Flame-retardant treatment agent, fiber product, and method for producing fiber product

Abstract

To provide a technique capable of exhibiting sufficient flame retardancy and imparting a soft feel to a fiber product.SOLUTION: A flame-retardant treatment agent disclosed herein includes a polyester resin (X). The polyester resin (X) includes a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b). In the formulas (a) and (b), R1 is a substituted or unsubstituted hydrocarbon group having 7 to 48 carbon atoms, and R2 is a substituted or unsubstituted hydrocarbon group having 1 to 48 carbon atoms.SELECTED DRAWING: None

Description

Technical Field

[0001] This application discloses a flame retardant processing agent, a fiber product, and a method for manufacturing a fiber product.

Background Art

[0002] Conventionally, for flame retardant processing agents for vehicle seat materials such as automobile seat materials and railway vehicle seat materials, and non-woven fabrics and felts in the field of weak electricity, acrylic resins, urethane resins, etc. are used as binder components to adhere the flame retardant together with halogen-based compounds and non-halogen-based flame retardants. Here, acrylic resins and urethane resins have poor flame retardancy and require a large amount of flame retardant, resulting in a problem of increased cost. In addition, there is also a problem that the amount of acrylic resin and urethane resin used to adhere the flame retardant increases, and the texture becomes hardened. Under such circumstances, a method of applying a polyester resin to flame retardant processing has been proposed as a method for improving flame retardancy. For example, Patent Document 1 proposes a flame retardant resin composition characterized by containing at least one resin emulsion selected from an acrylic resin emulsion and a urethane resin emulsion, a polyester resin emulsion, a liquid phosphorus-based flame retardant, and a surfactant having an aromatic group. Patent Document 2 proposes a method of mixing polyester resin powder with an aqueous dispersion or emulsion of a thermoplastic resin such as a copolymerized polyester resin or a polyolefin resin having an average particle diameter of 5 μm or less, and coating at least one side of a fabric such as a woven or knitted fabric of polyester fibers. However, in these methods using polyester resins, there is a problem that the flame retardancy is insufficient and the texture of the processed fiber product becomes very hard.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] In view of the above prior art, the present application discloses a technique capable of exhibiting sufficient flame retardancy and imparting a soft texture (flexibility) to textile products.

Means for Solving the Problems

[0005] As means for solving the above problems, the present application discloses the following multiple aspects. <Aspect 1> A flame-retardant finishing agent containing a polyester resin (X), wherein the polyester resin (X) contains a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b), Flame-retardant finishing agent.

Chemical formula

Chemical formula

Advantages of the Invention

[0006] The flame retardant processing agent having the polyester resin (X) of the present disclosure has good flame retardancy and a soft texture. According to the technology of the present disclosure, it is possible to impart not only high flame retardancy and a soft texture but also high resistance to fraying, high rubbing fastness, and high fiber convergence to fiber products.

Modes for Carrying Out the Invention

[0007] Hereinafter, a flame retardant processing agent, a fiber product, and a method for producing a fiber product according to one embodiment will be described, but the technology of the present disclosure is not limited to this embodiment.

[0008] 1. Flame retardant processing agent The flame retardant processing agent according to one embodiment contains a polyester resin (X). The polyester resin (X) contains a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b).

Chemical formula

[0009] 1.1 Structural unit (A) of polyester resin (X) The structural unit (A) may be derived from a compound having the structural unit (A). The compound having the structural unit (A) may be, for example, a polyhydric alcohol having 7 to 48 carbon atoms, or a compound derived from a polyester resin synthesized from a raw material containing a polyhydric alcohol having 7 to 48 carbon atoms and a polyvalent carboxylic acid, or a combination thereof. The polyhydric alcohol may have a substituent. Examples of the substituent include hydroxy groups such as alcoholic hydroxy groups and phenolic hydroxy groups, carboxy groups, acyl groups, acyloxy groups, halogen atoms, alkoxy groups, and alkoxycarbonyl groups.

[0010] 1.1.1 Compound derived from a polyester resin synthesized from a raw material containing a polyhydric alcohol having 7 to 48 carbon atoms and a polyvalent carboxylic acid The "compound derived from a polyester resin synthesized from a raw material containing a polyhydric alcohol and a polycarboxylic acid having 7 to 48 carbon atoms" refers to at least one of the polyester resin synthesized from these raw materials, the polyester resin oligomer obtained by depolymerization of the synthesized polyester resin, and the polyhydric alcohol having 7 to 48 carbon atoms obtained by depolymerization of the synthesized polyester resin. The polyester resin synthesized from these raw materials may be at least one of a polyester manufactured from a petrochemical-derived raw material, a biopolyester manufactured from a biomass-derived raw material, and a recycled polyester recovered from waste. The polyhydric alcohol and the polycarboxylic acid having 7 to 48 carbon atoms may be derived from petrochemicals, biomass, or recycled polyester resin. Among the compounds having such a structural unit (A), from the viewpoint of a soft texture, it is preferably a polyhydric alcohol having 7 to 48 carbon atoms.

[0011] 1.1.2 Polyhydric alcohol having 7 to 48 carbon atoms As the polyhydric alcohol having 7 to 48 carbon atoms, from the viewpoints of flame retardancy and flexibility, a diol having 7 to 48 carbon atoms is preferable. The diol having 7 to 48 carbon atoms may be aromatic or aliphatic, and may be a linear or branched diol, or may be a linear diol.

[0012] Examples of the straight-chain aliphatic diols having 7 to 48 carbon atoms include 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecanediol, 1,16-hexadecanediol, 1,18-octadecanediol, 1,20-icosanediol, 1,24-tricosanediol, 1,28-pentacosanediol, 1,32-hexacosanediol, 1,36-heptacosanediol, 1,40-tetracosanediol, 1,44-pentacosanediol, 1,48-hexacosanediol, etc. As the aliphatic diol having 7 to 48 carbon atoms, one kind or two or more kinds can be used. From the viewpoints of flame retardancy and flexibility, the number of carbon atoms of the diol having 7 to 48 carbon atoms is more preferably 7 to 20.

[0013] Examples of the branched-chain aliphatic diols having 7 to 48 carbon atoms include 2,4-dimethyl-2,4-pentanediol, 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, 2,7-octanediol, 2,7-nonanediol, 3,8-nonanediol, 2,9-nonadecanediol, 5,14-pentacosanediol, dotriacontanediol, dimer diol (Pripol 2033 manufactured by Croda), etc.

[0014] Examples of the alicyclic diols include isosorbide, tricyclodecane dimethanol, cyclohexane dimethanol, etc., and examples of the aromatic diols include alkylene (having 2 to 3 carbon atoms) oxide adducts of bisphenol A, etc.

[0015] 1.1.3 Content The content of the compound having the structural unit (A) relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 10 to 60 mol%, more preferably 25 to 50 mol%, and even more preferably 25 to 35 mol%. Also, the content of the diol having 7 to 48 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 10 to 60 mol%, more preferably 25 to 50 mol%, and even more preferably 25 to 35 mol%. Further, the content of the polyhydric alcohol having 3 or more valences and 7 to 48 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 10 mol% or less, more preferably 0.1 to 10 mol%, and even more preferably 0.3 to 8 mol%.

[0016] 1.2 Structural unit (B) of the polyester resin (X) The structural unit (B) may be derived from a compound having the structural unit (B). The compound having the structural unit (B) may be a polyvalent carboxylic acid having 1 to 48 carbon atoms (the carbon number does not include the carbon of the carbonyl group (CО). The same applies throughout this application.), a compound derived from a polyester resin synthesized from a raw material containing a polyvalent carboxylic acid having 1 to 48 carbon atoms and a polyhydric alcohol, or a combination thereof. The polyvalent carboxylic acid may have a substituent. Examples of the substituent include hydroxy groups such as alcoholic hydroxy groups and phenolic hydroxy groups, carboxy groups, acyl groups, acyloxy groups, halogen atoms, alkoxy groups, and alkoxycarbonyl groups.

[0017] 1.2.1 Compound derived from a polyester resin synthesized from a raw material containing a polyvalent carboxylic acid having 1 to 48 carbon atoms and a polyhydric alcohol The "compound derived from a polyester resin synthesized from a raw material containing a polyvalent carboxylic acid and a polyhydric alcohol having 1 to 48 carbon atoms" refers to at least one of a polyester resin synthesized from these raw materials, a polyester resin oligomer obtained by depolymerization of the synthesized polyester resin, and a polyvalent carboxylic acid having 1 to 48 carbon atoms obtained by depolymerization of the synthesized polyester resin. The polyester resin synthesized from a raw material containing a polyvalent carboxylic acid and a polyhydric alcohol having 1 to 48 carbon atoms may be at least one selected from polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), poly naphthalene terephthalate (PEN), and polyethylene furanoate (PEF). These polyester resins may be polyesters manufactured from petrochemical-derived raw materials, biopolyesters manufactured from biomass-derived raw materials, or recycled polyesters recovered from waste. The polyvalent carboxylic acid and polyhydric alcohol having 1 to 48 carbon atoms may be derived from petrochemicals, biomass, or recycled polyester resins.

[0018] 1.2.2 Polyvalent Carboxylic Acid Having 1 to 48 Carbon Atoms Examples of the polyvalent carboxylic acid having 1 to 48 carbon atoms include aliphatic polyvalent carboxylic acids, alicyclic polyvalent carboxylic acids, aromatic polyvalent carboxylic acids, and carboxylic acids having a heterocyclic aromatic ring. In this specification, the term "component" used for polyvalent carboxylic acids means one or more of polyvalent carboxylic acids, their acid anhydrides, and lower alkyl (for example, having 1 to 3 carbon atoms) esters. The polyvalent carboxylic acid may be either a dicarboxylic acid or a polyvalent carboxylic acid having a valence of 3 or more, but is preferably a dicarboxylic acid from the viewpoints of flame retardancy and flexibility.

[0019] One or more polyvalent carboxylic acids can be used. From the viewpoint of flame retardancy, the number of carbon atoms of the polyvalent carboxylic acid is preferably 4 to 12, and more preferably 6 to 10. One or more polyvalent carboxylic acid components can be used.

[0020] 1.2.2.1 Dicarboxylic acids with carbon numbers from 1 to 48 Examples of dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, carboxylic acids having a heterocyclic aromatic ring, and the like.

[0021] Examples of aliphatic dicarboxylic acids include those having 2 to 16 carbon atoms, such as malonic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid, dodecenyl succinic acid, or esters or acid anhydrides thereof. From the viewpoint of flexibility, the number of carbon atoms of the aliphatic dicarboxylic acid may be 6 to 12. The aliphatic dicarboxylic acid may be a straight-chain or branched-chain dicarboxylic acid, and may be a straight-chain dicarboxylic acid.

[0022] Examples of alicyclic dicarboxylic acids include dimer diacids obtained by dimerizing carboxylic acids having an unsaturated bond (Pripol 1009, Pripol 1006, Pripol 1004 manufactured by Croda), and the like.

[0023] Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. Examples of heterocyclic aromatic compounds include furandicarboxylic acid and the like.

[0024] The raw materials constituting the polyester resin (X) may contain an isophthalic acid component in order to adjust the Tg of the resin (X).

[0025] Examples of dicarboxylic acids having a metal sulfonate group include alkali metal salts such as 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfonaphthalene-2,6-dicarboxylic acid, and esters, acid chlorides, halides, etc. thereof. In order to impart good water dispersibility or water solubility to the polyester resin, the alkali metal is preferably sodium, potassium or lithium.

[0026] 1.2.2.2 Trivalent or higher polycarboxylic acids having 1 to 48 carbon atoms Examples of the trivalent or higher polycarboxylic acid component having 1 to 48 carbon atoms include trimellitic acid, naphthalenetricarboxylic acid, hexanetricarboxylic acid, pyromellitic acid, octanetetracarboxylic acid, and the like. Trimellitic acid or its acid anhydride is preferred in terms of easy industrial availability.

[0027] 1.2.3 Content When using a polyvalent carboxylic acid having 1 to 48 carbon atoms as the compound having the structural unit (B), the content of the polyvalent carboxylic acid having 1 to 48 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 30 to 90 mol%, more preferably 40 to 70 mol%. Also, the content of the dicarboxylic acid having 1 to 48 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 30 to 90 mol%, more preferably 40 to 70 mol%.

[0028] When including a trivalent or higher polycarboxylic acid component in the raw materials constituting the polyester resin (X), from the viewpoints of flame retardancy and flexibility, the content of the trivalent or higher polycarboxylic acid having 1 to 48 carbon atoms relative to the total amount of the raw materials is preferably 10 mol% or less, more preferably 0.1 to 10 mol%, and even more preferably 0.3 to 8 mol%.

[0029] 1.2.4 Other matters The polyvalent carboxylic acid component having a valence of 3 or more may be subjected to an esterification reaction with the polycondensate of the raw materials from the viewpoint of acid value adjustment. In this case, the polyester resin (X) is a reaction product of the polycondensate obtained by the polycondensation reaction and the polyvalent carboxylic acid component having a valence of 3 or more. Specific examples of the "polyvalent carboxylic acid component having a valence of 3 or more" used here include those exemplified as components contained in the aforementioned raw materials. The amount of the polyvalent carboxylic acid component having a valence of 3 or more used in the esterification reaction may be adjusted according to the acid value of the finally obtained polyester resin. Assuming the total amount of the raw materials used for polycondensation is 100 mol parts, the polyvalent carboxylic acid component having a valence of 3 or more can be 10 mol parts or less, 0.1 to 10 mol parts, or 0.3 to 5 mol parts. When the raw materials further contain a polyvalent carboxylic acid component having a valence of 3 or more, the water dispersibility of the obtained polyester resin tends to improve.

[0030] 1.3 Structural unit (C) of the polyester resin (X) In addition to the above structural units (A) and (B), the polyester resin (X) may contain other structural units. For example, the polyester resin (X) may contain a structural unit (C) represented by the following formula (c). When the polyester resin (X) contains the structural unit (C), the flame retardancy tends to improve.

Chemical formula

[0031] The structural unit (C) may be derived from a compound having the structural unit (C). The compound having the structural unit (C) may be a polyhydric alcohol having 1 to 6 carbon atoms, a compound derived from a polyester resin synthesized from a raw material containing a polyhydric alcohol having 1 to 6 carbon atoms and a polycarboxylic acid, or a combination thereof. The polyhydric alcohol may have a substituent. Examples of the substituent include hydroxy groups such as alcoholic hydroxy groups and phenolic hydroxy groups, carboxy groups, acyl groups, acyloxy groups, halogen atoms, alkoxy groups, and alkoxycarbonyl groups.

[0032] 1.3.1 Compounds derived from polyester resins synthesized from raw materials containing polyhydric alcohols having 1 to 6 carbon atoms and polycarboxylic acids The "compounds derived from polyester resins synthesized from raw materials containing polyhydric alcohols having 1 to 6 carbon atoms and polycarboxylic acids" refers to at least one of the polyester resins synthesized from these raw materials, polyester resin oligomers obtained by depolymerization of the synthesized polyester resins, and polyhydric alcohols having 1 to 6 carbon atoms obtained by depolymerization of the synthesized polyester resins. The polyester resins synthesized from raw materials containing polyhydric alcohols having 1 to 6 carbon atoms and polycarboxylic acids may be at least one selected from PET, PBT, PTT, PEN, PEF, etc. These polyester resins may be at least one selected from polyesters manufactured from petrochemical-derived raw materials, biopolyesters manufactured from biomass-derived raw materials, and recycled polyesters recovered from waste. The polyhydric alcohols having 1 to 6 carbon atoms and the polycarboxylic acids may be of petrochemical origin, of biomass origin, or of recycled polyester resin origin.

[0033] 1.3.2 Polyhydric alcohols having 1 to 6 carbon atoms The polyhydric alcohol having 1 to 6 carbon atoms may be a diol or a polyhydric alcohol having a valence of 3 or more.

[0034] 1.3.2.1 Diols with 1 to 6 carbon atoms Examples of diols with 1 to 6 carbon atoms include aliphatic diols, aromatic diols, alicyclic diols, etc. Examples of aliphatic diols with 1 to 6 carbon atoms include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.

[0035] 1.3.2.2 Polyhydric alcohols with 3 or more valences and 1 to 6 carbon atoms From the perspective of flame retardancy, the raw materials constituting the polyester resin (X) may contain polyhydric alcohols with 3 or more valences. Examples of polyhydric alcohols with 3 or more valences include glycerin, trimethylolpropane, pentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, sorbitol, or their alkylene (2 to 3 carbon atoms) oxide adducts, etc. Among these, at least one of glycerin, trimethylolpropane, and pentaerythritol is preferred.

[0036] 1.3.3 Content When using polyhydric alcohols with 1 to 6 carbon atoms as the compound having the structural unit (C), the content of polyhydric alcohols with 1 to 6 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 75 mol% or less, more preferably 10 to 60 mol%. Also, the content of diols with 1 to 6 carbon atoms relative to the total amount of the raw materials constituting the polyester resin (X) is preferably 75 mol% or less, more preferably 10 to 60 mol%.

[0037] When including a polyhydric alcohol component with 3 or more valences in the raw materials constituting the polyester resin (X), from the perspectives of flame retardancy and flexibility, the content of polyhydric alcohols with 3 or more valences and 1 to 6 carbon atoms relative to the total amount of the raw materials is preferably 10 mol% or less, more preferably 0.1 to 10 mol%, and even more preferably 0.3 to 8 mol%.

[0038] 1.4 Polyester resin (X1) as a raw material In this embodiment, the above structural unit (B) and structural unit (C) may be derived from a polyester resin (X1) containing the structural unit (B) and the structural unit (C). In other words, the polyester resin (X) may contain a structural unit derived from the polyester resin (X1), and the polyester resin (X1) may contain the structural unit (B) and the structural unit (C).

[0039] The polyester resin (X1) may be a polyester resin containing the polycarboxylic acid having 1 to 48 carbon atoms and the polyhydric alcohol having 1 to 6 carbon atoms, and polyester resins such as PET, PBT, PTT, PEN, and PEF may be used. However, from the viewpoints of monomerization in the use for polyester fibers, easy availability of raw materials, and the circulation volume as recycled raw materials, PET is preferred. There are no restrictions on the molecular weight distribution, composition, production method, form in use, etc. of the polyester resin (X1). Further, the polyester resin (X1) may be produced from petrochemical-derived raw materials, may be produced from biomass-derived raw materials, or may be a recycled polyester resin recovered from waste. The recycled polyester resin is usually processed into flakes or pellets and may have a weight average molecular weight of about 30,000 to 90,000.

[0040] Examples of the compound having the structural unit (B) and the structural unit (C) derived from the polyester resin (X1) include at least one of the polyester resin (X1), an oligomer of the polyester resin (X1) obtained by depolymerizing the polyester resin (X1), a polycarboxylic acid having 1 to 48 carbon atoms obtained by depolymerizing the polyester resin (X1), and a polyhydric alcohol having 1 to 6 carbon atoms obtained by depolymerizing the polyester resin (X1). Among these, from the viewpoints of the flame retardancy of the flame retardant and consideration for the environment, the polyester resin (X1) is preferred.

[0041] When using a polyester resin (X1), for example PET, as a compound containing structural unit (B) and structural unit (C), compared with the case of using terephthalic acid as the compound containing structural unit (B) and ethylene glycol as the compound containing structural unit (C) as raw materials, it is considered that the polyethylene terephthalate block represented by the following structural unit (i) is continuously introduced into the polyester resin (X).

Chemical formula

[0042] The reason why the flame retardant processing agent according to this embodiment is excellent in flame retardancy is not necessarily clear. However, since the polyester resin (X) has a continuous polyethylene terephthalate block, the heat resistance of the resin is improved, and it is considered to be excellent in flame retardancy. For example, the raw materials constituting the polyester resin (X) of this embodiment include polyethylene terephthalate (PET) in order to introduce a polyethylene terephthalate block into the polyester resin, and may further include a polyhydric alcohol having 7 to 48 carbon atoms as a polyhydric alcohol component. The raw materials may optionally contain a polycarboxylic acid component or a polyhydric alcohol other than the polyhydric alcohol having 7 to 48 carbon atoms. PET is incorporated into the polymer chain of the polyester resin by polycondensation with the polyhydric alcohol component or polycarboxylic acid component contained in the raw materials. In the polycondensation reaction, all the raw materials may be mixed and reacted, or the reaction may be carried out in multiple steps in two or more stages. The PET as the raw material may be depolymerized in advance before the polycondensation reaction, or may be depolymerized during the polycondensation reaction.

[0043] 1.5 Physical property values of the polyester resin (X) In the composition of the raw materials constituting the polyester resin (X), from the viewpoint of making the reaction proceed more smoothly, the range of the COOH / OH ratio of all the components contained in the raw materials is preferably 0.55 to 1.10. When the polyester resin (X1) is, for example, PET, it is regarded as 1 mol of COOH and 1 mol of OH per 1 mol of the above structural unit (1).

[0044] When using the polyester resin (X) as a chemical for fiber flame retardant processing, it is desirable that the polyester resin (X) be formulated as an aqueous dispersion or emulsion. Accordingly, from the viewpoint of controlling the particle size when dispersing or emulsifying the resin, the acid value of the polyester resin (X) is preferably 5 to 20 mgKOH / g, more preferably 5.5 to 15 mgKOH / g, and even more preferably 6 to 13 mgKOH / g. When the acid value is 5 mgKOH / g or more, poor emulsification tends to be suppressed. Also, when it is 20 mgKOH / g or less, hydrolyzability is suppressed and the flame retardancy tends to be further improved. The acid value of the polycondensed polyester resin (X) can also be adjusted within the above range by appropriately reacting a polyvalent carboxylic acid component having a valence of 3 or more. Examples of the polyvalent carboxylic acid component having a valence of 3 or more include the above polyvalent carboxylic acid components having a valence of 3 or more. From the viewpoint of reactivity, the temperature during acid value adjustment can be set to a reaction temperature of 180°C to 230°C, preferably under normal pressure or under pressure at a temperature condition of 190°C to 220°C for 0.1 hour to 1 hour.

[0045] From the viewpoint of flexibility, the glass transition temperature of the polyester resin (X) is preferably 50°C or lower, and more preferably 40°C or lower.

[0046] From the viewpoints of flame retardancy and flexibility, the weight average molecular weight of the polyester resin (X) is preferably 10,000 or more, and more preferably 15,000 or more. Also, from the viewpoint of ease of emulsification and dispersion, it is preferably 200,000 or less, more preferably 150,000 or less, and particularly preferably 100,000 or less.

[0047] In the polyester resin (X), the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is preferably 0.1 or more and 1.2 or less, more preferably 0.1 or more and 1.0 or less, and even more preferably 0.1 or more and 0.6 or less, from the viewpoints of flame retardancy and flexibility.

[0048] When the structural unit (B) and the structural unit (C) constituting the polyester resin (X) are derived from a polyester resin (X1) containing the structural unit (B) and the structural unit (C), the content of the polyester resin (X1) relative to the total amount of the raw materials is preferably 5 to 80%, more preferably 30 to 80%, and even more preferably 40 to 70% from the viewpoints of flame retardancy and flexibility. When it exceeds 80%, since there are too many robust structures, the resin becomes hard and the flame retardant processed fabric becomes hard, and there is a possibility that it cannot follow the elongation and bending of the base material. The total content of the depolymerized products in the above raw materials can be calculated from the charged mass of the polyester resin (X1) in terms of the number of moles of the unit of [polyhydric alcohol containing structural unit (C): polyvalent carboxylic acid containing structural unit (B)] (for example, in the case of PET, the unit of [terephthalic acid: ethylene glycol] (structural unit of the general formula (1))).

[0049] 1.6 Method for producing polyester resin (X) Examples of the method for producing the polyester resin (X) include the following methods (1), (2), (3), etc.

[0050] Method (1): A method of polycondensing a raw material containing a polyhydric alcohol having 7 to 48 carbon atoms and containing the structural unit (A) and a polyvalent carboxylic acid having 1 to 48 carbon atoms and containing the structural unit (B) to obtain a polycondensate. Method (2): A method of polycondensing a raw material containing a polyhydric alcohol having 7 to 48 carbon atoms and containing the structural unit (A), a polyvalent carboxylic acid having 1 to 48 carbon atoms and containing the structural unit (B), and a polyhydric alcohol having 1 to 6 carbon atoms and containing the structural unit (C) to obtain a polycondensate. Method (3): A method of polycondensing a raw material containing a polyhydric alcohol having 7 to 48 carbon atoms and containing the structural unit (A) and a polyester resin (X1) to obtain a polycondensate. In this case, the polycondensation reaction and the esterification reaction of the polyester resin (X1) may proceed simultaneously or stepwise.

[0051] The method for producing the polyester resin (X) may further include a step of reacting a polyvalent carboxylic acid component having a valence of 3 or more with the polycondensate obtained by the methods (1), (2), and (3).

[0052] In this embodiment, the temperature during the polycondensation reaction can be set to 200°C to 300°C, preferably 210°C to 270°C, and more preferably 220°C to 250°C, from the viewpoints of shortening the reaction time and suppressing the decomposition of the resin. The reaction is carried out at normal pressure, reduced pressure, or increased pressure, preferably under reduced pressure, for 3 to 20 hours.

[0053] For the polycondensation reaction, if necessary, conventionally known catalysts such as antimony trioxide, organotin-based polymerization catalysts such as dibutyltin oxide, germanium-based catalysts, inorganic titanium-based catalysts, organotitanium-based catalysts such as n-tetrabutoxytitanium and tetraisopropoxytitanium, organoaluminum-based catalysts, organocobalt-based catalysts, organozirconium-based catalysts, and transesterification catalysts such as zinc acetate and manganese acetate can be used. Among these, germanium-based catalysts, inorganic titanium-based catalysts, organotitanium-based catalysts, organozirconium-based catalysts, organoaluminum-based catalysts, etc. are preferred.

[0054] An antioxidant may be added to the polyester resin (X) at any stage during its production process or after production for the purpose of preventing coloring and thermal decomposition. Such antioxidants are not particularly limited, and examples include hindered phenol-based antioxidants, phosphite-based antioxidants, sulfur-containing antioxidants, etc.

[0055] 1.7 Polyester Resin (X) Aqueous Emulsion Dispersion The polyester resin (X) is preferably blended with a flame retardant processing agent as a water-emulsified dispersion. The polyester resin (X) may be dispersed as particles in an aqueous or non-aqueous medium. In other words, the flame retardant processing agent according to this embodiment may include an aqueous dispersion comprising an aqueous or non-aqueous medium and particles containing the polyester resin (X) dispersed in the medium. Examples of the aqueous medium include water and a mixed solvent of water and a solvent miscible with water (for example, lower alcohols or glycols having 1 to 4 carbon atoms, ketones such as methyl ethyl ketone and acetone, tetrahydrofuran, ester-based, acetate-based, etc.). Examples of the non-aqueous medium include esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and normal propyl acetate. Examples of the method of dispersion or emulsification include a method using a media type disperser (bead mill) or a high-pressure type disperser (homogenizer, altimizer), and a phase inversion emulsification method in which water is added to a solution dissolved in an organic solvent to cause phase inversion from an oil phase to an aqueous phase. Further, a surfactant can be used as an emulsifier as necessary. The type of the surfactant is not particularly limited, and may be, for example, at least one of known nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0056] 1.8 Flame Retardant (F) The flame retardant processing agent of the present disclosure may contain one or more flame retardants. For example, the flame retardant processing agent according to one embodiment may contain at least one flame retardant (F) selected from the group consisting of a halogen-based compound (F1), a phosphorus-based compound (F2), a metal hydroxide (F3), and a nitrogen compound (F4). Further, the flame retardant processing agent of the present disclosure may contain other flame retardants in addition to the flame retardants according to (F1) to (F4) above.

[0057] 1.8.1 Halogen-Based Compound (F1) As the halogen-based compound (F1), any known halogen-based compound that can exhibit the function as a flame retardant can be adopted. For example, as the halogen-based compound (F1), bromine-based compounds such as tetrabromobisphenol A (TBBA), decabromodiphenyl ether, bispentabromophenyl ethane, polybromostyrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, pentabromobenzyl acrylate, tris(dibromopropyl)isocyanurate, etc. may be used. Among these, when tris(dibromopropyl)isocyanurate is used, excellent flame retardancy is easily ensured.

[0058] 1.8.2 Phosphorus-based compound (F2) As the phosphorus-based compound (F2), any known phosphorus-based compound that can exhibit the function as a flame retardant can be adopted. For example, as the phosphorus-based compound (F2), compounds represented by the following general formulas (1) to (6) may be used, or a phosphoric acid compound may be used. Among the compounds represented by general formulas (1) to (6), from the viewpoint of suppressing kink, those having a melting point of 95 °C or higher or a melting point of 20 °C or lower are preferable. Those having a melting point of 95 °C or higher can give a hard texture to the fiber, and those having a melting point of 20 °C or lower can give a soft texture. There is also an advantage that the texture can be arbitrarily adjusted by combining those having a melting point of 95 °C or higher and those having a melting point of 20 °C or lower.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0059] 1.8.2.1 Compounds of General Formula (1) Examples of the compound represented by the general formula (1) include triphenyl phosphate (melting point: 50 °C), naphthyldiphenyl phosphate (melting point: 61 °C), dinaphthylphenyl phosphate, trinaphthyl phosphate (melting point: 111 °C), biphenyldiphenyl phosphate (liquid at 20 °C), tricresyl phosphate (liquid at 20 °C), trixylenyl phosphate (liquid at 20 °C), phenoxyethyldiphenyl phosphate (melting point: 80 °C), ethylhexyldiphenyl phosphate (liquid at 20 °C), tri(isopropylphenyl) phosphate (liquid at 20 °C), di(phenoxyethyl)phenyl phosphate, phenoxyethyldinaphthyl phosphate, di(phenoxyethyl)naphthyl phosphate, naphthoxyethyldiphenyl phosphate, di(naphthoxyethyl)phenyl phosphate, naphthoxyethyldinaphthyl phosphate, di(naphthoxyethyl)naphthyl phosphate, anilinodiphenyl phosphate (melting point: 130 °C), dianilinophenyl phosphate, trianilinophosphate, triphenylphosphine oxide (melting point: 157 °C), and the like. Among these, excellent flame retardancy is easily ensured when at least one of phenoxyethyldiphenyl phosphate (melting point: 80 °C), anilinodiphenyl phosphate, triphenylphosphine oxide, and trixylenyl phosphate (liquid at 20 °C) is used.

[0060] 1.8.2.2 Compound of General Formula (2) Examples of the compound represented by the general formula (2) include 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (melting point 115°C), 10-(4-methylbenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-phenethyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1-naphthylmethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2-naphthylmethyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, butyl [3-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methyl] succinimide, phenyl [3-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methyl] succinimide, benzyl [3-(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-yl)methyl] succinimide (melting point 143°C), and the like. Among these, when 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is used, excellent flame retardancy is easily ensured.

[0061] 1.8.2.3 Compound of General Formula (3) In the general formula (3), R 19The arylene group represented by [[ID=]] may have a substituent. Examples of such substituents include an alkyl group having 1 to 4 carbon atoms, a hydroxy group, etc. Examples of the arylene group include a phenylene group, a biphenylene group, a methylenebisphenylene group, a dimethylmethylenebisphenylene group, a sulfonebisphenylene group, etc. Examples of the compound represented by the general formula (3) include resorcinol di-2,6-xylyl phosphate (melting point 95 °C), resorcinol diphenyl phosphate (liquid at 20 °C), hydroquinone di-2,6-xylyl phosphate, 4,4'-biphenol di-2,6-xylyl phosphate, 4,4'-biphenol diphenyl phosphate, 4,4'-biphenol dicresyl phosphate, bisphenol A diphenyl phosphate (liquid at 20 °C), bisphenol A dicresyl phosphate (liquid at 20 °C), etc. Among these, when at least one of resorcinol di-2,6-xylyl phosphate and resorcinol diphenyl phosphate (liquid at 20 °C) is used, excellent flame retardancy is easily ensured.

[0062] 1.8.2.4 Compound of general formula (4) Examples of the compound represented by the general formula (4) include 5,5-dimethyl-2-(2'-phenylphenoxy)-1,3,2-dioxaphospholane-2-oxide (melting point 129 °C), 5,5-dimethyl-2-(4'-phenylphenoxy)-1,3,2-dioxaphospholane-2-oxide, 5-butyl-5-ethyl-2-(4'-phenylphenoxy)-1,3,2-dioxaphospholane-2-oxide, 5,5-dimethyl-2-(2'-naphthyloxy)-1,3,2-dioxaphospholane-2-oxide, etc. Among these, when 5,5-dimethyl-2-(2'-phenylphenoxy)-1,3,2-dioxaphospholane-2-oxide is used, excellent flame retardancy is easily ensured.

[0063] 1.8.2.5 Compound of general formula (5) Examples of the compound represented by the general formula (5) include 5-ethyl-5-[[[methoxy(methyl)phosphinyl]oxy]methyl]-2-methyl-1,3,2-dioxaphospholane 2-oxide (liquid at 20 °C).

[0064] 1.8.2.6 Compounds of general formula (6) Examples of the compound represented by the general formula (7) include phosphoramidates. Commercially available products may be used as the phosphoramidates. Examples of commercially available phosphoramidates include, for example, Diagard 850 manufactured by Daihachi Chemical Industry Co., Ltd.

[0065] 1.8.2.7 Phosphoric acid compounds Examples of the phosphoric acid compounds include polyphosphoric acid, ammonium polyphosphate, polyphosphoric acid amide, polyphosphoric acid carbamate, sodium polyphosphate, potassium polyphosphate, ammonium potassium polyphosphate, guanidine polyphosphate, guanidine phosphate, melamine polyphosphate, guanylurea phosphate, ammonium polyphosphate with a coated surface, aluminum phosphate, etc. Among these, when guanidine phosphate is used, excellent flame retardancy is easily ensured. Alternatively, when ammonium polyphosphate with a coated surface is used, a dripping suppression effect can be easily obtained together with the flame retardancy. The ammonium polyphosphate with a coated surface may be ammonium polyphosphate coated with silane or melamine. Among them, when silane-coated ammonium polyphosphate is used, there is no generation of VOC. Examples of silane-coated ammonium polyphosphate include FRCROS486 (manufactured by Budenheim), ExflamAPP-204 (manufactured by Wellchem), APP-102, APP-105 (manufactured by JLS), APP-5 (manufactured by Xi'an Chemical Industry), etc.

[0066] 1.8.2.7 Other matters regarding phosphorus-based compounds (F2) When the phosphorus-based compound (F2) is water-insoluble, the sharpness is more easily suppressed. Water-insoluble means that when the phosphorus-based compound (F2) is solid, after being made into powder, 10 g of the phosphorus-based compound (F2) is put into 100 g of ion-exchanged water at 20 °C, and when it is strongly shaken for 1 minute at 20 °C ± 0.5 °C, the degree of dissolution (g) of the phosphorus-based compound (F2) in 100 g of ion-exchanged water is 1.0 g or less. Here, "dissolve" means to give a transparent solution or to mix transparently at an arbitrary ratio.

[0067] Among the phosphorus-based compounds (F2), when at least one of biphenyl diphenyl phosphate, tricresyl phosphate, tri-2,6-xylyl phosphate, 10-benzyl-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, resorcinol di-2,6-xylyl phosphate, and phosphoroamidate is used, it is easy to achieve both flame retardancy, suppression of sharpness, and low cost.

[0068] 1.8.3 Metal hydroxide (F3) As the metal hydroxide (F3), any known metal hydroxide that can exhibit the function as a flame retardant can be adopted. For example, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc. can be mentioned. Among these, when at least one of aluminum hydroxide and magnesium hydroxide is used, especially when aluminum hydroxide is used, excellent flame retardancy is easily ensured. The shape and size of the metal hydroxide (F3) are not particularly limited. The metal hydroxide (F3) may be, for example, in the form of particles. From the viewpoints of flame retardancy and whitening or powdering of the coating surface, its average particle size may be 20 μm or less or 10 μm or less. The average particle size of the metal hydroxide (F3) is the particle diameter (median diameter) at the integrated value of 50% in the volume-based particle size distribution determined by the laser diffraction / scattering method. Incidentally, the metal hydroxide (F3) may contain impurities, but excellent flame retardancy is easily ensured when the impurities are few. For example, less SiO2 in aluminum hydroxide is excellent in flame retardancy and may be 0.02% or less.

[0069] 1.8.4 Nitrogen Compounds (F4) As the nitrogen compound (F4), any known nitrogen compound that can exhibit the function as a flame retardant can be adopted. For example, melamine compounds; guanamine compounds; triazine compounds; cyanuric acid compounds; salts of at least one selected from the group consisting of melamine compounds, guanamine compounds and triazine compounds and an acid; and the like. Incidentally, by using the nitrogen compound (F4) and the above-mentioned phosphorus-based compound (F2) in combination, it becomes easier to achieve both excellent flame retardancy and suppression of the occurrence of sharpness against hot water, which is more than when each compound is used alone.

[0070] 1.8.4.1 Melamine Compounds Examples of the melamine compound include melamine; alkyl melamines such as 2-methylmelamine, and substituted melamine compounds such as guanylmelamine; deammoniation condensates of melamine such as melam, melem, melon, and meton.

[0071] 1.8.4.2 Guanamine Compounds Examples of the guanamine compound include guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, 3,9-bis[2-(3,5-diamino-2,4,6-triazaphenyl)ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, and the like.

[0072] 1.8.4.3 Triazine Compounds Examples of the triazine compound include 1,2,3-triazine, 1,2,4-triazine, 1,3,5-triazine, benzotriazine, and amino group-containing triazines in which 1 to 3 amino groups are substituted on their carbon atoms.

[0073] 1.8.4.4 Cyanuric Acid Compounds Examples of the cyanuric acid compound include (iso)cyanuric acid (representing both cyanuric acid and isocyanuric acid), ammeline, ammelide, and the like. The cyanuric acid compound may be a hydrate or an anhydride.

[0074] 1.8.4.5 Salt Examples of the acid that forms a salt with at least one selected from the group consisting of melamine compounds, guanamine compounds, and triazine compounds include organic acids such as (iso)cyanic acid, formic acid, acetic acid, oxalic acid, malonic acid, lactic acid, citric acid, benzoic acid, isophthalic acid, and terephthalic acid; inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, pyrosulfuric acid, methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, sulfamic acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphonic acid, phenylphosphonic acid, alkylphosphonic acid, phosphorous acid, boric acid, and tungstic acid. In particular, when melamine cyanurate, which is a salt of melamine and cyanuric acid, is used, excellent flame retardancy is easily ensured.

[0075] 1.9 Mass ratio of polyester resin (X) to flame retardant (F) The mass ratio (F / X) of the flame retardant (F) to the polyester resin (X) may be, for example, 0.01 or more and 100 or less. In particular, when the mass ratio (F / X) is 0.1 or more and 50 or less, more excellent chipping resistance and fraying resistance are easily obtained, and whitening of fibers derived from the flame retardant is easily suppressed.

[0076] 1.10 Other components The flame-retardant processing agent of the present disclosure may contain at least polyester resin (X) alone or a combination of polyester resin (X) and a flame retardant (F). The flame-retardant processing agent of the present disclosure may include, for example, polyester resin (X) alone or a mixture of polyester resin (X) and a flame retardant (F), or a mixture of polyester resin (X), a flame retardant (F), and other components. In the mixture, polyester resin (X) and flame retardant (F) may each be present in particulate form. Also, in the mixture, polyester resin (X) does not necessarily cover the entire surface of flame retardant (F). Examples of other components include solvents such as water and surfactants for improving the dispersibility of polyester resin (X) in the solvent. That is, the flame-retardant processing agent of the present disclosure may be a dispersion in which polyester resin (X) and flame retardant (F) are each dispersed or dissolved in a solvent such as water. In this case, the solid content concentration in the dispersion is not particularly limited. Further, the flame-retardant processing agent of the present disclosure may contain various additives other than the above-described components. For example, flame retardants other than the above, deodorants, antibacterial agents, softeners, water absorbents, water and oil repellents, smoothing agents, penetrants, disperse leveling agents, antistatic agents, chelating agents, antioxidants, defoaming agents, pH adjusters, solvents, resins other than polyester resin (acrylic resin, silicone resin, urethane resin, amide resin, glyoxal resin, melamine resin, etc.), crosslinking agents, freeze stabilizers, matting agents, pigments, dyes, carrier agents, fixing agents, wetting agents, light stabilizers, ultraviolet absorbers, thickeners, film-forming aids, rust preventives, preservatives, fungicides, yellowing inhibitors, and other additives may be included. Hereinafter, an example of other components will be described in detail.

[0077] 1.10.1 Solvent In the flame retardant processing agent of the present disclosure, when using polyester resin (X) alone or mixing polyester resin (X) and a flame retardant (F), water may be used as a solvent. The water may be ion-exchanged water or distilled water. Alternatively, an organic solvent may be used in combination as a solvent. Examples of the organic solvent include glycols such as ethylene glycol, diethylene glycol, butyl glycol, and butyl diglycol; alcohols such as methanol, ethanol, and isopropanol; and esters such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, and normal propyl acetate. From the viewpoints of urgency, cost, dangerous goods, fastness, viscosity, and bleeding, the organic solvent may be 50% by mass or less, 40% by mass or less, or 30% by mass with respect to water.

[0078] 1.10.2 Surfactant The type of the surfactant is not particularly limited, and for example, it may be at least one of known nonionic surfactants, anionic surfactants, and amphoteric surfactants.

[0079] 1.10.3 pH Adjusting Agent In the flame retardant processing agent of the present disclosure, a pH adjusting agent may be included as an additive. The pH adjusting agent may be, for example, at least one selected from sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, ammonia, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, etc.

[0080] 1.10.4 Thickener In the flame retardant processing agent of the present disclosure, a thickener may be included as an additive. The thickener may be, for example, a natural water-soluble organic polymer such as gum arabic, tragacanth gum, guar gum, locust bean gum, sodium alginate, carrageenan, xanthan gum, pullulan, etc.; a semi-synthetic water-soluble organic polymer such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose, etc.; or a synthetic water-soluble organic polymer such as polyvinyl alcohol, urethane resin, acrylic resin, etc. At least one selected from these thickeners may be used. Among these thickeners, excellent coatability is easily obtained when xanthan gum, hydroxyethyl cellulose, polyvinyl alcohol, urethane resin, or acrylic resin is used.

[0081] Examples of the urethane resin include polyether polyol-based urethane polymers. As such polyether polyol-based urethane polymers, commercially available products can be used, for example, Adekanol UH-420, Adekanol UH-450, Adekanol UH-540, Adekanol UH-752 (all manufactured by ADEKA CORPORATION), SN Thicker 601, SN Thicker 612, SN Thicker 621N, SN Thicker 623N (all manufactured by San Nopco Limited), Rheolate 244, Rheolate 278, Rheolate 300 (all manufactured by Elementis Japan Co., Ltd.), DK Thicker SCT-275 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the like.

[0082] Examples of the alkali-thickening type acrylic resin include polymers of a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth)acrylic acid ester monomer. More specifically, the alkali-thickening type acrylic resin may be obtained by emulsion polymerization of a monomer composition containing at least one monomer selected from the group consisting of a carboxyl group-containing monomer and a (meth)acrylic acid ester monomer in the presence of a polymerization initiator, a surfactant, a chain transfer agent, a crosslinking agent, etc., if necessary.

[0083] 1.11 Use of the flame retardant processing agent The flame-retardant treating agent of the present disclosure is used, for example, for treating to impart flame retardancy to a fiber material or improving the flame retardancy of a fiber material. The types of fiber materials and the details of the flame-retardant treatment for the fiber materials will be described later.

[0084] 2. Fiber Products The technology of the present disclosure also has an aspect as a fiber product. That is, the fiber product of the present disclosure is characterized in that the above-described flame-retardant treating agent of the present disclosure is adhered thereto. Specifically, the fiber product according to one embodiment is formed by adhering a polyester resin (X). Alternatively, the fiber product according to one embodiment is formed by adhering a polyester resin (X) and at least one flame retardant (F) selected from the group consisting of a halogen-based compound (F1), a phosphorus-based compound (F2), a metal hydroxide (F3), and a nitrogen compound (F4). The types and mass ratios of the polyester resin (X) and the flame retardant (F) are as described above, and detailed descriptions thereof are omitted here.

[0085] 2.1 Fiber Materials The fiber material to which the polyester resin (X) or the polyester resin (X) and the flame retardant (F) are to be adhered is not particularly limited. For example, natural fibers such as cotton, hemp, silk, and wool, or regenerated fibers such as rayon, semi-synthetic fibers such as acetate, polyamide-based fibers, polyvinyl chloride-based fibers, polyacrylonitrile-based fibers, polyester-based fibers, polyurethane-based fibers, polyethylene-based fibers, polypropylene-based fibers, and the like, woven fabrics, knitted fabrics, and non-woven fabrics made of these composite fibers and blended fibers. Among them, from the viewpoints of flame retardancy and rubbing fastness, it is preferably a fabric, knitted fabric, or non-woven fabric having a basis weight of 50 g / m 2 or more, and in the case of a fabric or knitted fabric, it is more preferably 100 to 500 g / m 2 , and in the case of a non-woven fabric, it is more preferably 50 to 200 g / m 2 .

[0086] 2.2 Adhesion Amount The adhesion amount (DRY standard) of the polyester resin (X) and the flame retardant (F) in the textile product is not particularly limited. However, if the adhesion amount is too small, the flame retardancy tends to decrease, and if it is too large, there is a risk that the quality of the textile product will deteriorate, such as becoming hard. In this regard, the total adhesion amount of the polyester resin (X) and the flame retardant (F) on the surface of the textile product is, for example, preferably 1 g / m 2 or more, more preferably 5 g / m 2 or more, and preferably 100 g / m 2 or less, more preferably 80 g / m 2 or less.

[0087] 2.3 Use of the textile product The use of the textile product of the present disclosure is not particularly limited. For example, it can be adopted as a vehicle seat material, a non-woven fabric for low-voltage electricity, or a felt for low-voltage electricity. Examples of the vehicle seat material include automobile seat materials and railway vehicle seat materials. The felt for low-voltage electricity and the non-woven fabric for low-voltage electricity mean non-woven fabrics and felts used in the low-voltage electricity field. Specifically, buffer materials, filters, sound-absorbing materials, mat members, etc. can be mentioned.

[0088] 3. Manufacturing method of the textile product The technology of the present disclosure also has an aspect as a manufacturing method of a textile product. That is, the manufacturing method of the textile product of the present disclosure includes subjecting the above-mentioned fiber material to flame retardant processing by bringing it into contact with the above-mentioned flame retardant processing agent of the present disclosure. The flame retardant processing agent of the present disclosure may contain the polyester resin (X) and the flame retardant (F), or may be a two-component type of the processing agent (1) containing the polyester resin (X) and the processing agent (2) containing the flame retardant (F). In this way, by subjecting the fiber material to flame retardant processing using the flame retardant processing agent of the present disclosure, it is possible to impart high flame retardancy, a soft texture, high resistance to fraying, high rubbing fastness, and high fiber convergence.

[0089] As a method of bringing the flame retardant treatment agent into contact with the fiber material, there are no particular restrictions, and known methods such as dipping, padding, coating, spraying, and transfer can be appropriately used. When bringing the flame retardant treatment agent into contact with the fiber material, the flame retardant treatment agent may be appropriately diluted with a solvent or the like before use. The concentrations of the polyester resin (X) and the flame retardant (F) contained in the treated liquid after dilution are not particularly limited, and for example, the total concentration of these may be in the range of 0.01 to 30% by mass. Also, the component concentrations in the treatment liquid may be adjusted so that the adhesion amounts of the polyester resin (X) and the flame retardant (F) to the fiber material are the amounts described above.

[0090] When using the dipping method, a generally used dyeing machine, for example, a winch, a jet dyeing machine, a jigger, a cheese dyeing machine, or a skein dyeing machine is used to treat the fiber material at a predetermined temperature for a predetermined time, and then the fiber material is dehydrated and dried to obtain a flame-retardant fiber product.

[0091] When using the padding method, the fiber material is immersed in the treatment liquid, adjusted to a predetermined pickup amount using a mangle, a roll, or the like, and then dried to obtain a flame-retardant fiber product. Specifically, for example, the fiber material is immersed in one bath or two baths using the treatment liquid that is the flame retardant treatment agent, and then squeezed with a roller so as to have a predetermined moisture content while allowing the polyester resin (X), the flame retardant (F), etc. to penetrate into the fiber material. In this case, the dipping time and the squeezing ratio may be appropriately selected according to the thickness and basis weight of the fiber material to be treated, and further according to the application amounts of the polyester resin (X) and the flame retardant (F). Although not particularly limited, for example, the dipping time can be 1 to 5 seconds, and the squeezing ratio can be 50 to 100%.

[0092] When using the coating method, a treatment liquid obtained by mixing a flame retardant processing agent and optionally a binder can be used. Examples of methods for coating the flame retardant processing agent on the fiber material include coating methods such as gravure coater, knife coater, roll coater, slit coater, comma coater, air knife coater, flow coater, brush, foaming, etc. After coating the flame retardant processing agent on the fiber material, laminating or bonding may be performed.

[0093] When using the spray method, for example, while continuously feeding the fiber material with a conveyor or the like, the treatment liquid which is a flame retardant processing agent may be sprayed onto the fiber material. The detailed conditions of spraying may be appropriately selected according to the thickness and basis weight of the fiber material to be treated, and further according to the application amount of the polyester resin (X) and the flame retardant (F).

[0094] In the method for manufacturing the fiber product of the present disclosure, after bringing the fiber material into contact with the flame retardant processing agent, a step of appropriately drying may be performed. The drying method is not particularly limited. For example, dry drying using hot air; wet drying using a high-temperature pressure steamer (H.T.S.), a high-pressure steamer (H.P.S.), etc.; drying by irradiating microwaves, etc. may be mentioned. The drying temperature and drying time are not particularly limited. For example, the drying temperature may be 0°C to 300°C, and the drying time may be 5 seconds to several days. Further, if necessary, heat treatment (curing) may be performed at a temperature of 100°C or higher for about 10 seconds to 10 minutes after drying.

[0095] When using the transfer method, a thickened flame retardant agent is applied onto a substrate such as high-quality paper at a predetermined thickness, and after drying, the fiber product and the substrate coated with the fiber processing agent are passed through a calendar roll at a predetermined temperature and laminated to create a fiber product onto which the flame retardant agent has been transferred. Depending on the application, coloring ink or the like may be mixed to create a colored transfer. The drying temperature and drying time are not particularly limited. For example, the drying temperature may be 0°C to 300°C, and the drying time may be 5 seconds to several days. Neither the temperature of the calendar roll nor the drying temperature after coating is particularly limited. For example, the drying temperature may be 0°C to 300°C.

Example

[0096] As described above, one embodiment of the technology of the present disclosure has been described. However, the technology of the present disclosure can be variously modified other than the above embodiments without departing from the gist thereof. Hereinafter, while showing examples, the technology of the present disclosure will be described in more detail, but the technology of the present disclosure is not limited to the following examples.

[0097] 1. Production of polyester resin 1.1 Synthesis Examples 1 to 6, 28, 29 Raw materials having the compositions shown in Table 1 or 3 below were charged into a reaction vessel that had been sufficiently dried in advance, and heated to 180°C while stirring under nitrogen ventilation. Here, n-tetrabutoxytitanium was charged as a catalyst, the temperature was raised to 230°C, and finally, the pressure in the reaction vessel was reduced until it reached 3 kPa, and a polycondensation reaction was carried out until the acid value was in the range of 5 to 10 mgKOH / g to obtain polyester resins (X-1 to X-6, Y-1, Y-2). The charged amount of the catalyst is the amount added with 0.1 mol when the total number of moles of the alcohol component, carboxylic acid component, and other components is 100.

[0098] 1.2 Synthesis Examples 7 to 27 A reaction vessel that had been sufficiently dried in advance was charged with raw materials having the compositions shown in any of Tables 1 to 3 below, and heated to 180 °C with stirring under nitrogen ventilation. Here, as a catalyst, n-tetrabutoxytitanium (TBT) was charged, the temperature was raised to 230 °C, and finally the pressure in the reaction vessel was reduced until it reached 3 kPa, and a polycondensation reaction was carried out until the acid value was in the range of 10 mgKOH / g or less. Then, the pressure was returned to normal pressure, and it was cooled to 200 °C with stirring under nitrogen ventilation. Trimellitic anhydride was added to the polycondensed polyester resin, and the polycondensation reaction was further advanced until the acid value was in the range of 5 to 15 mgKOH / g, to obtain a polyester resin (X-7 to X-27).

[0099] In Tables 1 to 3 below, trimellitic anhydride (1) refers to the trimellitic anhydride contained in the raw materials during polycondensation with PET, and trimellitic anhydride (2) refers to the trimellitic anhydride added after polycondensation. Also, in Tables 1 to 3 below, the total raw materials are the total amount of the monomer components (PET, polyhydric alcohol component, and polyvalent carboxylic acid component (excluding trimellitic anhydride for acid value adjustment)) used in the polycondensation reaction, and the amounts of the catalyst and trimellitic anhydride (2) are the addition amounts (mole parts) when the total number of moles of the raw materials is 100 mole parts. Also, in Table 2 below, EG refers to ethylene glycol, and in Table 3 below, DMIS refers to dimethyl 5-sulfoisophthalate.

[0100] [Table 1]

[0101] [Table 2]

[0102] [Table 3]

[0103] Also, Tables 4 to 6 below show the amounts of the raw materials used in each of Synthesis Examples 1 to 29 in parts by mass.

[0104]

Table 4

[0105]

Table 5

[0106]

Table 6

[0107] 2. Measurement of Physical Property Values of Polyester Resin 2.1 Weight-Average Molecular Weight (Mw) 2 mg of polyester resin was added to 5 mL of tetrahydrofuran and dissolved, and the weight-average molecular weight was determined in terms of polystyrene by gel permeation chromatography (GPC)-HLC-8220GPC (manufactured by Tosoh Corporation). The measurement conditions of GPC are as follows. The results are shown in Tables 7 to 9 below. <Measurement Conditions> Detector: RI detector Mobile phase: Tetrahydrofuran Column: Two Tsk-gel Super HZ 2000 columns and one Tsk-gel Super HZ 4000 column were connected in series. The results are shown in Tables 5 and 6 below. Temperature of sample injector and column: 40 °C Temperature of RI detector: 40 °C Sample injection volume: 5 μL Flow rate: 0.35 mL / min Measurement time: 20 minutes

[0108] 2.2 Glass Transition Temperature (Tg) The glass transition temperature of the polyester resin was measured by DSC. A differential scanning calorimeter DSC-7020 (manufactured by Hitachi High-Tech Science Corporation) was used as the measurement device. The measurement conditions of Tg are as follows. The results are shown in Tables 7 to 9 below. <Measurement Conditions> Heating and cooling rate: 10 °C / min Heating program: The aluminum pan was heated from -50 °C to 100 °C and then cooled to -50 °C. Next, the temperature at the intersection of the baseline of the chart when heating to 100 °C and the tangent line of the endothermic curve near the glass transition temperature was defined as the glass transition temperature (Tg). The results are shown in Tables 7-9 below. Atmosphere: In a nitrogen stream (30 mL / min) Cell: Sealed aluminum Sample amount: 5.0 mg ± 1.0 mg Standard substances: Indium, tin

[0109] 2.3 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 7-9 below. Titration solvent: 0.1 mol / L aqueous sodium hydroxide solution Measurement solvent: Mixed solvent of tetrahydrofuran:water = 10:1 (volume ratio) Solvent amount: 100 mL Sample amount: 5.0 g ± 0.5 g

[0110] 3. Preparation of polyester resin water emulsion dispersion 3.1 Preparation example LX-1 100 parts by mass of polyester resin (X-1) and 150 parts by mass of tetrahydrofuran were added to dissolve the resin. While maintaining the temperature at 40 °C to 50 °C, 5 parts by mass of a 5% aqueous ammonia solution was added, and then 400 parts by mass of ion-exchanged water was gradually added to perform phase inversion emulsification. Then, tetrahydrofuran was distilled off under reduced pressure conditions. Thereafter, ion-exchanged water was added to adjust the solid content concentration to 30% by mass to obtain a polyester resin emulsion (LX-1).

[0111] 3.2 Preparation examples LX-2 to LX-27, LY-1, LY-2 Polyester resin water emulsion dispersions (LX-2 to LX-27, LY-1, LY-2) were obtained in the same manner as above, except that polyester resins (X-2) to (X-27), (Y-1), or (Y-2) were used instead of polyester resin (X-1).

[0112]

Table 7

[0113]

Table 8

[0114]

Table 9

[0115] 4. Preparation of Other Resin Dispersions 4.1 Preparation of Acrylic Resin Dispersion Nipol LX874 (manufactured by Nippon Zeon Co., Ltd., 45% acrylic resin) was used as the acrylic resin dispersion.

[0116] 4.2 Preparation of Urethane Resin Dispersion In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 216.13 parts of polytetramethylene glycol (average molecular weight 1000) and 50.91 parts of polyoxyethylene-polypropylene random copolymer glycol (average molecular weight 1000, 70% ethylene oxide group content) as polyols, 4.50 parts of 1,4-butanediol and 0.62 parts of trimethylolpropane as low molecular chain extenders, 0.002 parts of dibutyltin dilaurate as a reaction catalyst, and 98.36 parts of methyl ethyl ketone as a solvent were charged and uniformly mixed. Then, 121.26 parts of dicyclohexylmethane 4,4'-diisocyanate (H12MDI) as a polyisocyanate was added, and the mixture was reacted at 75 °C for 300 minutes to obtain a methyl ethyl ketone solution of an isocyanate group-terminated urethane prepolymer. After cooling this solution to 30 °C or lower, 2 parts of decyl phosphate as a reaction terminator and 18 parts of polyoxyethylene tristyrylphenyl ether (HLB = 15) as a nonionic surfactant were added and uniformly mixed. Then, the mixture was transferred to another container, and 646.80 parts of water was gradually added, and phase inversion emulsification and dispersion were carried out using a dispersing blade. To this, an aqueous polyamine solution prepared by dissolving 22.90 parts of piperazine hexahydrate and 1.43 parts of diethylenetriamine as polyamine compounds in 56.76 parts of water was added, and the mixture was stirred for 90 minutes to obtain a urethane resin aqueous dispersion. By further performing solvent removal on the obtained urethane resin aqueous dispersion at 35 °C under reduced pressure, a water-emulsion dispersion (40% urethane resin) of a stable heat-sensitive coagulation type forced-emulsified aqueous urethane resin with an average particle diameter of 0.2 μm was obtained.

[0117] 5. Preparation of Flame Retardant Dispersion 5.1 Preparation of Ammonium Polyphosphate (APP) Dispersion In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 5 parts of sodium lauryl sulfate was dissolved in 595 parts of water, and 400 parts of ammonium polyphosphate (Exflam APP-204, manufactured by Wellchem) was introduced little by little and mixed for 30 minutes to obtain an ammonium polyphosphate (APP) dispersion (40% flame retardant dispersion).

[0118] 5.2 Preparation of Guanidine Phosphate Dispersion Abinon 307 (manufactured by Sanwa Chemical Co., Ltd., a 50% dispersion of flame retardant) was used as the guanidine phosphate-based flame retardant dispersion liquid.

[0119] 5.3 Preparation of melamine cyanurate dispersion liquid In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 5 parts of sodium lauryl sulfate was dissolved in 595 parts of water, and 400 parts of melamine cyanurate (MC-4500, manufactured by Nissan Chemical Industries, Ltd.) was introduced little by little and mixed for 30 minutes to obtain a melamine cyanurate dispersion liquid (a 40% dispersion of flame retardant).

[0120] 5.4 Preparation of aluminum hydroxide dispersion liquid In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 5 parts of sodium lauryl sulfate was dissolved in 595 parts of water, and 400 parts of aluminum hydroxide (B53, manufactured by Nippon Light Metal Co., Ltd.) was introduced little by little and mixed for 30 minutes to obtain an aluminum hydroxide dispersion liquid (a 40% dispersion of flame retardant).

[0121] 5.5 Preparation of tris(dibromopropyl) isocyanurate (TBC) dispersion liquid In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 5 parts of sodium lauryl sulfate was dissolved in 595 parts of water, and 400 parts of tris(dibromopropyl) isocyanurate (TAIC-6B, manufactured by Nippon Kasei Co., Ltd.) was introduced little by little and mixed for 30 minutes to obtain a tris(dibromopropyl) isocyanurate (TBC) dispersion liquid (a 40% dispersion of flame retardant).

[0122] 5.6 Preparation of phosphoroamidate dispersion liquid In a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 5 parts of sodium lauryl sulfate was dissolved in 595 parts of water, and 400 parts of phosphoroamidate (Digard 850, Daihachi Chemical Industry) was introduced little by little and mixed for 30 minutes to obtain a phosphoroamidate dispersion liquid (a 40% dispersion of flame retardant).

[0123] 6. Preparation of test fiber materials In a pot of a mini-color dyeing machine (manufactured by Texam Giken Co., Ltd.), water, the disperse dyes shown in Table 10 below, a disperse leveling agent, and a pH adjuster were put in and mixed uniformly to prepare a dyeing bath. Next, a polyester fabric as a fiber material (areal density: 350 g / m 2 ) was put into the dyeing bath so that the bath ratio became 1:10, and the temperature of this dyeing bath was raised from 40°C to 80°C at a rate of 2°C per minute, and then from 80°C to 130°C at a rate of 1°C per minute. After that, dyeing was carried out by holding at 130°C for 30 minutes. Next, the temperature of the dyeing bath was lowered to 80°C, and the polyester fabric was taken out of the pot, and reduction washing (80°C × 15 minutes, bath ratio = 1:10) was carried out with the treatment liquid shown in Table 11 below. Then, washing, dehydration, and drying were carried out to obtain a dyed fabric (100% polyester black fabric, areal density 350 g / m 2 ).

[0124]

Table 10

[0125]

Table 11

[0126] 7. Flame retardant treatment of fiber products 7.1 Example 1: Padding 95 parts of water and 5 parts of a polyester resin dispersion (LX-1) were mixed to prepare a treatment liquid for flame retardant treatment. The dyed fabric was dipped in the treatment liquid and squeezed with a mangle roll. The pickup of the treatment liquid was 70%. The squeezed fabric was dried at 150°C for 3 minutes to produce a flame retardant vehicle seat material. The pickup was calculated as [(mass of the flame retardant vehicle seat material after mangle squeezing - mass of the vehicle seat material) ÷ mass of the vehicle seat material].

[0127] 7.2 Examples 2 to 28, Examples 32 to 36, Comparative Examples 1 to 5: Padding In the treatment liquid for flame-retardant processing, except that various dispersions were mixed in the amounts described in Tables 12 to 14 below instead of 5 parts of the polyester resin dispersion (LX-1), flame-retardant processing of the dyed fabric was carried out in the same manner as in Example 1 to produce a flame-retardant vehicle seat material.

[0128] 7.3 Example 29: Spray 95 parts of water and 5 parts of the polyester resin dispersion (LX-14) were mixed to prepare a treatment liquid for flame-retardant processing. The prepared treatment liquid was applied to the dyed fabric by spraying so as to be 70% of the fabric weight. Then, the fabric was dried at 150 °C for 3 minutes to produce a flame-retardant vehicle seat material with a dry coating amount of about 3 g / m 2

[0129] 7.4 Example 30: Coating 50 parts of the polyester resin dispersion (LX-14) and 3 parts of Neo Sticker N were mixed to obtain a viscous liquid (coating liquid A) with a viscosity of 5,000 mPa·s. The obtained viscous liquid was coated on the dyed fabric with a J-bar to a WET of about 10 g / m 2 and then the fabric was dried at 150 °C for 5 minutes to produce a flame-retardant vehicle seat material with a dry coating amount of about 3 g / m 2

[0130] 7.5 Example 31: Transfer The coating liquid prepared in Example 30 was coated on high-quality paper with a thickness of 20 μm and dried in an oven at 150 °C for 3 minutes. Then, the fiber product and the fiber processing agent were passed through a calendar roll at 180 °C and laminated with the coated high-quality paper to produce a flame-retardant vehicle seat material with a dry coating amount of about 3 g / m 2

[0131] 7.6 Comparative Example 6: Coating ​​​To a reaction vessel, 250 parts by solid content of FP-600 (trade name, manufactured by ADEKA), which is a reaction product of phenol, 4,4´-(propane-2,2-diyl)diphenol and trichlorophosphine oxide as a liquid phosphorus-based flame retardant, and 15 parts by solid content of Emulgen A-90 (trade name, manufactured by Kao Corporation), which is polyoxyethylene distyrenated phenyl ether as a surfactant having an aromatic group, were added, and the mixture was stirred and mixed at 40 °C for 30 minutes. Then, while stirring, 143 parts of water was added to emulsify it into a flame retardant dispersion. To this flame retardant dispersion, 85 parts of an acrylic resin dispersion and 15 parts of Eter KT-8701 (manufactured by Unitika, solid content 30%, Tg 12 °C) as a polyester resin emulsion were blended, and 10 parts of Neo Sticker V (manufactured by Nikka Chemicals), which is an acrylic thickener as a thickener, was mixed to obtain a flame retardant resin composition having a solid content of 50%. The obtained flame retardant resin composition was coated on a dyed fabric with a J bar to a WET of about 33 g / m 2 such that it became, and then the fabric was dried at 150 °C for 5 minutes to obtain a flame retardant vehicle seat material with a dry coating amount of about 16 g / m 2 .

[0132] 8. Evaluation of textile products The flame retardancy, rubbing fastness, fraying at the edges (fiber convergence), edge fraying, and stiffness-flexibility of the produced vehicle seat material were evaluated by the following methods.

[0133] 8.1 Edge fraying A 10 mm thick urethane foam sheet was placed on a table, and the vehicle seat material was placed on it. Then, 2 mL of pure water at 90 °C was dropped onto its surface. After air-drying at room temperature, the presence or absence of edge fraying (appearance of whitening or dark-colored parts) on the surface of the vehicle seat material was visually observed, and the edge fraying was evaluated according to the following five-level criteria. A: No edge fraying is visible (qualified level) B: Less than 10% of edge fraying is observed compared to D. (qualified level) C: Edge fraying is observed at less than 30% but 10% or more compared to D (unqualified level) D: Edge fraying is clearly visible (at or above the level of C, unqualified level)

[0134] 8.2 Flame retardancy According to FMVSS-302 (safety standard for automotive interior products), the burning distance, burning time and burning speed of the vehicle seat material were measured, and the flame retardancy was evaluated according to the following burning score criteria. The burning score was calculated by averaging the scores measured ten times and comparing them to one decimal place. 5 points: No flame. 4 points: Flame ignites but does not burn beyond the A mark (extinguishes before the A mark). 3 points: Burns beyond the A mark, but the burning distance is less than 50 mm and the burning rate is less than 80 mm / min. 2 points: Burns beyond the A mark, the burning distance is 50 mm or more, and the burning rate is less than 80 mm / min. 1 point: Burns beyond the A mark, the burning distance is 50 mm or more, and the burning rate is 80 mm / min or more.

[0135] 8.3 Rubbing fastness Using the JISL0849:2013 (dry, wet) method, the surface of the fiber fabric was abraded 100 times with a rubbing cloth under a load of 2N using a friction tester Type II (Gakushin type) (manufactured by Daiei Chemical Precision Machinery Co., Ltd.: model number RT-300). A cotton cloth was used as the friction cloth. Based on the degree of contamination of the cotton cloth after rubbing and the contamination gray scale, the friction fastness was evaluated according to a five-level evaluation standard. Evaluation was performed under both dry and wet conditions. Grade 5: No contamination found, good ~ Grade 1: Significant contamination found, poor

[0136] 8.4 End fraying (fiber convergence) Based on JIS L 1076:2012 Method A (method using an ICI type testing machine), a cut was made in the center of each side of a piece of fabric cut to 100 mm length and 100 mm width, with a 3 mm base and 2 mm height. The fabric was placed in the ICI type testing machine and rotated for 10 hours. The fabric was then removed and the series was determined based on the visibility of the cuts. The intermediate series of each series is expressed, for example, as 4-5. Grade 5: No deformation or fraying in any of the four cuts. Level 4: There is no deformation of the incision at two or more of the four locations, but deformation is observed at other locations. Level 3: Deformation of the incision is observed at all four locations. Or, there are four or more frayed threads with a length of 20 mm or more. Level 2: Fraying has occurred to such an extent that the shape of the incision cannot be confirmed at one or more of the four incisions. Level 1: Fraying has occurred to such an extent that the shape cannot be confirmed at all four incisions.

[0137] 8.5 Stiffness The stiffness was measured in accordance with JIS L 1096:2010, Test Methods for Fabrics and Knitted Fabrics. It can be said that the smaller the value, the softer the texture, and the larger the value, the coarser the texture.

[0138] 9. Evaluation Results The evaluation results are shown in Tables 12 to 14 below.

[0139]

Table 12

[0140]

Table 13

[0141]

Table 14

[0142] As is clear from the results shown in Tables 12 to 14, when the fiber material was subjected to flame retardant processing, for Examples 1 to 36 in which polyester resin (X) was used in combination in the flame retardant processing liquid, excellent flame retardancy, soft texture (low stiffness), resistance to fraying, fiber convergence (resistance to splitting), and rubbing fastness could be ensured in the fiber material after the flame retardant processing. On the other hand, in Comparative Examples 1 and 2 using a polyester resin not containing a diol having 7 to 48 carbon atoms as the diol component instead of polyester resin (X), Comparative Examples 3 to 4 using other resins, Comparative Example 5 not using resins in combination, and Comparative Example 6 which is a coating agent using a combination of a polyester resin and an acrylic resin, any one of flame retardancy, texture hardening (high stiffness), fiber convergence (resistance to splitting), rubbing fastness, and resistance to fraying decreased as compared with Examples 1 to 36.

[0143] As described above, it was found that a flame retardant agent containing polyester resin (X) or a flame retardant agent containing polyester (X) and a flame retardant (F) can impart a high level of flame retardancy and a soft texture (low stiffness) to the fiber material, and can also improve high fiber convergence, prevention of migration of dyes and pigments (rubbing fastness), and resistance to fraying.

Claims

1. A flame-retardant processing agent containing a polyester resin (X), wherein the polyester resin (X) contains a structural unit (A) represented by the following formula (a) and a structural unit (B) represented by the following formula (b), Flame-retardant processing agent. 【Chemical Formula 1】 In formula (a) and formula (b), R １ is a substituted or unsubstituted hydrocarbon group having 7 to 48 carbon atoms, R ２ is a substituted or unsubstituted hydrocarbon group having 1 to 48 carbon atoms.

2. The flame-retardant processing agent according to claim 1, wherein the polyester resin (X) contains a structural unit (C) represented by the following formula (c), Flame-retardant processing agent. 【Chemical Formula 2】 In formula (c), R ３ is a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.

3. The flame-retardant processing agent according to claim 2, wherein the polyester resin (X) contains a structural unit derived from a polyester resin (X1), and the polyester resin (X1) contains the structural unit (B) and the structural unit (C), Flame-retardant processing agent.

4. The flame-retardant processing agent according to any one of claims 1 to 3, wherein in the polyester resin (X), the molar ratio (A / B) of the structural unit (A) to the structural unit (B) is 0.1 or more and 1.2 or less, Flame-retardant processing agent.

5. The flame-retardant processing agent according to any one of claims 1 to 3, A flame retardant (F) containing at least one selected from the group consisting of a halogen-based compound (F1), a phosphorus-based compound (F2), a metal hydroxide (F3), and a nitrogen compound (F4). Flame retardant processing agent.

6. A textile product to which the flame retardant processing agent according to any one of claims 1 to 3 is attached. Textile product.

7. A method for manufacturing a textile product, comprising: contacting a fiber material with the flame retardant processing agent according to any one of claims 1 to 3 to perform flame retardant processing. A method for manufacturing a textile product.

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