JP7438520B2 - Halogen-containing polymers, flame retardants for fibers containing the same, and flame-resistant fiber products - Google Patents

Description

The present invention relates to a novel halogen-containing polymer, a flame retardant containing the same, and a flame retardant fiber product.

In general, textile products, with the exception of some flame-retardant fibers such as glass fibers, have poor self-extinguishing properties and are easily combustible, and therefore are required to be made flame-retardant.

As a method for making textile products flame retardant, for example, a method is known in which textile products are brought into contact with a flame retardant agent during the manufacturing stage of the raw yarn or the post-processing stage of the fibers. As a flame retardant, compounds containing halogen or phosphorus are used as main ingredients for organic materials, and flame retardants or flame retardant aids such as aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, and antimony trioxide are used as main ingredients for inorganic materials. , dissolved, dispersed or emulsified in water or an aqueous medium containing an organic solvent.

In addition to being flame-retardant, flame-retardant textile products are also required to have the ability to maintain a desired flame-retardant effect even after repeated washing (washing durability). Among the above-mentioned general halogen- or phosphorus-containing compounds, if low molecular weight compounds are simply attached to the fiber surface, they will completely fall off from the fiber surface when washed. For this reason, there is a method of applying heat after adhesion to infiltrate the inside of the fiber, but there are few methods that can fix the adhesive to a degree that can be expected to improve washing durability.

Therefore, in order to fix the flame retardant, at the same time as the flame retardant adheres to the fibers, coating with synthetic resin such as glue to prevent the flame retardant from falling off has been carried out. The inherent characteristics of textile products are significantly impaired.

There is also a method in which a polymeric flame retardant such as brominated polystyrene, brominated epoxy oligomer/polymer, or brominated polycarbonate is attached to a textile product and then heated and fused. However, many of the above-mentioned polymeric flame retardants are given heat resistance by polymerization, and therefore the temperature at which the flame retardant is melted and fixed is too high, causing heat-sensitive textile products to deteriorate due to heat. There is also the problem of doing so.

When flame retardant is applied to textile products through post-processing, the flame retardant component adheres homogeneously to the fiber surface, and the flame retardant itself has adhesive properties to the fibers, making it possible to flame retardant products at relatively low temperatures. There is a need for a flame-retardant polymer material that can be melted and softened to penetrate and fix into fibers, giving it durability against washing. None are designed to be able to be prepared by

On the other hand, it is used in various fields such as paints, functional coatings, adhesives, and pressure-sensitive adhesives for textile products, regardless of the base material such as paper, wood, metal, glass, stone, or resin. There are macromonomer-based copolymers as materials that enable the design of functional polymers.

A macromonomer is defined as a high molecular weight monomer with a polymerizable functional group at the end [Glossary of Basic Terms in Polymer Science (Recommendations 1995)”, Pure Appl. Chem., 68, 2287-2311 (1996) http://www.iupac.org/reports/1996/6812jenkins/index.html Japanese translation “Glossary of basic terminology in polymer science”, Koichi Hatada, Kobunshi, 47, 696-714 (1998) ].By copolymerizing a macromonomer with another monomer, polymers with different physical properties can be easily incorporated into the molecular structure, so it is possible to prepare a polymer having a specific function.

In the field of flame-retardant resin compositions, flame-retardant polymer materials using a large number of macromonomers have been proposed.

For example, 1) A polystyrene system with improved processability and flame retardancy, including a graft polymer polymerized from a styrene-methyl methacrylate macromonomer, which is blended as a compatibilizer with a polystyrene resin and a polyvinyl chloride resin. Resin composition (Patent Document 1), 2) Flame-retardant polyester composition comprising a modified polyester copolymerized from a condensed macromonomer and having improved alkali resistance (Patent Document 2), 3) Vinyl chloride and a vinyl chloride resin composition copolymerized from an aromatic macromonomer, an aliphatic vinyl ester, and/or an alkyl (meth)acrylate ester, and has excellent flame retardancy, weather resistance, and solvent solubility resistance (Patent Document 3) A polyphenylene ether resin composition with improved processability and flame retardancy, which is obtained by copolymerizing a polyphenylene ether resin with a polystyrene macromonomer (Patent Document 4), is known.

In these flame-retardant resin compositions, in order to compensate for the disadvantageous physical properties of the resin base material itself, polymers with improved performance, namely copolymers polymerized from macromonomers, are incorporated as units. The purpose is to modify resin compositions.

For example, in order to add solvent solubility resistance to vinyl chloride resin, which has high flame retardancy and weather resistance, copolymerization is possible using vinyl chloride monomer (flame retardancy and weather resistance) and styrene macromonomer (solvent solubility resistance). It is sufficient to modify the vinyl chloride resin by synthesizing the polymer, and in order to impart high processability to the polyphenylene ether resin (flame retardant and heat resistant), it is necessary to modify the polyphenylene ether oligomer with a styrene macro. By modifying with a monomer (processability), it becomes possible to obtain a modified polyphenylene ether resin with improved processability.

However, both methods involve modifying the resin base material during polymerization to obtain a modified resin composition having flame retardancy. That is, by post-processing a flame retardant composition prepared from a polymer derived from a macromonomer that has a high degree of flame retardancy for non-flame retardant textile products, a flame retardant composition with excellent washing durability can be obtained. No method has yet been proposed for obtaining flame fiber products.

Japanese Patent Application Publication No. 60-92344 Japanese Unexamined Patent Publication No. 64-48822 Japanese Patent Application Publication No. 2-263810 Japanese Patent Application Publication No. 2010-126578

Therefore, the main object of the present invention is to provide a flame retardant for textiles that can effectively suppress or prevent the deterioration of flame retardant performance caused by washing.

As a result of intensive research to achieve the above object, the present inventors have discovered a polymer having a repeating unit of a halogen-containing macromonomer having a polymerizable unsaturated group at the end, or a polymer containing the macromonomer and a polymerizable unsaturated group. The present inventors have discovered that a halogen-containing polymer, which is a copolymer with a non-halogen monomer having the above, can achieve the above object, and have completed the present invention.

That is, the present invention relates to the following halogen-containing polymer, a flame retardant for textiles, and a flame retardant textile product containing the same.
1. General formula (I) below
[In formula (I), R ¹ is a hydrogen atom or a methyl group, and L is the following general formula (II) or general formula (III)
(However, in formula (III), R ² is a group represented by the following general formula (IV).
(However, in formula (IV), p satisfies 0≦p≦20, and q satisfies 1≦q≦20.)),
Y is the following general formula (V)
(However, in formula (V), Z is an ether group (-O-), a carbonyl group (-COO-) or an imino group (-NH-), R ³ is a methylene group or an ethylene group, and S is represents a sulfur atom),
M ^hal _n represents a halogen-containing oligomer consisting of n halogen-containing monomer (M ^hal ) units (where n satisfies 2≦n≦20). ]
A halogen-containing polymer comprising a repeating structure (A) having a halogen-containing macromonomer as a unit.
2. The halogen-containing monomer (M ^hal ) has the general formula (VI)
[In formula (VI), R ¹ is a hydrogen atom or a methyl group, R ⁴ is a hydrocarbon group which may have a substituent, and (R ⁴ -X _r ) means that R ⁴ is r It represents a group substituted with a halogen atom X, and the halogen atom X represents a chlorine atom, a bromine atom, or an iodine atom. m satisfies 0≦m≦20, and r satisfies 1≦r≦10. ] The halogen-containing polymer according to item 1 above.
3. A repeating structure (A) containing a halogen-containing macromonomer represented by the general formula (I) as a monomer unit, and a repeating structure containing a monomer unit that has a polymerizable unsaturated double bond and does not contain a halogen. The halogen-containing polymer according to item 1 above, which is a copolymer having structure (B).
4. The content of the repeating structure (A) consisting of halogen-containing monomer units is 10 to 100% in the total of 100% by weight of the repeating structure (A) consisting of halogen-containing monomer units and the repeating structure (B) consisting of halogen-free monomer units. The halogen-containing copolymer according to claim 3, which is % by weight.
5. The halogen-containing polymer according to item 1 above, which has a weight average molecular weight of 1,000 to 1,000,000.
6. A flame retardant for textiles comprising the halogen-containing polymer according to any one of items 1 to 5 above.
7. 7. The flame retardant for fibers according to item 6, which further contains an aqueous medium and is liquid in nature.
8. A flame retardant fiber product comprising fibers coated with the flame retardant for fibers according to item 6 or 7 above.

According to the present invention, it is possible to provide a flame retardant for textiles that can effectively suppress or prevent a decrease in flame retardant performance caused by washing. In particular, the flame retardant for textiles of the present invention can provide textile products with a high degree of flame retardancy and, at the same time, excellent washing durability (particularly water washing durability). As a result, good flame retardancy can be maintained for a relatively long period of time.

The flame retardant of the present invention allows non-flame retardant fiber products to be subjected to flame retardant treatment relatively easily through post-processing. In conventional techniques, even if it is possible to temporarily impart flame retardancy to textile products by post-processing them with a low-molecular flame retardant, the flame retardant falls off after washing, resulting in a decrease in flame retardant performance. In contrast, with the flame retardant for textiles of the present invention, it is possible to easily impart a high degree of flame retardancy to textile products, and the polymer itself has flame retardancy, adhesion, and flexibility. As a result, it is possible to obtain flame-retardant fiber products that have both high flame retardancy and washing durability.

1. Halogen-containing polymer The halogen-containing polymer of the present invention has the following general formula (I)
[In formula (I), R ¹ is a hydrogen atom or a methyl group, and L is the following general formula (II) or general formula (III)
(However, in formula (III), R ² is a group represented by the following general formula (IV).
(However, in formula (IV), p satisfies 0≦p≦20, and q satisfies 1≦q≦20.)),
Y is the following general formula (V)
(However, in formula (V), Z is an ether group (-O-), a carbonyl group (-COO-) or an imino group (-NH-), R ³ is a methylene group or an ethylene group, and S is represents a sulfur atom),
M ^hal _n represents a halogen-containing oligomer consisting of n halogen-containing monomer (M ^hal ) units (where n satisfies 2≦n≦20). ]
It is characterized by containing a repeating structure (A) having a halogen-containing macromonomer shown as a monomer unit.

In the present invention, the halogen-containing macromonomer of general formula (I) is expressed as (a-2), and the halogen-containing monomer M ^hal is expressed as (a-1).

Furthermore, in this specification, unless otherwise specified, acrylate and methacrylate are collectively referred to as "(meth)acrylate." Acrylic acid and methacrylic acid are collectively referred to as "(meth)acrylic acid." Acryloyl groups and methacryloyl groups are collectively referred to as "(meth)acryloyl groups."

The halogen-containing polymer of the present invention (polymer of the present invention) is produced by using, as an intermediate, a halogen-containing macromonomer (a-2) synthesized from a halogen-containing oligomer having the halogen-containing monomer (a-1) as a repeating unit. It is a polymer containing a repeating structure (A) derived from the above-described structure (A) as an essential component.

The polymer of the present invention may be a homopolymer consisting of a halogen-containing macromonomer (a-2), or has an unsaturated double bond that is polymerizable with the halogen-containing macromonomer (a-2), and It may also be a copolymer of a halogen-free monomer (b) and a halogen-containing macromonomer (a-2).

The polymer of the present invention is composed of a repeating structure (A) of a halogen-containing macromonomer (a-2) represented by general formula (I) as an essential component, and this halogen-containing macromonomer (a-2) is It is composed of an oligomer consisting of a halogen-containing monomer (a-1).

The polymer of the present invention is a polymer composed of the above-mentioned repeating structure (A) as an essential component, and is a monopolymer (A) (homopolymer) derived from a single halogen-containing macromonomer (a-2). In addition, a repeating structure (A) consisting of a halogen-containing macromonomer (a-2) and a repeating structure (B) consisting of a monomer (b) having a polymerizable unsaturated double bond and not containing a halogen. It may also be a copolymer containing.

In this case, the halogen-free monomer (b) having a polymerizable unsaturated double bond may be one that does not inhibit the polymerization of the halogen-containing macromonomer (a-2), and the halogen-containing polymer is a block It may be a copolymer or a random copolymer. Various monomers can be selected for the purpose of imparting hydrophilicity or flexibility to the halogen-containing polymer, improving solubility in organic solvents, or adhesion to substrates. The monomer (b) that can be used may be one type or a mixture of two or more types.

Specific examples of the monomer (b) include 2-hydroxyethyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta (Meth)acrylate monomers such as erythritol tetra(meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and cyclohexyl (meth)acrylate, polyethylene glycol having ethylene oxide as a repeating unit ( Examples include, but are not limited to, meth)acrylates.

The repeating structure (A) derived from the halogen-containing macromonomer (a-2) in the halogen-containing polymer of the present invention and the halogen-free monomer (b) having a polymerizable unsaturated double bond The ratio of the repeating structure (B) derived from the macromonomer (a-2) is not particularly limited, but for example, [the repeating structure (A) derived from the macromonomer (a-2)]/([the repeating structure derived from the macromonomer (a-2)] (A)] + [repetitive structure (B) derived from monomer (b)]) (weight ratio) = 10/100 to 100/100, preferably within the range of 20/100 to 90/100, as appropriate. Can be set. If the amount of halogen-containing macromonomer (a-2) units in the halogen-containing polymer is too small, the flame retardance may decrease.

Further, the weight average molecular weight of the halogen-containing polymer is usually about 1,000 to 1,000,000, and preferably 3,000 to 500,000. The weight average molecular weight in this case indicates a styrene equivalent molecular weight using gel permeation chromatography (GPC). When the weight average molecular weight is less than 1000, sufficient washing durability cannot be obtained because it is considered to be in almost the same state as a low molecular weight compound. On the other hand, if the weight average molecular weight exceeds 1,000,000, the solubility in organic solvents may be extremely reduced, or the viscosity of the polymer solution may be too high, making it difficult to handle.

The halogen-containing macromonomer (a-2) is subjected to radical polymerization using a radical polymerization initiator, for example, in the presence of a chain transfer agent (c) such as an active hydrogen-containing ^mercaptan together with the halogen-containing monomer (a-1) M hal. After obtaining a reactive halogen-containing oligomer having active hydrogen, it can be synthesized by subsequently reacting with a (meth)acroyl monomer (d) having a functional group that reacts with active hydrogen.

(1) Halogen-containing monomer (a-1)
The halogen-containing monomer (M ^hal ) is not limited as long as it has a polymerizable unsaturated group, but in particular, it has the following general formula (VI).
[In formula (VI), R ¹ is a hydrogen atom or a methyl group, R ⁴ is a hydrocarbon group which may have a substituent, and (R ⁴ -X _r ) means that R ⁴ is r It represents a group substituted with a halogen atom X, and the halogen atom X represents a chlorine atom, a bromine atom, or an iodine atom. m satisfies 0≦m≦20, and r satisfies 1≦r≦10. ] can be suitably used.

R ⁴ in the above formula (VI) represents a hydrocarbon group that may have a substituent, and is chain-shaped (either linear or branched) or cyclic (monocyclic, fused polycyclic, bridged ring). and a spiro ring.). Therefore, for example, a cyclic hydrocarbon group having a side chain can also be employed. Further, the hydrocarbon group may be saturated or unsaturated.

Examples of the hydrocarbon group include, but are not limited to, an alkyl group, an aryl group, an alkylaryl group, and the like. The alkyl group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and may have a substituent such as a hydroxyl group. The aryl group is preferably a phenyl group or a naphthyl group, and may have an alkyl group having 1 to 4 carbon atoms or a hydroxyl group. As for the alkylaryl group, the aryl group in the alkylaryl group is the same as the above-mentioned aryl group, and the alkyl group in the alkylaryl group is also the same as the above-mentioned alkyl group. The hydrocarbon group is not particularly limited, but is preferably, for example, a phenyl group or a linear alkyl group having 1 to 10 carbon atoms.

Examples of the alkyl group include methyl group, ethyl group, propyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group, t-pentyl group, hexyl group, isohexyl group, Examples include heptyl group, octyl group, nonyl group, and decyl group. The alkyl group may be linear or branched. In the present invention, the number of carbon atoms in the alkyl group is not limited, but it is generally preferably about 1 to 20, particularly preferably 2 to 6.

The above aryl group may be any cyclic (monocyclic, condensed polycyclic, bridged ring, and spirocyclic) group that may have a substituent. For example, monocyclic, bicyclic or tricyclic aryl groups such as phenyl group, biphenyl group, terphenyl group, pentalenyl group, indenyl group, naphthyl group, azulenyl group, fluorenyl group, phenanthryl group, and propyldiphenyl group. Examples include alkylaryl groups such as. R ⁴ in the present invention is preferably an aryl group having 6 to 18 carbon atoms, such as phenyl group, naphthyl group, and the like.

The above-mentioned alkylaryl group is preferably one in which an aryl group which may have a substituent is substituted with a linear or branched alkyl group having 1 to 4 carbon atoms, such as a benzyl group. .

As a substituent for the above hydrocarbon group R ⁴ , a halogen atom may be mentioned, but it may also have other substituents. Examples include nitrogen-based substituents such as an amino group, amide group, and nitro group, sulfur-based substituents such as a sulfonic acid group, and carbon-based substituents such as a carboxyl group and an alkoxy group. Further, the preferable number of carbon atoms in R ⁴ is 1 to 20, and the number of carbon atoms includes the substituent when it has a substituent.

X in the above formula (VI) represents a halogen atom, and is a chlorine atom, a bromine atom, or an iodine atom, and is particularly preferably a chlorine atom or a bromine atom.

The number of halogen atoms substituted for the above hydrocarbon group R ⁴ depends on the number of carbon atoms in R ⁴ but is usually about 1 to 10. In addition, when substituted with a plurality of halogen atoms, the halogen atoms may be composed of the same type of halogen atoms, or may be composed of halogen atoms of different types.

The halogen-containing monomer (M ^hal ) represented by the general formula (VI) may be used alone or in combination of two or more different types. Specific examples of the halogen-containing monomer (M ^hal ) include, but are not limited to, the following compounds.

(2) Halogen-containing oligomer (M ^hal _n )
The halogen-containing oligomer (M ^hal _n ) may be one obtained by polymerizing one type of halogen-containing monomer, or may be one obtained by polymerizing two or more types of halogen-containing monomer. The repeating structure derived from two or more halogen-containing monomers may be a block polymer or a random polymer, and the repeating structures may not necessarily be arranged like the compounds described below. good.

The degree of polymerization n (repeating structure of halogen-containing monomer (a-1)) of the halogen-containing oligomer M ^hal _n is not particularly limited as long as it is a dimer or larger, but usually n=2 to 20 (more preferably n= 2 to 10). If n exceeds 20, depending on the number of halogen substitutions, it may become insoluble in general-purpose organic solvents, which may hinder the subsequent synthesis of the halogen-containing macromonomer (a-2).

Specific examples of the halogen-containing oligomer (M ^hal _n ) derived from the halogen-containing monomer (a-1) include the following compounds (18) and (19), respectively, in the case of the above compound (1) and compound (13). become that way.
(However, in compound (18), n represents a number from 2 to 20.)
(However, in compound (19), n represents a number from 2 to 20.)

(3) Halogen-containing macromonomer (a-2)
The halogen-containing macromonomer (a-2) is a monomer represented by general formula (I). Below, the content of general formula (I) will be explained.

R ¹ in formula (I) is a hydrogen atom or a methyl group.

In addition, the above L is represented by the following general formula (II) or general formula (III)
(However, in formula (III), R ² is represented by the following general formula (IV)
(However, in formula (IV), p satisfies 0≦p≦20, and q satisfies 1≦q≦20.)).

The above p is preferably 0≦p≦10. Moreover, it is preferable that the said q is 1<=q<=6.

The above Y is the following general formula (V)
(However, in formula (V), Z is an ether group (-O-), a carbonyl group (-COO-) or an imino group (-NH-), R ³ is a methylene group or an ethylene group, and S is represents a sulfur atom). The combination of Z and R ³ is not particularly limited, but for example, a combination in which Z is an ether group or a carbonyl group and R ³ is a methylene group or an ethylene group can be suitably employed.

M ^hal _n represents the halogen-containing oligomer shown in "(2) Halogen-containing oligomer (M ^hal _n )" above.

Specific examples of the halogen-containing macromonomer (a-2) include the following compounds.
(However, compound (31) uses compound (1) as halogen-containing monomer (a-1), compound (20) as chain transfer agent (c), and active hydrogen-reactive (meth)acryloyl monomer (d). It is synthesized using compound (28) as a raw material, and n represents a number from 2 to 20.)
(However, in compound (32), compound (13) is used as the halogen-containing monomer (a-1), compound (23) is used as the chain transfer agent (c), and compound (23) is used as the active hydrogen-reactive (meth)acryloyl monomer (d). It is synthesized using compound (29) as a raw material, and n represents a number from 2 to 20.)

In the case of the above compound (31) and compound (32), when applying general formula (I) to general formula (VI), it can be shown as shown in Table 1 below.

2. Production of the polymer of the present invention The polymer of the present invention can be produced by, for example, (1) a step (A step) of obtaining a halogen-containing macromonomer (a-2) from a starting material containing a halogen-containing monomer (a-1); A halogen-containing polymer can be obtained by a production method including a step (Step B) of obtaining a halogen-containing polymer from a starting material containing a halogen-containing macromonomer. That is, the active ingredient (flame retardant component) of the flame retardant of the present invention can be suitably prepared by this manufacturing method.

(1) Step A (manufacture of halogen-containing macromonomer (a-2))
The halogen-containing macromonomer (a-2) is, for example, a reactive halogen-containing oligomer having active hydrogen by radical polymerizing (A1) the halogen-containing monomer (a-1) and the chain transfer agent (c) containing active hydrogen. (Step A1), and (B) a step of reacting the oligomer with a (meth)acryloyl monomer (d) having a functional group that reacts with active hydrogen (Step A2).

Step A1 In Step A1, various methods such as bulk polymerization, solution polymerization, and emulsion polymerization are performed to obtain a reactive halogen-containing oligomer having active hydrogen from the halogen-containing monomer (a-1) and the active hydrogen-containing chain transfer agent (c). Polymerization methods can be used. Among these, a solution polymerization method using an organic solvent is most preferable when considering the reaction of macromonomerization after polymerization.

By the solution polymerization method, it is possible to more reliably synthesize a reactive halogen-containing oligomer having active hydrogen using a known method as described below. For example, a halogen-containing monomer (a-1) and an active hydrogen-containing chain transfer agent (c) are added to an organic solvent, and while being heated while substituting with an inert gas such as nitrogen or argon in the coexistence of a polymerization initiator. A reactive halogen-containing oligomer can be obtained by stirring the solution.

Although the reaction conditions depend on the reaction solvent used, etc., it is usually possible to obtain a reactive halogen-containing oligomer having active hydrogen by continuing stirring at a temperature of about 40 to 120°C for about 1 to 10 hours. can.

As the active hydrogen-containing chain transfer agent (c), a known or commercially available alkylenethiol-based chain transfer agent or arylthiol-based chain transfer agent can be used, and active hydrogen-containing mercaptan can be particularly preferably used.

Examples of the active hydrogen-containing reactive functional group in the active hydrogen-containing mercaptan include a hydroxyl group, a carboxylic acid group, and an amino group. More specifically, as shown below, for example, 2-mercaptoethanol (20), 2-mercaptobutanol (21), 2-mercaptoacetic acid (22), 3-mercaptopropionic acid (23), 4-mercaptophenol (24), 4-mercaptobenzoic acid (25), 4-aminothiophenol (26), etc., but are not limited to these.

The amount of the active hydrogen-containing chain transfer agent added during polymerization is not particularly limited, but it is preferably about 0.01 to 0.5 equivalent, particularly 0.01 to 0.5 equivalent per equivalent of halogen-containing monomer (a-1). More preferably, the amount is 1 to 0.3 equivalent.

As the organic solvent, any general organic solvent can be used as long as it does not contain active hydrogen. For example, ester organic solvents such as ethyl acetate and butyl acetate, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, hydrocarbon organic solvents such as n-hexane, toluene, and xylene, acetonitrile, tetrahydrofuran, A combination of one or more of a number of organic solvents capable of dissolving halogen-containing monomers, such as aprotic polar solvents such as , 4-dioxane, etc., can be used in the reaction.

The amount of the organic solvent used is not particularly limited, but it can usually be used in the range of 100 to 5000 parts by weight per 100 parts by weight of the halogen-containing monomer.

As the polymerization initiator, known or commercially available radical polymerization initiators can be used. For example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2' -Dimethyl azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, etc. can be used.

The amount of the polymerization initiator to be used is not limited, but it is usually preferably used in the range of 0.01 to 5 parts by weight per 100 parts by weight of the halogen-containing monomer.

Step A2 In Step A2, a halogen-containing macromonomer (a-2 ) can be obtained.

As the above (meth)acryloyl monomer (d), as shown below, glycidyl (meth)acrylate, 2-(meth)acryloyloxyethyl isocyanate, etc. are suitably used, but are not limited thereto. do not have.

The reaction method is similar to the synthesis conditions for the reactive halogen-containing oligomer, for example, using approximately the same amount (for example, 0.8 to 1.2 times equivalent) of (meth)acryloyl monomer (d ) into an organic solvent, and if necessary, stir the solution while heating in the presence of a reaction catalyst to obtain a halogen-containing macromonomer. As the reaction catalyst at this time, known catalysts can be used, and suitable examples include organic amine catalysts such as alkylamines, quaternary ammonium salts, and the like.

In the above reaction, in order to suppress unexpected polymerization that may occur during the synthesis of the macromonomer, it is preferable to carry out the reaction in the presence of a polymerization inhibitor. As the polymerization inhibitor, any known or commercially available one may be used. For example, hydroquinone, 1,4-bensoquinone, 4-methoxyphenol, t-butylhydroquinone, 6-t-butyl-2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t- Examples include butyl-4-cresol, 4-t-butylpyrocatechol, phenothiazine, etc., and the reaction may be carried out under aeration (air/oxygen bubbling) if necessary.

The reaction conditions depend on the reaction solvent used, etc., but the halogen-containing macromonomer (a-2) is usually stirred at a temperature of room temperature (for example, 15°C) to 120°C for about 1 to 10 hours. can be obtained effectively.

(2) B process (manufacture of halogen-containing polymer)
The method for producing the polymer of the present invention is not particularly limited, and for example, known polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be employed. Among these, solution polymerization is suitably used for halogen-containing polymers, similar to the polymerization method for halogen-containing oligomers.

Regarding the specific polymerization method, as with the halogen-containing oligomer, the halogen-containing macromonomer (a-2) and, if necessary, the halogen-free monomer (b) having a polymerizable unsaturated double bond are combined into an organic polymerization method. A halogen-containing polymer is obtained by adding the solution to a solvent and stirring the solution while heating it while purging it with an inert gas such as nitrogen or argon in the presence of a polymerization initiator.

The organic solvent, polymerization initiator, etc. used may be the same as those shown in "(1) Step A (manufacture of halogen-containing macromonomer (a-2))" above. Therefore, polymerization can be carried out in a general-purpose organic solvent such as an ester organic solvent, a ketone organic solvent, or a hydrocarbon organic solvent, using, for example, an azo compound or peroxide as a polymerization initiator.

The organic solvent is not particularly limited, and includes, for example, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, hydrocarbon organic solvents such as n-hexane, toluene, and xylene, and esters such as ethyl acetate and butyl acetate. Among the many organic solvents capable of dissolving halogen-containing monomers, such as organic solvents, aprotic polar solvents such as acetonitrile, tetrahydrofuran, and 1,4-dioxane, one or a combination of two or more solvents can be used in the reaction. I can do it.

The amount of the organic solvent to be used can be set appropriately depending on the type of starting material used, etc., but it is usually 100 parts by weight per 100 parts by weight of the total amount of the halogen-containing macromonomer (a-2) and the monomer (b). It may be used in a range of about 5,000 parts by weight.

As the polymerization initiator, known or commercially available radical polymerization initiators can be used. For example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2' -Dimethyl azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), benzoyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, etc. can be used.

Although the amount of the polymerization initiator used is not limited, it is generally about 0.01 to 5 parts by weight per 100 parts by weight of the total amount of the halogen-containing macromonomer (a-2) and monomer (b). It can be suitably used within a range.

Moreover, in order to control the molecular weight of the halogen-containing polymer, the above-mentioned active hydrogen-containing chain transfer agent (c) can also be used. As the active hydrogen-containing chain transfer agent, a known or commercially available alkylenethiol chain transfer agent or arylthiol chain transfer agent can be used. Specific examples include 2-mercaptoethanol, 2-mercaptobutanol, 2-mercaptoacetic acid, 3-mercaptopropionic acid, 4-mercaptophenol, 4-mercaptobenzoic acid, and 4-aminothiophenol.

The amount of active hydrogen-containing chain transfer agent added during polymerization is not particularly limited, but is usually 0.01 to 3 parts by weight per 100 parts by weight of the total amount of halogen-containing macromonomer (a-2) and monomer (b). It can be suitably used within a range of about 100%.

The reaction conditions depend on the reaction solvent used, but after the inside of the reaction vessel is sufficiently replaced with an inert gas such as nitrogen or argon gas, stirring is continued for about 1 to 10 hours at a temperature of usually 40 to 120°C. By doing so, a halogen-containing polymer can be obtained more reliably.

3. Flame retardant for textiles The present invention includes a flame retardant for textiles (flame retardant of the invention) containing the polymer of the invention. The flame retardant of the present invention may contain subcomponents as necessary within a range that does not impede the effects of the present invention.

For example, flame retardants or flame retardant aids (hereinafter both are collectively referred to as "flame retardant aids") other than the polymer of the present invention can be suitably used as a subcomponent. Such flame retardant aids include halogen-containing compounds other than the halogen-containing polymer, phosphorus-containing compounds, nitrogen-containing compounds, sulfur-containing compounds, silicon-containing compounds, inorganic metal compounds, etc. It can be blended as appropriate within a range that does not interfere with its flame retardant function. In the present invention, these flame retardant aids can be used alone or in combination of two or more.

Examples of the halogen-containing compound include tetrabromobisphenol A, bisdibromopropyl ether of tetrabromobisphenol A, tetrabromobisphenol A epoxy oligomer, tetrabromobisphenol A carbonate oligomer, and tetrabromobisphenol S bisdibromopropyl ether. Derivative compounds of tetrabrominated bisphenols, aromatic polybrominated compounds such as decabromodiphenylethane, brominated polystyrene, polybrominated styrene, decabromodiphenylethane, tris(2,3-dibromopropyl) isocyanurate etc.

Examples of the above-mentioned phosphorus-containing compounds include red phosphorus, phosphoric acid, phosphorous acid, and other uncondensed or condensed phosphoric acids and amine salts, metal salts, inorganic phosphorus-containing compounds such as boron phosphate, orthophosphoric acid esters, or Condensates thereof, phosphoric acid ester amides, phosphonic acid esters other than those mentioned above, phosphorus-containing ester compounds such as phosphinic acid esters, triazines or triazole compounds, or salts thereof [metal salts, (poly)phosphates, sulfates] , urea compounds, (poly)phosphoric acid amides, nitrogen-containing compounds such as hindered amine (HALS, especially NOR type HALS, etc.)-containing compounds, organic sulfonic acids [alkanesulfonic acids, perfluoroalkanesulfonic acids, arenesulfonic acids] or their Sulfur-containing compounds such as metal salts, sulfonated polymers, organic sulfonic acid amides or their salts [ammonium salts, metal salts], silicone compounds such as resins, elastomers, and oils containing (poly)organosiloxane, zeolites, etc. silicon-containing compounds, metal salts of inorganic acids such as antimonates and borates, metal oxides such as antimony trioxide, antimony pentoxide, etc., metal hydroxides such as aluminum hydroxide, magnesium hydroxide, etc. , metal sulfides, and other inorganic metal compounds.

The content of the flame retardant aid is not particularly limited, but for example, the polymer of the present invention/flame retardant aid (weight ratio) is about 1/100 to 100/1, preferably in the range of 10/100 to 100/10. It can be set as appropriate within.

The properties of the flame retardant of the present invention are not particularly limited, and can be changed as appropriate depending on the mode of use, purpose, application, intended use, and the like. Moreover, the same form as a publicly known or commercially available flameproofing agent can also be adopted. Therefore, for example, forms such as solutions, dispersions, emulsions, aerosols, etc. can be suitably employed. That is, the halogen-containing polymer can be dissolved or dispersed in water, an organic solvent, etc., depending on the type, shape, etc. of the textile product. The concentration (solid content) of the halogen-containing polymer during dissolution or dispersion is not limited, but is usually suitably adjusted within the range of 1 to 50% by weight, but is not limited thereto.

In the case of a solution in which the flame retardant of the present invention (especially the polymer of the present invention) is dissolved in an organic solvent, it is sufficient to simply stir and dissolve the halogen-containing polymer in the organic solvent, but in the case of a dispersion or emulsion in an aqueous medium, It is desirable to improve the dispersibility and emulsification properties by adding a dispersant, an emulsifier, etc. as necessary. The dispersant or emulsifier is not particularly limited as long as it can improve dispersibility and emulsification properties, and various dispersants or emulsifiers can be used.

As the aqueous medium in this case, 1) water alone or 2) a mixed solvent containing water and an organic solvent can be used.

Examples of organic solvents include methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol, dipropylene glycol, tripropylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, In addition to polar organic solvents that are extremely soluble in water such as ethylene glycol monobutyl ether, ethylene glycol mono t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether, toluene, xylene, mineral turpentine, etc. can be emulsified with water. Examples include petroleum-based solvents. These may be used alone or in combination of two or more.

When using a mixed solvent, the content of the organic solvent is not particularly limited and can be set as appropriate considering the type of organic solvent, degree of dispersion or emulsification, etc., but is usually 1 to 50% by weight, preferably 3% by weight. It is preferably used in a range of 30% by weight.

Moreover, the above-mentioned dispersant or emulsifier is not limited, and known or commercially available surfactants and the like can be used. In particular, in the present invention, at least one of anionic surfactants and nonionic surfactants is suitable.

Examples of anionic surfactants include higher alcohol sulfate ester salts, polyoxyethylene alkylphenyl sulfate ester salts, sulfated fatty acid ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, and higher alcohol phosphate ester salts. . Examples of the nonionic surfactant include polyoxyalkylene natural oil alkyl ether, polyoxyalkylene higher alcohol alkyl ether, polyoxyalkylene alkylphenyl ether, and polyhydric alcohol fatty acid ester.

The amount of surfactant added is not particularly limited, and can be set as appropriate by considering the type of surfactant, the degree of dispersion or emulsification, etc., but when the dispersion medium (emulsification medium) is an aqueous medium, it is usually The amount may be about 0.1 to 30% by weight, preferably about 0.3 to 20% by weight.

Further, a dispersion stabilizer or an emulsion stabilizer can also be used as required. Examples of the dispersion stabilizer include polyvinyl alcohol, polyvinylpyrrolidone, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, xanthan gum, starch paste, and the like. Examples of the emulsion stabilizer include triglycerides such as castor oil and rapeseed oil; esters such as phosphoric acid esters and phthalic acid esters; and higher alcohols.

The amount of these stabilizers added is not particularly limited, and can be set as appropriate by considering the type of stabilizer, the degree of dispersion or emulsification, etc., but when the dispersion medium (emulsifying medium) is an aqueous medium, , usually about 0.1 to 10% by weight, preferably about 0.3 to 3% by weight.

As other additives, additives used in known or commercially available flameproofing agents can be used. Examples include glues, colorants, softeners, light stabilizers, antioxidants, ultraviolet absorbers, penetrants, humectants, deodorizing agents, antistatic agents, antifouling agents, and the like. The amount of these additives can be set as appropriate depending on the type of flameproofing.

The flame retardant of the present invention preferably contains both the above-described surfactant (at least one of anionic surfactants and nonionic surfactants) and a dispersion or emulsion stabilizer. For example, when the dispersion medium (emulsifying medium) is an aqueous medium, a suitable composition of the flame retardant is about 1 to 50% by weight of the halogen-containing polymer, preferably about 5 to 50% by weight; The amount of the dispersion or emulsion stabilizer is about 0.1 to 30% by weight, preferably about 0.3 to 20% by weight; the dispersion or emulsion stabilizer is about 0.1 to 10% by weight, preferably about 0.3 to 3% by weight. Examples include compositions that

The flame retardant of the present invention can be prepared by, for example, mixing predetermined components and then atomizing the mixture using an emulsifying device such as a homogenizer, high-pressure homogenizer, or ultrasonic homogenizer, or a dispersing device such as a ball mill or bead mill. .

The atomization conditions are not particularly limited, but may be such that the average particle diameter of the dispersed fine particles (fine particles containing a halogen-containing polymer, etc.) in the resulting dispersion or emulsion is 10 μm or less, particularly 0.0 μm or less. It is preferable to set the thickness to 1 to 5 μm.

4. Flame Retardant Fiber Products The present invention includes flame retardant fiber products in which fibers are coated with a flame retardant for fibers (hereinafter also referred to as "flame retardant"). That is, the flameproofing agent of the present invention can be suitably applied to the production of flameproof textile products. In particular, it is effective as a flame retardant for imparting flame retardancy or flame retardancy to fibers through post-processing.

The fibers are not particularly limited, and any of natural fibers, synthetic fibers, and composite fibers thereof can be used. Specifically, examples of natural fibers include cotton, linen, silk, and wool. Examples of synthetic fibers include rayon, acetate, polyester, nylon, acrylic, polyurethane, polypropylene, and cellulose. Examples of the inorganic fiber include glass fiber, carbon fiber, and metal fiber. Further, mixed fibers of these fibers can also be used.

Furthermore, the fibers may be in the form of woven or nonwoven fabrics in addition to single fibers (short fibers or long fibers). Therefore, the flameproofing agent of the present invention can also be applied to ready-made woven or nonwoven fabrics or textile products using these (clothes, furniture, automobile parts, daily necessities, etc.).

Flameproofing can be carried out by fixing a halogen-containing polymer to fibers. Therefore, the method for producing a flame-retardant fiber product of the present invention includes a step of bringing a flame-retardant into contact with fibers.

The method for producing the flame retardant fiber product of the present invention (especially the fixing method) is applicable as long as the flame retardant can be brought into contact with the fibers (especially as long as the surface of the fibers constituting the fibers can be coated with the flame retardant of the present invention). Either method is fine. Therefore, flame-retardant treatment is applied to at least one entire surface of the fabric by using, for example, a dipping method, a coating method, a spraying method, or a brushing method, to provide a flame retardant treatment corresponding to about 1 to 50% by weight of solids based on the average weight per unit area of the fabric. A curing treatment can also be performed to attach the agent and, if necessary, to infiltrate the inside by heat treatment.

Specifically, after bringing the flame retardant into contact with the fibers, the fibers are dried at a temperature of 120°C or less, and then the fibers are heat-treated at about 140 to 180°C. The method of bringing the flame retardant into contact with the fibers is not particularly limited, and examples include methods such as immersing the fibers in the flame retardant and spraying or applying the flame retardant to the fibers, as described above. It will be done. The contact time is not particularly limited and can be set as appropriate depending on the type of fibers used, the degree of flame retardancy, etc.

The drying method is not particularly limited, and natural drying or heat drying can be adopted. In the case of heat drying, the drying temperature is particularly preferably about 60 to 120°C. Further, the drying time is preferably about 10 seconds to 30 minutes.

Further, if necessary, the fibers may be subjected to heat curing treatment usually at about 140 to 180°C (preferably 140 to 160°C) after drying. This treatment allows the halogen-containing polymer to be more reliably fixed inside and on the surface of the fibers. The treatment method is not particularly limited, and can be carried out by, for example, heating a roll carrying the fibers (fabric) to the above temperature, passing it through an atmospheric furnace set at the above temperature, or the like. The treatment time can be set as appropriate depending on, for example, the heat treatment temperature and the degree of fixation of the flameproofing agent, but it is usually about 30 seconds to 5 minutes, preferably about 1 minute to 2 minutes.

The halogen-containing polymer contained in the flame retardant (halogen-containing polymer fine particles or flame retardant or flame retardant aid fine particles added at the same time) has a sufficiently small average particle size of 0.1 to 10 μm. By thermal curing treatment, the halogen-containing polymer is easily diffused and fixed throughout the structure of the surface of the fibers, making it possible to produce high-quality flame-resistant fibers. Therefore, it is preferable that the above-mentioned fine particles have an average particle size within the above range, particularly preferably 0.1 to 5 μm.

The flame retardant fiber product of the present invention is characterized in that a flame retardant containing a halogen-containing polymer having a unit of a halogen-containing macromonomer represented by general formula (I) as a flame retardant component is fixed therein. Since it itself has extremely flammable properties, it can prevent the spread of fire to the fibers. In addition, the halogen-containing polymer has high washing durability because it does not fall off when washed unlike low-molecular compounds. suppressed. Particularly, excellent effects can be exhibited for washing using polar solvents such as water and ethanol.

Furthermore, unlike flame-retardant textile products that are manufactured exclusively from fabrics or woven or knitted fabrics made from flame-retardant fibers, general-purpose textile products that are not flame-retardant are treated with post-processing flame retardant treatment. Since it can impart flame retardancy, it does not significantly impair the inherent performance of textile products, and is also suitable for mass production of flame-resistant textile products.

Hereinafter, the present invention will be explained in more detail by giving Examples and Comparative Examples. However, the present invention is not limited to these examples.

<1. Synthesis of compounds>
According to the following synthesis example, a halogen-containing macromonomer was prepared from a halogen-containing monomer, and this was further polymerized to prepare a halogen-containing polymer. The molecular weight of the synthesized halogen-containing macromonomer and halogen-containing polymer was measured by the following method.
(1) Tracking reaction progress: GC
The progress of the reaction was monitored using gas chromatography with a flame ionization detector (FID) (GC-2010: manufactured by Shimadzu Corporation).
(2) Measurement of molecular weight: GPC
The weight average molecular weight was determined from a polystyrene equivalent value using gel permeation chromatography with a refractive index differential (RID) detector (GPC Alliance system: manufactured by Waters). In the above GPC, the product name "Styragel (registered trademark) HR1 (column length: 4.6 x 300 mm)" manufactured by WATERS was used as a column.
(3) Identification of chemical structure: ¹ H-NMR, ¹³ C-NMR
Structural identification of each product compound using hydrogen nuclear magnetic resonance ( ¹ H-NMR) and carbon nuclear magnetic resonance ( ¹³ C-NMR) using a 300 MHz nuclear magnetic resonance analyzer (JNM-AL300: manufactured by JEOL Ltd.) I did it.
(4) Identification of halogen-containing oligomers: Identification and absolute identification of halogen-containing oligomers using a (MALDI-TOFMS) matrix-assisted laser desorption ionization time-of-flight mass spectrometer (MALDI-TOFMS AXIMA Confidence: manufactured by Shimadzu Corporation) The average molecular weight was measured.

<1-1. Synthesis of halogen-containing macromonomer>
Synthesis example 1
In a 4-necked flask with a stirrer equipped with a thermometer, nitrogen inlet tube, and calcium chloride tube, add 20.0 g (160 mmol) of 2-bromoethanol [Tokyo Kasei Kogyo Co., Ltd.] and triethylamine [Kishida Kagaku Co., Ltd.]. After adding 19.43 g (192 mmol) and 150 g of toluene, stirring was started while nitrogen was introduced, and cooling was performed. When the liquid temperature became 10° C. or less and nitrogen substitution was completed, 17.38 g (192 mmol) of acryloyl chloride [Tokyo Kasei Kogyo Co., Ltd.] was slowly added dropwise over 1 hour while keeping the temperature below 10° C. After reacting and aging at room temperature for 1 hour with stirring, the mixture was thoroughly washed with water, 1% aqueous phosphoric acid, and 1% sodium bicarbonate, further washed with saturated saline, and dried over a small amount of anhydrous magnesium sulfate. The reaction solution was filtered through a filter paper (Toyo Roshi Co., Ltd. No. 2) and concentrated by evaporation under reduced pressure to obtain 22.9 g (yield: 80%) of a pale yellow liquid compound.
¹ H-NMR and ¹³ C-NMR measurements revealed that the obtained compound was 2-dibromoethyl acrylate of the following compound (9).

¹ H-NMR (300 MHz, CDCl ₃ ; internal standard TMSδppm
6.47 (dd, J=17.4, 1.5Hz, 1H), 6.15 (dd, J=17.4, 10.2Hz, 1H), 5.89 (dd, J=10.2Hz, 1H), 4.47 (t, J=6.3Hz, 2H) 3.55 (t, J=6.3Hz, 2H)
^13C -NMR (300MHz, CDCl ₃ ; internal standard TMSδppm
165.5, 131.6, 127.8, 63.8, 28.5ppm

Synthesis example 2
10.0 g (52 mmol) of the previously obtained 2-bromoethyl acrylate [compound (9)] and 3-mercaptopropion were placed in a four-necked flask equipped with a stirrer and equipped with a thermometer, nitrogen inlet tube, and Dimroth condenser. After adding 1.06 g (10 mmol) of acid [Tokyo Kasei Kogyo Co., Ltd., compound (23)] and 200 g of ethyl acetate, stirring was started while introducing nitrogen, and after sufficient nitrogen substitution, 2.2 After adding 0.1 g of '-azobis(isobutyronitrile) [Wako Pure Chemical Industries, Ltd.], the mixture was heated under reflux at 80° C. for 8 hours. After confirming the disappearance of 2-bromoethyl acrylate and 3-mercaptopropionic acid by GC, the reaction solution was cooled to room temperature. The product was extracted from the reaction solution obtained in this way, and the halogen-containing oligomer was identified using MALDI-TOFMS. It was found that a 2-bromoethyl acrylate oligomer (peak top: 1023) with a molecular weight distribution of 800 to 1,600 was identified. Confirmed generation.
MALDI-TOFMS: m/z [M+Na] ⁺ ;844,1023,1200,1379,1558
0.02 g of 4-methoxyphenol [Seiko Kagaku Co., Ltd.] and 0.1 g of tetramethylammonium chloride [Tokyo Kasei Kogyo Co., Ltd.] were added to the reaction solution, and the air was replaced while bubbling dehydrated air. , and gently heated with stirring until the temperature reached 60°C. When the temperature of the reaction solution reached 60° C., 1.42 g (10 mmol) of glycidyl methacrylate [Light Ester G, manufactured by Kyoeisha Kagaku Co., Ltd.] was gradually added, and the reaction was continued for 6 hours. When the disappearance of glycidyl methacrylate was confirmed by GC, the reaction solution was cooled to room temperature, thoroughly washed with water and saturated brine, and then dried over a small amount of anhydrous magnesium sulfate. After filtering the reaction solution through filter paper (Toyo Roshi Co., Ltd. No. 2), the reaction solution was concentrated by evaporation under reduced pressure, and further vacuum-dried to obtain 10.2 g of colorless viscous compound (33). I got it.
When the obtained compound was measured by GPC, the weight average molecular weight of the following compound (33) was about 1,200 (polystyrene equivalent value), so the average degree of polymerization of this macromonomer was about 5.3. there were. Furthermore, when the macromonomer was identified by MALDI-TOFMS, the peak of 2-bromoethyl acrylate oligomer disappeared, and the 2-bromoethyl acrylate macromer (peak top: 965) had a molecular weight distribution of 800 to 1,200. The generation of was confirmed.
MALDI-TOFMS: m/z [M+H] ⁺ ;786,965,1144

Synthesis example 3
Except that 2-bromoethyl acrylate was changed to 2,4,6-tribromophenyl acrylate [Tokyo Kasei Kogyo Co., Ltd., compound (14)] 20.0 g (52 mmol), and the organic solvent was changed from ethyl acetate to methyl isobutyl ketone. The reaction was carried out in the same manner as in Synthesis Example 1 to obtain 20.8 g of white powdery compound (34).
When the obtained compound was measured by GPC, the weight average molecular weight of the following compound (34) was approximately 2,000 (polystyrene equivalent value), so the average degree of polymerization of this macromonomer was approximately 5.1. there were.

<1-2. Synthesis of halogen-containing polymer>
Synthesis example 4
In a four-necked flask with a stirrer equipped with a thermometer, nitrogen inlet tube, and Dimroth condenser, 5.0 g of the compound (33) obtained in Synthesis Example 1, 2-ethylhexyl methacrylate [Kyoeisha Chemical Co., Ltd. "Light" After adding 3.0 g of 2-hydroxyethyl methacrylate [Light Ester HO-250, manufactured by Kyoeisha Chemical Co., Ltd.] and 50 g of methyl isobutyl ketone, the mixture was stirred for 1 hour while bubbling with nitrogen. As a result, the inside of the reaction system was completely replaced with nitrogen.
After the reaction solution was gently heated to 80° C., 0.1 g of 2,2′-azobis(isobutyronitrile) [Wako Pure Chemical Industries, Ltd.] was added, and polymerization was continued for 10 hours. After the reaction was completed, the reaction solution was cooled to room temperature, concentrated by evaporation under reduced pressure, and further vacuum-dried to obtain 10.5 g of a colorless viscous compound (35). When the molecular weight of this halogen-containing polymer was measured by GPC, the weight average molecular weight was 11,000 (value in terms of polystyrene).

Synthesis example 5
The reaction was carried out at 65° C. in the same manner as in Synthesis Example 3, except that compound (33) was changed to compound (34) and methyl isobutyl ketone was changed to chloroform, to obtain 10.8 g of colorless viscous compound (36). When the molecular weight of this halogen-containing polymer was measured by GPC, the weight average molecular weight was 9,000 (value in terms of polystyrene).

<2. Preparation of flameproofing liquid>
A flameproofing liquid was prepared as follows using the halogen-containing polymer obtained in each of the above synthesis examples.

Example 1
In a container equipped with a stirrer containing 45 parts by weight of water, 4 parts by weight of polyoxyethylene styrenated phenyl ether sulfate ammonium salt as an anionic surfactant, 1 part by weight of polyoxyethylene styrenated phenyl ether as a nonionic surfactant, and polyethylene After adding 2 parts by weight of glycol (PEG-400), sufficient stirring was performed. A solution of 20 parts by weight of the halogen-containing polymer obtained in Synthesis Example 4, previously dissolved in 30 parts by weight of methyl isobutyl ketone as an organic solvent, was gradually added to the aqueous solution and emulsified and dispersed to form a uniform white dispersion liquid. A flameproofing liquid was obtained.

Example 2
Instead of the halogen-containing polymer obtained in Synthesis Example 4, the halogen-containing polymer obtained in Synthesis Example 5 was used and emulsified and dispersed in the same manner as in Example 1 to obtain a flameproofing liquid in the form of a uniform white dispersion. I got it.

Example 3
Further, 5 parts by weight of a 60% antimony trioxide fine particle dispersion (Nonne KN-W; manufactured by Marubishi Yuka Kogyo Co., Ltd.) was added to 100 parts by weight of the flameproofing liquid obtained in Example 1 to obtain a uniform white color. A flameproofing liquid in the form of a dispersion liquid was obtained.

Example 4
Further, 5 parts by weight of a 60% antimony trioxide fine particle dispersion (Nonne KN-W; manufactured by Marubishi Yuka Kogyo Co., Ltd.) was added to 100 parts by weight of the flameproofing liquid obtained in Example 2, and a uniform white color was obtained. A flameproofing liquid in the form of a dispersion liquid was obtained.

Example 5
To 100 parts by weight of the flameproofing liquid obtained in Example 1, 6 parts by weight of a 50% antimony pentoxide fine particle dispersion (Nonne SM-4; Marubishi Yuka Kogyo Co., Ltd.) was added to obtain a uniform white color. A flameproofing liquid in the form of a dispersion liquid was obtained.

Example 6
To 100 parts by weight of the flameproofing liquid obtained in Example 2, 6 parts by weight of a 50% antimony pentoxide fine particle dispersion (Nonne SM-4; Marubishi Yuka Kogyo Co., Ltd.) was added to obtain a uniform white color. A flameproofing liquid in the form of a dispersion liquid was obtained.

Comparative example 1
Instead of the halogen-containing polymer obtained in Synthesis Example 4, a 70% aqueous dispersion of the low molecular weight brominated flame retardant (37) decabromodiphenylethane [Marubishi Yuka Kogyo Co., Ltd. "Nonne R1511-2"] was used to emulsify and disperse in the same manner as in Example 1 to obtain a flameproofing liquid in the form of a uniform white dispersion.

Comparative example 2
In place of the halogen-containing polymer obtained in Synthesis Example 4, chlorine-based flame retardant oligomer (38) polyoxyalkylene bisdichloroalkyl phosphate [Daihachi Chemical Industry Co., Ltd. "CR-504L"] was used to produce an example. The mixture was emulsified and dispersed in the same manner as in 1 to obtain a flameproofing liquid in the form of a uniform white dispersion.

Comparative example 3
To 100 parts by weight of the flameproofing liquid obtained in Comparative Example 1, 5 parts by weight of a 60% antimony trioxide fine particle dispersion (Nonne KN-W; manufactured by Marubishi Yuka Kogyo Co., Ltd.) was further added to produce a uniform white color. A flameproofing liquid in the form of a dispersion liquid was obtained.

Comparative example 4
To 100 parts by weight of the flameproofing liquid obtained in Comparative Example 2, 5 parts by weight of a 60% antimony trioxide fine particle dispersion (Nonne KN-W; manufactured by Marubishi Yuka Kogyo Co., Ltd.) was further added to produce a uniform white color. A flameproofing liquid in the form of a dispersion liquid was obtained.

Test example 1
A combustion test was conducted on samples in which fibers were flameproofed using the flameproofing fluids (flameproofing agents) obtained in the Examples and Comparative Examples.

(1) Flameproofing on textile products Using each of the flameproofing solutions prepared in Examples 1 to 6 and Comparative Examples 1 to 4, polyester fibers were flameproofed. The polyester fabric used was a regular polyester fabric with a basis weight of 120 g/m ² .
After immersing the polyester cloth in each of the flameproofing liquids prepared in Examples 1 to 6 and Comparative Examples 1 to 4, padding treatment (squeezing ratio of 100%) was performed and drying was performed at 80° C. for 5 minutes. Next, each of the padded fabrics was cured at 150° C. for 1 minute to prepare flame-retardant fabrics. These flame-retardant fabrics were further washed with water, and flame-retardant fabrics were separated into the initial flame-retardant fabric and the flame-retardant fabric after water washing, and a combustion test was conducted on each fabric.

(2) Evaluation of flame-retardant performance of flame-retardant treated textile products The flame-retardant fabric obtained above was evaluated using JIS L-1091 A-1 (micro burner method) and JIS L-1091 D method (coil method). A combustion test was conducted using In addition, the combustion test was also conducted on products that had been washed with water five times in accordance with Fire and Disaster Management Agency Notification No. 19 "Standards for Washing Resistance Performance Related to Flame Retardant Performance" dated May 31, 2004. For evaluation, the afterflame time and number of flame contacts specified in JIS L-1091 were each measured three times. Table 2 shows the flame retardant performance test results of the flame retardant fabric samples treated with each flame retardant liquid. In addition, a similar test was also conducted on a flame-retardant untreated fabric made of polyester fibers that had been subjected to flame-retardant treatment.

As is clear from the results in Table 2, by applying a halogen flame retardant to flame retardant polyester fibers, which do not have any flame retardancy in non-flame retardant fabrics, Examples 1 to 6 and Comparative Example 1 It can be seen that all of 4 to 4 were provided with flame retardancy in the initial state, and had flame retardance that was acceptable as a flame retardant fiber product.

Furthermore, when comparing Examples 3 and 5 with Example 1 and Examples 4 and 5 with Example 2, it was found that the halogen-containing polymers of the present invention [Compound (35) and Compound ( 36)], when polyester fibers are flame-retardantly treated with a flame-retardant composition consisting of a flame-retardant composition containing antimony oxide, which is a flame-retardant aid, the flame-retardant property is higher than that of a halogen-containing polymer alone. I can see that it is improving.

Furthermore, in the case of flame-retardant fibers treated with the flame-retardant agent made of the halogen-containing polymer of the present invention, there is no noticeable decrease in flame-retardant performance even after washing with water, and the flame-retardant fibers can be used as flame-retardant fiber products. It can be seen that flame retardancy is maintained (Examples 1 to 6).

On the other hand, in the case of the low-molecular-weight brominated flame retardant [Compound (37)] or chlorine-based flame retardant oligomer [Compound (38)] of the comparative example, the flame retardant component was removed by washing with water, resulting in flame retardant It can be seen that a significant decrease in performance was observed (Comparative Examples 1 to 4).

Claims (7)

General formula (I) below
[In formula (I), R ¹ is a hydrogen atom or a methyl group, and L is the following general formula (II)
is a group represented by
Y is the following general formula (V)
(However, in formula (V), Z is an ether group (-O-), a carbonyl group (-COO-) or an imino group (-NH-), R ³ is a methylene group or an ethylene group, and S is represents a sulfur atom),
M ^hal _n represents a halogen-containing oligomer consisting of n halogen-containing monomer (M ^hal ) units (where n satisfies 2≦n≦20). ]
A flame retardant for fibers containing a halogen-containing polymer characterized by containing a repeating structure (A) having a halogen-containing macromonomer as a unit. The halogen-containing monomer (M ^hal ) has the general formula (VI)
[In formula (VI), R ¹ is a hydrogen atom or a methyl group, R ⁴ is a hydrocarbon group which may have a substituent, and (R ⁴ -X _r ) means that R ⁴ is r It represents a group substituted with a halogen atom X, and the halogen atom X represents a chlorine atom, a bromine atom, or an iodine atom. m satisfies 0≦m≦20, and r satisfies 1≦r≦10. ] The flame retardant for textiles according to claim 1, which is represented by: A repeating structure (A) containing a halogen-containing macromonomer represented by the general formula (I) as a monomer unit, having a polymerizable unsaturated double bond, and containing a halogen-free monomer as a monomer unit. The flame retardant for fibers according to claim 1, which is a copolymer containing as structure (B). The content of the repeating structure (A) consisting of halogen-containing monomer units is 10 to 90 % in the total of 100% by weight of the repeating structure (A) consisting of halogen-containing monomer units and the repeating structure (B) consisting of halogen-free monomer units. The flame retardant for textiles according to claim 3, which is % by weight. The flame retardant for fibers according to claim 1, having a weight average molecular weight of 1,000 to 1,000,000. The flame retardant for fibers according to claim 1 , further comprising an aqueous medium and having a liquid state. A flame retardant fiber product comprising fibers coated with the flame retardant for fibers according to any one of claims 1 to 6 .