JPH06240154A - Polyamine composition and its use - Google Patents

Abstract

PURPOSE:To obtain a polyamine composition hardly to be colored. CONSTITUTION:This polyamine composition comprises at least one polyamine containing one or more of a primary, a secondary and a tertiary amino groups in the molecule and at least one selected from an oxygen acid of phosphorus, a hydroxy acid and their derivatives.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel polyamine composition which is extremely resistant to coloration and its use. More specifically, the present invention relates to various papermaking process agents (water drainage improving agents, paper strength enhancers, sizing agents and their fixing agents) and various paper surface treatment agents in the papermaking industry, and various fiber processing in the textile industry. Agent (softening agent, surface coating type antistatic agent, hygroscopicity imparting agent, adhesion improving agent, dye fixing agent),
Various plastic processing agents in the plastic processing industry (antistatic agents for kneading, surface coating type antistatic agents, hygroscopicity imparting agents, antioxidants, dyeability improving agents) and anchor coating agents for extrusion lamination in the film forming industry The present invention relates to a polyamine composition which is extremely difficult to be colored and can be used as an antioxidant, an antistatic agent, an adhesion improver and the like.

[0002]

2. Description of the Related Art Conventionally, polyamines containing one or more of primary, secondary and tertiary amino groups in the molecule have been used in the textile industry, paper industry, water treatment industry, oil drilling industry, photography. It is widely used in various fields such as industry, plastic processing industry, and film forming industry. However, this polyamine has a common drawback that it turns yellow in the air, and it is often colored brown when heated.
Even if it has such drawbacks, depending on the field of use, there may be practically no hindrance, but the paper manufacturing industry, the textile industry,
In fields such as the plastic processing industry and the film forming industry where the coloring of products is disliked, the use of polyamines is restricted.

The use of polyamines in which coloring is a problem will be described in detail. In the paper industry, various paper-making process agents (water drainage improving agents, paper strength enhancers, sizing agents and fixing agents therefor) are used.
And various paper surface treatment agents, and in the textile industry various textile finishing agents (softening agents, surface coating type antistatic agents, hygroscopicity imparting agents, adhesion improving agents, dye fixing agents), plastic processing industry Are various plastic processing agents (antistatic agents for kneading, surface coating type antistatic agents, hygroscopicity imparting agents, antioxidants, dyeability improving agents). In the film manufacturing industry, anchor coating for extrusion lamination. Agents, antioxidants, antistatic agents, adhesion improvers and the like.

To explain this point in more detail, when polyethyleneimine, polyamidepolyamine or the like is used as a drainage improver and a paper strength enhancer in the papermaking process, the whiteness of the paper is lowered, so a fluorescent brightening agent is added (or Increase)
Will be required. If higher whiteness is required, these polyamines cannot be used.

Synthetic fibers treated with polyethyleneimine or an antistatic agent derived therefrom are often yellowed or discolored (dyed) by ironing.

Further, when the printing cloth is treated with a dye fixing agent synthesized from polydiallylamine or the like, yellowing is observed in the white spot (the portion not printed) as the day passes after the treatment. .

When various films are produced by extrusion lamination, the base material and resin (polyethylene etc.)
Anchor coat agents containing polyethyleneimine as the main component are often used to promote adhesion with polyethylene, but in this case polyethyleneimine discolors because the resin such as polyethylene is extrusion coated at high temperature, and the entire film is colored. I have something to do. When these laminated films are used as a packaging film, they may be colored by heating during heat sealing.

Further, a synthetic fiber such as polyester or polyamide is used as a reinforcing material in combination with polyurethane resin, halogen-containing vinyl resin or ethylene-vinyl acetate resin to form a film structure such as a canvas tent or a curing sheet. At this time, a method of treating the fibers with polyethyleneimine or the like in order to improve the adhesiveness between the reinforcing fibers and the resin has been proposed, but since the fibers are colored, the appearance of the final product in a transparent resin composite is Getting worse.

As a method for preventing the coloring of polyamine, the method described in JP-A-54-29356 is known. In this method, a polymer solution of an amino acrylate compound contains a thiophosphite compound or a hindered phenol compound.

[0010]

However, recently, as the demand for improving the quality of products has increased especially in the above-mentioned fields of use of polyamines, the use of polyamines alone or JP-A-54-29356 has been described. The method is no longer sufficient, especially
There is an urgent need to develop a polyamine composition that is extremely resistant to coloration when heated.

[0011]

As a result of intensive studies, the present inventors have developed a polyamine composition which is extremely unlikely to be colored even when subjected to heating.

That is, the present invention provides at least one polyamine containing one or more of primary, secondary and tertiary amino groups in the molecule, an oxygen acid of phosphorus, an oxyacid and a compound thereof. The present invention provides a polyamine composition containing at least one selected from derivatives, which is extremely difficult to be colored.

The polyamine containing one or more of primary, secondary and tertiary amino groups in the molecule used in the composition of the present invention includes the following (1)-(16):
The following are listed.

(1) Homopolymer of mono- or diallylamine derivative; (2) Copolymer of two or more mono- or diallylamine derivatives; (3) Copolymer of mono- or diallylamine derivative and dialkyldiallyl ammonium salt; 4) Homopolymer of unsaturated carboxylic acid derivative having tertiary amino group; (5) Copolymer of two or more monomers selected from the group of unsaturated carboxylic acid derivative having tertiary amino group (6) A copolymer of an unsaturated carboxylic acid derivative having a tertiary amino group and a quaternary ammonium salt and / or dialkyldiallylammonium salt obtained by alkylating or protonating the tertiary amino group of the derivative. (7) Unsaturated carboxylic acid derivative having a tertiary amino group and alkylation or protonation of the tertiary amino group of the derivative And a ternary copolymer of a quaternary ammonium salt and / or a dialkyldiallylammonium salt and another vinyl monomer capable of being polymerized therewith; (8) Unsaturated carboxylic acid and polymerizable with the unsaturated carboxylic acid (9) polyalkyleneimine; (10) polyalkylenepolyamine; (11) (2-methacryloyloxy Ethyl) ethyleneimine polymer and copolymer of the (2-methacryloyloxyethyl) ethyleneimine and a polymerizable unsaturated monomer; (12) Polyamide polyamine; (13) Polyamide polyamine-epichlorohydrin resin; (14) Mannich reaction modified products of polyacrylamide and polymethacrylamide; ) Polyvinylamine, a copolymer of vinylamine and an unsaturated monomer polymerizable with the vinylamine; (16) dicyandiamide / diethylenetriamine polycondensate; and the like.

The molecular weight of the polyamine is preferably 100 or more, more preferably 200 to 10,000,000, more preferably 300 to 1,000,000, and particularly preferably 500 to 1,000,000.

As the homopolymer of the mono- or diallylamine derivative of the above (1), polyallylamine, polydiallylamine, poly (N-benzyldiallylamine),
Examples are poly (N-alkylallylamine) and poly (N-alkyldiallylamine). However, the alkyl group of poly (N-alkylallylamine) or poly (N-alkyldiallylamine) is methyl, ethyl,
Hydroxyethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,
A cyclohexyl group is preferred.

The copolymer of (2) two or more kinds of mono- or diallylamine derivatives is a copolymer of monoallylamine and diallylamine, or monoallylamine and N.
A copolymer with an alkylallylamine, a copolymer with a monoallylamine and an N-alkyldiallylamine, a copolymer with a diallylamine and an N-alkyldiallylamine,
Copolymer of diallylamine and N-alkylallylamine, copolymer of N-alkylallylamine and N-alkyldiallylamine, copolymer of two or more N-alkylallylamine, two or more N-alkyldiallylamine The copolymers of However, the term "alkyl" in the above-mentioned copolymer is to be understood in a broad sense, such as a chain alkyl group such as methyl, ethyl, propyl, isopropyl, sec-butyl and tert-butyl, a cycloalkyl group such as cyclohexyl, It includes an aralkyl group such as benzyl and an alkyl group having a functional group such as a hydroxyl group and a cyano group.

As the copolymer of the mono- or diallylamine derivative and the dialkyldiallylammonium salt (3), a copolymer of monoallylamine and dialkyldiallylammonium salt, a copolymer of diallylamine and dialkyldiallylammonium salt, N Examples thereof include a copolymer of -alkylallylamine and a dialkyldiallylammonium salt and a copolymer of N-alkyldiallylamine and a dialkyldiallylammonium salt. However,
The above-mentioned “alkyl” is to be understood in a broad sense, and is a chain alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, a cycloalkyl group such as cyclohexyl, An alkyl group such as a benzyl group, and an alkyl group containing a functional group such as a hydroxyl group and a cyano group are included. Examples of the salt include chloride, bromide, methyl sulfate and the like.

As the homopolymer of the unsaturated carboxylic acid having a tertiary amino group of the above (4), poly (dimethylaminoethyl acrylate), poly (diethylaminoethyl acrylate), poly (dimethylaminopropyl acrylate), poly (Diethylaminopropyl acrylate), poly (dimethylaminoethyl methacrylate),
Poly (diethylaminoethylmethacrylate), poly (dimethylaminopropylmethacrylate), poly (diethylaminopropylmethacrylate), poly (dimethylaminoethylacrylamide), poly (diethylaminoethylacrylamide), poly (dimethylaminopropylacrylamide), poly (diethylaminopropylacrylamide) ), Poly (dimethylaminoethyl methacrylamide), poly (diethylaminoethyl methacrylamide), poly (dimethylaminopropyl methacrylamide), poly (diethylaminopropyl methacrylamide), and the inorganic or organic acid salts thereof. it can. The inorganic acid salts include mineral acid salts, and the organic acid salts include carboxylate salts.

The above (5) is a copolymer of two or more kinds of monomers selected from the group of unsaturated carboxylic acid derivatives having a tertiary amino group. Examples of the unsaturated carboxylic acid derivative having a tertiary amino group used for the production of this copolymer (5) include dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminopropyl acrylate, diethylaminopropyl acrylate, dimethylaminoethyl methacrylate and diethylamino. Ethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminoethyl acrylamide, diethylaminoethyl acrylamide, dimethylaminopropyl acrylamide, diethylaminopropyl acrylamide, dimethylaminoethyl methacrylamide, diethylaminoethyl methacrylamide, dimethylaminopropyl methacrylamide, diethylaminopropyl meta Ku (Such as mineral) Ruamido or their inorganic acid salts can be exemplified organic acid salts (such as carboxylate).

(6) The unsaturated carboxylic acid derivative having a tertiary amino group, and a quaternary ammonium salt and / or dialkyldiallylammonium salt obtained by alkylating or protonating the tertiary amino group of the derivative. It is a copolymer with.

The unsaturated carboxylic acid derivative having a tertiary amino group used for the production of this copolymer (6) is as described in the above (5).
The same as that used in the copolymer of 1) is used.
The comonomer used in the production of this copolymer (6) is
A quaternary ammonium salt (a) and / or a dialkyldiallylammonium salt (b) obtained by alkylating or protonating the tertiary amino group of the derivative, which is an alkyl for obtaining the comonomer (a). The protonation and protonation are carried out by acting an alkyl halide or hydrohalic acid on the derivative. The term "alkylation" is understood in a broad sense, and in addition to introducing a lower chain alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, a hydroxyl group , Introducing a lower chain alkyl group having a functional group such as a cyano group (for example, a hydroxyethyl group, a cyanoethyl group, etc.), introducing a cycloalkyl group such as a cyclohexyl group, introducing an aralkyl group such as a benzyl group This includes things to do. Moreover, chloride, bromide, methyl sulfate, etc. are mentioned as an anion component which comprises a "quaternary aluminium salt."

On the other hand, in the comonomer (b), that is, the dialkyldiallylammonium salt, "alkyl" is also broadly understood to include a lower chain alkyl group as described above, a functional group-containing chain alkyl group, and cycloalkyl. Group and aralkyl group.

The above-mentioned (7) is an unsaturated carboxylic acid derivative having a tertiary amino group, and a quaternary ammonia salt and / or dialkyldiallylammonium obtained by alkylating or protonating the tertiary amino group of the derivative. It is a terpolymer of salts and other vinyl monomers capable of being polymerized therewith. 3 used in the production of this terpolymer (7)
Among the two kinds of comonomers, the same two kinds of comonomers as those used in the production of the copolymer (6) are used. Another vinyl monomer that can be polymerized with the other two types of comonomers is styrene, acrylonitrile, acrylamide, vinyl acetate, acrylic acid and methacrylic acid, and their esters. Can be exemplified.

The above (8) is a copolymerization product obtained by reacting an carboxylic acid group of an unsaturated carboxylic acid and a carboxyl group of a copolymer produced from another unsaturated monomer capable of being polymerized with the unsaturated carboxylic acid with an alkyleneimine. It is united. The unsaturated carboxylic acid used for the production of this copolymer is preferably acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, maleic acid, fumaric acid, or monoesters of the unsaturated dicarboxylic acid, and the unsaturated The other unsaturated monomer polymerizable with a carboxylic acid is not particularly limited as long as it can be copolymerized with the unsaturated monomer, and examples thereof include methacrylamide, N-methylolmethacrylamide, and 2-hydroxyethyl. Methacrylate, 2-hydroxypropyl methacrylate,
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate,
n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
Methacrylonitrile, styrene, α-methylstyrene,
Vinyl acetate, vinyl propionate, methacrolein, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate and the like are preferable. Further, as the alkyleneimine for reacting with the carboxyl group of the copolymer obtained from the above two kinds of comonomers, ethyleneimine and propyleneimine are preferable.

Examples of the polyalkyleneimine (9) include linear polyethyleneimine and branched polyethyleneimine.

Examples of the polyalkylene polyamine (10) include polyethylene polyamine, polypropylene polyamine and polybutylene polyamine.

Examples of the polyamide polyamine (12) include condensates of dicarboxylic acids and polyalkylene polyamines. However, in this case, the dicarboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the polyalkylene polyamine is diethylene triamine, triethylene tetramine, tetraethylene. Polyethylene polyamines such as pentamine and pentaethylene hexamine, polypropylene polyamines,
Polybutylene polyamine is preferred.

The polyamide polyamine / epichlorohydrin resin (13) is a resin containing a crosslinkable epoxy group, which is obtained by reacting the polyamide polyamine of (12) with an epichlorohydrin resin. The molecular weight is, for example, 1,000 to 5,000.

As the modified Mannich reaction product of polyacrylamide and polymethacrylamide of (14), an aminated modified product synthesized by reacting polyacrylamide or polymethacrylamide with formaldehyde and diethylamine can be exemplified.

The copolymer (15) of vinylamine and an unsaturated monomer polymerizable with the vinylamine is as follows:
Examples thereof include copolymers of vinylamine and acrylamide or methacrylamide, copolymers of vinylamine and acrylonitrile or methacrylonitrile, copolymers of vinylamine and styrene, and copolymers of vinylamine and acrylic acid or methacrylic acid. .

The dicyandiamide / diethylenetriamine polycondensation product (16) is obtained by polycondensing dicyandiamide and diethylenetriamine.

The composition of the present invention contains, as an essential component, at least one selected from the oxygen acids of phosphorus, oxyacids and derivatives thereof, in addition to the above polyamine. hydrochloric acid,
Mineral acids such as sulfuric acid, nitric acid and their derivatives are excluded.

Examples of phosphorus oxyacids used in the present invention include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphoric acid, and metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and ultraphosphoric acid. The condensed phosphoric acids of

Examples of the derivative of phosphorus oxyacid used in the present invention include inorganic and organic salts of phosphorus oxyacid, and alkyl esters of phosphorus oxyacid. However, the alkyl group is methyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, isobutyl, sec-
Examples thereof include lower alkyl groups such as butyl and tert-butyl groups.

Preference is given to monoalkyl esters, dialkyl esters and trialkyl esters of phosphorous acid and orthophosphoric acid.

The oxygen acid derivatives of phosphorus may be used either individually or in combination of two or more. Among the acid derivatives, those having at least one free acid are preferred.

The oxyacid used in the present invention may be a compound having at least one hydroxyl group and at least one carboxyl group in the molecule.

As oxyacids, glycolic acid, lactic acid, hydroacrylic acid, α-hydroxybutyric acid, β-hydroxybutyric acid, α-hydroxyisobutyric acid, 2-hydroxypropionic acid, α-hydroxyisocaproic acid, β, β, β −
Aliphatic oxyacids such as trichlorolactic acid, glyceric acid, malic acid, α-methylmalic acid, tartaric acid, citric acid, tartronic acid, tetrahydroxysuccinic acid, β-hydroxyglutaric acid, hydroxymalonic acid, and gluconic acid, and salicylic acid, Aromatic oxyacids such as m-hydroxybenzoic acid, p-hydroxybenzoic acid, gallic acid, mandelic acid, tropic acid and the like can be mentioned.

Examples of the oxyacid derivative include inorganic and organic salts of oxyacid, and esters of oxyacid.

The inorganic and organic salts of oxyacids include potassium hydrogen malate, sodium hydrogen malate, ammonium hydrogen malate, potassium hydrogen tartrate, sodium hydrogen tartrate, lithium hydrogen tartrate, calcium hydrogen tartrate, ammonium hydrogen tartrate and citric acid. Examples thereof include monopotassium, dipotassium citrate, monosodium citrate, disodium citrate, monoammonium citrate, and diammonium citrate.

Examples of the esters of oxy acids include alkyl esters of oxy acids (provided that the alkyl group is methyl, ethyl, hydroxyethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, ter).
t-butyl group and the like), and preferably monoalkyl esters of malic acid, monoalkyl esters of tartaric acid, and monoalkyl esters and dialkyl esters of citric acid. Alkyl esters of oxyacids also have at least one hydroxyl group and at least one carboxyl group in the molecule, and their inorganic and organic salts can also be used.

The oxyacid and the derivative of the oxyacid include all optical isomers.

A typical method for producing the polyamine composition of the present invention will be described below. The polyamine composition of the present invention is produced by adding an oxygen acid of phosphorus, an oxyacid or a derivative thereof to a solution or dispersion of a polyamine and mixing them, or by dropping as a solution. The reaction solvent is not particularly limited, but water or alcohol is preferable, and a mixed solvent of water and alcohol can also be used. The reaction temperature at this time is 0 to 100 ° C, preferably 0 to 50 ° C. When the oxygen acid, oxyacid or derivative of phosphorus is a monovalent acid, the addition amount is usually 1 to 100 mol% of the total of primary, secondary and tertiary amino groups of the polyamine, preferably Is 2 to 50%, more preferably 3 to 30%, and in the case of a polyvalent acid, 1 to 100 mol%, preferably 2 to
It is 50%, more preferably 3 to 30% in mol% divided by its valence. Thus, the polyamine composition of the present invention is obtained as an aqueous solution, an organic solvent solution, a mixed solvent solution or a dispersion, and can be used in the above-mentioned fields of use.
The solid polyamine composition can be obtained by distilling the solvent from the solution or dispersion of the above polyamine composition and drying.

The polyamine composition of the present invention is a novel composition which can be used as it is for most applications of conventional polyamines. On the other hand, the polyamine composition of the present invention is extremely difficult to be colored. Therefore, when the use of polyamines is restricted in fields where coloring of products is disliked, such as the paper industry, textile industry, plastics processing industry, and film-forming industry, the polyamine composition of the present invention is extremely excellent. Show the effect. Therefore, the composition of the present invention can be used as a papermaking process agent, a fiber processing agent, a plastic processing agent, an anchor coating agent and the like which are extremely difficult to be colored. The details will be described below.

The paper-making process agent containing the polyamine composition of the present invention as an essential component can be used in most of the fields where polyamines have been conventionally used for the purpose of producing paper which is difficult to be colored. For example, the composition of the present invention can be used as a drainage improver, a paper strength enhancer, a sizing agent and a fixing agent thereof.

When the polyamine composition of the present invention is used as a paper-strengthening agent in the paper-making process, it can be used in most conventionally known paper-strengthening methods. If paper is made by adding it to the pulp slurry as an internal additive, the effect becomes remarkable. When used as an internal additive, for example, a concentration of 1 to 3
Concentration of the polyamine composition corresponding to 0.005 to 10% by weight, preferably 0.05 to 2% by weight, more preferably 0.2 to 1% by weight, based on the dry weight of the pulp, in the weight% pulp slurry. The paper is prepared by adding 0.005 to 10% by weight, preferably 0.05 to 5% by weight, and more preferably 0.5 to 2% by weight of an aqueous solution. You may use together a sulfuric acid band and an anionic paper strengthening agent as needed.

Next, the polyamine composition of the present invention can be used as a drainage improver in the paper making process. The polyamine composition is used in water at an appropriate concentration, usually 0.01
To 2% by weight, preferably 0.02-1% by weight,
It is added to the stock before the papermaking process. Also, it may be added to the recovered white water. The paper stock to which the polyamine composition is applied is not particularly limited, and is not limited by pulp, filler, internally added sizing agent, paper strength enhancer and the like.

Further, the polyamine composition of the present invention can be used as a sizing agent or one component thereof in a papermaking process. The method of use can be handled in the same manner as a conventionally known sizing agent for neutral papermaking, and it is used as an internally added sizing agent. Cationizing agents such as commonly used cationized starch and cationized cellulose may be used in combination. When added to the pulp slurry, the polyamine composition is added in an amount of 0.001 to 5% by weight, preferably 0.01 to 1% by weight, based on the dry weight of the pulp slurry. It goes without saying that the addition level of the polyamine composition is adjusted depending on the size required for the target paper.

The polyamine composition of the present invention can also be used as a fixing agent for neutral papermaking sizing agents such as alkyl ketene dimers. When added to the pulp slurry, the polyamine composition is added in an amount of 0.005 to 1% by weight, preferably 0.05 to 0.2% by weight, based on the dry weight of the pulp slurry, and the yield of expensive alkyl ketene dimer is increased. Improve.

The paper-making process agent of the present invention has the effect that it is extremely unlikely to be colored during use, as compared with the conventional paper-making process agent using free polyethyleneimine, polyamide polyamine or hydrochloric acid or sulfate of polyamine. In particular,
Since it is extremely difficult for the composition of the present invention to be colored even if it is heated in the drying step after paper making or heated in the secondary processing,
The difference in the effect is extremely remarkable as compared with the conventional method. Further, the papermaking process agent of the present invention is difficult to be colored even after being stored for a long time. Therefore, the paper manufactured using the papermaking process agent of the present invention is extremely excellent in whiteness and has a good appearance. As a result, when using the papermaking process agent of the present invention,
Addition of expensive optical brighteners is rarely needed or in very small quantities. Further, the paper of the present invention does not easily turn yellow even in a hot place over time.

Further, the polyamine composition of the present invention can be used as various paper surface treating agents such as a waterproofing agent for ink jet color printer paper and a conductive processing agent for electrostatic recording paper.

The polyamine composition of the present invention can be used as various fiber processing agents in the textile industry (softening agents, surface coating type antistatic agents, hygroscopicity imparting agents, adhesion improving agents, dye fixing agents). In terms of dye fixatives, the compositions of the present invention can be used in the production of dyeings dyed with reactive dyes and direct dyes. The method of use is not particularly limited, and a conventionally known method can be appropriately used. For example, the dyed product to be treated may be immersed in an aqueous solution of the polyamine composition having a concentration of 0.1 to 2 g / l for a predetermined time, washed with water and dried. The bath ratio is usually 1:10 to 20, the treatment temperature is usually room temperature to 80 ° C., and the treatment time is usually 5 to 20 minutes. The composition of the present invention is used for improving the dyeing fastness of a dyed product using a reactive dye and a direct dye, and the produced dyed product is extremely unlikely to yellow.

When the composition of the present invention is used as a surface coating type antistatic agent for fibers or a hygroscopicity-imparting agent, the composition of the present invention is dissolved in water, an organic solvent or a mixed solvent of water and an organic solvent. However, conventionally known spray coating method,
It is applied onto various fibers and their knitted fabrics by a method such as a roll coating method, a dipping method, a brush coating method. The amount of adhesion depends on the material and is not particularly limited,
It is generally 0.01 to 10.0% by weight, preferably 0.1 to 2% by weight, based on the material. Then, the antistatic property and the hygroscopic property can be imparted by standing at room temperature, blowing with hot air, heat treatment and the like.

When the composition of the present invention is used as an antistatic agent for fibers or a hygroscopicity-imparting agent, it is possible to produce fibers having an excellent appearance which is extremely difficult to be colored.

The polyamine composition of the present invention comprises a reinforcing fiber and a halogen-containing vinyl resin, ethylene vinyl acetate resin or polyurethane resin in the production of a sheet-like membrane structure reinforced with polyester and polyamide synthetic fibers. It can be used to improve adhesion. The fiber to be treated may have any form such as filament, yarn, woven fabric, knitted fabric, non-woven fabric and the like. The fiber adhesiveness improver comprising the composition of the present invention is attached to the fiber by a conventionally known roll coating method, dipping method, spray coating method or the like, and then dried in an oven. The amount of the polyamine composition deposited is not particularly limited, but is 0.1 to 0.1 as the solid content relative to the fiber weight.
It is 5.0% by weight, preferably 0.4 to 1.5% by weight. Next, extruding a polyvinyl chloride resin containing a plasticizer to the pretreated reinforcing fiber by a usual calendering method,
After being formed into a film, the sheet-like film structure is manufactured by heating and pressing. The fiber adhesion-improving agent comprising the composition of the present invention has the effect of being less likely to be colored during use, as compared with the conventional one using free polyethyleneimine, polyamide polyamine or polyamine hydrochloric acid or sulfate. In particular, the reinforcing fiber treated with the adhesiveness improver of the fiber made of the composition of the present invention is dried or heated and pressed with the resin,
Since it is difficult to color, the difference in the effect becomes extremely remarkable as compared with the conventional method. Further, the fiber adhesiveness improver comprising the composition of the present invention is difficult to be colored even when stored for a long time. Therefore, the fibers produced by using the composition of the present invention as an adhesion improver for fibers are extremely resistant to yellowing and have a good appearance. Further, it does not easily turn yellow even in a hot place or over time, and has excellent weather resistance.

The polyamine composition of the present invention comprises various plastic processing agents in the plastic processing industry (surface coating type antistatic agents, kneading antistatic agents, hygroscopic agents,
It can be used as an antioxidant and a dyeability improving agent). Examples of materials to which surface coating type antistatic agents and hygroscopicity-imparting agents are applied include synthetic resin moldings, sheet-like materials such as plastic films, synthetic resin foams, synthetic resin powders, synthetic rubber moldings, and synthetic leather. It is illustrated. The composition of the present invention as a surface coating type antistatic agent or a hygroscopicity imparting agent is water,
It is dissolved in an organic solvent or a mixed solvent of water and an organic solvent and applied to the plastic material by a conventionally known method such as a spray coating method, a roll coating method, a dipping method and a brush coating method. The amount of adhesion varies depending on the material and is not particularly limited, but is 0.01 to 1 for the material
It is generally 0.0% by weight, preferably 0.1 to 2% by weight. Then, the material can be given an antistatic property and a hygroscopic property by standing at room temperature, blowing with hot air, heat treatment and the like.

When the composition of the present invention is used as a surface coating type antistatic agent and a hygroscopicity-imparting agent for plastic materials, it is possible to produce fibers and plastic materials which are extremely resistant to coloring and have an excellent appearance.

The polyamine composition of the present invention is used as it is,
It can be used as an antistatic agent for kneading or as a dyeability improving agent. To knead the polyamine composition of the present invention into a resin such as polyamide, polyvinyl chloride, or polyolefin,
Conventional blending methods can be utilized. That is, the polyamine composition can be mixed with resin powder or pellets and mixed using a kneader, a mixing roll, an extruder or the like. The resin composition containing the polyamine composition is a plate, tube, pipe, film, tape,
It can be molded into a molded product of any shape such as a ribbon or a fiber.

The antistatic agent for kneading comprising the composition of the present invention is less likely to be colored during use, as compared with the conventional free polyethyleneimine, polyamide polyamine or polyamine hydrochloride or sulfate. Have an effect. In particular, in the heating step and the drying step such as extrusion molding and melt spinning, the antistatic agent for kneading of the present invention is less likely to be colored, so that the difference in effect is extremely remarkable as compared with the conventional method. Further, the antistatic agent for kneading, which comprises the composition of the present invention, is unlikely to be colored even after being stored for a long time. Therefore, the plastic molded product produced by using the antistatic agent for kneading, which comprises the composition of the present invention, does not easily turn yellow, and thus has a good appearance. In addition, it is extremely resistant to yellowing even in hot places and over time, and has excellent weather resistance.

The polyamine composition of the present invention can be used as it is as an anchor coating agent for producing a film structure which is extremely difficult to be colored.

The anchor coating agent comprising the composition of the present invention can be used for promoting the adhesion between the substrate and the extruded resin in the process of processing a multilayer film by extrusion lamination. The polyamine composition is dissolved in water or an organic solvent or a mixed solvent as an anchor coat liquid,
Films such as polyester, nylon, polypropylene, polyvinylidene chloride, surface-treated films coated with aluminum vapor deposition and ceramic vapor deposition or polyvinylidene chloride, metal foils such as aluminum foil, cellophane, after being applied to base materials such as paper, It is dried with hot air in an oven. Next, polyethylene heated and melted at about 300 ° C. is extruded on this base material, and pressure-bonded with a cooling roll and a nip roll to perform bonding. The anchor coating liquid is 0.005-0.1 g / m ² as an active ingredient, preferably 0.01-
It is applied so as to be 0.05 g / m ² . As a coating method, a known method such as a roll coating method, a lot bar coating method, an air knife coating method, a spray coating method or a dipping method can be used.
As the extruded resin, polypropylene, ethylene / vinyl acetate copolymer resin, ethylene / acrylic acid copolymer resin, etc. can be used in addition to polyethylene.

When the composition of the present invention is used as an anchor coating agent, it is much less likely to be colored than conventional ones,
Moreover, it is possible to manufacture a film-like structure having excellent adhesive strength. Therefore, particularly when the composition of the present invention is used for producing a laminated film, an extremely excellent effect is exhibited. For example, a laminated film produced by using the composition of the present invention as an anchor coating agent is processed into a food packaging film or the like, and when used, it is heated in heat sealing or in a steam atmosphere such as retort and cooking. Even when heated, it does not become colored, and the appearance and adhesive strength are extremely excellent.

[0064]

EXAMPLES Various fields of application of the polyamine composition of the present invention, for example, anchor coating agents for extrusion lamination, antistatic agents for kneading and dyeability improving agents, film adhesion improving agents, coating type antistatic agents. Examples will be shown when used as a papermaking process agent, but it goes without saying that the present invention is not limited to these examples.

Example 1 Polyamine is an adhesion promoter (anchor) such as a laminated film for food packaging produced by heating and melting a resin such as polyethylene or polypropylene on a substrate such as aluminum foil, cellophane and a plastic film. It is used as a coating agent. However, when a polyamine or an anchor coating agent containing polyamine as a main component is used, the polyamine is easily colored by heating during extrusion laminating, and it is difficult to produce a laminated film having an excellent appearance. When the polyamine composition of the present invention is used as an anchor coating agent, a laminated film having excellent appearance and adhesive strength can be produced.

The polyamine composition of the present invention and the polyamine for comparison were diluted with a mixed solution of water / methanol (3/7 weight ratio) to prepare an anchor coating solution having a concentration of 1%. These anchor coat liquids were laminated with an in-line type melt extrusion laminating machine at a laminating speed of 80 m / min.
Molten resin temperature 290 ℃, anchor coat liquid application amount 0.0
Under the condition of 4 g / m ² (polyamine composition or polyamine), aluminum foil (Al), nylon film (N
Y), polyethylene for plain cellophane (PT),
Then, polypropylene was melt-extruded and laminated on the polyester film (PET) to a thickness of 40 μm to form a laminated film. The results of the adhesive strength (T-shaped peeling) of each laminate film measured using an Instron type tester and the degree of coloring (appearance) of each laminate film after heating for 8 hours in a drier at 120 ° C. They are collectively shown in Table 1 and Table 2.

PAA in Tables 1 and 2 is polyallylamine (Nitto Boseki Co., Ltd., molecular weight 10,000), P (A
A / DA) is a copolymer of allylamine and diallylamine in a molar ratio of 1: 1 (Nitto Boseki Co., Ltd., molecular weight 30,
000), PEI is polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., Epomin P-1000, molecular weight 70000).
0), PEHA is pentaethylenehexamine, PVAn
Represents polyvinylamine synthesized by Hoffmann decomposition of polyacrylamide (degree of substitution of primary amino group: 70 mol%, molecular weight: 500,000).

[0068]

[Table 1]

[0069]

[Table 2]

(Note 1) Al: Aluminum foil (thickness 20 μ) NY: Biaxially stretched nylon film (thickness 25 μ) PT: Plain cellophane (thickness 20 μ) PET: Biaxially stretched polyester film (thickness 25 μ) Table 1, it is clear from the results shown in Table 2 that the use of the polyamine composition of the present invention makes it possible to produce a laminated film having an excellent appearance and adhesive strength as compared with the case of using the corresponding polyamine.

Example 2 The anchor coating solution used in Example 1 and Comparative Example 1 was laminated on an in-line type melt extrusion laminating machine at a laminating speed of 80 m / min and an anchor coating solution coating amount of 0.04 g / min.
An anchor coating solution was applied to an aluminum foil under the condition of m ² (polyamine composition or polyamine), and an aluminum foil was simply dried. Further, an anchor coat liquid was applied. Molten resin temperature 290 ℃ on these aluminum foils
Then, polyethylene was melt extrusion laminated to a thickness of 30 μm to form a laminated film. These aluminum foils and laminated films were placed on a 1-liter beaker in which 400 g of distilled water boiled, and the polyethylene surface of the aluminum foil and laminated film coated with the anchor coating agent was brought into contact with steam for 3 minutes and 5 minutes to obtain steam. The degree of coloring (appearance) of the aluminum foil in the atmosphere was examined. The results are shown in Table 3.

[0072]

[Table 3]

As is clear from the results shown in Table 3, the use of the polyamine composition of the present invention makes it possible to produce a film having an excellent appearance that does not color even in a steam atmosphere under heating, as compared with the corresponding polyamine alone.

Example 3 As an antistatic agent for kneading a nylon resin and a dyeability improving agent, the compatibility of the polyamine composition of the present invention with various inorganic and organic acids of polyamine was used. We compared and examined. After mixing 100 g of 6-NY (nylon-6 manufactured by Toyobo Co., Ltd.) with 1.0 g of the polyamine composition and polyamine shown in Table 4 below, the mixture was subjected to a conventional method (cylinder temperature 270 ° C., mold surface temperature). 1
Injection molding, width 15mm, length 120mm,
A plate-shaped test piece having a thickness of 1.5 mm was obtained. The results of the molar ratio of the acid of the present invention to the polyamine and the inorganic and organic acids used for comparison, the degree of visual coloring, and the surface resistance value are shown in Table 4. The polyamine composition was prepared by adding and mixing the acid components shown in Table 4 to the aqueous solution of PAA and PEI used in Example 1 and then drying to obtain a solid. This powder was mixed with 6-NY chips and molded.

[0075]

[Table 4]

As is clear from the results shown in Table 4, the composition of PAA and PEI of the present invention and an oxyacid can be used without coloring and can be used without affecting the subsequent dyeing treatment with an acid dye, and is required at the time of handling. It is possible to obtain a molded product having excellent antistatic ability.

Example 4 Polyamine composition of the present invention, comparison of polyamine with various acids other than those used in the present invention Polyamine composition, and adhesion of polyester (PET) fiber cloth and PVC resin film using polyamine alone We conducted a comparative study on the improvement of sex. 7,000 denier, 1200 filament polyester yarn is drawn and then twisted (6 T / m) to give a basis weight of 30.
A plain weave having a weight of 0 g / m ² was prepared. The polyamine composition of the present invention shown in Table 5, a polyamine composition for comparison between the polyamine and various acids other than the acid used in the present invention,
And a treatment solution containing polyamine alone are attached to the fiber cloth so as to be 1.0 to 1.5% by weight,
A vinyl chloride resin consisting of 100 parts by weight of polyvinyl chloride, 3 parts by weight of barium stearate, and 50 parts by weight of diisooctyl phthalate was extruded by an ordinary calendering method to form a film having a thickness of 0.5 mm, which was heated and pressed to form an adhesive cloth. Obtained.
The adhesive force between the fiber and the vinyl chloride resin is JIS 6329-196.
8 6.3.7 (peel test-180 °). Peel strength of untreated cloth is usually 0.9-1.0kg
/ Inch. The results are shown in Table 5, and the peeling force is expressed as an index for the untreated cloth used as a comparative example. DD in the table is dicyandiamide / formalin / ammonium chloride condensate (Nikafloc D-Nippon Carbide Co., Ltd.)
100), PDAM is poly (dimethylaminoethylmethacrylate) (molecular weight 1,000,000). P
AA and PEI are the same as in Example 1.

[0078]

[Table 5]

The yellowing of the adhesive cloth is ◯: good without coloring,
Δ: Slightly yellowing and poor, X: Strong yellowing and bad.

As shown in Table 5, the adhesive fabric using the polyamine composition of the present invention did not yellow and markedly improved the adhesiveness.

Example 5 The copolymer of ethyl acrylate and methyl methacrylate (monomer charge molar ratio of 1 to 1) was used as a binder, and the polyamine composition of the present invention shown as an example in Table 6 was further shown for comparison. An antistatic agent composed of a polyamine alone or a composition of polyamine and various acids is mixed at a weight ratio of 1: 1 with respect to the binder so that the concentration of the mixture of the binder and the antistatic agent becomes 2%. An aqueous emulsion was prepared and used as an antistatic agent treatment liquid. The above treatment liquid was applied to the surface of a polyethylene terephthalate (PET) film (thickness: 50 μm) using a wire bar so that the applied amount was 4.5 g / m ^2, and the amount was 1 in a hot air drier.
It was dried at 50 ° C. for 5 minutes. Then, visually check for yellowing,
Using an electrometer (manufactured by Takeda Riken Co., Ltd.), use J
The surface resistance value was measured according to the method of IS-K6911-1979.

[0082]

[Table 6]

Here, the antistatic agent composition was prepared by mixing an aqueous solution of polyamine and an acid to adjust the concentration to 10%, and then preparing an aqueous emulsion as described above.

PAA, PEI and P (AA /
DA) are those used in Example 1, PDAM and D
D is the same as that used in Example 4. P (AA /
DADMAC) is obtained by neutralizing and desalting a copolymer (molecular weight 20,000) of allylamine hydrochloride and dimethyldiallylammonium chloride in a molar ratio of 1: 1. The yellowing of the film is indicated by ◯: good without coloring, Δ: slightly yellowing and poor, and ×: strong yellowing and poor.

As is clear from the results in Table 6, untreated PE
Compared with the T film, the antistatic property of the film to be treated is not lowered at all, and a PET film having excellent yellowing resistance can be produced by adding the polyamine composition of the present invention.

Example 6 Polyamine was used in the paper-making process in a water-improving agent, paper-strengthening agent,
It is widely used as a filler yield improver, etc.
In either case, it is required that the whiteness of the paper is kept as good as possible and that the effect of the optical brightener is not hindered as much as possible. However, in reality, the reduction of whiteness due to the addition of polyamine is inevitable. When the polyamine composition according to the present invention is used, a decrease in whiteness can be considerably suppressed.

Water Degree 250m Measured by Canadian Standard Method
In a 0.6% slurry of bleached sulphite pulp with 1%, 0.15% of optical brightener (Uvitex) is added to the pulp.
BHT), a sulfuric acid band of 0.5%, and then polyamine (0.5%) or a polyamine composition shown in Table 7 (amount corresponding to 0.5% of polyamine),
60g basis weight using TAPPI standard square paper machine
Of paper. The wet paper was dried at 130 ° C for 3 minutes. Since the purpose of this example is to compare the whiteness of paper,
No inorganic filler or sizing agent was added. The whiteness of the obtained paper is measured by a known method using a reflectometer (JIS P-8
123Z-8701). The results are summarized in Table 7
It was shown to.

[0088]

[Table 7]

PAA, PEI and P (AA /
DA) is the same as that used in Example 1.

As is clear from the results shown in Table 7, when the polyamine composition of the present invention is used, the decrease in whiteness of the obtained paper is remarkably small as compared with the case where the corresponding polyamine is used alone.

[0091]

As described above, according to the present invention, a polyamine composition which is extremely difficult to be colored is provided. This polyamine composition is used in various papermaking process agents in the paper industry (water-raising agent, paper strength enhancer, sizing agent and its fixing agent), various surface treatment agents for paper, and various processing agents in the textile industry (softening agents, softeners, Antistatic agent, hygroscopicity imparting agent, adhesiveness improving agent, dye fixing agent), antistatic agent for kneading in plastics processing industry, surface coating type antistatic agent, antioxidant, dyeability improving agent and film forming industry It is used as an anchor coating agent for extrusion lamination, an antioxidant, an antistatic agent, an adhesion improver, etc. and does not cause the coloring problem peculiar to polyamines.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 30, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0044

[Correction method] Change

[Correction content]

A typical method for producing the polyamine composition of the present invention will be described below. The polyamine composition of the present invention is produced by adding an oxygen acid of phosphorus, an oxyacid or a derivative thereof to a solution or dispersion of a polyamine and mixing them, or by dropping as a solution. The reaction solvent is not particularly limited, but water or alcohol is preferable, and a mixed solvent of water and alcohol can also be used. The reaction temperature at this time is 0 to 100 ° C, preferably 0 to 50 ° C. When the oxygen acid, oxyacid or derivative of phosphorus is a monovalent acid, the addition amount is usually 1 to 100 mol% of the total of primary, secondary and tertiary amino groups of the polyamine, preferably Is 2 to 50 mol %, more preferably 3 to 30 mol %, and in the case of a polyvalent acid, 1 to 100 mol%, preferably 2 to 50 mol %, more preferably 3 to 30 mol %. It is the mol% divided by the valence. Thus, the polyamine composition of the present invention is obtained as an aqueous solution, an organic solvent solution, a mixed solvent solution or a dispersion, and can be used in the above-mentioned fields of use. The solid polyamine composition can be obtained by distilling the solvent from the solution or dispersion of the above polyamine composition and drying.

Front page continuation (51) Int.Cl. ⁵ Identification code Office reference number FI Technical display location C08L 39/02 LJY 7921-4J 79/02 LQZ 9285-4J D06M 15/61 D21H 17/56

Claims (15)

[Claims] 1. At least one polyamine containing one or more of primary, secondary and tertiary amino groups in the molecule, and an oxygen acid of phosphorus, an oxyacid and derivatives thereof. A polyamine composition comprising at least one kind. 2. A papermaking process agent containing the polyamine composition according to claim 1 as an essential component. 3. The papermaking process agent according to claim 2, which is a drainage agent, a paper strength enhancer, a sizing agent, or a fixing agent thereof. 4. A paper surface treating agent containing the polyamine composition according to claim 1 as an essential component. 5. A paper obtained by using the paper-making process agent or the paper surface-treating agent according to any one of claims 2 to 4. 6. A fiber processing agent containing the polyamine composition according to claim 1 as an essential component. 7. The fiber processing agent according to claim 6, which is a softening agent, a surface coating type antistatic agent, a hygroscopicity imparting agent, an adhesion improving agent or a dye fixing agent. 8. A fiber treated with the fiber finishing agent according to claim 6. 9. A plastic processing agent containing the polyamine composition according to claim 1 as an essential component. 10. The plastic processing agent according to claim 9, which is an antistatic agent for kneading, a surface coating type antistatic agent, a hygroscopicity imparting agent, an antioxidant, and a dyeability improving agent. 11. A plastic treated with the plastic processing agent according to claim 9. 12. An anchor coating agent for extrusion lamination in the film-forming industry, which comprises the polyamine composition according to claim 1 as an essential component. 13. A film-like structure obtained by treating a substrate with the anchor coating agent according to claim 12. 14. A film-like structure obtained by extruding a resin onto the film-like structure according to claim 13 and adhering predetermined portions of both. 15. An antioxidant for film formation, an antistatic agent or an adhesiveness improver, which comprises the polyamine composition according to claim 1 as an essential component.