JPH03269032A - Latex composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition for water-based printing inks, excel lent in fluidity, alcohol miscibility and antiblocking properties of films by carry ing out emulsion polymerization of an unsaturated monomer mixture containing a diene monomer in a specific proportion in the presence of a specified neutral resin in an aqueous medium. CONSTITUTION:The objective composition prepared by copolymerizing (B) 100 pts.wt. unsaturated monomer mixture composed of 7-80wt.% diene-based monomer and 93-20wt.% ethylenically unsaturated monomer in the presence of (A) 20-100 pts.wt. resin, obtained by copolymerizing an ethylenically unsaturat ed monomer mixture containing an ethylenically unsaturated carboxylic acid and neutralizing at least part of the resultant resin having 50-300 acid value in an aqueous medium.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel latex composition, and more specifically, the present invention relates to a novel latex composition, and more specifically, it has properties such as fluidity, alcohol miscibility, blocking resistance of coating film, adhesion, flexibility, etc. The present invention relates to a latex composition that has excellent properties and is suitable for water-based printing inks, non-slip varnishes, water-based flexo inks, etc.

[Prior Art] Conventionally, a diene latex obtained by emulsion polymerization of an unsaturated monomer mixture containing a diene monomer in the presence of a low-molecular emulsifier is known. Latex has a wide variety of uses, and is used in fields such as paper processing, fiber processing, paint (coating), various additives, and impregnation.

However, diene-based latexes obtained using low-molecular emulsifiers have insufficient fluidity, far from Newtonian flow (221 Tonian flow), and exhibit high structural viscosity. In applications, there are problems such as poor workability (and the inevitable occurrence of roll marks).Also, this latex has poor miscibility with alcohol, so hydrophilic organic solvents such as alcohol are added to it. In addition, when forming a coating film, it is difficult to balance rubber elasticity, blocking resistance, and adhesion, and increasing the proportion of diene monomer used Although the flexibility of the film is improved, blocking resistance and adhesion are reduced.Therefore, diene latexes obtained using conventionally known low-molecular emulsifiers have limited application in the coating field.

On the other hand, acrylic emulsions obtained using alkali-soluble resins (resins made water-soluble by neutralizing acidic resins with organic amines, ammonia, or alkaline inorganic compounds) as emulsifiers are known, and are used in water-based inks, coating agents, and paints. used in the field (for example, Japanese Patent Application Laid-Open No. 53-97083,
JP-A-50-157484, etc.). This acrylic emulsion has relatively good fluidity and alcohol miscibility. However, the coating film has high rigidity (and poor flexibility such as bending resistance).

In addition, an aqueous dispersion obtained by copolymerizing an ethylenically unsaturated monomer mixture in the presence of a neutralized water-soluble vinyl copolymer resin has been proposed as a coating agent for coating or paper printing gloss. (Special Publication No. 61-37282,
JP-A-62-282095, JP-A-62-28209
No. 6), Shikashi, and these aqueous dispersions have poor coating film flexibility and do not necessarily have sufficient blocking resistance or adhesion.

Recently, an alkali-soluble resin latex is first prepared by emulsion polymerization using a low-molecular-weight emulsifier, and then, in the presence of the alkali-soluble resin latex, unsaturated monomers mainly composed of hydrophobic monomers are emulsion-polymerized to form a latex. Methods have been proposed to obtain the
number, etc.).

However, the alkali-soluble resin latex obtained in an aqueous system by emulsion polymerization has a large molecular weight, and when used as an emulsifier, the latex has strong thickening properties (and has a low flowability improvement effect).

[Problem to be solved by the invention]

An object of the present invention is to provide a latex composition that is excellent in fluidity, alcohol miscibility, blocking resistance and adhesion of a coating film, and flexibility (bending resistance).

Another object of the present invention is to provide a latex composition that is particularly suitable for water-based printing inks, non-slip varnishes, water-based flexo inks, and the like.

As a result of intensive research to overcome the problems of the prior art, the present inventors have discovered that a specific range of monomers obtained by copolymerizing an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated carboxylic acid A resin obtained by neutralizing or partially neutralizing a resin having an acid value (neutralized resin (A); alkali-soluble resin) is used as an emulsion stabilizer, and in the presence of the neutralized resin, in an aqueous medium, It has been found that a latex composition having excellent properties can be obtained by emulsion polymerizing an unsaturated monomer mixture containing a specific proportion of diene monomers.

The latex composition of the present invention provides a highly flexible coating film that takes advantage of the characteristics of diene latex. In the present invention,
For diene latex with a low glass transition temperature Tg, Tg
By introducing an alkali-soluble resin (neutralized resin (A)) with a relatively high temperature of 20 to 80°C, characteristics such as latex fluidity, alcohol miscibility, coating film blocking resistance, and adhesion are imparted. It is something.

The present invention has been completed based on these findings.

[Means for Solving the Problems] Thus, according to the present invention, at least a resin having an acid value of 50 to 300 obtained by copolymerizing an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated carboxylic acid is used. In the presence of 20 to 100 parts by weight of partially neutralized resin (A), 7 to 80% by weight of diene monomer and 93 to 20% by weight of ethylenically unsaturated monomer in an aqueous medium. A latex composition is provided, characterized in that it is formed by copolymerizing 100 parts by weight of an unsaturated monomer mixture (B) consisting of:

The present invention will be explained in detail below.

[Neutralized Resin (A): Emulsion Stabilizer] In the present invention, as an emulsion stabilizer, an acid value obtained by copolymerizing an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated carboxylic acid is 50 to A resin (A) obtained by at least partially neutralizing a resin of No. 300 is used.

The resin (^) is prepared by first adding an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated carboxylic acid in a conventional manner.
It can be obtained by copolymerizing by solution polymerization or bulk polymerization, and then equivalence or partial neutralization of the carboxyl groups in the obtained copolymer with ammonia, organic amine, etc.

Examples of ethylenically unsaturated carboxylic acids include carboxyl group-containing ethylenically unsaturated monomers such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid. Further, dicarboxylic acid monoesters such as monooctyl maleate, monobutyl maleate, and monooctyl itaconate can also be used.

Examples of ethylenically unsaturated monomers other than ethylenically unsaturated carboxylic acids include styrene monomers such as styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene; methyl acrylate; , ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, n-amyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, 2-hydroxy acrylate Acrylic acid ester monomers such as ethyl, hydroxypropyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, in-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate , methacrylic acid ester monomers such as 2-ethylhexyl methacrylate, n-octyl methacrylate, 2-hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide, N
- Acrylamide monomers such as methylol acrylamide and N-butoxymethyl acrylamide; Methacrylamide monomers such as methacrylamide, N-methylol methacrylamide and N-butoxymethyl methacrylamide; glycidyl acrylate, glycidyl methacrylate, allyl Examples include glycidyl group-containing monomers such as glycidyl ether.

The ethylenically unsaturated monomer containing an ethylenically unsaturated carboxylic acid can be obtained by conventionally known solution polymerization or bulk polymerization, but solution polymerization is preferred because it can be easily made aqueous.

Examples of organic solvents for solution polymerization include methyl alcohol,
Alcohols such as ethyl alcohol, propyl alcohol, isopropyl alcohol, and butyl alcohol; Ethers such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; Esters such as methyl acetate and ethyl acetate; Aromatic hydrocarbons such as toluene and xylene, etc. can.

The polymerization conditions are usually in the presence of a radical polymerization initiator, a polymerization temperature of 50 to 150°C, and a polymerization time of about 1 to 10 hours.

The resin obtained by copolymerizing an ethylenically unsaturated monomer containing an ethylenically unsaturated carboxylic acid has an acid value of 50 to 300.
The acid value is preferably in the range of 80 to 200.

If the acid value is less than 50, the water solubility will not be sufficient even if it is neutralized, and the emulsion stability during polymerization of the unsaturated monomer mixture (B) containing the diene monomer will decrease. On the other hand, if the acid value is higher than 300, the water resistance and drying properties of the coating film will decrease, resulting in poor practicality.

Moreover, the weight average molecular weight of the resin is 3.000 to 50,
000, preferably in the range of 8.000 to 20.000. If the weight average molecular weight is too small,
Not only does the polymerization stability decrease, but a practical viscosity cannot be achieved. On the other hand, if the amount is too large, the viscosity of the latex becomes too high, which may cause aggregation during polymerization.

Contains ethylenically unsaturated carbonate as a copolymerization component,
As long as the acid value is within the above range, the type and composition of each monomer are not particularly limited. However, since the neutralizing resin (A) is used as an emulsion stabilizer and plays an important role in imparting properties to the latex composition for each application, the neutralizing resin (A) is It is preferable to have a composition that takes into account solubility and properties required for each application.

For example, if a monomer mixture containing a diene monomer (latex obtained by emulsion polymerization of Bl) contains a copolymer with a relatively low glass transition temperature (Tg), thermally speaking, the Tg is relatively low. By using a neutralized resin (A) having a composition that provides a copolymer with high properties, a latex composition with excellent blocking resistance can be obtained.

Therefore, the monomer composition of the neutralized resin (A) is, for example, 10 to 40% by weight of ethylenically unsaturated carboxylic acid, 10 to 75% by weight of (meth)acrylic acid ester monomer, and styrene monomer. It is preferably a monomer mixture containing 5 to 40% by weight of monomer and 0 to 10% by weight of (meth)acrylamide monomer. It is preferable to use such a monomer composition.

For neutralization, ammonia or organic amines are usually used as neutralizing agents. As the organic amine, for example, methylamine, ethylamine, isopropylamine, dimethylamine, N,N-dimethylethanolamine, diisopropylamine, trimethylamine, triethanolamine, etc. or a mixture thereof can be used. Water-soluble neutralizers may be used as an aqueous solution. Neutralization is carried out by equivalence or partial neutralization with carboxyl groups in the resin. In the case of partial neutralization, it is desirable that the degree of neutralization is 70 or more, more preferably 90 or more.

The neutralized resin (A) is dissolved or dispersed in water and used as an emulsion stabilizer. The resin obtained by solution polymerization in an organic solvent can be made into an aqueous dispersion (water-based) by adding water and removing the organic solvent by distilling it off, etc., at the same time as the neutralization treatment, or before or after the neutralization treatment. It is preferable for operation to do so. Further, it is preferable that the neutralized resin (A) is made into a water-soluble resin by equivalently neutralizing the carboxyl groups so that it acts as an emulsion stabilizer.

When the neutralized resin (A) is used as an aqueous solution or an aqueous dispersion, the resin concentration is usually preferably 20 to 30% by weight.

[Unsaturated Monomer Mixture (81)] In the present invention, a monomer mixture (B) consisting of 7 to 80% by weight of a diene monomer and 93 to 20% by weight of an ethylenically unsaturated monomer is used.

Z3-Eshiko 11 Examples of diene monomers include 1,3-butadiene, isoprene, 2,3-dimethyl-1°3-butadiene, and 1,3-pentadiene, particularly 1.3-butadiene. -Butadiene and/or isoprene are preferred.

Examples of the ethylene 1 ethylenically unsaturated monomer include styrene,
Styrenic monomers such as a-methylstyrene, vinyltoluene, pt-butylstyrene, chlorostyrene; methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, n-amyl acrylate , isoamyl acrylate, acrylic acid n
- Acrylic acid ester monomers such as hexyl, 2-ethylhexyl acrylate, n-octyl acrylate, 2-hydroxyethyl acrylate, and hydroxypropyl acrylate; methyl methacrylate, ethyl methacrylate,
Propyl methacrylate, butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, isoamyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate,
Methacrylic acid ester monomers such as 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate;
Acrylamide, N-methylolacrylamide, N-
Acrylamide monomers such as butoxymethylacrylamide; methacrylamide monomers such as methacrylamide, N-methylolmethacrylamide, and N-butoxymethylmethacrylamide; glycidyl groups such as glycidyl acrylate, glycidyl methacrylate, and allylglycidyl ether Containing monomers: (meth)acrylonitrile monomers such as acrylonitrile and methacrylonitrile;
Carboxyl group-containing monomers such as acrylic acid, methacrylic acid, crotonic acid, fumaric acid, maleic acid, and itaconic acid; Sulfonic acid group-containing monomers such as sodium styrene sulfonate and acrylamide methylpropanesulfonic acid; dimethylamino methacrylate Examples include amino group-containing monomers such as ethyl, diethylaminoethyl methacrylate, etc., and are not particularly limited as long as they are ethylenically unsaturated monomers that can be copolymerized with diene monomers.

The proportion of the diene monomer in the monomer mixture is 7 to 80% by weight, preferably 20 to 40% by weight. If the proportion of the diene monomer used is less than 7% by weight, the resulting latex composition may not have sufficient flexibility, or may not have the properties of a diene latex using the diene monomer. I can't perform. On the other hand, the proportion of diene monomer used is 80
When the amount exceeds 1% by weight, the coating film becomes too soft (too soft) and the anti-blocking property cannot be improved even if the neutralized resin (A) is used.

[Polymerization method] A method of polymerizing the unsaturated monomer mixture (B) containing a diene monomer in the presence of a neutralized resin (AJ) as an emulsion stabilizer is, for example, using a radical polymerization initiator. may be polymerized all at once in an aqueous medium, or may be preliminarily polymerized with a neutralized resin (A
) may be used to emulsify the unsaturated monomer mixture (B) and then continuously add it to the reactor for polymerization. however,
When used in the field of water-based printing inks, it is preferable to employ a -batch polymerization method in order to improve the strength of the coating film.

The polymerization temperature is 0 to 100°C, preferably 30 to 80°C,
Polymerization time is 1 to 20 hours.

Examples of radical polymerization initiators include aqueous initiators such as kawarum persulfate, ammonium persulfate, and hydrogen peroxide; benzoyl peroxide, di-t-butyl peroxide, and 2,2-azobis-2,4-dimethylvaleronitrile. Oil-soluble initiators; redox initiators in which peroxide is combined with reducing agents such as sodium bisulfite and triethanolamine; and the like.

The amount of the radical polymerization initiator used is usually in the range of 0.05 to 5 parts by weight per 100 parts by weight of the unsaturated monomer mixture (B), and it can be added all at once or in parts at the start of the reaction. good.

Further, a common emulsifier may be used in combination as long as the object of the present invention is not impaired.

Gel content (insoluble matter in tetrahydrofuran) is 20 to 8
A range of 0% by weight is preferred. Gel content is adjusted with molecular weight modifiers such as mercaptans, xanthogen disulfides, and halogenated hydrocarbons. Further, in order to prevent the gel content from increasing after one polymerization, a terminator such as sodium nitrite, hydroxylamine sulfate, N,N-diethylhydroxylamine, etc. may be added at the end of the polymerization.

The mixing ratio of the neutralized resin (A) and the monomer mixture (B) is
Neutralized resin (A) is added to 100 parts by weight of monomer mixture (B).
)20 to 100 parts by weight, preferably 20 to 50 parts by weight.

Furthermore, an alkali-soluble resin may be added to the latex composition as necessary. As the alkali-soluble resin, a resin corresponding to the neutralized resin (A) used as an emulsion stabilizer is suitable. The amount used is the total amount including the neutralized resin (A) used as an emulsion stabilizer during polymerization, and the amount used is the total amount of the monomer mixture FB.
) 20 to 900 parts by weight or less, preferably 25 to 100 parts by weight, relative to 100 parts by weight.

Overall, the proportion of neutralized resin (A) used is too high (if it is too large, the drying rate of the latex composition will be slow and the water resistance of the coating will be reduced. Conversely, the proportion of neutralized resin (A) used) is If the amount of neutralizing resin (A) is too small from the polymerization stage, the particle size will not only increase, but also the emulsion stability during polymerization will decrease.Also, if the overall proportion of the neutralizing resin (A) used is too small, the leveling property after coating will deteriorate. becomes insufficient.

In addition, the latex composition of the present invention may contain, if necessary,
Acrylic emulsion, vinyl acetate emulsion, and various other additives can be blended. Further, water-compatible solvents such as alcohols, cellosolves, glycols, and glycerin may be added as appropriate depending on the purpose of use, such as improving drying properties and film-forming properties.

〔Effect of the invention〕

The latex composition of the present invention has many excellent characteristics as described below, and is particularly suitable for the field of coatings such as water-based printing inks.

(1) Fluidity can be brought close to Newtonian flow.

(2) Since it has excellent miscibility with alcohol, addition of alcohol not only makes it possible to bring the fluidity closer to Newtonian flow, but also increases the drying rate.

(3) By selecting a neutralized resin (A) with a relatively high Tg, blocking resistance can be improved.

(4) By selecting the neutralized resin (A), it is possible to improve the adhesion to various materials (subjects to be coated).

(5) The rigidity, which is a drawback of coating films using acrylic emulsions, can be improved by using diene latex (B).

(The following is a blank space) [Example] The present invention will be specifically described below with reference to Examples, Reference Examples, and Comparative Examples. In addition, parts and percentages in these examples are
Unless otherwise specified, measurements are based on weight.

<Methods for measuring physical properties> The methods for measuring various physical properties in Examples and Comparative Examples are as follows.

1: Calculated as the number of mg of potassium hydroxide required to neutralize (titrate) 1 g of resin using phenolphthalein as an indicator.

7JL Uni! I■1: Changes in viscosity of latex compositions to which alcohol had been added were examined and evaluated in three stages: 1st;

×: The viscosity change is more than double that immediately after a reaction and after 3 months.

Δ: The viscosity change immediately after mixing and after 3 months is in the range of 10% to 50%.

O: The viscosity change immediately after mixing and after 3 months is within 10%.

After coating the paper with latex and drying it, the coating layers are stacked on top of each other for 24 hours.
The ease of peeling after being left for a period of time was investigated. The storage conditions were 40℃,
The relative humidity is 80% and the load is 500 g/cd.

The ease of peeling was evaluated on the following four levels and used as an index of blocking resistance.

X: The coating layer is destroyed when peeled off.

△: Peels off when removed by hand.

○: Easily peels off when touched.

0: It peels off extremely easily when touched.

tJu: The viscosity is measured using a B-type viscometer at 60 r, p, m and 6 r, p, m, and is expressed as a ratio.

[Viscosity at 6r, p, n+, / Viscosity at 60 r, p, m,] ￥; JLf1 = Corona discharge treated polyester discharge treated polyethylene sheet paper, dried at room temperature, then applied to cellophane tape manufactured by Chill 2 Co., Ltd. , width 12 mm) and rub it firmly with your thumb five times. Thereafter, the cellophane tape was gradually peeled off, and then suddenly peeled off halfway to evaluate the degree of peeling of the ink film.

×: The coated surface is almost peeled off.

△: Approximately half of the coated surface peels off.

○: The coated surface hardly peels off.

0: The coated surface does not peel off at all.

-&: Apply latex to corona discharge treated polyethylene coated paper, dry at room temperature, and then apply the printed surface 1 to 3 times 3 to 5 times.
The degree of peeling of the coating layer was evaluated by bending it at an angle of 80°.

×: The coated surface is almost peeled off.

△: Approximately half of the coated surface peels off.

○: The coated surface hardly peels off.

0: The coated surface does not peel off at all.

The coating method is to coat paper or treated polyethylene coated paper using a N016 wire bar.

[Reference Example 1] A of A 100 parts of isopropyl alcohol was charged into a reactor and 80 parts of isopropyl alcohol was charged into a reactor.
℃, 100 parts of the ethylenically unsaturated monomer mixture shown in Table 1 and 4 parts of 2,2-azobis-2,4-dimethylvaleronitrile/12.5 parts of toluene as radical polymerization initiators, respectively. Continuous additions were made to the reactor over a period of 4 hours. Thereafter, the reaction continued for 2 hours until the polymerization was completed.

After cooling the reactor, add 4 of the ammonia water and resin necessary for neutralization.
Add twice the amount (weight ratio) of water, then heat to 90°C or higher, distill off isopropyl alcohol and excess water, and aqueous neutralized resins (A-1) to (A- 7
) was obtained.

Table 1 shows the charged composition of the ethylenically unsaturated monomer mixture, the acid value and weight average molecular weight of the resin.

(Margin below) [Examples 1 to 4, Comparative Examples 1 to 2] In a pressure-resistant container with contents of 1 lρ in width, 70 parts of water and aqueous neutralized resin (
A-1) 80 parts (concentration 25%; 20 parts as resin), 0.05 parts of ethylenediaminetetraacetic acid tetrasodium salt as a chelating agent and 0.0 parts of potassium persulfate as a polymerization initiator.
．． 02 parts, 100 parts of each monomer shown in Table 2, and a molecular weight regulator (tertiary dodecyl mercaptan) were charged, and porous polymerization was carried out with stirring at 60° C. to obtain a latex composition.

The conversion rate of monomers into polymers was 90% or more in all cases. After polymerization, unreacted monomers were distilled off under reduced pressure to obtain a latex with a solid content concentration of 45%.

The measurement results of the physical properties of the latex are summarized in Table 4.

(Left below) [Examples 5 to 9, Comparative Examples 3 to 5] In the same manner as in Example 1, latex compositions were obtained by changing the type and amount of the aqueous neutralizing resin as shown in Table 3. . As in Example 1, the monomer mixture contained 30 parts of butadiene,
35 parts of styrene and 35 parts of methyl methacrylate were used.

The polymerization conversion rates were all 90% or higher. A latex composition with a solid content of 45% was prepared in the same manner as in Example 1. In Example 7, the aqueous neutralized resin (A-1) (concentration 25%) was
An additional 30 parts was added to 100 parts of the latex in terms of solid content (parts by dry weight) to obtain a latex composition with a solid content of 38%.

The measurement results of the physical properties of the latex are summarized in Table 4. In addition, in Comparative Examples 3 to 5, a large amount of aggregates were generated during polymerization, and it was not possible to obtain a latex that could be used for practical purposes, so they are not shown in Table 4.

(Margins below C) [Comparative Example 6] In a pressure-resistant container with an internal volume of 1 cm, 100 parts of water, 1.0 part of sodium dodecylbenzenesulfonate as an emulsifier, and uncontained salt (
30 parts of butadiene, 35 parts of styrene, 3 parts of methyl methacrylate, along with 0.5 parts of sodium salt of ethylenediaminetetraacetic acid as a chelating agent and 1.0 parts of persulfate as a polymerization initiator.
5 parts and 0.7 parts of a molecular weight regulator (tertiary dodecyl mercaptan) were charged, and polymerized at 60°C. After polymerization, unreacted monomers were distilled off under reduced pressure to obtain a latex with a solid content of 50%.

The evaluation results of the obtained latex are shown in Table 4.

[Comparative Example 7] 60 parts of deionized water and 5 parts of aqueous neutralized resin (A-7) as an emulsion stabilizer (resin content ) (A-7)
An aqueous solution of was charged and the temperature was maintained at 70°C while stirring.

In a nitrogen gas stream, a vinyl stopper mixture consisting of 20 parts of styrene, 45 parts of methyl methacrylate, and 35 parts of 2-ethylhexyl acrylate was pre-neutralized with the resin (A to 7).
A dispersion emulsified with 140 parts of a 25% aqueous solution of 1.5 parts of ammonium persulfate and a solution of 1.5 parts of ammonium persulfate dissolved in 15 parts of deionized water were separately added dropwise continuously over 3 hours to a reactor heated to 70°C. . After the dropwise addition, the reaction was continued at 85° C. for 2 hours to obtain an aqueous dispersion with a solid content of 40%.

Table 4 shows the evaluation results of the obtained latex.

(The following is a blank space) As is clear from Table 4, the latex composition of the present invention exhibits excellent performance in all of fluidity, alcohol miscibility, blocking resistance, adhesion, and bending resistance.

On the other hand, when the proportion of butadiene in the monomer mixture (B) is too small (Comparative Example 1), the adhesion and bending resistance are poor, and when it is too large (Comparative Example 2), the The latex obtained by polymerization using a low-molecular emulsifier (Comparative Example 6) has insufficient fluidity, and has poor alcohol miscibility, blocking resistance, and adhesion. It has a strong adhesiveness.

In addition, the latex (Comparative Example 7) obtained by polymerizing ethylenically unsaturated monomers that do not contain diene monomers in the presence of aqueous neutralized resin (A) as an emulsifier has good bending resistance (poor Flexibility) is poor, and blocking resistance and adhesion are also insufficient.

In addition, for Comparative Examples 3 to 4 in which the neutralization resin value shown in Table 3 is outside the range of the present invention, or Comparative Example 5 in which the amount of neutralized resin used is too small, as described above, the polymerization A large amount of agglomerates are generated in the process, making it impossible to obtain a practical latex.

Claims (2)

[Claims] (1) The acid value obtained by copolymerizing an ethylenically unsaturated monomer mixture containing an ethylenically unsaturated carboxylic acid is 50 to 3.
In the presence of 20 to 100 parts by weight of resin (A) obtained by at least partially neutralizing the resin No. 00, 7 to 80 weight % of a diene monomer and an ethylenically unsaturated monomer Unsaturated monomer mixture (B) 1 consisting of 93 to 20% by weight
A latex composition characterized by copolymerizing 0.00 parts by weight. (2) The latex composition according to claim 1 is further blended with the neutralized resin (A) to form a monomer mixture (B) of 100%
A latex composition in which the total amount of neutralized resin (A) used is more than 20 parts by weight and less than 900 parts by weight.