JPH06220138A - Carbonyl group-containing copolymer aqueous dispersion - Google Patents

Abstract

PURPOSE:To provide the subject dispersion containing carbonyl group-containing copolymer particles each comprising a specific core part and a specific shell part in a specified ratio and a hydrazine derivative having a hydrazine residue, giving processed resins excellent in fastness and dry cleaning resistance, and useful as a binder for processing resins. CONSTITUTION:The objective dispersion contains a hydrazine derivative having a hydrazine residue and carbonyl group-containing copolymer particles each comprising (A) 100 pts.wt. of a core part having a TgA of -60 to -10 deg.C and comprising a (co)polymer produced from (i) 65-100wt.% of a monomer of the formula [R<1> is H, methyl; X is COOR<2> (R<2> is 1-18C alkyl, etc.), etc.,], (ii) 0-20wt.% of a vinyl cyanate monomer, (iii) 0-5wt.% of a carbonyl group- containing monomer, and (iv) 0-10wt.% of a monomer having a radically polymerizable unsaturated group and one or more functional groups and excluding the component iii, and (B) 5-100 pts.wt. of a shell part having a Tg of -30 to 100 deg.C and produced from (v) 45-95wt.% of the component i, (vi) 0.05-5wt.% of the component ii, (vii) 0.05-5wt.% of the component iii, and (viii) 0-10wt.% of the component iv.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous dispersion of carbonyl group-containing copolymer particles having a multi-layer structure, which gives a film having excellent adhesion, blocking resistance and heat resistance. It is composed of a core portion made of a (co) polymer having a glass transition point, and a shell portion made of a copolymer containing a vinyl cyanide monomer and a carbonyl group-containing monomer as its essential components as its essential components. In an aqueous dispersion of multi-layer particles, the glass transition point of the shell copolymer is higher than the glass transition point of the core (co) polymer, and the weight ratio of the core and the shell is The present invention relates to a carbonyl group-containing copolymer aqueous dispersion having a specific range.

The copolymer aqueous dispersion of the present invention is a copolymer aqueous dispersion for resin processing used for textile products such as woven fabrics, knitted fabrics, non-woven fabrics, felts and the like made of natural fibers, recycled fibers, synthetic fibers and the like. It can be suitably used as a liquid, particularly as a binder for pigment printing which gives a flexible printing cloth having fastness and dry cleaning resistance, and also excellent in blocking resistance, and also to a substrate. It is useful as a binder for coating agents for papers, fabrics, etc., which has excellent adhesiveness and heat resistance, and a binder for backing agents for carpets.

[0003]

2. Description of the Related Art It has been conventionally known to impregnate or coat an aqueous emulsion of a thermoplastic resin on a textile product for processing various textile products, for example, Japanese Patent Laid-Open No. 59-76974. One of the most suitable emulsions that can be used for the same purpose is "Tg + 80-1
A mixture of 50 to 97% by weight, preferably 55 to 95% by weight, of a resin aqueous emulsion at 55 ° C and 50 to 3% by weight, preferably 45 to 5% by weight of an aqueous resin emulsion having a Tg of -85 ° C to less than + 80 ° C. Is illustrated.

However, even if the aqueous emulsion of the thermoplastic resin in these proposals is used, it is possible to obtain a fiber resin processed product having sufficient adhesiveness, heat resistance, dry cleaning resistance, blocking resistance and flexibility. Is not easy.

For example, in the textile printing field, many compounds have been proposed as binders for producing pigment printing on fiber materials, and the use of water-soluble synthetic resins or water-dispersible resins is known, but mainly Acrylic ester copolymer emulsions or synthetic rubber latices, either alone or blended, have been used.

[0006] These are widely used at present because they are relatively inexpensive and the brazing strength is obviously improved, but there is a drawback that the brazing degree becomes large depending on the type of fiber. Further, there are binders that give a flexible printing cloth, but at the same time, few of them satisfy the fastness, dry cleaning resistance and blocking resistance.

Recently, a self-crosslinking or reactive acrylic or reactive synthetic rubber latex having a self-crosslinking functional group or a reactive functional group added is often used. It may cause deformation or discoloration, and there is a problem that harmful substances such as formaldehyde are generated during the cross-linking reaction and remain in processed products, which is not a fundamental modification. . Therefore, in the field of textile printing, there has been a strong demand for the appearance of a binder which can sufficiently meet the current requirements for pigment textile printing under mild processing conditions.

In the carpet field, synthetic rubber latex such as styrene / butadiene rubber or butadiene / acrylonitrile rubber is used as a backing agent binder in order to prevent the pile yarns of the rug stock from coming off and to stabilize the shape. However, when a carpet is applied to an uneven part such as an automobile or a building, a backing agent coating using a synthetic rubber latex as a binder has too much impact resilience, which makes shaping difficult. The shape of the formed one is not sharp and the shape is not sufficiently retained.

Melt extrusion laminate backing using a thermoplastic resin such as polyethylene or an ethylene / vinyl acetate copolymer is also performed. In this case, it is possible to mold the uneven shape by heating, and this one is superior in shape-retaining force of the shaped carpet, as compared with the one using the synthetic rubber latex as the binder for the backing agent, Although it has the advantage of being sharp in shape, it has the drawbacks that it is hard to touch and inferior in the pile thread locking effect.

In order to improve the drawbacks of these backing agents, alternatives to synthetic rubber latex have been investigated, and styrene / acrylic copolymers, vinyl chloride
Synthetic resin emulsions such as vinyl acetate copolymers and ethylene / vinyl acetate copolymers are often used.

On the other hand, an aqueous dispersion of a carbonyl group-containing copolymer containing a hydrazine derivative is known (see JP-A-54-110248 and JP-A-54-144432). It is described that these aqueous dispersions form a film at a film-forming temperature of 5 to 25 ° C. and, moreover, give a film having a strong adhesion to an adherend such as cloth or metal.

Further, for example, in Japanese Patent Application Laid-Open No. 57-3850, a carbonyl group-containing copolymer containing a hydrazine derivative having a multi-layer structure of two or more layers having an inner core portion and an outer shell portion is provided. In the particles, the glass transition temperature (Tg) of the copolymer forming the core part of the particles is −32 ° C. to + 60 ° C., that on the shell side is −30 ° C. to + 58 ° C., and the film forming temperature of the composition is 2 to The type and amount of the vinyl monomer of the core and the shell to be polymerized are respectively selected so that the temperature becomes 60 ° C., and the Tg of the copolymer constituting the shell is preferably the Tg of the copolymer constituting the core. By lowering the temperature by 2 ° C or more to improve the film-forming property of the composition, a coating excellent in solvent resistance, durability, and yellowing resistance is provided as a coating material for paints, and is also useful as a repair agent for old coating films. Is described.

However, in any of the aqueous dispersions specifically disclosed in the examples of the above publications, the Tg of the shell-structured copolymer is 2 ° C. higher than the Tg of the copolymer constituting the core.
It was proved to be insufficient in terms of blocking resistance when used for resin processing of textiles, for example. Further, there is no specific disclosure of a copolymer obtained by copolymerizing a vinyl cyanide monomer such as acrylonitrile, which is an essential component of the aqueous copolymer dispersion of the present invention, and therefore, the vinyl cyanide monomer is not disclosed. There is no description or suggestion of the specific effects of the copolymerization of the monomers.

[0014]

DISCLOSURE OF THE INVENTION The inventors of the present invention, as described above, have found that the resin processing using the conventional thermoplastic resin aqueous emulsion has not yet been sufficient, and the fastness and dry resistance of the textile product are not impaired. As a result of the improvement research of the resin water-based emulsion in order to improve the cleaning property, blocking resistance, and heat resistance,

A core portion made of a (co) polymer having a specific glass transition point, and a shell portion made of a copolymer containing a vinyl cyanide monomer and a carbonyl group-containing monomer as its essential components as essential components. And a glass transition point of the shell part copolymer is at least 2 ° C. higher than a glass transition point of the core part (co) polymer, and By resin-processing the fiber product using the carbonyl group-containing copolymer aqueous dispersion whose weight ratio with the shell part is in a specific range,

It is possible to impart a good texture with excellent flexibility to the textile product and to impart fastness, dry cleaning resistance, blocking resistance, and heat resistance. Particularly, in the textile printing process, the flexibility of the printing cloth is improved. The present invention has been completed by discovering that it can be increased, and that the fastness to rubbing can be dramatically improved and that the heat resistance, adhesiveness, and waterproofness of the backing layer in the carpet backing can be improved.

[0017]

Means for Solving the Problems The present invention is an aqueous dispersion containing a carbonyl group-containing copolymer particle and a hydrazine derivative having a hydrazine residue, wherein the copolymer particle has the following (A) and (B),

(A) (a-1) to (a-4) below, (a-1) 65 to 100% by weight of a monomer represented by the following general formula (1),

(Wherein, R ¹ is hydrogen or a methyl group, X is COOR ² , OCOR ³ or an aryl group having 6 to 8 carbon atoms, and R ² is a straight chain or branched chain having 1 to 18 carbon atoms. Alkyl group, cycloalkyl group having 6 to 8 carbon atoms or 7 carbon atoms
To 12 aralkyl groups, R ³ is hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms) (a-2) 0 to 20% by weight of vinyl cyanide monomer, (a-3) carbonyl 0 to 5% by weight of a group-containing monomer, and (a-4) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, wherein Monomers other than monomer (a-3) 0 to 10% by weight, provided that the total of (a-1) to (a-4) is 100% by weight (co) polymer , Its glass transition point Tg _A is −
A core portion having a temperature of 60 to + 10 ° C, and (B) the following (b-1) to (b-4) and (b-1) a monomer represented by the following general formula (1) 45 to 95% by weight ,

(Wherein R ¹ and X are the same as above) (b-2) 4 to 40% by weight of vinyl cyanide monomer, (b-3) carbonyl group-containing monomer 0.05 to 5% by weight, and (b-4) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, wherein the monomer (a-3) Other monomers 0 to 10% by weight, provided that the total of (b-1) to (b-4) is 100% by weight

A copolymer of the glass transition point T
g _B is −30 to + 100 ° C. and is higher than Tg _{A of the} core (co) polymer, and comprises a shell that covers the core.
It is an object of the present invention to provide an aqueous dispersion of a carbonyl group-containing copolymer, characterized in that the shell part is 5 to 100 parts by weight with respect to 00 parts by weight.

The dispersion particles of the carbonyl group-containing copolymer aqueous dispersion of the present invention are multi-layer structure copolymer particles composed of at least two kinds of acrylic (co) polymers having different Tg.

Such an aqueous dispersion of the copolymer of the present invention can be easily produced by using ordinary emulsion polymerization.
The production method is not particularly limited, but, for example, first, in the presence of a surfactant and / or a protective colloid, the monomers (a-1) to (a-4) (hereinafter referred to as M _A May be referred to as)) in an aqueous medium to prepare an acrylic copolymer emulsion (first stage polymerization), and then the monomers (b-1) to (b- 4) (hereinafter M _B
(Sometimes referred to as)) and further (co) polymerize (second stage polymerization) can be preferably used. At this time, since the synthetic resin particles produced have a two-layer structure, in the second-stage emulsion polymerization, an emulsifier is not added, or even if added, the amount is such that new particles are not formed,
It is advantageous to take care so that the polymerization substantially proceeds in the polymer particles formed by the first stage emulsion polymerization.

The structure of the copolymer particles in the aqueous dispersion of the present invention does not necessarily have to be a two-layer structure, and the monomer composition may be changed as necessary to carry out the third stage polymerization or more. It is also possible to have a structure of three layers or more.

The multi-layer structure copolymer particles are particles having a two-layer structure or more including at least a core inner side portion and an outer shell portion. The glass transition temperature (Tg _A ) of the copolymer (A) forming the core of the particle is −60 to + 10 ° C., preferably
-50 to 0 ° C, the glass transition temperature (Tg _B ) of the shell-forming copolymer ( _B ) is -30 to + 100 ° C, preferably -25 to 6
It is 0 ° C. More preferably, the Tg of the total composition of the core and the shell is -50 to 40 ° C, preferably -30 to 30 ° C, and particularly preferably -40 to 20 ° C, respectively.

The glass transition temperature (T
g) is obtained by calculation according to the method described in "Mechanical Properties of Macromolecules", pages 11 to 35, translated by Noriharu Ono, by LE Nielsen.

Calculation of glass transition temperature (Tg): Tg of the copolymer is calculated by the following formula.

[0026]

[Equation 1]

Here, Tg ₁ , Tg ₂ ... and Tg _n are the glass transition temperatures of the homopolymers of component 1, component 2 ... and component n, respectively, and are converted into absolute temperatures. And calculate. W
₁ , W ₂ ..., And W _n are weight fractions of the respective components.

Further, the type and amount of the monomer of the general formula (1) of (a-1) and (b-1) is selected, and Tg _{B of the} copolymer (B) constituting the shell part is selected. Is required to be higher than the Tg _A of the copolymer (A) constituting the core to give the copolymer particles flexibility and improve the blocking resistance, and preferably 2 ° C.
Above, it is particularly preferable to raise the temperature by 10 ° C or more.

Further, the amount of the vinyl cyanide monomer (b-2) constituting the shell copolymer is 4 to 4 out of 100% by weight of all the monomers constituting the shell copolymer. It is 50% by weight, preferably 4-40% by weight. If it is lower than the lower limit and too low, the resulting resin processed product is inferior in solvent resistance, heat resistance, strong gin property and shapeability, which is not preferable. On the other hand, when the amount exceeds the upper limit and is too much, the coating film of the resin processed product obtained becomes brittle and the texture is impaired, which is not preferable.

The weight ratio of the copolymer constituting the core portion and the shell portion is set in consideration of water resistance, solvent resistance, blocking resistance and adhesiveness of the resulting coating film, based on 100 parts by weight of the core portion. Emulsion polymerization is carried out so that the shell portion is 5 to 100 parts by weight, preferably 10 to 60 parts by weight.

The core composed of the monomer component M _A acts to impart flexibility to the coating film, while the shell composed of the monomer component M _B forms the coating film. It acts to impart strong gin properties, blocking resistance, and solvent resistance.

The aqueous dispersion of a carbonyl group-containing copolymer containing a hydrazine derivative of the present invention is one in which the hydrazine derivative undergoes a cross-linking reaction with the carbonyl group of the copolymer to give a film when dried. It provides a film with strong adhesion to the adherend such as fiber, heat resistance,
Improve solvent resistance. The carbonyl group-containing monomer of the component (b-3) of the shell is more economical and more effective when used in a proportion equal to or greater than the quantitative proportion of the component (a-3) of the core. It is preferable because crosslinking can be carried out.

As the hydrazine derivative having such a hydrazine residue, for example, a water-soluble dicarboxylic acid dihydrazide containing 2 to 10 carbon atoms can be preferably used. Examples of such dicarboxylic acid dihydrazide include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, and itaconic acid dihydric acid. it can. Also, the carbon number is 2 to 4
Water-soluble dihydrazine, for example, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-
Examples thereof include dihydrazine. Among these, adipic acid dihydrazide, isophthalic acid dihydrazide,
It is preferred to use succinic acid hydrazide.

The hydrazine derivative having these hydrazine residues is based on 1 mol of the carbonyl group of a carbonyl group-containing copolymer particle having a multilayer structure composed of the (co) polymer (A) and the copolymer (B). It is desirable that it is blended in a ratio of 0.1 to 3 mol, preferably 0.2 to 2.5 mol.

Monomer component (a-1) represented by the general formula (1)
And (b-1), R ¹ is hydrogen or a methyl group, and X is C
OOR ² , a monomer in which R ² is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms, or an aralkyl group having 7 to 12 carbon atoms, that is, (meth)
Acrylic acid ester monomers can be preferably used. Specifically, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, i-butyl acrylate, t-butyl acrylate, n-
Butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, n-nonyl acrylate, i-nonyl acrylate, tridecyl acrylate, stearyl acrylate, oleyl acrylate, cyclohexyl acrylate, benzyl acrylate, etc. Acrylic ester monomer;

For example, methylmethacrylate, ethylmethacrylate, n-propylmethacrylate, n-butylmethacrylate, i-butylmethacrylate, t-butylmethacrylate, n-octylmethacrylate, 2-ethylhexylmethacrylate, i-nonylmethacrylate, i-decylmethacrylate. , Lauryl methacrylate, tridecyl methacrylate, cetyl methacrylate, stearyl methacrylate, oleyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and the like;

As the monomer components (a-1) and (b-1),
A saturated fatty acid vinyl monomer in which R ¹ is hydrogen, X is OCOR ³ , and R ³ is hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms can also be used. Specific examples of such a monomer include, for example, vinyl formate, vinyl acetate, vinyl propionate, “vinyl versatate” [trade name:
Shell company] and the like.

Further, as the monomer components (a-1) and (b-1), an aromatic vinyl monomer in which R ¹ is hydrogen or a methyl group and X is an aryl group having 6 to 8 carbon atoms is also used. it can. Specific examples of such a monomer include styrene and α
-Methylstyrene, vinyltoluene, ethylvinylbenzene and the like can be mentioned.

The amount of the monomer component (a-1) used is within the total 100% by weight of the monomer components M _A constituting the core (co) polymer (A).
65 to 100% by weight, and the amount of the monomer component (b-1) used is 45 to 95% by weight of the total 100% by weight of the monomer component M _B constituting the shell copolymer (B). %.

Examples of the vinyl cyanide monomer as the monomer components (a-2) and (b-2) include acrylonitrile and methacrylonitrile. The amount of the monomer component used is such that for the monomer component (a-2), the core (co) polymer (A) is used.
It is 0 to 20% by weight of the total 100% by weight of the monomer component M _A constituting the component, and the monomer component (b-2) is a shell copolymer.
4 to 4 out of 100% by weight of the total of the monomer components M _B constituting (B)
It is 0% by weight.

When the amount of the above-mentioned monomer component (b-2) used is too small, less than 4% by weight, based on 100% by weight of the total of the monomer components M _B , the copolymer aqueous dispersion obtained is obtained. The resin processing binder, especially dry cleaning resistance of the processed fiber product when used as a binder for pigment printing, heat resistance, blocking resistance and the like tends to be insufficient, while the monomer component (a- If the amount of 2) or (b-2) used is too much over the upper limit with respect to 100% by weight of the total of the monomer components M _A or M _B , the flexibility of the resulting fiber product will be low. It tends to be damaged, which is not preferable.

Further, as the carbonyl group-containing monomer of the monomer components (a-3) and (b-3), at least one aldo group or keto group and one polymerizable double bond are included in the molecule. Monomers having a bond, that is, particularly polymerizable monoethylenically unsaturated ald compounds and keto compounds, which are compounds having only an ester bond (-COO-) and a carboxyl group (-COOH) are excluded. .

Specific examples of such a monomer include acrolein, diacetone acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone, vinyl isobutyl ketone, (meth) acryloxyalkyl propanal, diacetone acrylate. , Acetonyl acrylate, diacetone acrylate, diacetone methacrylate, 2-hydroxypropyl acrylate
-Acetyl acetate, butanediol-1,4-acrylate-acetyl acetate can be mentioned. Among these, diacetone acrylamide, acrolein and vinyl methyl ketone are preferable.

Shell part (b-3) of the carbonyl group-containing monomer
It is preferable to use the component in an amount equal to or more than the quantitative ratio of the core (a-3) component, because the crosslinking can be performed more economically and more effectively. And monomer component (a-3)
The amount used is 0 to 5% by weight of the total 100% by weight of the monomer components M _A constituting the core (co) polymer (A). For the monomer components (b-3), It is 0.05 to 5% by weight of the total 100% by weight of the monomer component M _B constituting the shell copolymer (B).

When the amount of the above-mentioned monomer component (b-3) used is too small, less than 0.05% by weight based on 100% by weight of the total of the monomer components M _B , the resulting copolymer aqueous dispersion is obtained. Dry cleaning resistance and heat resistance of processed textile products when the liquid is used as a binder for resin processing, especially as a binder for pigment printing.
Blocking resistance tends to be insufficient, which is not preferable. On the other hand, the amount of the monomer component (a-3) or (b-3) used is 100% by weight in total of the monomer component M _A or M _B. On the other hand, if the amount exceeds the upper limit and the amount is too large, the film of the resulting copolymer aqueous dispersion tends to be brittle, and the fastness of the processed fiber product may be rather deteriorated, which is not preferable.

As the comonomer component of the monomer components (a-4) and (b-4), an α, β-unsaturated mono- or di- having 3 to 5 carbon atoms is used.
Carboxylic acids can be used. Specific examples of such a monomer include acrylic acid, methacrylic acid, crotonic acid,
Examples thereof include citraconic acid, itaconic acid, maleic acid and fumaric acid.

As the comonomer component of the monomer components (a-4) and (b-4), other than the above, for example, acrylamide, methacrylamide, N-methylolacrylamide, N-methylolmethacrylamide, etc. Amides of (meth) acrylic acid or derivatives thereof; for example, esters of (meth) acrylic acid such as glycidyl acrylate and glycidyl methacrylate with a saturated alcohol having an epoxy group;

For example, esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate and the like and polyvalent saturated alcohols; for example, dimethylaminoethyl (Meth) such as methacrylate and diethylaminoethyl methacrylate
Esters of acrylic acid and a saturated alcohol having an amino group;

For example, two or more of divinylbenzene, diallyl phthalate, triallyl cyanurate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, diethylene glycol dimethacrylate, allyl methacrylate and the like. A monomer group having a radically polymerizable unsaturated group;

Of these, acrylic acid, methacrylic acid, itaconic acid, maleic acid and acrylamide are preferred.

The amount of these monomer components (a-4) and (b-4) used is the sum of all the monomer components constituting the copolymers (A) and (B).
It is 0 to 10% by weight, preferably 0.5 to 5% by weight, out of 100% by weight. If the amount used exceeds the upper limit and is too large, the water resistance of the obtained resin processed product tends to be insufficient, which is not preferable. On the other hand, storage stability and mechanical stability of the aqueous resin dispersion obtained by adjusting the amount used to 0.5% by weight or more (dispersion fracture resistance when the dispersion is filled in a narrow gap and shearing force is applied) Is preferable, since

Among the monomer components (a-4) and (b-4), the amount of the monomer having two or more radically polymerizable unsaturated groups is particularly 0 to 2% by weight. Good to do. When the amount used is 2% by weight or less, the storage stability of the obtained copolymer aqueous dispersion is lowered, the texture of a resin processed product obtained by using the dispersion, and the effect during thermoforming. It is preferable because problems such as insufficient shape and shape retention do not occur.

As the surfactant used for the polymerization in the present invention, as nonionic surfactants, for example, polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether; for example, polyoxyethylene Polyoxyalkylene alkylphenol ethers such as octylphenol ether, polyoxyethylene nonylphenol ether,

For example, sorbitan monolaurate, sorbitan monostearate, sorbitan trioleate and other sorbitan fatty acid esters; for example, polyoxyethylene sorbitan monolaurate and other polyoxyalkylene sorbitan fatty acid esters; for example, polyoxyethylene monolaurate. Polyoxyalkylene fatty acid esters such as laurate and polyoxyethylene monostearate;

Examples thereof include glycerin fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride; polyoxyethylene / polypropylene / block copolymers;

Examples of the anionic surfactants include fatty acid salts such as sodium stearate, sodium oleate and sodium laurate; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; sodium lauryl sulfate and the like. Alkyl sulfate ester salts of

For example, alkyl sulfosuccinate ester salts such as sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate and derivatives thereof; for example, polyoxyalkylene alkyl such as sodium polyoxyethylene lauryl ether sulfate. Ether sulfate salts;

For example, polyoxyalkylene alkylaryl ether sulfate ester salts such as sodium polyoxyethylene nonylphenol ether sulfate;

Examples of the cationic surfactants include alkylamine salts such as laurylamine acetate; quaternary ammonium salts such as lauryltrimethylammonium chloride and alkylbenzyldimethylammonium chloride; and polyoxyethylalkylamines. Etc.

Examples of the amphoteric surfactants include alkyl betaines such as lauryl betaine.

It is also possible to use those obtained by substituting part of the hydrogen atoms of the alkyl group of these surfactants with fluorine.

Further, a so-called reactive surfactant having a radical copolymerizable unsaturated bond in the molecular structure of these surfactants can also be used.

Among these surfactants, the nonionic surfactants include polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenol ethers, from the viewpoint of less generation of aggregates during emulsion polymerization.

Examples of the anionic surfactants include alkylaryl sulfonates; alkyl sulfates; alkyl sulfosuccinic acid ester salts and their derivatives; polyoxyalkylene alkyl ether sulfuric acid ester salts; polyoxyalkylene alkylphenol ether sulfuric acid ester salts; And the like are preferred.

These surfactants may be used alone or in appropriate combination.

The amount of these surfactants used is usually about 0.3 to 10 parts by weight based on 100 parts by weight of all the monomer components constituting the dispersed particles of the aqueous copolymer dispersion. From the viewpoint of good polymerization stability of the aqueous emulsion polymerization, ease of forming dispersed multilayer particles, good storage stability of the copolymer aqueous dispersion, and excellent adhesion to the base material, about 0.5 to 5
It is preferred to use parts by weight, especially about 1 to 3 parts by weight.

Examples of protective colloids that can be used in the production of the aqueous copolymer dispersion of the present invention include polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol and modified polyvinyl alcohol;

Examples thereof include cellulose derivatives such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose salt; and natural polysaccharides such as guar gum.

The amount of these protective colloids used is, for example, about 0 to 3 parts by weight with respect to 100 parts by weight of all the monomer components constituting the dispersed particles of the aqueous copolymer dispersion.

In the first-stage polymerization and the second-stage polymerization described below (hereinafter sometimes simply referred to as emulsion polymerization) in the present invention, as a polymerization initiator, for example, ammonium persulfate, potassium persulfate, persulfate is used. Persulfates such as sodium; t-butyl hydroperoxide,
Organic peroxides such as cumene hydroperoxide and p-menthane hydroperoxide; hydrogen peroxide; and the like can be used alone or in combination of two or more.

The amount of the polymerization initiator to be used can be appropriately selected, but with respect to the total 100 parts by weight of all the monomer components used,
For example, about 0.05 to 1 part by weight, more preferably about 0.1 to 0.7.
The amount used may be exemplified by parts by weight, particularly preferably about 0.1 to 0.5 parts by weight.

In emulsion polymerization, a reducing agent may be used in combination if desired. Examples of the reducing agent include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, glucose; and reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. .

The amount of the reducing agent used can be appropriately selected. For example, with respect to the total 100 parts by weight of all the monomer components used,
The amount used may be, for example, about 0.05 to 1 part by weight.

Further, a chain transfer agent may be optionally used in the emulsion polymerization. Examples of such a chain transfer agent include cyanoacetic acid; cyanoacetic acid having 1 to 8 carbon atoms; bromoacetic acid; bromoacetic acid having 1 to 8 carbon atoms; for example, anthracene, phenanthrene, fluorene, 9 -Aromatic compounds such as phenylfluorene;

Aromatic nitro compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol, p-nitrotoluene; for example, benzoquinone, 2,3,5,6-tetra Methyl-p-
Benzoquinone derivatives such as benzoquinone; Borane derivatives such as tributylborane;

For example, carbon tetrabromide, carbon tetrachloride, 1,1,
Halogenated hydrocarbons such as 2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane and 3-chloro-1-propene;

For example, aldehydes such as chloral and furaldehyde; alkyl mercaptans having 1 to 18 carbon atoms;
For example, aromatic mercaptans such as thiophenol and toluene mercaptan; mercaptoacetic acid; C1-10 alkyl esters of mercaptoacetic acid; C1-12 hydroxyalkyl mercaptans; for example, terpenes such as binene and terpinolene. And the like.

When the above chain transfer agent is used, its amount is about 0.005 with respect to 100 parts by weight as the total of all the monomer components.
It is preferably about 3.0 parts by weight.

In a preferred embodiment of polymerization, the components (a-1) to (a-4) described above are added to an aqueous medium containing or not containing a surfactant and / or a protective colloid,
Surfactant and / or protective colloid, polymerization initiator,
Moreover, the aspect which adds the reducing agent used sequentially as needed can be illustrated.

The carbonyl group-containing copolymer aqueous dispersion of the present invention may optionally contain an inorganic dispersant (eg,
Sodium hexametaphosphate, sodium tripolyphosphate, etc.), organic dispersants [eg, Nopco spar 44C
(Trade name, polycarboxylic acid type; manufactured by San Nopco Ltd.) and the like; for example, silicon type and the like defoaming agent;

For example, polyvinyl alcohol, cellulose-based derivatives, polycarboxylic acid-based resins, surfactant-based thickeners and viscosity improvers; for example, terpene ethylene glycol, butyl cellosolve, butyl carbitol, butyl carbitol acetate, etc. Organic solvents; anti-aging agents; preservatives and mildew-proofing agents; ultraviolet absorbers; anti-static agents; pH adjusting agents such as ammonia water, water-soluble amines and aqueous solutions of alkali hydroxides; it can.

The carbonyl group-containing copolymer dispersion of the present invention may further contain a water-soluble polyvalent metal salt; an aziridine compound; a water-soluble epoxy resin; a water-soluble melamine resin;
A cross-linking agent such as a water-dispersible blocked isocyanate can be added.

Examples of the above water-soluble polyvalent metal salts include zinc salts such as zinc acetate, zinc formate, zinc sulfate and zinc chloride; aluminum salts such as aluminum acetate, aluminum nitrate and aluminum sulfate; , Calcium salts such as calcium formate, calcium chloride, calcium nitrate and calcium nitrite;

For example, barium salts such as barium acetate, barium chloride, barium nitrite; magnesium salts such as magnesium acetate, magnesium formate, magnesium chloride, magnesium sulfate, magnesium nitrate, magnesium nitrite; lead acetate, formic acid, etc. Lead salt such as lead;

For example, nickel salts such as nickel acetate, nickel chloride, nickel nitrate, nickel sulfate; manganese salts such as manganese acetate, manganese chloride, manganese sulfate, manganese nitrate; copper chloride, copper nitrate, copper sulfate, etc. And the like, and examples of the aziridine compound include
A reaction product of a polyisocyanate compound and ethyleneimine can be used,

Examples of the polyisocyanate compound include m- or p-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate, m- or p-xylylene diisocyanate, and 4,4'-diphenylmethane diisocyanate. Aromatic diisocyanate compound;

Aliphatic or alicyclic diisocyanate compounds such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated products of the above aromatic diisocyanate compounds, and dimer acid diisocyanates;

Examples thereof include dimers or trimers of these isocyanates; adducts of these isocyanates with divalent or trivalent polyols such as ethylene glycol and trimethylolpropane.

Examples of the water-soluble epoxy resin include glycerol diglycidyl ether, and examples of the water-soluble melamine resin include methylol melamine; at least a part of the hydroxyl group of the methylol melamine is methyl alcohol, ethyl alcohol, n-butyl. Examples thereof include those etherified with alcohol and the like.

Examples of the water-dispersible blocked isocyanate include trimethylol propane tritolylene diisocyanate methyl ethyl ketoxime adduct and the like, in which the volatile low molecular weight active hydrogen compound is added to the polyisocyanate compound,

Examples of such a volatile low molecular weight active hydrogen compound include methyl alcohol, ethyl alcohol, n-butyl alcohol, cyclohexyl alcohol,
Aliphatic, alicyclic or aromatic alcohols such as benzyl alcohol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and phenol;

For example, hydroxy tertiary amines such as dimethylaminoethanol and diacylaminoethanol; ketoxime compounds such as acetoxime and methylethylketoxime; active methylene compounds such as acetylacetone, acetoacetic acid ester and malonic acid ester;
lactams such as ε-caprolactam; and the like.

The amount of these cross-linking agents to be used is, for example, 0 to 10 parts by weight, preferably 100 parts by weight, with respect to 100 parts by weight of the acrylic copolymer, from the viewpoint of suppressing the change with time of the viscosity of the resulting composition after compounding. Can be exemplified in an amount of 0.5 to 10, particularly preferably 1 to 5 parts by weight.

The aqueous copolymer dispersion of the present invention is useful as a treatment agent for impregnating or coating a thermoplastic resin into a fiber product such as a pigment and dyeing printing, carpet / backing, non-woven fabric and flocking.

Hereinafter, the present invention will be described in more detail with reference to examples. The test method and evaluation method in this example are as follows.

(1) Preparation of test sheet A cotton broad was printed using a printing paste prepared by the following composition, and dried at 25 ° C. for 24 hours to obtain a test sheet.

Blending of printing paste Reducer 65 Copolymer aqueous dispersion 25 Blue pigment paste 10

(2) Fastness to rubbing The test sheet prepared in the above (1) was immersed in water for 10 minutes, and then the fastness to rubbing was measured using a Gakushin-type tester.

Friction conditions Friction element 45R, coated with kanaquin (wet enough with water) Load 200g 100 times

The evaluation criteria are as follows. ○ ・ ・ ・ ・ There is almost no color change to the friction element △ ・ ・ ・ ・ ・ ・ There is a little color change to the friction element × ・ ・ ・ ・ ・ ・ There are many color changes to the friction element

(3) Texture The texture of the test sheet prepared in (1) above was evaluated by touch. The evaluation criteria are as follows.

○ ・ ・ ・ ・ Very flexible △ ・ ・ ・ ・ ・ ・ Slightly hard × ・ ・ ・ ・ Hard

(4) Anti-Parklen Resistance Aqueous copolymer dispersion was applied on a release paper to a film thickness of about 80 μm, dried at 25 ° C. for 24 hours, and the obtained film was dipped in Parklen for 30 minutes. The area swelling ratio was measured.

(5) Blocking resistance With respect to the test sheet prepared in the above (1), the processed surfaces were put together and left at 25 ° C for 16 hours under a load of 200 g / cm ² to be peeled off, and the resistance against peeling resistance The blocking property was evaluated. The evaluation criteria are as follows.

○ ・ ・ ・ ・ Almost no resistance during peeling △ ・ ・ ・ ・ ・ ・ Slight resistance during peeling × ・ ・ ・ ・ Resistance during peeling

However, the test sheet obtained in Example 4 was evaluated in comparison with the test sheet obtained in Comparative Example 4. The test sheet obtained from Example 4 was
The blocking resistance was obviously better than that of Comparative Example 4 having the same resin composition. The textures of both were almost the same.

(6) PET Adhesiveness A polyester terephthalate (PET) film was coated with a copolymer aqueous dispersion so as to have a thickness of 0.3 mm in a wet state, and a cotton broad cloth was immediately stuck and dried at 25 ° C. for 1 day. 300
The 180 ° peel strength was measured at a tensile speed of mm / min.

(7) Heat resistance An aqueous dispersion of a copolymer was applied on a release paper so as to have a film thickness of about 80 μ and dried at 25 ° C. for 24 hours, and the elastic modulus at 150 ° C. of the obtained film was measured. The heat resistance was judged by measuring.

Instrument: Fully automatic low drive viscoelasticity measuring instrument [Reovibron DDV-III-EP; manufactured by Toyo Baldwin Co., Ltd.] Drive: Shear, frequency 110Hz, temperature rise: 3 ° C / min

Example 1 A 2000 ml separable flask equipped with a stirrer, a reflux condenser and a thermometer was charged with 310 g of deionized water, and the temperature was raised to 55 ° C. while flowing nitrogen. Then 110g deionized water,
19.2 g of nonionic surfactant (polyethylene glycol nonylphenyl ether), 214 g of butyl acrylate (BA) as a monomer component M _A , methyl methacrylate (MM
A) 141 g, acrylonitrile (AN) 40 g, itaconic acid (I
A) 4.0 g and diacetone acrylamide (DAAM) 1.2 g
Monomer mixture of and was mixed uniformly, 3g% potassium persulfate (KPS) 69g, 3% sodium metabisulfite (SMBS) 69g continuously added over 3 hours, then at the same temperature After holding for 1 hour, copolymer particles (A) to be the core were obtained.

Next, as monomer component M _B , ethyl acrylate (EA) 52.8 g, AN 16 g, MMA 8.8 g, methacrylic acid
(MAA) 1.6g and DAAM 0.8g homogeneously mixed monomer mixture, 3wt% KPS 13g, 3wt% SMBS 13g continuously added in 1 hour, kept at the same temperature for 2 hours After that, the mixture was cooled to room temperature, and 1.5 g of adipic acid dihydrazide (ADHZ) was added as a hydrazine derivative to obtain a carbonyl group-containing copolymer aqueous dispersion.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Example 2 In Example 1, 240 g of BA and EA were used as the monomer component M _A.
19.2g, MMA 48.0g, acrylic acid (AA) 6.4g and DAAM
6.4 g, BA 19.2 g as monomer component M _B , EA 125 g, AN 8.
A carbonyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that 0 g, AA (3.2 g) and DAAM (4.8 g) were used, and succinic acid dihydrazide (SDHZ) (2.9 g) was added as a hydrazine derivative.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Example 3 In Example 1, 372 g of EA and MMA as the monomer component M _A were used.
36.1g, AN 34.3g, AA6.8g and DAAM 2.3 g, EA 21.6 g as a monomer component _{M B, MMA 2.3g, AN 4.3g} , AA 0.43g
And 0.14g DAAM, AD as hydrazine derivative
A carbonyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that HZ (3.0 g) was added.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Example 4 In Example 1, as a monomer component M _A , EHA 153 g, MM
A 142g, AN 135g, Methacrylic acid (MAA) 7.1g and DAA
M 1.8g, BA 30.9g as monomer component M _B , MMA 43.6g, AN
A carbonyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that 47.3 g, AA 2.5 g and DAAM 0.25 g were used and ADHZ 4.9 g was added as a hydrazine derivative.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Comparative Example 1 In Example 3, the monomer component M _A and the monomer component M _B
A carbonyl group-free copolymer aqueous dispersion was obtained in the same manner as in Example 3, except that DAAM was not copolymerized and the amount of MMA copolymerized was increased accordingly.

Table 1 shows the monomer composition of each of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Comparative Example 2 In Example 3, the monomer component M _A and the monomer component M _{B were used.}
As a result, an aqueous carbonyl group-free copolymer dispersion was obtained in the same manner as in Example 1 except that AN was not copolymerized and the amount of MMA copolymerized was increased accordingly.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Comparative Example 3 A carbonyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 3, except that the hydrazine derivative was not added.

Table 1 shows the monomer compositions of the core and the shell.
Table 2 shows the amount of the hydrazine derivative added, the properties of the copolymer dispersion and the constitution of the copolymer particles, and Table 3 shows the physical properties of the film and the printed physical properties.

Comparative Example 4 In a separable flask similar to that used in Example 1, deionized water 2
88 g was charged and the temperature was raised to 55 ° C while flowing nitrogen. Next, 132 g of deionized water, 19.2 g of nonionic surfactant (polyethylene glycol nonyl phenyl ether), and MMA
186g, EHA 153g, BA 30.8g, AN 101g, MAA 7.1g, AA
Monomer mixture liquid in which 2.5 g and DAAM 0.25 g are uniformly mixed,
In addition, 82 g of 3% by weight KPS and 82 g of 3% by weight SMBS were continuously added over 3 hours, kept at the same temperature for 2 hours, then cooled to room temperature, and 0.6 g of adipic acid dihydrazide as a hydrazine derivative was added to the core. To obtain a uniform carbonyl group-containing copolymer aqueous dispersion that does not form a shell or shell.

Table 1 shows the monomer composition, and Table 2 shows the amount of the hydrazine derivative added, the properties of this copolymer dispersion and the composition of the particles.

[0127]

[Table 1]

[0128]

[Table 2]

[0129]

[Table 3]

[0130]

The carbonyl group-containing copolymer aqueous dispersion of the present invention comprises a core comprising a (co) polymer having a specific glass transition point, a vinyl cyanide monomer and a carbonyl group-containing unit as essential components. An aqueous dispersion of multi-layer particles comprising a shell comprising a copolymer containing a copolymer as its copolymerization component, wherein the glass transition point of the shell copolymer is the core
It is higher than the glass transition point of the (co) polymer, and the weight ratio of the core part to the shell part is within a specific range.

Since the film obtained from the aqueous dispersion of the copolymer of the present invention is excellent in flexibility, adhesiveness, blocking resistance and heat resistance, for example, woven fabrics made of natural fibers, recycled fibers, synthetic fibers and the like. It can be preferably used as an aqueous dispersion of a copolymer for resin processing of textile products such as cloth, knitted fabric, non-woven fabric, felt, etc. In particular, it has fastness and dry cleaning resistance, and is also excellent in blocking resistance. As a binder for pigment printing that gives a flexible printing cloth, and also as a binder for coating agents for carpets and carpets, which has excellent adhesiveness to substrates, heat resistance, etc. and is flexible It is useful as a binder.

[Chemical 3]

[Chemical 4]

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Claims (1)

[Claims] 1. An aqueous dispersion comprising carbonyl group-containing copolymer particles and a hydrazine derivative having a hydrazine residue, wherein the copolymer particles have the following (A) and (B), (A) (a-1) to (a-4), (a-1) 65 to 100% by weight of a monomer represented by the following general formula (1), (However, in the formula, R ¹ is hydrogen or a methyl group, and X is COO.
R ^{2 is} OCOR ³ or an aryl group having 6 to 8 carbon atoms, and R ² is a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 6 to 8 carbon atoms or 7 to 7 carbon atoms.
12 aralkyl groups, R ³ is hydrogen or a linear or branched alkyl group having 1 to 12 carbon atoms) (a-2) 0 to 20% by weight of vinyl cyanide monomer, (a-3) carbonyl group 0 to 5% by weight of a monomer, and (a-4) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, wherein Monomers other than the body (a-3) 0 to 10% by weight, provided that the total amount of the above (a-1) to (a-4) is 100% by weight (co) polymer, Its glass transition point Tg _A
A core having a temperature of 60 to + 10 ° C, and (B) the following (b-1) to (b-4) and (b-1) the monomer represented by the following general formula (1) 45 to 95% by weight , [Chemical formula 2] (However, R ¹ and X in the formula are the same as above) (b-2) vinyl cyanide monomer 4 to 40% by weight, (b-3) carbonyl group-containing monomer 0.05 to 5% by weight, And (b-4) a monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, which is a monomer other than the monomer (a-3). A copolymer of 0 to 10% by weight, provided that the total amount of the above (b-1) to (b-4) is 100% by weight, and having a glass transition point Tg _B of -30.
_A shell part covering the core part at a temperature of up to + 100 ° C. and higher than the Tg _{A of the} core (co) polymer, and the shell part is 5 to 100 parts by weight with respect to 100 parts by weight of the core part. A carbonyl group-containing copolymer aqueous dispersion characterized by being present.