Flame retardant components and flame retardant processing agents

Abstract

To provide a flame-retardant processing agent that does not contain halogen-based compound or phosphorus-based compound, and contains flame-retardant component.SOLUTION: A flame-retardant component is (A) polyvalent carboxylic acid or (B) polyhydric alcohol. In the flame-retardant component, Tc1: [temperature at which state change associated with heat absorption occurs] of the (A) polyvalent carboxylic acid and the(B) polyhydric alcohol satisfies Tm1≤Tc1≤Td1 which is a relationship among itself, Tm1: [melting point temperature of (S) objective material], and Td1: [thermal decomposition temperature of(S) objective material], with Tm1: melting point temperature of(S) objective material, Tc1: temperature at which state change associated with heat absorption occurs, of (A) polyvalent carboxylic acid or (B) polyhydric alcohol, and Td1: thermal decomposition temperature of (S) objective material. Furthermore, the (A) polyvalent carboxylic acid and the (B) polyhydric alcohol satisfy n×MFRs1<MFRp1 which is a relationship of MFR values measured at a temperature higher than Tm1: [melting point temperature of (S) objective material], with MFRs1: MFR value of (S) objective material, MFRp1: MFR value of objective material including (P) flame-retardant component, and n: value of 3 or greater.

Description

[Technical field]

[0001] The present invention relates to a flame retardant component and a flame retardant processing agent, which are selected from at least one polyvalent carboxylic acid, and which have Tc1 (temperature at which an endothermic state change occurs) between Tm1 (the melting point temperature of the target material (S)) and Td1 (the thermal decomposition temperature of the target material (S)). [Background technology]

[0002] Conventionally, halogen-based flame retardant processing agents containing halogen compounds such as bromine atoms and chlorine atoms have been used as flame retardant components that impart flame retardant properties to (S) target materials, such as polyester resins (see, for example, Patent Document 1). However, halogen-based flame retardants have problems such as generating harmful halogen gases when heated, which have harmful effects on the environment and human body.

[0003] Furthermore, as an alternative to halogen-based flame retardants, phosphorus-based flame retardants containing phosphorus as a flame retardant component have been used (see, for example, Patent Document 2). However, phosphorus-based flame retardants (S) have problems such as significantly reducing the mechanical properties of the target material and placing a large burden on the environment due to the discharged liquid.

[0004] Furthermore, flame retardants containing hydrated metal compounds are used (see, for example, Patent Document 3). However, flame retardants containing hydrated metal compounds (S) have problems such as significantly reducing the mechanical properties of the target material and imposing limitations on processing methods. [Prior art documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 57-137377 [Patent Document 2] JP 2019-025673 A [Patent Document 3] WO2013 / 154200 publication Summary of the Invention [Problem to be solved by the invention]

[0006] It is known that combustion occurs based on the combustion cycle of thermoplastic resins. What is the combustion cycle? A) Combustion of flammable gas: flammable gas, oxygen supplement B) Radiant heat generated by combustion: Temperature rise on the material surface C) Heat conduction into the material: Temperature rise of the material D) Thermal decomposition of materials: Generation of flammable gases E) Diffusion of flame retardant gas to the material surface: Diffusion in the material F) Diffusion of flammable gas into the combustion field: Diffusion in the gas phase A) → B) → C) → D) → E) → F) → A) Repeated By The combustion continues. (Reference: Japan Flame Retardant Association, "What is a flame retardant?", [online], Japan Flame Retardant Association, [Retrieved June 18, 2021], Internet <URL:https: / / www.frcj.jp / flame-retardants / > )

[0007] To date, halogen compounds and phosphorus compounds have been used as flame retardant components. and The flame retardant processing agents containing hydrated metal flame retardants have been used because the flame retardant components are halogen compounds, phosphorus compounds, etc. and This is because the flame retardant agent containing a hydrated metal compound has high flame retardant performance.

[0008] Flame retardant agents that contain halogenated compounds as flame retardant components are A) Combustion of flammable gas: Supply of flammable gas and oxygen By preventing this, high flame retardant performance is achieved.

[0009] Flame retardant processing agents containing phosphorus compounds as flame retardant components and hydrated metal flame retardants containing hydrated metals are C) Heat conduction into the material: Temperature rise of the material It has flame retardant properties by preventing flames from escaping.

[0010] However, as mentioned above, flame retardant agents that contain halogen-based compounds, phosphorus-based compounds, and hydrated metal compounds as flame retardant components have limitations on their use, such as in some situations where they cannot be used due to environmental impact. In response to this issue, the present inventors have focused on the combustion cycle of the (S) target material and have come to a demand for a flame retardant agent that contains a new flame retardant component that does not contain halogen-based compounds, phosphorus-based compounds, or hydrated metal compounds. [Means for solving the problem]

[0011] The present inventors have taken inspiration from the prior art approaches to combustion cycles and have identified the following issues related to the temperature rise of organic materials in a combustion cycle: B) Radiant heat generated by combustion: Temperature rise on the material surface C) Heat conduction into the material: Temperature rise of the material We have developed flame-retardant components that can prevent this. Effect of the Invention

[0012] According to the present invention, Polycarboxylic acid satisfying claim 1 Less and Another flame retardant component is added to the 2 It is possible to impart flame retardancy to the thermoplastic resins of polyester resins or polyamide resins, which are the (S) target materials described in 2010. The (S) target materials to which flame retardancy has been imparted have made it possible to reduce harmful substances generated when heated, reduce the environmental impact caused by their use, and expand the environments in which they can be used. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] The present invention will be described in detail below. In the present specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit, respectively.

[0014] <Flame retardant components> The polyvalent carboxylic acid described in claim 1 is a flame retardant component. The above flame retardant components can be used alone or in combination of two or more.

[0015] <Polycarboxylic acid> The polyvalent carboxylic acid (A) according to claim 1 is preferably a dicarboxylic acid containing two carboxyl groups in one molecule, and is represented by the structural formula (1): R-(C(=O)-(OH))x (1) It is a flame retardant component expressed by the formula: Examples of the substituent of the R group include an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, and an alkoxyl group. An aryl group is preferable. An alkyl group and a phenyl group are more preferable. These may contain a hydroxyl group.

[0016] Specific examples of polyvalent carboxylic acids include isatoic acid, fumaric acid, azelaic acid, terephthalic acid, dipicolinic acid, sebacic acid, anthraquinone-2,3-dicarboxylic acid, 1H-imidazole-4,5-dicarboxylic acid, norbornane-5-ene-2,3-dicarboxylic acid, 2,2'-bipyridine-6,6'-dicarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. Among the flame retardant components listed above, azelaic acid and terephthalic acid have been confirmed to be particularly effective.

[0017] <(S)Target material> Claim 2 The target material of (S) described in is polyester. system The resin is a resin selected from the group consisting of thermoplastic resins. The above thermoplastic resins may be used alone or in combination.

[0018] Examples of polyester-based resins include polyethylene terephthalate, polyalkylene terephthalate (for example, polyethylene terephthalate in which part of the ethylene glycol has been replaced with 1,4-cyclohexanedimethanol, diethylene glycol, or the like, known as PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, and polyethylene naphthalate-isophthalate copolymers.

[0019] <Characteristics of flame retardant components> Claim 3 The polyvalent carboxylic acid according to claim 1 and the polyvalent carboxylic acid according to claim 2 The following relationship must be established between the (S) target materials listed in the above. Tm1 ≦ Tc1 ≦ Td1 Tm1: The method according to claim 2 (S) Melting point temperature of the material (℃) Tc1: A flame-retardant component that renders the polyester resin according to claim 1 flame-retardant. Polycarboxylic acids , the temperature at which an endothermic change of state occurs (℃) Td1: The method according to claim 2 (S) Thermal decomposition temperature of the target material (℃)

[0020] As a specific example, the following claims 2 When the (S) target material described in is polyethylene terephthalate, Tm1: [melting point temperature of (S) target material] and Td1: [thermal decomposition temperature of (S) target material] are generally, Tm1: [(S) melting point temperature of target material] = 2 6 0℃ Td1: [(S) Thermal decomposition temperature of the target material] = 350℃ It is. Therefore, the Tc1 of the flame retardant polycarboxylic acid (the temperature at which a change in state occurs accompanied by endothermic heat) is as follows: of It needs to be at a temperature that meets 2 6 0℃≦Tc1≦350℃

[0021] In claim 4, the polyvalent carboxylic acid according to claim 1 is required to have an effect of reducing the viscosity of the target material (S) according to claim 2 when melted.

[0022] Specifically, the melt mass flow rate (MFR), which represents the flow of molten thermoplastic resin, is measured according to JIS K 7210-1 under the temperature condition of Tm1 [melting point temperature of the target material (S)], and the following relationship must be established between MFRs1: [MFR value of the target material (S)] and MFRp1: [MFR value of the target material containing a flame retardant (P)]. n × MFRs1 < MFRp1 MFRs1: (S) MFR value of the target material MFRp1: (P) MFR value of the target material containing flame retardant n=3 In the above formula, n is a value of 3 or more, and more preferably a value of 4 or more.

[0023] <Flame retardant processing agent> Claim 5 The flame retardant described in claim 1, 3 and 4 The flame retardant described in Growth At least one type Includes The (S) processing agent according to claim 2 is a processing agent that imparts flame retardant properties to the target material.

[0024] According to an embodiment of the present invention, in addition to the flame retardant component, the flame retardant processing agent can be mixed with any other components than the above components within a range that does not impair the effects of the present invention. Such components are not particularly limited, but include, for example, water, aqueous solvents, organic solvents, pH adjusters, surfactants (anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants, etc.), preservatives, defoamers, and discoloration inhibitors. The content of these components is not particularly limited, and can be appropriately determined within a range that does not cause problems in production or storage, taking into account performance and processing stability.

[0025] The aqueous solvent is preferably a hydrophilic solvent that is miscible with water. Examples include methanol, ethanol, 2-propanol, ethylene glycol, propylene glycol, diethylene glycol, hexylene glycol, glycerin, butyl glycol, butyl diglycol, 3-methoxy-3-methyl-1-butanol, N-methylpyrrolidone, dimethylformamide, and dimethylsulfoxide.

[0026] The pH adjuster may be any suitable alkali or acid. Examples of the alkali include hydroxides such as potassium hydroxide and sodium hydroxide, carbonates such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and sodium sesquicarbonate, borates such as potassium borate and sodium borate, hydrogen sulfates such as potassium hydrogen sulfate and sodium hydrogen sulfate, inorganic alkali metal salts such as potassium silicate, potassium metasilicate, sodium silicate, and sodium metasilicate, organic alkali metal salts such as sodium formate, sodium acetate, and sodium oxalate, organic amines such as monoethanolamine, diethanolamine, triethanolamine, and triethylamine, and ammonia. Preferred are organic amines and ammonia. Examples of the acid include organic acids such as acetic acid, lactic acid, propionic acid, maleic acid, formic acid, oxalic acid, methanesulfonic acid, and toluenesulfonic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. These pH adjusters may be used alone or in combination of two or more.

[0027] The flame retardant according to the embodiment of the present invention may further contain a finishing agent as an option, which is not particularly limited, but may include, for example, a yarn breakage prevention agent, a hydrophilizing agent that imparts water absorption, moisture absorption, antistatic properties, etc. (polyethylene glycol derivatives, various hydrophilic polymer-containing treatment agents, etc.), a water / oil repellent (higher aliphatic, silicone, fluorine-based, etc.), a mildewproofing agent (phenol-based, etc.), a fabric softener (silicone-based, anionic, cationic, etc.), etc.

[0028] <Application> The flame retardant component or flame retardant processing agent in the present invention is used for the purpose of obtaining a target material containing a flame retardant component (P) having flame retardant properties by adhering to, penetrating into, or kneading into a target material (S).

[0029] In the above applications, one or more flame retardant components not related to the present invention may be used in combination.

[0030] The amount of the flame retardant component added in the above applications is preferably 1 part by mass or more, and more preferably 1 part by mass or more and 30 parts by mass or less, per 100 parts by mass of the target material (S).

[0031] <(S) Adhesion and penetration of flame retardant components into target materials> (S) To the target material, Polycarboxylic Acid By attaching or penetrating one or more flame retardant components selected from the above into the target material (S), a target material containing a flame retardant component (P) having flame retardant properties can be obtained.

[0032] <Fire retardant attachment and penetration method> The method for attaching or penetrating the flame retardant component of the present invention into the target material (S) is not particularly limited, and specifically, a padding method using a flame retardant, an exhaustion method, a spray method, etc. can be used.

[0033] <(S) Form of target material> (S) The form of the target material is not particularly limited. Specific examples include textile materials, automobile parts, decorative plates, and other molded products. The form is determined according to the intended use.

[0034] Among the forms of the above-mentioned (S) target material, the form that can best impart flame retardancy is a fiber material, and examples of such forms include woven fabrics such as plain weave, satin weave, and twill weave, tricots such as velour, double raschels such as high-bye raised fabrics, circular knits such as sinker pile, knitted fabrics such as jersey, and nonwoven fabrics such as needle punch, stitch pound, and spun lace. Among these forms, woven fabrics such as plain weave, satin weave, and twill weave are preferably used. The thickness and basis weight of the fiber product are not particularly limited and can be appropriately selected depending on the material.

[0035] (S) Various known treatments can be performed before and after imparting flame retardancy to the target material using a flame retardant component, such as textile printing, dyeing, heat setting, and various finishing processes (softening, water repellency, gloss, etc.).

[0036] <(S) Incorporating flame-retardant components into target materials> By kneading one or more flame retardant components selected from polyvalent carboxylic acids into the target material (S), a target material containing a flame retardant component (P) having flame retardant properties can be obtained.

[0037] <Other ingredients> (P) The target material containing the flame retardant component may contain fillers and additives, etc., within the scope of the present invention. Examples of fillers include silica, talc, clay, mica, titanium oxide, glass beads, glass flakes, calcium carbonate, and carbonated water. R Um, calcium sulfate, barium sulfate, Kay Examples of the additives include calcium borate, potassium titanate, aluminum borate, magnesium borate, etc. Examples of the additives include plasticizers, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, conductivity imparting agents, release agents, lubricants, dyes, pigments, etc. One or more of these other components may be contained.

[0038] <(S) Method of incorporating flame retardant components into target materials> (S) Polyvalent carboxylic acids and other ingredients are mixed into the target material. 、 The melt-kneading is carried out by melt-kneading. The method of melt-kneading is not particularly limited, and any known melt-kneading method can be used. Specific examples include methods of melt-kneading using kneading devices such as a Banbury mixer, a roll, a plastograph, a single-screw extruder, a twin-screw extruder, and a kneader.

[0039] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples in any way. EXAMPLES

[0040] <Preparation of flame retardant> Working Example 1, 2 and 3 Comparative Examples 2, 3 and 4 Flame retardant used in 1, 2 and 3 The comparative processing agent was prepared as follows. <Flame retardant 1> 3.5 g of an aqueous ammonia solution (25% concentration) and 2 g of high-purity terephthalic acid (manufactured by Mitsui Chemicals, Inc.) were diluted with water to obtain 100 g of flame retardant 1 (pH 9.0). <Flame retardant 2> 7.5 g of an aqueous ammonia solution (25% concentration) and 5 g of fumaric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were diluted with water to obtain 100 g of flame retardant 2 (pH 8.6). <Flame retardant 3> 5 g of an aqueous ammonia solution (25% concentration) and 5 g of azelaic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were diluted with water to obtain 100 g of flame retardant 3 (pH 9.1). <Comparative Processing Agent 1> Dimethyl terephthalate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.): 4 g was diluted with ethyl acetate to obtain 100 g of a comparative processing agent. <Comparative Processing Agent 2> 12 g of an aqueous ammonia solution (25% concentration) and 10 g of maleic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were diluted with water to obtain 100 g of a comparative processing agent (pH 7.6). <Comparative Processing Agent 3> 12.5 g of an aqueous ammonia solution (25% concentration) and 10 g of phthalic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were diluted with water to obtain 100 g of a comparative processing agent (pH 8.8). EXAMPLES

[0041] Using flame retardant 1, polyester pongee (thread thickness warp x weft: 75D x 75D, thread count warp x weft: 90 threads / inch x 80 threads / inch, weight: 58g / m 2) was subjected to a padding treatment at a drawing rate of 65%. Next, the padded polyester pongee was dried at 80 to 100°C for 2 minutes using a heat cylinder to produce a flame-retardant fiber material to which a flame-retardant component was attached. The amount of the attached flame-retardant component was 1.5 parts by mass per 100 parts by mass of the polyester pongee. EXAMPLES

[0042] A flame-retardant fiber material having a flame-retardant component attached thereto was produced in the same manner as in Example 1, except that flame retardant processing agent 2 was used. EXAMPLES

[0043] A flame-retardant fiber material having a flame-retardant component attached thereto was produced in the same manner as in Example 1, except that flame retardant processing agent 3 was used. EXAMPLES

[0044] Polyethylene terephthalate (manufactured by Mitsubishi Chemical Corporation) and high-purity terephthalic acid (manufactured by Mitsui Chemicals, Inc.), a flame-retardant component, were placed in a twin-screw extruder as shown in Table 3. 200~230 °C temperature The mixture was mixed at 100° C., discharged as a strand, and pelletized. 200~230 The flame-retardant material was produced by molding at a temperature of 100°C.

[0045] <Comparative Example 1> A polyester pongee was prepared before being treated with a flame retardant.

[0046] <Comparative Example 2> Comparative processing agent 1 of A comparative fiber material having a comparative component attached thereto was produced in the same manner as in Example 1, except that a comparative component was used.

[0047] <Comparative Example 3> Comparative processing agent 2 of A comparative fiber material having a comparative component attached thereto was produced in the same manner as in Example 1, except that a comparative component was used.

[0048] <Comparative Example 4> Comparative processing agent 3 of A comparative fiber material having a comparative component attached thereto was produced in the same manner as in Example 1, except that a comparative component was used.

[0049] <Comparative Example 5> No high-purity terephthalic acid was used. thing Other than that, the same procedure as in Example 4 of A comparative material was prepared.

[0050] <Flame retardancy evaluation> The flame retardancy of Examples 1, 2, and 3 and Comparative Examples 1, 2, 3, and 4 was evaluated according to the following criteria by measuring the number of times the fiber material was exposed to flame in accordance with JISL-1091 D method (45° coil method). A rating of A was considered to be acceptable, and a rating of B was considered to be unacceptable. [Table 1]

[0051] The flame retardancy of Example 4 or Comparative Example 5 was tested according to the UL-94 V method (vertical flame test) product safety standard established by Underwriters Laboratories Inc. and evaluated according to the following criteria. V-0, V-1, and V-2 were considered to be pass, Non-conformance The cases were deemed to be failures. [Table 2] TIFF0007641465000003.tif149148

[0052] Referring to Table 3, it was found that the flame retardant components used in Examples 1 to 4 imparted flame retardant properties to the (S) target materials. [Table 3]

[0053] To confirm whether each component used in the examples and comparative examples is a flame retardant component of the present invention, Tm1: [(S) melting point temperature of the target material], Td1: [(S) thermal decomposition temperature of the target material], and Tc1: [temperature at which a state change accompanied by endotherm occurs] were compared, and the results are summarized in Table 4 below.

Table 4

[0054] Referring to Table 4, it was found that the flame retardant component used in the example of Claim 3 was satisfied and the comparative component used in the comparative example was not satisfied.

[0055] <MFR Measurement> As described in Table 5 below, each component was charged into a twin-screw extruder and mixed at a temperature of 200 to 230 ℃ and discharged as strands and pelletized. The obtained pellets were measured using a melt indexer (F-F01, manufactured by Toyo Seiki Seisakusho Co., Ltd.) in accordance with JIS K 7210-1 under the conditions of a load of 2.15 kgf and a temperature of 250 °C. The results are shown in Table 5 below.

Table 5

[0056] Referring to Table 5, it was found that the flame retardant component used in the example of Claim 4 was satisfied and the comparative component used in the comparative example was not satisfied.

Claims

1. A flame retardant component for imparting flame retardancy to a polyester resin, comprising at least one polycarboxylic acid selected from the group consisting of fumaric acid, azelaic acid, and terephthalic acid.

2. A flame-retardant target material (P) comprising the polyvalent carboxylic acid according to claim 1 in a target material (S) which is a polyester-based resin.

3. A flame-retardant target material (P) containing the polycarboxylic acid according to claim 2, which satisfies the following formula between the polycarboxylic acid according to claim 1 and the target material (S) according to claim 2. Tm1 ≦ Tc1 ≦ Td1 Tm1: melting point temperature of the target material (S) according to claim 2 Tc1: The temperature at which the polyvalent carboxylic acid according to claim 1 undergoes an endothermic state change. Td1: Thermal decomposition temperature of the target material (S) according to claim 2

4. A flame-retardant (P) target material comprising the polycarboxylic acid of claim 3, wherein the relationship between the melt mass-flow rate (MFR) value, which is a value representing the flow of a molten thermoplastic resin at a temperature higher than Tm1: [the melting point temperature of the (S) target material] of claim 3, satisfies the following formula: n × MFRs1 < MFRp1 MFRs1: (S) MFR value of the target material MFRp1: (P) MFR value of the flame-retardant target material n=3

5. A flame retardant processing agent for rendering the (S) target material described in claim 4 flame retardant, comprising a flame retardant component for rendering the polyester resin described in claim 1 flame retardant, which satisfies the formula of claim 3 and claim 4.

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