Polyester-based flame retardant coating agent

Abstract

To provide a flame-retardant coating agent which can impart high flame retardance to a fibrous material and can effectively maintain texture inherent in the fibrous material.SOLUTION: A polyester-based flame-retardant coating agent for making a fibrous material flame retardant includes: (1) a water-based polyester resin whose glass transition temperature (Tg) is -30 to 30°C; (2) a flame-retardant component; (3) a thickening component; and (4) a water-based solvent.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a novel polyester-based flame retardant coating agent. More specifically, the present invention relates to a novel composition for imparting flame retardancy to fiber members.

Background Art

[0002] For example, fiber fabrics used in industrial materials such as automotive fiber products (car seats, car mats, ceiling materials, etc.) are generally coated and dried on the back surface with a back coating agent (BC agent) containing a resin component by a method called back coating, and the fibers are coated with the resin to perform fraying prevention treatment. In this case, in order to impart flame retardancy at the same time, a flame retardant may be added to the back coating agent, and it is a flame retardant treatment method that can be said to be essential especially in the field of car seats.

[0003] In addition, in knitted fabrics, synthetic leathers, artificial leathers, etc. where the purpose of preventing fraying is not necessary, a similar back coating may be applied solely for the purpose of imparting flame retardancy, and the demand for this has been increasing in recent years.

[0004] As the resin components contained in such BC agents, acrylic resins, urethane resins, etc. have been generally used mainly so far (for example, Patent Documents 1 to 6).

[0005] However, although acrylic resins can produce inexpensive and flexible materials, those with high flexibility tend to have tack (stickiness) on the surface of the coating film after drying. Texture (flexibility) and tack are in a trade-off relationship, and it is difficult to satisfy both of them completely. In addition, the flammability of acrylic resins themselves is very high, and thus a large amount of flame retardants (flame retardant treatment agents to be applied) is required. That is, there may be a need for an application amount that is excessive compared to the amount required to impart the fraying prevention performance, which is the main purpose.

[0006] Urethane resin is easier to impart flame retardancy to compared with acrylic resin, and its strong physical properties make it highly effective at preventing fraying. On the other hand, urethane resin is relatively expensive and has the disadvantage of having a somewhat hard texture. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2006-233152 [Patent Document 2] Japanese Patent Publication No. 2007-16357 [Patent Document 3] Japanese Patent Publication No. 2014-141598 [Patent Document 4] Japanese Patent Publication No. 2015-187317 [Patent Document 5] Japanese Patent Publication No. 2021-54924 [Patent Document 6] International release WO2014 / 2958 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] Thus, conventional BC agents have the problem of inhibiting the flexibility of fibrous materials when attempting to impart the desired flame retardancy to them. In this respect, there is room for further improvement.

[0009] Therefore, the main object of the present invention is to provide a flame-retardant coating agent that can impart high flame retardancy to fibrous materials while effectively maintaining the texture inherent to the fibrous materials. [Means for solving the problem]

[0010] In light of the problems of the prior art, the inventors conducted extensive research and, as a result, discovered that the above objective can be achieved by adopting a composition containing a specific resin component, thus completing the present invention.

[0011] In other words, the present invention relates to the following polyester-based flame-retardant coating agent. 1. A flame-retardant coating agent for making fibrous materials flame-retardant, (1) A water-based polyester resin having a glass transition temperature (Tg) of -30 to 30°C. (2) Flame retardant components, (3) Thickening agents and (4) Aqueous solvents A polyester-based flame-retardant coating agent characterized by containing the following: 2. The polyester-based flame-retardant coating agent according to claim 1, wherein the flame-retardant component is at least one of a phosphoramidate compound and a phosphonic acid ester compound. 3. Solid content, (1) Water-based polyester resin with a glass transition temperature (Tg) of -30 to 30°C: 5 to 30 Mass % (2) Flame retardant components: 5-25 Mass % (3) Thickening agent: 0.1~3.0 Mass % A polyester-based flame retardant coating agent according to item 1, comprising the above-mentioned material. 4. The flame retardant component is water-based polyester resin 100 Parts by mass 15-400 Parts by mass The polyester-based flame retardant coating agent described in item 1 above. 5. The polyester-based flame retardant coating agent described in item 1 above, wherein the viscosity (at 20°C) is 1,000 to 1,000,000 mPa·s. 6. A polyester-based flame retardant coating agent according to any one of items 1 to 5, used to form a back coat layer on the surface of a sheet-like fibrous material. 7. A flame-retardant product comprising a back coat layer formed on the surface of a sheet-like fibrous material using a polyester-based flame-retardant coating agent as described in any one of items 1 to 5 above. 8. A car seat, which is a flame-retardant product as described in item 7 above. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a flame-retardant coating agent that can impart high flame retardancy to fibrous materials while effectively maintaining the texture inherent to the fibrous materials.

[0013] Since the polyester-based flame retardant coating agent of the present invention employs an aqueous polyester resin having a specific glass transition point (Tg) as a resin component, it has higher flame retardant performance compared to conventional acrylic-based and urethane-based BC agents. As a result, it is possible to use a relatively small coating amount, contributing to weight reduction and suppressing manufacturing costs.

[0014] Moreover, when using a powdery material as the flame retardant component, each desired performance can be obtained without substantially inhibiting the flame retardancy and other physical properties (texture, sharpness, heat resistance).

[0015] Furthermore, especially when applied to a fibrous material containing polyester fibers, both the polyester-based flame retardant coating agent of the present invention and the fibrous material become polyester materials that are easily recyclable. Therefore, reuse after use becomes easy, and it is also very valuable from the perspective of SDGs.

Brief Description of the Drawings

[0016]

Figure 1

Modes for Carrying Out the Invention

[0017] 1. Polyester-based flame retardant coating agent The polyester-based flame retardant coating agent (the coating agent of the present invention) of the present invention is a flame retardant coating agent for making a fibrous material flame retardant, (1) An aqueous polyester resin having a glass transition temperature (Tg) of -30 to 30°C (hereinafter, also simply referred to as "aqueous polyester resin"). (2) A flame retardant component, (3) A thickening component and (4) An aqueous solvent and is characterized by containing the above.

[0018] A. Composition of the coating agent of the present invention (1) Water-based polyester resin The aqueous polyester resin is primarily a component that functions as a binder in the coating agent of the present invention.

[0019] Generally, polyester resins are easier to flame retardant than acrylic or urethane resins, and the amount of flame retardant added can be reduced. However, because polyester resins have a harder texture than acrylic or urethane resins, in practice only a limited number of grades are used as hardening agents for sheet fabrics, such as in dipping. Furthermore, due to its properties, it rapidly liquefies above its softening point, and concerns arise regarding the stickiness and fluidity of the BC layer, making it unsuitable for fixing large quantities to sheet fabrics as a BC agent. In other words, when using polyester resin as a resin component of a BC agent, its use is generally avoided due to a) the resulting rigid texture, b) concerns about heat resistance, and c) its relatively high cost. In contrast, the present invention employs a water-based polyester resin with a specific Tg range as a resin component of the BC agent, thereby enabling high flame retardancy while effectively maintaining the original texture of the fibrous material.

[0020] The Tg of water-based polyester resins is typically around -30 to 30°C, and is particularly preferably -10 to 20°C, with -10 to 15°C being the most preferable. If the Tg is too high, it becomes difficult to maintain the texture of fibrous materials when used as a BC agent. Conversely, if the Tg is too low, problems such as decreased heat resistance and increased tack will occur.

[0021] Generally, Tg is a factor usually linked to the softening point. A lower Tg allows for the acquisition of a more flexible BC agent. However, if the Tg is too low, the softening point also decreases, leading to problems with the physical properties at high temperatures (heat resistance). Conversely, if the Tg is too high, flexibility is lost. Therefore, the Tg of the aqueous polyester resin used in this invention is set to -30 to 30°C.

[0022] Furthermore, in the present invention, two or more water-based polyester resins with different Tg values ​​can be blended and used. In other words, it is possible to blend a high-Tg resin with a low-Tg resin to adjust the texture to an appropriate level. Therefore, as long as the present invention contains a water-based polyester resin with a Tg of -30 to 30°C, it is acceptable to include a water-based polyester resin with a Tg in the range of -30 to 30°C, as long as it does not hinder the effects of the present invention.

[0023] When blending two or more types of aqueous polyester resins, it is sufficient that at least one of the aqueous polyester resins has a Tg of -30 to 30°C, but it is particularly desirable that the Tg detected after blending (i.e., the Tg of the mixed resin) be within the -30 to 30°C range. In other words, when blending an aqueous polyester resin with a Tg in the -30 to 30°C range with an aqueous polyester resin with a Tg outside the -30 to 30°C range, it is desirable that the Tg of the mixed resin after blending be within the -30 to 30°C range. In particular, it is even more desirable that the Tg of all two or more aqueous polyester resins with different Tg values ​​be within the -30 to 30°C range.

[0024] Water-based polyester resins with a Tg in the range of -30 to 30°C can be those that are known or commercially available. They can also be synthesized by known manufacturing methods. For example, the method for synthesizing a Tg within the above range is not particularly limited, but a method that introduces a specific soft segment into the monomer composition is particularly effective.

[0025] Typically, such water-based polyester resins can preferably be made from monomers that use a dibasic acid, a diol, and a small amount of a dibasic or polybasic acid with a polar functional group (sulfonate group) introduced as hydrophilic units.

[0026] Examples of the aforementioned dibasic acid groups include aromatic dibasic acids such as phthalic acid, isophthalic acid, terephthalic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, and 2,5-franzicarboxylic acid; and aliphatic dibasic acids such as succinic acid, adipic acid, sebacic acid, and dodecanediic acid.

[0027] Among these, relatively long-chain aliphatic dibasic acids are more effectively utilized as effective soft segments, with those having 6 or more carbon atoms being particularly preferred, and even more preferably containing those with 6 to 12 carbon atoms. By copolymerizing these long-chain aliphatic dibasic acids with aromatic dibasic acids such as isophthalic acid and terephthalic acid in any proportion, it is possible to provide a water-based polyester resin that has a flexible texture and excellent water resistance and adhesion to fabric. The content ratio is not limited, but it is desirable to use approximately 0.1 to 3 moles per mole of aromatic dibasic acid.

[0028] Examples of the aforementioned diol components include aliphatic diols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol; aromatic diols such as 1,4-benzenedimethanol and 9,9--bis[4-(2-hydroxyethoxy)phenyl]fluorene; and ether diols such as diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0029] While it is possible to flexibly adjust the texture by using relatively long-chain diols for the diol component, adjustment using the dibasic acid component composition is simpler and more practical. Examples of diols suitably used in the present invention include at least one of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, and diethylene glycol.

[0030] Furthermore, it is preferable to use a water-dispersed polyester resin for the present invention, in which case a monomer unit that imparts hydrophilicity may be introduced. Suitable hydrophilicity-imparting components include, for example, metal salts or ammonium salts of carboxylic acids. More specifically, metal salts or ammonium salts of 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 5-sulfoisophthalic acid, etc., can be suitably used. In addition, metal salts or ammonium salts of aromatic tricarboxylic acids such as trimellitic acid, hemimedic acid, and trimedic acid can also be suitably used.

[0031] Commercially available water-based polyester resins can also be used. Examples include product names "CY-190" (manufactured by Marubishi Yuka Kogyo Co., Ltd.), "Vaironal MD-1930", "Vaironal MD-1480", and "Vaironal MD-1985" (all manufactured by Toyobo Co., Ltd.), and "Pluscoat Z-3310", "Pluscoat Z-592", and "Pluscoat Z-880" (all manufactured by Go-o Kagaku Co., Ltd.).

[0032] The solid content of the aqueous polyester resin in the coating agent of the present invention is not limited, but is usually 5 to 30 Mass % To the extent of, especially 10-25 Mass % It is preferable to do so, and among them 12 to 20 Mass % This is the most preferable course of action.

[0033] (2) Flame retardant components The flame retardant component is not particularly limited, and any of the following can be used: phosphorus-based flame retardants, nitrogen-based flame retardants, metal compound-based flame retardants, halogen-based flame retardants, etc.

[0034] Examples of phosphorus-based flame retardants include phosphate ester compounds, phosphoramidate compounds, phosphonic acid ester compounds, organophosphinates, polyphosphate melamine compounds, and phosphazene compounds. These can be used individually or in combination of two or more.

[0035] Examples of nitrogen-based flame retardants include melamine cyanurate and compounds containing hindered amines (HALS, especially NOR-type HALS). These can be used individually or in combination of two or more.

[0036] Suitable inorganic flame retardant components include, for example, ammonium polyphosphate, zinc polyphosphate, aluminum hydroxide, magnesium hydroxide, zinc hydroxide, zinc borate, zinc oxide, antimony trioxide, antimony pentoxide, and sodium antimonate. These can be used individually or in combination of two or more.

[0037] Examples of halogen-based flame retardants include brominated compounds and chlorinated compounds. More specifically, examples include bis(3,5-dibromo-4-dibromopropyloxyphenyl)sulfone, tris(2,3-dibromopropyl)isocyanurate, and decabromodiphenylethane. These can be used individually or in combination of two or more.

[0038] In this invention, it is preferable to include a phosphorus-based flame retardant component because it provides a very high flame retardant effect. Furthermore, by adding at least one of a nitrogen-based flame retardant component and an inorganic flame retardant component as auxiliary components, an even higher flame retardant effect can be obtained. Also, from the standpoint of environmental protection, it is preferable that the flame retardant component does not contain a halogen-based flame retardant component.

[0039] Among phosphorus-based flame retardant components, at least one phosphorus-based flame retardant component consisting of a phosphoramidate compound and a phosphonic acid ester compound is particularly preferred. In particular, the phosphorus-based flame retardant components shown in the following chemical formulas (1) to (3) can be suitably used in the present invention.

[0040] [ka]

[0041] These compounds can be those that are publicly known or commercially available. They can also be those synthesized by known manufacturing methods. For example, the compound of chemical formula (1) can be obtained by the manufacturing method disclosed in Patent Document 6. The compound of chemical formula (2) can be obtained by the manufacturing method disclosed in Patent Document 4. The compound of chemical formula (3) can be obtained by the manufacturing method disclosed in Japanese Patent Application Publication No. 2021-123572.

[0042] In this invention, the flame retardant component is preferably a powdered flame retardant with a melting point of 80°C or higher (particularly 150°C or higher). By using a powdered flame retardant component, the stickiness (surface tackiness) characteristic of low-Tg resins can be further reduced, and good resistance to dye bleeding or edge formation can be achieved. In addition, by adding a powdered flame retardant, the fluidity at high temperatures is mitigated, which can improve the shape retention of the formed coating layer.

[0043] However, liquid flame retardant components (flame retardants) can also be used, as long as they do not interfere with the effects of the present invention. Phosphate ester-based flame retardants are commonly used as liquid flame retardants. Adding large amounts of liquid phosphate ester-based flame retardants may cause dye transfer, but using relatively small amounts as a texture adjuster does not pose any particular problem.

[0044] The solid content of the flame retardant component in the coating agent of the present invention is not limited, but is usually 5 to 25 Mass % To the extent, especially 7-20 Mass % It is preferable to do so, and among them, 10 to 18 Mass % This is the most preferable course of action.

[0045] Furthermore, the amount of flame retardant is preferably 15 to 400 parts by weight per 100 parts by weight of solids of the water-based polyester resin, more preferably 20 to 250 parts by weight, and most preferably 30 to 150 parts by weight.

[0046] (3) Thickening agents In the present invention, the thickening component plays a role in controlling the temporal stability of the coating agent of the present invention, the coating properties on the fabric, etc. (function as a rheology control agent).

[0047] The type of thickening agent is not particularly limited, and thickening agents contained in acrylic thickeners (such as polyacrylic acid-based alkaline thickeners), association-type thickeners, polysaccharide-based thickeners, etc., can be suitably used. Known or commercially available thickeners or thickening agents can also be used.

[0048] By adding thickening agents, the viscosity can be adjusted to suit the application of the coating equipment used. For example, when coating by knife coating, maintaining a viscosity (at 20°C) of approximately 10,000 to 100,000 mPa·s, preferably 10,000 to 80,000 mPa·s, and more preferably 15,000 to 50,000 mPa·s, results in a BC agent with excellent long-term stability and excellent coating suitability for the material. Furthermore, by performing rheology control and adjusting the PVI value to 0.15 to 0.30, preferably 0.18 to 0.25, more stable coating becomes possible. Also, for example, when performing kiss roll processing or gravure roll processing, the viscosity should be adjusted to approximately 1,000 to 10,000 mPa·s.

[0049] (4) Aqueous solvents As the aqueous solvent, a) water alone or b) a mixture containing water and a water-soluble organic solvent can be used.

[0050] Examples of water-soluble organic solvents include monohydric alcohols such as ethanol, methanol, isopropyl alcohol, and butanol; polyhydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, 1,8-propanediol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 2,3-butylene glycol, neopentyl glycol, hexylene glycol, thiodiglycol, glycerin, trimethylolethane, trimethylolpropane, and diglycerin; and glycol ethers such as ethylene glycol monoethyl ether (ethyl cellosolve), ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether (ethyl carbitol), and diethylene glycol monobutyl ether. These can be used individually or in combination of two or more.

[0051] When using a mixture of water and a water-soluble organic solvent, the mixing ratio of the two is usually sufficient to be around 1:0.02-0.25 by weight, but it is not limited to this.

[0052] (5) Other additives The coating agent of the present invention may contain other additives as long as they do not interfere with the effects of the present invention. Examples include dispersants, liquid flame retardants, texture modifiers, preservatives, pigments, defoamers, antioxidants, lightfasteners, antiviral agents, adsorbents, deodorizers, fragrances, antibacterial agents, fungicides, antiviral agents, insecticides, antistatic agents, weather resistance enhancers, heat resistance enhancers, crosslinking agents, polymer compounds, etc. In addition, a small amount (total solid content of approximately 5%) may be added to fine-tune the final physical properties. Mass % Other resin components (such as acrylic resin or urethane resin) may be blended within the limits specified below.

[0053] As for the dispersant, nonionic or anionic dispersants can be suitably used as low-molecular-weight compounds.

[0054] Examples of nonionic dispersants include polyalkylene glycol, polyoxyalkylene naphthyl ether, polyoxyalkylene (mono-penta)styrylphenyl ether, polyoxyalkylene cumyl ether, and polyoxyalkylene acetylene glycol ether.

[0055] Examples of anionic dispersants include sulfate ester salts of nonionic dispersants and sodium dioctyl sulfosuccinate.

[0056] Furthermore, as dispersants, polymer compounds such as copolymers obtained by copolymerizing hydrophilic monomers such as acrylic acid, methacrylic acid, and maleic acid with hydrophobic monomers such as styrene, vinyl acetate, alkyl acrylate, alkyl methacrylate, and acrylonitrile, or salts thereof, can be suitably used.

[0057] Commonly used preservatives include benzimidazole, isothiazolone, triazine, zinc pyrithione, and bronopol.

[0058] Commonly used pigments include, for example, carbon black, titanium dioxide, and zinc oxide.

[0059] As for defoaming agents, silicone-based and fluorine-based defoaming agents are preferable because they can achieve the desired effect with only a small amount of addition, thus not impairing the effects of the present invention.

[0060] Examples of crosslinking agents include blocked isocyanates. This makes it possible to further improve heat resistance.

[0061] B. Properties of the coating agent of the present invention The coating agent of the present invention is usually in liquid form, but it can also take the form of an aqueous dispersion in which particles of an aqueous polyester resin are dispersed in an aqueous solvent.

[0062] In this case, the viscosity (at 20°C), as explained above, can usually be set appropriately within a range of approximately 1,000 to 100,000 mPa·s, depending on the application of the coating equipment, the type of fibrous material, etc.

[0063] 2. Method for producing the coating agent of the present invention The coating agent of the present invention can be prepared by uniformly mixing the above-mentioned components. Therefore, the order in which the components are added is not particularly limited. Furthermore, the mixing can be carried out using known or commercially available equipment such as a mixer or kneader.

[0064] In particular, the present invention allows for the preparation of the coating agent by a method comprising (1) preparing a mixed solution containing an aqueous solvent, an aqueous polyester resin, and a flame retardant component, and (2) adding a thickening component to the mixed solution.

[0065] The above mixture is usually a state in which a water-based polyester resin and flame retardant components are dispersed in an aqueous solvent, but the present invention also includes cases in which a portion of them are dissolved. In addition, other additives may be dissolved in the aqueous solvent or dispersed without dissolving.

[0066] In this case, as mentioned above, it is desirable to use a powdered flame retardant component. By using a powdered flame retardant component, staining and dye bleeding can be more effectively suppressed, resulting in the provision of a product with a better appearance.

[0067] 3. Use of the coating agent of the present invention The coating agent of the present invention is used to make fibrous materials flame-retardant. That is, the method is not particularly limited as long as the surface of the fibers constituting the fibrous material is covered with the coating agent of the present invention. Accordingly, the method of use can be the same as, for example, known or commercially available flame-retardant coating agents.

[0068] The form of the fibrous material is not particularly limited, and it can be applied not only to fibrous materials that require fray prevention (e.g., woven fabrics, knitted fabrics, nonwoven fabrics, etc.) but also to materials that do not require fray prevention, such as synthetic leather and artificial leather.

[0069] The present invention is applicable to any of the fibers that make up fibrous materials, including synthetic fibers such as polyester fibers, polyamide fibers, polyurethane fibers, and polyacrylic fibers, as well as natural fibers such as rayon, cotton, and linen, and blends thereof. In particular, if the fibrous material contains highly recyclable polyester fibers, it can be recycled together with the aqueous polyester resin of the present invention's coating agent, making it possible to provide products that are even more suitable for the Sustainable Development Goals (SDGs).

[0070] The coating agent of the present invention can be used, in particular, to form a back coat layer on the surface of a sheet-like fibrous material. That is, the coating agent of the present invention can be suitably used as a back coat agent.

[0071] For example, as shown in Figure 1, a back coat layer 12 can be suitably formed by applying the coating agent of the present invention to the back surface of a sheet-like fibrous material fabric 11. This prevents fraying of the threads in the fabric 11 and also provides the fabric 11 with high flame retardancy.

[0072] The coating method is not particularly limited and can be carried out by known coating methods such as knife coating, gravure roll coating, kiss roll coating, and calender coating. After coating, drying steps may be carried out as needed.

[0073] Figure 1 shows the fabric as consisting of two layers, a fabric 11 and a back coat layer 12. However, the coating agent of the present invention may be impregnated into the fabric 11, and a composite layer (not shown) containing the coating agent of the present invention may be formed between the fabric and the back coat layer. In other words, the coating agent of the present invention may penetrate to a certain depth from the surface of the fabric 11 on the back coat layer side and solidify to form a composite layer, resulting in a layer configuration of "back coat layer / composite layer / fabric". In this case, the degree to which the coating agent of the present invention impregnates the fabric (i.e., the thickness of the composite layer) can be appropriately adjusted by adjusting the viscosity of the coating agent of the present invention according to, for example, the type of fabric, weight, etc.

[0074] In this way, it is possible to provide a flame-retardant product 10 by using the coating agent of the present invention. Such a flame-retardant product 10 is also included in the present invention. In Figure 1, the back coat layer 12 is formed only on one side (back side) of the sheet-like fibrous material, but the back coat layer may be formed on both sides.

[0075] Examples of flame-retardant products include seats for automobiles, ships, aircraft, and trains, as well as interior furnishings such as wallpaper, carpets, and curtains, clothing such as work clothes, and various industrial materials. [Examples]

[0076] Examples and comparative examples are shown below to more specifically describe the features of the present invention. However, the scope of the present invention is not limited to these examples. In these examples, "%" means Mass % It means "...".

[0077] 1. Raw materials The following materials were used as raw materials for the flame-retardant coating agent.

[0078] (1) Resin components • "CY-190" (manufactured by Marubishi Yuka Kogyo Co., Ltd., water-based polyester resin, solids content 25%, Tg: 20℃) • "Vaironal MD-1930" (manufactured by Toyobo Co., Ltd., water-based polyester resin, solids content 30%, Tg: -10℃) (hereinafter abbreviated as "MD-1930") • "Pluscoat Z-3310" (manufactured by Go-O Chemical Co., Ltd., water-based polyester resin, solids content 25%, Tg: -20℃) (hereinafter abbreviated as "Z-3310") • "Pluscoat Z-592" (manufactured by Go-O Chemical Co., Ltd., water-based polyester resin, solids content 25%, Tg: 40℃) (hereinafter abbreviated as "Z-592") • "Pluscoat RZ-105" (manufactured by Go-O Chemical Co., Ltd., water-based polyester resin, solids content 25%, Tg: 52℃) (hereinafter abbreviated as "RZ-105") • "CY-255" (manufactured by Marubishi Yuka Kogyo Co., Ltd., water-based acrylic resin, solids content 50%, Tg: -40℃) • "CY-234" (manufactured by Marubishi Yuka Kogyo Co., Ltd., water-based urethane resin, solids content 40%, Tg: -60℃)

[0079] (2) Flame retardant components • Compound (1) was synthesized by a known manufacturing method. • Compound (2) was synthesized by a known manufacturing method. • Compound (3) was synthesized by a known manufacturing method. • Melamine cyanurate (manufactured by Shandong Shi'an Chemical Co., Ltd.) (hereinafter abbreviated as "MCA")

[0080] (3) Thickening agents • "CY-260" (manufactured by Marubishi Oil & Chemical Industry Co., Ltd., acrylic thickener, solids content 28%)

[0081] (4) Dispersants and defoaming agents • "Blaunon DSP-12.5" (manufactured by Aoki Oil & Fat Industry Co., Ltd., a 12.5 molar ethylene oxide adduct of distyrenated phenol) (hereinafter abbreviated as "Blau DSP") • "SN Dispersant 5027" (manufactured by Sunopco Corporation, special polycarboxylate ammonium salt) (hereinafter abbreviated as "SN Dispersant") • "FS Antifoam 1266" (manufactured by Toray Dow Corning, a silicone-based defoaming agent) (hereinafter abbreviated as "FS Anti")

[0082] 2. Examples and Comparative Examples [Example 1] Ion-exchanged water (29.3 Parts by mass ) vs. Blau DSP (0.1 parts by weight), SN Dis (0.7 Parts by mass ) and FS Anti (0.2 parts by weight) were added and stirred using a stirrer until homogeneous. While continuing to stir, CY-190 (48.0 Parts by mass ), Compound (2) (18.0 Parts by mass ) was gradually added, and stirred for another 20 minutes after addition. Then, 25% ammonia water (abbreviated as "25% ammonia water" in the table) (0.6 Parts by mass ) and CY-260 (3.0 Parts by mass The mixture was thickened by adding the following ingredients and stirring. In this way, the flame retardant coating agent (BC agent) was prepared.

[0083] [Examples 2-13 and Comparative Examples 1-6] Flame retardant coating agents (BC agents) were prepared by performing the same procedure as in Example 1, except that the compositions of each component were as shown in Tables 1 to 5.

[0084] [Test Example 1] Samples were prepared by applying the flame-retardant coatings obtained in each example and comparative example to fibrous materials, and then evaluated. These results are shown in Tables 1-5. The flame-retardant coatings obtained in each example and comparative example had a pH of 8.0 to 9.0, a viscosity of 20,000 to 26,000 mPa·s (BM type viscometer, No. 4 × 6 rpm, 20℃), and a PVI value in the range of 0.18 to 0.20 (60 / 6 rpm).

[0085] (1) Preparation of evaluation samples The BC agent prepared in each example and comparative example was applied to one side of fabric 1 and fabric 2 shown below using a doctor's knife. Then, it was pre-dried at 80°C and cured at 150°C for 1 minute. Next, it was acclimatized at 20°C × 50% RH for 24 hours or more. Evaluation samples were prepared in this manner. Fabric 1: Weight 250g / m 2Polyester fabric for car seats (color: beige) Fabric 2: Weight 205g / m 2 Amunzen polyester fabric (color: white) Fabric 2 was subjected to a special processing method: it was pre-soaked in a 0.2% silicone-based texture improver ("Poron MF-29," manufactured by Shin-Etsu Chemical Co., Ltd.) as an active ingredient, followed by drying.

[0086] (2) Evaluation of flame retardancy The above sample (coated fabric) was cut to a size of 35cm x 20cm and used as a sample for flame retardancy testing. The flame retardancy test was conducted in accordance with the "FMVSS-302 method," which is the safety standard for automotive interior materials. Normally, this test is performed with n=10, but this time it was performed with n=20. The evaluation criteria are as follows: • Test specimens that do not ignite or extinguish before mark A: "Non-flammable" • Self-extinguishing material with a burning distance of 51 mm or less (and within 60 seconds): "Flame-retardant" • Burning rate of 102 mm / min or less: "Slow-burning" • Burning speed exceeding 102 mm / min: "Easily flammable" In the table, the number of times each evaluation was performed is listed in the order of non-flammable / flame-retardant / flame-slow / flame-easy. Fabric samples that passed were those that passed as non-flammable to flame-slow, and those that received a flame-easy rating even once out of 20 tests were marked as "failed".

[0087] (3) Evaluation of texture The above sample (coated fabric) was cut into pieces measuring 2 cm x 15 cm, and its stiffness was measured using the cantilever method (JIS L1096, 8.21.1A method), and its texture was quantified. For evaluation, a cantilever tester with a 45-degree slope was used. The sample was held down with a metal plate and moved along the horizontal surface of the tester, pushing it onto the slope. The distance traveled (cm) when the test piece sagged and one end touched the slope was measured. The more flexible the sample, the shorter the distance it traveled to touch the slope. The evaluation criteria are shown below. "〇"... Distance traveled is less than 10cm "×" ... Movement distance of 10cm or more

[0088] (4) Evaluation of heat resistance (change in texture) A heat resistance test was conducted using the remaining fabric from the material that had undergone the flame retardancy evaluation described above. The remaining fabric was treated in a constant temperature environment test chamber at 110°C for 400 hours, and the flame retardancy and texture were checked for any changes. This evaluation was performed using fabric 1. Flame retardancy was evaluated using the FMVSS-302 method according to the method described in "(2) Evaluation of Flame Retardancy" above. Similarly, we checked the texture and feel before and after the test to see if there was any change in the material's appearance. "〇" ... No change in texture was observed after the test. (Change in the aforementioned travel distance was 10% or less) "×" ...The texture has changed after the test. (The change in the aforementioned travel distance exceeds 10%)

[0089] [Table 1]

[0090] [Table 2]

[0091] [Table 3]

[0092] [Table 4]

[0093] [Table 5]

[0094] As is clear from the results in Tables 1-5, BC agents using polyester resins consistently achieved non-combustible and flame-retardant results even with reduced coating amounts and lower flame retardant ratios, demonstrating stable flame retardancy. Furthermore, no significant changes were observed in flame retardancy or texture after the heat resistance test.

[0095] In contrast, when acrylic resin was used, the flame retardancy was significantly inferior under the same conditions. Furthermore, when urethane resin was used, the flame retardancy was slightly better than that of acrylic resin, but it was not as good as that of polyester resin, and changes in appearance or texture were observed in the heat resistance test.

Claims

1. A flame-retardant coating agent for making fibrous materials flame-retardant, (1) A water-based polyester resin having a glass transition temperature (Tg) of -30 to 30°C. (2) At least one flame retardant component consisting of phosphate ester compounds, phosphoramidate compounds, phosphonic acid ester compounds, organic phosphinates, polyphosphate melamine compounds, and phosphazene compounds. (3) Thickening agents and (4) Aqueous solvents A polyester-based flame-retardant coating agent characterized by containing the following:

2. The polyester-based flame-retardant coating agent according to claim 1, comprising, by solid content: (1) a water-based polyester resin having a glass transition temperature (Tg) of -30 to 30°C: 5 to 30% by weight, (2) a flame retardant component: 5 to 25% by weight, and (3) a thickening component: 0.1 to 3.0% by weight.

3. The polyester-based flame-retardant coating agent according to claim 1, wherein the flame-retardant component is 15 to 400 parts by weight per 100 parts by weight of the water-based polyester resin.

4. The polyester-based flame retardant coating agent according to claim 1, wherein the viscosity (at 20°C) is 1,000 to 100,000 mPa·s.

5. A polyester-based flame-retardant coating agent according to any one of claims 1 to 4, used for forming a back coat layer on the surface of a sheet-like fibrous material.

6. A flame-retardant product comprising a back coat layer formed on the surface of a sheet-like fibrous material using a polyester-based flame-retardant coating agent according to any one of claims 1 to 4.

7. The layer configuration including the back coat layer is (a) Composed of two layers: the sheet-like fibrous material and the back coat layer, (b) In the above (a), a composite layer containing the flame retardant coating agent is further formed between the sheet-like fibrous material and the back coat layer. The flame-retardant product according to claim 6.

8. A car seat, the flame-retardant product according to claim 6.

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