WO2017183535A1

WO2017183535A1 - Fiber treatment agent, method for producing processed fiber article, and processed fiber article

Info

Publication number: WO2017183535A1
Application number: PCT/JP2017/014965
Authority: WO
Inventors: 勇汰川原; 一成深瀬; 康宏中川
Original assignee: 昭和電工株式会社
Priority date: 2016-04-18
Filing date: 2017-04-12
Publication date: 2017-10-26
Also published as: CN108603332A; JP7012007B2; TWI724154B; JPWO2017183535A1; TW201809402A

Abstract

The present invention provides a fiber treatment agent that has excellent flame resistance and also has excellent rust resistance. A processed fiber article obtained by a method for producing a processed fiber article using this fiber treatment agent has both excellent flame resistance and excellent rust resistance, and is therefore suitable as a fiber material for use in home appliances, electronic materials, and automotive interior materials. This fiber treatment agent comprises a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomers (B), and a rust inhibitor (C) and flame retardant (D). The polymerizable unsaturated monomers (B) comprise a (meth)acrylic acid alkyl ester unsaturated monomer (b1) and at least one type of unsaturated monomer (b2) having a 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 prevention to a fiber, a method for producing a fiber processed product using the fiber treatment agent, and a fiber obtained using the method for producing the fiber processed product Regarding processed products.
This application claims priority based on Japanese Patent Application No. 2016-082714 filed in Japan on April 18, 2016, the contents of which are incorporated herein by reference.

In recent years, there has been a demand for flame-retarded fiber processed products used in building materials, home appliances, electronic materials, vehicle interior materials such as automobiles, and the like. Moreover, the fiber processing agent containing a synthetic resin and various additives is widely used for such a textile processed product as a physical property improvement agent and an adhesive agent. In order to obtain the flame-retardant fiber processed product as described above, a fiber treatment agent that imparts flame retardancy and rust resistance to the fiber is required. Development of such fiber treatment agents is underway.

Generally, as a method of making a fiber flame retardant, a method of adding a flame retardant to a fiber treatment agent is mainly mentioned. Examples of such flame retardants include inorganic flame retardants such as red phosphorus, phosphates, antimony trioxide, aluminum hydroxide, and magnesium hydroxide; halogen flame retardants such as pentabromobiphenyl, octabromobiphenyl, and decabromobiphenyl. Flame retardants: Non-halogen flame retardants such as guanidine phosphate, triphenyl phosphate and sulfamic acid are well known.

However, since these flame retardants generally have a problem in compatibility with the synthetic resin in the fiber treatment agent, the flame retardant component may cause separation, sedimentation and choking in the fiber processed product.
Furthermore, when these flame retardants are used in a fiber treatment agent containing a synthetic resin, such fiber treatment agents not only impart flame retardancy to fiber processed products, but also strength, texture, rust prevention, etc. It is required not to adversely affect other physical properties of the processed fiber product. However, in general, it is necessary to add a large amount of a flame retardant in order to impart flame retardancy to a fiber processed product, which is a cause of hindering physical properties of the fiber processed product.

In particular, inorganic flame retardants have poor flame retardancy and need to be added in large amounts to the fiber treatment agent, so sedimentation is likely to occur due to the difference in specific gravity with other additive components such as synthetic resins. In addition, the fiber processed product using the inorganic flame retardant is likely to have a problem that the texture becomes hard.

On the other hand, since halogen-based flame retardants have excellent flame retardancy, they can be added to the fiber treatment agent in a small amount. For this reason, there is little influence on the physical properties of the fiber processed product processed using the fiber processing agent containing these. However, since it contains halogen elements such as chlorine and bromine, incineration of textile processed products using these elements may generate harmful substances such as dioxins and hydrogen halides. Regulations and use are being reviewed in each country.

Since non-halogen flame retardants are superior to halogen flame retardants, many flame retardants including phosphorus-based flame retardants have been studied. However, the flame retardant performance of phosphorus flame retardants is lower than that of halogen flame retardants and must be used in relatively large amounts. Therefore, the fiber treatment agent containing a phosphorus flame retardant reduces the physical properties of a fiber processed product processed using the fiber treatment agent. For example, water-soluble phosphorus-based flame retardants have high deliquescence and apparently plasticize the resin, which causes a decrease in strength and texture of fiber processed products using them. Oil-soluble phosphorus-based flame retardants not only reduce strength and texture by plasticizing the resin and bleeding on the surface of the fiber treatment agent, but they also provide stickiness and choking with processed fiber products using the fiber treatment agent. It is a cause to cause.

Also, as a method of imparting rust prevention to the fiber, a method of adding a rust inhibitor to the fiber treatment agent is mainly mentioned. For example, inorganic rust preventives such as nitrite, chromate, phosphate, silicate; alkyl sulfonic acid or barium salt of benzene sulfonic acid, barium soap, organic amine carboxylate, benzoate, etc. Organic rust inhibitors are well known.

Since inorganic rust preventives are excellent in rust prevention compared to organic rust preventives, many studies have been made. However, in general, inorganic rust inhibitors contain substances harmful to the human body, and there are concerns about the impact on the environment. For example, nitrite is known to exhibit high rust prevention properties, but has been pointed out to be harmful to the human body, and nitrite-free rust preventive agents are required. Chromates are also known to exhibit high anti-rust properties, but contain heavy metals and, like nitrites, are harmful to the human body and have restrictions on drainage in the treatment process. Its use is avoided.

Organic rust preventives are widely used to solve problems such as harmfulness to human bodies and environmental burdens as pointed out in the inorganic rust preventives. As organic rust preventives exhibiting high rust preventive properties, for example, barium salts of alkyl sulfonic acid or benzene sulfonic acid, barium soap, etc. are known, but in recent years, the harmfulness of barium salts to the human body has been pointed out. European and American regulations on use are in place. Various carboxylic acid esters such as alkyl succinic acid half esters and alkenyl succinic acid half esters exhibit a certain level of rust prevention, but are not sufficient. On the other hand, benzoates are known to exhibit rust prevention properties and are also used as additives for antifreeze coolants for automobile engines. In addition, benzoate generally has a slight influence on the human body and has an advantage that it has a lower environmental impact than inorganic rust preventives, such as being used as a food preservative. However, organic rust preventives are generally flammable, and fiber treatment agents using these are a cause of reducing the flame retardancy of processed textile products.

For example, a non-halogen obtained by copolymerizing an unsaturated monomer having a phosphate group or a phosphite group skeleton, an acrylic acid unsaturated monomer, and a vinyl acetate monomer disclosed in Patent Document 1 Although a flame retardant resin composition has been proposed, processed products using the flame retardant resin composition do not satisfy strength and stiffness, and further improvements in physical properties have been desired.

For example, Patent Document 2 discloses a processed product using a flame retardant resin composition, but does not disclose rust prevention. There has been a demand for a fiber treatment agent that can provide a processed product having both flame retardancy and rust prevention.

JP-A-7-18028 Japanese Patent No. 5669363

Therefore, the present invention is to provide a fiber treatment agent from which a processed product excellent in both flame retardancy and rust prevention can be obtained. Another object of the present invention is to provide a method for producing a fiber processed article using the fiber treating agent and a fiber processed article obtained by using the method for producing the fiber processed article.

That is, the present invention relates to the following [1] to [11].
[1] 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) is a (meth) acrylic acid alkyl ester unsaturated monomer (b1), (meth) acrylic acid, and itaconic acid. A fiber treatment agent comprising: at least one unsaturated monomer (b2) selected.
[2] The fiber treatment agent according to [1], wherein the phosphorus-containing unsaturated monomer (A) includes a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
[3] The fiber treatment agent according to [2], wherein the monomer (a1) having a phosphoric acid group or a phosphorous acid group contains an acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate.
[4] The fiber treatment agent according to any one of the above [1] to [3], wherein the rust inhibitor (C) comprises an amine carboxylate or benzoate.
[5] The fiber treatment agent according to any one of [1] to [4], wherein the flame retardant (D) contains phosphorus.
[6] The above-mentioned [1] to [5], wherein the polymerizable unsaturated monomer (B) is contained in an amount of 40% by mass or more based on the total monomers in the copolymer (P). Fiber treatment agent.
[7] The fiber treatment agent according to any one of [1] to [6], wherein the rust inhibitor (C) is contained 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 [1] to [7], wherein the flame retardant (D) is contained in an amount of 0.1 to 70% by mass with respect to the total fiber treatment agent.
[9] The fiber treatment agent according to any one of the above [1] to [8], wherein the amount of phosphorus atom in the fiber treatment agent is 0.01 to 30% by mass.
[10] A method for producing a processed fiber product, comprising a step of treating a fiber substrate with the fiber treatment agent according to any one of [1] to [9] to obtain a processed fiber product.
[11] A processed fiber product, wherein the amount of the fiber treatment agent according to any one of [1] to [9] after drying is 50 to 100 parts by mass with respect to 100 parts by mass of the fiber substrate.

In the fiber treatment agent of the present invention, the processed product has excellent flame retardancy and is excellent in rust prevention. The fiber processed product obtained by the method for manufacturing a fiber processed product using the fiber treating agent is excellent in both flame retardancy and rust resistance, and is therefore suitable as a fiber material for use in home appliances, electronic materials, and automotive interior materials. is there.

Hereinafter, the present invention will be described in detail.
[Fiber treatment agent]

The fiber treatment agent of the present invention comprises 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 fiber treatment agent according to the present embodiment is excellent in both flame retardancy and rust prevention properties for the processed product, is useful as a flame retardant treatment for fibers, and can be suitably used for various fibers. .
Here, “to” in this specification means a value not less than the value before the description of “to” and not more than the value after the description of “to”.

In addition, the description of “(meth) acrylate” and the like in this specification is synonymous with “acrylate and / or methacrylate” and the like.

(Copolymer (P))
The copolymer (P) according to the present invention is a copolymer obtained by polymerizing the phosphorus-containing unsaturated monomer (A) and the 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 dimethyl vinyl phosphonate, diethyl vinyl phosphonate, diphenyl vinyl phosphonate, diphenyl vinyl phosphonate, dimethyl (1,2-diphenyl-ethenyl) phosphonate, dimethyl -P-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, diphenyl-p-vinylbenzylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-p- Vinyl benzyl, acid phosphooxyethyl (meth) acrylate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, (meth) acryloyl oxyethyl acid phosphate Ethanolamine salt, may be mentioned Acid phosphoxypolyoxyethylene glycol mono (meth) acrylate and acid-phosphoxy polyoxypropylene glycol (meth) acrylate, arrangement these metal salts, ammonium salts and amine salts. These compounds can be used alone or as a mixture of two or more.

[Monomer (a1) having phosphoric acid group or phosphorous acid group]
As said phosphorus containing unsaturated monomer (A), the monomer (a1) which has a phosphoric acid group or a phosphorous acid group is preferable. Examples of the monomer (a1) having a phosphoric acid group or a phosphorous acid group include, for example, the 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 group having 1 to 3 carbon atoms) Z represents a hydrogen 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), In addition, metal salts, ammonium salts, amine salts and the like of this compound can be mentioned. These compounds can be used alone or as a mixture of two or more. R ¹ , R ² , Y, and Z are each preferably hydrogen or a methyl group. N is preferably 1 to 3.

Specific examples of the monomer (a1) having a phosphoric acid group or a phosphorous acid group include acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate. More specifically, acid phosphooxyethyl (meth) acrylate, 2-acryloyloxyethyl acid phosphate, 2-methacryloxyethyl acid phosphate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and acid phospho An oxypolyoxypropylene glycol (meth) acrylate etc. can be mentioned. These compounds can be used alone or as a mixture of two or more. Of these, acid phosphooxyethyl (meth) acrylate is preferred because of its high phosphorus content per molecule.

The phosphorus-containing unsaturated monomer (A) is based on the total monomers in the copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). It is preferably used in the range of 20% by mass to 60% by mass, more preferably in the range of 23-50% by mass, and further preferably in the range of 26% by mass to 40% by mass. The flame retardancy of the processed product treated with the present fiber treatment agent is sufficient if it is 20% by mass or more, and the polymerization is stable if it is 60% by mass or less, the strength of the processed product using the present fiber treatment agent and There is a tendency that heat yellowing does not decrease.

In addition, the polymerization rate of the phosphorus-containing unsaturated monomer (A) is as follows in the phosphorus-containing unsaturated monomer (A), the polymerizable unsaturated monomer (B), and the copolymer (P): In the components A) and (B), the phosphorus atom content calculated from the atomic weight of phosphorus and the molecular weight of the phosphorus-containing unsaturated monomer (A) is appropriately determined to be 3 to 13% by mass. Good. In consideration of the balance between imparting flame retardancy, polymerization stability of the copolymer (P), and expression of physical properties in the processed product, the polymerization is preferably performed so that the phosphorus content is 3 to 10% by mass. If it is more than 3% by mass, the flame retardancy of the copolymer (P) itself is sufficient, so that the flame retardancy as a fiber treatment agent is sufficient, and if it is less than 13% by mass, the copolymer (P) is polymerized. Stabilize.

<Polymerizable unsaturated monomer (B)>
The polymerizable unsaturated monomer (B) used in the present invention has an ethylenically unsaturated bond in the molecule, expresses polymerizability, and is copolymerized with the phosphorus-containing unsaturated monomer (A). If it does, it will not be restrict | limited in particular. A plurality of types of monomers may also be used.

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

Specific examples of the polymerizable unsaturated monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate , Hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol (Meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene glycol polytetramethylene glycol mono (meth) acrylate, polypropylene glycol polytetramethylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meta) ) Acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, ethanediol di (meth) acrylate, propanediol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, diethylene glycol di ( (Meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylo (Meth) acrylic esters such as tricyclodecane di (meth) acrylate, isobornyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate; dimethyl fumarate, diethyl fumarate, dibutyl fuma Rate, di- (2-ethylhexyl) fumarate and other fumaric acid esters; dimethyl maleate, diethyl maleate, dibutyl maleate, maleic acid esters such as di- (2-ethylhexyl) maleate; methacrylamide; N-methyl (meta) ) (Meth) acrylamide derivatives such as acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide; methoxystyrene, ethoxystyrene vinyl Styrene derivatives such as perfume acid, vinyl benzoate methyl, vinyl benzyl acetate, hydroxystyrene, divinylbenzene; vinyl acetate; vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate; N-substituted maleimide compounds such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monobutyl itaconate, dibutyl Itaconic acid esters such as itaconate; Crotonic acid esters such as methyl crotonate, ethyl crotonate and butyl crotonate; Dimethylphthalate , Diethyl phthalate, dipropyl phthalate, dibutyl phthalate, phthalic acid esters such as dihexyl phthalate; and the like. These may be used alone or in combination of two or more.

Among the polymerizable unsaturated monomers (B), in particular, (meth) acrylic acid alkyl ester unsaturated monomer from the viewpoint of the expression of flame retardancy in a fiber processed product obtained by treating with the present fiber treating agent. The body (b1) and at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid are preferably used together. When the (meth) acrylic acid alkyl ester unsaturated monomer (b1) is used, the bleeding resistance of the flame retardant (D) component in the processed fiber product treated with the fiber treatment agent of the present invention is improved. ,preferable. When at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid is used, the rust prevention property of the fiber processed product treated with the fiber treating agent of the present invention is improved. It is preferable in terms of

[(Meth) acrylic acid alkyl ester unsaturated monomer (b1)]
The alkyl group of the (meth) acrylic acid alkyl ester unsaturated monomer (b1) is preferably an alkyl having 1 to 5 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and the like. Among them, methyl (meth) acrylate, ethyl ( (Meth) acrylate is preferred. These can be used alone or in combination of two or more.

Further, another (meth) acrylic acid alkyl ester unsaturated monomer (b1) may be used. Specific examples include 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylamino Ethyl (meth) acrylate etc. are mentioned, These can be used individually or in combination of 2 or more types.

[At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid]
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 treatment agent of the present invention. Among these, acrylic acid is preferable in that the stability of the polymerization is not impaired and the content in the copolymer (P) can be increased.
Further, in combination with at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid, a carboxyl selected from other than the group consisting of (meth) acrylic acid and itaconic acid An unsaturated monomer having a group may be used. Specific examples of the unsaturated monomer having a carboxyl group selected from those other than the group consisting of (meth) acrylic acid and itaconic acid include fumaric acid, maleic acid, crotonic acid, and the like. The above can be used in combination.

The polymerizable unsaturated monomer (B) is contained in a copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent. The total amount is preferably 40% by mass or more, more preferably 50% by mass to 80% by mass.
When it is 40% by mass or more, polymerization of the fiber treatment agent of the present invention is stable, and when it is 80% by mass or less, the flame-treated product processed with the fiber treatment agent of the present invention has sufficient flame retardancy. There is a tendency.
In the polymerizable unsaturated monomer (B), at least one unsaturated monomer selected from the group consisting of (meth) acrylic acid alkyl ester unsaturated monomer (b1) and (meth) acrylic acid and itaconic acid 90 mass% or more is preferable, as for the total amount of a body (b2), More preferably, it is 95 mass% or more, More preferably, it is 100 mass%.
In the polymerizable unsaturated monomer (B), at least one unsaturated monomer selected from the group consisting of (meth) acrylic acid alkyl ester unsaturated monomer (b1) and (meth) acrylic acid and itaconic acid The mass ratio (b1 / b2) to the body (b2) is preferably, for example, 96/4 to 4/96, more preferably 79/21 to 21/79, and 75/25 to 30 / More preferably, it is 70. Within the range, the bleeding resistance of the flame retardant (D) component tends to be improved in the fiber processed product treated with the fiber treating agent of the present invention. Moreover, it exists in the tendency for the flame retardance or rust prevention property of the fiber processed goods processed using the fiber processing agent of this invention to improve.

(Production method of copolymer (P))
The copolymer (P) of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) contained in the fiber treatment agent of the present invention is a suspension polymerization method, an emulsion polymerization method, It can manufacture using well-known copolymerization methods, such as a solution polymerization method and a block polymerization method. Further, it can be produced by either a continuous polymerization method or a batch polymerization method.

(Antirust agent (C))
The rust inhibitor (C) used in the present invention is not particularly limited as long as it does not significantly impair the flame retardancy of the processed product treated with the fiber treatment agent of the present invention.

Specific examples of the rust inhibitor (C) include nitrites such as mono and diisopropylamine nitrite, mono and dicyclohexylamine nitrite, triethylamine nitrite, pyridine nitrite and aniline nitrite; alkyl succinic acid half ester, alkenyl Various carboxylic acid esters such as succinic acid half ester; dicyclohexylammonium salicylate, dicyclohexylammonium cyclohexanecarboxylate, cyclohexylaminecyclohexanecarboxylate, dicyclohexylammonium acrylate, cyclohexylamine acrylate and their carbamates, naphthenates, octylates, etc. Amine carboxylates; ethylmorpholine benzoate, di- and monocyclohexyla Benzoates such as benzoate, monoethanolamine benzoate, sodium benzoate, etc .; various chromates; phosphates; silicates; sulfonates, etc. Amine carboxylates or benzoates are preferred from the standpoint of regulation and efficient rust prevention. These compounds can be used alone or in combination of two or more.

The content of the rust inhibitor (C) in the fiber treatment agent of the present invention is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, and 1 to 5% by mass. More preferably. When the amount is less than 0.1% by mass, the rust preventive property of the processed product treated with the fiber treatment agent of the present invention is lowered. When the amount is more than 15% by mass, the drying property of the fiber treatment agent is lowered, and the fiber treatment agent is reduced. There exists a tendency for the physical property of the fiber processed article obtained by processing this to inhibit the processing property of this fiber processed article to fall. Moreover, when it is in this range, the flame retardancy of the processed product is also reduced by the combined use with the following appropriate amount of flame retardant, without reducing the rust prevention property of the processed product treated with the fiber treatment agent of the present invention. There is nothing to do.

(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 guanidine phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, tris (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 their metal salts, etc. Phosphorus flame retardants; inorganic flame retardants such as antimony trioxide, antimony tetroxide, antimony pentoxide, antimony soda, aluminum hydroxide, magnesium hydroxide; nitrogen flame retardants such as melamine cyanurate; penta Halogenated flame retardants such as bromobiphenyl, octabromobiphenyl, decabromobiphenyl, and the like. Especially, it is preferable to use the flame retardant containing phosphorus from the point of low environmental impact and efficient flame-resistant expression. These compounds can be used alone or in combination of two or more.

The content of the flame retardant (D) in the fiber treatment agent of the present invention is preferably 0.1 to 70% by mass, more preferably 0.5 to 50% by mass, and 1 to 30% by mass. Is more preferable. When the amount is 0.1% by mass or more, the flame retardant of the processed product treated with the fiber treatment agent of the present invention becomes sufficient, and when it is 70% by mass or less, the fiber treatment agent of the present invention is used for treatment. There is a tendency that choking, stickiness, and the like are suppressed in the processed fiber product obtained in (1).
The content of the flame retardant (D) in the fiber treatment agent of the present invention is preferably 40% by mass or less in total with the content of the rust inhibitor (C). When it is 40% by mass or less, bleeding tends to be suppressed, and choking and stickiness tend to be suppressed in a fiber processed product obtained by processing using the fiber treatment agent of the present invention.

The total phosphorus atom content in the fiber treatment agent of the present invention is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, and 0.1 to 20% by mass. Is more preferable. When it is 0.01% by mass or more, the processed product treated with the fiber treatment agent of the present invention has sufficient flame retardancy, and when it is 30% by mass or less, the fiber treatment agent of the present invention is used for treatment. There is a tendency that choking, stickiness and the like are suppressed in the processed fiber product.

<Other ingredients>
[Initiator]
When obtaining a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) by radical polymerization, the polymerization is carried out in the presence of an initiator. The radical polymerization initiator used in this polymerization reaction is not particularly limited as long as radical polymerization can be initiated, and a generally used peroxide or azo compound can be used. Specific examples thereof include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate. , T-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t-butylperoxy) -3,3 , 5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyl-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide Oxide, bis (4-tert-butylcyclo Xyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t-hexylperoxy) -3,3 Examples thereof include 5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide, and a suitable reducing agent may be used depending on the reaction. The initiator is used in an amount of 0.01 to 20 with respect to 100 parts by mass in total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) in the copolymer (P). Part by mass is preferable, and 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 treatment agent of the present invention is produced by an emulsion polymerization method In the presence of a surfactant. As the surfactant, commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable surfactants can be used. Moreover, these surfactants can be used individually or in combination of 2 or more types. The amount of the surfactant used is preferably 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). Is more preferable. From the viewpoint of polymerization stability, water-soluble polymers such as water-soluble (meth) acrylic acid resins, water-soluble (meth) acrylic acid ester resins, polyoxyethylene alkyl ethers and the like may be used as protective colloids. These protective colloids can be used regardless of the degree of saponification, the average degree of polymerization, and the presence or absence of modification. The average degree of polymerization should be 200 to 2,400 from the viewpoints of polymerization stability and product viscosity. The degree of saponification is preferably 80% to 100% from the viewpoint of polymerization stability. The amount of these protective colloids to be used is not particularly limited. From the viewpoint of polymerization stability, the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). The amount is preferably 1 to 100 parts by mass, more preferably 10 to 30 parts by mass with respect to 100 parts by mass.

[Other additives]
In the fiber treatment agent of the present invention, fillers, preservatives, colorants, antifoaming agents, foaming agents, dispersants, emulsifiers, fluidity modifiers, plasticizers, and pH adjustments are within the range that does not impair the effects of the present invention. You may mix additives, such as an agent and various oil agents.

[Other additive resins]
In addition, the fiber treatment agent of the present invention may contain various resin compositions such as other resin emulsions, solution resins, epoxy resins, and urethane resins as binders as long as the effects of the present invention are not impaired.

〔solvent〕
As the solvent used for the production of the fiber treatment agent of the present invention, water or a commonly used organic solvent can be used. Specific examples thereof include alcohols such as methanol, ethanol, propanol, isopropanol and butanol; ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate, diethylene glycol monomethyl ether acetate and carbitol acetate. , Acetate esters such as diethylene glycol monoalkyl ether acetates such as butyl carbitol acetate, propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, Diethylene glycol dialkyl esters such as butyl carbitol Tells, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, ethers such as methyl ether, ethyl ether, 1,4-dioxane, tetrahydrofuran; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Ketones such as benzene, toluene, xylene, hexane, octane, decane, etc .; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; methyl lactate, ethyl lactate, butyl lactate, etc. Lactic acid esters; dimethylformamide; N-methylpyrrolidone and the like. These water and organic solvents can be used alone or in combination of two or more.

[fiber]
In the present specification, the fiber includes non-woven fabrics, woven fabrics, knitted fabrics, and the like made of various fibers and their blends. Examples of the fiber include cotton, hemp, silk, wool, collagen fiber, acrylic fiber, cellulosic fiber, polyimide fiber, polyamideimide fiber, rayon fiber, nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, poly Non-woven fabric made of vinyl chloride fiber, polyethylene fiber, polymetaphenylene isophthalamide fiber, aramid fiber, polyarylate fiber, polytetrafluoroethylene fiber, polybenzimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber and blended products thereof, Examples include woven fabrics and knitted fabrics.

[Manufacturing method of processed fiber products]
Various known methods can be employed without particular limitation as a method for producing a processed fiber product by treating the fiber (base material) with the fiber treatment agent of the present invention. For example, examples of the method for applying the fiber treatment agent of the present invention to the fiber and processing include a direct coating method, a spray coating method, a roll coater method, a slot coater method, a knife coat method, a printing method, a roll transfer method, and the like. . Moreover, for example, as a method for immersing and treating fibers in the fiber treatment agent of the present invention, a horizontal roller method, a metalling roller method, a screen conveyor method, a foam method, and the like can be given.
For example, the processing method in the case of processing a fiber such as a nonwoven fabric with the fiber treatment agent of the present invention includes a spray coating method, a printing method, a roll transfer method, a horizontal roller method, a metering roller method, a screen conveyor method, a foam method, etc. Can be mentioned. Examples of processing methods for treating fibers such as woven fabrics with the fiber treatment agent of the present invention include a direct coating method, a spray coating method, a roll coater method, a slot coater method, and a knife coating method. In addition, when a web is formed by forming fibers into a sheet and the web is further bonded or entangled to form a cloth, the fiber treatment may be performed on the fibers before being formed into a web, You may carry out after making web into various methods. As the fiber web forming method, various known methods can be employed without particular limitation, and examples thereof include an air array method.

The amount of the fiber treatment agent used for various fiber substrates depends on the flame retardancy of the substrate itself, but the resin adhesion amount (the adhesion amount after drying the adhered fiber treatment agent) is 10 to 200 parts by mass / 100. The amount to be parts by mass is preferable, the amount to be 30 to 150 parts by mass / 100 parts by mass is more preferable, and the amount to be 50 to 100 parts by mass / 100 parts by mass is still more preferable. When it is 10 parts by mass / 100 parts by mass or more, the flame-retardant and rust prevention properties of the fiber processed product obtained using the fiber treatment agent of the present invention are sufficient, and when it is more than 200 parts by mass / 100 parts by mass, There exists a tendency for the fall of the intensity | strength of a fiber processed product obtained using the fiber processing agent of this invention, and a texture to be suppressed. Drying may be air drying, vacuum drying, or pressure drying. Moreover, you may heat. When heating at the time of drying, the temperature range when heating at the time of drying is preferably 50 to 250 ° C, more preferably 80 to 190 ° C. If the heating temperature is too low, drying may take time or drying may be insufficient. If the heating temperature is too high, alteration may occur.

[Fiber processed products]
The fiber processed product of the present invention is obtained using the method for producing a fiber processed product of the present invention. The amount that the resin adhesion amount (attachment amount of the fiber treatment agent after drying) is 10 to 200 parts by mass / 100 parts by mass, which is 50 to 100 parts by mass / 100 parts by mass with respect to the fiber (base material), is preferably 30 An amount of ˜150 parts by mass / 100 parts by mass is more preferred, and an amount of 50˜100 parts by mass / 100 parts by mass is still more preferred. When the amount is 10 parts by mass / 100 parts by mass or more, the fiber processed product of the present invention has sufficient flame retardancy and rust resistance, and when the amount is 200 parts by mass / 100 parts by mass or less, There is a tendency for the decrease in strength and texture to be suppressed.
The processed fiber product of the present invention can be applied to various fields by taking advantage of excellent flame retardancy and rust prevention properties that are compatible with each other. For example, the processed fiber product of the present invention is suitably used as a cushioning material for electronic materials, a cushioning material for home appliances, an automotive interior cushioning material, and the like.

Hereinafter, the present invention will be further described using examples and comparative examples, but the present invention is not limited to the examples and comparative examples.

Example 1
150 g of ion-exchanged water was placed in a 1 L 5-neck separable flask and heated to 80 ° C. with stirring. Acid phosphooxypolyoxyethylene glycol monomethacrylate (manufactured by Kyoeisha Chemical Co., Ltd., light ester P-1M, phosphorus content 15 mass%) 60 g, methyl methacrylate 36 g, ethyl acrylate 36 g, acrylic acid 18 g, dodecylbenzenesulfonic acid soda 5 g, 7.5 g of polyoxyethylene alkyl ether and 150 g of ion exchange water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping of the monomer emulsion. The monomer emulsion was added to the separable flask over 4 hours, and at the same time, 30 g of 3% aqueous potassium persulfate solution was added over 4 hours. After the addition of the monomer emulsion was completed, the reaction was terminated by stirring at 80 ° C. for 2 hours. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the system.

Then, with stirring, flame retardant ammonium polyphosphate diluted with 20 g of ion-exchanged water (manufactured by Suzuhiro Co., Ltd., FCP-770, phosphorus content 24%), rust inhibitor carboxybenzotriazole diluted with 10 g of ion-exchanged water. 10 g (CBT-1 manufactured by Johoku Chemical Co., Ltd.) was added, and 10 g of ion-exchanged water was added. After the addition of the flame retardant and the rust inhibitor, the fiber treatment agent 1 was prepared by stirring for 1 hour. The composition is shown in Table 1.
Using the obtained fiber treating agent 1, a fiber processed product was produced by the method described later. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method described later. The evaluation results are shown in Table 4.

(Examples 2 to 12)
The fiber treatment agents 2 to 12 were prepared in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were used.
In addition, the detail of each component in Table 1 and Table 2 is as follows.
Diphenyl-2-methacryloyloxyethyl phosphate: Daihachi Chemical Industry Co., Ltd., MR-260, phosphorus content 8%
1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole: manufactured by Johoku Chemical Industry Co., Ltd., BT-LX
Triphenyl phosphate: manufactured by Daihachi Chemical Industry Co., Ltd., TPP, phosphorus content 10%
Polyvinyl alcohol: manufactured by Kuraray Co., Ltd., PVA205 (saponification degree: 86.5 to 89.0%, average polymerization degree: 500)
Using the obtained fiber treating agents 2 to 12, fiber processed products were produced by the method described below. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method described later. The evaluation results are shown in Table 4.

(Comparative Examples 1 to 6)
Preparations were made in the same manner as in Example 1 except that the compositions shown in Table 3 were used, and fiber treatment agents 13 to 18 were prepared.
Using the obtained fiber treating agents 13 to 18, fiber processed products were produced by the method described later. The physical property evaluation of the obtained fiber processed product was performed by the evaluation method described later. The evaluation results are shown in Table 5.

(Production and evaluation method of processed fiber products)
Using the fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6, fiber processed products were produced. The physical property evaluation of the obtained fiber processed product was performed. Fabrication and evaluation of processed fiber products were performed according to the following methods.

<Base material>
The fiber base materials in Examples and Comparative Examples of the present invention were as follows.
(1) Fiber Polyester-cellulose nonwoven fabric (2) Weight per unit area 35 g / 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 diluted with ion-exchanged water so that the solid content was 15% by mass, and then the base fiber was treated with the fiber treatment agent. Was impregnated. Thereafter, the base fiber impregnated with the fiber treating agent was squeezed with two mangles and dried at 130 ° C. for 10 minutes with a hot air dryer. The adhesion amount of the fiber treatment agent was 40 to 50% by mass with respect to the fiber weight.
<Method for evaluating solid content>
Take a predetermined amount of sample in a clean aluminum pan (height: about 17mm, caliber: about 40mm), weigh accurately using a direct weighing scale with a sensitivity of 0.5mg or less, and then the internal temperature is 105 ℃ ± 2 ℃. Leave in a drier adjusted to 1 hour for 1 hour. The sample after drying is cooled to room temperature in a desiccator, then precisely weighed with the same direct balance, and the solid content is calculated by the following formula.
Solid content (%) = sample weight after drying (g) / original sample weight (g) × 100
<Method for evaluating phosphorus atom content>
Any method such as a colorimetric determination method or ICP emission analysis may be used. For example, the phosphorus atom content can be determined by elemental analysis.

<Evaluation of processed textile products>
The fiber processed products were evaluated for flammability, rust prevention, and bleeding.

(1) Flame retardance After preparing a processed fiber product, the specimen was allowed to stand for 12 hours or longer at 23 ° C. and 50% RH. The UL-94 vertical combustion test (V-0, V-1, V-2) Based on the standard, a combustion test was conducted. The size of the test piece was 127 mm in length and 12.7 mm in width. About five test pieces, the flame contact was performed twice, 10 times in total, and the average number of seconds and the maximum number of seconds of the flame extinguishing time were measured and judged.
UL-94 Vertical Flammability Test (V)
V-0: The total burning time by the first and second flame contact of the five test pieces is within 50 seconds and the maximum burning time is within 10 seconds, and there is no dripping of material due to combustion.
V-1: The total burning time by the first and second flame contact of the five test pieces is 250 seconds or less and the maximum burning time is 30 seconds or less, and there is no dripping of material due to combustion.
V-2: The total combustion time by the first and second flame contact of five test pieces is within 250 seconds, and the maximum combustion time is within 30 seconds.

(2) Rust prevention After the processed product was prepared, the specimen that had been allowed to stand for 12 hours or longer at 23 ° C. and 50% RH was cut into a length of 50 mm and a width of 70 mm, and brass (vertical: 120 mm, width: 30 mm). , Thickness: 0.1 mm), and was allowed to stand for 14 days under conditions of 60 ° C. and 95% RH to confirm the presence or absence of rust on the brass surface. In Tables 4 and 5, the evaluation results are shown as follows.
Rust occurrence: ×
No rust generation: ○

(3) Bleeding After preparing the processed product, the test specimen that was allowed to stand for 12 hours or more at 23 ° C. and 50% RH was cut into a length of 50 mm and a width of 70 mm, and filtered (filter: 100 mm, width: 60 mm, No. .2, manufactured by Toyo Roshi Kaisha, Ltd.) and left for 5 days under conditions of 60 ° C. and 95% RH, and the presence or absence of bleeding on the surface of the processed product was confirmed.
In Tables 4 and 5, the evaluation results are shown as follows.
With bleeding: ×
No bleeding: ○

From the results in Table 4, it can be seen that the fiber processed products treated with the fiber treating agent of the present invention (Examples 1 to 12) are both excellent in both flame retardancy and rust resistance. It can also be seen that bleeding is sufficiently suppressed.
On the other hand, as shown in Table 5, when using the fiber processing agent which does not contain a flame retardant (D) (comparative example 1), it turns out that a flame retardance is inadequate. When using a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with a flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 2.6% (Comparative Example 2) It can be seen that significant bleeding occurs under the conditions of 60 ° C. and 95% RH. When using a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with a flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 1.4% (Comparative Example 3) It can be seen that the flame retardancy is insufficient. When using the fiber processing agent which does not contain a rust preventive agent (C) (comparative example 4), it turns out that rust preventive property is inadequate on 60 degreeC and 95% RH conditions. A fiber treatment agent that does not contain an unsaturated monomer (b2) having at least one carboxyl group selected from the group consisting of (meth) acrylic acid and itaconic acid as a polymerizable unsaturated monomer (B) component is used. In the case (Comparative Example 5), it can be seen that significant bleeding is caused.
When a fiber treatment agent that does not contain the (meth) acrylic acid alkyl ester unsaturated monomer (b1) as the polymerizable unsaturated monomer (B) component is used (Comparative Example 6), the rust prevention property is insufficient. I know that there is.

The fiber treatment agent of the present invention has excellent flame retardancy in processed fiber products and excellent rust prevention under high humidity conditions, and is particularly suitable for fiber treatment. Moreover, the manufacturing method of the fiber processed goods using the fiber processing agent of this invention is suitable for manufacturing various fiber processed goods excellent in a flame retardance and rust prevention property, and uses the manufacturing method of this fiber processed goods. As a result, a fiber processed product excellent in flame retardancy and rust prevention can be produced. And by using this fiber processed product, it becomes possible to manufacture a shock-absorbing material for electronic materials, a shock-absorbing material for home appliances, a shock-absorbing material for automobile interiors, and the like, which are excellent in flame retardancy and rust prevention.

Claims

A copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B);
A rust inhibitor (C),
Flame retardant (D),
A fiber treatment agent comprising:
The polymerizable unsaturated monomer (B) is
(Meth) acrylic acid alkyl ester unsaturated monomer (b1);
At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid;
A fiber treatment agent comprising:
The fiber treatment agent according to claim 1, wherein the phosphorus-containing unsaturated monomer (A) includes a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
The fiber treatment agent according to claim 2, wherein the monomer (a1) having a phosphoric acid group or a phosphorous acid group contains acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate.
The fiber treatment agent according to any one of claims 1 to 3, wherein the rust inhibitor (C) comprises an amine carboxylate or benzoate.
The fiber treatment agent according to any one of claims 1 to 4, wherein the flame retardant (D) contains phosphorus.
The fiber treatment agent according to any one of claims 1 to 5, wherein the polymerizable unsaturated monomer (B) is contained in an amount of 40% by mass or more based on the total amount of monomers in the copolymer (P).
The fiber treatment agent according to any one of claims 1 to 6, wherein the rust inhibitor (C) is contained in an amount of 0.1 to 15% by mass based on the total fiber treatment agent.
The fiber treatment agent according to any one of claims 1 to 7, wherein the flame retardant (D) is contained in an amount of 0.1 to 70 mass% with respect to the total fiber treatment agent.
The fiber treatment agent according to any one of claims 1 to 8, wherein the amount of phosphorus atom in the fiber treatment agent is 0.01 to 30% by mass.
A method for producing a processed fiber product, comprising a step of processing a fiber base material using the fiber treatment agent according to any one of claims 1 to 9 to obtain a processed fiber product.
A processed fiber product, wherein 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 with respect to 100 parts by weight of the fiber substrate.