JP7036377B2 - Resin composition for printing pretreatment - Google Patents

Description

The present disclosure relates to a resin composition for printing pretreatment.

Techniques for printing on cloth using water-based inks are known. Generally, in printing on a cloth, a decrease in designability (decrease in image sharpness) due to fluffing on the surface of the cloth becomes a problem. Therefore, before printing an image on the cloth, a pretreatment liquid is applied to the surface of the cloth, and various pretreatment liquids have been developed.

For example, Patent Document 1 discloses an aqueous base material pretreatment material containing a nonionic acrylic, a water-soluble polyvalent metal, an organic acid component and / or an inorganic acid component.
Patent Document 2 discloses a binder composition for forming an ink adsorption layer (so-called pretreatment liquid) containing inorganic porous fine particles, a fixing agent (for example, an acrylic resin) and the like.
Patent Document 3 describes fine particles of an acrylic copolymer obtained by emulsifying and copolymerizing a carboxy group-containing monomer, an epoxy group-containing monomer, and the like in the presence of a succinate ester-type anionic copolymerizable surfactant. However, an aqueous composition of an acrylic copolymer for printing, which contains fine particles having a specific glass transition temperature (Tg) and an average particle size, is disclosed.
Patent Document 4 discloses a treatment liquid for an ink holding layer containing an acrylic copolymer and a water-soluble organic solvent (for example, polyethylene glycol).

Special Table 2017-517640 Japanese Unexamined Patent Publication No. 2016-117975 Japanese Unexamined Patent Publication No. 2005-139340 Japanese Unexamined Patent Publication No. 2005-154936

By the way, a crosslinked resin emulsion is used as a pretreatment liquid used for cloth printing (so-called printing) using water-based ink. That is, by cross-linking the resin emulsion, fluffing on the surface of the cloth before printing the image is suppressed, and the deterioration of the design (the deterioration of the sharpness of the image) is improved.

Inorganic metal salts are generally used as the metal-based cross-linking agent in the pretreatment liquid. However, when the pretreatment liquid contains the emulsion particles of the resin and the inorganic metal salt, a cross-linking reaction may occur between the emulsion particles of the resin and the inorganic metal salt, and aggregates may be generated.
Further, it is desirable that the film formed on the surface of the cloth by the pretreatment liquid is as thin as possible from the viewpoint of enhancing the sharpness of the image printed after the treatment, and for that purpose, the concentration of the resin emulsion used in the pretreatment liquid. Needs to be adjusted low. As the solvent, a mixed solvent of water and a water-soluble organic solvent (for example, a glycol-based solvent) is generally used as the pretreatment liquid. In this case, as the proportion of water in the mixed solvent increases, the surface tension of the pretreatment liquid increases, and the permeability of the pretreatment liquid to the cloth changes, so that a uniform film is formed on the surface of the cloth. It becomes difficult and cannot function as a pretreatment liquid for printing.
On the other hand, if a mixed solvent having a large proportion of a water-soluble organic solvent (for example, a glycol-based solvent) is used in order to adjust the concentration of the resin emulsion in the pretreatment liquid to be low, the pretreatment liquid may thicken.

If agglomerates are generated in the pretreatment liquid or the pretreatment liquid is thickened, for example, in screen printing, there may be a problem that mesh clogging occurs. Further, for example, in inkjet printing, there may be a problem that nozzle clogging occurs. When these problems occur, the amount of the pretreatment liquid applied cannot be controlled, so that it becomes difficult to form a uniform film on the surface of the cloth, and the function as the pretreatment liquid for printing cannot be exhibited.

Further, in general, the pretreatment liquid used for printing is required to prevent the film formed on the surface of the cloth from peeling off when washed (so-called washing resistance).

Regarding the above points, the pretreatment liquids described in Patent Documents 1 to 4 do not pay attention to the problem of miscibility with inorganic metal salts and water-soluble organic solvents. Further, there is room for further improvement in the washing resistance of the film formed by using the pretreatment liquids described in Patent Documents 1 to 4.

The problem to be solved by the present invention is a resin composition for printing pretreatment that can form a film having excellent miscibility with an inorganic metal salt and a water-soluble organic solvent (for example, a glycol-based solvent) and excellent washing resistance. To provide things.

Specific means for solving the above problems include the following aspects.
<1> A structural unit derived from a (meth) acrylic acid alkyl ester monomer, a structural unit derived from a monomer having a crosslinkable functional group, and an anion-type reactive surfactant having an ethylenically unsaturated double bond. Resin particles having a constituent unit derived from, and a constituent unit derived from a nonionic reactive surfactant having an ethylenically unsaturated double bond, and
Aqueous medium and
A resin composition for pretreatment for printing.
<2> Both the anion-type reactive surfactant and the nonionic-type reactive surfactant have an oxyalkylene group, and the average number of moles of the oxyalkylene group contained in the anion-type reactive surfactant. The resin composition for printing pretreatment according to <1>, wherein a and the average number of moles of oxyalkylene groups added by the nonionic reactive surfactant b satisfy the following formula (1).
b> a ... Equation (1)
<3> The average number of moles of oxyalkylene group added by the anion-type reactive surfactant and the average number of moles of oxyalkylene group added by the nonionic reactive surfactant are the following formula (2). The resin composition for printing pretreatment according to <2>, which satisfies the above conditions.
1.5 ≦ b / a ≦ 5.0 ・ ・ ・ Equation (2)

According to the present invention, there is provided a resin composition for printing pretreatment capable of forming a film having excellent miscibility with an inorganic metal salt and a water-soluble organic solvent (for example, a glycol-based solvent) and excellent washing resistance. To.

Hereinafter, specific embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention.

The numerical range indicated by using "-" in the present specification means a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. .. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the value shown in the examples.
In the present specification, a combination of two or more preferred embodiments is a more preferred embodiment.
In the present specification, the amount of each component means the total amount of a plurality of kinds of substances when there are a plurality of kinds of substances corresponding to each component, unless otherwise specified.

As used herein, "(meth) acrylic" is a term that includes both acrylic and methacrylic, and "(meth) acrylate" is a term that includes both acrylate and methacrylate, and is a "(meth) acryloyl group." Is a term that includes both acryloyl and methacryloyl groups.

In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Is done.

Specific examples of the inorganic metal salt include magnesium sulfate, calcium sulfate, calcium carbonate, aluminum acetate, calcium nitrate, aluminum nitrate, calcium silicate, magnesium silicate and the like.
Examples of the "water-soluble organic solvent" in the present specification include glycol-based solvents. As used herein, the term "glycol-based solvent" refers to a solvent having a structure in which one hydroxyl group is substituted for each of two or more carbon atoms of a hydrocarbon.

The "washing resistance" in the present specification includes resistance to washing with water (so-called wet cleaning) (hereinafter, also referred to as "wet cleaning resistance") and washing with a solvent (so-called dry cleaning). (Hereinafter referred to as "dry cleaning resistance") and both are included.

[Resin composition for printing pretreatment]
The resin composition for printing pretreatment of the present invention (hereinafter, also simply referred to as “resin composition”) is a structural unit derived from a (meth) acrylic acid alkyl ester monomer, a monomer having a crosslinkable functional group. A structural unit derived from, an anionic reactive surfactant having an ethylenically unsaturated double bond (hereinafter, also simply referred to as “anionic reactive surfactant”), and an ethylenically unsaturated constituent unit. Resin particles having a structural unit derived from a nonionic reactive surfactant having a double bond (hereinafter, also simply referred to as “nonionic reactive surfactant”) (hereinafter, also referred to as “resin particles”). A resin composition containing an aqueous medium and an aqueous medium.

The resin composition of the present invention is a resin composition used for pretreatment for printing, and is a structural unit derived from a (meth) acrylic acid alkyl ester monomer and a configuration derived from a monomer having a crosslinkable functional group. So-called resin particles having a unit, a structural unit derived from an anionic reactive surfactant, and a structural unit derived from a nonionic reactive surfactant may exist in a dispersed state in an aqueous medium. , Resin emulsion.
The resin composition of the present invention can be suitably used as it is as a pretreatment liquid for printing and as a raw material for a pretreatment liquid for printing.
According to the resin composition of the present invention, a film having excellent miscibility with an inorganic metal salt and a water-soluble organic solvent (for example, a glycol-based solvent) and having excellent washing resistance can be formed.
Although it is not clear why the resin composition of the present invention can exert such an effect, the present inventors speculate as follows.

Inorganic metal salts are generally used as the metal-based cross-linking agent in the pretreatment liquid. However, when the pretreatment liquid contains the emulsion particles of the resin and the inorganic metal salt, a cross-linking reaction may occur between the emulsion particles of the resin and the inorganic metal salt, and aggregates may be generated.
In the resin emulsion used for the pretreatment liquid, a surfactant is used to form the emulsion particles of the resin. When a non-reactive surfactant is used as the surfactant, the non-reactive surfactant is physically adsorbed on the resin particles. The non-reactive surfactant physically adsorbed on the resin particles is in an equilibrium state between the state of being adsorbed on the resin particles and the state of being separated from the resin particles in the aqueous medium. In the undiluted solution of the resin emulsion, the non-reactive surfactant is predominantly adsorbed on the resin particles, so that the emulsion particles of the resin are stable, but the non-reactive surfactant in the aqueous medium is relatively hot. In the pretreatment liquid in which the proportion is small, the probability that the non-reactive surfactant is separated from the resin particles increases, so that the emulsion particles of the resin become unstable. Then, in the pretreatment liquid, a cross-linking reaction may occur between the emulsion particles of the resin from which the non-reactive surfactant has been removed and the inorganic metal salt, and aggregates may be generated. When agglomerates are generated in the pretreatment liquid, for example, in screen printing, there may be a problem that mesh clogging occurs. Further, in inkjet printing, there may be a problem that nozzle clogging occurs. When these problems occur, the pretreatment liquid cannot be applied, or the amount of the pretreatment liquid applied cannot be controlled. As a result, it becomes difficult to form a uniform film on the surface of the cloth, and the function as a pretreatment liquid for printing cannot be exhibited.

On the other hand, in the resin composition of the present invention, a reactive surfactant is used for forming resin particles (resin emulsion particles; hereinafter the same). The reactive surfactant forms resin particles by chemically bonding (specifically, covalently bonding) with the monomer forming the resin. That is, in the resin particles contained in the resin composition of the present invention, a monomer [(meth) acrylic acid alkyl ester monomer and a monomer having a crosslinkable functional group] and a reactive surfactant (anionic reaction) Since it is copolymerized with the sex surfactant and the nonionic reactive surfactant), it is difficult for the surfactant to come off even when the resin composition is diluted. Therefore, it is considered that the resin composition of the present invention is unlikely to generate agglomerates when mixed with an inorganic metal salt.

Further, it is desirable that the film formed on the surface of the cloth by the pretreatment liquid is as thin as possible from the viewpoint of enhancing the sharpness of the image printed after the treatment, and for that purpose, the concentration of the resin emulsion used in the pretreatment liquid. Needs to be adjusted low. As the solvent, a mixed solvent of water and a water-soluble organic solvent (for example, a glycol-based solvent) is generally used as the pretreatment liquid. In this case, as the proportion of water in the mixed solvent increases, the surface tension of the pretreatment agent increases, and the permeability of the pretreatment liquid to the cloth changes, so that a uniform film is formed on the surface of the cloth. It becomes difficult and cannot function as a pretreatment liquid for printing.
On the other hand, if a mixed solvent having a large proportion of a water-soluble organic solvent (for example, a glycol-based solvent) is used in order to adjust the concentration of the resin emulsion in the pretreatment liquid to a low level, the pretreatment liquid may thicken. The thickening of the pretreatment liquid causes the same problems as when agglomerates are generated in the pretreatment liquid. As a result, it becomes difficult to form a uniform film on the surface of the cloth, and the function as a pretreatment liquid for printing cannot be exhibited.

On the other hand, in the resin composition of the present invention, since the resin particles have a structural unit derived from an anionic reactive surfactant and a structural unit derived from a nonionic reactive surfactant, the anionic reactive surfactant has an anionic reactive surfactant. The electrochemical action of the agent (so-called charge repulsion) and the physical action of the nonionic reactive surfactant (for example, physical damage due to alkylene oxide chains, etc.) are synergistic with respect to the resin particles. Work on. As a result, in the resin composition of the present invention, it is considered that the resin particles can be dispersed in the aqueous medium in a very stable state. Therefore, it is considered that the resin composition of the present invention is difficult to thicken as a result of maintaining the dispersion stability of the resin particles even when miscible with a water-soluble organic solvent (for example, a glycol-based solvent).

In the resin composition of the present invention in a liquid state before forming a film, resin particles and an inorganic metal are subjected to an electrochemical action by an anionic reactive surfactant and a physical action by a nonionic reactive surfactant. The cross-linking reaction with the salt is hindered. When the resin composition of the present invention in a liquid state is applied to the surface of a cloth and the formed coating film is dried, resin particles having a structural unit derived from a monomer having a crosslinkable functional group are formed in the film. It is considered that an appropriate cross-linking reaction occurs because the inorganic metal salt is tightly packed. As described above, the resin composition of the present invention has excellent miscibility with inorganic metal salts and water-soluble organic solvents (for example, glycol-based solvents), and can form a uniform coating film on the surface of the cloth, and thus is crosslinked. It is unlikely that variations will occur. As a result, the formed film is considered to have excellent washing resistance.

It should be noted that the above guess does not limitly interpret the effect of the resin composition of the present invention, but is described as an example.

Hereinafter, each component of the resin composition of the present invention will be described.

[Resin particles]
The resin constituting the resin particles contained in the resin composition of the present invention is a structural unit derived from a (meth) acrylic acid alkyl ester monomer, a structural unit derived from a monomer having a crosslinkable functional group, and an anion type. It has a structural unit derived from a reactive surfactant and a structural unit derived from a nonionic reactive surfactant.
First, the constituent units of the resin will be described.

<Constituent unit derived from (meth) acrylic acid alkyl ester monomer>
The resin has a structural unit derived from the (meth) acrylic acid alkyl ester monomer.
The structural unit derived from the (meth) acrylic acid alkyl ester monomer contributes to the improvement of the toughness of the formed film.

As used herein, the term "constituent unit derived from the (meth) acrylic acid alkyl ester monomer" means a structural unit formed by addition polymerization of the (meth) acrylic acid alkyl ester monomer.

As the (meth) acrylic acid alkyl ester monomer, an unsubstituted (meth) acrylic acid alkyl ester monomer is preferable, and the type thereof is not particularly limited.
The alkyl group of the (meth) acrylic acid alkyl ester monomer may be linear, branched or cyclic.
The number of carbon atoms of the alkyl group of the (meth) acrylic acid alkyl ester monomer is preferably in the range of 1 to 12, more preferably in the range of 1 to 8, and even more preferably in the range of 1 to 4.

Specific examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, and s-butyl (meth). Acrylate, t-butyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) acrylate, i-nonyl (meth) acrylate, Examples thereof include n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.
Among these, examples of the (meth) acrylic acid alkyl ester monomer include methyl acrylate (MA), ethyl acrylate (EA), n-butyl acrylate (n-BA), methyl methacrylate (MMA), and ethyl methacrylate. At least one selected from the group consisting of (EMA) is preferable, and at least one selected from the group consisting of ethyl acrylate (EA), n-butyl acrylate (n-BA), and methyl methacrylate (MMA) is more preferable. A combination of n-butyl acrylate (n-BA) and methyl methacrylate (MMA) or a combination of n-butyl acrylate (n-BA) and ethyl acrylate (EA) is more preferable, and n-butyl acrylate (n-) is more preferable. A combination of BA) and methyl methacrylate (MMA) is particularly preferred.

The resin may have only one type of structural unit derived from the (meth) acrylic acid alkyl ester monomer, or may have two or more types.

The ratio (content rate) of the structural unit derived from the (meth) acrylic acid alkyl ester monomer in the resin is, for example, the structural unit of the resin (provided that the anionic reactive surfactant and the nonionic reactive surfactant are used. 55% by mass or more is preferable, 65% by mass or more is more preferable, and 75% by mass or more is further preferable, based on the total mass of the constituent units derived from the reactive surfactant contained therein.
The proportion (content) of the structural unit derived from the (meth) acrylic acid alkyl ester monomer in the resin is the reaction including the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant). When it is 55% by mass or more with respect to the total mass of the constituent units derived from the sex surfactant), the toughness of the formed film tends to be further improved. Increasing the toughness of the membrane can improve wet cleaning resistance.
The proportion (content rate) of the structural unit derived from the (meth) acrylic acid alkyl ester monomer in the resin is, for example, the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant). 98% by mass or less is preferable, and 95% by mass or less is more preferable, with respect to the total mass of the constituent units derived from the reactive surfactant containing the agent.

<Constituent unit derived from a monomer having a crosslinkable functional group>
The resin has a structural unit derived from a monomer having a crosslinkable functional group.
The structural units derived from the monomer having a crosslinkable functional group are miscibility with an inorganic metal salt, miscibility with a water-soluble organic solvent (for example, a glycol-based solvent), and washing resistance of the formed film. Contribute to improvement.

As used herein, the "constituent unit derived from a monomer having a crosslinkable functional group" means a structural unit formed by addition polymerization of a monomer having a crosslinkable functional group.

The crosslinkable functional group is not particularly limited as long as it is a functional group capable of forming a crosslinked structure by a crosslinking reaction with a crosslinking agent, and for example, a carboxy group, a ketone group, a hydroxyl group, an amide group, an N-substituted amide group, and the like. Examples thereof include functional groups such as an epoxy group.
As the crosslinkable functional group, for example, at least one selected from the group consisting of a carboxy group, a hydroxyl group, an amide group, and an N-substituted amide group is preferable from the viewpoint of reactivity with a crosslinker and a crosslink density, and an inorganic metal is preferable. From the viewpoint of compatibility with salts and water-soluble organic solvents (for example, glycol-based solvents), at least one selected from a carboxy group and a hydroxyl group is more preferable, and a carboxy group is even more preferable.

The type of the monomer having a carboxy group is not particularly limited.
Specific examples of the monomer having a carboxy group include (meth) acrylic acid, crotonic acid, maleic anhydride, fumaric acid, itaconic acid, glutaconic acid, citraconic acid, and ω-carboxy-polycaprolactone (n≈2) mono. Examples include (meth) acrylate.
Among these, the monomer having a carboxy group includes, for example, a group consisting of acrylic acid (AA), methacrylic acid (MAA), and itaconic acid (IA) from the viewpoint of reactivity with a cross-linking agent and cross-linking density. At least one selected from the above is preferable, and acrylic acid (AA) is more preferable from the viewpoint of miscibility with an inorganic metal salt and a water-soluble organic solvent (for example, a glycol-based solvent).

The type of the monomer having a ketone group is not particularly limited.
Specific examples of the monomer having a ketone group include diacetone acrylamide (DAAD) and the like.

The type of the monomer having a hydroxyl group is not particularly limited.
Specific examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-. Hydroxyhexyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, 3-methyl-3-hydroxybutyl (meth) acrylate, 1,1-dimethyl-3-hydroxybutyl (meth) ) Acrylate, 1,3-dimethyl-3-hydroxybutyl (meth) acrylate, 2,2,4-trimethyl-3-hydroxypentyl (meth) acrylate, 2-ethyl-3-hydroxyhexyl (meth) acrylate, glycerin mono Examples thereof include (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, and poly (ethylene glycol-propylene glycol) mono (meth) acrylate.

The type of the monomer having an amide group or an N-substituted amide group is not particularly limited.
Specific examples of the monomer having an amide group or an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N. -Ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, Nt-butyl acrylamide, N-octyl acrylamide and the like can be mentioned.

The resin may have only one type of structural unit derived from the monomer having a crosslinkable functional group, or may have two or more types.

The ratio (content rate) of the structural unit derived from the monomer having a crosslinkable functional group in the resin is, for example, the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant described later). 0.1% by mass or more is preferable, 0.5% by mass or more is more preferable, and 1% by mass or more is further preferable with respect to the total mass of the constituent units derived from the reactive surfactant containing.).
The ratio (content rate) of the structural unit derived from the monomer having a crosslinkable functional group in the resin includes the structural unit of the resin (provided that the anionic reactive surfactant and the nonionic reactive surfactant described later are included. When it is 0.1% by mass or more with respect to the total mass of (excluding the structural units derived from the reactive surfactant), the washing resistance of the formed film tends to be more excellent.
Further, the ratio (content rate) of the structural unit derived from the monomer having a crosslinkable functional group in the resin is, for example, the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive interface described later). 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is further preferable, based on the total mass of the constituent units derived from the reactive surfactant containing the activator.
The ratio (content rate) of the structural unit derived from the monomer having a crosslinkable functional group in the resin includes the structural unit of the resin (provided that the anionic reactive surfactant and the nonionic reactive surfactant described later are included. When it is 20% by mass or less with respect to the total mass of (excluding the structural units derived from the reactive surfactant), the copolymerizability with the (meth) acrylic acid alkyl ester monomer tends to be further improved. .. In addition, the formed film tends to be more stretchable, which is suitable for the pretreatment film for printing.

<Constituent unit derived from vinyl cyanide monomer>
The resin may have a structural unit derived from the vinyl cyanide monomer.
The structural units derived from the vinyl cyanide monomer contribute to the improvement of the dry cleaning resistance of the formed film.

As used herein, the "constituent unit derived from the vinyl cyanide monomer" means a structural unit formed by addition polymerization of the vinyl cyanide monomer.

Specific examples of the vinyl cyanide monomer include acrylonitrile (AN) and methacrylonitrile.
Among these, as the vinyl cyanide monomer, for example, acrylonitrile (AN) is preferable from the viewpoint that the dry cleaning resistance of the formed film can be further improved.

When the resin has a structural unit derived from the vinyl cyanide monomer, the resin may have only one type of structural unit derived from the vinyl cyanide monomer, or may have two or more types.

When the resin has a structural unit derived from the vinyl cyanide monomer, the proportion (content rate) of the structural unit derived from the vinyl cyanide monomer in the resin is, for example, the structural unit of the resin (however, the anion described later). 2% by mass or more is preferable, and 5% by mass or more is more preferable with respect to the total mass of the reactive surfactant including the type-reactive surfactant and the nonionic-type reactive surfactant. It is preferable, and 10% by mass or more is more preferable.
The proportion (content rate) of the structural unit derived from the vinyl cyanide monomer in the resin is the structural unit of the resin (however, the reactive interface containing the anionic reactive surfactant and the nonionic reactive surfactant described later). When it is 2% by mass or more with respect to the total mass of the constituent units derived from the activator), the dry cleaning resistance of the formed film tends to be more excellent.
The ratio (content rate) of the structural unit derived from the vinyl cyanide monomer in the resin is, for example, the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant described later). 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on the total mass of the constituent units derived from the reactive surfactant contained therein.
The proportion (content rate) of the structural unit derived from the vinyl cyanide monomer in the resin is the structural unit of the resin (however, the reactive interface containing the anionic reactive surfactant and the nonionic reactive surfactant described later). When it is 25% by mass or less with respect to the total mass of (excluding the structural units derived from the activator), the reactivity with the (meth) acrylic acid alkyl ester monomer and the monomer having a crosslinkable functional group is possible. Tends to improve.

<Constituent units derived from other monomers>
The resin is a structural unit derived from a (meth) acrylic acid alkyl ester monomer, a monomer having a crosslinkable functional group, and a monomer other than the vinyl cyanide monomer (hereinafter, “other monomers”). It may also have a "constituent unit derived from").
The "monomer" referred to in the present specification does not include a reactive surfactant.

The types of other monomers are not particularly limited.
Specific examples of other monomers include aromatic monovinyls [styrene, α-methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, vinyltoluene, etc.], vinyl esters [vinyl formate, vinyl acetate, etc.]. Vinyl propionate, vinyl versaticate, etc.], various derivatives of these monomers, and the like can be mentioned.

When the resin has a structural unit derived from another monomer, the resin may have only one type of structural unit derived from the other monomer, or may have two or more types.

<Constituent unit derived from anionic reactive surfactant>
The resin has a structural unit derived from an anionic reactive surfactant.
The structural unit derived from the anionic reactive surfactant contributes to the improvement of miscibility with an inorganic metal salt and a water-soluble organic solvent (for example, a glycol-based solvent).

As used herein, the term "constituent unit derived from an anionic reactive surfactant" means a structural unit formed by addition polymerization of an anionic reactive surfactant.

The type of the anionic reactive surfactant is not particularly limited as long as it has an ethylenically unsaturated double bond.
The ethylenically unsaturated double bond of the anionic reactive surfactant is derived from a group having an ethylenically unsaturated double bond.
Specific examples of the group having an ethylenically unsaturated double bond include (meth) acryloyl group, vinyl group, allyl group, isopropenyl group, 1-propenyl group, allyloxy group, styryl group and the like.
Among these, as the group having an ethylenically unsaturated double bond, at least one selected from the group consisting of an isopropenyl group, a 1-propenyl group, an allyloxy group, and a styryl group is preferable.

The anionic reactive surfactant has an oxyalkylene group from the viewpoint of copolymerizability with a monomer such as a (meth) acrylic acid alkyl ester monomer or a monomer having a crosslinkable functional group. It is preferable to do so.
Examples of the oxyalkylene group include an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group and an oxybutylene group.
Among these, the oxyethylene group is preferable as the oxyalkylene group. The oxyethylene group is, for example, more hydrophilic than the oxypropylene group or the oxybutylene group, and can form a dense hydrated layer on the surface of the resin particles, so that the dispersibility of the resin particles in the aqueous medium is further enhanced. Therefore, it tends to be more miscible with inorganic metal salts and water-soluble organic solvents (for example, glycol-based solvents).

When the anionic reactive surfactant has an oxyalkylene group, the average number of moles of the oxyalkylene group added is not particularly limited, but for example, 5 or more is preferable from the viewpoint of dispersibility of the resin particles in an aqueous medium. 10 or more is more preferable.
Further, the average number of moles of the oxyalkylene group added is preferably 30 or less, more preferably 20 or less, for example, from the viewpoint that the dispersibility of the resin particles based on charge repulsion can be further improved.

As an example of a commercially available anion-type reactive surfactant, Aqualon (registered trademark) KH-05 [active ingredient: polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester [type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 5], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) KH-10 [active ingredient: polyoxyethylene-1- (Allyloxymethyl) Alkyl oxymethyl Alkyl ether Sulfate ammonium ester [Type of oxyalkylene group: oxyethylene group (EO), average number of moles added: 10], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (Registered Trademark) AR-10 [Active ingredient: Polyoxyethylene styrenated propenylphenyl ether sulfate ammonium [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 10], amount of active ingredient: 99 mass %, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) HS-10 [Active ingredient: Polyoxyethylene nonylpropenylphenyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), average addition mol Number: 10], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) BC-10 [active ingredient: polyoxyethylene nonylpropenylphenyl ether sulfate ammonium ester [type of oxyalkylene group] : Oxyethylene group (EO), average number of moles added: 10], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) BC-20 [active ingredient: polyoxyethylene nonylpropenyl Ammonium phenyl ether sulfate [Type of oxyalkylene group: oxyethylene group (EO), average number of moles added: 20], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Adecaria soap (registered trademark) ) SR-10 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium [Type of oxyalkylene group: Oxyethylene group (EO), average number of moles added: 10], amount of active ingredient: 100% by mass, ADEKA Co., Ltd.], Adecaria Soap (registered trademark) SR-20 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 20], Amount of active ingredient: 100% by mass, ADEKA Corporation], ADEKA CORPORATION SR-3025 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium [type of oxyalkylene group] : Oxyethylene group (EO), average number of moles added: 30], amount of active ingredient: 25% by mass, ADEKA Corporation], eleminol (registered trademark) JS-2 [active ingredient: sodium alkylallyl sulfosuccinate, active ingredient Amount: 38% by mass, Sanyo Kasei Kogyo Co., Ltd.] and the like.

The resin may have only one type of structural unit derived from the anionic reactive surfactant, or may have two or more types.

The proportion (content rate) of the structural unit derived from the anionic reactive surfactant in the resin is, for example, the reactivity including the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant). 0.1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, and 1.5 parts by mass or more is further preferable with respect to 100 parts by mass of the total (excluding the structural unit derived from the surfactant).
The proportion (content rate) of the structural unit derived from the anionic reactive surfactant in the resin is the structural unit of the resin (however, the reactive surfactant including the anionic reactive surfactant and the nonionic reactive surfactant). When it is 0.1% by mass or more with respect to 100 parts by mass of the total (excluding the constituent units derived from the agent), the resin is more excellent in the reactivity with the inorganic metal salt and the water-soluble organic solvent (for example, a glycol-based solvent). The composition can be realized.
Further, the ratio (content rate) of the structural unit derived from the anionic reactive surfactant in the resin includes, for example, the structural unit of the resin (provided that the anionic reactive surfactant and the nonionic reactive surfactant are included. It is preferably 15 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, based on 100 parts by mass of the total of (excluding the structural units derived from the reactive surfactant).
When a large amount of anionic reactive surfactant is contained, the strength of the formed film decreases due to the plastic action of the excess anionic reactive surfactant that cannot contribute to the formation of resin particles. In some cases.
The proportion (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin is the structural unit of the resin (however, the reactive surfactant including the anionic reactive surfactant and the nonionic reactive surfactant). If it is 15 parts by mass or less with respect to 100 parts by mass in total (excluding the structural units derived from the agent), the film strength is unlikely to decrease due to the large amount of the anionic reactive surfactant. , There is a tendency to form an excellent film due to washing resistance.

<Constituent unit derived from nonionic reactive surfactant>
The resin has a structural unit derived from a nonionic reactive surfactant.
The structural unit derived from the nonionic reactive surfactant contributes to the improvement of miscibility with the inorganic metal salt and the water-soluble organic solvent (for example, a glycol-based solvent).

As used herein, the term "constituent unit derived from a nonionic reactive surfactant" means a structural unit formed by addition polymerization of a nonionic reactive surfactant.

The type of the nonionic reactive surfactant is not particularly limited as long as it has an ethylenically unsaturated double bond.
The ethylenically unsaturated double bond of the nonionic reactive surfactant is derived from a group having an ethylenically unsaturated double bond.
Specific examples and preferred embodiments of the group having an ethylenically unsaturated double bond in the nonionic reactive surfactant are specific examples and preferred embodiments of the group having an ethylenically unsaturated double bond in the anionic reactive surfactant. Since it is the same as the above, the description thereof is omitted here.

The nonionic reactive surfactant has an oxyalkylene group from the viewpoint of copolymerizability with a monomer such as a (meth) acrylic acid alkyl ester monomer or a monomer having a crosslinkable functional group. It is preferable to do so.
Examples of the oxyalkylene group include an oxyalkylene group having an alkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group and an oxybutylene group.
Among these, the oxyethylene group is preferable as the oxyalkylene group. The oxyethylene group is more hydrophilic than, for example, an oxypropylene group or an oxybutylene group, and a dense hydrated layer can be formed on the surface of the resin particles, so that the dispersibility of the resin particles in the aqueous medium is further enhanced. .. Therefore, it tends to be more miscible with inorganic metal salts and water-soluble organic solvents (for example, glycol-based solvents).

When the nonionic reactive surfactant has an oxyalkylene group, the average number of moles of the oxyalkylene group added is not particularly limited, but is preferably 10 or more, more preferably 30 or more, for example.
When the average number of moles of oxyalkylene groups contained in the nonionic reactive surfactant is 10 or more, the dispersion stability of the resin particles based on the physical bulk tends to be further improved.
The average number of moles of the oxyalkylene group added is, for example, preferably 60 or less, more preferably 40 or less.
When the average number of moles of the oxyalkylene group added to the nonionic reactive surfactant is 60 or less, a monomer such as a (meth) acrylic acid alkyl ester monomer or a monomer having a crosslinkable functional group is used. There is a tendency for the copolymerizability with and to be further improved.

Examples of commercially available nonionic reactive surfactants include adecaria soap (registered trademark) ER-10 [active ingredient: polyoxyethylene-1- (allyloxymethyl) alkyl ether [type of oxyalkylene group: oxy]. Ethylene group (EO), average number of moles added: 10], amount of active ingredient: 100% by mass, ADEKA Co., Ltd.], Adecaria soap (registered trademark) ER-20 [active ingredient: polyoxyethylene-1- (allyl) Oxymethyl) alkyl ether [Type of oxyalkylene group: oxyethylene group (EO), average number of added moles: 20], amount of active ingredient: 75% by mass, ADEKA Co., Ltd.], Adecaria soap (registered trademark) ER- 30 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 30], amount of active ingredient: 65% by mass, Co., Ltd. ) ADEKA], Adecaria Soap (registered trademark) ER-40 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average number of moles added: 40], amount of active ingredient: 60% by mass, ADEKA Co., Ltd.], Aqualon (registered trademark) RN-20 [active ingredient: polyoxyethylene nonylpropenylphenyl ether [type of oxyalkylene group: oxyethylene group (EO), Average number of moles added: 20], amount of active ingredient: 100% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) RN-30 [active ingredient: polyoxyethylene nonylpropenylphenyl ether [type of oxyalkylene group] : Oxyethylene group (EO), average number of moles added: 30], amount of active ingredient: 100% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) RN-50 [active ingredient: polyoxyethylene nonylpropenyl Phenyl ether [Type of oxyalkylene group: oxyethylene group (EO), average number of added moles: 50], amount of active ingredient: 65% by mass, Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon (registered trademark) KN-5065 [ Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 50], amount of active ingredient: 65% by mass, ADEKA Co., Ltd. ], Latemul (registered trademark) PD-420 [Active ingredient: Polyoxyalkylene alkenyl ether [Type of oxyalkylene group: Oxyethylene Group (EO) / Oxybutylene group (BO), average number of moles added: 20], amount of active ingredient: 100% by mass, Kao Co., Ltd.], Latemul (registered trademark) PD-430S [active ingredient: polyoxyalkylene alkenyl] Ether [Type of oxyalkylene group: oxyethylene group (EO) / oxybutylene group (BO), average number of added moles: 30], amount of active ingredient: 25% by mass, Kao Co., Ltd.], Latemul (registered trademark) PD -450 [Active ingredient: Polyoxyalkylene alkenyl ether [Type of oxyalkylene group: Oxyethylene group (EO) / Oxybutylene group (BO), average number of added moles: 50], amount of active ingredient: 100% by mass, Kao ( Co., Ltd.] and the like.

The resin may have only one type of structural unit derived from the nonionic reactive surfactant, or may have two or more types.

The proportion (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin is, for example, the reactivity including the structural unit of the resin (however, the anionic reactive surfactant and the nonionic reactive surfactant). 0.1 part by mass or more is preferable, 0.5 part by mass or more is more preferable, and 1.5 parts by mass or more is further preferable, based on 100 parts by mass of the total of (excluding the structural units derived from the surfactant).
The proportion (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin is the structural unit of the resin (however, the reactive surfactant including the anionic reactive surfactant and the nonionic reactive surfactant). When it is 0.1% by mass or more with respect to 100 parts by mass of the total (excluding the constituent units derived from the agent), the resin is more excellent in the reactivity with the inorganic metal salt and the water-soluble organic solvent (for example, a glycol-based solvent). The composition can be realized.
Further, the ratio (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin includes, for example, the structural unit of the resin (provided that the anionic reactive surfactant and the nonionic reactive surfactant are included. 25 parts by mass or less is preferable, 20 parts by mass or less is more preferable, and 15 parts by mass or less is further preferable with respect to a total of 100 parts by mass (excluding the structural units derived from the reactive surfactant).
When a large amount of nonionic reactive surfactant is contained, the strength of the formed film is lowered by the plastic action of the excess nonionic reactive surfactant that cannot contribute to the formation of resin particles. In some cases.
The proportion (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin is the structural unit of the resin (however, the reactive surfactant including the anionic reactive surfactant and the nonionic reactive surfactant). If it is 25 parts by mass or less with respect to 100 parts by mass in total (excluding the structural units derived from the agent), the film strength is unlikely to decrease due to the large amount of the nonionic reactive surfactant. , There is a tendency to form an excellent film due to washing resistance.

When both the anionic reactive surfactant and the nonionic reactive surfactant have an oxyalkylene group, the average number of moles a of the oxyalkylene group added to the anionic reactive surfactant and the nonionic reactivity a. The average number of moles b of the oxyalkylene group contained in the surfactant preferably satisfies the following formula (1).
b> a ... Equation (1)

When the charge on the surface of the resin particles is kept anionic, they are easily crosslinked by the interaction with the inorganic metal salt and aggregates are easily generated. When the average number of moles of oxyalkylene group added to the anionic reactive surfactant and the average number of moles of oxyalkylene group added to the nonionic reactive surfactant b satisfy the formula (1), the nonionic reaction The physical damage caused by the oxyalkylene chain of the sex surfactant can prevent the cross-linking reaction between the resin particles and the inorganic metal salt, so that the generation of agglomerates can be further suppressed.

Further, the average number of moles of oxyalkylene group added to the anionic reactive surfactant and the average number of moles of oxyalkylene group added to the nonionic reactive surfactant b satisfy the following formula (2). Is more preferable.
1.5 ≦ b / a ≦ 5.0 ・ ・ ・ Equation (2)
When the average number of moles of oxyalkylene group added by the anionic reactive surfactant and the average number of moles of oxyalkylene group b of the nonionic reactive surfactant satisfy the formula (2), the inorganic metal salt The miscibility with can be further improved.

As a more preferable embodiment, the average number of moles of oxyalkylene group added to the anionic reactive surfactant and the average number of moles of oxyalkylene group added to the nonionic reactive surfactant are set to the following formula (3). ) Is satisfied.
2.0 ≤ b / a ≤ 3.5 ... Equation (3)

-Average particle size of resin particles-
The average particle size of the resin particles is preferably 30 nm or more and 700 nm or less, more preferably 70 nm or more and 500 nm or less, still more preferably 100 nm or more and 300 nm or less, from the viewpoint of dispersibility in an aqueous medium.
In the present specification, "average particle size of resin particles" is referred to as "New Experimental Chemistry Course 4 Basic Technology 3 Hikari (II)" edited by The Chemical Society of Japan, pp. 725-741 (July 20, 1976, Maruzen (July 20, 1976). It is a value measured by the dynamic light scattering method described in (issued by Co., Ltd.). The specific method is as follows.
After diluting the resin composition with distilled water and thoroughly stirring and mixing, 5 mL was collected in a 10 mm square glass cell using a Pasteur pipette, and this was collected by a dynamic light scattering photometer (for example, Sysmex Co., Ltd.). Set in the Zetasizer 1000HS). After setting the set value of the attenuation rate (Attenuator) to x16 (16 times) and adjusting the concentration of the diluted solution of the resin composition so that the Count Rate of the attenuation rate is 150 kCps to 200 kCps, the measurement temperature is 25 ° C. ± The average particle size of the resin particles in the resin composition is obtained by computer processing the results measured under the conditions of 1 ° C. and a light scattering angle of 90 °. Further, as the value of the average particle diameter, the value of the Z average is used.

-Content rate of resin particles-
The content of the resin particles in the resin composition of the present invention is not particularly limited, and is preferably 15% by mass or more and 65% by mass or less, and 25% by mass or more and 55% by mass or less, for example, with respect to the total mass of the resin composition. Is more preferable, and 30% by mass or more and 45% by mass or less is further preferable.
When the content of the resin particles in the resin composition of the present invention is within the above range with respect to the total mass of the resin composition, the industrial productivity tends to be better. In addition, the agglomeration of the resin particles tends to be less likely to occur.

[Aqueous medium]
The resin composition of the present invention contains an aqueous medium.
The aqueous medium contained in the resin composition of the present invention can function as a dispersion medium for resin particles.
The aqueous medium is not particularly limited and can be appropriately selected depending on the intended purpose.
Examples of the aqueous medium include water and a mixed solution of water and an alcohol solvent.
As the aqueous medium, for example, water is preferable from the viewpoint of dispersibility of the resin particles.
The content of the aqueous medium in the resin composition of the present invention is not particularly limited, and is preferably 35% by mass or more and 85% by mass or less, and 45% by mass or more and 75% by mass or less, for example, with respect to the total mass of the resin composition. Is more preferable, and 55% by mass or more and 70% by mass or less is further preferable.
When the content of the aqueous medium in the resin composition of the present invention is within the above range with respect to the total mass of the resin composition, the industrial productivity tends to be superior. In addition, the dispersibility of the resin particles tends to be better.

[Other ingredients]
The resin composition of the present invention may contain components other than the above-mentioned components (so-called other components), if necessary, as long as the effects of the present invention are not impaired.
Examples of other components include various additives such as a cross-linking agent, an antioxidant, an antistatic agent, a pH adjuster, and an antifoaming agent.

Specific examples of the cross-linking agent include a hydrazide-based cross-linking agent, an oxazoline-based cross-linking agent, an epoxy-based cross-linking agent, a blocked isocyanate-based cross-linking agent, a melamine-based cross-linking agent, a carbodiimide-based cross-linking agent, and the like.
Examples of the hydrazide-based cross-linking agent include compounds having a hydrazide group such as adipic acid dihydrazide (ADH), sebacic acid dihydrazide (SDH), dodecandiohydrazide (DDH), isophthalic acid dihydrazide (IDH) and salicylate hydrazide (SAH).
Examples of the oxazoline-based cross-linking agent include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, and the like. 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4-acryloyl-oxymethyl-2,4-dimethyl-2-oxazoline, 4-methacryloyloxymethyl-2,4-dimethyl-2-oxazoline, 4- Methacyoyloxymethyl-2-phenyl-4-methyl-2-oxazoline, 2- (4-vinylphenyl) -4,4-dimethyl-2-oxazoline, 4-ethyl-4-hydroxymethyl-2-isopropenyl-2 Examples thereof include compounds having an oxazoline group such as -oxazoline and 4-ethyl-4-carboethoxymethyl-2-isopropenyl-2-oxazoline. Further, a polymer composition having a structural unit derived from these compounds having an oxazoline group can also be preferably used.
The content of the cross-linking agent in the resin composition of the present invention is not particularly limited, and for example, the composition of the resin can be more effectively imparted to the film to be formed, such as wash resistance. For a total of 100 parts by mass of units (excluding structural units derived from reactive surfactants including anionic reactive surfactants and nonionic reactive surfactants), in terms of active ingredient equivalent. It is preferably 0.01 parts by mass or more and 20 parts by mass or less.

[PH of resin composition]
The pH of the resin composition of the present invention is preferably 2 to 10, for example, from the viewpoint of dispersibility of the resin particles in an aqueous medium.
The method for measuring the pH of the resin composition of the present invention is not particularly limited.
For the pH of the resin composition of the present invention, a value measured under the condition of a liquid temperature of 25 ° C. by a method based on JIS Z 8802: 2011 using a pH meter is adopted. As the measuring device, for example, a pH meter (trade name: F-51) manufactured by HORIBA, Ltd. can be used.

[Manufacturing method of resin composition]
The method for producing the resin composition of the present invention is not particularly limited as long as the above-mentioned resin composition can be produced.
As a method for producing the resin composition of the present invention, for example, the method for producing the resin composition of the present embodiment described below is preferable from the viewpoint of easy production of the resin composition.

The method for producing the resin composition of the present embodiment (hereinafter, also referred to as “the production method of the present embodiment”) is in the presence of an anionic reactive surfactant, a nonionic reactive surfactant, and an aqueous medium. At least, it includes a step of polymerizing a (meth) acrylic acid alkyl ester monomer and a monomer having a crosslinkable functional group to obtain resin particles (hereinafter, also referred to as “emulsion polymerization step”). ..

Hereinafter, each step in the production method of the present embodiment will be described, but the details of the matters common to the above-mentioned resin composition, for example, the components contained in the resin composition will be omitted.

<Emulsion polymerization process>
The emulsion polymerization step is a single amount having at least a (meth) acrylic acid alkyl ester monomer and a crosslinkable functional group in the presence of an anionic reactive surfactant, a nonionic reactive surfactant, and an aqueous medium. This is a step of polymerizing the body and the body to obtain resin particles.
In the emulsion polymerization step, at least the (meth) acrylic acid alkyl ester monomer, the monomer having a crosslinkable functional group, the anionic reactive surfactant, and the nonionic reactive surfactant are copolymerized. By polymerization, resin particles having a hydrated layer formed on the surface of an anionic reactive surfactant and a nonionic reactive surfactant are obtained.

The polymerization method is not particularly limited, and examples thereof include the methods (1) to (3) shown below.
(1) In a reaction vessel equipped with a thermometer, a stirring rod, a reflux cooler, a dropping funnel, etc., at least a (meth) acrylic acid alkyl ester monomer, a monomer having a crosslinkable functional group, and an anion A type-reactive surfactant, a nonionic-type reactive surfactant, and an aqueous medium (for example, water) are charged, the temperature inside the reaction vessel is heated, and then a polymerization initiator, a reducing agent, etc. are appropriately added. A method for advancing the emulsion polymerization reaction (so-called batch charging method),
(2) At least an anionic reactive surfactant, a nonionic reactive surfactant, and an aqueous medium (for example, water) are placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux cooler, a dropping funnel, and the like. ) And, and after raising the temperature in the reaction vessel, a monomer component [at least, a (meth) acrylic acid alkyl ester monomer and a monomer having a crosslinkable functional group] is added dropwise, as appropriate. A method of advancing the emulsion polymerization reaction by adding a polymerization initiator, a reducing agent, etc. (so-called monomer dropping method).
(3) A monomer component [at least, a (meth) acrylic acid alkyl ester monomer and a monomer having a crosslinkable functional group] is previously added to at least an anionic reactive surfactant and a nonionic reactive surfactant. After emulsifying with an agent and an aqueous medium (for example, water) to obtain a pre-emulsion, the obtained pre-emulsion is placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux cooler, a dropping funnel and the like. A method of advancing the emulsification polymerization reaction by dropping and appropriately adding a polymerization initiator, a reducing agent, etc. (so-called emulsification monomer dropping method).
And so on.
Among these, as the polymerization method, for example, the emulsified monomer dropping method of (3) above is preferable from the viewpoint of industrial productivity.

The polymerization temperature is, for example, 50 ° C to 80 ° C, preferably 60 ° C to 80 ° C.
The polymerization time is, for example, 4 hours to 10 hours, preferably 4 hours to 8 hours.

The amount of the (meth) acrylic acid alkyl ester monomer used is, for example, preferably 55 parts by mass or more, more preferably 65 parts by mass or more, and further preferably 75 parts by mass or more with respect to 100 parts by mass of the total amount of the monomers. preferable.
When the amount of the (meth) acrylic acid alkyl ester monomer used is 55 parts by mass or more with respect to 100 parts by mass of the total amount of the monomers, for example, copolymerizability with a monomer having a crosslinkable functional group Since it is difficult for the molecular weight of the resin to decrease due to the decrease in the amount of the resin, the washing resistance of the formed film tends to be better.
The amount of the (meth) acrylic acid alkyl ester monomer used is, for example, preferably 98 parts by mass or less, more preferably 95 parts by mass or less, based on 100 parts by mass of the total amount of the monomers.
When the amount of the (meth) acrylic acid alkyl ester monomer used is large, the proportion of the monomer having a relatively crosslinkable functional group decreases, so that the crosslink density of the formed film decreases.
When the amount of the (meth) acrylic acid alkyl ester monomer used is 98 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers, the crosslink density of the formed film is a single amount having a crosslinkable functional group. The wash resistance of the membrane tends to be better because it is less susceptible to the effects of reduced body proportions.

The amount of the monomer having a crosslinkable functional group is 0.1 mass by mass with respect to 100 parts by mass of the total amount of the monomer, for example, from the viewpoint that the washing resistance of the formed film can be further improved. More than parts are preferable, 0.5 parts by mass or more are more preferable, and 1 part by mass or more is further preferable.
When the amount of the monomer having a crosslinkable functional group used is 0.1 part by mass or more with respect to 100 parts by mass of the total amount of the monomers, the washing resistance of the formed film tends to be more excellent.
The amount of the monomer having a crosslinkable functional group to be used is, for example, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and 10 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers. More preferred.
If the amount of the monomer having a crosslinkable functional group is large, the crosslinking reaction proceeds between the same copolymers at the time of crosslinking, and there is a tendency that a three-dimensional crosslinked structure cannot be formed.
When the amount of the monomer having a crosslinkable functional group used is 20 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers, the three-dimensional crosslinked structure can be satisfactorily formed, so that the washing resistance of the membrane is improved. Tends to be better.

The amount of the anionic reactive surfactant used is, for example, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and 1 part by mass or more with respect to 100 parts by mass of the total amount of the monomers. More preferred.
When the amount of the anion-type reactive surfactant used is 0.1 part by mass or more with respect to 100 parts by mass of the total amount of the monomers, the inorganic metal salt and the water-soluble organic solvent (for example, a glycol-based solvent) are used. A resin composition having better miscibility can be realized.
The amount of the anionic reactive surfactant used is, for example, preferably 15 parts by mass or less, more preferably 8 parts by mass or less, still more preferably 5 parts by mass or less, based on 100 parts by mass of the total amount of the monomers. ..
When a large amount of anionic reactive surfactant is contained, the strength of the formed film decreases due to the plastic action of the excess anionic reactive surfactant that cannot contribute to the formation of resin particles. In some cases.
The proportion (content rate) of the structural unit derived from the nonionic reactive surfactant in the resin is the structural unit of the resin (however, the reactive surfactant including the anionic reactive surfactant and the nonionic reactive surfactant). If it is 15 parts by mass or less with respect to 100 parts by mass in total (excluding the structural units derived from the agent), the film strength is unlikely to decrease due to the large amount of the anionic reactive surfactant. , There is a tendency to form an excellent film due to washing resistance.

The amount of the nonionic reactive surfactant used is, for example, preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and 1.5 parts by mass with respect to 100 parts by mass of the total amount of the monomers. The above is more preferable.
When the amount of the nonionic reactive surfactant used is 0.1 part by mass or more with respect to 100 parts by mass of the total amount of the monomer, the inorganic metal salt and the water-soluble organic solvent (for example, a glycol-based solvent) are used. A resin composition having better miscibility can be realized.
The amount of the nonionic reactive surfactant used is, for example, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, based on 100 parts by mass of the total amount of the monomers. ..
When a large amount of nonionic reactive surfactant is used, the strength of the formed film decreases due to the thermoplastic action of the excess nonionic reactive surfactant that cannot contribute to the formation of resin particles. There is.
When the amount of the nonionic reactive surfactant used is 25 parts by mass or less with respect to 100 parts by mass of the total amount of the monomer, the membrane strength due to the use of a large amount of the nonionic reactive surfactant is high. Since it is unlikely to be lowered, it tends to be possible to form a film having better washing resistance.

When a vinyl cyanide monomer is used in the emulsion polymerization step, the amount of the vinyl cyanide monomer used is preferably, for example, 2 parts by mass or more, preferably 5 parts by mass, based on 100 parts by mass of the total amount of the monomers. More than 10 parts by mass is more preferable.
When the amount of the vinyl cyanide monomer used is 2 parts by mass or more with respect to 100 parts by mass of the total amount of the monomers, the dry cleaning resistance of the formed film tends to be more excellent.
The amount of the vinyl cyanide monomer used is, for example, preferably 25 parts by mass or less, more preferably 20 parts by mass or less, still more preferably 15 parts by mass or less, based on 100 parts by mass of the total amount of the monomers.
When the amount of the vinyl cyanide monomer used is 25 parts by mass or less with respect to 100 parts by mass of the total amount of the monomers, the (meth) acrylic acid alkyl ester monomer and the monomer having a crosslinkable functional group are used. There is a tendency for the copolymerizability with and to be further improved.

In the emulsion polymerization step, various additives such as a polymerization initiator, a reducing agent, a chain transfer agent, and a pH adjuster may be used.

(Polymer initiator)
The polymerization initiator may be used without particular limitation as long as it can be used for ordinary emulsion polymerization.
Examples of the polymerization initiator include ammonium persulfate, sodium persulfate, persulfate represented by potassium persulfate, organic peroxide represented by t-butylhydroperoxide and cumenehydroperoxide, and hydrogen peroxide. Can be mentioned.
When a polymerization initiator is used in the emulsion polymerization step, only one type of polymerization initiator may be used, or two or more types may be used.

The polymerization initiator is used in commonly used amounts.
The amount of the polymerization initiator used is, for example, 0.1 part by mass to 2 parts by mass, preferably 0.3 part by mass to 1.5 parts by mass, based on 100 parts by mass of the total amount of the monomer as a raw material. Is.

(Reducing agent)
In the emulsion polymerization step, a reducing agent may be used together with the above-mentioned polymerization initiator.
Examples of the reducing agent include sodium metabisulfite, sodium sulfite, sodium hydrogen sulfite, sodium pyrosulfite (also referred to as "sodium disulfite"), sodium pyrophosphate, thioglycolic acid, sodium thiosulfate, ascorbic acid, tartrate acid, and citric acid. , Glucose, etc.
When a reducing agent is used in the emulsion polymerization step, only one kind of reducing agent may be used, or two or more kinds of reducing agents may be used.

The reducing agent is used in commonly used amounts.
The amount of the reducing agent used is, for example, 0.1 part by mass to 2 parts by mass, preferably 0.3 part by mass to 1.5 parts by mass with respect to 100 parts by mass of the total amount of the monomer as a raw material. be.

<Other processes>
The production method of the present embodiment may have a step other than the emulsion polymerization step, if necessary.

In the production method of the present embodiment described above, the emulsion polymerization method is given as an example as a method for obtaining resin particles, but the method for obtaining resin particles in the present invention is limited to the above-mentioned emulsion polymerization method. Instead, for example, a suspension polymerization method can also be used.

Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited to the following examples as long as the gist is not exceeded.
In the examples, the average particle size of the resin particles and the pH of the resin composition were measured by the methods described above. In addition, the same measuring device as described as an example was used.

[Manufacturing of resin composition]
[Example 1]
59.5 parts by mass of deionized exchanged water was placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, and the temperature inside the reaction vessel was raised to 60 ° C. while substituting with nitrogen.
On the other hand, in another container, 28.7 parts by mass of deionized exchanged water and 2.0 mass of "Aquaron (registered trademark) KH-10" [Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant. A part and 3.1 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a nonionic reactive surfactant, were added and stirred, and then n-butyl acrylate was further added. (N-BA) [(meth) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid. (MAA) 5.0 parts by mass of [crosslinkable functional group: carboxy group, monomer having crosslinkable functional group] and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] are added. To prepare a preemulsion by stirring.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 1.5% by mass (2.0 parts by mass) of the preemulsion prepared above was added to the reaction vessel, and then 2.0% by mass. An emulsion polymerization reaction was started by adding 3.6 parts by mass of a% potassium persulfate aqueous solution [polymerization initiator] and 3.6 parts by mass of a 2.0% by mass sodium diosulfate aqueous solution [reducing agent].
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 3 hours, and a 2.0% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 8.3 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 8.3 parts by mass were uniformly added sequentially over 3 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 9 .4 parts by mass and 2.1% by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 9.4 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 1.8 parts by mass of 12.5% by mass of aqueous ammonia was added to obtain a resin composition having a pH of 7.6. The solid content of the obtained resin composition was 42.0% by mass.

[Example 2]
38.5 parts by mass of deionized exchanged water was placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, and the temperature inside the reaction vessel was raised to 60 ° C. while substituting with nitrogen.
On the other hand, in another container, 82.8 parts by mass of deionized exchanged water and 5.0 mass of "Aquaron (registered trademark) AR-10" [Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant. 5.7 parts by mass of "Adecaria Soap (Registered Trademark) ER-10" [ADEKA Co., Ltd.] and "Adecaria Soap (Registered Trademark) ER-30" [(Registered Trademark) ER-10, which is a nonionic reactive surfactant. ADEKA Co., Ltd.] 8.8 parts by mass and stirred, and then n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester monomer] 70.6 parts by mass and methyl methacrylate. (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass and methacrylic acid (MAA) [crosslinkable functional group: carboxy group, monomer having crosslinkable functional group] 5.0 mass by mass A preemulsion was prepared by adding a portion and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 1.5% by mass (3.0 parts by mass) of the preemulsion prepared above was added to the reaction vessel, and then 5.0 mass by mass. 2.8 parts by mass of a% potassium persulfate aqueous solution [polymerization initiator] and 2.8 parts by mass of a 5.0% by mass sodium disulfide aqueous solution [reducing agent] were added to initiate an emulsifying polymerization reaction.
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 3 hours, and a 2.0% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 18.5 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 18.5 parts by mass were uniformly added sequentially over 3 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 11 1. 1 part by mass and 2.1% by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 11.1 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 0.8 part by mass of 12.5% by mass of aqueous ammonia was added to obtain a resin composition having a pH of 7.4. The solid content of the obtained resin composition was 38.2% by mass.

[Example 3]
A resin composition having a pH of 7.5 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.8% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 17.5 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkability. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a functional group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 4]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 38.0% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 15.2 parts by mass of "Adecaria Soap (registered trademark) ER-20" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkability. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a functional group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 5]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.5% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. 19.0 parts by mass of "Adecaria Soap (registered trademark) ER-40" [ADEKA Co., Ltd.], which is a sex surfactant, was added and stirred, and then n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkability. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a functional group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 6]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.8% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 17.5 parts by mass of "Aqualon (registered trademark) KN-5065" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [(meth). ) Acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkable functional group A preemulsion was prepared by adding 5.0 parts by mass of [a monomer having an ester] and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 7]
A resin composition having a pH of 7.3 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.6% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) KH-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 17.5 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkability. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a functional group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 8]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.7% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Adecaria Soap (registered trademark) SR-10 "[ADEKA Co., Ltd.], which is an anion-type reactive surfactant, and nonionic-type reactivity. 17.5 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a surfactant, was added and stirred, and then n-butyl acrylate (n-BA) [( Metal) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkable functionality. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 9]
A resin composition having a pH of 7.5 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.8% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Adecaria Soap (registered trademark) SR-20 "[ADEKA Co., Ltd.], which is an anion-type reactive surfactant, and nonionic-type reactivity. 17.5 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a surfactant, was added and stirred, and then n-butyl acrylate (n-BA) [( Metal) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkable functionality. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 10]
A resin composition having a pH of 7.1 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.8% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 17.5 parts by mass of "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, acrylic acid (AA) [crosslinkability Functional group: 5.1 part by mass of a monomer having a carboxy group and a crosslinkable functional group] and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] are added and stirred. A preemulsion was prepared. "

[Example 11]
An emulsion polymer was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 0.7 parts by mass of 12.5% by mass of aqueous ammonia and a cross-linking agent "azipic acid dihydrazide (ADH)" [hydrazide]. A system cross-linking agent, Nippon Finechem Co., Ltd., amount of active ingredient: 98% by mass] 0.2 parts by mass was added to obtain a resin composition having a pH of 7.1. The solid content of the obtained resin composition was 41.7% by mass.
"78.7 parts by mass of deionized exchanged water and 5.0 parts by mass of" Aqualon (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. 8. Sexual surfactant "Adecaria Soap (registered trademark) ER-10" [ADEKA Co., Ltd.] 5.7 parts by mass and "Adecaria Soap (registered trademark) ER-30" [ADEKA Co., Ltd.] 8. After adding 8 parts by mass and stirring, 43.0 parts by mass of n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester monomer] and ethyl acrylate (EA) [(meth) ) Acryloacid alkyl ester monomer] 43.0 parts by mass, itaconic acid (IA) [bridgeable functional group: monomer having carboxy group, crosslinkable functional group] 1.0 part by mass, diacetone acrylamide (DAAD) [Cross-linking functional group: ketone group, monomer having cross-linking functional group] 0.7 parts by mass and acrylonitrile (AN) [vinyl cyanide monomer] 12.3 parts by mass are added. To prepare a preemulsion by stirring. "

[Example 12]
A resin composition having a pH of 7.5 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 37.8% by mass.
"82.8 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aquaron (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. After adding 11.4 parts by mass of "Adecaria Soap (registered trademark) ER-10" [ADEKA Co., Ltd.], which is a sex surfactant, and stirring, further n-butyl acrylate (n-BA) [ (Meta) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkability. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a functional group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 13]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 42.5% by mass.
"82.8 parts by mass of deionized exchanged water, 20.0 parts by mass of" Adecaria soap (registered trademark) SR-3025 "[ADEKA Co., Ltd.], which is an anion-type reactive surfactant, and nonionic-type reactivity. 19.0 parts by mass of "Adecaria Soap (registered trademark) ER-40" [ADEKA Co., Ltd.], which is a surfactant, was added and stirred, and then n-butyl acrylate (n-BA) [( Metal) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkable functionality. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Example 14]
A resin composition having a pH of 7.4 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 44.6% by mass.
"82.8 parts by mass of deionized exchanged water and 13.2 parts by mass of" eleminol (registered trademark) JS-2 "[Sanyo Kasei Kogyo Co., Ltd.] which is an anion-type reactive surfactant, and nonionic-type reactivity. 11.4 parts by mass of "Adecaria Soap (registered trademark) ER-10" [ADEKA Co., Ltd.], which is a surfactant, was added and stirred, and then n-butyl acrylate (n-BA) [( Metal) acrylic acid alkyl ester monomer] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylic acid (MAA) [crosslinkable functionality. A preemulsion was prepared by adding 5.0 parts by mass of a monomer having a group and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring the mixture. "

[Comparative Example 1]
50.0 parts by mass of deionized exchanged water was placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, and the temperature inside the reaction vessel was raised to 60 ° C. while substituting with nitrogen.
On the other hand, in another container, 68.7 parts by mass of deionized exchanged water, 0.1 part by mass of the non-reactive surfactant "HITENOL (registered trademark) 08E" [Daiichi Kogyo Seiyaku Co., Ltd.] and "Emulgen (registered trademark) 1135S-70" [Kao Co., Ltd.] 4.1 parts by mass was added and stirred, and then n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester single. Weight] 43.0 parts by mass, ethyl acrylate (EA) [(meth) acrylic acid alkyl ester monomer] 43.0 parts by mass, and itaconic acid (IA) [monomer with crosslinkable functional group] 1.0 part by mass of diacetone acrylamide (DAAD) [monomer having a crosslinkable functional group] 0.7 part by mass, acrylonitrile (AN) [vinyl cyanide monomer] 12.3 parts by mass, Was added and stirred to prepare a pre-emulsion.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 3% by mass (5.1 parts by mass) of the preemulsion prepared above was added into the reaction vessel, and then 5.0% by mass was added. 1.7 parts by mass of a potassium persulfate aqueous solution [polymerization initiator] and 1.3 parts by mass of a 5.0% by mass sodium disulfide aqueous solution [reducing agent] were added to initiate an emulsification polymerization reaction.
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 5 hours, and a 2.5% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 8.2 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 8.2 parts by mass were uniformly added sequentially over 5 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 3 .4 parts by mass and 2.1 parts by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 6.1 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer is aged at 60 ° C. for 30 minutes, cooled to room temperature, 0.8 part by mass of 12.5% by mass of aqueous ammonia is added, and then the cross-linking agent "dihydrazide adipic acid (ADH)" is added. [Hydrazide-based cross-linking agent, Nippon Finechem Co., Ltd., amount of active ingredient: 98% by mass] 0.2 parts by mass was added to obtain a resin composition having a pH of 7.2. The solid content of the obtained resin composition was 40.6% by mass.

[Comparative Example 2]
38.5 parts by mass of deionized exchanged water was placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, and the temperature inside the reaction vessel was raised to 60 ° C. while substituting with nitrogen.
On the other hand, in another container, 82.0 parts by mass of deionized exchanged water, 2.1 parts by mass of "HITENOL (registered trademark) 08E" [Daiichi Kogyo Seiyaku Co., Ltd.], which is a non-reactive surfactant, and "Emulgen (registered trademark) 1135S-70" [Kao Co., Ltd.] 2.9 parts by mass was added and stirred, and then n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester single. Weight] 70.6 parts by mass, methyl methacrylate (MMA) [(meth) acrylic acid alkyl ester monomer] 13.9 parts by mass, and methacrylate (MAA) [monomer with crosslinkable functional group] A preemulsion was prepared by adding 5.0 parts by mass and 10.5 parts by mass of acrylonitrile (AN) [vinyl cyanide monomer] and stirring.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 4.0% by mass (7.5 parts by mass) of the preemulsion prepared above was added into the reaction vessel, and then 5.0 mass by mass was added. 2.8 parts by mass of a% potassium persulfate aqueous solution [polymerization initiator] and 2.8 parts by mass of a 5.0% by mass sodium disulfide aqueous solution [reducing agent] were added to initiate an emulsifying polymerization reaction.
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 4 hours, and a 2.0% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 18.5 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 18.5 parts by mass were uniformly added sequentially over 4 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 11 1. 1 part by mass and 2.1% by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 11.1 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 0.8 part by mass of 12.5% by mass of aqueous ammonia was added to obtain a resin composition having a pH of 7.3. The solid content of the obtained resin composition was 35.9% by mass.

[Comparative Example 3]
In a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, 38.5 parts by mass of deionized exchanged water and "Adecaria Soap (registered trademark) ER, which is a nonionic reactive surfactant, are placed. -10 ”[ADEKA CORPORATION] 2.1 parts by mass was charged, and the temperature was raised to 60 ° C. while substituting nitrogen in the reaction vessel.
On the other hand, in another container, 82.0 parts by mass of deionized exchanged water and 9.3 parts by mass of "Adecaria Soap (registered trademark) ER-10" [ADEKA Co., Ltd.], which is a nonionic reactive surfactant. After adding and stirring, 70.6 parts by mass of n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester monomer] and methyl methacrylate (MMA) [(meth) acrylic acid) were further added. Alkyl ester monomer] 13.9 parts by mass, methacrylic acid (MAA) [monomer having crosslinkable functional group] 5.0 parts by mass, acrylonitrile (AN) [vinyl cyanide monomer] 10. A preemulsion was prepared by adding 5 parts by mass and stirring.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 1.5% by mass (2.9 parts by mass) of the preemulsion prepared above was added into the reaction vessel, and then 5.0 mass by mass. 2.8 parts by mass of a% potassium persulfate aqueous solution [polymerization initiator] and 2.8 parts by mass of a 5.0% by mass sodium disulfide aqueous solution [reducing agent] were added to initiate an emulsifying polymerization reaction.
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 3 hours, and a 2.0% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 18.5 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 18.5 parts by mass were uniformly added sequentially over 3 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 11 1. 1 part by mass and 2.1% by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 11.1 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 0.8 part by mass of 12.5% by mass of aqueous ammonia was added to obtain a resin composition having a pH of 7.2. The solid content of the obtained resin composition was 37.4% by mass.

[Comparative Example 4]
38.5 parts by mass of deionized exchanged water was placed in a reaction vessel equipped with a thermometer, a stirring rod, a reflux condenser, and a dropping funnel, and the temperature inside the reaction vessel was raised to 60 ° C. while substituting with nitrogen.
On the other hand, in another container, 82.0 parts by mass of deionized exchanged water and 10.0 mass of "Aquaron (registered trademark) AR-10" [Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant. After adding the parts and stirring, 70.6 parts by mass of n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester monomer] and methyl methacrylate (MMA) [(meth) acrylic) are further added. Acid alkyl ester monomer] 13.9 parts by mass, methacrylic acid (MAA) [bridgeable functional group: monomer having carboxy group, crosslinkable functional group] 5.0 parts by mass, acrylonitrile (AN) [ [Vinyl cyanide monomer] 10.5 parts by mass was added and stirred to prepare a preemulsion.
Next, while maintaining the internal temperature of the reaction vessel at 60 ° C., 1.0% by mass (1.9 parts by mass) of the preemulsion prepared above was added to the reaction vessel, and then 5.0% by mass. 2.8 parts by mass of a% potassium persulfate aqueous solution [polymerization initiator] and 2.8 parts by mass of a 5.0% by mass sodium disulfide aqueous solution [reducing agent] were added to initiate an emulsifying polymerization reaction.
After confirming that the internal temperature of the reaction vessel was 60 ° C., the remaining total amount of the preemulsion prepared above was sequentially added uniformly over 3 hours, and a 2.0% by mass potassium persulfate aqueous solution [polymerization] was added. Initiator] 18.5 parts by mass and 2.0% by mass sodium disulfate aqueous solution [reducing agent] 18.5 parts by mass were uniformly added sequentially over 3 hours and 30 minutes for emulsion polymerization.
Next, from 1 hour after the completion of the sequential addition of the pre-emulsion, a 3.2 mass% t-butyl hydroperoxide aqueous solution [trade name: Perbutyl (registered trademark) H, Nichiyu Co., Ltd., polymerization initiator] 11 1. 1 part by mass and 2.1% by mass of thiourea dioxide [trade name: Techlite, ADEKA Corporation, reducing agent] 11.1 parts by mass were uniformly added sequentially over 30 minutes to obtain an emulsion polymer. Got
The obtained emulsion polymer was aged at 60 ° C. for 30 minutes and then cooled to room temperature, and 0.8 part by mass of 12.5% by mass of aqueous ammonia was added to obtain a resin composition having a pH of 7.2. The solid content of the obtained resin composition was 37.1% by mass.

[Comparative Example 5]
A resin composition having a pH of 7.6 was obtained in the same manner as in Example 2 except that the method for preparing the preemulsion was changed as follows in Example 2. The solid content of the obtained resin composition was 39.0% by mass.
"82.0 parts by mass of deionized exchanged water, 5.0 parts by mass of" Aqualon (registered trademark) AR-10 "[Daiichi Kogyo Seiyaku Co., Ltd.], which is an anion-type reactive surfactant, and a nonionic reaction. 8. "Adecaria Soap (Registered Trademark) ER-10" [ADEKA Co., Ltd.] 5.0 parts by mass and "Adecaria Soap (Registered Trademark) ER-30" [ADEKA Co., Ltd.] which are sex surfactants. After adding 8 parts by mass and stirring, 70.6 parts by mass of n-butyl acrylate (n-BA) [(meth) acrylic acid alkyl ester monomer] and methyl methacrylate (MMA) [(meth) ) Acrylonitrile alkyl ester monomer] 18.9 parts by mass and acrylonitrile (AN) [vinyl cyanide monomer] 10.5 parts by mass were added and stirred to prepare a preemulsion. "

[evaluation]
The resin compositions of Examples 1 to 14 and Comparative Examples 1 to 5 obtained above were evaluated as follows. In each of the following evaluations, a resin composition having a solid content adjusted to 30% by mass by adding deionized water to each resin composition (hereinafter referred to as "evaluation resin composition") was used.

1. 1. Miscibility with Inorganic Metal Salt Deionized water was further added to the evaluation resin composition to adjust the solid content to 20% by mass to obtain a diluted solution of the evaluation resin composition. Next, 10 g of the diluted solution of the resin composition for evaluation was weighed in a beaker having a capacity of 50 mL. Next, the diluted solution of the evaluation resin composition weighed is stirred using a rotor, and 20% by mass of the magnesium sulfate (pipette ₄ ) aqueous solution 2 is added to the stirred solution of the evaluation resin composition. .5 g was added dropwise using a pipette. After the dropping was completed, the state of the liquid and the presence or absence of agglomerates were visually confirmed. Further, the liquid after the completion of the dropping was filtered using a stainless steel wire mesh, and the ratio of the obtained aggregate to the total mass (12.5 g) of the diluted liquid of the resin composition for evaluation and the _regsvr4 aqueous solution was measured. did. Then, the miscibility of the resin composition with the inorganic metal salt was evaluated according to the following evaluation criteria. "# 400" in the following evaluation criteria indicates the number of meshes of the wire mesh used for filtration. The results are shown in Table 2.
Resin compositions having excellent miscibility with inorganic metal salts are classified into "5", "4", or "3".

(Evaluation criteria)
5: Almost no agglomerates were generated (aggregate ratio: less than 2% by mass).
4: A small amount of agglomerates were generated (percentage of agglomerates: 2% by mass or more and less than 5% by mass).
3: A small amount of agglomerates were generated (percentage of agglomerates: 5% by mass or more and less than 10% by mass).
2: A large amount of agglomerates were generated (percentage of agglomerates: 10% by mass or more).
1: The whole liquid solidified and stirring stopped.

2. 2. Miscibility with a water-soluble organic solvent 200 g of ethylene glycol monobutyl ether (hereinafter, also referred to as "butyl cellosolve") was weighed in a beaker having a capacity of 50 mL. Then, the weighed butyl cellosolve was stirred using a rotor, and 100 g (solid content equivalent amount: 30 g) of the evaluation resin composition was added dropwise to the stirred butyl cellosolve using a pipette. After the dropping was completed, the state of the liquid and the presence or absence of insoluble matter were visually confirmed. Further, the liquid after completion of the dropping was filtered using a stainless steel wire mesh, and the ratio of the insoluble matter to the total mass (300 g) of the butyl cellosolve and the resin composition for evaluation was measured. Further, the viscosity of the liquid after the completion of dropping was measured using a B-type viscometer [Eiko Seiki Co., Ltd.] by a method according to JIS Z 8803 (measurement temperature: 25 ° C., rotation speed: 20 rpm). Then, the miscibility of the resin composition with the water-soluble organic solvent was evaluated according to the following evaluation criteria. "# 400" in the following evaluation criteria indicates the number of meshes of the wire mesh used for filtration. The results are shown in Table 2.
Resin compositions having excellent miscibility with water-soluble organic solvents are classified into "5", "4", or "3".

(Evaluation criteria)
5: No insoluble matter was generated, and the liquid was hardly thickened (no filter was confirmed by filtration, and the viscosity of the liquid was less than 10 times the viscosity of the resin composition for evaluation. rice field.).
4: No insoluble matter was generated, but the liquid was slightly thickened (no filter was confirmed by filtration, but the viscosity of the liquid was 10 times or more the viscosity of the resin composition for evaluation. .).
3: A small amount of insoluble matter was generated (filters were confirmed to be less than 1% by mass by filtration).
2: A large amount of insoluble matter was generated (filters of 1% by mass or more were confirmed by filtration, except for those corresponding to "1").
1: The liquid separated.

3. 3. Washing resistance (1) Preparation of printing paste A printing paste was prepared by mixing the components shown in the following composition. The reducer shown in the composition below uses 65 parts by mass of mineral tarpen and 4 parts by mass of a nonionic surfactant [trade name: DKS-NL-70, Dai-ichi Kogyo Seiyaku Co., Ltd.] to deionize water 31. It is emulsified and dispersed in parts by mass.

-Composition of printing paste-
・ Reducer 63.5 parts by mass ・ Evaluation resin composition 30.0 parts by mass ・ 5% by mass ammonia water 1.5 parts by mass ・ Pigment paste 5.0 parts by mass [Product name: BLUE FL2B Conc, blue color, Dainichi Seisei Industry Co., Ltd.]

(2) Preparation of test sheet Using the printing paste prepared above, a striped pattern with a width of 10 mm and a length of about 160 mm is spaced 10 mm apart from a cotton broadcloth (24 cm x 36 cm) using a 300 mesh silk screen. It was printed with 10 lines and dried in a room at 23 ° C. and 65% RH for 24 hours to prepare a test sheet.

(3) Evaluation test (3-1) Dry cleaning resistance A test was conducted on the test sheet based on the B-2 method of the dyeing fastness test method (JIS L 0860: 2016) for dry cleaning, and the degree of fading of the test sheet was determined. The degree of coloring of the attached white cloth was visually observed, and the dry cleaning resistance was evaluated according to the following evaluation criteria. The results are shown in Table 2.
Resin compositions capable of forming a film having excellent dry cleaning resistance are classified into "5", "4", or "3".

(Evaluation criteria)
5: Neither fading of the test sheet nor coloring of the attached white cloth could be confirmed.
4: No fading of the test sheet was confirmed, but slight coloring was confirmed on the attached white cloth.
3: Slight fading was confirmed on the test sheet, and coloring was confirmed on the attached white cloth.
2: Fading was confirmed on the test sheet.
1: Severe fading was confirmed on the test sheet.

(3-2) Wet cleaning resistance Put 30L of warm water at 40 ℃ in a 40L (liter) capacity swirl reversing household washing machine, detergent [trade name: Top Platinum Clear, Lion Co., Ltd.] 120g, and load cloth. Put 1 kg of new cotton towel and 1 cotton towel sewn with a test sheet, and wash for 15 minutes, rinse for 5 minutes, dehydrate for 1 minute, and dry at room temperature for a total of 5 cycles. Cycle washing was done. The test sheet after washing was visually observed, and the wet cleaning resistance was evaluated according to the following evaluation criteria. The results are shown in Table 2.
Resin compositions capable of forming a film having excellent wet cleaning resistance are classified into "5" or "4".

(Evaluation criteria)
5: No damage was confirmed on the test sheet.
4: Slight damage was confirmed on the test sheet.
3: Clear damage was confirmed on the test sheet.
2: The damage to the test sheet was conspicuous.
1: The test sheet was significantly damaged.

In Table 1, "-" means that the corresponding ingredient is not blended.
The blending amount of the surfactant shown in Table 1 is an active ingredient conversion value.

Details of each component shown in Table 1 are as shown below.
<Anionic reactive surfactant>
"AR-10": Aqualon (registered trademark) AR-10 [Active ingredient: Polyoxyethylene styrenated propenylphenyl ether sulfate ammonium [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 10] , Active ingredient amount: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.]
"KH-10": Aqualon (registered trademark) KH-10 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), average addition Number of moles: 10], amount of active ingredient: 99% by mass, Daiichi Kogyo Seiyaku Co., Ltd.]
"SR-10": Adecaria Soap (registered trademark) SR-10 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), Average number of moles added: 10], amount of active ingredient: 100% by mass, ADEKA Corporation]
"SR-20": Adecaria Soap (registered trademark) SR-20 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), Average number of moles added: 20], amount of active ingredient: 100% by mass, ADEKA Corporation]
"SR-3025": Adecaria Soap (registered trademark) SR-3025 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ester ammonium [Type of oxyalkylene group: Oxyethylene group (EO), Average number of moles added: 30], amount of active ingredient: 25% by mass, ADEKA Corporation]
"JS-2": Eleminor (registered trademark) JS-2 [Active ingredient: Sodium alkylallyl sulfosuccinate, Active ingredient amount: 38% by mass, Sanyo Chemical Industries, Ltd.]
<Nonion-type reactive surfactant>
"ER-10": Adecaria Soap (registered trademark) ER-10 [Active ingredient amount: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average addition Number of moles: 10], amount of active ingredient: 100% by mass, ADEKA Corporation]
"ER-20": Adecaria soap (registered trademark) ER-20 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average addition mol Number: 20], amount of active ingredient: 75% by mass, ADEKA Corporation]
"ER-30": Adecaria soap (registered trademark) ER-30 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average addition mol Number: 30], amount of active ingredient: 65% by mass, ADEKA Corporation]
"ER-40": Adecaria Soap (registered trademark) ER-40 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average addition mol Number: 40], amount of active ingredient: 60% by mass, ADEKA Corporation]
"KN-5065": Aqualon (registered trademark) KN-5065 [Active ingredient: Polyoxyethylene-1- (allyloxymethyl) alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average number of moles added: 50], amount of active ingredient: 65% by mass, ADEKA Corporation]
<Non-reactive surfactant>
"08E": Hytenol (registered trademark) 08E [Active ingredient: Polyoxyethylene oleylcetyl ether sulfate ammonium ester [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 10], amount of active ingredient: 95% by mass, Daiichi Kogyo Seiyaku Co., Ltd.]
"1135S-70": Emargen (registered trademark) 1135S [Active ingredient: Polyoxyethylene alkyl ether [Type of oxyalkylene group: Oxyethylene group (EO), average number of added moles: 40], amount of active ingredient: 70% by mass , Kao Corporation]
<(Meta) Acrylic Acid Alkyl Ester Monomer>
"N-BA": n-butyl acrylate "EA": ethyl acrylate "MMA": methyl methacrylate <monomer having a crosslinkable functional group>
"AA": Acrylic acid (crosslinkable functional group: carboxy group)
"IA": itaconic acid (crosslinkable functional group: carboxy group)
"DAAD": Diacetone acrylamide (crosslinkable functional group: ketone group)
"MAA": Methacrylic acid (crosslinkable functional group: carboxy group)
<Vinyl cyanide monomer>
"AN": Acrylonitrile <crosslinking agent>
"ADH": Adipic acid dihydrazide [Hydrazide-based cross-linking agent, Japan Finechem Co., Ltd., active ingredient amount: 98% by mass]

As shown in Table 2, the resin compositions of Examples 1 to 14 were all excellent in miscibility with the inorganic metal salt and the water-soluble organic solvent. Further, according to the resin compositions of Examples 1 to 14, a film having excellent washing resistance could be formed.
On the other hand, the resin composition of Comparative Example 1 containing resin particles having neither a structural unit derived from an anionic reactive surfactant nor a structural unit derived from a nonionic reactive surfactant is an anionic resin composition. Inorganic as compared to the resin composition of Example (eg, Example 11) comprising resin particles having both a constitutive unit derived from a reactive surfactant and a constitutive unit derived from a nonionic reactive surfactant. It tended to be inferior in miscibility with metal salts. It also tended to be inferior in miscibility with water-soluble organic solvents. Furthermore, it showed a tendency that the washing resistance of the formed film was inferior.
These tendencies were also confirmed in the resin composition of Comparative Example 2 in which the composition of the monomers constituting the resin was different.
The resin composition of Comparative Example 3 containing resin particles having a structural unit derived from a nonionic reactive surfactant and not having a structural unit derived from an anionic reactive surfactant is an anionic reactive resin composition. Inorganic metal salts as compared to the resin compositions of Examples (eg, Example 12) comprising resin particles having both structural units derived from surfactants and structural units derived from nonionic reactive surfactants. It showed a tendency to be inferior in miscibility with. It also tended to be inferior in miscibility with water-soluble organic solvents.
The resin composition of Comparative Example 4 containing resin particles having a structural unit derived from an anionic reactive surfactant and having no structural unit derived from a nonionic reactive surfactant is an anionic reactive surfactant. Miscibility with inorganic metal salts as compared to Examples (eg, Example 12) containing resin particles having both structural units derived from surfactants and structural units derived from nonionic reactive surfactants. Showed a tendency to be inferior to.
The resin composition of Comparative Example 5 containing resin particles having no structural unit derived from a monomer having a crosslinkable functional group has an example having a structural unit derived from a monomer having a crosslinkable functional group (for example,). , Showed a tendency to be inferior in miscibility with the inorganic metal salt as compared with Example 2). It also tended to be inferior in miscibility with water-soluble organic solvents. Furthermore, it showed a tendency that the washing resistance of the formed film was inferior.

Claims (3)

(Meta) A structural unit derived from an acrylic acid alkyl ester monomer, a structural unit derived from a monomer having a crosslinkable functional group, a structural unit derived from a vinyl cyanide monomer, an ethylenically unsaturated double bond. Resin particles having a constituent unit derived from an anionic reactive surfactant having an ethylenically unsaturated double bond and a constituent unit derived from a nonionic reactive surfactant having an ethylenically unsaturated double bond.
Aqueous medium and
A resin composition for pretreatment for printing. Both the anion-type reactive surfactant and the nonionic-type reactive surfactant have an oxyalkylene group and have an oxyalkylene group.
A claim that the average number of moles of oxyalkylene group added by the anionic reactive surfactant and the average number of moles of oxyalkylene group added by the nonionic reactive surfactant satisfy the following formula (1). Item 2. The resin composition for printing pretreatment according to Item 1.
b> a ... Equation (1) A claim that the average number of moles of oxyalkylene group added by the anionic reactive surfactant and the average number of moles of oxyalkylene group added by the nonionic reactive surfactant satisfy the following formula (2). Item 2. The resin composition for printing pretreatment according to Item 2.
1.5 ≦ b / a ≦ 5.0 ・ ・ ・ Equation (2)