CN110869401B - Copolymer, resin composition, treating agent, and processed product - Google Patents

Abstract

A copolymer comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), wherein the constituent derived from the polymerizable unsaturated monomer (B) comprises a constituent derived from an unsaturated carboxylic acid monomer (B-1) having a main chain of 4 to 10 in total of the number of carbon atoms and the number of oxygen atoms, and the content of the constituent derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group of 1 to 4 carbon atoms is 0.00 to 1.00 mass% relative to the total content of the constituent derived from the phosphorus-containing unsaturated monomer (A) and the constituent derived from the polymerizable unsaturated monomer (B).

Description

Copolymer, resin composition, treating agent, and processed product

Technical Field

The invention relates to a copolymer, a resin composition, a treating agent and a processed product.

This application claims priority based on Japanese application No. 2017-125089, filed on 27.6.2017, the contents of which are incorporated herein by reference.

Background

A processed product in which a treating agent such as a paper treating agent, a fiber treating agent, or an adhesive is attached to a base material (hereinafter, may be referred to as "processed product or the like") is widely used in applications such as building materials, home electric appliances, electronic materials, and vehicle interior materials for automobiles. As materials for treating agents used for processed products and the like, synthetic resins are widely used as physical property improvers, binders, and dispersants.

In recent years, from the viewpoint of safety, flame retardancy of processed products and the like has been demanded. As a method for making a processed product or the like flame retardant, there is a method of using a treating agent containing a flame retardant as a treating agent used for the processed product or the like.

As the flame retardant, inorganic flame retardants such as red phosphorus, antimony trioxide, aluminum hydroxide, and magnesium hydroxide; halogen flame retardants such as pentabromobiphenyl, octabromobiphenyl and decabromobiphenyl; non-halogen flame retardants such as phosphates, guanidinium phosphates, triphenyl phosphate, and sulfamic acid.

The halogen-based flame retardant has excellent flame retardancy. Therefore, in the case of using a halogen-based flame retardant as the flame retardant, the amount of the flame retardant to be used may be made small. Therefore, in the case of a processed product or the like produced using a treating agent containing a halogen-based flame retardant, the flame retardant has little influence on the physical properties of the processed product or the like.

However, the halogen-based flame retardant contains halogen elements such as chlorine, bromine, and fluorine. Therefore, if a processed product or the like containing a halogen-based flame retardant is incinerated, harmful substances such as dioxin and hydrogen halide may be generated. Therefore, the halogen-based flame retardants have been newly studied for control and use in countries around the world, including EU countries.

Further, it is known that a halogen-based flame retardant exhibits higher flame retardancy by being used in combination with an antimony compound. Therefore, the halogen-based flame retardant is often used in combination with an antimony compound. However, in recent years, the antimony compounds have been newly studied for control and use, and their use tends to be avoided.

The non-halogen organic flame retardant is superior in safety to halogen flame retardants. As a non-halogen organic flame retardant, many phosphorus flame retardants composed of phosphorus compounds have been studied.

However, phosphorus flame retardants generally have lower flame retardancy than halogen 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 retardancy. Therefore, a large amount of flame retardant needs to be added to a processed product or the like using a treating agent containing a phosphorus-based flame retardant, and therefore the processed product or 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 paper and fiber-processed products processed using the resin composition.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 7-18028

Patent document 2: japanese patent laid-open publication No. 2010-235830

Disclosure of Invention

Problems to be solved by the invention

However, conventional processed products containing flame retardant resins do not satisfy all of the properties of flame retardancy, bleed resistance and blocking resistance.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a resin excellent in flame retardancy and excellent in bleed-out resistance and blocking resistance.

Further, an object of the present invention is to provide a resin composition and a treating agent which can give a coating film having good flame retardancy, bleed-out resistance and blocking resistance.

Further, an object of the present invention is to provide a processed article having excellent flame retardancy, bleed-out resistance and blocking resistance.

Means for solving the problems

The present inventors have made extensive studies to solve the above problems and provide a resin satisfying all of flame retardancy, bleed-out resistance and blocking resistance.

As a result, the present invention has been found to be a copolymer including a constituent derived from a phosphorus-containing unsaturated monomer (a) and a constituent derived from a polymerizable unsaturated monomer (B), wherein the constituent derived from the monomer (B) includes a constituent derived from an unsaturated carboxylic acid monomer (B-1) having a main chain of 4 to 10 total carbon atoms and oxygen atoms, and a content of the constituent derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group of 1 to 4 carbon atoms is 0.00 to 1.00% by mass relative to a total content of the constituent derived from the monomer (a) and the constituent derived from the monomer (B).

That is, the first embodiment of the present invention is the following copolymer.

[ 1] A copolymer which is characterized by comprising a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B),

the component derived from the polymerizable unsaturated monomer (B) contains a component derived from an unsaturated carboxylic acid monomer (B-1) having a main chain with a total of 4 to 10 carbon atoms and oxygen atoms, and the content of the component derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1 to 4 carbon atoms is 0.00 to 1.00 mass% relative to the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B).

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

The copolymer according to [ 1], wherein the constituent derived from the phosphorus-containing unsaturated monomer (A) comprises a constituent derived from a monomer (a-1) having either a phosphoric group or a phosphorous group.

[ 3] the copolymer according to [ 2], wherein the monomer (a-1) having either one of a phosphoric acid group and a phosphorous acid group is an acid phosphonooxy polyoxyalkylene glycol mono (meth) acrylate.

[ 4] the copolymer according to any one of [ 1] to [ 3], which has a phosphorus atom content of 0.1 to 10% by mass.

[ 5] the copolymer according to any one of [ 1] to [ 4], wherein the unsaturated carboxylic acid monomer (b-1) is at least 1 selected from acrylic acid, methacrylic acid, itaconic acid, and β -carboxyethyl acrylate.

[ 6] the copolymer according to any one of [ 1] to [ 5], wherein the content of the constituent derived from the unsaturated carboxylic acid monomer (B-1) is 30 to 95% by mass based on the total content of the constituent derived from the phosphorus-containing unsaturated monomer (A) and the constituent derived from the polymerizable unsaturated monomer (B).

The copolymer according to any one of [ 1] to [ 6], which further comprises a constituent derived from a chain transfer agent (C).

[ 8] the copolymer according to [ 7], wherein the chain transfer agent (C) is a mercaptoalkylcarboxylic acid ester (C-1).

[ 9] the copolymer according to [ 7] or [ 8], wherein the content of the component derived from the chain transfer agent (C) is 0.1 to 10 parts by mass based on 100 parts by mass of the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B).

[ 10] the copolymer according to any one of [ 1] to [ 9], which has a mass average molecular weight of 25000 to 70000.

The copolymer according to any one of [ 1] to [ 10], which has an acid value of 300 to 800 mgKOH/g.

The second embodiment 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 resin composition is also preferably a composition having the following characteristics.

[ 13 ] the resin composition according to [ 12], which further comprises a surfactant.

The third embodiment of the present invention is the following treating 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 substrate and the copolymer according to any one of [ 1] to [ 11] attached to the substrate.

The processed product is preferably a composition having the following characteristics.

A processed product wherein a solid component of the treating agent of [ 14 ] is attached to a substrate, wherein the solid component is attached to the processed product by 5 to 70% by mass.

ADVANTAGEOUS EFFECTS OF INVENTION

The copolymer of the present invention is excellent in flame retardancy, bleed-out resistance and blocking resistance.

Furthermore, by adhering the copolymer of the present invention to a substrate, a processed article excellent in flame retardancy, bleed-out resistance and blocking resistance can be obtained.

The resin composition and the treating agent of the present invention contain the copolymer of the present invention, and therefore, a coating film excellent in flame retardancy and good in bleed-out resistance and blocking resistance can be obtained.

The processed product of the present invention comprises a substrate and the copolymer of the present invention adhered to the substrate. Therefore, it has excellent flame retardancy, bleed-out resistance and blocking resistance.

Detailed Description

Preferred examples of the copolymer, the resin composition, the treating agent and the processed product of the present invention will be described in detail below. The present invention is not limited to the embodiments described below. For example, the type, number, amount, material, configuration, and the like may be added, omitted, or modified without departing from the scope of the present invention.

In the present specification, "to" means not less than the value before the description of "to" and not more than the value after the description of "to".

In the present specification, the term "(meth) acrylate" and the like are used as the same as the term "acrylate and/or methacrylate".

In addition, the description of "unsaturated monomer" and the like in the present specification is the same as the meaning of "monomer having an α, β -ethylenically unsaturated group" and the like.

[ copolymer ]

The copolymer of the present embodiment contains, as essential components, a constituent component derived from the phosphorus-containing unsaturated monomer (a) (hereinafter, sometimes referred to as "constituent component derived from (a)") and a constituent component derived from the polymerizable unsaturated monomer (B) (hereinafter, sometimes referred to as "constituent component derived from (B)"). However, the constituent derived from (a) is not included in the constituent derived from (B).

In the copolymer, both the constituent derived from the phosphorus-containing unsaturated monomer (a) and the constituent derived from the polymerizable unsaturated monomer (B) are repeating units. In the copolymer, the order of arrangement 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 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 a 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 dimethyl vinylphosphonate, diethyl vinylphosphonate, diphenyl vinylphosphonate, 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 phosphonooxyethyl (meth) acrylate, 2-acryloxyethyl acid phosphate, 2-methacryloxyethyl acid phosphate, diphenyl-2-methacryloxyethyl phosphate, and the like, (meth) acryloyloxyethyl acid phosphate monoethanol amine salt, acid phosphonooxy polyethylene glycol (meth) acrylate, acid phosphonooxy polypropylene glycol (meth) acrylate, and metal salts, ammonium salts, and amine salts thereof.

These compounds may be used alone or as a mixture of two or more.

(monomer (a-1) having either one of phosphoric acid group and phosphorous acid group)

The phosphorus-containing unsaturated monomer (a) used as a raw material of the copolymer is preferably a monomer (a-1) having either a phosphate group represented by the following formula (1) or a phosphite group represented by the following formula (2). By using the monomer (a-1), a copolymer having more excellent flame retardancy can be obtained.

(in the formula (1), represents a bonding part with an atom constituting an unsaturated monomer.)

(in the formula (2), represents a bonding part with an atom constituting an unsaturated monomer.)

Examples of the monomer (a-1) having either a phosphoric group or a phosphorous group include a compound represented by the general formula (3), and a metal salt, an ammonium salt, an amine salt and the like of the compound, and two or more of them may be used alone or in combination.

(in the formula (3), R¹And R²Each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Z represents a hydrogen atom or a hydroxyl group. n is an integer of 1 to 20. )

In the formula (3), R¹And R²Each independently represents 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 to 20, more preferably an integer of 1 to 8, and still more preferably an integer of 1 to 3.

Specific examples of the monomer (a-1) having either a phosphoric acid group or a phosphorous acid group include acid phosphonooxy polyoxyalkylene glycol mono (meth) acrylate. If the monomer (a-1) having a phosphoric acid group or a phosphorous acid group is an acid phosphonooxy polyoxyalkylene glycol mono (meth) acrylate, a copolymer having higher flame retardancy can be obtained, and thus it is preferable. In the acid phosphonooxy polyoxyalkylene glycol mono (meth) acrylate, acid phosphonooxyethyl (meth) acrylate is particularly preferable in view of a high proportion of phosphorus atoms per 1 molecule.

The content of the constituent derived from the phosphorus-containing unsaturated monomer (a) may be arbitrarily selected, but is preferably 5 to 60% by mass, more preferably 7 to 50% by mass, and still more preferably 10 to 40% by mass, based on the total content of the constituent derived from the phosphorus-containing unsaturated monomer (a) and the constituent derived from the polymerizable unsaturated monomer (B). When the content of the constituent component derived from (A) is 5% by mass or more based on the total content, a copolymer having more excellent flame retardancy is obtained. Further, if the content of the constituent component derived from (a) is 60% by mass or less with respect to the total content, the copolymer can be stably polymerized, and the storage stability of the copolymer becomes good. When the copolymer having a content of the component derived from (a) of 60% by mass or less is used as a material for a processed product, the processed product can be obtained which is suppressed in the decrease in strength and thermal yellowing resistance due to an excessive content of the component derived from (a) and is excellent in bleed resistance and blocking resistance.

< polymerizable unsaturated monomer (B) >)

The flame retardancy of the copolymer is improved by using a component derived from the polymerizable unsaturated monomer (B) in combination with a component derived from the phosphorus-containing unsaturated monomer (a). Further, the constituent derived from the polymerizable unsaturated monomer (B) improves the adhesion and appearance stability of a processed article using the copolymer as a material. The constituent derived from the polymerizable unsaturated monomer (B) is derived from the polymerizable unsaturated monomer (B) used as a raw material of the copolymer.

The component derived from the polymerizable unsaturated monomer (B) contained in the copolymer contains a component derived from an unsaturated carboxylic acid monomer (B-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms.

The polymerizable unsaturated monomer (B) used as a raw material of the copolymer may be only the unsaturated carboxylic acid monomer (B-1). The polymerizable unsaturated monomer (B) may contain, in addition to the unsaturated carboxylic acid monomer (B-1), another unsaturated monomer having an ethylenically unsaturated bond in the molecule, exhibiting polymerizability, and copolymerizable with the phosphorus-containing unsaturated monomer (A).

(unsaturated carboxylic acid monomer (b-1) having a main chain containing 4 to 10 total carbon atoms and oxygen atoms.)

The constituent derived from the unsaturated carboxylic acid monomer (B-1) having a main chain of 4 to 10 total carbon atoms and oxygen atoms contained in the constituent (B) improves flame retardancy of the copolymer. Only a part of the constituent derived from (B) may be the constituent of the unsaturated carboxylic acid monomer (B-1). It is preferable that the constituent derived from (B) is a copolymer having more excellent flame retardancy if the whole is the constituent of the unsaturated carboxylic acid monomer (B-1).

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) is the longest molecular chain among 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 for methacrylic acid and 6 for maleic acid. When the unsaturated carboxylic acid monomer used as a raw material of the copolymer has a main chain in which the total of the 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 of the number of carbon atoms and the number of 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, and β -carboxyethyl acrylate.

Among them, in particular, in order to stably polymerize the copolymer, the content of the unsaturated carboxylic acid monomer (b-1) in the copolymer is preferably high in acrylic acid, methacrylic acid or itaconic acid, more preferably acrylic acid or methacrylic acid, and still more preferably acrylic acid.

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

(alkyl (meth) acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms)

In the present embodiment, the content of the constituent component derived from the alkyl (meth) acrylate monomer (B-2) having an alkyl group having 1 to 4 carbon atoms (including the case of being not included) needs to be 0.00 to 1.00 mass% with respect to the total content of the constituent component derived from (a) and the constituent component derived from (B).

Examples of the alkyl (meth) acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms, which is used as a raw material of the copolymer, include monomers represented by the following formula (4).

(in the formula (4), R³～R⁵Each independently represents a hydrogen atom or a methyl group. R⁶Is a linear or branched alkyl group having 1 to 4 carbon atoms. )

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

The content of the constituent component 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% relative to the total content of the constituent component derived from (A) and the constituent component derived from (B). The content of the constituent derived from the alkyl (meth) acrylate monomer (b-2) is more preferably 0.75% by mass or less, and still more preferably 0.50% by mass or less. If the content of the constituent derived from the alkyl (meth) acrylate monomer (b-2) exceeds 1.00 mass%, the flame retardancy of the copolymer is lowered.

The polymerizable unsaturated monomer (B) may contain a component derived from another unsaturated monomer other than the components derived from the unsaturated carboxylic acid monomer (B-1) and the alkyl (meth) acrylate monomer (B-2) having an alkyl group having 1 to 4 carbon atoms.

Examples of polymerizable unsaturated monomers other than (b-1) and (b-2) that can be used as the raw material of the copolymer include amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, allyl (meth) acrylate, ethylene glycol di (meth) acrylate, methoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, ethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, polyethylene glycol polybutylene glycol mono (meth) acrylate, and mixtures thereof, (meth) acrylates such as polypropylene glycol polybutylene glycol mono (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dimethylol tricyclodecane di (meth) acrylate, isobornyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, pentaerythritol tetra (meth) acrylate; fumaric acid esters such as dimethyl fumarate, diethyl fumarate, dibutyl fumarate, and di- (2-ethylhexyl) fumarate; maleic acid esters such as dimethyl maleate, diethyl maleate, dibutyl maleate, di- (2-ethylhexyl) maleate and the like; (ii) methacrylamide; (meth) acrylamide derivatives such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-propyl (meth) acrylamide; styrene derivatives such as methoxystyrene, ethoxystyrene vinylbenzoic acid, methyl vinylbenzoate, vinylbenzylacetate, hydroxystyrene and divinylbenzene; vinyl acetate; vinyl esters such as vinyl propionate, vinyl caproate, vinyl caprate, vinyl laurate, and vinyl stearate; n-substituted maleimide compounds such as methylmaleimide, ethylmaleimide, isopropylmaleimide, cyclohexylmaleimide, phenylmaleimide, benzylmaleimide and naphthylmaleimide; itaconates such as monomethyl itaconate, dimethyl itaconate, monoethyl itaconate, diethyl itaconate, monobutyl itaconate and dibutyl itaconate; crotonates such as methyl crotonate, ethyl crotonate and butyl crotonate; phthalic acid esters such as dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, and dihexyl phthalate; succinic acid esters such as 2-acryloyloxyethyl-succinate, and these may be used alone or in combination.

The content of the constituent derived from the polymerizable unsaturated monomer (B) may be arbitrarily selected, but is preferably 40 to 95% by mass relative to the total content of the constituent derived from (a) and the constituent derived from (B).

The content of the constituent component derived from (B) is more preferably 50% by mass or more, and still more preferably 60% by mass or more, relative to the lower limit of the total content. The content of the constituent component derived from (B) is more preferably 90 mass% or less, and still more preferably 85 mass% or less, with respect to the upper limit of the total content. If the content of the constituent component derived from (B) is 40% by mass or more based on the total content, the copolymer can be stably polymerized. Further, if the content of the constituent component derived from (B) is 95% by mass or less with respect to the total content, the synergistic effect between the constituent component derived from (a) and the constituent component derived from (B) becomes more remarkable, and therefore the flame retardancy of the copolymer is further improved.

< chain transfer agent (C) >

The copolymer of the present embodiment may contain a constituent derived from the chain transfer agent (C). The constituent derived from the chain transfer agent (C) is a component derived from the phosphorus-containing unsaturated monomer (a) and a component derived from the polymerizable unsaturated monomer (B), and is bonded to the copolymer in order to adjust the mass average molecular weight of the copolymer.

Examples of the chain transfer agent (C) include sulfur-containing compounds such as thiodiglycol, ethylenethioethanol, di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, diisopropyl sulfide, thioglycolic acid, mercaptopropionic acid, mercaptobutyric acid, mercaptohexanoic acid, 2-ethylhexyl thioglycolate, mercaptosuccinic acid, thioacetic acid, and thiourea; phosphorus-containing compounds such as bisulfite, hypophosphorous acid and salts thereof, and phosphorous acid and salts thereof; aldehyde compounds such as formaldehyde, acetaldehyde and propionaldehyde; organic acids such as formic acid, sodium formate, and ammonium formate; alcohol compounds such as isopropyl alcohol; and the like. These chain transfer agents (C) may be used singly or in combination of two or more.

When the constituent derived from the chain transfer agent (C) is also a constituent derived from the phosphorus-containing unsaturated monomer (a), the constituent is regarded as a constituent derived from the phosphorus-containing unsaturated monomer (a).

Among the above, the chain transfer agent (C) is particularly preferably one containing a mercaptoalkylcarboxylate from the viewpoints of polymerization stability and improvement in flame retardancy due to a synergistic effect of a terminal carboxylic acid in a constituent derived from the polymerizable unsaturated monomer (B) and a constituent derived from the phosphorus-containing unsaturated monomer (a). Examples of the mercaptoalkylcarboxylate include mercaptoacetic acid, mercaptopropionic acid, mercaptobutyric acid, and mercaptohexanoic acid.

The content of the constituent derived from the chain transfer agent (C) may be arbitrarily selected, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total content of the constituent derived from (a) and the constituent derived from (B).

The content of the constituent component derived from the chain transfer agent (C) is more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more, relative to the lower limit of the total content. The content of the constituent component derived from the chain transfer agent (C) is more preferably 9 parts by mass or less, and still more preferably 8 parts by mass or less, relative to the upper limit of the total content. When the content of the constituent derived from the chain transfer agent (C) is 0.1 parts by mass or more relative to the total content, the effect of adjusting the mass average molecular weight of the copolymer having the chain transfer agent (C) is obtained, and thus a copolymer having excellent polymerization stability and storage stability is obtained. Further, if the content of the constituent derived from the chain transfer agent (C) is 10 parts by mass or less relative to the total content, the constituent derived from the chain transfer agent (C) does not hinder the flame retardancy of the copolymer, and the flame retardancy is further excellent. The content of the constituent derived from the chain transfer agent (C) may be determined by¹H-NMR and the like. In order to set the content of the constituent component derived from the chain transfer agent (C) within the above range, it is preferable to use a slightly larger amount than the content during polymerization.

"Mass average molecular weight"

The copolymer of the present embodiment preferably has a mass average molecular weight of 25000 to 70000. The lower limit of the mass average molecular weight is more preferably 27000 or more, and still more preferably 30000 or more. The upper limit of the mass average molecular weight is more preferably 60000 or less, and still more preferably 55000 or less. If the mass average molecular weight of the copolymer is 25000 or more, the flame retardancy of the copolymer is more excellent. When the mass average molecular weight of the copolymer is 70000 or less, the polymerization stability of the copolymer becomes good.

The mass average molecular weight of the copolymer was measured as follows using a Gel Permeation Chromatography (GPC) trade name "Shodex GPC-101" (manufactured by showa electric corporation, "Shodex" is a registered trade mark).

An aqueous solution containing 34.5g of disodium hydrogenphosphate 12 hydrate and 46.2g of sodium dihydrogenphosphate 2 hydrate, to which ultrapure water was added to thereby prepare 5.000g of the total amount, was prepared as a carrier liquid. The copolymer was dissolved in the carrier liquid, and the measurement was carried out using a pump (< DU-H2000>, manufactured by Shodex) at a flow rate of 0.5ml/min.

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

"acid value"

The acid value of the copolymer of the present embodiment is preferably 300 to 800 mgKOH/g. The lower limit of the acid value is more preferably 350mgKOH/g or more, and still more preferably 450mgKOH/g or more. The upper limit of the acid value is more preferably 785mgKOH/g or less, and still more preferably 750mgKOH/g or less. If the acid value of the copolymer is 300mgKOH/g or more, the flame retardancy of the copolymer is further excellent. When the acid value of the copolymer is 800mgKOH/g or less, the polymerization stability and storage stability of the copolymer become good.

"phosphorus atom content"

The content of phosphorus atoms in the copolymer can be arbitrarily selected, but is preferably 0.1 to 10% by mass. The lower limit of the phosphorus atom content is more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. The upper limit of the phosphorus atom content is more preferably 9.0 mass% or less, and still more preferably 8.0 mass% or less. When the phosphorus atom content is 0.1 mass% or more, a copolymer having more excellent flame retardancy is obtained. When the content of the phosphorus atom is 10% by mass or less, the copolymer can be stably polymerized, and the storage stability of the copolymer becomes good. Further, if the content of the phosphorus atom is 10% by mass or less, when the composition is used as a material for a processed article, the composition can provide a processed article which is suppressed in the decrease in adhesion to a base material and the change in appearance due to an excessive content of the phosphorus atom, and is excellent in bleeding resistance and blocking resistance.

[ method for producing copolymer ]

The copolymer of the present embodiment can be produced, for example, by radical copolymerization of an unsaturated monomer as a raw material of the copolymer by a conventionally known method.

The unsaturated monomer as a raw material contains the phosphorus-containing unsaturated monomer (A) and the polymerizable unsaturated monomer (B).

As a method for copolymerizing an 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. Further, a continuous polymerization method may be used, or a batch polymerization method may be used.

When the unsaturated monomer is copolymerized to produce a copolymer, a chain transfer agent (C), a solvent shown below, a surfactant, an initiator, and a neutralizer may be used as necessary.

As a method for producing the copolymer, it is preferable to use: emulsion polymerization using a surfactant, or solution polymerization without a surfactant.

In the emulsion polymerization method, first, an unsaturated monomer as a raw material, a solvent, a surfactant (emulsifier), and the chain transfer agent (C) are mixed to prepare a monomer emulsion. The chain transfer agent (C) is used as needed, and may not be contained in the monomer emulsion. Next, the obtained monomer emulsion is mixed with an initiator and reacted at a predetermined reaction temperature to prepare a resin composition (aqueous emulsion) in which a copolymer is dispersed in a solvent. In the resin composition, a part of the copolymer may be dissolved in the solvent. Then, a neutralizing agent is added to the resin composition as needed to neutralize it. Further, the solvent in the resin composition is removed and dried, whereby a resin solid content containing the copolymer can be separated from the resin composition.

In the solution polymerization method, first, an unsaturated monomer as a raw material, a solvent, and the chain transfer agent (C) are mixed to prepare a monomer solution. The chain transfer agent (C) is used as needed, and may not be contained in the monomer solution. Next, the obtained monomer solution is mixed with an initiator, and reacted at a predetermined reaction temperature to prepare a resin composition in which a copolymer is dissolved in a solvent. In the resin composition, a part of the copolymer may be insoluble in the solvent by increasing the molecular weight of the copolymer. Then, a neutralizing agent is added to the resin composition as needed to neutralize it. Further, the solvent in the resin composition is removed and dried, whereby a resin solid content containing the copolymer can be separated from the resin composition.

In the emulsion polymerization method (or solution polymerization method), a conventionally known method can be used as a method for mixing a monomer emulsion (monomer solution in the solution polymerization method) with an initiator.

For example, a method of adding a monomer emulsion (monomer solution in the solution polymerization method) dropwise to an initiator and stirring the mixture can be used. In this case, a part of the initiator may be added dropwise to the initiator together with the monomer emulsion (monomer solution in the solution polymerization method). In addition, a method of mixing the entire amount of the initiator with the entire amount of the monomer emulsion (monomer solution in the solution polymerization method) may 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, and examples thereof include a method using a chain transfer agent (C), a method for adjusting the concentration of an initiator, and a method for adjusting the reaction temperature. The reaction temperature may be changed depending on the kind of the initiator.

< solvent >

The solvent used for producing the copolymer can be arbitrarily selected, and for example, an aqueous solvent such as water, an organic solvent generally used, or the like can be used, and an aqueous solvent is preferred.

Examples of the solvent include alcohols such as water, methanol, ethanol, propanol, isopropanol, and butanol; ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate, butyl cellosolve acetate and the like; diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate and the like; acetates such as propylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ether acetates, etc.; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl ethers; propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; methyl ether, ethyl ether, 1, 4-bis

Ethers such as alkane and tetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; hydrocarbons such as benzene, toluene, xylene, hexane, octane, and decane; petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha, and solvent naphtha; lactic acid esters such as methyl lactate, ethyl lactate, and butyl lactate; dimethylformamide, N-methylpyrrolidone, diethylene glycol monoethyl ether, and the like. These solvents may be used alone or in combination of two or more.

< initiator >

In the case of producing a copolymer by copolymerizing an unsaturated monomer as a raw material by radical polymerization, the unsaturated monomer is copolymerized in the presence of an initiator.

The initiator is not particularly limited as long as it can initiate radical polymerization, and a generally used peroxide, azo compound, or the like can be used.

Specific examples of the initiator include sodium persulfate, potassium persulfate, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyl-3, 3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, di-isopropylperoxydicarbonate, and di-isopropylperoxyl, Isobutyl peroxide, 3, 5-trimethylhexanoyl peroxide, lauryl peroxide, 1-bis (t-hexylperoxy) -3,3, 5-trimethylcyclohexane, azobisisobutyronitrile, azodicarbonamide, etc., and an appropriate reducing agent may be used depending on the reaction.

The amount of the initiator to be used may be arbitrarily selected, but is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, and still more preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (a) and the polymerizable unsaturated monomer (B) as raw materials, in order to obtain an appropriate polymerization rate.

< surfactant >

The surfactant is used when the copolymer is produced by an emulsion polymerization method.

As the surfactant, a commercially available anionic surfactant, nonionic surfactant, cationic surfactant, and copolymerizable surfactant can be used. Among them, as the surfactant, an anionic surfactant and a nonionic surfactant are preferably used.

Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl sulfate, polyoxyethylene alkyl ether sulfate, and fatty acid salt.

Examples of the nonionic surfactant include polyvinyl alcohol, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polycyclic phenyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and the like.

Examples of the cationic surfactant include cetyltrimethylammonium bromide and laurylpyridine

Chlorides, and the like.

As the copolymerizable surfactant, an anionic or nonionic surfactant having at least 1 or more unsaturated double-bonded groups capable of radical polymerization in the molecule can be used. Examples of the copolymerizable surfactant include surfactants having an ammonium sulfate group (-SO)^3-NH⁴⁺) Iso sulfate group and allyl (-CH)₂-CH＝CH₂) The hydrocarbon compound of (2), having an ammonium sulfate group (-SO)^3-NH⁴⁺) Isosulfate group and methacryloyl [ -CO-C (CH)₃)＝CH₂Hydrocarbon compounds or compounds having an ammonium sulfate group (-SO)^3-NH⁴⁺) Isosulfate group and 1-propenyl (-CH ═ CH)₂CH₃) And aromatic hydrocarbon compounds of (2).

The amount of the surfactant to be used may be arbitrarily selected, but is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 20 parts by mass, and still more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (a) and the polymerizable unsaturated monomer (B) as raw materials, in order to maintain emulsion stability.

< neutralizer >

The neutralizing agent is used as needed when producing a resin composition containing the copolymer. By adjusting the pH of the resin composition containing the copolymer using the neutralizing agent, the effect of improving the mixing stability in the resin composition or suppressing bleeding can be obtained.

As the neutralizing agent, conventionally known compounds can be used. For example, a monoalkylamine such as an aqueous sodium hydroxide solution, an aqueous ammonia solution, and monomethylamine can be used.

< Water-soluble Polymer >

The water-soluble polymer is used as needed when producing the copolymer. The water-soluble polymer is a polymer which is protected and gelled by a copolymer and stably dispersed in an aqueous solvent. As the water-soluble polymer, a water-soluble (meth) acrylic resin, a water-soluble (meth) acrylate resin, a polyoxyethylene alkyl ether, or the like 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 polymerization degree of the water-soluble polymer is preferably 200 to 2,400 from the viewpoints of polymerization stability in the production of a copolymer and viscosity of the copolymer. The saponification degree of the water-soluble polymer is preferably 80% to 100% from the viewpoint of polymerization stability in the production of a copolymer.

When the water-soluble polymer is also the polymerizable unsaturated monomer (B), it is regarded as the polymerizable unsaturated monomer (B).

The amount of the water-soluble polymer used may be arbitrarily selected, but is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 20 parts by mass, and still more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the total of the phosphorus-containing unsaturated monomer (a) and the polymerizable unsaturated monomer (B) as raw materials, in order to maintain dispersion stability.

The copolymer of the present embodiment comprises a constituent derived from a phosphorus-containing unsaturated monomer (A) and a constituent derived from a polymerizable unsaturated monomer (B), wherein the constituent derived from (B) comprises a constituent derived from an unsaturated carboxylic acid monomer (B-1) having a main chain in which the total of the number of carbon atoms and the number of oxygen atoms is 4 to 10, and the content of the constituent derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1 to 4 carbon atoms is 0.00 to 1.00 mass% relative to the total content of the constituent derived from (A) and the constituent derived from (B), and is excellent in flame retardancy.

It is presumed that the flame retardancy of the copolymer of the present embodiment is obtained by promoting the formation of a carbonized layer during combustion by the synergistic effect of the constituent derived from (a) and the carboxyl group contained in the constituent of the unsaturated carboxylic acid monomer (b-1).

The copolymer of the present embodiment has excellent flame retardancy. Therefore, the content of the flame retardant can be made relatively small for a processed product containing the copolymer of the present embodiment as the flame retardant. Therefore, in the processed product containing the copolymer of the present embodiment as a flame retardant, the influence of the flame retardant on the physical properties of the processed product is small.

Further, since the copolymer of the present embodiment contains both the constituent component derived from (a) and the constituent component derived from (B), a processed product having good bleed-out resistance and blocking resistance can be obtained when used as a material for a processed product.

[ resin composition ]

The resin composition of the present embodiment contains the copolymer of the above embodiment. The resin composition of the present embodiment may contain the copolymer of the above embodiment, and may contain the above-mentioned solvent, surfactant, initiator, neutralizer, and the like, in addition to the copolymer of the above embodiment. The resin composition of the present embodiment may be obtained in the process of producing the copolymer of the above embodiment. The resin composition may contain the copolymer in any amount, and for example, the amount of the copolymer in the composition is preferably 1.0 to 90% by mass, more preferably 10 to 85% by mass, and still more preferably 15 to 80% by mass. However, the method is not limited to these ranges. For example, the amount of the inorganic filler is 0.1 to 1.0 mass% or 90 to 95 mass%.

[ treating agent ]

The treating agent of the present embodiment contains the copolymer of the above embodiment. Examples of the treating agent of the present embodiment include a copolymer dispersed or dissolved in the solvent. Such a treating agent adheres to a substrate by coating the substrate, and a coating film containing a copolymer is formed by removing a solvent. Therefore, the treating agent of the present embodiment can be used as a coating material, a paper treating agent, a fiber treating agent, an adhesive, or the like.

As the treating agent of the present embodiment, a resin composition in which the copolymer produced by the above-described production method is dispersed or dissolved in a solvent can be used as it is.

The term "treating agent" in the present specification is defined to include a coating material and an adhesive binder in addition to a paper treating agent and a fiber treating agent.

The "solid content" of the treating agent is defined as a component obtained by drying a solvent contained in the treating agent.

< other resins >

The treating agent of the present embodiment may contain another resin different from the copolymer of the above embodiment depending on the application, within a range not impairing the effects of the present invention.

Examples of the other resin include various resins such as acrylic resin, epoxy resin, urethane resin, and polyester resin. The other resin may be in the state of resin emulsion or solution resin. The mixing ratio of the copolymer of the above embodiment to other various resins in the treating agent of the present embodiment may be arbitrary.

< other ingredients >

The treating agent of the present embodiment may contain other components in addition to the copolymer, as necessary.

The other components may be selected from conventionally known additives such as a crosslinking agent, a thickener, a pH adjuster such as an acid or an alkali, a film-forming aid, a plasticizer, an antiseptic, a defoaming agent, a pigment, a dispersant, a light stabilizer, an ultraviolet absorber, an antioxidant, a rust preventive, a penetrant, an antistatic agent, a leveling agent, and a thickener, in a range not to impair the object of the present invention, depending on the application.

The treating agent of the present embodiment can be produced, for example, by mixing at least 1 of the copolymer of the above embodiment, the solvent, and if necessary, other resins and other components by a conventionally known method. In the production of the treating agent, for example, mixing may be carried out using a mixing device such as various mills or dissolvers.

The treating agent of the present embodiment contains the copolymer of the present embodiment, and therefore, a coating film having excellent flame retardancy and good bleed-out resistance and blocking resistance can be obtained.

The treating agent of the present embodiment can impart excellent flame retardancy to a substrate, and thus can be applied to various fields.

[ processed product ]

The processed product of the present embodiment includes a base material, and the copolymer, the resin composition, or the treatment agent of the above embodiment attached to the base material.

Examples of the processed product of the present embodiment include a paper processed product, a fiber processed product, a general processed product, an adhesive processed product, and an adhesive processed product.

In the processed product of the present embodiment, the solid content of the treating agent adhering to the base material is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, relative to the processed product. When the amount of the solid component adhering to the treating agent is 5% by mass or more, a processed product having good flame retardancy can be easily obtained. If the amount of the solid content of the treating agent to be adhered is 70% by mass or less, appearance defects caused by adhesion of the copolymer in the treating agent to the surface of the substrate can be suppressed.

In the processed product of the present embodiment, the content of the copolymer is preferably 1 to 70 parts by mass with respect to 100 parts by mass of the substrate. The lower limit of the content of the copolymer is more preferably 20 parts by mass or more, and still more preferably 40 parts by mass or more. The upper limit of the content of the copolymer is more preferably 65 parts by mass or less, and still more preferably 60 parts by mass or less. If the content of the copolymer is 1 part by mass or more, the flame retardancy-improving effect by the inclusion of the copolymer can be more effectively obtained. If the content of the copolymer is 70 parts by mass or less, a processed product corresponding to the use can be easily obtained.

The processed product of the present embodiment can be produced, for example, by a method of coating or impregnating a substrate with the treating agent of the present embodiment, drying the coating, and adhering the copolymer to the substrate.

The processed product of the present embodiment includes a substrate and the copolymer of the present embodiment attached to the substrate. Therefore, the processed product of the present embodiment has excellent flame retardancy, bleed-out resistance, and blocking resistance. Therefore, the processed product of the present embodiment can be applied to various fields.

Specific example "

Next, as specific examples of the treating agent and the processed product of the present embodiment, "paper treating agent and paper processed product," "fiber treating agent and fiber processed product," "general coating material and general processed product," "adhesive and adhesive processed product" will be described.

In the present specification, the term "adhesive agent" refers to a treatment agent having the functions of either or both of an adhesive agent and an adhesive agent.

Paper treating agent and paper processed product "

(paper treating agent)

As the paper-treating agent of the present embodiment, a paper-treating agent in which the copolymer of the present embodiment is dissolved or dispersed in a solvent in an arbitrarily selected amount can be used.

In the present embodiment, the content of the copolymer in the paper treatment agent is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass. By making the paper treatment agent in which the content of the copolymer is in the above range, the effect by containing the copolymer becomes remarkable.

(paper processed product)

In the paper processed product of the present embodiment, paper is used as a base material. Examples of the paper include general-purpose paper made of pulp cellulose.

The amount of the paper-treating agent used (amount of adhesion) to the paper-processed product can be appropriately changed depending on the flame retardancy of the substrate itself used. The amount of the paper-treating agent (solid content) to be attached after drying can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, based on the paper-processed product. If the amount of the paper-treating agent adhered is 5% by mass or more, a paper-processed product having excellent flame retardancy can be easily obtained. If the amount of the paper-treating agent attached is 70% by mass or less, the decrease in strength and feel caused by the copolymer in the paper-treating agent attaching to the surface of the base formed of paper can be suppressed.

The amount (content) of the copolymer to be adhered 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, and still more preferably 5 to 50 parts by mass, based on 100 parts by mass of the paper (substrate). When the amount of the copolymer to be adhered is 1 part by mass or more, a paper-processed product having excellent flame retardancy can be easily obtained. If the amount of the copolymer to be attached is 70 parts by mass or less, the strength and the texture can be prevented from being lowered due to the attachment of the copolymer to the surface of the base material made of paper.

(method for producing paper processed product)

The method for producing the paper-processed product of the present embodiment may be any conventionally known method without particular limitation. For example, a method of applying or impregnating a base material made of paper with the paper treatment agent of the present embodiment and then drying the paper treatment agent is exemplified.

As a method of applying the paper-treating agent to the substrate made of paper, a conventionally known method can be used. Examples thereof include a method of immersing the substrate in the paper treatment agent (dipping), spraying, roll coating, and the like. The amount of the paper treatment agent adhering to or impregnated into the substrate can be adjusted by applying the paper treatment agent to the substrate by these application methods, and then pressing the substrate coated with the paper treatment agent using a mangle roll or the like.

As a method for drying the base material coated with the paper-treating agent, a conventionally known method can be used. For example, the paper-treating agent-coated base material may be air-dried, dried under reduced pressure, or dried under pressure.

When drying the paper-treating agent-coated substrate, the paper-treating agent-coated substrate may be heated. The heating temperature for heating and drying the paper-treating agent-coated substrate can be arbitrarily selected, but is preferably 50 to 250 ℃, more preferably 80 to 190 ℃, and still more preferably 90 to 150 ℃. When the heating temperature is 50 ℃ or higher, the drying of the substrate coated with the paper-treating agent is promoted by heating. When the heating temperature is 250 ℃ or lower, the substrate coated with the paper-treating agent can be inhibited from being deteriorated by heating.

The paper-processed product of the present embodiment has excellent flame retardancy, bleed-out resistance, and blocking resistance. Further, the paper-processed product of the present embodiment has excellent strength because the copolymer adheres to the base material formed of paper. Thus, the paper-processed product of the present embodiment is suitable as a material for building materials such as wallpaper and lining paper for wallpaper, home appliances, electronic materials, and automobile interior materials.

Fiber treatment agent and fiber processed product "

(fiber treatment agent)

As the fiber treatment agent of the present embodiment, a fiber treatment agent 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 may be arbitrarily selected, but is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass. By making the fiber treatment agent in which the content of the copolymer is in the above range, the effect by containing the copolymer becomes remarkable.

(fiber processed product)

In the fiber-processed product of the present embodiment, fibers are used as the base material.

The shape of the fibers is not particularly limited, and examples thereof include a nonwoven fabric, a woven fabric, a knitted fabric, a shape in which fibers formed into a sheet are formed into a web, and the obtained web is bonded or entangled to form a cloth.

The material of the fiber is not particularly limited, and examples thereof include kapok, hemp, silk, wool, collagen fiber, acrylic fiber, cellulose fiber, polyimide fiber, polyamideimide fiber, rayon fiber, nylon fiber, vinylon fiber, polyester fiber, polypropylene fiber, polyvinyl chloride fiber, polyethylene fiber, polymetaphenylene isophthalamide fiber, aramid fiber, polyarylate fiber, polytetrafluoroethylene fiber, polybenzimidazole fiber, polyetheretherketone fiber, polyphenylene sulfide fiber, and a blend thereof.

The amount of the fiber treatment agent (amount of adhesion) to the processed fiber product may be appropriately changed depending on the flame retardancy of the base material itself to be used. The amount of the fiber treatment agent (solid content) adhering to the fiber after drying is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, based on the processed fiber product. When the amount of the fiber treatment agent adhered is 5% by mass or more, a fiber-processed product having excellent flame retardancy can be easily obtained. If the amount of the fiber treatment agent attached is 70% by mass or less, the decrease in strength and texture due to the attachment of the copolymer in the fiber treatment agent to the surface of the base material formed of fibers can be suppressed.

The amount (content) of the copolymer to be attached to 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, and still more preferably 5 to 50 parts by mass, based on 100 parts by mass of the fiber (substrate). When the amount of the copolymer to be adhered is 1 part by mass or more, a fiber-processed product having excellent flame retardancy can be easily obtained. If the amount of the copolymer to be attached is 70 parts by mass or less, the strength and the texture can be prevented from being lowered due to the attachment of the copolymer to the surface of the base material formed of fibers.

(method for producing fiber-processed product)

The method for producing the fiber processed product of the present embodiment may be any conventionally known method without any particular limitation. For example, a method of applying or impregnating a base material made of fibers with the fiber treatment agent of the present embodiment and then drying the base material is exemplified.

As a method of applying the fiber treatment agent to the base material formed of fibers, a conventionally known method can be used. Examples thereof include a method of immersing the base material in the fiber treatment agent (dipping), a direct coating method, a spray coating method, a roll coater method, a slot coater method, a knife coating method, a printing method, a roll transfer method, a back coating method, and the like. Examples of the method of immersing the base material in the fiber treatment agent include a horizontal roll method, a metering roll method, a mesh conveyor method, a foam method, and the like.

When the fibers are in the form of a nonwoven fabric, the fiber treatment agent is preferably applied to the fibers by a spray coating method, a printing method, a roll transfer method, a horizontal roll method, a metering roll method, a mesh conveyor method, a foam method, or the like.

When the fibers are woven in shape, the fiber treatment agent is preferably applied to the fibers by a direct application method, a spray method, a roll coater method, a slot coater method, a knife coater method, or the like.

When a substrate is used in which fibers formed into a sheet are formed into a web by forming the web into a net and the obtained web is bonded or entangled to form a cloth, the fiber treatment agent may be applied to the substrate either before or after the fibers are formed into a net.

As a method for forming a web, various known methods can be used without particular limitation, and examples thereof include an air-laid method and the like.

As a method for drying the base material coated with the fiber treatment agent, a conventionally known method can be used. 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 base material coated with the fiber treatment agent, the base material coated with the fiber treatment agent may be heated. The heating temperature for drying the substrate coated with the fiber treatment agent by heating can be arbitrarily selected, but is preferably 50 to 250 ℃, and more preferably 80 to 190 ℃. When the heating temperature is 50 ℃ or higher, the drying of the base material coated with the fiber treatment agent is promoted by heating. When the heating temperature is 250 ℃ or lower, the base material coated with the fiber treatment agent can be inhibited from being deteriorated by heating.

The processed fiber product of the present embodiment has excellent flame retardancy, bleed-out resistance, and blocking resistance. In addition, the fiber-processed product of the present embodiment has excellent strength because the copolymer adheres to the base material formed of the fiber. Thus, the fiber-processed product of the present embodiment is suitable as a material for use in, for example, interior materials such as curtains, home appliances such as home appliance cushioning materials, electronic materials such as electronic material cushioning materials, automobile interior cushioning materials, automobile seats, and other automobile interior materials.

General coating and general processed product "

(general coating)

The general coating material of the present embodiment is applied to a substrate, and the treating agent of the present embodiment is used.

In the present embodiment, the content of the copolymer in the general coating material can be arbitrarily selected, but is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass. By making a general coating material in which the content of the copolymer is in the above range, the effect caused by the inclusion of the copolymer becomes more remarkable.

(general processed product)

The general processed product of the present embodiment is formed by applying a general coating to a substrate.

Examples of the material of the substrate used for general processed products include, but are not limited to, glass, polyolefin resins, polyester resins, polycarbonate resins, resins such as acrylonitrile butadiene styrene copolymers (ABS resins) and polystyrene resins, metals, wood, and paper.

The shape of the substrate used for general processed products is not particularly limited, and for example, the substrate can be formed into a film, a sheet, a cup or the like.

The amount of the general coating material (amount of deposition) to be used for general processed products can be appropriately changed in accordance with the flame retardancy of the substrate itself to be used. The amount of adhesion (solid content) of the general coating after drying can be arbitrarily selected, but is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass, based on the general processed product. When the amount of the general coating material adhered is 5% by mass or more, general processed products having good flame retardancy can be easily obtained. When the amount of the general coating material adhered is 70% by mass or less, appearance defects caused by the copolymer in the general coating material adhering to the surface of the substrate can be suppressed.

(method for producing general processed product)

As a method for producing a general processed product according to the present embodiment, a conventionally known method can be employed without particular limitation. For example, a method of applying the general coating material of the present embodiment to a substrate made of a resin, a metal, or the like and then drying the coating material is exemplified.

As a method for applying a general coating to a substrate used for a general processed product, a conventionally known method can be used. Examples thereof include a method of immersing the substrate in a general coating material (dipping), a method using a sprayer, brush coating, roller coating, trowel coating, air knife, flow coating, bar coating, roll coating, gravure coating, and applicator.

The film thickness when a general coating material is applied to a substrate can be arbitrarily selected without particular limitation. For example, it is preferably 1 to 200 μm, more preferably 10 to 150 μm, and still more preferably 10 to 100 μm. When the thickness of the coating film applied is 1 μm or more, general processed products having excellent flame retardancy can be easily obtained. When the thickness of the coating film applied is 200 μm or less, the occurrence of appearance defects due to insufficient drying of the coating film is suppressed.

As a method for drying the substrate coated with the general coating material, a conventionally known method can be used. When drying the substrate coated with the general coating material, the substrate coated with the general coating material may be heated. The heating temperature for drying the substrate coated with the general coating material by heating can be arbitrarily selected, but is preferably 80 to 170 ℃, more preferably 90 to 150 ℃. When the heating temperature is 80 ℃ or higher, the drying of the substrate coated with the general coating material is promoted by heating. When the heating temperature is 170 ℃ or lower, deterioration of the substrate coated with a general coating material due to heating is less likely to occur.

A general processed product as the processed product of the present embodiment has excellent flame retardancy, bleed-out resistance, and blocking resistance. In addition, since the general processed product of the present embodiment includes the copolymer containing the constituent component derived from the polymerizable unsaturated monomer (B), the adhesion between the coating film and the substrate and the stability of the appearance are excellent. Therefore, the general processed product of the present embodiment is suitable as a material for building materials, electronic materials, and automobile interior materials.

Adhesive and adhesive-processed product "

(adhesive agent)

As the adhesive of the present embodiment, an adhesive obtained by dissolving or dispersing the copolymer of the present embodiment in a solvent can be used.

The content of the copolymer in the pressure-sensitive adhesive of the present embodiment may be arbitrarily selected, but is preferably 1 to 90% by mass, and more preferably 10 to 80% by mass. By making the content of the copolymer in the adhesive agent in the above range, the effect of the copolymer can be more effectively obtained.

(pressure-sensitive adhesive processed product)

The base material in the pressure-sensitive adhesive processed product of the present embodiment is at least 1 of an adherend to be bonded with a pressure-sensitive adhesive and a support for supporting a pressure-sensitive adhesive layer containing a pressure-sensitive adhesive.

Examples of the material of the substrate include polyesters such as polyethylene terephthalate; polymers such as polyolefin, polyamide, and polyimide; natural or synthetic rubber; paper; a metal; glass cloth; and the like, but is not limited thereto.

The surface of the substrate may be subjected to various easy adhesion treatments such as formation of an adhesion-promoting layer or corona treatment or plasma treatment in order to improve adhesion to an adhesive layer containing an adhesive agent adhering to the substrate.

Examples of the substrate used as the support include paper, plastic films, plastic or rubber foams, metals, glass, woven fabrics, nonwoven fabrics, and inorganic boards.

The shape of the substrate used as the support is preferably a film or a tape.

When a pressure-sensitive adhesive layer is formed by applying a pressure-sensitive adhesive to a substrate used as a support and drying the adhesive, a release film formed of a resin film or the like may be bonded to the pressure-sensitive adhesive layer.

The thickness (thickness after drying) of the adhesive layer containing the copolymer to be adhered to the base material may be any thickness, and may be appropriately determined depending on the application. Specifically, the thickness of the pressure-sensitive adhesive layer is preferably 5 to 200. mu.m, more preferably 10 to 150. mu.m, and still more preferably 10 to 100. mu.m. When the thickness of the pressure-sensitive adhesive layer is 5 μm or more, a processed pressure-sensitive adhesive article having excellent flame retardancy can be easily obtained. When the thickness of the pressure-sensitive adhesive layer is 200 μm or less, a sufficiently dried pressure-sensitive adhesive layer can be obtained.

(method for producing pressure-sensitive adhesive processed product)

The method for producing the pressure-sensitive adhesive processed product of the present embodiment may be any conventionally known method without particular limitation.

When the substrate is an adherend to be bonded with an adhesive, for example, there is a method in which the adhesive of the present embodiment is applied to the surface to be bonded of the substrate, and then another material bonded to the substrate is placed in contact with the coating film formed of the adhesive, and the coating film formed of the adhesive is dried.

As a method of applying the pressure-sensitive adhesive to a substrate as an adherend to be bonded with the pressure-sensitive adhesive, a conventionally known method can be used. Examples of the method of applying the adhesive include a wire bar, an applicator, a brush, a sprayer, a roll, a gravure coater, a die coater, a slot coater, a comma coater, a knife coater, a reverse coater, and a spin coater.

When the substrate is a film-like substrate used as a support, for example, a method of applying the pressure-sensitive adhesive of the present embodiment to one surface or both surfaces of the substrate and then drying the adhesive is exemplified. Thus, a film-like processed adhesive article can be obtained. Further, a film-shaped processed adhesive product is wound and cut according to the application, whereby a tape-shaped processed adhesive product can be obtained.

When the adhesive is applied to a film-like substrate used as a support, for example, a coating method such as roll coating, kiss roll coating, roll brushing, dip roll coating, bar coating, air knife coating, curtain coating, or extrusion coating using a die coater can be used.

As a method for drying the adhesive applied to the substrate, a conventionally known method can be used. When the adhesive-coated substrate is dried, the adhesive-coated substrate may be heated. The heating temperature for drying the adhesive-coated substrate by heating can be arbitrarily selected, but is preferably 80 to 170 ℃, and more preferably 90 to 150 ℃. When the heating temperature is 80 ℃ or higher, the drying of the adhesive-coated base material is promoted by heating. When the heating temperature is 170 ℃ or lower, the substrate coated with the pressure-sensitive adhesive is less likely to be deteriorated by heating.

In the present embodiment, the surface of the pressure-sensitive adhesive layer obtained by drying the base material to which the pressure-sensitive adhesive is applied can be subjected to an easy adhesion treatment.

Further, a release film formed of a resin film or the like may be bonded to the pressure-sensitive adhesive layer.

The pressure-sensitive adhesive processed product as the processed product of the embodiment has excellent flame retardancy, bleed-out resistance and blocking resistance, and is excellent in initial adhesion and heat-resistant holding power. Therefore, the pressure-sensitive adhesive processed product of the present embodiment is suitably used as, for example, articles for daily use such as pressure-sensitive adhesive tapes, double-sided tapes, and pressure-sensitive adhesive labels, building materials such as wall papers, floor tiles, floor mats (floor mats), carpets, ceiling tiles, and adhesive sheets for windows, automobile products, household electrical appliances, and electronic components.

Examples

The present invention will be described in more detail below with reference to examples and comparative examples. The present invention is not limited to the following examples.

[ resin composition ]

(example 1)

A solution containing the monomers was prepared by uniformly mixing 100g of acid phosphonooxyethyl methacrylate as the phosphorus-containing unsaturated monomer (A) shown in Table 1, 100g of acrylic acid as the polymerizable unsaturated monomer (B) which is the unsaturated carboxylic acid monomer (B-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms, 0.5g of methyl acrylate as the alkyl (meth) acrylate monomer (B-2) having an alkyl group having 1 to 4 carbon atoms, 4.0g of mercaptopropionic acid as the chain transfer agent (C), 1.5g of sodium dodecylbenzenesulfonate and 7.5g of polyoxyethylene alkyl ether as the surfactant, and 150g of ion-exchanged water as the solvent.

150g of ion exchange water as a solvent (1L) was charged into a five-neck separable flask, and the mixture was heated to 80 ℃ with stirring. To the separable flask was added 3.0g of potassium persulfate as an initiator. Then, the solution containing the monomers and a 10 mass% aqueous solution of potassium persulfate were dropped into the separable flask to start the polymerization reaction. The solution containing the monomers was added to the removable flask at approximately constant supply over 4 hours. 70g of a 10 mass% aqueous potassium persulfate solution was also added together with the monomer-containing solution at an approximately constant feed rate over 4 hours. After the addition of the monomer-containing solution and the 10 mass% aqueous potassium persulfate solution was completed, the reaction was stirred at 80 ℃ for 2 hours to complete the reaction.

After the reaction was completed, the separable flask was cooled, and 20g of a 30 mass% aqueous sodium hydroxide solution was added as a neutralizing agent to neutralize the reaction system. After the addition of the neutralizing agent was completed, the mixture was stirred for 1 hour. Through the above steps, a resin composition in which the copolymer of example 1 was dispersed or dissolved in water was obtained.

The raw materials and the amounts used for producing the resin composition of example 1 are shown in table 1.

(examples 2 to 30 and comparative examples 1 to 8)

Resin compositions of examples 2 to 30 and comparative examples 1 to 8 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.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

The details of each component in tables 1 to 6 are as follows.

(phosphorus-containing unsaturated monomer (A))

Acid Phosphonoyloxyethyl methacrylate (manufactured by ユニケミカル K.K., ホスマー M, phosphorus atom content: 15% by mass)

Acid phosphonooxyethyl acrylate (Kyoeisha chemical Co., Ltd., P-1A, phosphorus atom content 16% by mass)

Diphenyl-2-methacryloyloxyethyl phosphate (manufactured by Daba chemical industries Co., Ltd., MR-260, phosphorus atom content 8% by mass)

Acid phosphonooxy polyethylene glycol monomethacrylate (ホスマー PE, manufactured by ユニケミカル K.K., phosphorus atom content 9 mass%)

(polymerizable unsaturated monomer (B))

(unsaturated carboxylic acid monomer (b-1) having a main chain containing 4 to 10 total carbon atoms and oxygen atoms.)

Acrylic acid (Mitsubishi ケミカル Co., Ltd.)

Methacrylic acid (Mitsubishi ガス chemical Co., Ltd.)

Itaconic acid (Hibiscus chemical industry Co., Ltd.)

Beta-carboxyethyl acrylate (ダイセル, オルネクス K.K.)

(alkyl (meth) acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms.)

Methyl acrylate (manufactured by Toya Synthesis Co., Ltd.)

Ethyl acrylate (manufactured by east Asia synthetic Co., Ltd.)

Butyl acrylate (manufactured by Toya Synthesis Co., Ltd.)

Methyl methacrylate (Mitsubishi ガス chemical corporation)

(other (B))

2-Acryloxyethyl succinate (Kyoeisha chemical Co., Ltd.)

(chain transfer agent (C))

Beta-mercaptopropionic acid (product of Kabushiki Kaisha Co., Ltd.) 2-ethylhexyl thioglycolate (product of Tokyo Kasei Co., Ltd.)

(surfactant)

Sodium dodecyl benzene sulfonate (made by Kao corporation)

Polyoxyethylene lauryl ether (Kao Co., Ltd.) polyvinyl alcohol (manufactured by Kao クラレ, PVA205 (degree of saponification: 86.5-89.0%, average degree of polymerization: 500))

(initiator)

Potassium persulfate (Mitsubishi ガス chemical Co., Ltd.)

Ammonium persulfate (Mitsubishi ガス chemical Co., Ltd.)

Azobisisobutyronitrile (produced by Otsuka chemical Co., Ltd.)

(neutralizing agent)

30% by mass sodium hydroxide aqueous solution (キシダ chemical products) 25% by mass ammonia water solution (Yu department of the product of the Kyoho Co., Ltd.)

Monomethylamine (Mitsubishi ガス chemical corporation)

(solvent)

Diethylene glycol monoethyl ether (manufactured by Tokyo Kasei Co., Ltd.)

"phosphorus atom content"

The phosphorus atom content in the unsaturated monomer components in tables 1 to 6 is calculated by the following formula. The results are shown in tables 1 to 6. The calculated phosphorus atom contents were regarded as the phosphorus atom contents of the copolymers of examples 1 to 30 and comparative examples 1 to 8.

Phosphorus atom content (% by mass) of [ mass of phosphorus atom in phosphorus-containing unsaturated monomer (a)/total mass of phosphorus-containing unsaturated monomer (a) and polymerizable unsaturated monomer (B) ] × 100

The resin compositions of examples 1 to 30 and comparative examples 1 to 8 were dried by removing water as a solvent, thereby separating a resin solid component including a copolymer from the resin compositions.

Further, the resin compositions and resin solid contents 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.

[ Table 7]

[ Table 8]

Evaluation item

Comparative example 1

Comparative example 2

Comparative example 3

Comparative example 4

Comparative example 5

Comparative example 6

Comparative example 7

Comparative example 8

Flame retardancy

×

×

×

Cannot measure

×

×

×

×

Storage stability

○

○

×

Cannot measure

○

○

○

○

Stability of polymerization

○

○

△

×

△

△

△

○

"Mass average molecular weight"

Gel Permeation Chromatography (GPC) was used under the following conditions: the mass average molecular weight of the copolymer was measured under the trade name "Shodex GPC-101" (manufactured by Showa Denko K.K., "Shodex" is a registered trademark).

An aqueous solution was prepared by adding ultrapure water to 34.5g of disodium hydrogenphosphate 12 hydrate and 46.2g of sodium dihydrogenphosphate 2 hydrate to give a total amount of 5.000g as a carrier liquid. The solid resin component containing the copolymer was dissolved in the carrier liquid and measured at a flow rate of 0.5ml/min using a pump (< DU-H2000, manufactured by Shodex).

As the column, a water-based GPC column (analytical column: < Ohpak SB-806M Q >, manufactured by Shodex, reference column: < Ohpak SB-800RL >, manufactured by Shodex) was used. An RI detector (< RI-71S >, manufactured by Shodex) was used as the detector. As a molecular weight standard, sodium polyacrylate (Sigma-Aldrich) was used.

"acid value"

The acid value of the copolymer was evaluated in accordance with the neutralization titration method of JIS K0070 in the following manner.

About 2g of a sample (resin solid content including a copolymer) was precisely weighed using a precision balance and charged into a 100ml conical flask, and 10ml of a mixed solvent of ethanol/diethyl ether (mass ratio) 1/1 was added thereto to dissolve the sample. Further, 1 to 3 drops of phenolphthalein ethanol solution as an indicator was added to the conical flask, and the mixture was sufficiently stirred until the sample became homogeneous. This was titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization was taken as the light red color of the indicator lasting 30 seconds. The value obtained from the result using the following formula (5) was defined as the acid value of the copolymer.

Acid value (mgKOH/g) ═ B.times.f.times. 5.611)/S (5)

B: amount of 0.1N Potassium hydroxide-ethanol solution used (ml)

f: factor of 0.1N Potassium hydroxide-ethanol solution

S: sample Collection volume (g)

(flame retardancy)

The resin film produced by the method described later was allowed to stand at 23 ℃ and a relative humidity of 50% for 12 hours or more to prepare a test piece. Next, a test piece having a length of 150mm and a width of 60mm was taken from the test piece. Further, according to JIS K7201-2: 1999, the method was that the test piece was mounted on a U-shaped holder, the lowest oxygen concentration required for the test piece to burn continuously for a length of 50mm after ignition and the lowest oxygen concentration required for the test piece to burn for 180 seconds or longer were measured, and the smaller one was taken as the oxygen index. As a standard for flammability, flammability is defined as when the oxygen index is 22% or less, self-extinguishing is defined as when the oxygen index is 23 to 27%, and flame retardancy is defined as when the oxygen index is 28% or more.

O (good): oxygen index of more than 50%

Δ (optional): the oxygen index is more than 40 percent and less than 50 percent

X (not): the oxygen index is less than 40 percent

< preparation of resin film >

Resin solutions for resin film production were prepared by diluting the resin compositions of examples 1 to 30 and comparative examples 1 to 8 with ion-exchanged water so that the solid content became 20 mass%, respectively. The resin liquid was uniformly injected into a column made of a silicone sealing material so as to form a glass plate: 200mm, transverse: 50mm inside. The glass plate into which the resin solution was injected was confirmed to be horizontal, and the resin film of examples 1 to 30 and comparative examples 1 to 8 was obtained by drying the glass plate at 70 ℃ for 24 hours using a vacuum dryer.

(storage stability)

The change in pH was used as an indicator for confirming the storage stability. The pH at 23 ℃ was measured for the resin composition immediately after production. In a colorless and transparent glass bottle having a capacity of 140mL, the resin composition immediately after production was filled up to a volume of 90% of the capacity, sealed, and stored at 23 ℃ and a relative humidity of 50% for half a year. Further, the resin composition after half a year of storage was measured for pH at 23 ℃. Then, the amount of change in pH between the resin composition immediately after production and the resin composition half a year after storage was evaluated by the following criteria.

"Standard"

O (good): the variation of pH is +/-0-2

Δ (optional): the variation of pH is more than +/-2.0 and less than 3

X (not): the variation of pH is more than + -3.0

(polymerization stability)

The amount of the residual monomer in the resin composition immediately after the production (the content of the residual unsaturated monomer component in the resin composition, out of all the unsaturated monomer components used) and the presence or absence of gelation during polymerization were evaluated by the following criteria. The amount of residual monomers was determined by gas chromatography.

"Standard"

O (good): not gelled, and the residual monomer content is 0% or more and less than 0.1% by mass

Δ (optional): not gelled, and the residual monomer content is 0.1% or more and less than 1% by mass

X (not): the polymerization is stopped due to gelation, or the residual monomer content is 1 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 excellent 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, the resin films produced using the resin compositions of comparative example 1 containing no phosphorus-containing unsaturated monomer (A), comparative examples 2 and 5 to 8 containing a large amount of alkyl (meth) acrylate monomer (b-2) having an alkyl group having 1 to 4 carbon atoms, and comparative example 3 containing no unsaturated carboxylic acid monomer (b-1) having a main chain having a total of 4 to 10 carbon atoms and oxygen atoms were poor in flame retardancy.

Further, the resin composition of comparative example 4 containing no unsaturated carboxylic acid monomer (b-1) had significantly low polymerization stability, and the flame retardancy and storage stability could not be evaluated.

Paper processed product and fiber processed product "

(examples 31 to 33, 35 to 37, comparative examples 9 and 10)

The resins shown in tables 9 and 10 and water as a diluent were mixed in the proportions shown in tables 9 and 10 to prepare treating agents 1 to 4 used in examples 31 to 33 and 35 to 37 and comparative examples 9 and 10.

"resin 1" shown in tables 9 and 10 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 resin composition of comparative example 1.

(examples 34 and 38)

Treatment agents 5 used in examples 34 and 38 were prepared by mixing the resins shown in tables 9 and 10, ammonium polyphosphate (made by ク ラ リ ア ン ト ケミカル ズ, Exolit AP422, phosphorus atom content 32 mass%) as a flame retardant, and water as a diluent in the proportions shown in tables 9 and 10.

The paper processed products of examples 31 to 34 and comparative example 9 were produced by the following method using the treating agents 1 to 5 obtained in this way as paper treating agents. The fiber-processed products of examples 35 to 38 and comparative example 10 were produced by the method described below using the treating agents 1 to 5 as fiber treating agents.

< preparation of paper-processed product >

As a substrate, a filter paper (No.2 Toyo Filter paper Co., Ltd., thickness of 0.25mm, basis weight 130 g/m) was prepared²). Further, the base material was impregnated with the treating agents 1 to 5 shown in Table 9 and coated. Then, the base material impregnated with the treating agent was squeezed by 2 squeezing rolls to attach the treating agents 1 to 5 to the base material. Subsequently, the substrate to which the treatment agent was attached was dried at 130 ℃ for 10 minutes by a hot air dryer, and a processed paper product was obtained.

Then, with respect to the obtained paper processed product, the amount of the paper treating agent (treating agent) in terms of solid content (% by mass) to the paper processed product was determined by the following method. The results are shown in table 9.

The base material before impregnation was precisely weighed using a direct-reading balance with a sensitivity of 0.5mg or less. The substrate impregnated with the treating agent was dried by being left in a dryer adjusted to 105 ℃. + -. 2 ℃ for 1 hour. The dried base material was cooled in a desiccator to room temperature, precisely weighed with the same direct-reading balance, and the mass of the base material (processed product) impregnated with the treatment agent and dried was determined. Using the "mass of the processed product" obtained in this way and the "mass of the base material before application of the treatment agent", the amount of the solid component (mass%) of the treatment agent to the processed product was calculated by the following formula.

The amount (mass%) of the treating agent to the solid content of the processed product { (mass of processed product-mass of base material before impregnation with the treating agent)/(mass of processed product) } × 100

< preparation of fiber-processed product >

As the substrate, a polyester-cellulose nonwoven fabric (manufactured by Tokao バークシャー, thickness 200 μm, basis weight 35 g/m) was used²) A processed fiber product was obtained in the same manner as a paper product except for the formed fibers.

Then, with respect to the obtained fiber-processed product, the amount of the fiber treatment agent (treatment agent) in terms of solid content (% by mass) to the fiber-processed product was determined in the same manner as in the case of the paper-processed product. The results are shown in table 10.

The paper processed products of examples 31 to 34 and comparative example 9, and the fiber processed products of examples 35 to 38 and comparative example 10 were evaluated for flame retardancy, bleed-out resistance, blocking resistance and softness by the following evaluation methods. The results are shown in tables 9 and 10.

[ Table 9]

[ Table 10]

(flame retardancy)

The test pieces were prepared by leaving a paper-processed product or a fiber-processed product at 23 ℃ and a relative humidity of 50% for 12 hours or more, and 5 long test pieces each having a length of 127mm and a width of 12.7mm were taken from each test piece. The burning test was conducted on the basis of UL-94 vertical burning test (standards V-0, V-1, and V-2) for each test piece. The flame contact was performed 2 times for each test piece (10 times for each test piece), and the extinction time (combustion time) was measured.

Using the results, the total combustion time and the maximum combustion time of 10 contact flames in total were obtained for each test specimen, and evaluated by the following criteria.

Reference (benchmark) "

V-0: the total combustion time was 50 seconds or less, and the maximum combustion time was 10 seconds or less, and no material was dropped due to combustion in all the test pieces.

V-1: the total burning time was 250 seconds or less, and the maximum burning time was 30 seconds or less, and no material was dropped due to burning in all the test pieces.

V-2: the total burning time was 250 seconds or less and the maximum burning time was 30 seconds or less, but there were test pieces in which the material dropped due to burning.

(bleed resistance)

Rectangular test pieces 70mm in length and 50mm in width were obtained from the same test pieces as those used for the evaluation of flame retardancy. The test piece was sandwiched between rectangular filter papers (No.2, manufactured by Toyo Filter paper Co., Ltd.) having a longitudinal dimension of 100mm and a transverse dimension of 60mm, and the test piece was allowed to stand at 60 ℃ and a relative humidity of 95% for 5 days to confirm the presence or absence of bleeding on the surface of the test piece. The results were evaluated by the criteria shown below.

Reference (benchmark) "

X (not): the whitening of the test piece surface occurred at 10% or more of the test piece area.

And (b): the whitening of the test piece surface occurred at less than 10% of the test piece area.

O (good): there was no whitening of the test piece surface.

(blocking resistance)

From the same test piece as used for the evaluation of flame retardancy, a substantially square test piece having a length of 25mm and a width of 25mm was taken. The test piece was sandwiched between substantially square backing paper (manufactured by Suzuki Kaisha) having a vertical length of 35mm and a horizontal length of 35mm, and the test piece was allowed to stand at 60 ℃ and a relative humidity of 70% for 3 days to confirm the presence or absence of blocking of the test piece. The results were evaluated by the criteria shown below. Whether or not a sound is generated when the backing paper is peeled from the test piece is determined by: a peeling test was carried out in accordance with a T-type peeling test (テンシロン: オリエンテック RTA-100, manufactured by RTA-100) at 23 ℃ and 300mm/min, and the presence or absence of peeling noise at this time was evaluated.

"Standard"

X (not): when the mount was peeled off from the test piece, a sound was generated, and the mount peeled off from the test piece was peeled off (with sticking)

Δ (optional): the sound was generated when the backing paper was peeled off from the test piece, but the backing paper peeled off from the test piece did not peel off (slightly sticking)

O (good): no sound was produced when the backing paper was peeled off from the test piece, and the backing paper peeled off from the test piece was not peeled off (no blocking)

(rigid and soft)

From the same test piece as used for the evaluation of flame retardancy, a test piece having a substantially square shape with a length of 150mm and a width of 150mm was taken. The test pieces were measured according to JIS L1096: the softness was measured by the method 8.21.5E (hand-feeling measuring device method) described in the general woven fabric test method of 2010. The results were evaluated by the criteria shown below.

The softness (g) indicates the hardness (softness) of the fiber, and the higher the softness value, the harder the hand of the test piece.

"Standard"

O (good): 160g or more

And (b): more than 140g and less than 160g

X (not): less than 140g

As shown in tables 9 and 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. Further, the paper processed products of examples 31 to 34 and the fiber processed products of examples 35 to 38 were excellent in the evaluation of the bleed-out resistance, blocking resistance and stiffness as "good" or "Δ (fair)".

In contrast, the paper processed product of comparative example 9 had poor flame retardancy because the treating agent 4 used as a paper treating agent did not contain a constituent component derived from (a). In addition, the fiber-processed product of comparative example 10 was poor in flame retardancy because the treating agent 4 used as a fiber treating agent did not contain a constituent component derived from (a).

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 did not use ammonium polyphosphate as a phosphorus compound as a flame retardant, were particularly excellent in bleed-out resistance and blocking resistance.

General processed product "

(examples 39 to 41, comparative example 11)

The resins shown in Table 11 and pentaerythritol polyglycidyl ether (デナコール EX411, manufactured by ナガセケムテックス Co.) as a crosslinking agent were mixed in the proportions shown in Table 11 to prepare coatings 6 to 9 used in examples 39 to 41 and comparative example 11.

"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 resin composition of comparative example 1.

(example 42)

A resin composition as shown in Table 11, ammonium polyphosphate (Exolite AP422, manufactured by ク ラ リ ア ン ト ケミカル ズ Co., Ltd., phosphorus atom content: 32% by mass) as a flame retardant, and a crosslinking agent as shown in Table 11 were mixed in the proportions shown in Table 11 to prepare a coating material 10 used in example 42.

The general processed products of examples 39 to 42 and comparative example 11 were produced by the following method using the coatings 6 to 10 obtained in this way.

< preparation of general processed article >

As a substrate, a PET film having a thickness of 25 μm was prepared. Further, the coatings 6 to 10 shown in Table 11 were applied to a substrate so that the thickness after drying became 10 μm. Then, the substrate coated with the coating material was dried at 105 ℃ for 3 minutes by a hot air dryer, and cured at 40 ℃ for 3 days to obtain a general processed product.

Then, with respect to the obtained general processed product, the amount of the solid content (% by mass) of the coating material (treating agent) to the general processed product was determined in the same manner as for the paper processed product. The results are shown in table 11.

The general processed products of examples 39 to 42 and comparative example 11 were evaluated for flame retardancy, adhesion, and appearance change by the following evaluation methods. The results are shown in table 11.

[ Table 11]

(flame retardancy)

Films were produced in the same manner as in the above-described production of resin films using 6 to 10 of the coatings used for general processed products, respectively, and the flame retardancy of general processed products was evaluated in the same manner as in the resin films produced using the resin compositions.

(Adhesivity)

General processed products were allowed to stand at 23 ℃ and a relative humidity of 50% for 12 hours or more as test pieces, and セロテープ (registered trademark) peel test was performed on each test piece. The surface of a general processed product after the peeling test was visually observed and evaluated by the following criteria.

"Standard"

O (good): without peeling

Δ (optional): the area of peeling is less than 80% of the surface

X (not): the peeled area is more than 80% of the surface

(Change in appearance)

The same test piece as used for evaluation of adhesion was allowed to stand at 60 ℃ and 70% relative humidity for 3 days. Then, the general processed product was visually observed, and the presence or absence of the change in appearance was evaluated by the following criteria.

"Standard"

O (good): has no appearance change

Δ (optional): the whitening area is less than 80% of the surface

X (not): the whitening area is more than 80% of the surface

As shown in Table 11, the general processed products of examples 39 to 42 were excellent in flame retardancy. Further, the general processed products of examples 39 to 42 were evaluated for the adhesiveness and the appearance change as "good" or "Δ (fair)".

In contrast, the general processed product of comparative example 11 was poor in flame retardancy because the coating material 9 contained no constituent component derived from (a).

In examples 39 to 42, the general processed products of examples 39 to 41, which did not use ammonium polyphosphate as a phosphorus compound as a flame retardant, were particularly excellent in the evaluation of the adhesiveness and the change in appearance.

Processed product of adhesive "

(examples 43 to 45, comparative example 12)

Adhesive adhesives 1 to 4 used in examples 43 to 45 and comparative example 12 were prepared by mixing an acrylic resin (D) produced by the following method, a resin shown in Table 12, and pentaerythritol polyglycidyl ether (デナコール EX411, manufactured by ナガセケムテックス Co.) as a crosslinking agent at the ratio shown in Table 12.

"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 resin composition of comparative example 1.

Production of acrylic resin (D) "

In a reaction apparatus equipped with a stirrer, a temperature controller, a reflux condenser, a dropping funnel and a thermometer, 150g of n-butyl acrylate, 34g of methyl methacrylate, 2g of 2-hydroxyethyl acrylate and 195g of toluene were charged, and after the start of thermal reflux, 0.2g of azobisisobutyronitrile as a polymerization initiator was charged. After the reaction for 8 hours at the reflux temperature of toluene, the resultant was diluted with toluene to obtain an acrylic resin (D) having a solid content of 50 mass%.

(example 46)

An acrylic resin (D) produced by the above method, a resin shown in table 12, ammonium polyphosphate (product of ク ラ リ ア ン ト ケミカル ズ, Exolit AP422, phosphorus atom content 32 mass%) as a flame retardant, and pentaerythritol polyglycidyl ether (product of ナガセケムテックス, デナコール EX411) as a crosslinking agent were mixed at the ratios shown in table 12 to prepare pressure-sensitive adhesive 5 used in example 46.

Using the adhesive 1 to 5 thus obtained, the adhesive processed products of examples 43 to 46 and comparative example 12 were produced by the following method.

< preparation of adhesive processed article >

As a substrate, a PET film having a thickness of 25 μm was prepared. Adhesive adhesives 1 to 5 shown in table 12 were applied to a substrate so that the thickness after drying was 10 μm, thereby forming an adhesive layer.

Then, a release film was bonded to the pressure-sensitive adhesive layer, and the resultant was pressure-bonded with a roller and cured at 40 ℃ for 3 days to obtain a processed pressure-sensitive adhesive article.

Then, with respect to the resultant processed adhesive product, the amount of the solid content (mass%) of the adhesive (treating agent) to the processed adhesive product was determined in the same manner as in the case of the paper product. The "mass of the processed product" used herein is a value obtained by allowing a base material, to which an adhesive is applied, a release film is applied, and the base material is pressure-bonded with a roll, to stand in a dryer having an internal temperature adjusted to 105 ℃ ± 2 ℃ for 1 hour to dry, cooling the dried base material in the dryer to room temperature, and precisely weighing the base material with a direct-reading balance having a sensitivity of 0.5mg or less. That is, the amount of the release film contained in the substrate is calculated. The results are shown in table 12.

The processed products of the pressure-sensitive adhesive of examples 43 to 46 and comparative example 12 were evaluated for flame retardancy, initial adhesive force, and heat-resistant holding power by the evaluation methods shown below. The results are shown in table 12.

[ Table 12]

(flame retardancy)

Films were produced in the same manner as in the above-described production of resin films using the adhesive adhesives 1 to 5 used for the adhesive processed products, respectively, and the flame retardancy of the adhesive processed products was evaluated in the same manner as in the resin films produced using the resin compositions.

(initial adhesion)

A roughly rectangular processed adhesive article having an area of 25mm × 100mm was prepared, and the release film was peeled off to expose the adhesive layer. An adhesive-processed product was placed on a stainless steel polishing plate made of SUS304 with the side of the adhesive layer facing each other, and the adhesive-processed product was bonded to the stainless steel polishing plate by 1 reciprocation of a 2kg roller at 23 ℃ under a relative humidity of 50%. After 20 minutes from the bonding, the adhesive composition was measured according to JIS Z0237: the 180-degree peel strength (N/cm) was measured by the method for measuring the adhesive force defined in 2000, and evaluated by the following criteria.

"Standard"

O (good): 2.0N/cm or more

And (b): more than 1.5N/cm and less than 2.0N/cm

X (not): less than 1.5N/cm

(Heat-resistant Retention force)

The pressure-sensitive adhesive processed product was bonded to a stainless steel polishing plate in the same manner as in the measurement of the initial adhesive force except that the bonding area was set to a substantially square shape of 25mm × 25 mm. Then, the upper limit value of the temperature at which the sheet does not fall for 1 hour or more was measured by applying a load of 1kg according to the method for measuring holding power prescribed in JIS Z0237, and the evaluation was performed by the following criteria.

"Standard"

O (good): above 150 DEG C

Δ (optional): more than 100 ℃ to less than 150 DEG C

X (not): less than 100 deg.C

As shown in Table 12, all of the pressure-sensitive adhesive processed products of examples 43 to 46 were evaluated as "good" or "Δ", and were excellent in flame retardancy, initial adhesive force and heat-resistant holding power.

In contrast, the processed adhesive product of comparative example 12 has poor flame retardancy because the adhesive 4 does not contain a component derived from (a).

In examples 43 to 46, the processed adhesive products of examples 43 to 45, which did not use ammonium polyphosphate as a phosphorus compound as a flame retardant, were particularly excellent in the evaluation of initial adhesion force and heat-resistant holding power.

Industrial applicability

The present invention provides a resin which is excellent in flame retardancy and is excellent in bleed-out resistance and blocking resistance.

The copolymer of the present invention has excellent flame retardancy, and when used as a material for a processed article, the copolymer can provide a processed article having excellent bleed-out resistance and blocking resistance. Therefore, the treating agent comprising the copolymer of the present invention is suitable as a paper treating agent, a fiber treating agent, a general coating material, an adhesive and a sticking agent.

The treating agent comprising the copolymer of the present invention is suitable as a material for processed articles excellent in flame retardancy, bleed-out resistance, blocking resistance and rigidity and softness. Examples of the processed product whose base material is paper include wall paper, building materials such as lining paper for wall paper, and automobile interior materials. Further, as the processed product in which the base material is a fiber, there are mentioned an interior material such as a curtain, a cushioning material for electronic materials, a cushioning material for home electric appliances, an interior cushioning material for automobiles, an automobile seat and the like.

The coating material and the adhesive containing the copolymer of the present invention can be suitably used in the production of processed products such as general processed products and adhesive processed products. Examples of such processed products include adhesive tapes, household electrical appliances, electronic components, pressure-sensitive adhesive tapes, double-sided tapes, daily necessities such as adhesive labels, housing materials such as wall papers, floor tiles, floor sheets (mats), carpets, ceiling boards, and adhesive sheets for windows, automobile products, household electrical appliances, and electronic components.

Claims (13)

1. A paper or fiber treating agent comprising a copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A), a constituent derived from a polymerizable unsaturated monomer (B), and a constituent derived from a chain transfer agent (C),

the constituent derived from the phosphorus-containing unsaturated monomer (A) includes a constituent derived from a monomer (a-1) having either a phosphate group or a phosphite group,

in the copolymer, the component derived from the polymerizable unsaturated monomer (B) comprises a component derived from an unsaturated carboxylic acid monomer (B-1) having a main chain with 4-10 total carbon atoms and oxygen atoms, and the content of the component derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1-4 carbon atoms is 0.00-1.00 mass% relative to the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B),

the chain transfer agent (C) is mercaptoalkyl carboxylate (C-1),

the content of the constituent component derived from the chain transfer agent (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of the total content of the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the constituent component derived from the polymerizable unsaturated monomer (B),

the content of phosphorus atoms in the copolymer is 0.1 to 10 mass%,

the acid value of the copolymer is 300-800 mgKOH/g.

2. The paper or fiber treating agent according to claim 1, the monomer (a-1) having any one of a phosphoric acid group and a phosphorous acid group being an acid phosphonooxy polyoxyalkylene glycol mono (meth) acrylate.

3. The paper or fiber treating agent according to claim 1, wherein the unsaturated carboxylic acid monomer (b-1) is at least 1 selected from the group consisting of acrylic acid, methacrylic acid, itaconic acid, and β -carboxyethyl acrylate.

4. The paper or fiber-treating agent according to claim 1, wherein the content of the component derived from the unsaturated carboxylic acid monomer (B-1) is 30 to 95% by mass based on the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B).

5. The paper or fiber-treating agent according to claim 1, wherein the copolymer has a mass-average molecular weight of 25000 to 70000.

6. The paper-treating agent or fiber-treating agent according to claim 1,

the component derived from the polymerizable unsaturated monomer (B) does not include the component derived from the alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1 to 4 carbon atoms.

7. The paper or fiber-treating agent according to claim 1, wherein the component derived from the polymerizable unsaturated monomer (B) comprises the component derived from the alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1 to 4 carbon atoms.

8. The paper or fiber treatment according to claim 1, further comprising a solvent.

9. A processed product having a solid content of the paper-or fiber-treating agent according to any one of claims 1 to 8 attached to a substrate, wherein the solid content is attached to the processed product by 5 to 70% by mass.

10. A paper product comprising a paper and a copolymer adhered to the paper, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A), a constituent derived from a polymerizable unsaturated monomer (B), and a constituent derived from a chain transfer agent (C),

the constituent derived from the phosphorus-containing unsaturated monomer (A) includes a constituent derived from a monomer (a-1) having either a phosphate group or a phosphite group,

in the copolymer, the component derived from the polymerizable unsaturated monomer (B) comprises a component derived from an unsaturated carboxylic acid monomer (B-1) having a main chain with 4-10 total carbon atoms and oxygen atoms, and the content of the component derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1-4 carbon atoms is 0.00-1.00 mass% relative to the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B),

the chain transfer agent (C) is mercaptoalkyl carboxylate (C-1),

the content of the constituent component derived from the chain transfer agent (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of the total content of the constituent component derived from the phosphorus-containing unsaturated monomer (A) and the constituent component derived from the polymerizable unsaturated monomer (B),

the paper comprises 100 parts by mass of the paper and 1 to 70 parts by mass of the copolymer,

the content of phosphorus atoms in the copolymer is 0.1 to 10 mass%,

the acid value of the copolymer is 300-800 mgKOH/g.

11. A fiber-processed product comprising a fiber and a copolymer adhered to the fiber, the copolymer having a constituent derived from a phosphorus-containing unsaturated monomer (A), a constituent derived from a polymerizable unsaturated monomer (B), and a constituent derived from a chain transfer agent (C),

the constituent derived from the phosphorus-containing unsaturated monomer (A) includes a constituent derived from a monomer (a-1) having either a phosphate group or a phosphite group,

in the copolymer, the component derived from the polymerizable unsaturated monomer (B) comprises a component derived from an unsaturated carboxylic acid monomer (B-1) having a main chain with a total of 4 to 10 carbon atoms and oxygen atoms, and the content of the component derived from an alkyl (meth) acrylate monomer (B-2) having an alkyl group with 1 to 4 carbon atoms is 0.00 to 1.00 mass% relative to the total content of the component derived from the phosphorus-containing unsaturated monomer (A) and the component derived from the polymerizable unsaturated monomer (B),

the chain transfer agent (C) is mercaptoalkyl carboxylate (C-1),

the content of the constituent derived from the chain transfer agent (C) is 0.1 to 10 parts by mass relative to 100 parts by mass of the total content of the constituent derived from the phosphorus-containing unsaturated monomer (A) and the constituent derived from the polymerizable unsaturated monomer (B),

the fiber contains 1 to 70 parts by mass of the copolymer per 100 parts by mass of the fiber,

the content of phosphorus atoms in the copolymer is 0.1 to 10 mass%,

the acid value of the copolymer is 300-800 mgKOH/g.

12. A method for treating paper or fiber, which comprises processing the paper or fiber with the paper-treating agent or fiber-treating agent according to any one of claims 1 to 8.

13. The method of treating paper or fiber according to claim 12, comprising the steps of:

a step of coating or impregnating paper or fibers with the paper-treating agent or the fiber-treating agent; and

and drying the coated or impregnated paper or fiber treatment agent.