JP7012007B2 - Fiber treatment agents, manufacturing methods for processed fiber products, and processed fiber products - Google Patents

Description

The present invention is a fiber treatment agent capable of imparting flame retardancy and rust resistance to a fiber, a method for producing a processed fiber product using the fiber treatment agent, and a fiber obtained by using the method for producing the processed fiber 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-retardant textile processed products used in applications such as building materials, home appliances, electronic materials, and vehicle interior materials such as automobiles. Further, in such processed fiber products, fiber treatment agents containing synthetic resins and various additives are widely used as physical property improving agents and adhesives. In order to obtain the above-mentioned flame-retardant fiber processed product, there is a demand for a fiber treatment agent that imparts flame-retardant property and rust-preventive property to the fiber. Development of such fiber treatment agents is underway.

In general, as a method for 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, phosphate, antimony trioxide, aluminum hydroxide, and magnesium hydroxide; halogen-based 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 chalking in the processed fiber product.
Further, when these flame retardants are used in the fiber treatment agent containing a synthetic resin, such a fiber treatment agent not only imparts flame retardancy to the processed fiber product, but also has strength, texture, rust resistance and the like. It is required not to adversely affect other physical properties of the processed textile products of. However, in general, in order to impart flame retardancy to a processed fiber product, it is necessary to add a large amount of a flame retardant, which is a cause of impairing the physical properties of the processed fiber product.

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

On the other hand, since the halogen-based flame retardant has excellent flame retardant performance, it can be added to the fiber treatment agent in a small amount. From this, the influence on the physical characteristics of the fiber processed product processed by using the fiber treatment agent containing these is small. However, since it contains halogen elements such as chlorine and bromine, there is a risk of generating harmful substances such as dioxins and hydrogen halides when incinerating fiber processed products using these, and the world including EU countries. Regulations and usage are being reviewed in each country.

Since non-halogen flame retardants are superior in safety to halogen flame retardants, many flame retardants such as phosphorus are being studied. However, the flame retardant performance of the phosphorus-based flame retardant is lower than that of the halogen-based flame retardant, and it must be used in a relatively large amount. Therefore, the fiber treatment agent containing a phosphorus-based flame retardant deteriorates the physical characteristics of the fiber processed product processed using the fiber treatment agent. For example, water-soluble phosphorus-based flame retardants have high deliquescent properties and apparently plasticize resins, which causes a decrease in the strength and texture of processed fiber products using them. In addition, the oil-soluble phosphorus-based flame retardant not only reduces the strength and texture by plasticizing the resin and bleeding on the surface of the fiber treatment agent, but also makes the fiber processed product using the fiber treatment agent sticky and chalking. It is the cause of the occurrence.

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

Inorganic rust preventives have been studied many times because they are superior in rust preventive properties as compared with organic rust preventives. However, in general, inorganic rust inhibitors contain substances harmful to the human body, and there is concern about their impact on the environment. For example, nitrite is known to exhibit high rust preventive properties, but it has been pointed out that it is harmful to the human body, and nitrite-free rust preventive agents are required. Chromate is also known to exhibit high rust resistance, but it contains heavy metals and is harmful to the human body like nitrite, and there are restrictions on wastewater in the treatment process. Its use is avoided.

Organic rust preventives are widely used to solve problems such as harmfulness to the human body and environmental load as pointed out by the inorganic rust preventives. As an organic rust preventive agent exhibiting high rust preventive properties, for example, barium salt of alkyl sulfonic acid or benzene sulfonic acid, barium soap and the like are known, but in recent years, the harmfulness of barium salt to the human body has been pointed out. There are restrictions on use in Europe and the United States. Various carboxylic acid esters such as alkyl succinic acid half ester and alkenyl succinic acid half ester show a certain degree of rust resistance, but are not sufficient. On the other hand, benzoate is known to exhibit rust preventive properties, and is also used as an additive for antifreeze coolant for automobile engines. In addition, benzoate generally has a slight effect on the human body, and has an advantage that it has a lower environmental load than an inorganic rust preventive, such as being used as a food preservative. However, organic rust inhibitors are generally flammable, and fiber treatment agents using them are a cause of lowering the flame retardancy of processed fiber products.

For example, a non-halogen copolymerized with an unsaturated monomer having a phosphoric acid group or a phosphite group skeleton, an acrylic acid-based unsaturated monomer, and a vinyl acetate monomer disclosed in Patent Document 1. Although a flame-retardant resin composition of the system has been proposed, a processed product using the flame-retardant resin composition does not satisfy strength and rigidity, and further improvement in physical properties has been desired.

Further, 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 capable of obtaining a processed product having both flame retardancy and rust prevention.

Japanese Unexamined Patent Publication No. 7-18028 Japanese Patent No. 5669363

Therefore, the present invention is to provide a fiber treatment agent capable of obtaining a treated processed product having excellent flame retardancy and rust prevention. Another object of the present invention is to provide a method for producing a processed fiber product using the fiber treatment agent and a processed fiber product obtained by using the method for producing the processed fiber product.

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 preventive agent (C), and a flame retardant agent (D). A fiber treatment agent containing, wherein the polymerizable unsaturated monomer (B) is composed of 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 the above [1], wherein the phosphorus-containing unsaturated monomer (A) contains a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
[3] The fiber treatment agent according to the above [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 preventive agent (C) contains an amine carboxylate and a benzoate.
[5] The fiber treatment agent according to any one of [1] to [4] above, 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 all the monomers in the copolymer (P). Fiber treatment agent.
[7] The fiber treatment agent according to any one of the above [1] to [6], which contains the rust preventive agent (C) in an amount of 0.1 to 15% by mass with respect to the total fiber treatment agent.
[8] The fiber treatment agent according to any one of the above [1] to [7], which contains the flame retardant (D) 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 phosphorus atomic weight in the fiber treatment agent is 0.01 to 30% by mass.
[10] A method for producing a processed fiber product, which comprises a step of treating a fiber base material with the fiber treatment agent according to any one of the above [1] to [9] to obtain a processed fiber product.
[11] A processed fiber product in which the amount of the fiber treatment agent adhered to any one of the above [1] to [9] after drying is 50 to 100 parts by mass with respect to 100 parts by mass of the fiber base material.

In the fiber treatment agent of the present invention, the treated processed product has excellent flame retardancy and also has excellent rust prevention properties. The fiber processed product obtained by the method for manufacturing a fiber processed product using the fiber treatment agent is excellent in both flame retardancy and rust prevention, and is therefore suitable as a fiber material for home appliances, electronic materials, and automobile interior materials. be.

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

The fiber treatment agent of the present invention is 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) and is included.
The fiber treatment agent according to the present embodiment is excellent in both flame retardancy and rust prevention property for the treated processed product, is useful as a flame retardant treatment agent for fibers, and can be suitably used for various fibers. ..
Here, "-" in the present specification means not more than the value before the description of "-" and less than or equal to the value after the description of "-".

Further, the description of "(meth) acrylate" and the like in the present 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 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 dimethylvinylphosphonate, diethylvinylphosphonate, diphenylvinylphosphonate, diphenylvinylphosphonate, dimethyl (1,2-diphenyl-ethenyl) phosphonate, and dimethyl. -P-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, diphenyl-p-vinylbenzylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-p- Vinylbenzyl, acid phosphooxyethyl (meth) acrylate, 2-acryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl phosphate, (meth) acryloyl oxyethyl acid phosphate monoethanolamine salt, acid phosphooxypoly Examples thereof include oxyethylene glycol mono (meth) acrylate and acid phosphooxypolyoxypropylene glycol (meth) acrylate, as well as metal salts, ammonium salts and amine salts thereof. These compounds can be used alone or as a mixture of two or more.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素又は炭素数１～３のアルキル基を表し；Ｙは、ヒドロキシル基、炭素数１～３のアルキル基又は炭素数１～３のアルキルエステル基を表し；Ｚは、水素原子、ヒドロキシル基、炭素数１～３のアルキル基又は炭素数１～３のアルキルエステル基を表し；ｎは１～２０の整数である）で示される化合物、並びこの化合物の金属塩、アンモニウム塩及びアミン塩等が挙げられる。これらの化合物は、単独で又は二種以上の混合物として使用することができる。Ｒ^１、Ｒ^２、Ｙ、Ｚはそれぞれ、水素又はメチル基が好ましい。また、ｎは１～３が好ましい。[Monomer having a phosphoric acid group or a phosphorous acid group (a1)]
As the phosphorus-containing unsaturated monomer (A), a monomer (a1) having a phosphoric acid group or a phosphorous acid group is preferable. As the monomer (a1) having a phosphoric acid group or a phosphorous acid group, for example, the general formula (1):

(In the formula, R ¹ and R ² each independently represent hydrogen or an alkyl group having 1 to 3 carbon atoms; Y is a hydroxyl group, an alkyl group having 1 to 3 carbon atoms or an alkyl having 1 to 3 carbon atoms. A compound represented by an ester group; 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). Examples thereof include metal salts, ammonium salts and amine salts of this compound. These compounds can be used alone or as a mixture of two or more. Hydrogen or a methyl group is preferable for R ¹ , R ² , Y and Z, respectively. Further, 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-methacryloyloxyethyl acid phosphate, acid phosphooxypolyoxyethylene glycol mono (meth) acrylate and acid phospho. Oxypolyoxypropylene glycol (meth) acrylate and the like can be mentioned. These compounds can be used alone or as a mixture of two or more. Among them, acid phosphooxyethyl (meth) acrylate is preferable because the phosphorus content per molecule is high.

The phosphorus-containing unsaturated monomer (A) is used with respect to all the 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 to 50% by mass, and even more preferably in the range of 26% by mass to 40% by mass. If it is 20% by mass or more, the flame retardancy of the processed product treated with this fiber treatment agent is sufficient, and if it is 60% by mass or less, the polymerization is stable, and the strength of the processed product using this fiber treatment agent is increased. There is a tendency that heat-resistant yellowing does not decrease.

Further, the polymerization ratio 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). If the content of the phosphorus atom calculated from the atomic weight of phosphorus and the molecular weight of the phosphorus-containing unsaturated monomer (A) in the component A) and the component (B) is appropriately determined to be 3 to 13% by mass. good. Considering the balance between imparting flame retardancy, polymerization stability of the copolymer (P), and expression of physical properties in the processed product, it is preferable to polymerize 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, exhibits polymerizable properties, and is copolymerized with the phosphorus-containing unsaturated monomer (A). There are no particular restrictions as long as it does. 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 their esters; (meth) acrylamide and its derivatives; styrene and its derivatives; vinyl esters; N. Substituted maleimide compounds; itaconic acid, crotonic acid, fumaric acid and their esters and their metal salts, ammonium salts and the like can be mentioned.

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 mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, polyethylene Glycolpolytetramethylene glycol mono (meth) acrylate, polypropylene glycolpolytetramethylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, methylglycidyl (meth) 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, trimethyl propantri. (Meta) acrylic acid esters such as (meth) acrylates, dimethyloltricyclodecandi (meth) acrylates, isobolonyl (meth) acrylates, phenoxypolyethylene glycol (meth) acrylates, pentaerythrittetra (meth) acrylates; dimethyl fumarate Acrylate such as dimethylmalate, diethylmalate, dibutylmalate, di-(2-ethylhexyl) malate; methacrylic Amid; (meth) acrylamide derivatives such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide; methoxystyrene, ethoxystyrene vinyl benzo Stylized derivatives such as acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene, divinylbenzene; vinyl acetate; vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprice, vinyl laurate, vinyl stearate; methyl N-substituted maleimide compounds such as maleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide; monomethylitaconate, dimethylitaconate, monoethylitaconate, diethylitaconate, monobutylitaconate, dibutylitaco Itaconic acid esters such as nate; crotonic acid esters such as methylcrotonate, ethylcrotonate and butylcrotonate; phthalic acid esters such as dimethylphthalate, diethylphthalate, dipropylphthalate, dibutylphthalate and dihexylphthalate; and the like. These can be used alone or in combination of two or more.

Among the polymerizable unsaturated monomers (B), a single amount of (meth) acrylic acid alkyl ester unsaturated, particularly from the viewpoint of exhibiting flame retardancy in a fiber processed product obtained by treating with this fiber treatment agent. It is preferable to use at least one unsaturated monomer (b2) selected from the group consisting of the body (b1) and (meth) acrylic acid and itaconic acid. 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 resistance of the processed fiber product treated with the fiber treatment agent of the present invention is improved. It is preferable in terms of doing so.

[(Meta) 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 among them, methyl (meth) acrylate and ethyl (meth) acrylate in terms of flame retardancy. Meta) 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, and diethylamino. Ethyl (meth) acrylate and the like can be mentioned, and these can be used alone or in combination of two or more.

[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 them, acrylic acid is preferable in that the content in the copolymer (P) can be increased without impairing the stability of the polymerization.
In addition, a carboxyl selected from a group other than the group consisting of (meth) acrylic acid and itaconic acid in combination with at least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid. Unsaturated monomers having a group may be used. Specific examples of unsaturated monomers having a carboxyl group selected from the group other than the group consisting of (meth) acrylic acid and itaconic acid include fumaric acid, maleic acid, crotonic acid and the like, and these are one or two kinds. The above can be used in combination.

The polymerizable unsaturated monomer (B) is contained in a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) contained in a fiber treatment agent. It is preferable to use 40% by mass or more in total, and more preferably 50% by mass to 80% by mass, based on all the monomers.
When it 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 processed fiber product treated with the fiber treatment agent of the present invention is sufficient. There is a tendency.
In the polymerizable unsaturated monomer (B), at least one unsaturated single amount selected from the group consisting of (meth) acrylic acid alkyl ester unsaturated monomer (b1) and (meth) acrylic acid and itaconic acid. The total amount of the body (b2) is preferably 90% by mass or more, more preferably 95% by mass or more, and further preferably 100% by mass.
In the polymerizable unsaturated monomer (B), at least one unsaturated single amount 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 /. It is more preferably 70. Within that range, the bleeding resistance of the flame retardant (D) component in the processed fiber product treated with the fiber treatment agent of the present invention tends to be improved. Further, the flame retardant or rust preventive property of the processed fiber product treated with the fiber treatment agent of the present invention tends to be improved.

(Method for producing 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 emulsification polymerization method, or the like. It can be produced by using a known copolymerization method such as a solution polymerization method or a massive polymerization method. Further, it can be produced by either a continuous polymerization method or a batch polymerization method.

(Rust inhibitor (C))
The rust preventive agent (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 preventive agent (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 and 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 benzoates, di and monocyclohexylamine benzoates, monoethanolamine benzoates, benzoates such as sodium benzoate; various chromates; phosphates; silicic acid. Salts; sulfonates and the like can be mentioned, and among them, amine carboxylates or benzoates are preferable in terms of environmental load, usage regulation and efficient rust-preventive development. These compounds may be used alone or in combination of two or more.

The content of the rust preventive agent (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. Is even more preferable. When it is less than 0.1% by mass, the rust resistance of the processed product treated with the fiber treatment agent of the present invention is lowered, and when it is more than 15% by mass, the drying property of the fiber treatment agent is lowered, and the fiber treatment agent is said. There is a tendency that the physical properties of the processed fiber product obtained by the treatment are impaired or the processability of the processed fiber product is lowered. Further, within this range, the rust preventive property of the processed product treated with the fiber treatment agent of the present invention does not decrease, and the flame retardancy of the processed product also decreases when used in combination with the following appropriate flame retardant. 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, cresyldiphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (t-butylated phenyl) phosphate, and 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; Antimonite trioxide, Antimon tetroxide, Antimon pentoxide, Antimon soda, Aluminum hydroxide, Inorganic flame retardants such as magnesium hydroxide; Nitrogen flame retardants such as melamine cyanurate; Pentabromobiphenyl, Octa Examples thereof include halogen-based flame retardants such as bromobiphenyl and decabromobiphenyl. Above all, it is preferable to use a flame retardant containing phosphorus in terms of low environmental load and efficient flame retardant development. These compounds may 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 it is 0.1% by mass or more, the flame retardancy 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, it is treated with the fiber treatment agent of the present invention. Chalking, stickiness, etc. tend to be suppressed in the processed fiber products obtained in the above.
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 preventive agent (C). When it is 40% by mass or less, bleeding tends to be suppressed, and chalking, stickiness and the like tend to be suppressed in the processed fiber product obtained by treatment with 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 flame retardancy of the processed product treated with the fiber treatment agent of the present invention is sufficient, and when it is 30% by mass or less, it is treated with the fiber treatment agent of the present invention. Chalking, stickiness, etc. tend to be suppressed in the resulting fiber processed products.

<Other ingredients>
[Initiator]
When a copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B) is obtained 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 it can initiate radical polymerization, and commonly used peroxides and azo compounds can be used. For example, specific examples thereof include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, and 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-isopropylhydroperoxide, t-butylhydroperoxide, dicumylhydroperoxide, acetylper Oxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide, 1,1-bis (t- Hexylperoxy) -3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarboxylicamide and the like can be mentioned, and an appropriate reducing agent may be used depending on the reaction. The amount of the initiator used is 0.01 to 20 with respect to 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) in the copolymer (P). The 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 the emulsification 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. In addition, these surfactants can be used alone or in combination of two or more. The amount of the surfactant used is preferably 0.01 to 30 parts by mass, preferably 0.1 to 20 parts by mass with respect to the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B). Is more preferable. Similarly, from the viewpoint of polymerization stability, a water-soluble polymer such as a water-soluble (meth) acrylic acid resin, a water-soluble (meth) acrylic acid ester resin, or a polyoxyethylene alkyl ether may be used as a protective colloid. Further, these protective colloids can be used regardless of the degree of saponification, the average degree of polymerization, and the presence or absence of modification, but the average degree of polymerization is 200 to 2,400 from the viewpoint 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 used is not particularly limited, but is the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) from the viewpoint of polymerization stability. It 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]
The fiber treatment agent of the present invention includes fillers, preservatives, colorants, defoamers, foaming agents, dispersants, emulsifiers, fluidity regulators, plasticizers, and pH adjusters as long as the effects of the present invention are not impaired. Additives such as agents and various oils may be blended.

[Other additive resins]
Further, 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 producing the fiber treatment agent of the present invention, water or a commonly used organic solvent can be used. For example, 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. , Diethylene glycol monoalkyl ether acetates such as butyl carbitol acetate, acetate esters such as propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers, methyl carbitol, ethyl carbitol, Diethylene glycol dialkyl ethers such as butyl carbitol, triethylene glycol dialkyl ethers, propylene glycol dialkyl ethers, dipropylene glycol dialkyl ethers, methyl ethers, ethyl ethers, 1,4-dioxane, ethers such as tetrahydrofuran; acetone, Ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha; methyl lactate , Lactic acid esters such as ethyl lactate and butyl lactate; dimethylformamide; N-methylpyrrolidone and the like. These waters and organic solvents can be used alone or in combination of two or more.

[fiber]
In the present specification, the fiber includes a non-woven fabric, a woven fabric, a knitted fabric, etc. made of various fibers and blended products thereof. The fibers include, for example, cotton, linen, silk, wool, collagen fiber, acrylic fiber, cellulose fiber, polyimide fiber, polyamideimide fiber, rayon fiber, nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, poly. Non-woven fabric consisting of vinyl chloride fiber, polyethylene fiber, polymethaphenylene isophthalamide fiber, aramid fiber, polyallylate fiber, polytetrafluoroethylene fiber, polybenzoimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber and a blended product thereof. Examples include textiles and knitted fabrics.

[Manufacturing method of processed textile products]
As a method for producing a processed fiber product by treating the fiber (base material) with the fiber treatment agent of the present invention, various known methods can be adopted without particular limitation. For example, as a method of applying the fiber treatment agent of the present invention to a fiber and treating it, a direct coat method, a spray coat method, a roll coater method, a slot coater method, a knife coat method, a printing method, a roll transfer method and the like can be mentioned. .. Further, for example, as a method of immersing the fiber in the fiber treatment agent of the present invention for treatment, a horizontal roller method, a metering roller method, a screen conveyor method, a foam method and the like can be mentioned.
For example, when a fiber such as a non-woven fabric is treated with the fiber treatment agent of the present invention, the processing method 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, and the like. Can be mentioned. Further, for example, when a fiber such as a woven fabric is treated with the fiber treatment agent of the present invention, a direct coat method, a spray coat method, a roll coater method, a slot coater method, a knife coat method and the like can be mentioned. Further, when the fibers are formed into a sheet to form a web, and the web is further adhered or entangled to form a cloth, the fiber treatment may be performed on the fibers before the web formation, or the fibers may be treated. May be performed after the web is created by various methods. As the fiber web forming method, various known methods can be adopted without particular limitation, and examples thereof include an air array method.

The amount of the fiber treatment agent used for various fiber base materials depends on the flame retardancy of the base material itself, but the amount of resin adhesion (the amount of adhesion 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 further preferable. When it is 10 parts by mass / 100 parts by mass or more, the flame retardancy and rust resistance of the processed fiber product obtained by 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, it is said. The decrease in strength and texture of the processed fiber product obtained by using the fiber treatment agent of the present invention tends to be suppressed. The drying may be blast drying, vacuum drying, or pressure drying. It may also be heated. When heating during drying, the temperature range of the temperature when heating during drying is preferably 50 to 250 ° C, more preferably 80 to 190 ° C. If the heating temperature is too low, it may take a long time to dry or the drying may be insufficient. If the heating temperature is too high, it may cause deterioration.

[Processed textile products]
The processed fiber product of the present invention can be obtained by using the method for producing a processed fiber product of the present invention. The amount of resin adhered (the amount of adhering fiber treatment agent after drying) is preferably 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). An amount of up to 150 parts by mass / 100 parts by mass is more preferable, and an amount of 50 to 100 parts by mass / 100 parts by mass is further preferable. When it is 10 parts by mass / 100 parts by mass or more, the flame retardancy and rust resistance of the processed fiber product of the present invention are sufficient, and when it is 200 parts by mass / 100 parts by mass or less, the processed fiber product of the present invention is used. The decrease in strength and texture tends to be suppressed.
The processed fiber product of the present invention can be applied to various fields by taking advantage of its excellent flame retardancy and rust resistance. 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, a cushioning material for automobile interiors, and the like.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited to Examples and Comparative Examples.

(Example 1)
150 g of ion-exchanged water was placed in a 1 L five-necked 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% by mass) 60 g, methyl methacrylate 36 g, ethyl acrylate 36 g, acrylic acid 18 g, dodecylbenzene sulfonic acid soda 1. 5 g, 7.5 g of polyoxyethylene alkyl ether, and 150 g of ion-exchanged water were uniformly emulsified. The reaction was started by adding 0.2 g of potassium persulfate to the separable flask and starting dropping the monomeric emulsion. The monomeric emulsion was added into the separable flask over 4 hours, and at the same time, 30 g of a 3% potassium persulfate aqueous solution was also added over 4 hours. After the addition of the monomeric emulsion was completed, the mixture was stirred at 80 ° C. for 2 hours to complete the reaction. The inside of the separable flask was cooled, and 8 g of a 30% aqueous sodium hydroxide solution was added to neutralize the inside of the system.

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

(Examples 2 to 12)
Preparations were carried out in the same manner as in Example 1 except that the compositions shown in Tables 1 and 2 were used to prepare fiber treatment agents 2 to 12.
The details of each component in Tables 1 and 2 are as follows.
-Diphenyl-2-methacryloyloxyethyl phosphate: manufactured by 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
-Triphenylphosphine: 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 treatment agents 2 to 12, processed fiber products were produced by the method described later. The physical characteristics of the obtained processed fiber product were evaluated by the evaluation method described later. The evaluation results are shown in Table 4.

(Comparative Examples 1 to 6)
Preparations were carried out in the same manner as in Example 1 except that the compositions shown in Table 3 were used to prepare fiber treatment agents 13 to 18.
Using the obtained fiber treatment agents 13 to 18, a processed fiber product was produced by the method described later. The physical characteristics of the obtained processed fiber product were evaluated by the evaluation method described later. The evaluation results are shown in Table 5.

(Manufacturing and evaluation method of processed fiber products)
A processed fiber product was produced using the fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6. The physical characteristics of the obtained processed fiber products were evaluated. The processed fiber product was prepared and evaluated according to the following method.

<Base material>
The fiber base materials in the examples and comparative examples of the present invention are as follows.
(1) Fiber Polyester-Cellulose non-woven fabric (2) Metsuke 35 g / m ²
(3) Thickness 200 μm

<Manufacturing of processed products>
The fiber treatment agents obtained in Examples 1 to 12 and Comparative Examples 1 to 6 were diluted with ion-exchanged water so that the solid content was 15% by mass, and then the base fiber was used as the fiber treatment agent. Impregnated into. Then, the base fiber impregnated with the fiber treatment agent was squeezed with two mangles and dried at 130 ° C. for 10 minutes in a hot air dryer. The amount of the fiber treatment agent attached was 40 to 50% by mass with respect to the weight of the fiber.
<Evaluation method of solid content>
A predetermined amount of sample is placed in a clean aluminum dish (height: about 17 mm, diameter: about 40 mm) that has been precisely weighed in advance, and after precision weighing using a direct balance with a sensitivity of 0.5 mg or less, the internal temperature is 105 ° C ± 2 ° C. Leave it in the dryer adjusted to 1 hour. The dried sample is cooled to room temperature in a desiccator, then precisely weighed on 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) x 100
<Evaluation method of phosphorus atom content>
Any method such as a colorimetric method or ICP emission analysis may be used, and for example, the phosphorus atom content can be determined by elemental analysis.

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

(1) UL-94 vertical combustion test (V-0, V-1, V-2) with a test piece that has been allowed to stand for 12 hours or more under the conditions of 23 ° C. and 50% RH after producing a flame-retardant processed fiber product. A combustion test was conducted based on the standard). The size of the test piece was 127 mm in length and 12.7 mm in width. The flame contact was performed twice for each of the five test pieces, for a total of 10 times, and the average number of seconds and the maximum number of seconds for the flame extinguishing time were measured to make a judgment.
UL-94 Vertical Combustibility Test (V)
V-0: The total combustion time of the first and second flame contact of the five test pieces is within 50 seconds, the maximum combustion time is within 10 seconds, and there is no material dripping due to combustion.
V-1: The total combustion time of the first and second flame contact of the five test pieces is within 250 seconds, the maximum combustion time is within 30 seconds, and there is no material dripping due to combustion.
V-2: The total burning time of 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.

(2) Rust prevention After manufacturing the processed product, the test piece left to stand at 23 ° C. and 50% RH for 12 hours or more was cut into vertical: 50 mm and horizontal: 70 mm, and brass (vertical: 120 mm, horizontal: 30 mm). (Thickness: 0.1 mm), the brass surface was allowed to stand for 14 days under the conditions of 60 ° C. and 95% RH, and the presence or absence of rust on the brass surface was confirmed. In Tables 4 and 5, the evaluation results are shown as follows.
With rust: ×
No rust: ○

(3) After producing the bleeding processed product, the test piece left to stand at 23 ° C. and 50% RH for 12 hours or more was cut into vertical: 50 mm, horizontal: 70 mm, and filter paper (vertical: 100 mm, horizontal: 60 mm, No.). 2. It was sandwiched between Toyo Filter Paper Co., Ltd.) and allowed to stand for 5 days under the 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 processed fiber products treated with the fiber treatment agents of the present invention (Examples 1 to 12) are excellent in both flame retardancy and rust prevention. It can also be seen that bleeding is sufficiently suppressed.
On the other hand, as shown in Table 5, it can be seen that the flame retardancy is insufficient when the fiber treatment agent containing no flame retardant (D) is used (Comparative Example 1). When a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with the flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 2.6% is used (Comparative Example 2). , 60 ° C., 95% RH, found to cause significant bleeding. When a fiber treatment agent that does not contain the phosphorus-containing unsaturated monomer (A) and is added with the flame retardant (D) so that the amount of phosphorus in the fiber treatment agent is 1.4% is used (Comparative Example 3). , It turns out that the flame retardancy is insufficient. When a fiber treatment agent containing no rust preventive agent (C) is used (Comparative Example 4), it can be seen that the rust preventive property is insufficient under the conditions of 60 ° C. and 95% RH. 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. It can be seen that the case (Comparative Example 5) causes remarkable bleeding.
When a fiber treatment agent containing no (meth) acrylic acid alkyl ester unsaturated monomer (b1) as a component of the polymerizable unsaturated monomer (B) is used (Comparative Example 6), the rust resistance is insufficient. It turns out that there is.

The fiber treatment agent of the present invention is particularly suitable for fiber treatment because the treated fiber processed product has excellent flame retardancy and excellent rust prevention under high humidity conditions. Further, the method for producing a processed fiber product using the fiber treatment agent of the present invention is suitable for producing various processed fiber products having excellent flame retardancy and rust resistance, and the method for producing the processed fiber product is used. This makes it possible to manufacture a fiber processed product having excellent flame retardancy and rust resistance. By using this processed fiber product, it becomes possible to manufacture cushioning materials for electronic materials, cushioning materials for home appliances, cushioning materials for automobile interiors, etc., which are excellent in flame retardancy and rust resistance.

Claims (6)

A copolymer (P) of a phosphorus-containing unsaturated monomer (A) and a polymerizable unsaturated monomer (B),
Rust inhibitor (C) and
With flame retardant (D),
It is a fiber treatment agent containing
The polymerizable unsaturated monomer (B) is
(Meta) acrylic acid alkyl ester unsaturated monomer (b1) and
At least one unsaturated monomer (b2) selected from the group consisting of (meth) acrylic acid and itaconic acid,
Including
The rust inhibitor (C) contains carboxybenzotriazole or 1- [N, N-bis (2-ethylhexyl) aminomethyl] benzotriazole .
The phosphorus-containing unsaturated monomer (A) contains a monomer (a1) having a phosphoric acid group or a phosphorous acid group.
The polymerizable unsaturated monomer (B) is contained in an amount of 40% by mass or more based on all the monomers in the copolymer (P).
In the polymerizable unsaturated monomer (B), at least one unsaturated substance selected from the group consisting of the (meth) acrylic acid alkyl ester unsaturated monomer (b1) and the (meth) acrylic acid and itaconic acid. The mass ratio (b1 / b2) with the saturated monomer (b2) is 96/4 to 4/96.
The rust preventive agent (C) is contained in an amount of 0.1 to 15% by mass based on the total fiber treatment agent.
A fiber treatment agent comprising the flame retardant (D) in an amount of 0.1 to 70% by mass with respect to the total fiber treatment agent. The fiber treatment agent according to claim 1 , wherein the monomer (a1) having a phosphoric acid group or a phosphorous acid group contains an acid phosphooxypolyoxyalkylene glycol mono (meth) acrylate. The fiber treatment agent according to claim 1 or 2 , wherein the flame retardant (D) contains phosphorus. The fiber treatment agent according to any one of claims 1 to 3 , wherein the phosphorus atomic weight in the fiber treatment agent is 0.01 to 30% by mass. A method for producing a processed fiber product, which comprises a step of treating a fiber base material with the fiber treatment agent according to any one of claims 1 to 4 to obtain a processed fiber product. A processed fiber product in which the amount of the fiber treatment agent adhered to any one of claims 1 to 5 after drying is 50 to 100 parts by mass with respect to 100 parts by weight of the fiber base material.