TW201809402A - Fiber treatment agent, method for manufacturing fiber processed product, and fiber processed product - Google Patents

Abstract

The present invention provides a fiber treatment agent having both of an excellent flame retardancy and excellent rust prevention. Since the fiber processed product manufactured by the method of manufacturing the fiber processed product by using the fiber treatment agent has both excellent flame retardancy and excellent rust prevention, the fiber processed product is used as a fiber material for home appliances, electronic materials, interior materials of automobiles. The fiber treatment agent includes a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B); a rust inhibitor (C); and a flame retardant (D). The polymerizable unsaturated monomer (B) includes a (meth) acrylic acid alkyl ester unsaturated monomer (b1) and an unsaturated monomer (b2) having at least one carboxyl group selected from the group consisting of (meth) acrylic acid and itaconic acid.

Description

Fiber treatment agent, method for producing fiber processed product, and fiber processed product

The present invention relates to a fiber treatment agent capable of imparting flame retardancy and rust resistance to fibers, a method for producing a fiber processed product using the fiber treatment agent, and a fiber processed product obtained by using the method for producing the fiber processed article.

In recent years, it has been demanded for the incombustibility of fiber-processed products used for construction materials, home appliances, electronic materials, and automotive interior materials such as automobiles. Moreover, as such a fiber processed product, a fiber treatment agent containing a synthetic resin and various additives is widely used as a physical property improving agent and an adhesive. In order to obtain a flame-retardant fiber processed product as described above, a fiber treating agent which imparts flame retardancy or rust-preventing property to the fiber is expected. The development of such fiber treatment agents is progressing.

Generally, as a method of inflaming a fiber, a method of adding a flame retardant to a fiber treatment agent is mainly mentioned. As such a flame retardant, for example, red phosphorus or phosphate, antimony trioxide, aluminum hydroxide, and hydroxide are known. Inorganic flame retardant such as magnesium; halogen flame retardant such as pentabromobiphenyl, octabromobiphenyl or decabromobiphenyl; non-halogen flame retardant such as barium phosphate, triphenyl phosphate or amine sulfonic acid Agents, etc.

However, these flame retardants generally have problems in compatibility with synthetic resins in the fiber treating agent, and sometimes cause separation, precipitation, and smashing of the flame retardant component of the fiber processed product.

Further, when it is desired to use these flame retardants for the fiber treating agent containing a synthetic resin, the fiber treating agent not only imparts flame retardancy to the fiber processed product, but also various other physical properties such as strength, texture, and rust resistance. There will be no bad effects. However, in general, in order to impart flame retardancy to a fiber processed product, it is necessary to add a large amount of a flame retardant, which is a cause of hindering the physical properties of the fiber processed product.

In particular, the inorganic flame retardant lacks flame retardancy, and the fiber treatment agent must be added in a large amount. Therefore, precipitates are likely to be generated due to a difference in specific gravity from other additive components such as synthetic resins. Further, in the fiber-processed product using an inorganic flame retardant, there is a problem that the texture is also hard to be hardened.

On the other hand, a halogen-based flame retardant may have a small amount of a fiber treatment agent because of its excellent flame retardancy. From this, it was found that the influence of the physical properties of the fiber processed product containing the fiber treating agent containing the fiber processing product was small. However, when a fiber processed product such as chlorine or bromine is used, it is feared that a harmful substance called dioxin or hydrogen halide will be produced, and the countries in the EU countries have reregulated their regulations. Or how to use it.

Non-halogen flame retardant compared with halogen flame retardant Because of its excellent safety, most of the flame retardants based on phosphorus are reviewed. However, the flame retardancy of the phosphorus-based flame retardant must be lower than that of the halogen-based flame retardant and it is necessary to use a relatively large amount. Therefore, the fiber treatment agent containing a phosphorus-based flame retardant lowers the physical properties of the fiber-processed product processed using the fiber treatment agent. For example, the water-soluble phosphorus-based flame retardant has high deliquescent property and can be plasticized in appearance, which is a cause of reducing the strength and texture of the processed products. Further, the oil-soluble phosphorus-based flame retardant is also plasticized by the resin or Bleeding on the surface of the fiber treating agent, thereby not only lowering the strength and texture, but also becoming tacky in the fiber processed product using the fiber treating agent. Or the reason for swearing.

Moreover, as a method of imparting rust preventive property to a fiber, the method of adding a rust preventive agent to a fiber processing agent is mainly mentioned. For example, inorganic rust inhibitors such as nitrite, chromate, phosphate, and citrate are known; sulfonium salts of alkylsulfonic acid or benzenesulfonic acid, cerium soap, carboxylates of organic amines, and benzoate salts are known. Organic rust inhibitors.

The inorganic rust inhibitor is often discussed because it has excellent rust resistance as compared with the organic rust inhibitor. However, in general, inorganic rust inhibitors contain substances harmful to the human body, which may affect the environment. For example, although nitrite is known to exhibit high rust resistance, it is indicated to be harmful to the human body, and therefore a rust preventive agent without nitrous acid is required. Although chromate is also known to exhibit high rust resistance, it contains heavy metals, so it is harmful to the human body in the same manner as nitrite, and has drainage regulations during the treatment, and is now avoided.

Organic rust inhibitor is intended to be as described above in the inorganic rust inhibitor It is widely used because it is accused of a problem that is harmful to the human body or environmental load. As an organic rust preventive agent which exhibits high rust resistance, for example, an alkyl sulfonate or a sulfonium sulfonate, a sulfonium soap or the like is known, but in recent years, it has been pointed out that strontium salt is harmful to the human body, so that it is used for this purpose. The way is regulated in Europe and America. Various carboxylic acid esters such as an alkyl succinic acid half ester and an alkenyl succinic acid half ester exhibit insufficient rust resistance, but are not sufficient. On the other hand, it is known that benzoate exhibits rust preventive properties and is also used as an additive for preventing freezing liquids for automobile engines. Further, in general, benzoic acid salt has a slight influence on the human body, and has an advantage that it is used in food preservation materials and has a lower environmental load than an inorganic rust inhibitor. However, in general, an organic rust preventive is flammable, and when such a fiber treating agent is used, it is a cause of lowering the flame retardancy of a fiber processed product.

For example, a non-halogen flame retardant resin composition in which an unsaturated monomer having a phosphate group or a phosphite skeleton disclosed in Patent Document 1 and an acrylic unsaturated monomer and a vinyl acetate monomer are copolymerized has been proposed. However, the strength and rigidity of the processed product using the flame-retardant resin composition are not satisfactory, and the properties of the material are expected to be further improved.

Further, for example, Patent Document 2 discloses a processed product using a flame-retardant resin composition, but does not disclose rust-preventing properties. A fiber treatment agent which can obtain a processed product having both flame retardancy and rust resistance is expected.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 7-18028

[Patent Document 2] Japanese Patent No. 5669363

Accordingly, the present invention provides a fiber treating agent which can obtain a processed product having both excellent flame retardancy and rust preventive properties. Moreover, another object of the present invention is a method for producing a fiber processed product using the fiber treating agent, and a fiber processed product obtained by using the method for producing the fiber processed article.

That is, the present invention relates to the following [1] to [11].

[1] It is a fiber treatment agent containing a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust preventive agent (C), and a flame retardant (D). The polymerizable unsaturated monomer (B) is an alkyl (meth) acrylate unsaturated monomer (b1) and at least one unsaturated monomer selected from the group consisting of (meth)acrylic acid and itaconic acid ( B2) is a special fiber treatment agent.

[2] The phosphorus-containing unsaturated monomer (A) is a fiber treatment agent according to the above [1], which comprises a monomer (a1) having a phosphate group or a phosphorous acid group.

[3] The monomer (a1) having the aforementioned phosphate group or phosphorous acid group contains an acid. A fiber treating agent according to the above [2], which is a phosphorus-oxygen polyoxyalkylene glycol mono(meth)acrylate.

[4] The rust inhibitor (C) is a fiber treating agent according to any one of the above [1] to [3], which comprises an amine carboxylate or a benzoate.

[5] The flame retardant (D) is any one of the above [1] to [4] containing phosphorus. The fiber treatment agent described.

[6] The fiber treatment agent according to any one of the above [1] to [5], wherein the polymerizable unsaturated monomer (B) is 40% by mass or more based on the total monomer in the copolymer (P).

[7] The fiber treatment agent according to any one of the above [1] to [6], wherein the rust inhibitor (C) is used in an amount of 0.1 to 15% by mass based on the total fiber treatment agent.

[8] The fiber treatment agent according to any one of the above [1] to [7], wherein the flame retardant (D) is from 0.1 to 70% by mass of the total fiber treatment agent.

[9] The fiber treatment agent according to any one of the above [1] to [8], wherein the amount of the phosphorus atom in the fiber treatment agent is from 0.01 to 30% by mass.

[10] A method for producing a fiber processed product comprising the step of obtaining a fiber processed product by treating the fibrous base material with the fiber treating agent according to any one of the above [1] to [9].

[11] The amount of adhesion of the fiber treatment agent according to any one of the above [1] to [9], which is 50 to 100 parts by mass based on 100 parts by mass of the fiber base material.

The processed product treated with the fiber treating agent of the present invention has excellent flame retardancy and at the same time has excellent rust preventing properties. The fiber processed product obtained by the method for producing a fiber processed product using the fiber treating agent has both flame retardancy and rust preventive properties, and thus can be used as a material for fibers for use in home appliances, electronic materials, and automotive interior materials.

[Formation of the Invention]

The invention is described in detail below.

[Fiber treatment agent]

The fiber treating agent of the present invention contains a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust preventive (C), and a flame retardant (D).

The fiber treatment agent according to the embodiment of the present invention is excellent in both flame retardancy and rust resistance for both of the treated products, and is useful as a flame retardant treatment agent for fibers, and is applicable to various fibers.

Here, "~" in the present specification means a value equal to or greater than the value before the description of "~", and is less than the value after the description of "~".

In addition, the description of "(meth) acrylate" or the like in the present specification is equivalent to "acrylate and/or methacrylate".

(copolymer (P))

The copolymer (P) according to the present invention is a copolymer obtained by polymerizing a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B).

<Phosphorus-containing unsaturated monomer (A)>

The phosphorus-containing unsaturated monomer (A) used in the present invention is not particularly limited as long as it contains an ethylenically unsaturated bond and a phosphorus atom in the molecule.

Specific examples of the phosphorus-containing unsaturated monomer (A) include two Methyl vinyl phosphonate, diethyl vinyl phosphonate, diphenyl vinyl phosphonate, diphenyl vinyl phosphonate, dimethyl (1,2-diphenyl-vinyl) Phosphonate, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, diphenyl-p-vinylbenzylphosphine oxide, 9 ,10-Dihydro-9-oxa-10-phosphinophen-10-oxide-10-p-vinylbenzyl, acid ‧phosphoryloxyethyl (meth) acrylate, 2-propene oxime Ethyl ethyl phosphate, diphenyl-2-methyl propylene oxyethyl phosphate, (meth) acrylonitrile. Oxyethylethyl phosphate. Monoethanolamine ester, acid ‧ phosphorus oxypolyethylene glycol mono (meth) acrylate, acid ‧ phosphorus oxy polyoxypropylene glycol (meth) acrylate, and these metal salts, ammonium salts and amine salts, and the like. These compounds may be used singly or as a mixture of two or more.

[Monomer (a1) having a phosphate group or a phosphorous acid group]

As the phosphorus-containing unsaturated monomer (A), a monomer (a1) having a phosphate group or a phosphorous acid group is preferred. Examples of the monomer (a1) having the phosphate group or the phosphorous acid group include a general formula (1):

(wherein R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms; Y represents a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkyl ester group having 1 to 3 carbon atoms; and Z represents hydrogen; A compound represented by an atom, a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkyl ester group having 1 to 3 carbon atoms; n is an integer of 1 to 20), a metal salt, an ammonium salt and an amine salt of the compound. These compounds may be used singly or in combination of two or more. R ¹ , R ² , Y, and Z are each preferably hydrogen or methyl. Also, n is preferably 1 to 3.

Specific examples of the monomer (a1) having the aforementioned phosphate group or phosphorous acid group include an acid. Phosphoroxy polyoxyalkylene glycol mono (meth) acrylate. More specifically, acid ‧ phosphorus oxyethyl (meth) acrylate, 2-propenyl methoxyethyl phosphate, 2-methyl propylene methoxyethyl phosphate, acid ‧ phosphorus Polyoxyethylene glycol mono (meth) acrylate and acid ‧ phosphorus oxy polyoxypropylene glycol (meth) acrylate and the like. These compounds may be used singly or in combination of two or more. Among them, acid ‧ phosphorus oxyethyl (meth) acrylate is preferred from the viewpoint of a high phosphorus content per molecule.

The phosphorus-containing unsaturated monomer (A) is used in an amount of 20% by mass to 60% of the total monomer in the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). The range of the mass% is preferably in the range of 23 to 50% by mass, and more preferably in the range of 26% by mass to 40% by mass. When the content is 20% by mass or more, the flame retardancy of the processed product treated with the fiber treating agent is sufficient, and when it is 60% by mass or less, the polymerization is stable, and the strength of the processed product using the fiber treating agent or heat resistant yellow is obtained. There is no tendency for degeneration to decrease.

Further, the polymerization ratio of the phosphorus-containing unsaturated monomer (A) to the phosphorus-containing unsaturated monomer (A), the polymerizable unsaturated monomer (B) and the copolymer (P) is caused by (A) component ( B) The amount of phosphorus atoms in the composition and the phosphorus-containing unsaturated monomer (A) The content of the phosphorus atom calculated by the molecular weight is suitably determined to be 3 to 13% by mass. In view of the balance between the flame retardancy and the polymerization stability of the copolymer (P) and the physical properties in the processed product, it is preferred that the content of the phosphorus to be polymerized is 3 to 10% by mass. When the amount is more than 3% by mass, the flame retardancy of the copolymer (P) itself is sufficient, so that the flame retardancy of the fiber treating agent is sufficient, and when it is less than 13% by mass, the polymerization of the copolymer (P) is stable.

<Polymerizable unsaturated monomer (B)>

The polymerizable unsaturated monomer (B) used in the present invention may have an ethylenically unsaturated bond in the molecule and exhibit polymerizability, and may be copolymerized with the phosphorus-containing unsaturated monomer (A). There are no special restrictions. Further, it may be a plurality of types of monomers.

Examples of the polymerizable unsaturated monomer (B) include acrylic acid, methacrylic acid, fumaric acid, maleic acid, and these esters; (meth)acrylamide and its derivatives; styrene and Derivatives; vinyl esters; N-substituted maleimide compounds; itaconic acid, crotonic acid, phthalic acid and these esters and these metal salts, ammonium salts and the like.

Moreover, specific examples of the polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl ( Methyl) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di(meth) acrylate, methoxy ethyl (meth) acrylate , Butoxyethyl (meth) acrylate, dimethyl amino ethyl (meth) acrylate, diethyl amino ethyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (methyl) Acrylate, polytetramethylene glycol mono(meth)acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, polypropylene glycol polytetramethylene glycol mono(meth)acrylate, glycidol Base (meth) acrylate, methyl glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, ethane diol di(meth) acrylate, propane Diol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(methyl) Acrylate, trimethylolpropane tri(meth) acrylate, dimethylol tricyclodecane di(meth) acrylate, isobornyl (meth) acrylate, phenoxy polyethylene glycol (Meth) acrylate, (meth) acrylate such as pentaerythritol tetra(meth) acrylate; dimethyl fumarate, diethyl fumarate, dibutyl fumarate, di-( 2-ethyl Fumarate such as fumarate; maleic acid such as dimethyl maleate, diethyl maleate, dibutyl maleate, di-(2-ethylhexyl) maleate Ester; methacrylamide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (A (meth) acrylamide derivatives such as acrylamide; methoxy styrene, ethoxystyrene vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxybenzene Styrene derivatives such as ethylene and divinylbenzene; vinyl acetate; vinyl propionate, vinyl hexanoate, vinyl phthalate, vinyl laurate, vinyl stearate, etc.; methyl horse醯imine, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenyl mala N-substituted maleimide compounds such as imine, benzylmaleimide, naphthalene quinone, etc.; monomethyl itaconate, dimethyl itaconate, monoethyl itaconic acid Itaconate, such as ester, diethyl itaconate, monobutyl itaconate, dibutyl itaconate, etc.; croton, methyl crotonate, ethyl crotonate, butyl crotonate, etc. Acid ester; dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dihexyl phthalic acid These may be used alone or in combination of two or more kinds of phthalic acid esters such as esters.

Among the above polymerizable unsaturated monomers (B), in particular, from the viewpoint of the flame retardancy in the fiber processed product obtained by the treatment with the present fiber treating agent, the simultaneous use of the alkyl (meth)acrylate is unsaturated. It is preferred that at least one unsaturated monomer (b2) is a group of monomers (b1) and (meth)acrylic acid and itaconic acid. When the alkyl (meth) acrylate unsaturated monomer (b1) is used, the bleed resistance of the flame retardant (D) component in the fiber processed product treated with the fiber treating agent of the present invention is improved. good. When at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid is used, the rust resistance of the processed fiber product treated with the fiber treating agent of the present invention is improved. It is better.

[(A)alkyl acrylate unsaturated monomer (b1)]

The alkyl group of the (meth)acrylic acid alkyl ester unsaturated monomer (b1) is preferably an alkyl group having 1 to 5 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like, which are represented by flame retardancy. Methyl (a) Acrylate, ethyl (meth) acrylate is preferred. These can be used individually or in combination of 2 or more types.

Further, other alkyl (meth) acrylate unsaturated monomer (b1) can be further used. Specific examples include 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, and methoxy ethyl (meth) acrylate. Ester, butoxyethyl (meth) acrylate, dimethyl amino ethyl (meth) acrylate, diethyl amino ethyl (meth) acrylate, etc., these may be used alone or in combination Use after above.

[selected from at least one unsaturated monomer (b2) grouped by (meth)acrylic acid and itaconic acid]

The at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid is used to improve the flame retardancy of the fiber treating agent of the present invention. Among them, acrylic acid is preferred because it does not lose the stability of the polymerization and can increase the content of the copolymer (P).

Further, at least one unsaturated monomer (b2) selected from the group consisting of (meth)acrylic acid and itaconic acid may be used in combination, and a carboxyl group selected from the group consisting of (meth)acrylic acid and itaconic acid may be used. Unsaturated monomer. Specific examples of the unsaturated monomer having a carboxyl group selected from the group consisting of (meth)acrylic acid and itaconic acid include fumaric acid, maleic acid, crotonic acid, etc., which may be used alone or in combination. Use after above.

The polymerizable unsaturated monomer (B) is a copolymer of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) contained in a fiber treating agent. The total amount of the monomers in the above (P) is preferably 40% by mass or more, and preferably 50% by mass to 80% by mass.

When the content is 40% by mass or more, the polymerization of the fiber treatment agent of the present invention is stable, and when it is 80% by mass or less, the flame retardancy of the fiber processed product treated with the fiber treatment agent of the present invention tends to be sufficient.

For the polymerizable unsaturated monomer (B), the alkyl (meth)acrylate unsaturated monomer (b1) and at least one unsaturated monomer selected from the group consisting of (meth)acrylic acid and itaconic acid (b2) The total amount is preferably 90% by mass or more, preferably 95% by mass or more, and more preferably 100% by mass.

For the polymerizable unsaturated monomer (B), the alkyl (meth)acrylate unsaturated monomer (b1) and at least one unsaturated monomer selected from the group consisting of (meth)acrylic acid and itaconic acid (b2) The mass ratio (b1/b2) is preferably 96/4 to 4/96, preferably 79/21 to 21/79, and more preferably 75/25 to 30/70. In the range, the bleed resistance of the flame retardant (D) component in the fiber processed product treated with the fiber treating agent of the present invention tends to be improved. Moreover, the flame-retardant property or the rust-proof property of the fiber processed product processed by the fiber processing agent of this invention tends to improve.

(Manufacturing method of copolymer (P))

The copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treating agent of the present invention can be used in a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, or a block form. It is produced by a known copolymerization method such as a polymerization method. Further, it can also be produced by a continuous polymerization method or a stage polymerization method.

(rust inhibitor (C))

The rust preventive agent (C) used in the present invention is not particularly limited as long as the flame retardancy of the processed product treated with the fiber treating agent of the present invention is not significantly impaired.

Specific examples of the rust preventive agent (C) include mono- and diisopropylamine nitrite, mono- and dicyclohexylamine nitrite, triethylamine nitrite, pyridine nitrite, and aniline. Nitrite such as nitrite; various carboxylic acid esters such as alkyl succinic acid half ester and alkenyl succinic acid half ester; dicyclohexylammonium salicylate, dicyclohexylammonium cyclohexane carboxylate, cyclohexylamine a cyclocarboxylate, a dicyclohexylammonium acrylate, a cyclohexylamine acrylate, and a carboxylate of an amine such as a carbamate, a naphthenic acid salt or an octyl acid salt; an ethylmorpholine benzoate And benzoic acid salts such as monocyclohexylamine benzoate, monoethanolamine benzoate, sodium benzoate; various chromates; phosphates; citrates; sulfonates, etc., which are also regulated by environmental load and use. Or an amine carboxylate or benzoate is preferred from the viewpoint of efficient rust resistance. These compounds may be used alone or in combination of two or more.

In the fiber treatment agent of the present invention, the content of the rust inhibitor (C) is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 to 5% by mass. When the amount is less than 0.1% by mass, the rust resistance of the processed product treated with the fiber treating agent of the present invention is lowered, and when it is more than 15% by mass, the drying property of the fiber treating agent is lowered, which hinders the treatment with the fiber treating agent. The physical properties of the fiber-processed product or the tendency of the processed product of the fiber to be processed are lowered. Further, when it is in this range, the rust-preventing property of the treated product used in the fiber treating agent of the present invention is not lowered, and the following appropriate amount of flame retardant is used in combination. At the same time, the flame retardancy of the processed product is not lowered.

(flame retardant (D))

The flame retardant (D) used in the present invention is not particularly limited as long as it can be mixed in the fiber treatment agent.

Specific examples of the flame retardant (D) include bismuth phosphate, triphenyl phosphate, cresol diphenyl phosphate, tricresol phosphate, trimethylphenyl phosphate, and ginseng (t-butyl). Phenyl) phosphate, ginseng (i-propylated phenyl) phosphate, 2-ethylhexyl diphenyl phosphate, red phosphorus, 1,3-phenylene bis(diphenyl phosphate) , 1,3-phenylene bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate) and phosphorus-based flame retardants such as these metal salts; antimony trioxide, antimony tetroxide, pentoxide Inorganic flame retardants such as strontium, strontium soda, aluminum hydroxide, magnesium hydroxide; nitrogen-based flame retardants such as melamine cyanurate; halogens such as pentabromobiphenyl, octabromobiphenyl and decabromobiphenyl It is a flame retardant. Among them, from the viewpoint of low environmental load and efficient flame retardancy, it is preferred to use a flame retardant containing phosphorus. These compounds may be used alone or in combination of two or more.

In the fiber treatment agent of the present invention, the content of the flame retardant (D) is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, even more preferably 1 to 30% by mass. When the content is 0.1% by mass or more, the flame retardancy of the processed product treated with the fiber treating agent of the present invention is sufficient, and when it is 70% by mass or less, the fiber processed product obtained by treating the fiber treating agent of the present invention is used. There is also a tendency to suppress people or stickiness.

In the fiber treatment agent of the present invention, the content of the flame retardant (D) is It is preferable that the total content of the rust inhibitor (C) is 40% by mass or less. When the content is 40% by mass or less, the bleed out tends to be suppressed, and the fiber-processed product obtained by treating with the fiber treating agent of the present invention tends to suppress cockroaches or stickiness.

The content of the total phosphorus atom in the fiber treating agent of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and most preferably 0.1 to 20% by mass. When it is 0.01% by mass or more, the flame retardancy of the processed product treated by the fiber treating agent of the present invention is sufficient, and when it is 30% by mass or less, the fiber processing by the treatment with the fiber treating agent of the present invention is carried out. Among the products, there is a tendency to suppress people or stickiness.

<Other ingredients> [starting agent]

When the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is obtained by radical polymerization, the polymerization is carried out in the presence of a starter. The radical polymerization initiator used in the polymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used peroxide or azo compound can be used. For example, as such a specific example, sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzammonium peroxide, dicumyl peroxide, diisopropyl peroxide, and di- T-butyl peroxide, t-butyl peroxybenzoate, t-hexyl peroxybenzoate, t-butyl peroxy-2-ethylhexanoate, t-hexyl peroxy- 2-ethylhexanoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-double (t -butyl Peroxy)hexyl-3,3-isopropylhydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetam peroxide, bis(4-t-butylcyclohexyl) Peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1- A bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarboxamide or the like may be used, and a suitable reducing agent may be used in the compounding reaction. The amount of the initiator to be used is preferably 0.01 to 20 parts by mass based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) in the copolymer (P). 0.1 to 10 parts by mass is more preferable.

[Surfactant]

When the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treating agent of the present invention is produced by an emulsion polymerization method, the surfactant is used. Exist in the presence. As the surfactant, a commercially available negative ionic surfactant, a nonionic surfactant, a cationic surfactant, and a copolymerizable surfactant can be used. Further, these surfactants may be used singly or in combination of two or more kinds. The amount of the interface active agent to be used is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, based on the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). Further, from the viewpoint of polymerization stability, a water-soluble polymer such as a water-soluble (meth)acrylic resin, a water-soluble (meth)acrylate resin or a polyoxyethylene alkyl ether can be used as a protective colloid. Further, these protective colloids can be used regardless of the degree of saponification, average degree of polymerization, and denaturation, but the average degree of polymerization is determined by the viewpoint of polymerization stability and product viscosity. 200 to 2,400 is preferred, and the degree of saponification is preferably from 80% to 100% from the viewpoint of polymerization stability. In addition, the amount of the protective colloid used is not particularly limited, but in terms of polymerization stability, the total amount of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) is 100 parts by mass. It is preferably 1 to 100 parts by mass, more preferably 10 to 30 parts by mass.

[Other additives]

In the fiber treatment agent of the present invention, a filler, a preservative, a colorant, an antifoaming agent, a foaming agent, a dispersing agent, an emulsifier, a fluidity adjusting agent, and a plasticity may be added without impairing the effects of the present invention. Additives such as agents, pH adjusters, and various oils.

[Other added resin]

Further, in the fiber treatment agent of the present invention, various resin compositions such as other resin emulsions or solution resins, epoxy resins, and urethane resins may be contained as a binder without impairing the effects of the present invention.

[solvent]

The solvent used in the production of the fiber treating agent of the present invention may be water or an organic solvent generally used. Examples of such a specific example include alcohols such as methanol, ethanol, propanol, isopropanol, and butanol; and ethyl acetate, isopropyl acetate, cellosolve acetate, and butyl cellosolve acetate. Diethylene glycol monoalkyl ether acetates such as diol monoalkyl ether acetates, diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, Propylene glycol Acetate such as alkyl ether acetate or dipropylene glycol monoalkyl ether acetate; ethylene glycol dialkyl ether, methyl carbitol, ethyl carbitol, butyl carbitol, etc. Diol dialkyl ethers, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, methyl ethers, ethyl ethers, 1,4-dioxane, tetrahydrofuran Ethers; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane; petroleum ether, stone brain Petroleum solvent such as oil, hydrogenated naphtha, solvent naphtha; lactate such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide; N-methylpyrrolidone. These water and organic solvents may be used alone or in combination of two or more.

[fiber]

In the present specification, the fiber is a nonwoven fabric, a woven fabric, a knitted fabric or the like which contains various fibers and is formed from these blended products. Moreover, examples of the fiber include wood wool, hemp, crepe, wool, collagen fibers, acrylic fibers, cellulose fibers, polyimine fibers, polyamide fibers, and rayon fibers. Nylon fiber, vinyl fiber, polyester fiber, polypropylene fiber, polyvinyl chloride fiber, polyethylene fiber, polymethylphenylene isophthalamide fiber, aryl fluorene fiber, polyarylate fiber, polytetrafluoroethylene Ethyl fibers, polybenzimidazole fibers, polyetheretherketone fibers, polyphenylene sulfide fibers, and non-woven fabrics, woven fabrics, knitted fabrics and the like formed from these blended products.

[Manufacturing method of fiber processed products]

Manufactured as a fiber (substrate) by the fiber treating agent of the present invention The method of the fiber processed product is not particularly limited, and various known methods can be employed. For example, a method of applying the fiber treating agent of the present invention to a fiber for treatment may be a direct coating method, a spray coating method, a roll coater method, a slot coater method, a knife coating method, a printing method, or a cylinder transfer method. Law and so on. Further, for example, a method of immersing the fiber in the fiber treatment agent of the present invention and treating it may be a horizontal roller method, a metal roll method, a wire mesh transfer method, a table method, or the like.

For example, a processing method when the fiber of the nonwoven fabric is treated by the fiber treating agent of the present invention may, for example, be a spray coating method, a printing method, a roll transfer method, a horizontal roll method, a metal roll method, a wire mesh transfer method, or the like. Form methods, etc. Moreover, for example, a processing method when the fiber of the woven fabric is treated by the fiber treating agent of the present invention may, for example, be a direct coating method, a spray coating method, a roll coater method, a slot coater method, a knife coating method, or the like. Further, when the fibers are formed into a sheet shape and then formed into a web, and the web is further subjected to or interlaced to form a web, the fiber treatment may be performed on the fibers before the weaving, or the fibers may be borrowed. It is carried out by meshing by various methods. The fiber woven meshing method can be carried out by various known methods without particular limitation, and examples thereof include an air laying method and the like.

The amount of the fiber treatment agent used for the various fiber base materials depends on the flame retardancy of the base material itself, but the amount of resin adhered (the amount of adhesion after drying the adhered fiber treatment agent) is 10 to 200 parts by mass per 100 parts by mass. The amount is preferably from 30 to 150 parts by mass per 100 parts by mass, more preferably from 50 to 100 parts by mass per 100 parts by mass. When 10 parts by mass or more of 100 parts by mass or more, fiber processing using the fiber treating agent of the present invention The flame retardancy and the rust preventive property of the product are sufficient. When the amount is more than 200 parts by mass per 100 parts by mass, the strength and texture of the processed fiber obtained by using the fiber treating agent of the present invention tend to be suppressed. . The drying can be carried out by air drying, drying by drying under reduced pressure, and drying by pressure. Also, heating can be performed. When heating at the time of drying, the temperature is a temperature at which heating is performed during drying, and the range is preferably 50 to 250 ° C, preferably 80 to 190 ° C. If the heating temperature is too low, it may be related to the drying time, which may cause insufficient drying. If the heating temperature is too high, it may cause deterioration.

[Fiber processed products]

The fiber processed product of the present invention can be obtained by using the method for producing a fiber processed product of the present invention. The amount of the resin to be adhered (the amount of the fiber treatment agent after drying) is preferably 50 to 100 parts by mass per 100 parts by mass of the fiber (base material), and is preferably 10 to 200 parts by mass per 100 parts by mass. The amount is preferably from 30 to 150 parts by mass per 100 parts by mass, more preferably from 50 to 100 parts by mass per 100 parts by mass. When the amount is 10 parts by mass or more, the flame-retardant property and the rust-preventing property of the fiber-processed product of the present invention are sufficient, and when it is 200 parts by mass/100 parts by mass or less, the strength and texture of the fiber-processed product of the present invention are Reduce the tendency to be suppressed.

The fiber processed product of the present invention is suitable for use in various fields because of its excellent flame retardancy and rust resistance. For example, the fiber processed product of the present invention can be suitably used for a cushioning material for electronic materials, a cushioning material for home appliances, and an automobile interior cushioning material.

[Examples]

The present invention will be further illustrated by the following examples and comparative examples, but the present invention is not limited by the examples and comparative examples.

(Example 1)

150 g of ion-exchanged water was placed in a 1 L five-neck separable flask, and heated to 80 ° C while stirring. Acidic polyoxyethylene glycol monomethacrylate (light ester P-1M manufactured by Kyoei Chemical Co., Ltd., phosphorus content 15% by mass) 60 g, methyl methacrylate 36 g, ethyl acrylate 36 g, 18 g of acrylic acid, 1.5 g of dodecylbenzenesulfonic acid soda, 7.5 g of polyoxyethylene alkyl ether, and 150 g of ion-exchanged water were uniformly emulsified. When 0.2 g of potassium persulfate was added to the separable flask, the start of the reaction was started when the dropwise addition of the monomer emulsion was started. The monomer emulsion was added to the separable flask over 4 hours while 30 g of a 3% potassium persulfate aqueous solution was also added over 4 hours. After the addition of the monomer emulsion was completed, the mixture was stirred at 80 ° C for 2 hours to complete the reaction. The separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system.

Then, while stirring, 20 g of a flame retardant ammonium polyphosphate (FCP-770, manufactured by Sugi Co., Ltd., 24% phosphorus content) diluted with 20 g of ion-exchanged water and diluted with 10 g of ion-exchanged water was added. The rust agent carboxybenzotriazole (CBT-1 manufactured by Chengbei Chemical Industry Co., Ltd.) was 10 g, and 10 g of ion-exchanged water was added. After the addition of the flame retardant and the rust preventive agent was completed, the mixture was stirred for 1 hour to prepare the fiber treating agent 1. Its composition is shown in Table 1.

Using the obtained fiber treatment agent 1, a fiber processed product was produced by the method described later. The physical property evaluation of the obtained fiber processed product was carried out by the evaluation method described later. The evaluation results are shown in Table 4.

(Examples 2 to 12)

Except for the compositions shown in Tables 1 and 2, the same procedure as in Example 1 was carried out to prepare the fiber treating agents 2 to 12.

Further, the details of each component in Tables 1 and 2 are as follows.

. Diphenyl-2-methylpropenyloxyethyl phosphate: MR-260 manufactured by Da Ba Chemical Industry Co., Ltd., phosphorus content 8%

. 1-[N,N-bis(2-ethylhexyl)aminomethyl]benzotriazole: BT-LX manufactured by Chengbei Chemical Industry Co., Ltd.

. Triphenyl phosphate: TPP made by Da Ba Chemical Industry Co., Ltd., phosphorus content 10%

. Polyvinyl alcohol: PVA205 manufactured by Kuraray Co., Ltd. (saponification degree: 86.5 to 89.0%, average polymerization degree: 500)

Using the obtained fiber treatment agents 2 to 12, a fiber processed product was produced by the method described later. The physical properties of the obtained fiber processed product were evaluated by the evaluation method described later. The evaluation results are shown in Table 4.

(Comparative examples 1 to 6)

In addition to the composition shown in Table 3, the same procedure as in Example 1 was carried out to prepare fiber treatment agents 13 to 18.

Using the obtained fiber treatment agents 13 to 18, it is produced by the method described later. Fiber processed products. The physical property evaluation of the obtained fiber processed product was carried out by the evaluation method described later. The evaluation results are shown in Table 5.

(Production and evaluation methods of fiber processed products)

Using the fiber treating agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6, a fiber processed product was produced. The physical properties of the obtained fiber processed product were evaluated. The production and evaluation of the fiber processed product were carried out according to the following methods.

<Substrate>

The fibrous base materials in the examples and comparative examples of the present invention are shown below.

(1) fiber

Polyester-cellulose non-woven fabric

(2) basis weight 35g/m ²

(3) Thickness 200μm

<Production of processed products>

The fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were each ion-exchanged water, and the solid content was diluted to 15% by mass, and then the substrate fibers were immersed in the fiber treatment agent. Thereafter, the base fiber impregnated with the fiber treatment agent was extruded by two rolls and dried in a hot air dryer at 130 ° C for 10 minutes. The amount of the fiber treating agent adhered is 40 to 50% by mass based on the weight of the fiber.

<Evaluation method of solid content>

Pre-fine scales are sampled in a clean aluminum dish (height of about 17mm, caliber of about 40mm). After using a direct-reading scale with a sensitivity of 0.5mg or less, the internal temperature is adjusted in a dryer of 105°C±2°C. hour. After the dried sample was cooled to room temperature in a desiccator, the scale was weighed by the same direct-reading scale, and the solid content was calculated by the following formula.

Solid content (%) = sample weight after drying (g) / original sample weight (g) × 100

<Evaluation method of the content of phosphorus atoms>

Any method such as colorimetric quantification or ICP luminescence analysis can be used. For example, the content of the phosphorus atom can be determined by elemental analysis.

<Evaluation of fiber processed products>

The flammability, rust resistance, and bleed out of the fiber processed product were evaluated.

(1) Flame retardancy

After the fiber processed product was produced, the test piece was allowed to stand at 23 ° C and 50% RH for 12 hours or more, and subjected to a burning test according to the UL-94 vertical burning test (V-0, V-1, V-2 specifications). . The size of the test piece was 127 mm in length and 12.7 mm in width. For each of the five test pieces, the flame was ignited twice, and the total of the test pieces was performed 10 times, and the average number of seconds and the maximum number of seconds for extinguishing the flame time were measured.

UL-94 vertical flammability test (V)

V-0: The total burning time of the first and second ignition flames of the five test pieces is within 50 seconds, and the maximum burning time is within 10 seconds, and no material is dropped due to combustion.

V-1: The total burning time of the first and second ignition flames of the five test pieces was within 250 seconds, and the maximum burning time was within 30 seconds, and no material was dropped due to combustion.

V-2: The total burning time of the first and second ignition flames of the five test pieces was within 250 seconds, and the maximum burning time was within 30 seconds.

(2) rust resistance

After the processed product was produced, the test piece which was allowed to stand at 23 ° C and 50% RH for 12 hours or more was cut into a vertical shape: 50 mm, horizontal: 70 mm, and adhered to brass (vertical: 120 mm, horizontal: 30 mm, thickness: The main surface of 0.1 mm) was allowed to stand at 60 ° C and 95% RH for 14 days to confirm the presence or absence of rust on the brass surface. The evaluation results in Tables 4 and 5 are as follows.

There is rust: ×

No rust: ○

(3) Exudation

After the production of the processed product, the test piece which was allowed to stand at 23 ° C and 50% RH for 12 hours or more was cut into a vertical shape: 50 mm, horizontal: 70 mm, and a filter paper (vertical: 100 mm, horizontal: 60 mm, No. 2, Toyo The paper was placed at 60 ° C and 95% RH for 5 days, and it was confirmed whether or not the surface of the processed product was oozing out.

For Tables 4 and 5, the evaluation results are as follows.

Exudation: ×

No oozing: ○

As a result of the results of Table 4, the fiber processed product treated by the fiber treating agent (Examples 1 to 12) of the present invention was excellent in both flame retardancy and rust resistance. It is also known that the bleed is also sufficiently suppressed.

On the other hand, as shown in Table 5, when the fiber treatment agent containing no flame retardant (D) was used (Comparative Example 1), the flame retardancy was not sufficient. When it was found that a fiber treatment agent containing no phosphorus-containing unsaturated monomer (A) and adding the flame retardant (D) to the fiber treatment agent had a fiber amount of 2.6% (Comparative Example 2), at 60 ° C and 95 Significant exudation was caused under the conditions of %RH. It is known that when a fiber treatment agent containing no phosphorus-containing unsaturated monomer (A) and adding flame retardant (D) to the fiber treatment agent has a fiber amount of 1.4% (Comparative Example 3), the flame retardancy is insufficient. When the fiber treatment agent containing no rust inhibitor (C) was used (Comparative Example 4), the rust resistance was not sufficient under the conditions of 60 ° C and 95% RH. It is known that when a fiber treatment agent containing no unsaturated monomer (b2) selected from at least one carboxyl group grouped of (meth)acrylic acid and itaconic acid is used as the component of the polymerizable unsaturated monomer (B) ( Comparative Example 5) significantly caused exudation.

It is known that the use of alkyl (meth) acrylate unsaturated monomer is not contained. (b1) When the fiber treatment agent as the polymerizable unsaturated monomer (B) component (Comparative Example 6), the rust preventive property was not sufficient.

[Industrial availability]

The fiber treating agent of the present invention is characterized in that the processed fiber processed product has excellent flame retardancy or excellent rust resistance under high humidity conditions, and is particularly suitable for fiber treatment. Moreover, the method for producing a fiber processed product using the fiber treating agent of the present invention can produce various fiber processed products having excellent flame retardancy and rust preventing property, and can be produced by using the method for producing the fiber processed product. A fiber processed product having excellent flame retardancy and rust resistance. By using the fiber processed product, a cushioning material for an electronic material having excellent flame retardancy and rust resistance, a cushioning material for a home appliance, an automobile interior cushioning material, and the like can be produced.

Claims (11)

A fiber treating agent which is a fiber treated with a copolymer (P) containing a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B), a rust inhibitor (C) and a flame retardant (D) The polymerizable unsaturated monomer (B) is characterized in that it contains an alkyl (meth)acrylate unsaturated monomer (b1) and is at least selected from the group consisting of (meth)acrylic acid and itaconic acid. An unsaturated monomer (b2). The fiber treating agent of claim 1, wherein the phosphorus-containing unsaturated monomer (A) is a monomer (a1) having a phosphate group or a phosphorous acid group. The fiber treating agent of claim 2, wherein the monomer (a1) having the aforementioned phosphate group or phosphite group contains an acid. Phosphoroxy polyoxyalkylene glycol mono (meth) acrylate. The fiber treating agent according to any one of claims 1 to 3, wherein the rust preventive agent (C) is an amine-containing carboxylate or benzoate. The fiber treating agent according to any one of claims 1 to 4, wherein the flame retardant (D) is phosphorus. The fiber treating agent according to any one of claims 1 to 5, wherein the all-monomer in the copolymer (P) contains 40% by mass or more of the polymerizable unsaturated monomer (B). The fiber treatment agent according to any one of claims 1 to 6, wherein the total fiber treatment agent contains 0.1 to 15% by mass of the rust inhibitor (C). The fiber treating agent according to any one of claims 1 to 7, wherein the total fiber treating agent contains the flame retardant (D) in an amount of 0.1 to 70% by mass. The fiber treating agent according to any one of claims 1 to 8, wherein the amount of the phosphorus atom in the fiber treating agent is 0.01 to 30% by mass. A method for producing a fiber processed product, comprising the step of treating a fibrous base material using the fiber treating agent according to any one of claims 1 to 9 to obtain a fiber processed product. A fiber-processed product, which is characterized in that the amount of the fiber treatment agent according to any one of claims 1 to 9 after drying is 50 to 100 parts by mass based on 100 parts by weight of the fiber base material.