Polyester resin, binder for pigment printing, ink for pigment printing, and method for producing polyester resin

Abstract

The present invention pertains to a polyester resin which is a polycondensate of a starting material containing (a) polyethylene terephthalate and (b) an aliphatic diol having 6-16 carbon atoms, the content of component (a) in the starting material being 30-80 mol% relative to the total amount of the starting material, and the content of component (b) in the starting material being 20-50 mol% relative to the total amount of the starting material.

Description

Technical Field

[0001] The present disclosure relates to a polyester resin, a binder for pigment printing and dyeing, an ink for pigment printing and dyeing, and a method for producing the polyester resin. Background Art

[0002] Binder resins require various properties such as rubbing color fastness, heat resistance, and color development depending on their use. In particular, binder resins for printing and dyeing purposes for use in fiber products are required to have high washing durability, softness of the printed and dyed parts, and non-stickiness.

[0003] For example, in Patent Document 1, in an ink combination comprising an inkjet ink containing a pigment and a cationic dispersant and a processing liquid (i.e., a resin emulsion) containing polyester resin particles, a printed product with excellent rubbing color fastness can be formed by making the resin emulsion a forced emulsification type resin emulsion further containing an anionic surfactant, or making the polyester resin a self-emulsifying type resin emulsion having anionic properties.

[0004] In addition, in Patent Document 2, by using an ink containing coloring particles containing disperse dyes and polyester resins and water, the polyester resin in the ink is integrated with the polyester fibers through a simple heat treatment, and the disperse dye in the ink dispersed in a molecular state is diffused to the surface of the polyester fibers, thereby achieving a uniform appearance. Prior art literature

[0005] Patent Literature Patent Document 1: Japanese Patent Application Publication No. 2021-176935 Patent Document 2: Japanese Patent Application Publication No. 2019-182941 Summary of the invention Problems to be solved by the invention

[0006] However, the polyester resin of Patent Document 1 has a problem of insufficient durability in washing. In addition, the polyester resin of Patent Document 2 has a problem of hard feel and poor flexibility.

[0007] The present disclosure has been made in view of the above circumstances, and an object of the present disclosure is to provide a polyester resin having excellent washing durability and softness, a method for producing the polyester resin, and a pigment printing binder and a pigment printing ink containing such a polyester resin. Means of solving problems

[0008] The present disclosure includes the following embodiments [1] to

[10] . [1] A polyester resin which is a polycondensate of raw materials containing (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms, wherein: The content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material. The content of the component (b) in the raw material is 20 to 50 mol % based on the total amount of the raw material. [2] The polyester resin according to [1], wherein the aliphatic diol is a straight-chain aliphatic diol. [3] The polyester resin according to [1] or [2], wherein the raw material further contains at least one selected from a trivalent or higher polyol and a trivalent or higher polycarboxylic acid component. [4] The polyester resin according to [3], wherein the polycarboxylic acid contains 4 to 12 carbon atoms. [5] The polyester resin according to any one of [1] to [4], which is a reaction product obtained by reacting the polycondensate with a trivalent or higher polycarboxylic acid component. [6] The polyester resin according to any one of [1] to [5], which has an acid value of 5 to 20 mgKOH / g. [7] A binder for pigment printing and dyeing, comprising an aqueous emulsified dispersion of the polyester resin described in at least one of [1] to [6]. [8] A pigment printing ink comprising the pigment printing binder described in [7]. [9] A method for producing a polyester resin, comprising the step of polycondensing a raw material to obtain a polycondensate, The raw material contains (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms. The content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material. The content of the component (b) in the raw material is 20 to 50 mol % based on the total amount of the raw material.

[10] The method for producing a polyester resin according to [9], further comprising a step of reacting the obtained polycondensate with a trivalent or higher polycarboxylic acid component. Effects of the Invention

[0009] According to the present disclosure, a polyester resin having excellent washing durability and softness, a method for producing the polyester resin, a binder for pigment printing and textiles containing the polyester resin, and an ink for pigment printing and textiles can be provided. DETAILED DESCRIPTION

[0010] The polyester resin of the present embodiment is a condensation product of a raw material containing (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms, i.e., a polyester resin, wherein the content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material, and the content of the component (b) in the raw material is 20 to 50 mol% relative to the total amount of the raw material. Such a polyester resin has excellent washing durability and softness. In addition, the polyester resin of the present embodiment also tends to have excellent "non-stickiness".

[0011] The polyester resin of the present embodiment has a polyethylene terephthalate block. The polyethylene terephthalate block is a block having a structure in which two or more of the following structural units (1) are repeatedly bonded. It should be noted that in this specification, the content of the polyethylene terephthalate in the raw material or the polyethylene terephthalate block in the polyester resin is represented by the content (molar, etc.) of the following structural unit (1). [Chemistry 1]

[0012] The reason why the polyester resin of this embodiment is excellent in washing durability and softness is not necessarily clear, but since the PET used as a raw material is subjected to a polycondensation reaction, a polyethylene terephthalate block is introduced into the obtained polyester resin. It is believed that the strength of the resin is improved by the polyethylene terephthalate block, and the washing durability is excellent. In addition, since the polyester resin of this embodiment contains a unit derived from an aliphatic diol having 6 to 16 carbon atoms, it is believed that it is superior in softness compared to conventional polyester resins for printing and dyeing.

[0013] Typically, since polyethylene terephthalate blocks are introduced into the polyester resin, the raw material of the polyester resin of the present embodiment contains polyethylene terephthalate (PET) and also contains an aliphatic diol having 6 to 16 carbon atoms as a polyol component. The raw material may contain any polyol other than the polycarboxylic acid component or the component (b). PET is incorporated into the polymer chain of the polyester resin by polycondensation with the polyol component or the polycarboxylic acid component contained in the raw material. It should be noted that in the polycondensation reaction, all the raw materials may be mixed for reaction, or the raw materials may be divided into two or more stages for multi-stage reaction. The PET as a raw material may be pre-depolymerized before the polycondensation reaction, or may be depolymerized during the polycondensation reaction.

[0014] There is no limitation on the molecular weight distribution, composition, manufacturing method, form of the PET used, etc. In addition, PET may be PET made from petrochemical raw materials, bio-PET made from biomass raw materials, or recycled PET recovered from waste. Recycled PET is usually processed into flakes or pellets, and the weight average molecular weight may be about 30,000 to 90,000.

[0015] The intrinsic viscosity (IV) of PET at room temperature (25° C.) may be 0.6 to 0.9. IV can be measured according to the method of JIS K 7390 (2003).

[0016] The content of PET in the raw material is 30 to 80 mol% relative to the total amount of the raw material. From the viewpoint of further improving washing durability or softness, it is preferably 35 to 70 mol%, and more preferably 40 to 65 mol%. When it is less than 30 mol%, the strong polyethylene terephthalate block structure is reduced, the friction is weakened during washing, and the printed part is easy to fall off from the substrate. When it exceeds 80 mol%, the strong PET structure is too much, the printed part becomes hard, and it cannot follow the elongation and bending of the substrate. The total content of the PET depolymerized product in the above raw material can be calculated as the number of moles of the [terephthalic acid:ethylene glycol] unit (structural unit of the above general formula (1)) based on the charged mass of PET. The amount of components other than PET and the aliphatic diol having 6 to 16 carbon atoms (monomer components) in the raw material may be 50 mol% or less, 45 mol% or less, or 40 mol% or less relative to the total amount of the raw material.

[0017] <Polyol component> (Diol) The polyester resin of the present embodiment contains a unit derived from an aliphatic diol having 6 to 16 carbon atoms as a unit derived from a polyol component. Therefore, the raw material of the polyester resin contains an aliphatic diol having 6 to 16 carbon atoms. In this specification, the unit derived from a polyol component refers to a structural unit having a chemical structure obtained by polycondensing the polyol.

[0018] The aliphatic diol having 6 to 16 carbon atoms may be a straight-chain or branched diol, or a straight-chain diol. Examples of the straight-chain aliphatic diol having 6 to 16 carbon atoms include 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol. One or more aliphatic diols having 6 to 16 carbon atoms may be used. Examples of the branched aliphatic diol having 6 to 16 carbon atoms include 2,4-dimethyl-2,4-pentanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-decanediol, 2,2-diethyl-1,3-propanediol, 1,2-hexanediol, 1,2-octanediol, 1,2-hexadecanediol, 3-methyl-1,5-pentanediol, 1-tert-butyl-1,2-ethanediol, 3-ethoxypropane-1,2-diol, 1,4-octanediol, 1,5-heptanediol, and 2,7-octanediol. The content of the aliphatic diol having 6 to 16 carbon atoms in the raw material is preferably 25 to 47 mol %, more preferably 30 to 45 mol %, based on the total amount of the raw material.

[0019] The polyol component may contain a diol other than the aliphatic diol having 6 to 16 carbon atoms. Examples of such a diol include aliphatic diols having 5 or less carbon atoms or 17 or more carbon atoms, aromatic diols, alicyclic diols, etc. The aliphatic diol having 5 or less carbon atoms or 17 or more carbon atoms may be a straight chain or branched chain diol. Examples of the aliphatic diol having a carbon number of 5 or less include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, pentamethylene glycol, and neopentyl glycol, and 1,4-butanediol is preferred. The content of the aliphatic diol having a carbon number of 5 or less or 17 or more in the raw material may be 15 mol% or less, 1 to 12 mol%, or 3 to 10 mol% relative to the total amount of the raw material. Examples of the aliphatic diol having 17 or more carbon atoms include dotriacontanediol, tetratriacontanediol, and dimer diol (Pripol 2033 manufactured by Croda Corporation). Examples of the alicyclic diol include isosorbide, tricyclodecane dimethanol, cyclohexanedimethanol, etc. Examples of the aromatic diol include bisphenol A oxyalkylene (carbon number 2-3) adducts, etc.

[0020] (polyols with a valence of 3 or more) From the viewpoint of washing durability and softness, the polyester resin of the present embodiment may contain a trivalent or higher polyol. Examples of the trivalent or higher polyol include glycerol, trimethylolpropane, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, 1,3,5-trimethylolbenzene, 1,2,3,6-hexanetetralol, 1,4-sorbitan, dipentaerythritol, sorbitol, tripentaerythritol, or oxyalkylene (carbon number 2 to 3) adducts thereof. Among them, glycerol, trimethylolpropane, and pentaerythritol are preferred. When the raw material contains a trivalent or higher polyol component, the content of the trivalent or higher polyol component may be 10 mol % or less, 0.1 to 10 mol %, or 0.3 to 6 mol % based on the total amount of the raw material.

[0021] The content of the polyol component other than the aliphatic diol having 6 to 16 carbon atoms in the raw material may be 30 mol% or less, 0.1 to 25 mol% or less, or 1 to 20 mol% or less relative to the total amount of the raw material. One or more polyol components other than the aliphatic diol having 6 to 16 carbon atoms may be used.

[0022] (Polycarboxylic acid component) As the polycarboxylic acid component, there can be mentioned: aliphatic polycarboxylic acid, alicyclic polycarboxylic acid, aromatic polycarboxylic acid, etc. It should be noted that in this specification, the term "component" used for polycarboxylic acid refers to one or more of polycarboxylic acid, its anhydride and lower alkyl (for example, carbon number 1 to 3) ester. The polycarboxylic acid component can be any of dicarboxylic acid and polycarboxylic acid with a valence of 3 or more. One or more polycarboxylic acid components can be used. The number of carbon atoms possessed by the polycarboxylic acid is preferably 4 to 12, more preferably 6 to 10. The content of the polycarboxylic acid component can be less than 40 mol%, 0.1 to 40 mol%, 0.3 to 38 mol%, and 0.5 to 35 mol% relative to the total amount of the raw materials. One or more polycarboxylic acid components can be used.

[0023] (Dicarboxylic Acid) Examples of the dicarboxylic acid include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids having 2 to 16 carbon atoms, such as succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, dodecenylsuccinic acid, or esters or anhydrides thereof. The aliphatic dicarboxylic acid may have 6 to 12 carbon atoms, or 7 to 10 carbon atoms. The aliphatic dicarboxylic acid may be a straight-chain or branched-chain dicarboxylic acid, or a straight-chain dicarboxylic acid. Examples of the alicyclic dicarboxylic acid include dimer diacids obtained by dimerizing carboxylic acids having an unsaturated bond (Pripore 1009, Pripore 1006, and Pripore 1004 manufactured by Croda Corporation). Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and naphthalene dicarboxylic acid. The raw material may contain an isophthalic acid component to adjust Tg. The content of the isophthalic acid component in the raw material may be less than 40 mol%, less than 35 mol%, or greater than 10 mol% and less than 30 mol% relative to the total amount of the raw material.

[0024] (polycarboxylic acid with a valence of 3 or more) From the viewpoint of washing durability and softness, the polyester resin of the present embodiment may contain a polycarboxylic acid having a valence of three or more, or may contain a tricarboxylic acid. Examples of the trivalent or higher polycarboxylic acid include trimellitic acid, naphthalenetricarboxylic acid, hexanetricarboxylic acid, or esters or anhydrides thereof, pyromellitic acid, octanetetracarboxylic acid, or esters or anhydrides thereof, etc. From the viewpoint of industrial availability, trimellitic acid or anhydride thereof is preferred. When the raw material contains a trivalent or higher polycarboxylic acid component, the content of the trivalent or higher polycarboxylic acid component may be 10 mol% or less, 0.1 to 10 mol%, 0.3 to 8 mol%, or 0.5 to 6 mol% relative to the total amount of the raw material.

[0025] From the viewpoint of adjusting the acid value, the trivalent or higher polycarboxylic acid component can be subjected to an esterification reaction with the polycondensate of the raw material. In this case, the polyester resin is a reaction product of a polycondensate obtained by a polycondensation reaction and a trivalent or higher polycarboxylic acid component. As specific examples of the "trivalent or higher polycarboxylic acid component" used herein, there can be cited: those exemplified as components contained in the above-mentioned raw materials. The amount of the trivalent or higher polycarboxylic acid component used in the esterification reaction can be adjusted according to the acid value of the polyester resin finally obtained, and the total amount of raw materials used in the polycondensation is set to 100 mol parts, and the trivalent or higher polycarboxylic acid component is set to less than 5 mol parts, less than 3 mol parts, 0.01 to 2 mol parts, or 0.1 to 1 mol parts.

[0026] When the raw material further contains a trivalent or higher polyol or a trivalent or higher polycarboxylic acid component, the water dispersibility of the obtained polyester resin tends to be improved. From the viewpoint of controlling the molecular weight, the total content of the trivalent or higher polyol and the trivalent or higher polycarboxylic acid in the raw material is preferably 10 mol% or less, more preferably 8 mol% or less, and further preferably 6 mol% or less. This preferred range of the content of the trivalent or higher polyol and the trivalent or higher polycarboxylic acid component in the raw material is the range of the content of the contained components when the raw material contains only one of the trivalent or higher polyol and the trivalent or higher polycarboxylic acid component.

[0027] In the raw material composition, the COOH / OH ratio of all components contained in the raw material is preferably in the range of 0.55 to 1.10 from the viewpoint of making the reaction proceed more smoothly. In the case of PET as a raw material, assuming that the structural unit (1) is 1 mol, COOH is regarded as 1 mol and OH as 1 mol.

[0028] When the polyester resin of the present embodiment is used as a binder for pigment printing and dyeing, the polyester resin is preferably formulated as an aqueous dispersion or emulsion. At the same time, from the viewpoint of controlling the particle size when dispersing or emulsifying the resin, the acid value of the polyester resin is preferably 5 to 20 mgKOH / g, more preferably 5.5 to 15 mgKOH / g, and further preferably 6 to 13 mgKOH / g. When the acid value is 5 mgKOH / g or more, there is a tendency to suppress poor emulsification. In addition, if the acid value is 20 mgKOH / g or less, there is a tendency to suppress hydrolysis and further improve washing durability. The acid value of the polyester resin after polycondensation can be adjusted to the above range by appropriately reacting a trivalent or higher polycarboxylic acid component. As the trivalent or higher polycarboxylic acid component at this time, the above-mentioned trivalent or higher polycarboxylic acid component can be cited. Regarding the temperature when the acid value is adjusted, from the viewpoint of reactivity, the reaction temperature can be 180°C to 230°C, preferably at a temperature of 190°C to 220°C, at normal pressure or under pressure, for 0.1 hour to 1 hour.

[0029] From the viewpoint of flexibility, the glass transition temperature of the polyester resin of the present embodiment is preferably 50° C. or lower, and more preferably 40° C. or lower.

[0030] From the viewpoint of washing durability or non-tackiness, the weight average molecular weight of the polyester resin of the present embodiment is preferably 10,000 or more, more preferably 15,000 or more. From the viewpoint of fixing of printing ink, it is preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less.

[0031] The polyester resin of the present embodiment may be any one of a crystalline polyester resin and a non-crystalline polyester resin, and a mixture thereof, or may be a non-crystalline polyester resin. It should be noted that in this specification, a "non-crystalline" polyester resin refers to a polyester resin that does not show a clear crystalline melting endothermic peak and has a melting enthalpy of 5 mJ / mg or less calculated from the melting endothermic peak area of ​​the DSC (differential scanning calorimetry) curve. In contrast, a "crystalline" polyester resin shows a clear crystalline melting endothermic peak and refers to a polyester resin whose melting enthalpy is greater than 5 mJ / mg. It should be noted that the above-mentioned melting enthalpy values ​​are values ​​calculated using indium and tin as standard substances.

[0032] <Production Method of Polyester Resin> The method for producing a polyester resin of the present embodiment includes a step of polycondensing a raw material to obtain a polycondensate, wherein the raw material contains (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms, wherein the content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material, and the content of the component (b) in the raw material is 20 to 50 mol% relative to the total amount of the raw material. The raw material may optionally contain at least one of a polyol component and a polycarboxylic acid component other than the aliphatic diol having 6 to 16 carbon atoms. The method for producing a polyester resin of the present embodiment may further include a step of reacting a trivalent or higher polycarboxylic acid component with the obtained polycondensate.

[0033] In this embodiment, from the viewpoint of shortening the reaction time and inhibiting resin decomposition, the temperature during the polycondensation reaction can be 200°C to 300°C, preferably 210°C to 270°C, more preferably 220°C to 250°C, at normal pressure, reduced pressure or pressurized, preferably under reduced pressure, for 3 to 20 hours.

[0034] The polycondensation reaction can use conventionally known catalysts such as antimony trioxide, dibutyltin oxide and other organic tin polymerization catalysts, germanium catalysts, inorganic titanium catalysts, organic titanium catalysts such as n-tetrabutoxytitanium or tetraisopropoxytitanium, organic aluminum catalysts, organic cobalt catalysts, organic zirconium catalysts, zinc acetate or manganese acetate and other ester exchange catalysts as needed. Among them, germanium catalysts, inorganic titanium catalysts, organic titanium catalysts, organic zirconium catalysts, organic aluminum catalysts and the like are preferred.

[0035] For the polyester resin of this embodiment, an antioxidant may be added at any stage of the production process or after production to prevent coloration or thermal decomposition. Such antioxidants are not particularly limited, and examples thereof include hindered phenol antioxidants, phosphite antioxidants, sulfur-containing antioxidants, and the like.

[0036] <Polyester resin aqueous emulsion dispersion> The polyester resin of the present embodiment is preferably formulated in a binder for pigment printing and dyeing as an aqueous emulsified dispersion. The polyester resin of the present embodiment may be contained in an aqueous dispersion having an aqueous medium and particles containing a polyester resin dispersed in the aqueous medium. As aqueous media, there may be mentioned: water, and a mixed solvent of a solvent miscible with water (for example, a lower alcohol or glycol having 1 to 4 carbon atoms, ketones such as methyl ethyl ketone and acetone, tetrahydrofuran, etc.) and water, etc. As a method of dispersion or emulsification, for example, there may be mentioned: a method using a medium-type disperser (bead mill) or a high-pressure disperser (homogenizer, Ultimaizer (trade name)), a phase inversion emulsification method in which water is added to a solution dissolved in an organic solvent to invert the phase from the oil phase to the water phase, etc. In addition, as required, a nonionic surfactant or an anionic surfactant may be used as an emulsifier.

[0037] <Binders for pigment printing and dyeing> The pigment printing and dyeing adhesive of the present embodiment can contain components other than the polyester resin water emulsified dispersion. As this component, there is no particular restriction, and it can be appropriately selected according to the purpose, for example, it can include: coloring agents such as pigments, inorganic particles, organic particles, charge control agents, release agents and tackifiers and other known components in the past.

[0038] <Pigment printing ink> The ink for pigment printing and dyeing contains a binder for pigment printing and dyeing. The ink may contain other components such as white pigment for base shielding, coloring pigment, extender pigment, bright pigment, ultraviolet absorber, antioxidant, organic solvent, film-forming aid, rheology control agent as components other than the binder for pigment printing and dyeing. The other components may be a combination of multiple ones.

[0039] Examples of the white pigment for undercovering include white pigments having high shielding properties such as titanium dioxide and zinc oxide. Titanium dioxide is preferred from the viewpoint of obtaining high light shielding properties.

[0040] Examples of coloring pigments include titanium oxide, zinc flower, carbon black, molybdenum red, Prussian blue, cobalt blue, azo pigments, phthalocyanine pigments, quinacridone pigments, isoindoline pigments, anthracene pigments, and perylene pigments, and titanium oxide and / or carbon black are preferred. The coloring pigments may be a combination of multiple types.

[0041] Examples of the extender pigment include clay, kaolin, barium sulfate, barium carbonate, calcium carbonate, talc, silica, and alumina white, preferably barium sulfate and / or talc, and more preferably barium sulfate. The extender pigment may be a combination of multiple types.

[0042] As bright pigments, for example, there can be mentioned: metal pigments such as aluminum, brass, bronze, nickel, stainless steel, zinc, etc.; mica covered with titanium oxide, yellow iron oxide, etc.; thin flaky crystals or plate-like crystals such as aluminum silicate, alkaline carbonate, barium sulfate, titanium oxide, bismuth oxychloride, etc.; thin flaky glass powder, metal-evaporated thin flaky glass powder, etc. Among them, from the viewpoint of the mirror reflection intensity, metal pigments are preferred, and from the viewpoint of further improving the mirror reflection intensity, flat metal pigments are more preferred. Among metal pigments, aluminum pigments are preferred from the viewpoint of easily obtaining flat powders. The surface of the metal pigment can be covered with silica, acrylic resin, polyester resin, etc. The content of the pigment in the pigment printing ink is preferably 1 to 70 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the polyester resin of the present embodiment.

[0043] <Fiber base material> As the base material for the ink used for pigment printing and dyeing, there is no particular limitation. For example, when the base material is a fiber base material, it can be in the form of non-woven fabrics, fabrics, braids, etc. As the material of the fiber base material, there can be mentioned: natural fibers such as cotton (cellulose fiber), hemp, wool, silk, synthetic fibers such as acrylic, nylon, polyurethane, vinylon, semi-synthetic fibers such as acetate, triacetate, regenerated fibers such as cuprammonium fiber, lyocell (Tencel), rayon, and composite fibers obtained by blending, interweaving, and interweaving these fibers. In the case of a resin base material, it can be in the form of a film or a molded object, and as its material, there can be mentioned: polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, vinyl chloride resin, polystyrene, acrylic resin, polycarbonate, polyurethane, nylon, polyimide, PTFE (fluorine), etc.

[0044] <Dyeing and Printing Method> There is no particular limitation on the method of imparting the pigment printing ink of the present embodiment to the fiber substrate, and examples thereof include: screen, roller, inkjet, rod coater, etc., and the method can be applied to a portion or the entire surface of the fiber substrate, transfer paper, transfer sheet, etc. After coating, dry at a temperature of 50°C to 180°C for 5 minutes to 1 hour. When applied to transfer paper or transfer sheet, the ink-coated surfaces of the fiber substrate, transfer paper or transfer sheet are put together, and after hot pressing at 100°C to 200°C, the transfer paper or transfer sheet is peeled off from the fiber substrate, thereby obtaining a printed product in which the fiber substrate and the ink are integrated. Example

[0045] <Manufacture of polyester resin> (Synthesis Examples 1 to 2) The raw materials of the composition shown in Table 3 were placed in a reaction container that was fully dried in advance, and heated to 180° C. while stirring in a nitrogen aeration. Here, n-tetrabutoxytitanium was added as a catalyst, the temperature was raised to 230° C., and the pressure in the reaction container was finally reduced to 3 kPa to perform a polycondensation reaction to obtain polyester resins (A-1 and A-2). It should be noted that when the total molar number of the alcohol component, the carboxylic acid component and other components is 100, the amount of the catalyst added is 0.1 mol.

[0046] (Synthesis Examples 3 to 20) The raw materials of the composition shown in Table 3 or Table 4 were placed in a reaction container that was sufficiently dried in advance, and heated to 180°C while stirring in nitrogen gas flow. Here, n-tetrabutoxytitanium (TBT) was added as a catalyst, and the temperature was raised to 230°C. The pressure in the reaction container was finally reduced to 3 kPa to carry out polycondensation reaction. Then, the pressure was returned to normal pressure, and the reaction container was cooled to 200°C while stirring in nitrogen gas flow. Then, trimellitic anhydride was added to the polyester resin obtained by polycondensation, and polycondensation reaction was further carried out to obtain polyester resins A-3 to A-17 and B-1 to B-2. It should be noted that in Synthesis Example 19, the reaction mixture solidified during the polycondensation reaction and the polyester resin could not be synthesized (in Tables 3 to 8, this Synthesis Example is referred to as B-3). It should be noted that in Tables 3 and 4, trimellitic anhydride (1) refers to trimellitic anhydride contained in the raw materials during polycondensation with PET, and trimellitic anhydride (2) refers to trimellitic anhydride added after polycondensation. In Tables 3 and 4, the total amount of raw materials refers to the total amount of monomer components (PET, polyol components and polycarboxylic acid components (excluding trimellitic anhydride for adjusting the acid value) used in the polycondensation reaction, and the amount of the catalyst and trimellitic anhydride (2) is the amount (in parts by mole) added when the total molar number of the raw materials is set to 100 parts by mole.

[0047] In Table 5 and Table 6, the usage amounts of the raw materials used in Synthesis Examples 1 to 20 are shown by mass.

[0048] <Weight average molecular weight (Mw)> 2 mg of polyester resin was dissolved in 5 mL of tetrahydrofuran, and the weight average molecular weight was determined by gel permeation chromatography (GPC)-HLC-8220GPC (manufactured by Tosoh Corporation) in terms of polystyrene. The measurement conditions of GPC are as follows. The results are shown in Tables 7 and 8. <Measurement conditions> Detection device: RI detector Mobile phase: tetrahydrofuran Chromatographic columns: Two Tsk-gel Super HZ 2000 and one Tsk-gel Super HZ4000 directly connected Injector and column temperature: 40°C RI detector temperature: 40°C Sample injection volume: 5μL Flow rate: 0.35mL / min Measurement time: 20 minutes

[0049] <Glass transition temperature (Tg)> The glass transition temperature of the polyester resin was measured by DSC. As a measuring device, a differential scanning calorimeter DSC-7020 (manufactured by Hitachi High-Technologies Corporation) was used. The measurement conditions of Tg are as follows. The results are shown in Tables 7 and 8. <Measurement conditions> Heating and cooling speed: 10℃ / min Heating program: The aluminum pan was heated to -50°C to 100°C and then cooled to -50°C. Next, the temperature at the intersection of the base line of the graph when heated to 100°C and the tangent line of the endothermic curve near the glass transition temperature was taken as the glass transition temperature (Tg). Atmosphere: Nitrogen flow (30 mL / min) Pool: Sealed Aluminum Sample amount: 5.0mg±1.0mg Standard substances: Indium, Tin

[0050] <Acid Value (AV)> The acid value of the polyester resin was measured by changing only the following conditions of the potentiometric titration method in JIS K 0070 (1992) 3.2. The results are shown in Tables 7 and 8. Titration solvent: 0.1 mol / L sodium hydroxide aqueous solution Measurement solvent: tetrahydrofuran: water = 10:1 (volume ratio) mixed solvent Solvent volume: 100mL Sample weight: 5.0g±0.5g

[0051] <Preparation of Polyester Resin Aqueous Emulsion Dispersion> (Preparation Example LA-1) 100 parts by mass of polyester resin (A-1) and 150 parts by mass of tetrahydrofuran were placed in a container to dissolve the resin. While maintaining the temperature at 40°C to 50°C, 5 parts by mass of a 5% by mass ammonia solution were added, and then 400 parts by mass of ion exchange water were gradually added to perform phase inversion emulsification, and then tetrahydrofuran was distilled off under reduced pressure. Then, ion exchange water was added to adjust the solid content concentration to 20% by mass, to obtain a polyester resin emulsion (LA-1). As shown in Tables 7 and 8, polyester resin aqueous emulsion dispersions (LA-2 to LA-17, LB-1 to LB-2) were obtained in the same manner.

[0052] <Preparation of printing ink> 100 parts by mass of each polyester resin aqueous emulsion dispersion and 20 parts by mass of titanium oxide as a white pigment were placed in a stirring container and stirred with a homogenizer. After ensuring that the mixture was sufficiently uniformly mixed, 4 parts by mass of Neo Stecker V (manufactured by Nikka Chemical Co., Ltd.) was added as a thickener.

[0053] <Production of printed and dyed products> The PET transfer sheet was printed using a coater and dried in a dryer at 100°C. After the removed sheet was cooled to room temperature, the transfer sheet was overlapped so that the printed surface was in contact with the polyester substrate (black), and thermally pressed at 130°C for 30 seconds using a press. After the substrate and transfer sheet were cooled to room temperature, the transfer sheet was peeled off from the substrate. The polyester substrate used in the evaluation was produced by the following method and used for the production of printed products. 100% polyester woven fabric (weight per unit area 120g / m 2 ) is put into a dyeing bath of the composition shown in Table 1 below, with a bath ratio of 1:12, and the dyeing bath is heated from 60°C to 130°C at a heating rate of 2°C / min (heating time: 35 minutes), and maintained at 130°C for 30 minutes. Then, the temperature is lowered to 70°C, and the knitted fabric is taken out from the dyeing bath. Next, the knitted fabric taken out is subjected to reduction cleaning (80°C, 15 minutes, bath ratio 1:12) using a reduction cleaning bath of the composition shown in Table 2 below, and then washed, dehydrated and dried to produce a polyester dyed fabric and a polyester substrate.

[0054] [Table 1] Dispersing and leveling agent NICCASUNSOLT RM-3406 0.5g / l pH Adjusters 80% by mass acetic acid 0.4g / l Disperse dyes Disperseblack PB-SF300% 3% owf

[0055] [Table 2] Soaping agent SUNMORL RC-700Eコンク 0.5g / l Alkali Soda ash 1.0g / l reducing agent Sodium dithionite 1.0g / l

[0056] <Washing durability> The washing durability (color fastness to washing) of the image formed product was evaluated according to JIS L1930:2014C4M method. That is, the image formed product after washing with Attack Highly Active Bio EX (manufactured by Kao Corporation) as a detergent was compared with the image formed product without washing to evaluate the change of the printed part. Then, the evaluation was performed based on the following evaluation criteria. A: No change in printing and dyeing B: The printed part becomes thinner C: There are cracks in the printing and dyeing part D: The printed part is completely peeled off

[0057] <Softness> The printed cloth was used, and the printed surface portion of 2 cm was stretched for 3 seconds to 3 cm, and the extent to which the printed portion was stretched relative to the deformation of the cloth was evaluated. The results were visually evaluated according to the following grades. A: The printing and dyeing part extends along with the fabric. B: The printed part extends along the fabric, but there are a few cracks. C: The printed part extends along with the fabric, but with large cracks. D: The printed part does not follow the fabric, with large cracks and partial peeling.

[0058] <Tack-free> After printing with a printing transfer sheet, the stickiness is evaluated when the sheet is peeled off. The results are evaluated in the following grades in a functional test. In the method of the functional test, the index finger is pressed on the printed part for 3 seconds, and then the finger is removed from the top to evaluate the degree of adhesion of the printed part to the finger. A: When peeling off the transfer sheet, the printed part does not stick to your fingers. B: When peeling off the transfer sheet, the printed part adheres to the finger, but it falls off immediately. C: When peeling off the transfer sheet, the printed part comes off as the fingers are slightly lifted. D: When peeling the transfer sheet, the printed part is lifted with the fingers and does not separate.

Claims

1. A polyester resin which is a polycondensate of raw materials containing (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms, wherein: The content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material. The content of the component (b) in the raw material is 20 to 50 mol % based on the total amount of the raw material.

2. The polyester resin according to claim 1, wherein The aliphatic diol is a straight-chain aliphatic diol.

3. The polyester resin according to claim 1 or 2, wherein The raw material further contains at least one selected from the group consisting of trivalent or higher polyols and trivalent or higher polycarboxylic acid components.

4. The polyester resin according to claim 3, wherein The polycarboxylic acid contains 4 to 12 carbon atoms. 5 . The polyester resin according to claim 1 , which is a reaction product obtained by reacting the polycondensate with a trivalent or higher polycarboxylic acid component. 6 . The polyester resin according to claim 1 , which has an acid value of 5 to 20 mgKOH / g.

7. A binder for pigment printing and dyeing, comprising the aqueous emulsified dispersion of the polyester resin according to claim 1 or 2.

8. Pigment printing ink, comprising the pigment printing binder according to claim 7.

9. A method for producing a polyester resin, comprising the step of polycondensing a raw material to obtain a polycondensate. in, The raw materials contain (a) polyethylene terephthalate and (b) an aliphatic diol having 6 to 16 carbon atoms. The content of the component (a) in the raw material is 30 to 80 mol% relative to the total amount of the raw material. The content of the component (b) in the raw material is 20 to 50 mol % based on the total amount of the raw material. 10 . The method for producing a polyester resin according to claim 9 , further comprising a step of reacting the obtained polycondensate with a trivalent or higher polycarboxylic acid component.

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