JPH0762191A - Water-base acetoacetylated copolymer dispersion - Google Patents

Abstract

PURPOSE:To obtain the title dispersion which gives a film excellent in adhesiveness, blocking resistance, and heat resistance by dispersing polymer particles each of which comprises a core comprising a (co)polymer having a specified Tg and a shell comprising a copolymer contg. acetoacetylated monomer units. CONSTITUTION:The dispersion contains, together with a hydrazine deriv. and/or an amine, polymer particles each of which comprises 100 pts. core comprising a (co) polymer formed from 60-100% monomer of the formula (wherein R<1> is H or CH3; X is COOR<2>, 6-8C aryl, etc.; and R<2> is 1-18C alkyl, etc.), 0-20% acetoacetylated monomer, and 0-20% monomer having a radical-polymerizable unsatd. group and other functional group (s) and having a Tg of -60 deg.C to +80 deg.C and 5-100 pts. shell comprising a copolymer formed from 5-99.95% monomer of the formula, 0.05-30% acetoacetylated monomer, and 0-20% monomer having a radical-polymerizable unsatd. group and other functional group (s) and having a Tg of -40 deg.C to +100 deg.C provided the Tg of the shell polymer is higher than the Tg of the core polymer.

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 multi-layered acetoacetyl group-containing copolymer particles which gives a film having excellent adhesion, blocking resistance and heat resistance. Aqueous dispersion of multi-layer particles composed of a core part composed of a (co) polymer having a glass transition point and a shell part composed of a copolymer containing an acetoacetyl group-containing monomer as an essential component as its essential component. Acetoacetyl, which is a liquid, in which 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 to the shell is in a specific range. It relates to a group-containing copolymer aqueous dispersion.

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 preferably used as a liquid, especially as a non-woven fabric binder, which has fastness and dry cleaning resistance, and also as a pigment printing binder which gives a flexible printing cloth having excellent blocking resistance, It is also useful as a binder for coating agents and binder for carpet backing agents for papers, fabrics, etc., which have excellent adhesiveness to substrates and heat resistance and are flexible.

[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
50-97% by weight of resin aqueous emulsion at 55 ° C, preferably
A mixture of 55 to 95% by weight 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 exemplified.

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. These are relatively inexpensive and are widely used at the present time because the brazing degree is obviously improved, but there is a drawback that the brazing degree varies greatly 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, self-crosslinking or reactive acrylic or reactive synthetic rubber latex having a self-crosslinking functional group or reactive functional group added is often used. However, many of them require high temperature for processing, and the base cloth is 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 backing field, styrene-butadiene rubber or butadiene
Synthetic rubber latex such as acrylonitrile rubber is used as a binder for backing agent, but when constructing a carpet on an uneven portion of an automobile or a building, a backing agent coating using a synthetic rubber latex as a binder is required. Since the impact resilience is too large, it is difficult to shape the shape, and the shape of the shape-formed one is not sharp and the shape is not sufficiently retained.

Further, melt extrusion laminate backing using a thermoplastic resin such as polyethylene or an ethylene / vinyl acetate copolymer is also carried out. 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). These aqueous dispersions form a film at a film forming temperature of 5 to 25 ° C,
Moreover, it is described that a coating film having a strong adhesive force is applied to an adherend such as cloth or metal.

Further, for example, JP-A-57-3850 discloses a carbonyl group-containing copolymer containing a hydrazine derivative having a multi-layered structure of two or more layers having an inner core portion and an outer shell portion. In the particles, the glass transition temperature (Tg) of the copolymer forming the core 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 60 ° C., and the type and amount of the vinyl monomer of the nucleus and the shell to be polymerized are selected, Preferably, the Tg of the copolymer that constitutes the shell is the Tg of the copolymer that constitutes 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 all 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 an acetoacetyl group-containing monomer, which is an essential component of the aqueous copolymer dispersion of the present invention, and therefore, the acetoacetyl group-containing monomer is not disclosed. There is no description or suggestion of the unique effect of the polymer copolymer particles.

[0013]

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 multilayer structure composed of a core portion made of a (co) polymer having a specific glass transition point and a shell portion made of a copolymer containing an acetoacetyl group-containing monomer as an essential component as its copolymerization component. An aqueous dispersion of particles, wherein the glass transition point of the shell copolymer is higher than the glass transition point of the core copolymer, and the weight ratio of the core to the shell is in a specific range. By resin-processing a textile product using an aqueous dispersion of an acetoacetyl group-containing copolymer,

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, and particularly to the flexibility of the printing cloth in the printing process. The present invention has been completed by finding out that it can be increased, and that the friction fastness is dramatically improved, and in the backing of a carpet, the heat resistance, adhesiveness, and waterproofness of the backing layer are improved.

[0016]

The present invention provides an aqueous solution containing acetoacetyl group-containing copolymer particles and a hydrazine derivative having a hydrazine residue and / or amines having two or more amino groups. In the dispersion, the copolymer particles are the following (A) and (B),

(A) The following (a-1) to (a-3),

(A-1) A monomer represented by the following general formula (1) 60
~ 100% by weight,

[0019]

[Chemical 3]

(Wherein R ¹ is hydrogen or a methyl group,
X is COOR ² , OCOR ³ , an aryl group having 6 to 8 carbon atoms or CN, 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 a carbon number 7 to 12 aralkyl group, R ³ is hydrogen or a straight or branched alkyl group having 1 to 12 carbon atoms)

(A-2) Acetoacetyl group-containing monomer 0 to 20
Wt% and

(A-3) 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 above-mentioned monomer (a-2). 0 to 20% by weight,

[However, the total of (a-1) to (a-3) is 100% by weight]

_A core portion of the (co) polymer of (1), which has a glass transition point Tg _A of -60 to + 80 ° C;

(B) The following (b-1) to (b-3),

(B-1) Monomer represented by the following general formula (1) 50
~ 99.95% by weight,

[0027]

[Chemical 4]

(In the formula, R ¹ and X are the same as above)

(B-2) Acetoacetyl group-containing monomer 0.05
~ 30% by weight, and

(B-3) 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 above-mentioned monomer (b-2). 0 to 20% by weight,

[However, the total of the above (b-1) to (b-3) is 100% by weight]

A copolymer of the glass transition point T
g _B is −40 to + 100 ° C., and Tg of the core (co) polymer is
_It is higher than _A and consists of a shell that covers the core.
The purpose of the present invention is to provide an aqueous dispersion of an acetoacetyl group-containing copolymer, characterized in that the shell is 5 to 100 parts by weight with respect to parts by weight.

The dispersed particles of the acetoacetyl group-containing copolymer aqueous dispersion of the present invention are multi-layered structure copolymer particles composed of at least two kinds of acrylic (co) polymerization 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-3) (hereinafter, 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- 3) (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.

Further, 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 + 80 ° C., preferably
-50 to + 30 ° C, the glass transition temperature (Tg _B ) of the shell-forming copolymer ( _B ) is -40 to + 100 ° C, preferably -25.
~ 60 ° 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.

[0039]

[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.
More preferably, it is particularly preferably raised by 10 ° C. or more.

The weight ratio of the copolymer constituting the core portion and the shell portion is determined in consideration of water resistance, solvent resistance, blocking resistance and adhesiveness of the obtained 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 the hydrazine derivative having a hydrazine residue and / or the acetoacetyl group-containing copolymer containing amines having two or more amino groups according to the present invention is dried to give the hydrazine derivative and / or Alternatively, the amines cross-link with the acetoacetyl group of the copolymer to give a tough coating, which gives a coating having strong adhesion to the adherend such as cloth, paper, and fibers, and heat resistance. Property and solvent resistance are improved. And, the acetoacetyl group-containing monomer of the component (b-2) of the shell is more economical and more effective when used at a ratio equal to or more than the quantitative ratio of the component (a-2) of the core. It is preferable because it can be crosslinked.

As the hydrazine derivative having such a hydrazine residue, for example, a water-soluble dicarboxylic acid dihydrazide having 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. Further, water-soluble dihydrazine having 2 to 4 carbon atoms, such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine and the like can be mentioned. Among these, it is preferable to use adipic acid dihydrazide, isophthalic acid dihydrazide, and succinic acid hydrazide.

As amines having two or more amino groups, for example, aliphatic polyamines having 2 to 10 carbon atoms and aromatic polyamines having 6 to 16 carbon atoms can be preferably used. Examples of such aliphatic polyamines include, for example, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, triaminopropane, etc .; aromatic polyamines include o-phenylenediamine, m-phenylenediamine, p-
Phenylenediamine, triaminobenzene, triaminophenol and the like;

These hydrazine derivatives and / or amines are added to 1 mol of the acetoacetyl group of the acetoacetyl group-containing copolymer particles having the multilayer structure composed of the (co) polymer (A) and the copolymer (B). On the other hand, it is desirable that it is blended in a proportion of 0.1 to 5 moles, preferably 0.2 to 3 moles.

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, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, i-nonyl methacrylate, i-decyl methacrylate. , 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.

Further, as the monomer components (a-1) and (b-1), a vinyl cyanide monomer in which R ¹ is hydrogen or a methyl group and X is CN can be preferably used. Specific examples of such a monomer include acrylonitrile and methacrylonitrile.

The amount of the monomer component (a-1) used is 6% of the total 100% by weight of the monomer components M _A constituting the core (co) polymer (A).
The amount of the monomer component (b-1) used is 50 to 99.95 wt% of the total 100 wt% of the monomer components M _B constituting the shell copolymer (B). %.

The amount of the vinyl cyanide monomer that can be preferably used as the monomer components (a-1) and (b-1) constitutes the core copolymer (a- 1) Constituting the shell copolymer rather than the ratio of the vinyl cyanide monomer used as the component (the ratio of the vinyl cyanide monomer to the total monomers constituting the core copolymer) It is preferable that the ratio of the vinyl cyanide monomer used as the component (b-1) (the ratio of the vinyl cyanide monomer to the total monomers constituting the shell copolymer) be equal or higher. . The proportion of the vinyl cyanide monomer used as the component (b-1) is preferably 4 to 50% by weight, based on 100% by weight of all the monomers constituting the shell copolymer. Particularly preferably, it is 4 to 40% by weight. When the amount used is at least the lower limit value, the obtained resin processed product is excellent in solvent resistance, heat resistance, strong gin property, shapeability, etc., and is preferable. On the other hand, when it is at most the upper limit value, the coating film of the obtained resin processed product does not become brittle and the texture is not impaired, which is preferable.

The acetoacetyl group-containing monomer of the monomer components (a-2) and (b-2) is a monomer represented by the following general formula (2).

[0056]

[Chemical 5]

(In the formula, R ⁴ and R ⁵ are each independently hydrogen or a methyl group; Y is a single bond, a methylene group or COO.
R ⁶ and CONHR ⁷ , wherein R ⁶ and R ⁷ are linear or branched alkylene groups having 1 to 6 carbon atoms, and Z is hydrogen or CN)

Specific examples of such a monomer include, for example, acetoacetic acid alkenyl esters such as vinyl acetoacetate and allyl acetoacetate; for example, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate and 2-acetoacetoxyethyl methacrylate. Acetoacetoxypropyl acrylate,
(Meth) acrylic acid acetoacetic acid diester of alkylene glycol such as 2-acetoacetoxypropyl methacrylate, 2-cyanoacetoacetoxyethyl methacrylate;
For example, crotonic acid acetoacetic acid diesters of alkylene glycols such as 2-acetoacetoxyethyl crotonate and 2-acetoacetoxypropyl crotonate;
N- (acetoacetoxymethyl) acrylamide, N- (acetoacetoxymethyl) methacrylamide, N- (acetoacetoxyethyl) acrylamide, N- (acetoacetoxyethyl) methacrylamide, etc. Ester; Of these, allyl acetoacetate, 2-acetoacetoxyethyl acrylate, 2-acetoacetoxyethyl methacrylate, 2-acetoacetoxypropyl acrylate, and 2-acetoacetoxypropyl methacrylate are preferable.

The acetoacetyl group-containing monomer shell (b
The amount of the component (-2) used is preferably equal to or more than the quantitative ratio of the component of the core (a-2), because the crosslinking can be performed more economically and more effectively. And the monomer component (a-
The amount of 2) used is 0 to 20 wt% of the total 100 wt% of the monomer components M _A constituting the core (co) polymer (A), and the monomer component (b-2) Is 0.05 to 30% by weight of the total 100% by weight of the monomer component M _B constituting the shell copolymer (B).

If the amount of the above-mentioned monomer component (b-2) 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-2) or (b-2) 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-3) and (b-3), 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-3) and (b-3), 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;

[0064] For example, a (meth) acryl-based simple substance that generates an isocyanate group by thermal dissociation / transfer of N, N-dimethylhydroxypropylamine-N-methacrylimide, N, N-dimethylhydroxypropylamine-N-acrylimide, or the like. Quantity;

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 having a radically polymerizable unsaturated group;
And the like.

Among these, acrylic acid, methacrylic acid, itaconic acid, maleic acid and acrylamide are preferable.

The amount of these monomer components (a-3) and (b-3) used is the sum of all the monomer components constituting the copolymers (A) and (B).
0 to 20% by weight of 100% by weight, preferably 0.5 to 10% by weight
Is. 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-3) and (b-3), 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, polyoxyethylene stearyl ether and the like; for example, polyoxyethylene Polyoxyalkylene alkylphenol ethers such as octylphenol ether, polyoxyethylene nonylphenol ether,

[0070] For example, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monostearate and sorbitan trioleate; for example, polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate; 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 dodecylbenzene sulfonate; 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, nonionic surfactants include polyoxyalkylene alkyl ethers and polyoxyalkylene alkyl phenol ethers from the viewpoint of generation of aggregates during emulsion polymerization and the like.

As the anionic surfactants, alkylaryl sulfonates; alkyl sulfates; alkyl sulfosuccinic acid ester salts and derivatives thereof; 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 combination as appropriate.

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 It is preferable to use 5 parts by weight, particularly 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, for example, 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 based on 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, examples of the polymerization initiator include ammonium persulfate, potassium persulfate, and persulfate. 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, the amount used may be about 0.05 to 1 part by weight, more preferably about 0.1 to 0.7 part by weight, particularly preferably about 0.1 to 0.5 part by weight.

If desired, a reducing agent may be used in combination during emulsion polymerization. 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 100 parts by weight in total of all the monomer components used,
The amount used may be, for example, about 0.05 to 1 part by weight.

Furthermore, a chain transfer agent can 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, 1,1,2,
Halogenated hydrocarbons such as 2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, 3-chloro-1-propene;

For example, aldehydes such as chloral and furaldide; 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, the amount used is about 0.005 to 100 parts by weight based on the total weight of all the monomer components.
It is preferably 3 parts by weight.

In a preferred embodiment of the polymerization, the components (a-1) to (a-3) 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 acetoacetyl group-containing copolymer aqueous dispersion of the present invention may further contain an inorganic dispersant (eg, sodium hexametaphosphate, sodium tripolyphosphate, etc.), an organic dispersant [eg, Nopcospar 4
Dispersants such as 4C (trade name, polycarboxylic acid type; manufactured by San Nopco Ltd.); for example, silicone type defoaming agents;

For example, thickeners and viscosity improvers such as polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resins, and surfactants; 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 acetoacetyl 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 water-dispersible blocked isocyanate, etc. The cross-linking agent 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, and nickel sulfate; manganese salts such as manganese acetate, manganese chloride, manganese sulfate, and manganese nitrate; for example, copper chloride, copper nitrate, copper sulfate, and the like. 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 trimethylolpropane tritolylene diisocyanate methyl ethyl ketoxime adduct and the like in which the polyisocyanate compound is impregnated with a volatile low-molecular active hydrogen compound.

Examples of such volatile low molecular weight active hydrogen compounds 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 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 on 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 prepare a test sheet.

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

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

Friction conditions Friction element 45R, Kanakin coating (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 the item (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 coated on a release paper so as to have 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, peeled after being left for 16 hours at 25 ° C. under a load of 200 g / cm ² The blocking property was evaluated. The evaluation criteria are as follows.

○ ・ ・ ・ ・ Peeling almost no resistance during peeling △ ・ ・ ・ ・ ・ ・ Slight resistance during peeling × ・ ・ ・ ・ ・ ・ Resin during peeling

(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, immediately after which cotton broad was laminated and dried at 25 ° C. for 1 day. 300 m
The 180 ° peel strength was measured at a tensile speed of m / min.

(7) Heat resistance An aqueous copolymer dispersion was applied on a release paper to a film thickness of about 80 μm and dried at 25 ° C. for 24 hours. 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 110 Hz, 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. Next, 110 g of deionized water, 19.2 g of nonionic surfactant (polyethylene glycol nonylphenyl ether), 214 g of butyl acrylate (BA) as a monomer component MA, and methyl methacrylate (MMA) 1
40g, acrylonitrile (AN) 40g, itaconic acid (IA) 4.
0g and diacetylacetoxyethylmethacrylate (AAEM) 2.0g homogeneously mixed monomer mixture, 3% by weight potassium persulfate (KPS) 69g, 3% by weight sodium metabisulfite (SMBS) 69g for 3 hours Was continuously added, and then the mixture was kept at the same temperature for 1 hour to obtain copolymer particles (A) to be the core.

Next, as the monomer component MB, 52.8 g of ethyl acrylate (EA), 16 g of AN, 8.8 g of MMA, 1.6 g of methacrylic acid (MAA) and 0.8 g of AAEM were uniformly mixed, and 3 13 g of wt% KPS and 13 g of 3 wt% SMBS were continuously added over 1 hour, kept at the same temperature for 2 hours, cooled to room temperature, and added with 1.8 g of adipic acid dihydrazide (ADHZ) as a hydrazine derivative. An acetyl group-containing copolymer aqueous dispersion was obtained.

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, as the monomer component MA, BA 240 g, EA
19.2g, MMA 44.8g, acrylic acid (AA) 6.4g and AAEM
9.6g, BA 19.2g as monomer component MB, EA 121.6g, AN
An acetoacetyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that 8.0 g, AA 3.2 g and AAEM 8.0 g were used and hexamethylene diamine (HMDA) 1.4 g was added as the amines.

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, as the monomer component MA, EA 367.6 g, M
MA 36.1 g, AN 36.1 g, AA 6.8 g and AAEM 4.5, EA 21.6 g as monomer component MB, MMA 2.3 g, AN 4.4 g, AA 0.44 g and AAEM 0.29 g were used, and ADHZ 1.6 as a hydrazine derivative.
An acetoacetyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that 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 MA, EHA 153 g, MM
A 138.7g, AN 53.3g, Methacrylic acid (MAA) 7.1g and AAE
M 3.56g, BA as monomer component MB 31.1g, MMA 42.9g, A
An acetoacetyl group-containing copolymer aqueous dispersion was obtained in the same manner as in Example 1 except that N 47.3 g, AA 2.5 g and AAEM 0.6 g were used and ADHZ 2.6 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.

However, the Tg of the copolymers of Example 4 and Comparative Example 3 to be described later is considerably higher than the Tg of the copolymers obtained in the other Examples and Comparative Examples. And the test sheet obtained in Comparative Example 3 is, compared with the test sheets obtained in other Examples and Comparative Examples,
Since its blocking resistance was small and the texture was extremely hard, it could not be uniformly compared with those of other Examples and Comparative Examples. The test sheet obtained in Example 4 was evaluated in comparison with the test sheet obtained in Comparative Example 3, and it was found that the test sheet obtained in Example 4 had the same resin composition as Comparative Example 3. The blocking resistance was obviously better than that of the above. The textures of both were almost the same.

Comparative Example 1 In Example 3, the monomer component MA and the monomer component M were used.
An acetoacetyl group-free copolymer aqueous dispersion was obtained in the same manner as in Example 3 except that AAEM was not copolymerized as B 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 2 An acetoacetyl 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 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 3 In a separable flask similar to that used in Example 1, deionized water 28
8 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 18
1.6g, EHA 153.0g, BA 31.1g, AN 100.6g, MAA 7.1g, A
A monomer mixture in which A 2.5 g and AAEM 4.16 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, cooled to room temperature, and added with 2.6 g of ADHZ as a hydrazine derivative
A uniform acetoacetyl group-containing copolymer aqueous dispersion having no core or shell was obtained.

Table 1 shows the monomer composition, 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. .

[0141]

[Table 1]

[0142]

[Table 2]

[0143]

[Table 3]

[0144]

The acetoacetyl group-containing copolymer aqueous dispersion of the present invention comprises a core portion composed of a (co) polymer having a specific glass transition point and an acetoacetyl group-containing monomer as an essential component for copolymerization thereof. An aqueous dispersion of multi-layer particles composed of a shell part composed of a copolymer contained as a component, wherein the glass transition point of the shell part copolymer is the glass transition point of the core part (co) polymer. It is higher, and the weight ratio of the core portion and the shell portion 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, it is made of, for example, natural fibers, recycled fibers, synthetic fibers or the like. It can be suitably 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 also has excellent blocking resistance. As a binder for pigment printing that gives a flexible printing cloth, and also as a binder for coating agents for flexible paper and fabrics that has excellent adhesiveness to substrates, heat resistance, etc., and for backing agents for carpets It is useful as a binder.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09D 5/00 PPU 131/02 PFR

Claims (1)

[Claims] 1. An aqueous dispersion containing acetoacetyl group-containing copolymer particles and a hydrazine derivative having a hydrazine residue and / or amines having two or more amino groups, wherein the copolymer is obtained. Particles are the following (A) and (B), (A) the following (a-1) to (a-3), (a-1) monomer represented by the following general formula (1) 60 to 100% by weight , [Chemical 1] (However, in the formula, R ¹ is hydrogen or a methyl group, and X is COO.
R ² , OCOR ³ , an aryl group having 6 to 8 carbon atoms or CN
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 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 an acetoacetyl group-containing monomer, and (a- 3) A monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, and 0 to 20 weight% of the monomer other than the above-mentioned monomer (a-2). % (However, the total of (a-1) to (a-3) is 100% by weight), and its glass transition point Tg _A is -60 to + 80 ° C. Core part, and (B) the following (b-1) to (b-3) and (b-1) 50 to 99.95% by weight of a monomer represented by the following general formula (1): (Wherein R ¹ and X are the same as above) (b-2) 0.05 to 30% by weight of an acetoacetyl group-containing monomer, and (b-
3) A monomer having at least one functional group in addition to one radically polymerizable unsaturated group in the molecule, and a monomer other than the above monomer (b-2) 0 to 20 weight %, (However, above (b-
1) to (b-3) in 100% by weight], the glass transition point Tg _{B of which} is −40 to + 100 ° C., and
The core (co) polymer has a Tg _A higher than that of the core and covers the core, and the shell is 5 to 100 parts by weight based on 100 parts by weight of the core.
An acetoacetyl group-containing copolymer aqueous dispersion, characterized in that it is part by weight.