TWI778076B - Copolymer, resin composition, treatment agent and processed product - Google Patents

Abstract

A copolymer which includes a structural component originated from a phosphorous-including unsaturated monomer (A) and a structural component originated from a polymerizable unsaturated monomer (B), wherein the structural component originated from a polymerizable unsaturated monomer (B) includes a structural component originated from an unsaturated carboxylic acid monomer (b-1) having a main chain, wherein the total of the number of carbon atom and the number of oxygen atom is 4 to 10, and wherein the amount of a structural component originated from a (meth)acrylic acid alkyl ester monomer (b-2), which has an alkyl group with a carbon number of 1 to 4, is 0.00 to 1.00 % by mass with respect to the total of the amount of the structural component originated from the phosphorous-including unsaturated monomer (A) and the amount of the structural component originated from the polymerizable unsaturated monomer (B).

Description

Copolymers, resin compositions, treatment agents, and processed products

The present invention relates to a copolymer, a resin composition, a treatment agent, and a processed product. This application claims priority based on Japanese Patent Application No. 2017-125089 filed in Japan on June 27, 2017, the content of which is incorporated herein by reference.

Processed products (hereinafter, also referred to as "processed products, etc.") to which treatment agents such as paper treatment agents, fiber treatment agents, and adhesives are adhered to the substrate are widely used in construction materials, home appliances, electronic materials, automobiles, and the like. Vehicle interior materials, etc. Synthetic resins are widely used as materials for processing agents used in processed products, etc., as physical property improvers, binders, or dispersants.

In recent years, from the viewpoint of safety, flame retardancy of processed products and the like has been demanded. As a method of making a processed product etc. flame-retardant, the method of using what contains a flame-retardant agent as a processing agent used for a processed product etc. is mentioned. As flame retardants, inorganic flame retardants such as red phosphorus, antimony trioxide, aluminum hydroxide, magnesium hydroxide, etc.; halogen flame retardants such as pentabromobiphenyl, octabromobiphenyl, and decabromobiphenyl are known. ; Non-halogen flame retardants such as phosphate, guanidine phosphate, triphenyl phosphate, amine sulfonic acid, etc.

Halogen-based flame retardants have excellent flame retardant properties. Therefore, when a halogen-based flame retardant is used as the flame retardant, the amount of the flame retardant used can be made relatively small in many cases. Therefore, in the processed product etc. manufactured using the processing agent containing a halogen-type flame retardant, the flame retardant has little influence on physical properties, such as a processed product.

However, the halogen-based flame retardant contains halogen elements such as chlorine, bromine, and fluorine. Therefore, when a processed product or the like containing a halogen-based flame retardant is incinerated, there is a possibility that harmful substances such as dioxin and hydrogen halide are generated. Therefore, halogen-based flame retardants are being regulated or re-evaluated in countries around the world including EU countries. In addition, it is widely known that halogen-based flame retardants are used in combination with antimony compounds to exhibit higher flame retardancy. Therefore, halogen-based flame retardants are often used in combination with antimony compounds. However, in recent years, antimony compounds have also begun to be regulated or re-evaluated, and there is a tendency to avoid their use.

Compared with halogen-based flame retardants, non-halogen-based organic flame retardants are superior in safety. As the non-halogen-based organic flame retardant, a phosphorus-based flame retardant composed of a phosphorus-based compound has been reviewed in many cases. However, in general, the flame retardant performance of phosphorus-based flame retardants is lower than that of halogen-based flame retardants. Therefore, when a phosphorus-based flame retardant is used as the flame retardant, it is often necessary to use a large amount of the flame retardant in order to obtain sufficient flame retardant properties. Therefore, in processed products etc. using the treating agent containing a phosphorus-based flame retardant, since a large amount of flame retardant needs to be blended, the processed products and the like may have insufficient bleed resistance and blocking resistance.

Patent Document 1 proposes a flame-retardant copolymer resin composed of a terpolymer of a monomer containing a specific amount of phosphorus, an acrylic unsaturated monomer, and a vinyl acetate monomer. Patent Document 2 proposes a resin composition obtained by copolymerizing an unsaturated monomer having a phosphoric acid group or a phosphorous group, an alkyl (meth)acrylate monomer, and an acrylic unsaturated monomer, and processing using this paper and fiber products. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 7-18028 [Patent Document 2] Japanese Patent Laid-Open No. 2010-235830

[Problems to be solved by the invention]

However, conventional processed products containing flame retardant resins cannot satisfy all of flame retardancy, bleed resistance and blocking resistance.

The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to provide a resin having excellent flame retardancy and excellent bleed resistance and blocking resistance. Furthermore, an object of the present invention is to provide a resin composition and a treatment agent that can obtain a coating film having good flame retardancy, bleed resistance and blocking resistance. In addition, an object of the present invention is to provide a processed product having excellent flame retardancy, bleed resistance and blocking resistance. [Means to solve the problem]

In order to solve the above-mentioned problems, the inventors of the present invention have repeated intensive studies to provide a resin that satisfies all of flame retardancy, bleed resistance, and blocking resistance. As a result, it was found that it is only necessary to be a copolymer, which is a copolymer comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), which is derived from (B) The constituents of the compound include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms, and relative to the aforementioned constituents derived from (A) and The total content of the constituent components derived from the aforementioned (B) and the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms are 0.00 to 1.00 mass %, and came up with the present invention. That is, the first aspect of the present invention is the following copolymer.

[1] A copolymer comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that: The constituent component of the saturated monomer (B) includes the constituent component derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms, and is relative to the aforementioned constituent component derived from the unsaturated carboxylic acid monomer (b-1). The total content of the constituent components of the phosphorus unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) is derived from the alkyl (meth)acrylate monoester having an alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the body (b-2) is 0.00 to 1.00 mass %.

The copolymer described in the above [1] is also preferably a copolymer having the following characteristics. The following features can also be combined with each other.

[2] The copolymer according to [1], wherein the constituent component derived from the phosphorus-containing unsaturated monomer (A) includes a structure derived from the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group Element. [3] The copolymer according to [2], wherein the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group is an acidic phosphonooxypolyoxyalkylene glycol mono(methyl) Acrylate. [4] The copolymer according to any one of [1] to [3], wherein the phosphorus atom content is 0.1 to 10 mass %.

[5] The copolymer according to any one of [1] to [4], wherein the unsaturated carboxylic acid monomer (b-1) is composed of acrylic acid, methacrylic acid, itonic acid, β-carboxyethyl At least one selected from acrylic. [6] The copolymer according to any one of [1] to [5], wherein the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B)-derived As for the total content of the constituent components, the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass.

[7] The copolymer according to any one of [1] to [6], which further contains a structural component derived from a chain transfer agent (C). [8] The copolymer according to [7], wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1). [9] The copolymer according to [7] or [8], which is relative to the sum of the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) Content is 100 mass parts, and content of the said structural component derived from the chain transfer agent (C) is 0.1-10 mass parts. [10] The copolymer according to any one of [1] to [9], which has a mass-average molecular weight of 25,000 to 70,000. [11] The copolymer according to any one of [1] to [10], which has an acid value of 300 to 800 mgKOH/g.

The second aspect of the present invention is the following resin composition. [12] A resin composition comprising the copolymer according to any one of [1] to [11]. The above-mentioned resin composition is also preferably a composition having the following characteristics. [13] The resin composition according to [12], further comprising a surfactant. The third aspect of the present invention is the following treatment agent. [14] A treating agent comprising the copolymer according to any one of [1] to [11]. The fourth aspect of the present invention is the following processed product. [15] A processed product comprising a base material and the copolymer according to any one of [1] to [11] attached to the base material. The above-mentioned processed product is also preferably a composition having the following characteristics. [16] A processed product having a solid content of the treatment agent according to [14] adhered to a substrate, wherein the solid content is 5 to 70% by mass attached to the processed product. [Effect of invention]

The copolymer of the present invention is excellent in flame retardancy, exudation resistance and blocking resistance. In addition, by attaching the copolymer of the present invention to a substrate, a processed product having good flame retardancy, bleeding resistance and blocking resistance can be obtained. Since the resin composition and treatment agent of the present invention contain the copolymer of the present invention, a coating film with excellent flame retardancy, good bleed resistance and good blocking resistance can be obtained. The processed product of the present invention has a substrate and the copolymer of the present invention attached to the substrate. Therefore, it has excellent flame retardancy, exudation resistance and blocking resistance. [The form of carrying out the invention]

Hereinafter, preferred examples of the copolymer, resin composition, treatment agent, and processed product of the present invention will be described in detail. In addition, this invention is not limited only to embodiment shown below. For example, types, numbers, amounts, materials, structures, etc. can be added, omitted, or changed without departing from the gist of the present invention.

"-" in this specification means the value before the description of "-" or more and the value after the description of "-" or less. In addition, descriptions such as "(meth)acrylate" in this specification are synonymous with "acrylate and/or methacrylate" and the like. In addition, the description of "unsaturated monomer" and the like in this specification is synonymous with "monomer having an α,β-ethylenically unsaturated group" and the like.

[Copolymer] The copolymer of the present embodiment must contain a constituent derived from the phosphorus-containing unsaturated monomer (A) (hereinafter, also referred to as "a constituent derived from (A)") and a polymerizable unsaturated monomer ( The constituents of B) (hereinafter, also referred to as "the constituents derived from (B)"). However, among the components derived from (B), the components derived from (A) are not included. In the copolymer, the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) are both repeating units. In the copolymer, the arrangement order of the repeating units is not particularly limited. That is, the copolymer may be any of a random copolymer, a block copolymer, and an alternating copolymer.

<Phosphorus-containing unsaturated monomer (A)> The constituent component derived from the phosphorus-containing unsaturated monomer (A) contained in the copolymer improves the flame retardancy of the copolymer. The constituent component derived from the phosphorus-containing unsaturated monomer (A) is derived from the phosphorus-containing unsaturated monomer (A) used as a raw material of the copolymer. The phosphorus-containing unsaturated monomer (A) used as the raw material of the copolymer 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, and diphenylvinylphosphine acid ester, dimethyl(1,2-diphenyl-vinyl)phosphonate, dimethyl-p-vinylbenzylphosphonate, diethyl-p-vinylbenzylphosphonate, Diphenyl-p-vinylbenzylphosphine oxide, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-10-p-vinylbenzyl, acid phosphine oxide Ethyl (meth)acrylate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-methacryloyloxyethyl Phosphate ester, (meth)acryloyl/oxyethyl acid phosphoric acid ester/monoethanolamine salt, acid/phosphonooxypolyoxyethylene glycol mono(meth)acrylate and acid/phosphonooxypolyoxyethylene Propylene glycol glycol (meth)acrylates and their metal salts, ammonium salts, amine salts, and the like. These compounds can be used alone or as a mixture of two or more.

(Monomer (a-1) having either a phosphoric acid group or a phosphorous acid group) The phosphorus-containing unsaturated monomer (A) used as a raw material of the copolymer is preferably represented by the following formula (1) Monomer (a-1) of any one of the phosphoric acid group and the phosphorous acid group represented by the following formula (2). By using the monomer (a-1), a copolymer having more excellent flame retardancy can be obtained.

(式(1)中，＊表示與構成不飽和單體的原子之鍵結部)。

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer).

(式(2)中，＊表示與構成不飽和單體的原子之鍵結部)。

(In formula (2), * represents a bond with an atom constituting an unsaturated monomer).

Examples of the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group include a compound represented by the general formula (3), and metal salts, ammonium salts, and amine salts of the compounds. Use alone or in combination of two or more.

(式(3)中，R¹ 及R² 各自獨立地表示氫原子或碳數1～3的烷基；Z表示氫原子或羥基；n為1～20之整數)。

(In formula (3), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Z represents a hydrogen atom or a hydroxyl group; and n is an integer of 1 to 20).

In formula (3), R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. In formula (3), Z represents a hydrogen atom or a hydroxyl group, preferably a hydrogen atom. In formula (3), n is an integer of 1-20, Preferably it is an integer of 1-8, More preferably, it is an integer of 1-3.

As a specific example of the monomer (a-1) which has any one of a phosphoric acid group and a phosphorous acid group, an acid phosphinodioxy polyoxyalkylene glycol mono(meth)acrylate is mentioned. If the monomer (a-1) having a phosphoric acid group or a phosphorous acid group is an acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate, it is preferable to obtain a copolymer having higher flame retardancy. Among the acid-phosphonooxypolyoxyalkylene glycol mono(meth)acrylates, especially in the point where the ratio of phosphorus atoms per molecule is high, acid-phosphonooxyethyl (methyl) is preferable. base) acrylate.

The content of the constituent components derived from the phosphorus-containing unsaturated monomer (A) can be arbitrarily selected, but the total content of the constituent components derived from the phosphorus-containing unsaturated monomer (A) and the constituent components derived from the polymerizable unsaturated monomer (B) is relatively small. 5-60 mass % is preferable, 7-50 mass % is more preferable, 10-40 mass % is especially preferable. If the content of the constituent component derived from (A) with respect to the total content is 5 mass % or more, the copolymer will be more excellent in flame retardancy. Moreover, when content of the structural component derived from (A) with respect to the said total content is 60 mass % or less, a copolymer can be polymerized stably, and the storage stability of a copolymer becomes favorable. In addition, when the content of the constituent component derived from (A) is 60 mass % or less, when this is used as the material of the processed product, the strength and heat-resistant yellow caused by the excessive content of the constituent component derived from (A) are suppressed. The denaturation is reduced, and the processed products with good anti-bleeding and anti-blocking properties can be obtained at the same time.

<Polymerizable unsaturated monomer (B)> The constituent component derived from the polymerizable unsaturated monomer (B) contained in the copolymer is used together with the constituent component derived from the phosphorus-containing unsaturated monomer (A), And improve the flame retardancy of the copolymer. In addition, the structural component derived from the polymerizable unsaturated monomer (B) improves the adhesion and appearance stability of the processed product using the copolymer as a material. The constituent component derived from the polymerizable unsaturated monomer (B) is derived from the polymerizable unsaturated monomer (B) used as a raw material of the copolymer.

The constituent component derived from the polymerizable unsaturated monomer (B) contained in the copolymer includes: an unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms constituents. The polymerizable unsaturated monomer (B) used as the raw material of the copolymer may be only the unsaturated carboxylic acid monomer (b-1). In addition to the unsaturated carboxylic acid monomer (b-1), the polymerizable unsaturated monomer (B) may contain an ethylenically unsaturated bond in the molecule, exhibit polymerizability, and interact with the phosphorus-containing unsaturated monolayer. Other unsaturated monomers copolymerized with body (A).

(Unsaturated carboxylic acid monomer (b-1) having a main chain in which the total number of carbon atoms and oxygen atoms is 4 to 10) The constituent components derived from (B) have carbon atoms and oxygen atoms The constituent components of the main chain unsaturated carboxylic acid monomer (b-1) whose total is 4 to 10 improve the flame retardancy of the copolymer. The constituents derived from (B) may be constituents of the above-mentioned unsaturated carboxylic acid monomer (b-1) only in part. When all the constituent components derived from (B) are the constituent components of the unsaturated carboxylic acid monomer (b-1), it is preferable to obtain a copolymer having more excellent flame retardancy.

The unsaturated carboxylic acid monomer (b-1) used as a raw material of the copolymer has a main chain having a total of 4 to 10 carbon atoms and oxygen atoms. The main chain of the unsaturated carboxylic acid monomer (b-1) refers to the longest molecular chain among the molecular chains composed of carbon atoms and oxygen atoms in the structure of the compound. For example, the total of the number of carbon atoms and the number of oxygen atoms in the main chain is 4 in methacrylic acid and 6 in maleic acid. When the unsaturated carboxylic acid monomer used as the raw material of the copolymer is one having a main chain in which the total number of carbon atoms and the number of oxygen atoms does not exceed 10, the flame retardancy of the copolymer becomes sufficient. In addition, when an unsaturated carboxylic acid monomer having a main chain in which the total number of carbon atoms and oxygen atoms does not exceed 10 is used as a raw material of the copolymer, the polymerization stability of the copolymer becomes sufficient.

Specific examples of the unsaturated carboxylic acid monomer (b-1) include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, β-carboxyethyl acrylic acid, and the like. Among them, especially since the copolymer can be stably polymerized, the content of the constituent components of the unsaturated carboxylic acid monomer (b-1) in the copolymer is increased, and acrylic acid, methacrylic acid or itonic acid is preferred, More preferred is acrylic acid or methacrylic acid, and particularly preferred is acrylic acid.

The content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) can be arbitrarily selected, but is less than the total content of the constituent components derived from (A) and the constituent components derived from (B) in the copolymer. Preferably it is 30 mass % - 95 mass %. The lower limit of the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is more preferably 35% by mass or more, and particularly preferably 40% by mass or more, relative to the total content. The upper limit of the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is more preferably 90% by mass or less, and particularly preferably 85% by mass or less, relative to the total content. The copolymer (P) can be stably polymerized when the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30% by mass or more. When the content of the constituent components derived from the above-mentioned unsaturated carboxylic acid monomer (b-1) is 95% by mass or less, a copolymer having more excellent flame retardancy will be obtained.

(Alkyl (meth)acrylate monomer (b-2) having an alkyl group having a carbon number of 1 to 4) The total content must be 0.00 to 1.00 mass % of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms (b-2). . The alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms used as a raw material of the copolymer includes a monomer represented by the following formula (4).

(式(4)中，R³ ～R⁵ 各自獨立地表示氫原子或甲基；R⁶ 係碳數為1～4之直鏈或分枝的烷基)。

(In formula (4), R ³ to R ⁵ each independently represent a hydrogen atom or a methyl group; R ⁶ is a linear or branched alkyl group having 1 to 4 carbon atoms).

Specific examples of the alkyl (meth)acrylate monomer (b-2) represented by the formula (4) include methyl (meth)acrylate, ethyl (meth)acrylate, and (methyl) Propyl acrylate, butyl (meth)acrylate, etc.

Structural component derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms with respect to the total content of the structural component derived from (A) and the structural component derived from (B) The content is 0.00 to 1.00 mass %. The content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) is more preferably 0.75 mass % or less, particularly preferably 0.50 mass % or less. When content of the structural component derived from the alkyl (meth)acrylate monomer (b-2) exceeds 1.00 mass %, the flame retardance of a copolymer will fall.

In the structural component derived from the polymerizable unsaturated monomer (B), the alkane (meth)acrylate which is not derived from the unsaturated carboxylic acid monomer (b-1) and the alkyl group having 1 to 4 carbon atoms may be included Among the constituents of the ester monomer (b-2) are constituents derived from other unsaturated monomers. Examples of polymerizable unsaturated monomers other than (b-1) and (b-2) that can be used as raw materials for copolymers include amyl (meth)acrylate, hexyl (meth)acrylate, ( 2-ethylhexyl (meth)acrylate, allyl (meth)acrylate, ethylene glycol di(meth)acrylate, methoxyethyl (meth)acrylate, butoxy (meth)acrylate ethyl ester, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylate ) hydroxybutyl acrylate, ethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate ) acrylate, polyethylene glycol polytetramethylene glycol mono(meth)acrylate, polypropylene glycol polytetramethylene glycol mono(meth)acrylate, glycidyl (meth)acrylate, Methylglycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butyl Glycol di(meth)acrylate, hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate Meth)acrylate, Dimethyloltricyclodecane di(meth)acrylate, Isobornyl (meth)acrylate, Phenoxy polyethylene glycol (meth)acrylate, Pentaerythritol tetrakis(meth)acrylate ) (meth)acrylate of acrylate, etc.; fumarate of fumarate, diethyl fumarate, dibutyl fumarate, di-(2-ethylhexyl) fumarate, etc. acid esters; maleic acid esters of dimethyl maleate, diethyl maleate, dibutyl maleate, bis-(2-ethylhexyl) maleate, etc.; methacrylic acid amide; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-propyl (meth) acrylamide, etc. ( Methyl) acrylamide derivatives; methoxy styrene, ethoxy styrene vinyl benzoic acid, methyl vinyl benzoate, vinyl benzyl acetate, hydroxy styrene, divinyl benzene, etc. Styrene derivatives; vinyl acetate; vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, vinyl stearate, etc. vinyl esters; methylmaleimide, ethyl N-substituted maleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide, naphthylmaleimide, etc. Maleimide compounds; Iconic acid monomethyl ester, Iconic acid dimethyl ester, Iconic acid monoethyl ester, Iconic acid diethyl ester, Iconic acid monobutyl ester, Iconic acid dibutyl ester, etc. Iconic acid esters; crotonic acid esters of methyl crotonate, ethyl crotonate, butyl crotonate, etc.; dimethyl phthalate, diethyl phthalate, dipropyl phthalate, ortho Phthalates such as dibutyl phthalate, dihexyl phthalate, etc.; succinates such as 2-acryloyloxyethyl-succinic acid, etc. These can be used alone or in combination of two Use above.

The content of the structural component derived from the polymerizable unsaturated monomer (B) can be arbitrarily selected, but is preferably 40% by mass to the total content of the structural component derived from (A) and the structural component derived from (B). 95% by mass. The lower limit of the content of the constituent components derived from (B) with respect to the total content is more preferably 50 mass % or more, and particularly preferably 60 mass % or more. The upper limit of the content of the constituent components derived from (B) with respect to the total content is more preferably 90% by mass or less, and particularly preferably 85% by mass or less. The copolymer can be stably polymerized when the content of the constituent component derived from (B) is 40% by mass or more with respect to the total content. In addition, when the content of the constituent components derived from (B) with respect to the above-mentioned total content is 95% by mass or less, the synergistic effect of the constituent components derived from (A) and the constituent components derived from (B) changes remarkably, and the copolymer The flame retardancy is further increased.

<Chain transfer agent (C)> The copolymer of the present embodiment may contain constituent components derived from the chain transfer agent (C). The structural component derived from the chain transfer agent (C) is to adjust the mass average molecular weight of the copolymer containing the structural component derived from the phosphorus-containing unsaturated monomer (A) and the structural component derived from the polymerizable unsaturated monomer (B), The segment of the chain transfer agent (C) used in the polymerization is bound to the copolymer.

Examples of the chain transfer agent (C) include thiodiglycol, ethylene thioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl sulfide, and thioglycolic acid. , mercaptopropionic acid, mercaptobutyric acid, mercaptocaproic acid, 2-ethylhexyl thioglycolate, mercaptosuccinic acid, thioacetic acid, thiourea and other sulfur-containing compounds; bisulfite, hypophosphorous acid and its salts and sulfites Phosphorus-containing compounds such as phosphoric acid and its salts; aldehyde compounds such as formaldehyde, acetaldehyde, propionaldehyde, etc.; organic acids such as formic acid, sodium formate, ammonium formate, etc.; alcohol compounds such as isopropanol, etc. These chain transfer agents (C) can be used alone or in combination of two or more. In addition, when the structural component derived from the chain transfer agent (C) is also a structural component derived from the phosphorus-containing unsaturated monomer (A), it is regarded as a structural component derived from the phosphorus-containing unsaturated monomer (A).

As the chain transfer agent (C), among the above, in particular, the polymerization stability, and the terminal carboxylic acid in the constituent components of the polymerizable unsaturated monomer (B) and the phosphorus-containing unsaturated monomer (A) are derived. From the viewpoint of the improvement in flame retardancy due to the synergistic effect of the constituent components, it is preferable to contain a mercapto alkyl carboxylate. As a mercaptoalkyl carboxylate, mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptocaproic acid, etc. are mentioned.

The content of the structural component derived from the chain transfer agent (C) can be arbitrarily selected, but is preferably 0.1 to 10 mass parts relative to 100 parts by mass of the total content of the structural component derived from (A) and the structural component derived from (B). share. The lower limit value of the content of the constituent components derived from the chain transfer agent (C) is more preferably 1 part by mass or more, particularly preferably 2 parts by mass or more, with respect to the total content. The upper limit of the content of the constituent components derived from the chain transfer agent (C) is more preferably 9 parts by mass or less, particularly preferably 8 parts by mass or less, with respect to the total content. When the content of the constituent components derived from the chain transfer agent (C) is 0.1 part by mass or more with respect to the above-mentioned total content, the chain transfer agent (C) has an effect of adjusting the mass average molecular weight of the copolymer, which is excellent. The polymer stability and storage stability of the copolymer. In addition, when the content of the constituent components derived from the chain transfer agent (C) is 10 parts by mass or less relative to the above-mentioned total content, the constituent components derived from the chain transfer agent (C) do not interfere with the flame retardancy of the copolymer and become Those with better flame retardancy. The content of the constituent components derived from the chain transfer agent (C) can be measured by a well-known method such as ¹ H-NMR. Moreover, in order to make content of the structural component originating in a chain transfer agent (C) into the said range, it is preferable to use a slightly larger quantity than content at the time of superposition|polymerization.

"Mass average molecular weight" The mass average molecular weight of the copolymer of the present embodiment is preferably 25,000 to 70,000. The lower limit value of the mass average molecular weight is more preferably 27,000 or more, particularly preferably 30,000 or more. The upper limit value of the mass average molecular weight is more preferably 60,000 or less, particularly preferably 55,000 or less. When the mass average molecular weight of the copolymer is 25,000 or more, the copolymer is more excellent in flame retardancy. When the mass average molecular weight of the copolymer is 70,000 or less, the polymerization stability of the copolymer becomes good.

The mass average molecular weight of the copolymer was measured as follows using gel permeation chromatography (GPC) trade name "Shodex GPC-101" (manufactured by Showa Denko Co., Ltd., "Shodex" is a registered trademark). Prepared in 34.5 g of disodium hydrogen phosphate 12 hydrate and 46.2 g of sodium dihydrogen phosphate dihydrate, and added ultrapure water to make the total amount an aqueous solution of 5.000 g as a carrier liquid. The copolymer was dissolved in this carrier liquid, and the measurement was performed at a flow rate of 0.5 ml/min. using a pump (<DU-H2000>, manufactured by Shodex). As the column, an aqueous GPC column (analytical column: <OHpak SB-806M MQ>, manufactured by Shodex, reference column: <OHpak SB-800RL>, manufactured by Shodex) was used. An RI detector (<RI-71S>, manufactured by Shodex) was used as a detector, and sodium polyacrylate (Sigma-Aldrich) was used as a molecular weight standard sample.

"Acid value" The acid value of the copolymer of the present embodiment is preferably 300 to 800 mgKOH/g. The lower limit value of the acid value is preferably 350 mgKOH/g or more, more preferably 450 mgKOH/g or more. The upper limit of the acid value is preferably 785 mgKOH/g or less, more preferably 750 mgKOH/g or less. When the acid value of the copolymer is 300 mgKOH/g or more, the copolymer is more excellent in flame retardancy. When the acid value of the copolymer is 800 mgKOH/g or less, the polymerization stability and storage stability of the copolymer are improved.

"Phosphorus Atom Content" The phosphorus atom content in the copolymer can be arbitrarily selected, but is preferably 0.1 to 10% by mass. The lower limit value of the above-mentioned phosphorus atom content is more preferably 0.5 mass % or more, particularly preferably 1.0 mass % or more. The upper limit value of the above-mentioned phosphorus atom content is more preferably 9.0 mass % or less, and particularly preferably 8.0 mass % or less. When the above-mentioned phosphorus atom content is 0.1 mass % or more, a copolymer having more excellent flame retardancy will be obtained. When the above-mentioned phosphorus atom content is 10 mass % or less, the copolymer can be stably polymerized, and the storage stability of the copolymer is improved. In addition, when the above-mentioned phosphorus atom content is 10 mass % or less, when this is used as a material of a processed product, the decrease in adhesion to the base material and the appearance change due to the excessive phosphorus atom content can be suppressed, and the anti-aging can be obtained. Processed product with good bleed and anti-blocking properties.

[Production Method of Copolymer] The copolymer of the present embodiment can be produced by, for example, using a conventionally known method to radically copolymerize an unsaturated monomer as a raw material of the copolymer. The unsaturated monomer of the raw material includes the above-mentioned phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B).

As a method for copolymerizing the unsaturated monomer, for example, a suspension polymerization method, an emulsion polymerization method, a solution polymerization method, a bulk polymerization method, or the like can be used. In addition, a continuous polymerization method or a batch polymerization method may be used. When producing a copolymer by copolymerizing an unsaturated monomer, a chain transfer agent (C), a solvent shown below, a surfactant, an initiator, and a neutralizing agent can be used as necessary.

As a method for producing the copolymer, it is preferable to use an emulsion polymerization method using a surfactant or a solution polymerization method not using a surfactant. In the emulsion polymerization method, the unsaturated monomer, solvent, surfactant (emulsifier) and the above-mentioned chain transfer agent (C) of the raw materials are first mixed to form a monomer emulsion. The chain transfer agent (C) may be used as needed, and may not be included in the monomer emulsion. Next, the obtained monomer emulsion and the initiator are mixed and reacted at a predetermined reaction temperature to obtain a resin composition (aqueous emulsion) in which the copolymer is dispersed in a solvent. In the resin composition, a part of the copolymer may be dissolved in the solvent. Thereafter, a neutralizing agent is added to the resin composition for neutralization as necessary. Then, by removing the solvent in the resin composition and drying it, the resin solid content including the copolymer can be separated from the resin composition.

In the solution polymerization method, first, the unsaturated monomer, the solvent, and the above-mentioned chain transfer agent (C) of the raw materials are mixed to obtain a monomer solution. The chain transfer agent (C) may be used as needed, and may not be included in the monomer solution. Next, the obtained monomer solution and the initiator are mixed and reacted at a predetermined reaction temperature to obtain a resin composition in which the copolymer is dissolved in a solvent. In the resin composition, a part of the copolymer may not be dissolved in the solvent due to the high molecular weight of the copolymer or the like. Thereafter, neutralization is performed by adding a neutralizing agent to the resin composition as necessary. Then, by removing the solvent in the resin composition and drying it, the resin solid content including the copolymer can be separated from the resin composition.

In the emulsion polymerization method (or the solution polymerization method), a conventionally known method can be used as the method of mixing the monomer emulsion (monomer solution in the solution polymerization method) and the initiator. For example, a monomer emulsion (monomer solution in the solution polymerization method) can be added dropwise to the starter, followed by stirring. At this time, a part of the initiator may be dropped into the initiator together with the monomer emulsion (monomer solution in the solution polymerization method). Moreover, the method of mixing together the whole quantity of an initiator and the whole quantity of a monomer emulsion (monomer solution in a solution polymerization method) can also be used.

In the method for producing the copolymer of the present embodiment, the method for adjusting the mass average molecular weight of the copolymer is not particularly limited. For example, a method of using a chain transfer agent (C), or adjusting the concentration of the initiator method, the method of adjusting the reaction temperature, etc. The reaction temperature can be changed according to the type of the starting agent and the like.

<Solvent> The solvent used in the production of the copolymer can be arbitrarily selected. For example, an aqueous solvent such as water or a commonly used organic solvent can be used, and an aqueous solvent is preferred.

烷、四氫呋喃等之醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等之酮類；苯、甲苯、二甲苯、己烷、辛烷、癸烷等之烴類；石油醚、石油腦、氫化石油腦、溶劑油等之石油系溶劑；乳酸甲酯、乳酸乙酯、乳酸丁酯等之乳酸酯類；二甲基甲醯胺、N-甲基吡咯啶酮、二乙二醇單乙基醚等。此等之溶劑係可單獨或組合二種以上使用。Examples of the solvent include alcohols such as water, methanol, ethanol, propanol, isopropanol, butanol; ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate, and the like ethylene glycol monoalkyl ether acetates; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, etc. Esters; propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates, etc. acetates; ethylene glycol dialkyl ethers; methyl carbitol, ethyl carbitol, butyl Diethylene glycol dialkyl ethers such as carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; methyl ether, diethyl ether, 1,4-dialkyl ether

Ethers such as alkane, tetrahydrofuran, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; hydrocarbons such as benzene, toluene, xylene, hexane, octane, decane, etc. ; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, mineral spirits, etc.; lactic acid esters such as methyl lactate, ethyl lactate, butyl lactate, etc.; dimethylformamide, N-methylpyrrolidone , Diethylene glycol monoethyl ether, etc. These solvent systems can be used individually or in combination of 2 or more types.

<Initiator> When a copolymer is produced by copolymerizing the unsaturated monomer of the raw material by radical polymerization, the copolymer is carried out in the presence of an initiator.

The initiator is not particularly limited as long as it can initiate radical polymerization, and generally used peroxides, azo compounds, and the like can be used. Specific examples of the initiator include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzyl peroxide, dicumyl peroxide, diisopropyl peroxide compound, di-tert-butyl peroxide, tert-butyl peroxybenzoate, tert-hexyl peroxybenzoate, tert-butyl peroxy-2-ethylhexanoate, tertiary hexyl Peroxy-2-ethylhexanoate, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5- Bis(tert-butylperoxy)hexyl-3,3-isopropyl hydroperoxide, tert-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl Base peroxide, 1,1-bis(3rd-hexylperoxy)-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobisformamide, etc. can also be used according to the reaction appropriate reducing agent.

The usage-amount of the initiator can be arbitrarily selected, but in order to achieve an appropriate polymerization rate, it is more 0.01-20 mass parts is preferable, 0.1-15 mass parts is more preferable, 0.5-10 mass parts is especially preferable.

<Surfactant> Surfactant is used when the copolymer is produced by the emulsion polymerization method. As the surfactant, generally commercially available anionic surfactants, nonionic surfactants, cationic surfactants and copolymerizable surfactants can be used. Among these, it is preferable to use an anionic surfactant and a nonionic surfactant as a surfactant.

As anionic surfactant, alkylbenzenesulfonate, alkylsulfate, polyoxyethylene alkyl ether sulfate, fatty acid salt, etc. are mentioned, for example. Examples of nonionic surfactants include polyvinyl alcohol, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, and sorbose. Alcohol anhydride fatty acid ester, polyoxyethylene sorbitan fatty acid ester, etc. Examples of the cationic surfactant include cetyltrimethylammonium bromide, laurylpyridinium chloride, and the like.

As the copolymerizable surfactant, an anionic or nonionic surfactant having at least one radically polymerizable unsaturated double bond group in the molecule can be used. Examples of the copolymerizable surfactant include hydrocarbon compounds having a sulfate group such as an ammonium sulfate group (-SO ^3- NH ⁴⁺ ) and an allyl group (-CH ₂ -CH=CH ₂ ), Hydrocarbon compounds of sulfate groups such as ammonium sulfate groups (-SO ^3- NH ⁴⁺ ) and methacryloyl groups [-CO-C(CH ₃ )=CH ₂ ], or ammonium sulfate groups (-SO ^3- NH ⁴⁺ ) and other sulfate groups and 1-propenyl (-CH=CH ₂ CH ₃ ) aromatic hydrocarbon compounds and the like.

The amount of surfactant used can be arbitrarily selected, but in order to maintain the stability of the emulsification, it is more 0.01-40 mass parts is preferable, 0.05-20 mass parts is more preferable, 0.1-10 mass parts is especially preferable.

<Neutralizer> Neutralizers are used as necessary when producing a resin composition containing a copolymer. By adjusting the pH of the resin composition containing the copolymer using a neutralizing agent, the mixing stability in the resin composition can be improved, or the effect of suppressing bleeding can be obtained. As the neutralizing agent, a known compound can be used. For example, an aqueous sodium hydroxide solution, an aqueous ammonia solution, a monoalkylamine such as monomethylamine, and the like can be used.

<Water-soluble polymer> The water-soluble polymer is used as necessary when producing a copolymer. The water-soluble polymer is a protective colloid of the copolymer, which is stably dispersed in an aqueous solvent. As a water-soluble polymer, a water-soluble (meth)acrylic resin, a water-soluble (meth)acrylate resin, a polyoxyethylene alkyl ether, etc. can be used. These water-soluble polymers 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 of the water-soluble polymer is preferably 200 to 2,400 from the viewpoints of the polymerization stability and the viscosity of the copolymer when the copolymer is produced. The degree of saponification of the water-soluble polymer is preferably from 80% to 100%, from the viewpoint of the polymerization stability during the production of the copolymer. In addition, when the water-soluble polymer is also the polymerizable unsaturated monomer (B), it is regarded as the polymerizable unsaturated monomer (B).

The amount used when using the water-soluble polymer can be arbitrarily selected, but in order to maintain dispersion stability, it is based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B) of the raw material , preferably 0.01 to 40 parts by mass, more preferably 0.05 to 20 parts by mass, particularly preferably 0.1 to 10 parts by mass.

The copolymer of the present embodiment includes a component derived from the phosphorus-containing unsaturated monomer (A) and a component derived from a polymerizable unsaturated monomer (B), and the component derived from (B) includes a component derived from the unsaturated monomer having the number of carbon atoms and oxygen Constituents of the main chain unsaturated carboxylic acid monomer (b-1) whose total number of atoms is 4 to 10, and the total content of the constituents derived from (A) and the constituents derived from (B) is derived from The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %, and it is excellent in flame retardancy. The flame retardancy of the copolymer of the present embodiment is presumed to be due to the synergistic effect of the component derived from (A) and the carboxyl group contained in the component of the unsaturated carboxylic acid monomer (b-1), when combustion is accelerated. The carbide layer formed by this can be obtained.

The copolymer of this embodiment has excellent flame retardancy. Therefore, in the processed product containing the copolymer of this embodiment as a flame retardant, the content of the flame retardant can be made to be relatively small. Therefore, in the processed product containing the copolymer of this embodiment as a flame retardant, the effect of the flame retardant on the physical properties of the processed product is small. Furthermore, since the copolymer of the present embodiment contains both the constituents derived from (A) and the constituents derived from (B), when used as a material for a processed product, a processed product with good bleed resistance and blocking resistance can be obtained.

[Resin composition] The resin composition of the present embodiment includes the copolymer of the above-described embodiment. The resin composition of the present embodiment only needs to contain the copolymer of the above-mentioned embodiment, and for example, in addition to the copolymer of the above-mentioned embodiment, the above-mentioned solvent, surfactant, initiator, neutralizer, etc. may be contained. . The resin composition of this embodiment can be obtained in the process of manufacturing the copolymer of the said embodiment. The resin composition may contain the above-mentioned copolymer in any amount, but as an example, the amount of the above-mentioned copolymer in the composition is preferably 1.0 to 90% by mass, more preferably 10 to 85% by mass, particularly preferably 15 to 80 mass %. However, it is not limited to these ranges. For example, it may be 0.1 to 1.0 mass %, or 90 to 95 mass %.

[Treatment agent] The treatment agent of this embodiment contains the copolymer of the above-mentioned embodiment. As a processing agent of this embodiment, the thing which disperse|distributed or melt|dissolved a copolymer in the said solvent is mentioned, for example. Such a treatment agent is applied to a substrate to adhere to a substrate, and a coating film containing a copolymer is formed by removing the solvent. Therefore, the treatment agent of this embodiment can be used as a paint, a paper treatment agent, a fiber treatment agent, an adhesive, an adhesive, and the like. As the treatment agent of the present embodiment, a resin composition obtained by dispersing or dissolving the copolymer produced by the above-mentioned production method in a solvent can be used as it is.

The so-called "treatment agent" in this specification is defined to include a paint and an adhesive in addition to a paper treatment agent, a fiber treatment agent, and the like. The "solid content" of the treatment agent is defined as drying the solvent contained in the treatment agent.

<Other resins> The treatment agent of the present embodiment may contain other resins different from the copolymer of the above-mentioned embodiment in accordance with the application within the range that does not impair the effect of the present invention. As other resins, various resins such as acrylic resins, epoxy resins, urethane resins, and polyester resins can be mentioned. Other resins can also be in the state of resin emulsion or solution resin. The mixing ratio of the copolymer of the above-mentioned embodiment and other various resins in the treatment agent of the present embodiment is arbitrary.

<Other components> The treatment agent of the present embodiment may contain other components as necessary in addition to the copolymer. As other components, for example, cross-linking agents, tackifiers, pH adjusters such as acids or bases, film-forming aids, plasticizers, preservatives, Defoamers, pigments, dispersants, light stabilizers, ultraviolet absorbers, antioxidants, rust inhibitors, penetrants, antistatic agents, levelers, tackifiers and other well-known conventional additives are contained.

The processing agent of this embodiment can be manufactured by the method of mixing at least one of the copolymer of the said embodiment, the said solvent, other resin used as needed, and other components, for example using a conventionally known method. When producing the treatment agent, for example, mixing can be performed using various mixing devices such as a mill and a dissolver.

Since the treating agent of the present embodiment contains the copolymer of the present embodiment, a coating film having excellent flame retardancy and good bleed resistance and blocking resistance can be obtained. Since the treatment agent of this embodiment can impart excellent flame retardancy to the base material, it can be applied to various fields.

[Processed Product] The processed product of this embodiment has a base material and the copolymer, resin composition or treatment agent of the above-mentioned embodiment adhered to the base material. As the processed product of the present embodiment, for example, a paper processed product, a fiber processed product, a general processed product, an adhesive processed product, an adhesive processed product, and the like can be mentioned.

In the processed product of the present embodiment, the solid content of the treatment agent adhering to the substrate is preferably 5 to 70 mass %, more preferably 10 to 60 mass %, and particularly preferably 20 to 50 mass % with respect to the processed product %. When the adhesion amount of the solid content of the treatment agent is 5 mass % or more, a processed product with good flame retardancy can be easily obtained. If the adhesion amount of the solid content of the treatment agent is 70% by mass or less, it is possible to suppress poor appearance due to the adhesion of the copolymer in the treatment agent to the surface of the base material.

In the processed product of the present embodiment, the content of the copolymer is preferably 1 to 70 parts by mass relative to 100 parts by mass of the base material. The lower limit value of the content of the copolymer is more preferably 20 parts by mass or more, particularly preferably 40 parts by mass or more. The upper limit value of the content of the copolymer is more preferably 65 parts by mass or less, particularly preferably 60 parts by mass or less. When the content of the copolymer is 1 part by mass or more, the effect of improving the flame retardancy by including the copolymer is more effectively obtained. When the content of the copolymer is 70 parts by mass or less, it becomes easy to obtain a processed product according to the application.

The processed product of the present embodiment can be produced by, for example, applying or impregnating the treating agent of the present embodiment, drying it, and attaching the copolymer to a substrate.

The processed product of this embodiment has a base material and the copolymer of this embodiment attached to the said base material. Therefore, the processed product of this embodiment has excellent flame retardancy, bleed resistance and blocking resistance. Therefore, the processed strain of this embodiment can be applied to various fields.

"Specific examples" Next, as specific examples of the processing agent and processed product of the present embodiment, "paper processing agent and paper processed product", "fiber processing agent and fiber processed product", and "general paint and general processed product" will be described, respectively. , "Adhesives and Adhesives Processed Products". In addition, the term "adhesive agent" in this specification means a treatment agent having the functions of either or both of an adhesive agent and an adhesive agent.

"Paper processing agent and paper processed product" (paper processing agent) As the paper processing agent of the present embodiment, one in which an arbitrarily selected amount of the copolymer of the present embodiment is dissolved or dispersed in a solvent can be used. In the present embodiment, the content of the copolymer in the paper treating agent is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the paper processing agent whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(Paper processed product) In the paper processed product of the present embodiment, paper is used as a base material. As paper, general-purpose paper etc. which consist of pulp cellulose are mentioned, for example.

The usage-amount (adhesion amount) of a paper treating agent to a paper-processed product can be suitably changed according to the flame retardance of the base material itself used, etc.. The adhesion amount (solid content) after drying of the paper treatment agent can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass relative to the processed paper product. quality%. When the adhesion amount of the paper processing agent is 5 mass % or more, a paper processed product with good flame retardancy can be easily obtained. When the adhesion amount of the paper treatment agent is 70 mass % or less, the decrease in strength and texture due to the adhesion of the copolymer in the paper treatment agent to the surface of the substrate made of paper can be suppressed.

The adhesion amount (content) of the copolymer in the paper processed product can be arbitrarily selected, but is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the paper (substrate), especially Preferably it is 5-50 mass parts. When the adhesion amount of the copolymer is 1 part by mass or more, it is easy to obtain a paper processed product with good flame retardancy. If the adhesion amount of the copolymer is 70 parts by mass or less, the decrease in strength and texture due to the adhesion of the copolymer to the surface of the substrate made of paper can be suppressed.

(Manufacturing method of paper processed product) As the manufacturing method of the paper processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying or impregnating the paper treating agent of the present embodiment to a substrate made of paper, and drying the substrate can be mentioned. As a method of applying a paper treating agent to a substrate made of paper, a conventionally known method can be used. For example, the method of impregnating the substrate in the paper treatment agent (dipping), spray coating, roll coating, and the like are exemplified. By such a coating method, after the paper treatment agent is applied to the substrate, the substrate coated with the paper treatment agent is squeezed using a nip roll or the like, thereby adjusting the paper treatment that adheres to or impregnates the substrate. Adhesion amount of the agent.

As a method of drying the substrate coated with the paper treatment agent, a conventionally known method can be used. For example, the base material coated with the paper treatment agent may be air-dried, may be dried under reduced pressure, or may be dried under pressure. When drying the substrate coated with the paper treatment agent, the substrate coated with the paper treatment agent can also be heated. The heating temperature at the time of heating and drying the substrate coated with the paper treatment agent can be arbitrarily selected, but is preferably 50 to 250°C, more preferably 80 to 190°C, particularly preferably 90 to 150°C. When the said heating temperature is 50 degreeC or more, drying of the base material which apply|coated the paper processing agent will be accelerated|stimulated by heating. If the said heating temperature is 250 degrees C or less, it can suppress that the base material to which the paper processing agent was apply|coated by heating is changed in quality.

The paper processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance and blocking resistance. In addition, the paper-processing product of the present embodiment has excellent strength because the copolymer is attached to the substrate made of paper. Based on these, the paper-processed product of this embodiment is suitable for use as building materials such as wallpaper and backing paper for wallpaper, home appliances, electronic materials, and automotive interior materials, for example.

"Fiber-treating agent and fiber-processed product" (fiber-treating agent) As the fiber-treating agent of the present embodiment, one obtained by dissolving or dispersing the copolymer of the present embodiment in a solvent can be used. In the present embodiment, the content of the copolymer in the fiber treatment agent can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the fiber treatment agent whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(Fiber Processed Product) In the fiber processed product of the present embodiment, fiber is used as a base material. The shape of the fibers is not particularly limited. For example, nonwoven fabrics, woven fabrics, knitted fabrics, and flake-shaped fibers can be made into a fleece to form a web, and then the obtained fleece can be entangled to form a fabric, etc. .

The material of the fiber is not particularly limited, for example, cotton, hemp, silk, wool, collagen fibers, acrylic fibers, cellulose fibers, polyimide fibers, polyimide fibers, rayon fibers, Nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, polyvinyl chloride fiber, polyethylene fiber, polym-phenylene isophthalamide fiber, aromatic polyamide fiber, polyarylate fiber, poly Tetrafluoroethylene fiber, polybenzimidazole fiber, polyether ether ketone fiber, polyphenylene sulfide fiber and their blends, etc.

The usage amount (adhesion amount) of the fiber treatment agent to the fiber processed product can be appropriately changed according to the flame retardancy of the base material itself to be used. The adhesion amount (solid content) of the fiber treatment agent after drying is preferably 5 to 70 mass %, more preferably 10 to 60 mass %, and particularly preferably 20 to 50 mass % with respect to the fiber processed product. When the adhesion amount of the fiber treatment agent is 5 mass % or more, a fiber processed product with good flame retardancy can be easily obtained. If the adhesion amount of the fiber treatment agent is 70 mass % or less, the decrease in strength and texture due to adhesion of the copolymer in the fiber treatment agent to the surface of the base material composed of fibers can be suppressed.

The adhesion amount (content) of the copolymer in the fiber processed product can be arbitrarily selected, but is preferably 1 to 70 parts by mass, more preferably 3 to 60 parts by mass, relative to 100 parts by mass of the fiber (substrate), especially Preferably it is 5-50 mass parts. When the adhesion amount of the copolymer is 1 part by mass or more, a fiber processed product with good flame retardancy can be easily obtained. If the adhesion amount of the copolymer is 70 parts by mass or less, the decrease in strength and texture due to the adhesion of the copolymer to the surface of the base material composed of fibers can be suppressed.

(Manufacturing method of fiber processed product) As the manufacturing method of the fiber processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying or impregnating the fiber treatment agent of the present embodiment to a base material made of fibers, a method of drying it can be mentioned. As a method of applying a paper treatment agent to a substrate made of fibers, a conventionally known method can be used. For example, a method of dipping a substrate into a fiber treatment agent (dipping), a direct coating method, a spray coating method, a roll coating method, a slot coating method, a blade coating method, a printing method, a roll transfer method, Back coating method, etc. As a method of impregnating the base material in the fiber treatment agent, a horizontal roll method, a metal roll method, a web conveying method, a foaming method, etc. are mentioned.

When the shape of the fibers is non-woven, as a method for coating the fibers with the fiber treatment agent, spray coating, printing, roll transfer, horizontal roll, metal roll, web conveying, hair bubble method, etc. When the shape of the fiber is a fabric, as a method for coating the fiber with the fiber treatment agent, it is preferable to use a direct coating method, a spray coating method, a roll coating method, a slot coating method, a blade coating method, or the like.

As the base material, when the fibers formed into flakes are made into a fleece, and then the fleece obtained by entanglement is used to form a fleece, the coating of the fiber treatment agent on the base material can be used for the fleece formation. It can also be carried out after the previous fiber is made into a netting. As a method of making fibers into a fleece, various well-known methods can be used without particular limitation, for example, an air-laid method and the like can be mentioned.

A conventionally known method can be used as a method of drying the base material coated with the fiber treatment agent. For example, the base material coated with the fiber treatment agent may be air-dried, may be dried under reduced pressure, or may be dried under pressure. When drying the substrate coated with the fiber treatment agent, the substrate coated with the fiber treatment agent can also be heated. The heating temperature at the time of heating and drying the base material coated with the fiber treatment agent can be arbitrarily selected, but is preferably 50 to 250°C, more preferably 80 to 190°C. When the said heating temperature is 50 degreeC or more, drying of the base material which apply|coated the fiber treatment agent by heating will be accelerated|stimulated. If the said heating temperature is 250 degrees C or less, it can suppress that the base material to which the fiber processing agent was apply|coated by heating is changed in quality.

The fiber processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance and blocking resistance. In addition, the fiber-processed product of the present embodiment has excellent strength because the copolymer is attached to the base material made of fibers. Based on this, the fiber processed product of the present embodiment can be suitably used as, for example, interior materials such as curtains, home appliances such as home appliance cushioning materials, electronic materials such as cushioning materials for electronic materials, automobile interior cushioning materials, and automobile seat cushions. Materials used for automotive interior decoration materials, etc.

"General paint and general processed products" (general paint) The general paint of this embodiment is applied to a substrate, and the treatment agent of this embodiment is used. In this embodiment, the content of the copolymer in the general coating material can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into a general coating material whose content of a copolymer is the said range, the effect by containing a copolymer changes remarkably.

(General processed product) The general processed product of the present embodiment is formed by coating a general coating on a substrate. Examples of the material of the base material used in general processed products include glass, polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile butadiene styrene copolymer (ABS resin), polystyrene resin, and the like. Resin, metal, wood, paper, etc., are not limited by these. The shape of the substrate used in general processed products is not particularly limited, for example, it can be in the shape of a film, a sheet, a cup, etc.

The usage amount (adhesion amount) of general coatings to general processed products can be appropriately changed according to the flame retardancy of the substrate itself to be used. The adhesion amount (solid content) after drying of a general paint can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 20 to 50% by mass relative to a general processed product %. When the adhesion amount of a general paint is 5 mass % or more, a general processed product with good flame retardancy can be easily obtained. When the adhesion amount of a general paint is 70 mass % or less, it can suppress the appearance defect by the copolymer in a general paint adhering to the surface of a base material.

(Manufacturing method of general processed product) As the manufacturing method of the general processed product of the present embodiment, a conventionally known method can be adopted without particular limitation. For example, after applying the general coating material of this embodiment to a base material made of resin, metal, or the like, a method of drying it can be mentioned. As a method of applying a general paint to a substrate used in general processed products, a conventionally known method can be used. For example, as a method of dipping a substrate in a general coating material (dipping), spray coating, brush coating, roll coating, trowel coating, air knife coating, flow coating, bar coating, roll coating, gravure coating, painting method, etc.

The film thickness at the time of applying a general coating material to a base material is not particularly limited, and can be arbitrarily selected. For example, 1-200 micrometers are preferable, 10-150 micrometers are more preferable, 10-100 micrometers are especially preferable. When the film thickness of the general paint applied is 1 μm or more, a general processed product with good flame retardancy can be easily obtained. If the film thickness of a general coating material is 200 μm or less, the occurrence of poor appearance due to insufficient drying of the coating film can be suppressed.

A conventionally known method can be used as a method of drying a substrate coated with a general coating material. When drying the substrate coated with the general paint, the substrate coated with the general paint can also be heated. The heating temperature at the time of heating and drying the base material coated with a general coating material can be arbitrarily selected, but is preferably 80°C to 170°C, more preferably 90°C to 150°C. If the above-mentioned heating temperature is 80° C. or higher, drying of the substrate coated with a general coating material will be accelerated by heating. When the said heating temperature is 170 degrees C or less, the deterioration of the base material to which the general coating material was apply|coated by heating does not easily occur.

The general processed product of the processed product of the present embodiment has excellent flame retardancy, anti-bleeding property and anti-blocking property. Moreover, since the general processed product of this embodiment contains the copolymer containing the structural component derived from the polymerizable unsaturated monomer (B), it is excellent in the adhesiveness of a coating film and a base material, and the stability of an external appearance. Based on this, the general processed product of this embodiment is suitable for use as a building material, an electronic material, and an automobile interior material, for example.

"Adhesives and Adhesive Products" (Adhesives) As the adhesives of the present embodiment, those in which the copolymer of the present embodiment is dissolved or dispersed in a solvent can be used. The content of the copolymer in the adhesive of the present embodiment can be arbitrarily selected, but is preferably 1 to 90% by mass, more preferably 10 to 80% by mass. By making it into the adhesive agent whose content of a copolymer is the said range, the effect by containing a copolymer can be acquired more effectively.

(Adhesive agent processed product) The so-called base material in the adhesive agent processed product of the present embodiment refers to the substrate in the adherend bonded by the adhesive agent and the support body supporting the adhesive agent layer containing the adhesive agent. At least 1. Examples of the base material include polyesters such as polyethylene terephthalate; polymers such as polyolefin, polyamide, and polyimide; natural or synthetic rubber; paper; metal; glass cloth etc., are not limited by these. On the surface of the substrate, in order to improve the adhesion with the adhesive layer containing the adhesive attached to the substrate, an anchor layer can be formed, or various easy-bonding treatments such as corona treatment or plasma treatment can be applied. .

As the base material used for the support, paper, plastic film, foam of plastic or rubber, metal, glass, woven fabric, non-woven fabric, inorganic board, etc. are mentioned. The shape of the substrate used as the support is preferably a film or tape. When an adhesive agent is applied to a substrate used as a support and dried to form an adhesive agent layer, a release film formed of a resin film or the like can also be pasted on the adhesive agent layer.

The thickness (thickness after drying) of the adhesive layer containing the copolymer attached to the base material can be set to any thickness, and can be appropriately determined according to the application. Specifically, the thickness of the adhesive layer is preferably 5 to 200 μm, more preferably 10 to 150 μm, and particularly preferably 10 to 100 μm. When the thickness of the adhesive layer is 5 μm or more, a processed adhesive product with good flame retardancy can be easily obtained. When the thickness of the adhesive layer is 200 μm or less, an adhesive layer in which the adhesive is sufficiently dried can be obtained.

(Manufacturing method of the adhesive agent product) As the manufacturing method of the adhesive agent processed product of this embodiment, a conventionally known method can be used without particular limitation. When the substrate is an adherend bonded by an adhesive, for example, it can be used on the adhered surface of the substrate. In the film method, another material to be bonded is placed on the base material, and the coating film composed of the adhesive is dried. As the method of applying the adhesive to the base material of the adherend to be bonded by the adhesive, a conventionally known method can be used. For example, as a method of applying the adhesive, a wire bar, an applicator, a brush, a spray, a roll, a gravure coater, a die coater, a lip coater, a notch coater, and a knife coater can be mentioned. , reverse coater, spin coater, etc.

When the substrate is in the form of a film used as a support, for example, a method of applying the adhesive of the present embodiment to one or both surfaces of the substrate and then drying it may be mentioned. Thereby, a film-shaped adhesive agent processed product can be obtained. Moreover, by winding up and cutting the film-shaped adhesive agent processed product according to the application, a tape-shaped adhesive agent processed product can be obtained. When applying an adhesive to a film-like substrate used as a support, for example, roll coating, kiss roll coating, roll brush, dip roll coating, bar coating, air knife coating, curtain coating, die coating can be used. Coating methods such as extrusion coating methods caused by coating machines and the like.

As a method of drying the adhesive agent applied on the base material, a conventionally known method can be used. When drying the adhesive-coated substrate, the adhesive-coated substrate may be heated. The heating temperature at the time of heating and drying the base material coated with the adhesive can be arbitrarily selected, but is preferably 80°C to 170°C, more preferably 90°C to 150°C. When the said heating temperature is 80 degreeC or more, the drying of the base material to which the adhesive agent was apply|coated will be accelerated|stimulated by heating. When the said heating temperature is 170 degrees C or less, the deterioration by heating of the base material to which the adhesive agent was apply|coated is hard to generate|occur|produce.

In this embodiment, the surface of the adhesive agent layer obtained by drying the base material to which the adhesive agent was applied may be subjected to an easy-adhesion treatment. In addition, a release film formed of a resin film or the like may be pasted on the adhesive layer.

The adhesive processed product of the processed product of the present embodiment has excellent flame retardancy, bleed resistance, and blocking resistance, and is excellent in initial adhesion and heat-resistant retention. Based on this, the adhesive processed product of the present embodiment can be applied to, for example, adhesive tapes, double-sided tapes, adhesive labels, etc. for daily necessities, wallpapers, floor tiles, floor mats (buffer floors), carpets, ceiling materials, and adhesive sheets for windows. and other building materials, automotive products, home appliances, electronic parts, etc.

[Example]

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, this invention is not limited only to the following Example.

[Resin composition] (Example 1)

Uniformly mixed 100 g of acidic phosphinodonoxyethyl methacrylate of the phosphorus-containing unsaturated monomer (A) shown in Table 1, and the polymerizable unsaturated monomer (B) having the number of carbon atoms and the number of oxygen atoms. 100 g of acrylic acid of unsaturated carboxylic acid monomer (b-1) having a total of 4 to 10 main chains, and alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms 0.5 g of methacrylate, 4.0 g of mercaptopropionic acid as a chain transfer agent (C), 1.5 g of sodium dodecylbenzenesulfonate as a surfactant, 7.5 g of polyoxyethylene alkyl ether, and ion-exchanged water as a solvent 150 g as a solution containing monomers.

In a 5-neck separable flask, 1 L of ion-exchanged water as a solvent was put in 150 g, and the mixture was heated to 80° C. while stirring. In the above-mentioned separable flask, 3.0 g of potassium persulfate as a starter was added. Then, in the above-mentioned separable flask, a solution containing a monomer and a 10 mass % potassium persulfate aqueous solution were started to be dripped, and a polymerization reaction was started. The monomer-containing solution was added to the separable flask in a roughly constant supply amount over 4 hours. 70 g of a 10 mass % potassium persulfate aqueous solution was also added together with the monomer-containing solution in a roughly constant supply amount over 4 hours. After the addition of the solution containing the monomer and the 10 mass % potassium persulfate aqueous solution was completed, the reaction was completed by stirring at 80° C. for 2 hours.

After the completion of the reaction, the separable flask was cooled, and 20 g of a 30 mass % aqueous sodium hydroxide solution as a neutralizing agent was added to neutralize the inside of the reaction system. After the addition of the neutralizer was completed, it was stirred for 1 hour. Through the above steps, the resin composition in which the copolymer of Example 1 was dispersed or dissolved in water was obtained. Table 1 shows the raw materials and usage amounts used in the manufacture of the resin composition of Example 1.

(Examples 2 to 30, Comparative Examples 1 to 8) Examples 2 to 2 were obtained in the same manner as in Example 1, except that the raw materials shown in Tables 1 to 6 were used in the amounts shown in Tables 1 to 6. 30. The resin compositions of Comparative Examples 1-8.

The details of each component in Tables 1 to 6 are as follows. (Phosphorus-Containing Unsaturated Monomer (A)) Acidic Phosphonodonoxyethyl Methacrylate (Unichemical Co., Ltd., Phosmer M, Phosphorus Atom Content: 15% by Mass) Acidic Phosphonooxyethylacrylate (Co- Eisha Chemical Co., Ltd. product, P-1A, phosphorus atom content 16% by mass) Diphenyl-2-methacryloyloxyethyl phosphate (Daihachi Chemical Industry Co., Ltd. product, MR-260, phosphorus Atomic content of 8 mass %) Acid phosphinodioxy polyoxyethylene glycol monomethacrylate (UNICHEMICAL Co., Ltd., Phosmer PE, phosphorus atom content of 9 mass %)

(Polymerizable unsaturated monomer (B)) (Unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms) Acrylic acid (manufactured by Mitsubishi Chemical Corporation) ) Methacrylic acid (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Iconic acid (manufactured by Fuso Chemical Industry Co., Ltd.) β-carboxyethyl acrylic acid (manufactured by DAICEL-ALLNEX Co., Ltd.)

(Alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms) Methacrylate (manufactured by Toagosei Co., Ltd.) Ethyl acrylate (manufactured by Toagosei Co., Ltd.) Butyl acrylate (manufactured by Toagosei Co., Ltd.) Methyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) (Other (B)) 2-Propenyloxyethyl-succinic acid (Kyoeisha Chemical Co., Ltd. company system)

(Chain transfer agent (C)) β-Mercaptopropionic acid (manufactured by Dojin Chemical Research Institute Co., Ltd.) 2-ethylhexyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Surfactant) Sodium dodecylbenzenesulfonate (manufactured by Kao Co., Ltd.) Polyoxyethylene lauryl ether (manufactured by Kao Co., Ltd.) Polyvinyl alcohol (manufactured by KURARAY Co., Ltd., PVA205 (degree of saponification 86.5-89.0%) , the average degree of polymerization 500))

(Starter) Potassium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Ammonium persulfate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Azobisisobutyronitrile (manufactured by Otsuka Chemical Co., Ltd.)

(Neutralizing agent) 30 mass % sodium hydroxide aqueous solution (manufactured by Kishida Chemical Co., Ltd.) 25 mass % ammonia aqueous solution (manufactured by Ube Industries Co., Ltd.) Monomethylamine (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(Solvent) Diethylene glycol monoethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.)

"Phosphorus Atom Content" The phosphorus atom content in the unsaturated monomer components in Tables 1 to 6 was calculated by the following formula. The results are shown in Tables 1 to 6. The calculated phosphorus atom content can be regarded as the phosphorus atom content with respect to each of the copolymers of Examples 1 to 30 and Comparative Examples 1 to 8. Phosphorus atom content (mass %)=[mass of phosphorus atoms in phosphorus-containing unsaturated monomer (A)/total mass of phosphorus-containing unsaturated monomer (A) and polymerizable unsaturated monomer (B)]×100

The resin solid content containing the copolymer was separated from the resin composition by removing water from the solvent in the resin compositions of Examples 1 to 30 and Comparative Examples 1 to 8 and drying them. Next, the resin compositions or resin solid content of Examples 1 to 30 and Comparative Examples 1 to 8 were evaluated by the following evaluation methods. The results are shown in Tables 1 to 8.

"Mass average molecular weight" The mass of the copolymer was measured using gel permeation chromatography (GPC) under the following conditions: trade name "Shodex GPC-101" (manufactured by Showa Denko Co., Ltd., "Shodex" is a registered trademark) average molecular weight. Prepared in 34.5 g of disodium hydrogen phosphate dihydrate and 46.2 g of sodium dihydrogen phosphate dihydrate, and added ultrapure water to make an aqueous solution of 5.000 g in total, as a carrier liquid. The resin solid content containing the copolymer was dissolved in this carrier liquid, and the measurement was performed at a flow rate of 0.5 ml/min. using a pump (<DU-H2000>, manufactured by Shodex).

As the column, an aqueous GPC column (analytical column: <OHpak SB-806M MQ>, manufactured by Shodex, reference column: <OHpak SB-800RL>, manufactured by Shodex) was used, and as the detector, an RI detector (< RI-71S>, manufactured by Shodex). As a molecular weight standard sample, sodium polyacrylate (Sigma-Aldrich) was used.

"Acid value" The acid value of the copolymer was evaluated by neutralization titration according to JIS K 0070 as follows. Using a precision balance, accurately weigh about 2g of the sample (containing the resin solid content of the copolymer), put it into a 100ml conical flask, add 10ml of a mixed solvent of ethanol/diethyl ether=1/1 (mass ratio) and dissolve it. . In addition, 1 to 3 drops of a phenolphthalein ethanol solution as an indicator is added to this Erlenmeyer flask, and the mixture is sufficiently stirred until the sample becomes uniform. This was titrated with a 0.1N potassium hydroxide-ethanol solution, and when the light red color of the indicator continued for 30 seconds, it was regarded as the end point of neutralization. From the results, the value obtained by using the following formula (5) was used as the acid value of the copolymer.

Acid value (mgKOH/g)=(B´f´5.611)/S (5) B: Amount of 0.1N potassium hydroxide-ethanol solution used (ml) f: Factor S of 0.1N potassium hydroxide-ethanol solution: Sample collection amount (g)

(Flammability) The resin film produced by the method described later was allowed to stand for more than 12 hours under the conditions of 23°C and 50% relative humidity as a test body. Next, a test piece having a length of 150 mm and a width of 60 mm was collected from the test body. Then, according to the method of JIS K 7201-2:1999, the test piece was mounted on the U-shaped holder, and the minimum oxygen concentration required for the continuous burning length of 50mm burning of the test piece after ignition was measured, and the burning time was 180 seconds or more. The minimum oxygen concentration required, and the smaller value is used as the oxygen index. As an index of flammability, those with an oxygen index of 22% or less were regarded as flammable, those with an oxygen index of 23 to 27% were regarded as self-extinguishing properties, and those with an oxygen index of 28% or more were regarded as flame retardancy. ○(Good): Oxygen index is more than 50% △(Yes): Oxygen index is more than 40% to less than 50% ´(No): Oxygen index is less than 40%

<Preparation of resin film> The resin compositions of Examples 1 to 30 and Comparative Examples 1 to 8 were diluted with ion-exchanged water so that the solid content was 20% by mass, and used as resin liquids for resin film production. The resin liquid was uniformly poured into a frame made of silicone sealant with a length of 200 mm and a width of 50 mm to form a glass plate. It was confirmed that the glass plate into which the resin liquid had flowed was horizontal, and it was dried at 70° C. with a vacuum dryer for 24 hours to obtain resin films of Examples 1 to 30 and Comparative Examples 1 to 8.

(Storage stability) The pH change is used as an index to confirm the storage stability. About the resin composition just produced, pH at 23 degreeC was measured. In addition, a colorless and transparent glass bottle with a capacity of 140 mL was filled with the resin composition just produced until the volume reached 90% of the volume, sealed, and stored at 23° C. and a relative humidity of 50% for half a year. Then, the pH at 23°C was measured for the resin composition after storage for half a year. Then, the amount of pH change of the resin composition immediately after production and the resin composition after storage for half a year was evaluated according to the criteria shown below. "Standard" ○ (good): pH change is ±0 to less than 2 △ (good): pH change is more than ±2.0 to less than 3 ´ (not possible): pH change is ±3.0 or more

(Polymerization stability) According to the amount of residual monomers in the resin composition just produced (out of all the unsaturated monomer components used, the content of unsaturated monomer components remaining in the resin composition) and the presence or absence of polymerization Gelation was evaluated by the criteria shown below. The residual monomer amount was measured by gas chromatography. "Standard" ○ (Good): Not gelled, and the residual monomer is 0% or more to less than 0.1% by mass % ´ (not possible): The polymerization was terminated due to gelation, or the residual monomer was 1% by mass or more

As shown in Table 7, the resin films produced using the resin compositions of Examples 1 to 30 were excellent in flame retardancy. Among them, the resin compositions of Examples 1 to 27 containing the chain transfer agent (C) were particularly good in storage stability and polymerization stability. In addition, the resin compositions of Examples 1 to 27 have particularly good storage stability.

As shown in Table 8, Comparative Example 1 which does not contain phosphorus-containing unsaturated monomer (A), and alkyl (meth)acrylate monomer (b-2) having a carbon number of 1 to 4 alkyl groups were used. Comparative Examples 2, 5 to 8, and the resin composition of Comparative Example 3 which did not contain the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10 The resin film has poor flame retardancy. In addition, the resin composition of Comparative Example 4, which does not contain the unsaturated carboxylic acid monomer (b-1), has remarkably low polymerization stability, and the evaluation of flame retardancy and storage stability cannot be performed.

"Paper processed products and fiber processed products" (Examples 31 to 33, 35 to 37, Comparative Examples 9 and 10) The resins shown in Tables 9 and 10 were blended and diluted at the ratios shown in Tables 9 and 10. The water of the agent was used to prepare the treatment agents 1 to 4 used in Examples 31 to 33, 35 to 37, and Comparative Examples 9 and 10. "Resin 1" shown in Tables 9 and 10 indicates the resin composition of Example 1, "Resin 3" indicates the resin composition of Example 3, "Resin 5" indicates the resin composition of Example 5, "Resin 28" indicates the resin composition of Example 5 " represents the resin composition of Comparative Example 1.

(Examples 34 and 38) Ammonium polyphosphate (Exolit AP422, manufactured by Clariant Chemicals Co., Ltd., manufactured by Clariant Chemicals Co., Ltd., phosphorus atom Content 32 mass %) and the water of the diluent to prepare the treatment agent 5 used in Examples 34 and 38.

The processing agents 1 to 5 obtained in this way were used as paper processing agents, and the processed paper products of Examples 31 to 34 and Comparative Example 9 were produced by the method described later. Moreover, using the processing agents 1-5 as a fiber processing agent, the fiber processed goods of Examples 35-38 and Comparative Example 10 were produced by the method mentioned later.

<Preparation of processed paper product> As a base material, filter paper (No. 2 Toyo Filter Paper Co., Ltd. product, thickness 0.25 mm, basis weight 130 g/m ² ) was prepared. Then, the treatment agents 1 to 5 shown in Table 9 were immersed in the substrate and applied. After that, the base material impregnated with the treatment agent was squeezed with two nip rolls, and the treatment agent was adhered to the base materials 1 to 5. Next, the base material to which the treatment agent adhered was dried at 130° C. for 10 minutes with a hot air dryer to obtain a paper processed product.

Then, about the obtained paper processed product, the solid content amount (mass %) of the paper processing agent (processing agent) with respect to the paper processed product was calculated|required by the method shown below. The results are shown in Table 9.

Use a direct-reading balance with a sensitivity of 0.5 mg or less to precisely weigh the substrate before immersion with the treatment agent. Moreover, the base material impregnated with the treatment agent was left to stand in a dryer adjusted to an internal temperature of 105° C.±2° C. for 1 hour to be dried. The dried base material was cooled to room temperature in a desiccator, and the mass of the base material (processed product) dried as an immersion treatment agent was measured with the same direct-reading balance. Using the "quality of the processed product" and "the mass of the base material before coating of the processing agent" obtained in this way, the solid content amount (mass %) of the processing agent with respect to the processed product was calculated by the following formula. The solid content of the treatment agent relative to the processed product (mass %) = {(the mass of the processed product - the mass of the substrate before the treatment agent is dipped)/(the mass of the processed product)}´100

<Production of processed fiber product> Except for using a fiber made of polyester-cellulose nonwoven fabric (manufactured by Berkshire Co., Ltd., thickness 200 μm, basis weight 35 g/m ² ) as the base material, and paper processed product In the same way, a fiber processed product was obtained. Then, the solid content amount (mass %) of the fiber processing agent (processing agent) with respect to the fiber processed product was calculated|required about the obtained fiber processed product by the method similar to the paper processed product. The results are shown in Table 10.

With respect to the processed paper products of Examples 31 to 34 and Comparative Example 9, and the processed fiber products of Examples 35 to 38 and Comparative Example 10, the following evaluation methods were used to evaluate flame retardancy, bleed resistance, and blocking resistance. Sex, stiffness. The results are shown in Table 9 and Table 10.

(Flammability) Paper processed products or fiber processed products that have been left standing at 23°C and relative humidity of 50% for more than 12 hours were used as test objects. Long strip test piece. For each test piece, a burning test was performed based on the vertical burning test according to UL-94 (V-0, V-1, and V-2 specifications). For each test piece, contact with the flame was performed twice (for each test body, 10 times in total), and the flame extinction time (burning time) was measured. Using the results, the total burning time and the maximum burning time due to a total of 10 contact flames were obtained for each test body, and evaluated according to the criteria shown below.

"Standard" V-0: The total burning time is within 50 seconds, the maximum burning time is within 10 seconds, and there is no dripping of material due to burning in all test pieces. V-1: The total burning time is within 250 seconds, the maximum burning time is within 30 seconds, and there is no material dripping due to burning in all test pieces. V-2: The total burning time is within 250 seconds, and the maximum burning time is within 30 seconds, but there are test pieces where material drips due to burning.

(Bleed-out resistance) A rectangular test piece of 70 mm in length and 50 mm in width was collected from the same test body used in the evaluation of flame retardancy. A test piece was sandwiched between rectangular filter papers (No. 2, manufactured by Toyo Filter Paper Co., Ltd.) with a length of 100 mm and a width of 60 mm, and the test piece was allowed to stand for 5 days under the conditions of 60° C. and relative humidity of 95%, and the surface of the test piece was checked for exudation. . The results were evaluated according to the criteria shown below. "Standard" ´(No): The whitening of the surface of the test piece occurs at 10% or more of the area of the test piece. △ (possible): The whitening of the surface of the test piece occurs when it does not reach 10% of the area of the test piece. ○ (good): No whitening on the surface of the test piece.

(Blocking resistance) From the same test body used in the evaluation of flame retardancy, a roughly square test piece of 25 mm in length and 25 mm in width was collected. A test piece was sandwiched between slightly square base papers (manufactured by Yagyu Printing Co., Ltd., a joint stock company) with a length of 35 mm and a width of 35 mm. The results were evaluated according to the criteria shown below. In addition, whether or not a sound is generated when the backing paper is peeled from the test piece, the peeling test is performed according to the T-type peeling test (Tensilon: RTA-100 manufactured by ORIENTEC) under the conditions of 23° C. and 300 mm/min, and the presence or absence of peeling sound at that time is evaluated. method to judge.

"Standard" ´(No): A sound occurs when the backing paper is peeled from the test piece, and there is peeling (sticking) on the backing paper peeled from the test piece However, there is no peeling on the backing paper peeled from the test piece (slight blocking) ○ (good): No sound occurs when the backing paper is peeled from the test piece, and no peeling on the backing paper peeled from the test piece (no sticking). )

(Stiffness) From the same test body used in the evaluation of flame retardancy, a roughly square test piece of 150 mm in length and 150 mm in width was collected. The test piece was subjected to the measurement of stiffness according to the 8.21.5E method (fabric texture measurement method) described in the general fabric testing method of JIS L1096:2010. The results were evaluated according to the criteria shown below. Stiffness (g) represents the hardness (softness) of the fiber, and the higher the stiffness value, the harder the test piece feels. "Standard" ○ (good): 160g or more △ (ok): 140g or more to less than 160g ´ (no): less than 140g

As shown in Table 9 and Table 10, the paper processed products of Examples 31 to 34 and the fiber processed products of Examples 35 to 38 were excellent in flame retardancy. In addition, the paper processed products of Examples 31 to 34 and the fiber processed products of Examples 35 to 38 were evaluated by the evaluation of "○ (good)" or "△ (fair)" in anti-bleeding property, blocking resistance, and stiffness. good. On the other hand, since the processing agent 4 used as a paper processing agent does not contain the structural component derived from (A), the paper processed product of the comparative example 9 is inferior in flame retardance. Moreover, since the processing agent 4 used as a fiber processing agent does not contain the structural component derived from (A), the fiber processed product of the comparative example 10 was inferior in flame retardance.

In Examples 31 to 38, the paper processed products of Examples 31 to 33 and the fiber processed products of Examples 35 to 37, which do not use ammonium polyphosphate of phosphorus-based compound as the flame retardant, are particularly resistant to exudation and resistance. Good adhesion.

"General processed products" (Examples 39 to 41, Comparative Example 11) Pentaerythritol polyglycidyl ether (Nagase ChemteX Co., Ltd.) was blended with the resin and crosslinking agent shown in Table 11 at the ratio shown in Table 11. Coatings 6-9 used in Examples 39-41 and Comparative Example 11 were prepared. "Resin 1" shown in Table 11 represents the resin composition of Example 1, "Resin 3" represents the resin composition of Example 3, "Resin 5" represents the resin composition of Example 5, and "Resin 28" represents the comparison The resin composition of Example 1.

(Example 42) At the ratio shown in Table 11, the resin shown in Table 11 and ammonium polyphosphate (Exolit AP422, phosphorus atom content: 32 mass %, manufactured by Clariant Chemicals Co., Ltd.; Coating 10 used in Example 42 was prepared using the indicated crosslinking agent.

Using the paints 6 to 10 thus obtained, general processed products of Examples 39 to 42 and Comparative Example 11 were produced by the method described later.

<Production of general processed products> As a base material, a PET film with a thickness of 25 μm was prepared. Then, the coating materials 6-10 shown in Table 11 were apply|coated to a base material so that the thickness after drying might become 10 micrometers. Then, the base material applied with the coating material was dried at 105° C. for 3 minutes with a hot air dryer, and aged at 40° C. for 3 days to obtain a general processed product.

Then, with respect to the obtained general processed product, the solid content (mass %) of the coating material (treatment agent) with respect to the general processed product was determined by the same method as that of the paper processed product. The results are shown in Table 11. For the general processed products of Examples 39 to 42 and Comparative Example 11, flame retardancy, adhesion, and appearance changes were evaluated by the following evaluation methods. The results are shown in Table 11.

(Flammability) Coatings 6 to 10 used in general processed products were used, respectively, and films were produced in the same manner as in the above <Preparation of resin film>, and similarly to the resin films produced using the resin composition, the difficulty of general processed products was evaluated. flammability.

(Adhesion) A general processed product left standing at 23°C and a relative humidity of 50% for 12 hours or more was used as a test body, and a Cellotape (registered trademark) peeling test was performed for each test body. The surface of the general processed product after the peeling test was visually observed and evaluated according to the criteria shown below. "Standard" ○(Good): No peeling △(Yes): The peeled area is less than 80% of the surface ´(No): The peeled area is more than 80% of the surface

(Appearance change) The same test body as the user in the evaluation of adhesion was left to stand for 3 days under the conditions of 60°C and 70% relative humidity. Then, general processed products were visually observed, and the presence or absence of changes in appearance was evaluated according to the criteria shown below. "Standard" ○ (Good): No change in appearance △ (Yes): The whitened area is less than 80% of the surface ´(No): The whitened area is more than 80% of the surface

As shown in Table 11, the general processed strains of Examples 39 to 42 have good flame retardancy. In addition, the evaluation of the adhesiveness and the change in appearance of the general processed products of Examples 39 to 42 was the evaluation of "○ (good)" or "Δ (good)". On the other hand, the general processed product of Comparative Example 11 was poor in flame retardancy because the paint 9 did not contain the constituent components derived from (A). In addition, among Examples 39 to 42, the general processed products of Examples 39 to 41 in which ammonium polyphosphate without a phosphorus-based compound was used as a flame retardant were particularly good in evaluation of adhesion and appearance change.

"Adhesive products" (Examples 43 to 45, Comparative Example 12) In the ratio shown in Table 12, the acrylic resin (D) produced by the following method, the resin shown in Table 12 and the Adhesives 1 to 4 used in Examples 43 to 45 and Comparative Example 12 were prepared using pentaerythritol polyglycidyl ether (Denacol EX411, manufactured by Nagase ChemteX Co., Ltd.) as a crosslinking agent.

"Resin 1" shown in Table 12 represents the resin composition of Example 1, "Resin 3" represents the resin composition of Example 3, "Resin 5" represents the resin composition of Example 5, and "Resin 28" represents the comparison The resin composition of Example 1.

"Manufacture of Acrylic Resin (D)" In a reaction apparatus equipped with a stirrer, a temperature controller, a reflux cooler, a dropping funnel, and a thermometer, 150 g of n-butyl acrylate, 34 g of methyl methacrylate, and 2-hydroxy acrylate were added. After 2 g of ethyl ester and 195 g of toluene, 0.2 g of azobisisobutyronitrile as a polymerization initiator was added after the heating under reflux was started. After making it react at the reflux temperature of toluene for 8 hours, it diluted with toluene, and obtained the acrylic resin (D) with a solid content of 50 mass %.

(Example 46) In the ratio shown in Table 12, the acrylic resin (D) produced by the following method, the resin shown in Table 12, and the ammonium polyphosphate of flame retardant (Clariant Chemicals Co., Ltd.) were blended. Adhesive 5 used in Example 46 was prepared using Exolit AP422, phosphorus atom content: 32% by mass), and pentaerythritol polyglycidyl ether (Denacol EX411, manufactured by Nagase ChemteX Co., Ltd.) as a crosslinking agent.

Using the adhesive agents 1 to 5 obtained in this manner, the adhesive agent processed products of Examples 43 to 46 and Comparative Example 12 were produced by the method described later.

<Preparation of processed adhesive product> As a base material, a PET film with a thickness of 25 μm was prepared. Then, the adhesive agent 1-5 shown in Table 12 was apply|coated to a base material so that the thickness after drying might become 10 micrometers, and the adhesive agent layer was formed. After that, a release film was attached to the adhesive layer, bonded with a roll, and aged at 40°C for 3 days to obtain an adhesive processed product.

Then, the solid content amount (mass %) of the adhesive agent (treatment agent) with respect to the adhesive agent processed product was calculated|required by the method similar to the paper processed product about the obtained adhesive agent processed product. In addition, as "quality of processed products", use: the substrates coated with adhesive agent, pasted with release films, and bonded with rolls are placed in a dryer adjusted to an internal temperature of 105°C ± 2°C for 1 After 1 hour, it was dried, cooled to room temperature in a desiccator, and the value was precisely weighed by a direct reading balance with a sensitivity of 0.5 mg or less. That is, it calculated as what was also included in a base material as a release film. The results are shown in Table 12.

About the adhesive agent processed goods of Examples 43-46 and Comparative Example 12, flame retardance, initial stage adhesive force, and heat-resistant retention force were evaluated by the evaluation method shown below. The results are shown in Table 12.

(Flammability) Using the adhesive agents 1 to 5 used in the adhesive agent processed product, respectively, a film was prepared in the same manner as in the above <Preparation of resin film>, and the adhesiveness was evaluated in the same manner as the resin film prepared using the resin composition. The flame retardancy of adhesive processed products.

(Initial Adhesion) Prepare a roughly rectangular adhesive product with an area of 25mm×100mm, and peel off the release film to expose the adhesive layer. On a stainless steel lapping plate made of SUS304, the surface of the adhesive layer side is facing each other, and the adhesive product is placed, and a 2 kg roller is made to reciprocate once under the conditions of 23°C and 50% relative humidity. Grinding plate lamination adhesive processed product. 20 minutes after bonding, the 180-degree peel strength (N/cm) was measured in accordance with the method for measuring the adhesive force specified in JIS Z 0237:2000, and evaluated according to the following criteria. "Standard" ○(Good): 2.0N/cm or more △(Fair): 1.5N/cm or more to less than 2.0N/cm ´(No): less than 1.5N/cm

(Heat Resistant Retention) The adhesive product was attached to the stainless steel grinding plate in the same manner as in the measurement of the initial adhesion, except that the lamination area was made into a roughly square shape of 25mm x 25mm. Then, according to the method for measuring the holding force specified in JIS Z 0237, a load of 1 kg was applied, and the upper limit of the temperature that did not drop for 1 hour or more was measured, and the evaluation was performed according to the following criteria. "Standard" ○ (good): 150°C or more △ (ok): 100°C or more to less than 150°C ´ (not possible): less than 100°C

As shown in Table 12, the processed adhesive products of Examples 43 to 46 were all evaluated as "○ (good)" or "Δ (good)", and the flame retardancy, initial adhesion, and heat retention were good. On the other hand, since the adhesive agent 4 of the comparative example 12 does not contain the constituent component derived from (A), it is inferior in flame retardancy. In addition, among Examples 43 to 46, the processed adhesive products of Examples 43 to 45 in which ammonium polyphosphate of no phosphorus-based compound was used as the flame retardant were particularly good in the evaluation of initial adhesion and heat resistance. [Industrial availability]

The present invention provides a resin which is excellent in flame retardancy and good in bleed resistance and blocking resistance. The copolymer of the present invention is excellent in flame retardancy, and when used as a material for a processed product, a processed product with good bleed resistance and blocking resistance can be obtained. Therefore, the treatment agent containing the copolymer of the present invention is suitable as a paper treatment agent, a fiber treatment agent, a general paint, an adhesive, and an adhesive.

The treatment agent containing the copolymer of the present invention is suitable as a material for a processed product excellent in flame retardancy, bleed resistance, blocking resistance, and stiffness. For example, as a processed product of paper as a base material, building materials, such as a wallpaper and backing paper for wallpaper, an automobile interior material, etc. are mentioned. Moreover, as a processed product which a base material is a fiber, interior materials, such as a curtain, a cushion material for electronic materials, a cushion material for household appliances, an automobile interior cushion material, a car seat cushion, etc. are mentioned.

Moreover, the coating material and the adhesive agent containing the copolymer of this invention can be used suitably when manufacturing processed goods, such as a general processed product and an adhesive agent processed product. Examples of such processed products include adhesive tapes, household appliances, electronic parts, adhesive tapes, double-sided tapes, adhesive labels, and other daily necessities, wallpapers, floor tiles, floor mats (buffer floors), carpets, ceiling materials, and windows. Household materials such as adhesive sheets, automotive products, home appliances, electronic parts, etc.

Claims (20)

A paper treating agent comprising a copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that the aforementioned constituents derived from The constituents of the polymerizable unsaturated monomer (B) include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10, and the aforementioned copolymerization Among them, with respect to the total content of the aforementioned constituent components derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned constituent components derived from the polymerizable unsaturated monomer (B), it is derived from the ratio of the alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) is 0.00 to 1.00 mass %, and the constituent components derived from the phosphorus-containing unsaturated monomer (A) are derived from the components represented by the formula (1). The constituents of the monomer (a-1) of either the phosphoric acid group represented by the formula (2) or the phosphorous acid group represented by the formula (2),

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer)

(In the formula (2), * represents a bond with an atom constituting an unsaturated monomer.) The acid value of the copolymer is 300 to 800 mgKOH/g. The paper treating agent of claim 1, wherein the aforementioned has a phosphoric acid group and phosphorous The monomer (a-1) of any one of the acid groups is acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate. The paper treating agent according to claim 1 or 2, wherein the content of phosphorus atoms in the copolymer is 0.1 to 10% by mass. The paper treating agent according to claim 1, wherein the unsaturated carboxylic acid monomer (b-1) is at least one selected from acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl acrylic acid. The paper treating agent according to claim 1, wherein in the copolymer, the total content of the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) is , the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass. The paper treating agent according to claim 1, which further contains a structural component derived from a chain transfer agent (C). The paper treating agent according to claim 6, wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1). The paper treating agent according to claim 6 or 7, wherein, in the copolymer, with respect to the difference between the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the constituent component derived from the polymerizable unsaturated monomer (B) The total content is 100 parts by mass, The content of the constituent components derived from the chain transfer agent (C) is 0.1 to 10 parts by mass. The paper treating agent according to claim 1, wherein the mass-average molecular weight of the copolymer is 25,000 to 70,000. A fiber treatment agent comprising a copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), characterized in that the aforementioned constituents derived from The constituents of the polymerizable unsaturated monomer (B) include constituents derived from the unsaturated carboxylic acid monomer (b-1) having a main chain having a total number of carbon atoms and oxygen atoms of 4 to 10, and the aforementioned copolymerization Among them, with respect to the total content of the aforementioned constituent components derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned constituent components derived from the polymerizable unsaturated monomer (B), it is derived from the ratio of the alkyl group having 1 to 4 carbon atoms. The content of the constituent components of the alkyl (meth)acrylate monomer (b-2) is 0.00 to 1.00 mass %, and the constituent components derived from the phosphorus-containing unsaturated monomer (A) are derived from the components represented by the formula (1). The constituents of the monomer (a-1) of either the phosphoric acid group represented by the formula (2) or the phosphorous acid group represented by the formula (2),

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer)

(In the formula (2), * represents a bond with an atom constituting an unsaturated monomer.) The acid value of the copolymer is 300 to 800 mgKOH/g. The fiber treatment agent according to claim 10, wherein the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group is an acid phosphonooxypolyoxyalkylene glycol mono(meth)acrylate. The fiber treatment agent according to claim 10 or 11, wherein the content of phosphorus atoms in the copolymer is 0.1 to 10% by mass. The fiber treating agent according to claim 10, wherein the unsaturated carboxylic acid monomer (b-1) is at least one selected from acrylic acid, methacrylic acid, itaconic acid, and β-carboxyethyl acrylic acid. The fiber treating agent according to claim 10, wherein in the copolymer, the total content of the constituents derived from the phosphorus-containing unsaturated monomer (A) and the constituents derived from the polymerizable unsaturated monomer (B) is , the content of the constituent components derived from the unsaturated carboxylic acid monomer (b-1) is 30 to 95% by mass. The fiber-treating agent of Claim 10 which further contains the structural component derived from a chain transfer agent (C). The fiber treatment agent according to claim 15, wherein the chain transfer agent (C) is a mercapto alkyl carboxylate (c-1). The fiber-treating agent according to claim 15 or 16, wherein, in the copolymer, the ratio of the constituent component derived from the phosphorus-containing unsaturated monomer (A) to the constituent component derived from the polymerizable unsaturated monomer (B) The total content is 100 parts by mass, and the content of the constituent components derived from the chain transfer agent (C) is 0.1 to 10 parts by mass. The fiber treatment agent according to claim 10, wherein the mass-average molecular weight of the copolymer is 25,000 to 70,000. A paper processed product in which a copolymer is attached to paper, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B) , and the constituents derived from the chain transfer agent (C), wherein the aforementioned constituents derived from the polymerizable unsaturated monomer (B) include those derived from the main chain having a total of 4 to 10 carbon atoms and oxygen atoms. The constituent component of the unsaturated carboxylic acid monomer (b-1), and in the copolymer, the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B)-derived component The total content of the constituent components is 0.00 to 1.00 mass %, and the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %. The constituent component of the unsaturated monomer (A) is a constituent component derived from the monomer (a-1) having either a phosphoric acid group represented by the formula (1) or a phosphorous acid group represented by the formula (2),

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer)

(In the formula (2), * represents a bond with an atom constituting an unsaturated monomer) The acid value of the copolymer is 300 to 800 mgKOH/g, and the copolymer 1 is included with respect to 100 parts by mass of the paper. ~70 parts by mass. A fiber processed product comprising a fiber processed product in which a copolymer is adhered to the fiber processed product, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A), and a polymer derived from a polymerizable unsaturated monomer (B) The constituents of , and the constituents derived from the chain transfer agent (C), wherein the constituents derived from the polymerizable unsaturated monomer (B) are derived from those having a total of 4 to 10 carbon atoms and oxygen atoms. The constituent component of the unsaturated carboxylic acid monomer (b-1) in the main chain, and in the copolymer, with respect to the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the aforementioned polymerizable unsaturated monomer ( The total content of the constituent components of B), the content of the constituent components derived from the alkyl (meth)acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms is 0.00 to 1.00 mass %, and the aforementioned The constituent component derived from the phosphorus-containing unsaturated monomer (A) contains the monomer (a-1) derived from either the phosphoric acid group represented by the formula (1) and the phosphorous acid group represented by the formula (2). constituents,

(In formula (1), * represents a bond with an atom constituting an unsaturated monomer)

(In formula (2), * represents a bond with an atom constituting an unsaturated monomer), the acid value of the copolymer is 300 to 800 mgKOH/g, and the copolymer is contained in 100 parts by mass of the fiber. 1 to 70 parts by mass.