethylolpropane tri(meth)acrylate, polyethylene glycol di(meth)acrylate modified with ethylene oxide, polypropylene glycol di(meth)acrylate modified with propylene oxide, tetramethylene oxide modified Polytetramethylene glycol di(meth)acrylate, glycerol tri(meth)acrylate modified with ethylene oxide, glycerol tri(meth)acrylate modified with propylene oxide, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, hydroxypivalic acid modified trimethylolpropane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate modified with ethylene oxide, trimethylolpropane tri(meth)acrylate modified with propylene oxide trimethylolpropane tri(meth)acrylate, phosphoric acid tri(meth)acrylate modified with ethylene oxide, pentaerythritol tetra(meth)acrylate modified with ethylene oxide, pentaerythritol tetra(meth)acrylate modified with propylene oxide, pentaerythritol tetra(meth)acrylate modified with tetraethylene oxide, polyester(meth)acrylate compounds synthesized by condensation reaction of polyhydric alcohol with (meth)acrylic acid and polyfunctional carboxylic acid,Examples of the epoxy (meth)acrylate compound include an epoxy (meth)acrylate compound and an acrylic acrylate compound synthesized by an addition reaction between a novolac type epoxy resin, a glycidyl group-containing acrylic polymer, and (meth)acrylic acid.

[0045] The resin composition used in the present invention may contain a filler, inorganic fibers, or organic fibers.

[0046] As a filler, for example, silica can be blended for the purpose of improving abrasion resistance. The silica is not limited, and known silica particles such as powdered silica, colloidal silica, nanosilica, etc. can be used. Examples of commercially available powdered silica particles include Aerosil 50 and 200 manufactured by Nippon Aerosil Co., Ltd., Sildex H31, H32, H51, H52, H121, and H122 manufactured by Asahi Glass Co., Ltd., E220A and E220 manufactured by Nippon Silica Industry Co., Ltd., SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., and SG Flake manufactured by Nippon Sheet Glass Co., Ltd. Examples of commercially available colloidal silica include methanol silica sol, IPA-ST, MEK-ST, PGM-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, and ST-OL, all of which are manufactured by Nissan Chemical Industries, Ltd.

[0047] Silica may be reactive silica. Reactive silica may be, for example, reactive compound modified silica. Reactive compounds may be, for example, reactive silane coupling agents having hydrophobic groups, compounds having (meth)acryloyl groups, compounds having maleimide groups, and compounds having glycidyl groups. Examples of commercially available powdered silica modified with a compound having a (meth)acryloyl group include Aerosil RM50 and R711 manufactured by Nippon Aerosil Co., Ltd., and examples of commercially available colloidal silica modified with a compound having a (meth)acryloyl group include MIBK-SD, MIBK-SD-L, MIBK-AC-2140Z, MEK-AC-2140Z, and the like manufactured by Nissan Chemical Industries, Ltd. Examples of reactive silica include silica modified with a glycidyl group such as 3-glycidoxypropyltrimethoxysilane and then subjected to an addition reaction with acrylic acid, and silica modified with a compound having a urethane reaction of 3-isocyanatepropyltriethoxysilane, a hydroxyl group, and a (meth)acryloyl group.

[0048] Fillers other than silica include inorganic fillers and organic fillers. There is no limitation on the shape of the filler, and examples of the filler include particulate, plate-like, and fibrous fillers. Examples of fillers with excellent heat resistance include alumina, magnesia, titania, zirconia, etc.; examples of fillers with excellent thermal conductivity include boron nitride, aluminum nitride, alumina oxide, titanium oxide, magnesium oxide, zinc oxide, silicon oxide, etc.; examples of fillers with excellent electrical conductivity include metal fillers and / or metal-coated fillers using metals or alloys (e.g., iron, copper, magnesium, aluminum, gold, silver, platinum, zinc, manganese, stainless steel, etc.); examples of fillers with excellent barrier properties include minerals such as mica, clay, kaolin, talc, zeolite, wollastonite, and smectite, potassium titanate, magnesium sulfate, sepiolite, zonolite, aluminum borate, calcium carbonate, titanium oxide, etc. those with a high refractive index include barium titanate, zirconia oxide, titanium oxide, etc.; those exhibiting photocatalytic properties include photocatalytic metals such as titanium, cerium, zinc, copper, aluminum, tin, indium, phosphorus, carbon, sulfur, cerium, nickel, iron, cobalt, silver, molybdenum, strontium, chromium, barium, lead, etc., composites of these metals, and oxides thereof; those with excellent abrasion resistance include metals such as alumina, zirconia, magnesium oxide, etc., and composites and oxides thereof; those with excellent electrical conductivity include metals such as silver and copper, tin oxide, indium oxide, etc.; and those with excellent ultraviolet ray shielding properties include titanium oxide, zinc oxide, etc. These inorganic fine particles may be selected according to the intended use, and may be used alone or in combination of two or more kinds. In addition, the inorganic fine particles have various properties other than those exemplified, so that they may be selected according to the intended use.

[0049] Examples of inorganic fibers include inorganic fibers such as carbon fibers, glass fibers, boron fibers, alumina fibers, and silicon carbide fibers, as well as carbon fibers, activated carbon fibers, graphite fibers, glass fibers, tungsten carbide fibers, silicon carbide fibers (silicon carbide fibers), ceramic fibers, alumina fibers, natural fibers, mineral fibers such as basalt, boron fibers, boron nitride fibers, boron carbide fibers, and metal fibers. Examples of the metal fibers include aluminum fibers, copper fibers, brass fibers, stainless steel fibers, and steel fibers.

[0050] Examples of organic fibers include synthetic fibers made of resin materials such as polybenzazole, aramid, PBO (polyparaphenylene benzoxazole), polyphenylene sulfide, polyester, acrylic, polyamide, polyolefin, polyvinyl alcohol, and polyarylate; natural fibers such as cellulose, pulp, cotton, wool, and silk; and regenerated fibers such as protein, polypeptide, and alginic acid.

[0051] [Other ingredients] The resin composition used in the present invention may contain any other components in addition to the above components, as long as the effects of the present invention can be obtained. Examples of other components include organic solvents, polymerization initiators, stabilizers, ultraviolet absorbers, and leveling agents. In addition, the composition may further contain inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, catalysts, surfactants, flow control agents, coupling agents, dyes, rheology control agents, antioxidants, plasticizers, and the like.

[0052] Examples of the organic solvent include ester-based solvents, ketone-based solvents, ether-based solvents, aliphatic solvents, aromatic solvents, and alcohol-based solvents. Specifically, examples of ester solvents include ethyl acetate, propyl acetate, and butyl acetate; examples of ketone solvents include acetone, 2-butanone, methyl ethyl ketone, and methyl isobutyl ketone; examples of ether solvents include tetrahydrofuran and dioxolane; examples of aliphatic solvents include hexane and cyclohexane; examples of aromatic solvents include toluene and xylene; and examples of alcohol solvents include ethanol, methanol, propanol, butanol, and propylene glycol monomethyl ether.

[0053] In addition, liquid organic polymers may be used to adjust viscosity. The liquid organic polymers are liquid organic polymers that do not directly contribute to the curing reaction, and examples thereof include modified carboxyl-containing polymers (Floren G-900, NC-500: Kyoeisha), acrylic polymers (Floren WK-20: Kyoeisha), amine salts of special modified phosphoric acid esters (HIPLAAD ED-251: Kusumoto Chemicals), modified acrylic block copolymers (DISPERBYK2000; BYK-Chemie), etc.

[0054] Since the resin composition of the present invention may be cured by active energy rays, a polymerization initiator, particularly a photopolymerization initiator, may be used. As the photopolymerization initiator, a known one may be used, and for example, one or more selected from the group consisting of acetophenones, benzil ketals, and benzophenones may be preferably used.

[0055] Specific examples of photoinitiated polymerization initiators include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, dienes, acetophenone compounds such as acetophenone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} and 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methyl-propan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyl-diphenyl sulfide; methylbenzoyl formate, oxyphenone α-ketoester compounds such as 2-(2-oxo-2-phenylacetoxyethoxy)ethyl ester of phenylacetic acid and 2-(2-hydroxyethoxy)ethyl ester of oxyphenylacetic acid; phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide; benzoin, benzoin methyl ether, Examples of such photoinitiators include benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; titanocene-based compounds; acetophenone / benzophenone hybrid photoinitiators such as 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfinyl)propan-1-one; oxime ester photoinitiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; and camphorquinone.

[0056] The photopolymerization initiators may be used alone or in combination of two or more kinds.

[0057] The resin composition used in the present invention may be blended with an ultraviolet absorbing agent for the purpose of improving weather resistance. As the ultraviolet absorbing agent, various compounds or substances can be used. Specific examples of ultraviolet absorbers include 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-hydroxy-3-(2-ethylhexyloxy)propyl)oxy]-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine; benzotriazine-based ultraviolet absorbers such as 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-5-(2-(meth)acryloyloxyethyl)phenyl]-2H-benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate and octyl-2-cyano-3,3-diphenylacrylate; inorganic fine particles that absorb ultraviolet light such as titanium oxide fine particles, zinc oxide fine particles, and tin oxide fine particles. The ultraviolet absorbers listed above may be used alone or in combination of two or more.

[0058] The ultraviolet absorber may be a commercially available product. Examples of commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 234, TINUVIN 326, TINUVIN 329, TINUVIN 900, TINUVIN 928, TINUVIN 360, TINUVIN 384-2, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 (all manufactured by BASF); Adeka STAB LA-46, Adeka STAB LA-F70, Adeka STAB LA-29, Adeka STAB LA-31G, Adeka STAB LA-32, and Adeka STAB LA-36 (all manufactured by ADEKA); and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

[0059] The resin composition used in the present invention may contain a hindered amine light stabilizer (HALS) for the purpose of improving weather resistance. As the hindered amine-based light stabilizer, known hindered amine-based light stabilizers can be used. Specifically, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-methoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-propoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 -butoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-pentyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-heptyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-nonyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate bis(1-decyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-dodecyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-(4-methoxybenzylidene)malonate, tetrakis(2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate tetracarboxylate, a condensation product of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol, and a condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-pentamethyl-4-piperidinol, and β,β,β,β-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5])undecane)diethanol.

[0060] Commercially available hindered amine light stabilizers can also be used. Commercially available products include TINUVIN123, TINUVIN292, TINUVIN152, TINUVIN144, TINUVIN622SF), TINUVIN111FDL, TINUVIN249, and Adeka STAB LA-52 (all manufactured by BASF); Adeka STAB LA-57, Adeka STAB LA-63P, Adeka STAB LA-68, Adeka STAB LA-72, Adeka STAB LA-81, Adeka STAB LA-82, and Adeka STAB LA-87 (all manufactured by ADEKA).

[0061] Various surface modifiers may be added to the resin composition used in the present invention in order to improve the leveling, slipperiness, or scratch resistance of the molded article surface. As the surface modifier, various additives that modify surface properties, which are commercially available under the names of surface conditioners, leveling agents, slipperiness imparting agents, antifouling agents, etc., can be used. Among them, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specifically, silicone-based polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone-based polymers and oligomers having a silicone chain and a polyester chain, fluorine-based polymers and oligomers having a perfluoroalkyl group and a polyalkylene oxide chain, fluorine-based polymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain, etc. may be used. At least one of these may be used. For the purpose of increasing the durability of the slipperiness, one containing a (meth)acryloyl group in the molecule may be used. Specific surface modifiers include EBECRYL350 (Daicel-Allnex Co., Ltd.), BYK-333 (BYK Japan Co., Ltd.), BYK-377 (BYK Japan Co., Ltd.), BYK-378 (BYK Japan Co., Ltd.), BYK-UV3500 (BYK Japan Co., Ltd.), BYK-UV3505 (BYK Japan Co., Ltd.), BYK-UV3576 (BYK Japan Co., Ltd.), Megafac RS-75 (DIC Corporation), Megafac RS-76-E (DIC Corporation), Megafac RS-72-K (DIC Corporation), Megafac RS-76-NS (DIC Corporation), Megafac RS-90 (DIC Corporation), Megafac RS-91 (DIC Corporation), Megafac RS-55 (DIC Corporation), Optool DAC-HP (Daikin Industries, Ltd.), ZX-058-A (T&K Corporation), Examples of the ZX-22-164A (Shin-Etsu Chemical Co., Ltd.), X-22-164B (Shin-Etsu Chemical Co., Ltd.), X-22-164C (Shin-Etsu Chemical Co., Ltd.), X-22-164E (Shin-Etsu Chemical Co., Ltd.), and X-22-174DX (Shin-Etsu Chemical Co., Ltd.) can be mentioned.

[0062] The molded article of the present invention is made by molding a resin composition containing phycocyanin, and therefore can exhibit a vivid blue or a color close to it, which can affect human sensibility. In addition, compared with molded articles using only synthetic colorants as colorants, the molded article can be more biologically and environmentally friendly.

[0063] <Method of manufacturing molded products> As a method for producing the molded product according to the present invention, various molding methods such as compression molding, injection molding, extrusion molding of composites, sheets, pipes, etc., casting molding, foam molding, or optical three-dimensional modeling can be applied.

[0064] For example, when molding by injection molding, various molding conditions are not particularly limited, and molding can be performed by a general method. For example, in an injection molding machine, the resin composition is melted at a temperature range of the melting point of the polyarylene sulfide resin or higher, preferably at a temperature range of the melting point + 10°C or higher, more preferably at a temperature range of the melting point + 10°C to the melting point + 100°C, and further preferably at a temperature range of the melting point + 20 to the melting point + 50°C, and then the resin composition is injected into a mold from a resin outlet and molded.

[0065] For example, when molding by optical three-dimensional modeling, it can be produced by a known method. Examples of the optical three-dimensional modeling method include a stereolithography (SLA) method, a digital light processing (DLP) method, and an inkjet method. The stereolithography (SLA) method is a method in which an active energy ray such as a laser beam is irradiated at a point onto a tank of a liquid curable resin composition, and the tank is cured one layer at a time while moving a modeling stage to perform three-dimensional modeling. The digital light processing (DLP) method is a method in which an active energy ray such as an LED is irradiated at a surface onto a tank of a liquid curable resin composition, and the tank is cured one layer at a time while moving a modeling stage to perform three-dimensional modeling.

[0066] The inkjet stereolithography is a method in which minute droplets of a stereolithography curable resin composition are ejected from a nozzle so as to draw a predetermined pattern, and then ultraviolet light is applied to form a cured thin film.

[0067] The molded article of the present invention can also be produced by a production method including the following steps 1 to 3.

[0068] <Process 1> Step 1 is a step of applying a resin composition containing phycocyanin to a substrate to obtain a coated product.

[0069] The substrate is not particularly limited, and may be, for example, a substrate containing a thermoplastic resin.Specific examples of the thermoplastic resin include polyethylene resin, polypropylene resin, polystyrene resin, rubber-modified polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, polymethyl methacrylate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyethylene terephthalate resin, ethylene vinyl alcohol resin, cellulose acetate resin, ionomer resin, polyacrylonitrile resin, polyamide resin, polyacetal resin, polybutylene terephthalate resin, polylactic acid resin, polyphenylene ether resin, modified polyphenylene ether resin, polycarbonate resin, polysulfone resin, polyphenylene sulfide resin, polyetherimide resin, polyethersulfone resin, polyarylate resin, thermoplastic polyimide resin, polyamideimide resin, polyetheretherketone resin, polyketone resin, liquid crystal polyester resin, fluororesin, syndiotactic polystyrene resin, and cyclic polyolefin resin. These thermoplastic resins can be used alone or in combination of two or more. Preferred are ABS resin, acrylic resin, polymethyl methacrylic resin and polycarbonate resin, and particularly preferred is polycarbonate resin.

[0070] The base material may contain ingredients other than the thermoplastic resin, and may contain, within the scope of not impairing the effects of the invention, solvents, various resins, reactive compounds, catalysts, polymerization initiators, organic fillers, inorganic fillers, organic solvents, inorganic pigments, organic pigments, extender pigments, clay minerals, waxes, surfactants, stabilizers, flow adjusters, coupling agents, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, plasticizers, and the like.

[0071] The shape of the substrate is not particularly limited, and may be flat, sheet-like, rod-like, or may have a three-dimensional structure or may be solid. Any shape may be used depending on the purpose, such as a shape having a curvature on the entire surface or on a part of the surface. There is also no limitation on the hardness, thickness, etc. of the substrate. Since the manufacturing method of the present invention is characterized in that the laminate is bent after it is manufactured, a shape such as a flat plate or sheet is particularly preferred.

[0072] (Coatings) The composition of the present invention can be applied to a thermoplastic resin substrate to obtain a coating. The coating method is not particularly limited, and includes spraying, spin coating, dip coating, flow coating, roll coating, blade coating, doctor roll coating, doctor blade coating, curtain coating, slit coating, screen printing, inkjet coating, etc. In this case, the viscosity of the composition may be adjusted with a solvent or the like.

[0073] <Process 2> Step 2 of the present invention is a step of irradiating the coated product obtained in step 1 with active energy rays to cure the composition, thereby obtaining a laminate having a cured layer.

[0074] The term "active energy ray curing" refers to curing a coating by irradiating it with active energy rays. Examples of active energy rays include ultraviolet rays, electron beams, α rays, β rays, γ rays, and other ionizing radiation. Among these, ultraviolet rays (UV) are particularly preferred from the standpoint of curability and convenience.

[0075] The light used for UV curing can be, for example, a low pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, a xenon lamp, an argon laser, a helium-cadmium laser, etc. Using these, it is possible to cure the coating film by irradiating the coated surface with UV light having a wavelength of about 180 to 400 nm, thereby forming a cured layer and obtaining a laminate. The amount of UV irradiation is appropriately selected depending on the type and amount of the photopolymerization initiator used.

[0076] (cured material layer) The thickness of the cured layer in the laminate of the present invention is preferably 0.5 to 40 μm. With a film thickness of 0.5 μm or more, abrasion resistance is sufficiently exhibited and the substrate can be protected. With a film thickness of 40 μm or less, bending resistance is excellent. Furthermore, the thickness is preferably 0.5 to 30 μm, more preferably 0.5 to 15 μm. Further preferably, the thickness is 1.0 to 7.0 μm, and particularly preferably 1.5 to 7.0 μm.

[0077] <Process 3> Step 3 of the present invention is a step of bending the laminate obtained in step 2 to obtain a molded article. In the present invention, even after the cured material layer having hard coat properties is formed on the laminate, bending can be performed thereafter due to excellent processability.

[0078] Examples of the bending process include a process in which the laminate is directly bent, as well as press molding, free blow molding, vacuum molding, pressure molding, twin composite molding, and the like.

[0079] (Application) The molded article of the present invention can be used in various applications, such as automobile body exteriors, plastics for construction materials, steel sheets for construction materials, housing equipment, and daily necessities. EXAMPLES

[0080] The present invention will be described in more detail below using formulation examples and production examples, but the present invention is not limited to the following embodiments. In the examples, "parts" and "%" are by weight unless otherwise specified.

[0081] (Formulation example 1: Resin composition 1) Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%) 0.5 to 20% by mass Acrylic resin 0.05~20% Cellulose fiber 5~30% Polyethylene Remainder

[0082] (Formulation example 2: Resin composition 2) Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%) 0.05 to 20% by mass Olefin polymer 1~30% Glass fiber 1~30% Glass flakes 1~30% PPS resin remainder

[0083] (Formulation example 3: Resin composition 3) Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%) 0.05 to 20% by mass Urethane acrylate compound 10~90% Photopolymerization initiator 1~20%

[0084] (Production Example 1: Molded product using resin composition 1) The materials described in the above Blend Example 1 are fed into a grinder, a twin-screw kneader, a pelletizer, etc., and pelletized. The resulting pellets are fed into an injection molding machine to obtain a molded product having a desired shape.

[0085] (Production Example 2: Molded product using resin composition 2) The materials described in the above Blending Example 2 are mixed uniformly in a tumbler, then fed into a vented twin-screw extruder, melt-kneaded under any desired conditions, and pelletized. The resulting pellets are fed into an injection molding machine to obtain a molded product of any desired shape.

[0086] (Production Example 3: Molded product using resin composition 3) The materials described in the above Blending Example 3 are put into a mixer, and a dilution is obtained with a solvent such as propylene glycol monomethyl ether. The obtained dilution is applied to a polycarbonate plate with a bar coater, and dried for a desired time to obtain a coating having a desired thickness. The obtained coating is irradiated with ultraviolet light using a high-pressure mercury lamp or the like to obtain a laminate. The obtained laminate is heated under specified conditions in a thermostatic machine and then bent to obtain a molded product having a desired shape.

[0087] In each of the above formulation examples, Linablue G1 can be replaced with phycocyanin powder in which phycocyanin and a silica structure are combined. For example, the phycocyanin powder composited with the silica structure is obtained by adding the raw materials of Production Examples A1 to A3 described later and a stirrer to a 100 mL eggplant flask, stirring the solution at room temperature (20°C) for 10 minutes, and leaving it to stand for 24 hours under light-shielded conditions. The mixture is filtered through filter paper, washed with 200 mL of ion-exchanged water until the washing liquid is no longer colored, and the filtered solid is dried in a vacuum dryer (740 mmHg) at 20°C for 12 hours to obtain a powder.

[0088] Manufacturing example A1 Silica structure 500mg Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%) 1250mg Ion-exchanged water 5mL

[0089] Manufacturing example A2 Silica structure 500mg Linablue G1 (DIC Lifetech Co., Ltd., trehalose 55%, phycocyanin pigment 40%, trisodium citrate 5%) 1.25g Ethylene glycol solution 5mL

[0090] Manufacturing example A3 Silica structure 500mg Brilliant Blue FCF (blue dye, manufactured by Kanto Chemical Co., Ltd.) 500mg Ion-exchanged water 5mL

Claims

1. A molded article obtained by molding a resin composition containing a colorant, The molded article is characterized in that the colorant contains phycocyanin.

2. 2. The molded article according to claim 1, wherein the phycocyanin is derived from blue-green algae of the genus Spirulina.

3. The molded article according to claim 1 or 2, wherein the phycocyanin is Linablue G1 (trade name, manufactured by DIC Lifetech Co., Ltd.).

4. The molded article according to any one of claims 1 to 3, wherein the colorant contains phycocyanin insoluble (laked) in water.

5. The molded article according to any one of claims 1 to 3, wherein the colorant is a composite of phycocyanin and a silica structure.

6. The molded article according to claim 5, wherein the silica structure is a two-phase continuous silica structure comprising a phase mainly composed of silica whose chemical bonds are Q4 bonds, and an air phase.

7. The molded article according to claim 1 , wherein the resin composition contains a resin produced using a compound derived from a biomass resource.

8. The molded article according to claim 7 , wherein the compound derived from a biomass resource is a diol compound.

9. The molded article according to claim 1 , wherein the resin composition contains an active energy ray-curable compound.

10. The molded article according to claim 1 , wherein the resin composition contains a thermosetting resin or a thermoplastic resin.

11. The molded article according to claim 1 , further comprising a filler, an inorganic fiber, or an organic fiber.

12. The molded article according to any one of claims 1 to 11, which is used for automobile body exteriors, plastic building materials, steel sheets for building materials, housing equipment, and daily necessities.

13. The molded article according to any one of claims 1 to 12, which is molded by compression molding, injection molding, extrusion molding, casting molding, foam molding, or optical stereolithography.

14. Step 1: applying the resin composition to a resin substrate to obtain a coated product; a step 2 of obtaining a laminate having a cured material layer by irradiating the coated material with active energy rays or heating the coated material; The method for producing a molded article according to any one of claims 1 to 13, further comprising a step 3 of bending the obtained laminate.