JP2019127521A - Sealer - Google Patents

Abstract

To provide a novel sealer (sealer composition).SOLUTION: The sealer is formed of a resin emulsion (A) and a water soluble polymer (B). The sealer may comprise a crosslinking agent (C).SELECTED DRAWING: None

Description

  The present invention relates to a sealer (priming paint) and the like.

  The coating of a substrate, in particular, a ceramic base (inorganic porous base) is roughly divided into a base coat and an upper coat (further, an inner coat). Of these, the undercoat is applied to the surface of the substrate (the surface to be overcoated).

In the production of ceramic base materials and the like, there is a step of curing with an autoclave. In the case of going through such a process, for example, the following two types of undercoatings are made before and after the process.
Undercoating to be applied before autoclave curing to reinforce the substrate (pre-curing sealer)
Priming to be painted after autoclave curing (priming, post-curing sealer)

  On the other hand, in the case of a substrate to which a pre-cure sealer is not applied, a second coating solution is usually applied to reinforce the substrate, and then a second coating solution is applied to improve the water resistance and the adhesion between the top coating surface. Two types of post-cure sealers are applied by a method of applying a coating solution (two-coat method).

  In addition, paints are properly used according to the purpose of a coating, such as a primer, a sealer (primer paint), and a primer, an overcoat paint (paint for top coats etc.).

  For example, Japanese Patent No. 5290951 (Patent Document 1) discloses a coating material for a top coat containing a specific (meth) acrylic emulsion and a water-soluble resin (B) as essential components.

Japanese Patent No. 5290951 (Claims, paragraph [0001], Examples, etc.)

  An object of the present invention is to provide a novel sealer (priming paint).

  Another object of the present invention is to provide a sealable sealer with one coat.

  Still another object of the present invention is to provide a sealer capable of reinforcing a substrate.

  As a result of intensive studies on a sealer (base coat) of a base material such as a ceramic base material or a porous base material (inorganic type porous base material), the present inventors have combined specific components, etc. And that a novel sealer (primer coat) is obtained, and such a sealer makes it possible, surprisingly, that the primer coat (especially the pre-curing sealer) is efficient even with one coat (or even without combining a plurality of coating solutions). The present inventors have found that a post-curing sealer can be applied to a base material that has not been applied, and have further studied to complete the present invention.

  That is, the sealer (primer coating material) of the present invention includes a resin emulsion (A) and a water-soluble polymer (B).

  In such a sealer, the weight average molecular weight of the water soluble polymer (B) may be 100,000 or less.

  In the sealer of the present invention, the resin constituting the resin emulsion (A) may be an acrylic resin.

  In the sealer of the present invention, the resin constituting the resin emulsion (A) contains a monomer component (a) containing a (meth) acrylic monomer and a styrene monomer, wherein the proportion of the styrene monomer is 15% by mass or more. It may be a resin as a polymerization component, or may be a resin having a monomer component (a) containing a styrene monomer in a proportion of 55% by mass or more as a polymerization component.

  In the sealer of the present invention, the resin emulsion (A) includes a (meth) acrylic monomer, a styrene monomer, and a monomer having a functional group α, and the proportion of the styrene monomer is 60% by mass or more. A resin emulsion composed of a resin having component (a) as a polymerization component and a weight average molecular weight of 50,000 to 500,000 and a glass transition temperature of 15 ° C. or higher may be used.

  The resin emulsion (A) may have a multilayer structure.

In the sealer of the present invention, the water-soluble polymer (B) may be nonionic.
In the sealer of the present invention, the water-soluble polymer (B) may have a monomer component (b) containing a monomer having a functional group β as a polymerization component.

  In the sealer of the present invention, the water-soluble polymer (B) may have a monomer component (b) containing a lactam monomer as a polymerization component.

  Typically, the water-soluble polymer (B) contains a lactam monomer and a monomer having a functional group β, the proportion of the lactam monomer is 50% by mass or more, and the proportion of the monomer having an ionic group is It may be a water-soluble polymer having a monomer component (b) of 10% by mass or less as a polymerization component.

  The sealer of the present invention may further contain a crosslinking agent (C), for example, at least one water-soluble crosslinking agent selected from hydrazine-based crosslinking agents, oxazoline-based crosslinking agents, and carbodiimide-based crosslinking agents. (C) may be included.

  In the sealer of the present invention, the water-soluble polymer (B) may be capable of forming a crosslinked structure via the crosslinking agent (C).

  In the sealer of the present invention, the resin emulsion (A) and the water-soluble polymer (B) may be capable of forming a crosslinked structure.

  Typically, the sealer of the present invention further contains a hydrazine-based crosslinking agent, and the resin constituting the resin emulsion (A) contains, as a polymerization component, a monomer component (a) containing a carbonyl group-containing monomer, A resin constituting the water-soluble polymer (B) comprises a monomer component (b) containing a carbonyl group-containing monomer as a polymerization component, and a resin emulsion (A) and a water-soluble polymer (B) via a hydrazine-based crosslinking agent And may be a sealer capable of forming a crosslinked structure.

  The sealer of the present invention may contain a pigment at a pigment weight concentration (PWC) of 50% or more.

  The present invention is a coated substrate comprising a substrate and an undercoat layer (coating, first coating, sealer layer) formed (directly) on the substrate, wherein the undercoating layer comprises Also included are coated substrates formed with the sealer.

  In such a coated base material, the base material may be a ceramic base material.

  The coated substrate of the present invention may be a coated substrate in which a coated film (upper coated layer, second coated film) is further formed on the undercoat layer.

  The base material may be a base material that has not been subjected to a pre-curing sealer (a base material that has not been subjected to a pre-curing sealer treatment).

In one embodiment of the present invention, a novel sealer (priming paint) can be provided.
Such a sealer can usually be coated even with one coat (or one solution) (in other words, without combining a plurality of coating solutions).

In another aspect of the present invention, a sealer that can realize efficient primer can be provided. For example, according to the sealer of the present invention, the substrate can be reinforced. Usually, a reinforcing effect is obtained by permeating the base material, but a step of separately applying a sealer for forming a coating film on the surface of the base material is required. That is, both a sealer for reinforcement and a sealer for film formation are required for a substrate (in particular, a non-reinforcing substrate such as a non-cured sealer). In addition, in the case where the undercoating is performed a plurality of times such as in the case where the sealer is applied twice before and after the autoclave curing process for the ceramic base material, the manufacturing process becomes complicated.
However, according to the sealer of the present invention, surprisingly, it is possible to achieve both the reinforcement of the substrate and the formation of the coating film with one coat. In addition, the adhesion between the reinforcing portion and the coating portion is high (furthermore, crosslinking is formed between these two portions) or the adhesion to the substrate and the reinforcing property are efficiently achieved. Can be compatible. Therefore, according to the sealer of this invention, even if it is 1 coat, water permeability and adhesiveness can also be expressed, reinforcing a base material.

  In yet another aspect of the present invention, a relatively stable sealer can be provided even though it is one liquid. Therefore, the present invention can also provide a sealer that can be stored over a long period of time. Such a sealer can be used for continuous production of a base material (such as a ceramic base material) over a long period of time because the stability of the paint is high.

  The composition of the present invention contains at least a resin emulsion (A) and a water-soluble polymer (B). Such compositions can in particular be used as sealers (compositions for sealers).

<Resin emulsion (A)>
The resin (polymer, polymer) constituting the resin emulsion (A) (or emulsion particles (A)) is not particularly limited, and examples thereof include addition polymerization resins [for example, acrylic resins, vinyl alcohol resins (for example, , Polyvinyl alcohol, etc.), fluorine resins, etc.], condensation resins [eg, polyamide resins, polyester resins, polyurethane resins, etc.], heat or photo-curing resins (eg, alkyd resins, epoxy resins, etc.), etc. It can be mentioned.

  These resins (polymer, polymer) may be used alone or in combination of two or more to constitute the resin emulsion (A). Moreover, a resin emulsion (A) may be used independently or may combine 2 or more types of resin emulsions.

  Acrylic resin (acrylic resin which comprises an acryl-type emulsion) etc. are contained as typical resin. Such an acrylic resin only needs to contain at least a (meth) acrylic monomer as a polymerization component, and further an acrylic resin (eg, styrene-acrylic) containing another monomer (eg, a styrene monomer) as a polymerization component. And the like.

  The resin will be specifically described below. The resin (polymer, polymer) usually has the monomer component (a) as a polymerization component. Such a monomer component (a) may be usually an addition polymerizable monomer (or a radical polymerizable monomer, a monomer having an ethylenically unsaturated bond, etc.). The monomer components (a) may be used alone or in combination of two or more.

Specific monomer components (a) include, for example, (meth) acrylic monomers, styrene monomers, carbonyl group-containing monomers, fluorine-containing monomers {for example, fluorine atom-containing acrylic monomers [for example, fluoroalkyl (Meth) acrylates (eg, fluoro C _1-10 alkyl (meth) acrylates such as trifluoroethyl (meth) acrylate), etc.]}, silicon-containing monomers {eg, vinyl group-containing silanes (eg, vinyl trichlorosilane, etc.) Vinyl mono to trihalosilane), alkoxysilane having a vinyl group [vinylalkoxysilane (for example, vinyltrimethoxysilane, vinyltriethoxysilane), etc.], alkoxysilyl group-containing radical polymerizable monomer [for example, (meth) acryloyl group-containing alkoxy Sisilane (for example, (meth) acryloyloxyalkylmono to trialkoxysilane such as γ- (meth) acryloyloxypropyltrimethoxysilane), etc.], UV-absorbing monomer {for example, benzotriazole-based UV-absorbing monomer [for example 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole, etc.], benzophenone-based UV-absorbing monomers [for example, 2-hydroxy-4- (meth) acryloyloxybenzophenone, etc. Etc.], UV-stable monomers [for example, light stabilizers having a polymerizable group such as 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine (HALS)] and the like.

  Further, the monomer component (a) may contain a hydrophilic monomer, an acid group-containing monomer, a monomer having a functional group, and the like.

  Hereinafter, these monomers are described in detail.

[(Meth) acrylic monomer]
The monomer component (a) may contain a (meth) acrylic monomer.
As a (meth) acrylic-type monomer, aliphatic (meth) acrylate, aromatic (meth) acrylate, etc. are mentioned.

Examples of aliphatic (meth) acrylates include linear aliphatic (meth) acrylates {eg, alkyl (meth) acrylate [eg methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, 2- Ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate Stearyl (meth) _{C 1-20} alkyl, such as acrylates (meth) acrylate, alkoxyalkyl (meth) acrylates [for example, alkoxyalkyl (meth) acrylate (e.g., 2-methoxyethyl (meth) _{C 1-12} alkoxy acrylate C _1-12 alkyl methacrylate and the like) and the like, etc.}, alicyclic (meth) acrylate [eg, cycloalkyl (meth) acrylate (eg, C _4-20 cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate, Preferably, C _4-10 cycloalkyl (meth) acrylate), cycloalkyl alkyl (meth) acrylate (eg, cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexyl C _4-10 cycloalkyl C _1-4 alkyl (meth) acrylates such as ropir (meth) acrylate, 4-methylcyclohexylmethyl (meth) acrylate, crosslinked cyclic (meth) acrylates (eg, isobornyl (meth) acrylate, Adamantyl (meth) acrylate etc.], glycidyl (meth) acrylate, epoxy group-containing aliphatic (meth) acrylate [eg, glycidyl oxyalkyl (meth) acrylate (eg, glycidyl such as 2-glycidyloxyethyl (meth) acrylate) Oxy _C2-4 alkyl (meth) acrylate etc.] etc. are mentioned.

Examples of the aromatic (meth) acrylate include aryl (meth) acrylate (for example, C _6-10 aryl (meth) acrylate such as phenyl (meth) acrylate), aralkyl (meth) acrylate (for example, benzyl (meth) acrylate) , C _6-10 aryl C _1-4 alkyl (meth) acrylate such as phenethyl (meth) acrylate), aryloxyalkyl methacrylate (for example, C _6-10 aryloxy C _1-4 alkyl methacrylate such as phenoxyethyl methacrylate), etc. Can be mentioned.

  The (meth) acrylic monomers may be used alone or in combination of two or more.

Among them, linear aliphatic (meth) acrylates {especially alkyl (meth) acrylates [eg methyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) ) _{C 1-12} alkyl, such as acrylates (meth) acrylates _{(e.g., C 1-8} alkyl (meth) acrylate), etc.], etc.} may be preferably used.

  Therefore, the (meth) acrylic monomer may contain at least a chain aliphatic (meth) acrylate (particularly, alkyl (meth) acrylate).

  When the (meth) acrylic monomer contains a linear aliphatic (meth) acrylate, the ratio of the linear aliphatic (meth) acrylate to the entire (meth) acrylic monomer is, for example, 10% by mass or more (e.g. 100% by mass), preferably 20% by mass or more (eg, 25% by mass or more), more preferably 30% by mass or more (eg, 40% by mass or more), particularly preferably 50% by mass or more (eg, 60% by mass or more) ) Degree may be sufficient, and 70 mass% or more (for example, 80 mass% or more) may be sufficient.

  When the monomer component (a) contains a (meth) acrylic monomer, the proportion of the (meth) acrylic monomer in the monomer component (a) is, for example, 0.5% by mass or more (for example, 1% by mass) Or more) 1.5 mass% or more (eg, 2 mass% or more), preferably 3 mass% or more (eg, 4 mass% or more), more preferably 5 mass% or more (eg, 7 It may be 10% by mass or more, particularly 10% by mass or more (eg 12% by mass or more), particularly preferably 15% by mass or more (eg 18% by mass or more), 20% by mass or more (eg 22% by mass) Above, 25 mass% or more) may be sufficient.

When the monomer component (a) includes a (meth) acrylic monomer, the upper limit value of the proportion of the (meth) acrylic monomer is not particularly limited, but for the entire monomer component (a), for example, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 35 mass%, 30 mass%, 25 mass%, etc. may be sufficient.
In addition, these upper limits can each set a range combining arbitrarily with the said ratio (for example, 1.5-50 mass%, 5-30 mass%, etc.).

  Further, as described later, when the resin has a multilayer structure, the above range may be satisfied in the entire multilayer structure, but the above range is satisfied in each of the monomer components (a) constituting each layer. It may or may not be satisfied (the same applies hereinafter).

[Styrene monomer]
The monomer component (a) may contain a styrene monomer. By including a styrene monomer, excellent water resistance can be efficiently imparted to the coating film.

Examples of the styrene monomer include styrene, α-alkyl styrene (for example, α-C _1-4 alkyl styrene such as α-methyl styrene), alkyl styrene (for example, C _1-4 alkyl styrene such as vinyl toluene), Halostyrene (for example, chlorostyrene etc.) etc. are mentioned.

  You may use a styrene-type monomer individually or in combination of 2 or more types.

  Preferred styrenic monomers include styrene. Therefore, the styrenic monomer may contain at least styrene.

  When the styrene monomer contains styrene, the ratio of styrene to the whole styrene monomer is, for example, 10% by mass or more (for example, 15 to 100% by mass), preferably 20% by mass or more (for example, 25% by mass or more), More preferably, it may be 30% by mass or more (for example, 40% by mass or more), particularly preferably 50% by mass or more (for example, 60% by mass or more), or 70% by mass or more (for example, 80% by mass or more) It may be.

  When the monomer component (a) contains a styrenic monomer, the proportion of the styrenic monomer in the monomer component (a) can be selected, for example, from the range of about 1% by mass or more (eg, 3% by mass or more) , 5 mass% or more (for example, 10 mass% or more), preferably 15 mass% or more (for example, 18 mass% or more), more preferably 20 mass% or more (for example, 25 mass% or more), particularly 30 mass% or more (Eg, 35% by mass or more), particularly preferably 40% by mass or more (eg, 45% by mass or more), 50% by mass or more (eg, 55% by mass or more, 60% by mass or more, 65% by mass) 70 mass% or more) or 20 to 90 mass% or the like.

  When the monomer component (a) contains a styrene monomer, the upper limit of the ratio of the styrene monomer is not particularly limited, but is, for example, 95% by mass and 90% by mass with respect to the entire monomer component (a). %, 85 mass%, 80 mass%, etc. may be sufficient.

  When the monomer component (a) contains a styrene-based monomer and a (meth) acrylic-based monomer, the ratio of these components is as follows: styrene-based monomer / (meth) acrylic-based monomer (mass ratio) = 1 / 0.01 to 1 / 10, preferably 1 / 0.05 to 1/5, more preferably 1 / 0.1 to 1/1, especially about 1 / 0.2 to 1 / 0.5.

[Hydrophilic monomer]
The monomer component (a) may contain a hydrophilic monomer. By containing a hydrophilic monomer, it is easy to improve the mechanical stability of the emulsion.

  Examples of hydrophilic monomers (or monomers having a hydrophilic group) include monomers having a hydroxyl group (hydroxyl group), nitrogen-containing monomers, and monomers having an oxyalkylene group. The hydrophilic monomer may be a monomer which does not belong to the category of the acid group-containing monomer described later.

As a monomer having a hydroxyl group, hydroxyl group-containing (meth) acrylates, for example, hydroxyalkyl (meth) acrylates [eg, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl ( Hydroxy C _2-10 alkyl (meth) acrylates such as meta) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, preferably C _2-6 alkyl (meth) acrylate, more preferably such _{C 2-4} alkyl (meth) acrylate], dialkylene glycol mono (meth) acrylates [for example, diethylene glycol mono (meth) acrylate Di C _2-4 alkanediol such as rate (mono) methacrylate, etc.], polyalkylene glycol mono (meth) acrylate (described later compound), polyalkylene glycol mono (meth) acrylamide (described later compound), 3 or more And (meth) acrylates of polyols having a hydroxyl group (for example, (meth) acrylates of tri- to hexahydroxy C _3-10 polyols such as glycerol mono (meth) acrylate) and the like.

  The monomers having a hydroxyl group may be used alone or in combination of two or more.

Examples of the nitrogen-containing monomer include lactam monomers (for example, N-vinyl pyrrolidone and N-vinyl caprolactam), (meth) acrylamide compounds {for example, (meth) acrylamide, N-substituted (meth) acrylamide [for example, N -Alkyl (meth) acrylamide (for example, N, N- di C _1-4 alkyl (meth) acrylamide such as N, N- dimethyl (meth) acrylamide; N, N- dimethylaminopropyl (meth) acrylamide etc) and the like) , Polyalkylene glycol mono (meth) acrylamide (compound described later)}, nitrogen atom-containing (meth) acrylate compound {for example, N-substituted aminoalkyl (meth) acrylate [for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meta) a N, N-diC _1-4 alkylamino C _2-4 alkyl (meth) acrylate] such as acrylate}, (meth) acrylonitrile and the like.

  The nitrogen-containing monomers may be used alone or in combination of two or more.

Examples of the monomer having an oxyalkylene group (or polyoxyalkylene group) include polyalkylene glycol mono (meth) acrylate {or poly (oxyalkylene) mono (meth) acrylate such as polyethylene glycol mono (meth) acrylate, polypropylene Poly C _2-4 alkylene glycol mono (meth) acrylates such as glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (oxyethylene / oxypropylene) mono (meth) acrylate [or poly (oxy C _{2 -4} alkylene) mono (meth) acrylate], etc.}, polyalkylene glycol mono (meth) acrylamide {or poly (oxyalkylene) mono (meth) acrylamides, for example, polyethylene Glycol mono (meth) acrylamide, polypropylene glycol mono (meth) acrylamide, polybutylene glycol mono (meth) acrylate, poly (oxyethylene / oxypropylene) mono (meth) poly C _2-4 alkylene glycol mono acrylamide (meth) acrylamide [or poly (oxy-C _2-4 alkylene) mono (meth) acrylamide], etc.}, polyalkylene glycol monoalkenyl ether {or poly (oxyalkylene) monoalkenyl ethers, such as poly C _2, such as polyethylene glycol monoallyl ether _-4 alkylene glycol monoallyl ether etc.}, the hydroxyl group remaining in these polyalkylene glycol chains is blocked {eg, etherification [eg -Terminated (eg, C _1-4 alkyl etherified such as methyl ether)] compound [eg, poly C such as methyl polyethylene glycol mono (meth) acrylate (mono (meth) acrylate monomethyl ether of polyethylene glycol) _2-4 alkylene glycol mono (meth) acrylate monoalkyl ether; poly C _2-4 alkylene glycol mono (meth) acrylamide monoalkyl such as methyl polyethylene glycol mono (meth) acrylamide (mono (meth) acrylamide monomethyl ether of polyethylene glycol) Ether: Poly C _2-4 alkylene glycol mono, such as methyl polyethylene glycol monoallyl ether (monoallyl ether monomethyl ether of polyethylene glycol) Allyl ether monoalkyl ether] and the like.

  In the monomer having an oxyalkylene group, the number of oxyalkylene groups (alkylene oxide units and alkylene glycol units) [the number of repetition of oxyalkylene groups in poly (oxyalkylene)] is 2 or more, particularly 3 or more (for example, 3) -500, 3-200), for example, 3-100 (for example, 3-50), 4-40 (for example, 5-30) etc. may be sufficient.

  The monomers having an oxyalkylene group may be used alone or in combination of two or more.

  The hydrophilic monomers may be used alone or in combination of two or more.

  Among these, a monomer having a hydroxyl group and a monomer having an oxyalkylene group may be particularly preferably used. Therefore, the hydrophilic monomer may include at least one selected from a monomer having at least a hydroxyl group and a monomer having an oxyalkylene group.

  When the hydrophilic monomer contains at least one selected from a monomer having a hydroxyl group and a monomer having an oxyalkylene group, at least one selected from a monomer having a hydroxyl group and a monomer having an oxyalkylene group in the hydrophilic monomer The proportion of the species is, for example, 10% by mass or more (eg, 15 to 100% by mass), preferably 20% by mass or more (eg, 25% by mass or more), more preferably 30% by mass or more (eg, 40% by mass or more) ), Particularly preferably about 50 mass% or more (for example, 60 mass% or more), or 70 mass% or more (for example, 80 mass% or more).

  Among the monomers having a hydroxyl group, hydroxyalkyl (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate) and the like may be suitably used. Therefore, the monomer having a hydroxyl group may contain at least hydroxyalkyl (meth) acrylate.

  When the monomer having a hydroxyl group contains a hydroxyalkyl (meth) acrylate, the proportion of the hydroxyalkyl (meth) acrylate in the monomer having a hydroxyl group is, for example, 10% by mass or more (for example, 15 to 100% by mass), preferably Is at least 20% by mass (eg, 25% by mass or more), more preferably 30% by mass or more (eg, 40% by mass or more), particularly preferably 50% by mass or more (eg, 60% by mass or more) 70 mass% or more (for example, 80 mass% or more) may be sufficient.

  When the monomer component (a) contains a hydrophilic monomer, the proportion of the hydrophilic monomer in the monomer component (a) is, for example, about 0.1 mass% or more (for example, 0.2 mass% or more) The range can be selected from 0.3% by mass or more (eg, 0.5% by mass or more), preferably 0.7% by mass or more (eg, 0.8% by mass or more), more preferably 1% by mass or more (eg, 1.2% by mass or more), particularly 1.5% by mass or more (eg, 1.6% by mass or more), and particularly preferably 1.8% by mass or more (eg, 1.9% by mass or more). Alternatively, it may be 2% by mass or more (for example, 2.2% by mass or more, 2.5% by mass or more).

  When the monomer component (a) includes a hydrophilic monomer, the upper limit value of the ratio of the hydrophilic monomer is not particularly limited, but is, for example, 90% by mass, 80% by mass with respect to the entire monomer component (a). %, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 12 mass%, 10 mass%, 8 mass%, 7 mass%, 6 mass%, 5 mass%, 4 mass%, etc. may be sufficient.

  When the monomer component (a) contains a hydrophilic monomer and a styrenic monomer, the ratio thereof is such that hydrophilic monomer / styrenic monomer (mass ratio) = 0.001 / 1 to 10/1, preferably 0. 003/1 to 1/1, more preferably 0.005 / 1 to 0.5 / 1 (eg, 0.008 / 1 to 0.1 / 1), particularly 0.01 / 1 to 0.08 / 1. (For example, about 0.015 / 1 to 0.05 / 1) may be sufficient.

  In addition, when the monomer component (a) contains a hydrophilic monomer and a (meth) acrylic monomer, the ratio of these is: hydrophilic monomer / (meth) acrylic monomer (mass ratio) = 0.005 / 1 to 1 It may be 20/1, preferably 0.01 / 1 to 10/1, more preferably 0.02 / 1 to 1/1, especially about 0.05 / 1 to 0.5 / 1.

  As described later, when the resin has a multilayer structure, the above range may be satisfied in the entire multilayer structure, and the ratio of the hydrophilic monomer in the outer layer (the monomer component (a) constituting the outer layer) is also in the above range May be satisfied.

[Acid group-containing monomer]
The monomer component (a) may contain an acid group-containing monomer.

  In the acid group-containing monomer, examples of the acid group include a carboxyl group, an acid anhydride group, and a sulfonic acid group (sulfuric acid group). The acid group-containing monomer may have one or more acid groups or may have different acid groups.

  Examples of the acid group-containing monomer (acid group-containing monomer) include carboxylic acid groups or acid anhydride group-containing monomers [for example, unsaturated monocarboxylic acids (for example, acrylic acid, methacrylic acid, crotonic acid, etc. Aliphatic unsaturated monocarboxylic acids), unsaturated dicarboxylic acids (for example, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid), acid anhydrides thereof (for example, maleic anhydride etc.) and the like, sulfonic acids Group-containing monomers [for example, styrene-based monomers (for example, styrene sulfonic acid, etc.)] and the like.

  Representative acid group-containing monomers include acrylic acid, methacrylic acid and the like.

  You may use an acid group containing monomer 1 type or in combination of 2 or more types.

  When the monomer component (a) contains an acid group-containing monomer, the proportion of the acid group-containing monomer is not particularly limited, and, for example, 0.1% by mass with respect to the entire monomer component (a) Or more, 0.2 mass% or more, 0.3 mass% or more, 0.4 mass% or more, 0.5 mass% or more, 0.6 mass% or more, 0.7 mass% or more, 0.8 mass% or more It may be.

  In the monomer component (a), the proportion of the acid group-containing monomer may be relatively small, for example, less than 5% by mass (for example, 4.7% by mass) based on the whole of the monomer component (a) Or less), 4.5% by mass or less (eg, 4.2% by mass or less), preferably 4% by mass or less (eg, 3.8% by mass or less), and more preferably 3.5% by mass or less (eg, 3% or less). .2% by mass or less), particularly preferably 3% by mass or less (for example, 2.9% by mass or less), or 2.8% by mass or less (for example, 2.6% by mass or less), 2.5 % By mass or less (for example, 2.4% by mass or less), 2.2% by mass or less (for example, 2.1% by mass or less), 2% by mass or less (for example, 1.8% by mass or less), 1.5% by mass % Or less.

By containing the acid group-containing monomer, the mechanical stability of the emulsion can be easily improved. On the other hand, the water resistance of the coating film may be reduced as the amount of the acid group-containing monomer increases.
Therefore, as described above, the acid group-containing monomer may be appropriately contained.

  When the monomer component (a) contains a hydrophilic monomer and an acid group-containing monomer, in the monomer component (a), the ratio of the acid group-containing monomer to 1 part by mass of the hydrophilic monomer is, for example, 20 parts by mass or less (Eg, 15 parts by mass or less), preferably 10 parts by mass or less (eg, 8 parts by mass or less), more preferably 5 parts by mass or less (eg, 3 parts by mass or less), particularly 2 parts by mass or less (eg, 1. 9 parts by mass or less) and 1.8 parts by mass or less (eg, 1.7 parts by mass or less, 1.6 parts by mass or less, 1.5 parts by mass or less, 1.4 parts by mass or less, 1. 3 parts by mass or less, 1.2 parts by mass or less, 1 part by mass or less, 0.9 parts by mass or less, 0.8 parts by mass or less, 0.7 parts by mass or less, 0.6 parts by mass or less, 0.5 parts by mass Or the like).

  In addition, as described later, when the resin has a multilayer structure, it is sufficient to satisfy the above range in the entire multilayer structure, and in particular, the ratio of the acid group-containing monomer in the outer layer (monomer component (a) constituting the outer layer). May also satisfy the above range.

[Monomer having functional group]
The monomer component (a) may contain a monomer (monomer) having a functional group (referred to as a functional group α). By the resin emulsion having such a monomer having a functional group α (or a structural unit derived therefrom), bonding of the resin emulsions with each other, the resin emulsion (A) and a water-soluble polymer (B) described later [ Alternatively, it is possible to efficiently form a bond with a functional group (functional group β described below) possessed by the water-soluble polymer (B), and thus to easily realize the undercoating by the sealer of the present invention.

  The functional group α can be appropriately selected depending on the combination with the crosslinking agent C described later, the combination with the functional group β, etc. For example, a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, an acyl group etc.) And carboxyl group, acid anhydride group, acid halide group, carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group, mercapto group and the like.

  The monomer having the functional group α may have these functional groups alone or in combination of two or more.

  Among these functional groups, a carbonyl group, a carboxyl group, an oxazoline group, a hydrazino group, a hydroxyl group and the like are preferable from the viewpoint of coating film physical properties and the like, and a carbonyl group and a carboxyl group are particularly preferable.

  Specific examples of the monomer having a functional group α include a carbonyl group-containing monomer, a carboxyl group-containing monomer, an oxazoline group-containing monomer, and a hydroxyl group-containing monomer.

As the carbonyl group-containing monomer, for example, unsaturated aldehyde [eg, alkenal (eg, C _3-10 alkenal such as acrolein, methacrolein etc.), (meth) acryloxyalkyl alkenal (eg, acroxyalkyl propenal) , Methacryloxyalkylpropenal), formylstyrene, etc.], unsaturated ketones {eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone etc.), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) Acetonyl methacrylate etc., N- (meth) acryloylaminoalkanone (eg diacetone acrylamide, diacetone methacrylamide etc), alkanediol (meth) acrylate acetylene Acetate (for example, C _2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxy group Containing ethylenically unsaturated monomers [eg, acetoacetoxyalkyl (meth) acrylates (eg, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate), acetoacetoxy allyl ester etc.], etc. It can be mentioned.

  As the carboxyl group-containing monomer, acid group-containing monomers of the above-mentioned examples, for example, unsaturated monocarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid), unsaturated dicarboxylic acid (For example, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid).

As the oxazoline group-containing monomer, for example, alkenyl oxazoline (for example, C _2-6 alkenyl oxazoline such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C _2-6 alkenyl-C _1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C _1-4 alkyl oxazoline) and the like.

  Examples of the hydroxyl group-containing monomer include the hydroxy group-containing monomers exemplified above (for example, hydroxyl group-containing (meth) acrylate).

  The monomers having the functional group α may be used alone or in combination of two or more.

  Among these, carbonyl group-containing monomers and unsaturated monocarboxylic acids (acrylic acid and the like) are particularly preferable, and carbonyl group-containing monomers (particularly diacetone (meth) acrylamide) are particularly preferable.

  When the monomer component (a) contains a monomer having a functional group α, the content ratio (content ratio) of the monomer having a functional group α in the monomer component (a) is 50% by mass or less (For example, 40% by mass or less) can be selected, for example, 30% by mass or less (eg, 20% by mass or less), 0.001 to 10% by mass, preferably 0.01 to 5% by mass, more preferably May be about 0.02 to 3% by mass, or about 0.05 to 10% by mass (for example, 0.1 to 5% by mass).

  In particular, when a carbonyl group-containing monomer is used as the monomer having functional group α, the content ratio (content ratio) of the carbonyl group-containing monomer in the monomer component (a) is 5% by mass or less (For example, 0.001 to 4 mass%), preferably 3.5 mass% or less (for example, 0.005 to 3 mass%), more preferably 2.5 mass% or less (for example, 0.01 to 2. mass%). 5% by mass), particularly 2% by mass or less (for example, 0.05 to 1.8% by mass).

  In particular, when a carboxyl group-containing monomer is used as a monomer having a functional group α, the content ratio (content ratio) of the carboxyl group-containing monomer in the monomer component (a) is 5% by mass or less (For example, 0.001 to 4 mass%), preferably 3.5 mass% or less (for example, 0.005 to 3 mass%), more preferably 2.5 mass% or less (for example, 0.01 to 2. mass%). 5% by mass), particularly 2% by mass or less (for example, 0.05 to 1.8% by mass).

  When the resin (polymer) constituting the resin emulsion is a copolymer (for example, a monomer component (a) including a (meth) acrylic monomer, a styrene monomer, and a monomer having a functional group α) The copolymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

[Aspect of resin emulsion]
In the resin emulsion (emulsion particles), a resin (or a resin containing a monomer component (a) as a polymerization component) constitutes an emulsion (or the resin is in an emulsion state). Therefore, the resin emulsion may be composed of a resin (particle) and an emulsifier (an emulsifier that coats the resin particle). The resin emulsion may be a resin (resin particle) [or the resin (or resin particle)] dispersed in a solvent.

The particle size of the resin (resin particles) constituting the resin emulsion is not particularly limited, but may be, for example, an average particle size of 50 to 300 nm, preferably 100 to 200 nm, and more preferably about 130 to 170 nm.
In addition, as for the particle size, for example, the average particle size of the emulsion particles may be measured using a particle size distribution measuring instrument (such as Otsuka Electronics Co., Ltd. FPAR-1000) by a dynamic light scattering method.

  The emulsion (or resin emulsion, resin emulsion, emulsion composition) containing such a resin may usually be an aqueous emulsion.

  The method for producing such an emulsion is not particularly limited. For example, emulsion polymerization (polymerization in the presence of an emulsifier) of a monomer component (monomer component (a)) constituting the resin is carried out in a solvent. May be obtained.

Examples of the solvent generally include aqueous solvents (aqueous solvents) such as water and solvents containing water [mixed solvents of water and alcohol (such as C _1-4 alcohol such as methanol and ethanol, etc.)], and particularly water. By emulsion polymerization in such an aqueous solvent, an aqueous (aqueous) emulsion can be obtained efficiently.

  The emulsifier (dispersant, surfactant) is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, and an amphoteric emulsifier. The emulsifier may be a polymeric emulsifier or a reactive emulsifier.

  In particular, a non-nonylphenyl emulsifier may be suitably used from the viewpoint of environmental protection.

  As a specific emulsifier (for example, non-reactive emulsifier), for example, polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene oleyl ether sulfate sodium salt, polyoxyalkylene alkyl phenyl ether sulfate ester salt, alkyl diphenyl ether disulfonate , Polyoxyalkylene (mono, di, tri) styryl phenyl ether sulfate, polyoxy alkylene (mono, di, tri) benzyl phenyl ether sulfate, alkenyl succinic acid di salt; and sodium dodecyl sulfate, potassium dodecyl sulfate Alkyl sulfate salts such as ammonium alkyl sulfate; sodium dodecyl polyglycol ether sulfate; sodium sulforicinoate; sulfone Alkyl sulfonates such as paraffin salts; sodium dodecylbenzene sulfonates; alkyl sulfonates such as alkali metal sulfates of alkaline phenol hydroxyethylene; highly alkyl naphthalene sulfonates; naphthalene sulfonic acid formalin condensates; sodium laurate, triethanolamine oleate, tri Fatty acid salts such as ethanolamine abiolate; polyoxyalkyl ether sulfuric acid ester salts; polyoxyethylene carboxylic acid ester sulfuric acid ester salts; polyoxyethylene phenyl ether sulfuric acid ester salts; succinic acid dialkyl ester sulfonic acid salts; polyoxyethylene alkyl aryl sulfates Examples include salt.

  Moreover, as a reactive emulsifier, for example, propenyl-alkyl sulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [eg, Sanyo Chemical Industries, Ltd. , Trade name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate [for example, Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10, etc.], allyloxymethyl alkyl oxypolyoxy Sulfonate salt of ethylene [for example, Dai-ichi Kogyo Seiyaku Co., Ltd. product name: Aqualon KH-10, etc.], sulfonate salt of allyloxymethylnonyl phenoxyethyl hydroxypolyoxyethylene [for example, product name ADEKA, trade name : Adekaria Soap SE -10 etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene sulfuric acid ester salt [eg, manufactured by ADEKA Co., Ltd., trade name: Adekaria soap SR-10, SR-30 etc.], bis (polyoxyethylene polycyclic phenyl) Ether) methacrylated sulfonate salt [eg, Nippon Emulsifier Co., Ltd. product name: Antox MS-60, etc.], allyloxymethylalkoxyethyl hydroxypolyoxyethylene [eg, manufactured by ADEKA Corp., trade name: adekaria Soap ER-20 and the like], polyoxyethylene alkylpropenyl phenyl ether [eg, Dai-ichi Kogyo Seiyaku Co., Ltd. trade name: aqualon RN-20 etc.], allyloxymethylnonyl phenoxyethyl hydroxypolyoxyethylene [eg, ADEKA Corporation , Trade name: ADEKAREASOAP NE-10, etc.] and the like.

  In addition, as a commercially available emulsifier (for example, anionic emulsifier), for example, Latem WX, Latem 118B, Perex SS-H, Emulgen 1118 S, Emulgen A-60, B-66 (manufactured by Kao Corporation), Newcor 707SF, New Cole 707 SN, New Call 714 SF, New Call 714 SN (manufactured by Nippon Emulsifier), ABEX-26S, ABEX-2010, 2020, 2030, RHODACAL DSB (manufactured by Rhodia Nikka), Hytenor LA-10, Hytenor NF-08 (Made by Dai-ichi Kogyo Seiyaku Co., Ltd.) etc. can be mentioned.

  The emulsifying agents may be used alone or in combination of two or more.

  The proportion of the emulsifying agent is, for example, 0.5 parts by mass or more, more preferably 1 part by mass or more with respect to 100 parts by mass of the monomer component (a), and preferably 10 parts from the viewpoint of coating film properties and the like. It may be part or less, more preferably 7 parts by mass or less, further preferably 5 parts by mass or less.

In the emulsion polymerization, the polymerization initiator is not particularly limited, and a conventional polymerization initiator can be used. Emulsion polymerization may be carried out in the presence of a chain transfer agent such as a compound having a thiol group, a pH buffering agent, a chelating agent, a film-forming aid and the like.
In addition, emulsion polymerization conditions (temperature, time, etc.) can be selected appropriately.

  The resin emulsion (or the resin constituting the resin emulsion) may have a single layer structure (even one layer only) or a multilayer structure (or core-shell structure) (the inner layer is formed However, it may be composed of an outer layer and an inner layer). A multilayer structure (core-shell structure) may be advantageous in terms of physical properties of the coating film.

  When the resin emulsion has a multilayer structure, the number of outer layers may be one or more, and may be, for example, 1 to 5, preferably 1 to 4, more preferably 1 to 3 (for example, 1 or 2). , And in particular two.

  When the resin emulsion has a multilayer structure, the outer layer (shell) and the inner layer (core) may be different resins, as long as the monomer component (a) is a polymerization component throughout the multilayer structure.

  For example, the multilayer structure may be configured (relatively configured) with a hard layer (hard layer) and a soft layer (soft layer). In such a case, either the outer layer or the inner layer may be a hard layer, that is, the outer layer may be a hard layer and the inner layer may be a soft layer, and the outer layer may be a soft layer and a hard layer. There may be. Further, when the outer layer is composed of a plurality of layers, a hard layer and a soft layer may be configured between the plurality of outer layers.

  The mass ratio of the inner layer to the outer layer (resin constituting the inner layer / resin constituting the outer layer) is not particularly limited, and is, for example, 99/1 to 1/99 (for example, 95/5 to 3/97), preferably It may be about 90/10 to 5/95 (e.g. 80/20 to 8/92), more preferably 70/30 to 10/90 (e.g. 60/40 to 15/85), 55/45. To 15/85 or 50/50 to 25/75 (for example, 45/55 to 30/70, etc.).

  When the resin has a three-layer structure (two outer layers), when the mass of the first layer (inner layer) is 1, the mass of the second layer (outer layer) is 0.1 to 10 ( For example, the mass of the third layer (outermost layer among outer layers) may be 0.1 to 10 (for example, 0.5 to 5).

  In particular, when the resin emulsion uses the specific monomer component (a) as a polymerization component as described above, the embodiment of the hydrophilic monomer, the monomer having a functional group, the monomer having an acid group, etc. is a multilayer. It is preferable to satisfy also in the outer layer (the outermost layer) of the structure.

  For example, when the resin having a multilayer structure contains a hydrophilic monomer, at least the outer layer may contain the hydrophilic monomer (the inner layer may or may not contain the hydrophilic monomer), and the hydrophilicity contained in the outer layer The proportion of monomers may satisfy the above proportion (range).

  When the outer layer is composed of a plurality of layers, the whole of the plurality of layers may satisfy aspects such as a hydrophilic monomer, a monomer having a functional group or a monomer having an acid group, and at least the outermost layer ( For example, in the outermost layer only), an embodiment such as a hydrophilic monomer or a monomer having a functional group may be satisfied.

  The weight average molecular weight of the resin constituting the resin emulsion may be selected from the range of 10,000 or more (for example, 20,000 or more), for example, or 30,000 or more (for example, 40,000 to 1,000,000), preferably 50,000. Or more (e.g., 60,000 to 800,000), and more preferably 80,000 or more (e.g., 80,000 to 250,000), or more than 100,000 (e.g., 12 to 600,000), 150,000 or more (e.g. 200 to 500,000) or the like, or about 30,000 to 600,000 (for example, 5 to 500,000).

  The resin constituting the resin emulsion may contain relatively low molecular weight components (low molecular weight polymer, low molecular weight polymer component). Such low molecular weight components include, for example, components having a weight average molecular weight of 100,000 or less (for example, weight average molecular weight 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, etc.) It is also good. The lower limit of the weight average molecular weight of the low molecular weight component is not particularly limited, but may be 10,000, 20,000, 30,000, 40,000, for example.

When the resin contains such low molecular weight components, the ratio of low molecular weight components to the entire resin is 1% or more (eg, 3% or more) in area ratio in gel permeation chromatography (chart), Preferably, it may be 5% or more (eg, 7% or more), more preferably 10% or more (eg, 12% or more), and particularly 15% or more (eg, 18% or more), or 20% or more (eg, 22% or more, 25% or more, etc.).
The upper limit of the ratio of the low molecular weight component to the whole resin is not particularly limited, but the area ratio in gel permeation chromatography (chart) is, for example, 70%, 60%, 55%, 50%, 45 %, 40%, 35% and the like.

  When the resin constituting the resin contains such a low molecular weight component, it may be advantageous in terms of adhesion of the coating film.

  In addition, although the measuring method of the ratio of a weight average molecular weight and a component of a low molecular weight is not specifically limited, For example, you may measure by the below-mentioned method etc.

  When the resin constituting the resin emulsion has a low molecular weight component, the weight average molecular weight of the resin constituting the resin emulsion (the weight average molecular weight of the entire resin) can be selected according to the proportion of the low molecular weight component in the entire resin, It may be the same range as the above.

When the resin constituting the resin emulsion has a low molecular weight component, the form of presence is not particularly limited. For example, the resin may be comprised of a plurality of different weight average molecular weight polymers, and may be comprised of the same resin containing low molecular weight components.
In addition, when the resin or the emulsion has a multilayer structure, it is sufficient to have a low molecular weight component as the whole multilayer structure, and any layer (inner layer or outer layer) has a low molecular weight component The inner layer and the outer layer may have low molecular weight components, and in particular, at least the outer layer (particularly, only the outer layer) may contain (in a predetermined ratio) low molecular weight components.

  When the outer layer is composed of a plurality of layers, it is preferable that at least the outermost layer (particularly only the outermost layer) has a low molecular weight component. Moreover, in such a case, the layer forming the outermost layer may contain a low molecular weight component, as long as the effect of the low molecular weight component is not impaired. For example, a resin component having a weight average molecular weight of more than 80,000 may be present.

  In such a case, the proportion of the low molecular weight component in the outer layer (particularly the outermost layer) may be selected from the same range as described above, or may be a relatively large proportion. For example, the ratio of the low molecular weight component is 5% or more (for example, 10% or more) as an area ratio in gel permeation chromatography (chart) with respect to the entire resin constituting the outer layer (or outermost layer), It may be preferably 20% or more (eg, 25% or more), more preferably 30% or more (eg, 35% or more), and particularly 40% or more (eg, 45% or more), 50% or more (eg, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, etc.).

On the other hand, when the resin emulsion has a multilayer structure, each layer may be composed of a resin having a different molecular weight (weight average molecular weight, etc.). You may lower it.
When the outer layer has two or more layers (when it has an intermediate layer), the molecular weight of the resin that constitutes the outermost layer (outer layer that is not the intermediate layer) may be made lower than the molecular weight of the resin that constitutes the inner layer. Good.

In such a case, the weight average molecular weight of the low molecular weight resin (for example, the resin constituting the outer layer or the outermost layer) depends on the molecular weight and the like of the higher molecular weight resin (for example, the resin constituting the inner layer or the intermediate layer) For example, it may be 300,000 or less (eg, 1 to 250,000), preferably 200,000 or less (eg, 1 to 180,000), more preferably 150,000 or less (eg, 1 to 100,000) or so .
In addition, the difference between the weight average molecular weight of the high molecular weight resin (for example, the resin constituting the inner layer and the intermediate layer) and the weight average molecular weight of the low molecular weight resin (for example the resin constituting the outer layer or the outermost layer) is The number may be about 10,000 or more (for example, 30,000 or more), preferably about 50,000 or more (for example, 70,000 or more), and more preferably about 100,000 or more (for example, 150,000 or more).

  There are no particular limitations on the resin of the multilayer structure having a bias in molecular weight among the layers and the resin of the multilayer structure containing the low molecular weight component as described above. For example, the use of a chain transfer agent and the amount thereof used It may be manufactured by adjustment of. Specifically, when the monomer component used as a raw material for emulsion particles is subjected to multistage emulsion polymerization, the monomer component used as a raw material for a resin layer composed of a low molecular weight resin is added in the presence of a chain transfer agent. And emulsion polymerization of each layer, and even when the emulsion polymerization of each layer is carried out in the presence of a chain transfer agent, the emulsion polymerization is carried out by increasing the amount of the chain transfer agent in the resin layer composed of a low molecular weight resin Although it is mentioned, it is not limited to only such an illustration.

The chain transfer agent is not particularly limited. Examples of the thiol-based compound (or thiol-based chain transfer agent) include aliphatic thiols such as alkanethiols such as octyl mercaptan, dodecyl mercaptan and tert-dodecyl mercaptan. , C _1-20 alkanethiol such as decane trithiol), mercaptoalkanol (eg, mercaptoethanol, 3-mercapto-1-propanol, etc.), mercaptoalkane polyol (eg, 3-mercapto-1,3-propanediol, etc.) cycloalkyl mercaptans (e.g., _{C 3-20} cycloalkyl mercaptans such as cyclohexyl mercaptan) and the like], aromatic thiols (e.g., _{C 6-20} aryl mercaptans such as thiophenol and the like), Mel Putokarubon acid (e.g., mercapto C _2-10 carboxylic acids such as thioglycolic acid), mercaptocarboxylic acid esters [for example, thioglycolic acid esters (e.g., methyl thioglycolate, ethyl thioglycolate, thioglycolic acid propyl, thioglycolic butyl, tert- butyl thioglycolate, 2-ethylhexyl thioglycolate, octyl thioglycolate, isooctyl thioglycolate, decyl thioglycolate, etc. thioglycolic acid C _1-20 alkyl esters such as thioglycolic acid dodecyl), Mercaptopropionate (eg, mercaptopropion such as octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate) Mercaptoalkanoic acid ester such as _C1-20 alkyl acid], mercaptoalkyl alkanoic acid ester (for example, _C1-20 alkanoic acid mercapto _C1-20 alkyl such as 2-mercaptoethyl octoate), polyol mercapto, etc. Carboxylic acid esters [for example, thioglycolates of polyols (for example, C _2-10 alkane polyol thioglycolates such as ethylene glycol thioglycolate, neopentyl glycol thioglycolate, pentaerythritol thioglycolate, etc.)] and the like. .

  The chain transfer agent (in particular, the thiol compound) may be used alone or in combination of two or more. Among these chain transfer agents, octyl thioglycollate, dodecyl mercaptan and tert-dodecyl mercaptan are preferable from the viewpoint of obtaining a resin emulsion that forms a coating film having excellent water resistance and blocking resistance, and octyl thioglycollate Is more preferable.

The use ratio of the chain transfer agent may be, for example, 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and preferably 1 part by mass with respect to 100 parts by mass of the monomer component (a). Hereinafter, it may be 0.8 parts by mass or less, more preferably 0.5 parts by mass or less.
In addition, the proportion of the chain transfer agent used is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass, with respect to 100 parts by mass of the monomer component of the resin (for example, the resin constituting the outer layer or the outermost layer). The amount may be more than 0.5 parts by mass, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and still more preferably 2 parts by mass or less.

  When a chain transfer agent is used, the resin usually contains a chain transfer agent (or a residue or decomposition product thereof). Therefore, when the resin constituting the resin emulsion has a multilayer structure, at least a low molecular weight resin (or a layer composed of a resin, particularly an outer layer or an outermost layer) is a chain transfer agent (in particular, a thiol compound) or a chain transfer agent It may have (or contain) a structure of origin.

The glass transition temperature (Tg) of the resin constituting the resin emulsion (in the case of a multilayer structure, the entire resin) is preferably, for example, -20 ° C. or more (eg, -10 ° C. or more), preferably May be 0 ° C. or more (eg, 10 ° C. or more), more preferably 15 ° C. or more (eg, 20 ° C. or more), 30 ° C. or more [eg, 35 ° C. or more, 40 ° C. or more (eg, 40 to 55 ° C, 40 to 50 ° C., etc.) and the like. The upper limit of the glass transition temperature is not particularly limited, and may be, for example, 100 ° C., 80 ° C., 60 ° C., 50 ° C., or the like.
In addition, you may obtain | require the glass transition temperature, for example by the method [Formula of Fox (Fox)] etc. which are described in the below-mentioned Example.

When the resin constituting the resin emulsion has a multilayer structure, the inner and outer layers may have different glass transition temperatures, for example, a layer having a high glass transition temperature and a layer having a low glass transition temperature. May be formed. Typically, the glass transition temperature (Tg ₁ ) of the inner layer (the resin forming the inner layer) may not be too low compared to the glass transition temperature (Tg ₂ ) of the outer layer (the resin forming the outer layer) In particular, Tg ₁ may be higher than Tg ₂ (Tg ₁ > Tg ₂ ).
The glass transition temperature of the inner layer is, for example, preferably about 20 ° C. to 150 ° C., and the glass transition temperature of the outer layer is preferably, for example, about 0 ° C. to 50 ° C.

Select the glass transition temperature Tg ₁ of the inner layer, the difference between the glass transition temperature Tg ₂ of the outer layer _(Tg 1 -Tg ₂₎ is not particularly limited, from the range of about -20 ° C. or higher (for example, -18 ° C. or higher) For example, −15 ° C. or more (eg, −12 ° C. to 200 ° C.), preferably −10 ° C. or more (eg, −5 ° C. to 180 ° C.), more preferably 0 ° C. or more (eg, 0 to 0 ° C.). 150 ° C.) or higher than 0 ° C. [eg 1 to 200 ° C., 5 ° C. or higher (eg 8 to 150 ° C.), preferably 10 ° C. or higher (eg 15 to 120 ° C.), more preferably 20 ° C or higher (eg, 25 ° C or higher), particularly 30 ° C or higher (eg, 35 ° C or higher), particularly preferably 40 ° C or higher (eg, 45 ° C or higher), 50 ° C or higher (eg, 55 ° C or higher, 60 ° C or higher, etc.) ]].

The amount of resin (or solid content or non-volatile content) in the resin emulsion may be, for example, 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass or more. The upper limit value of the solid content is not particularly limited, and may be, for example, 80% by mass, 70% by mass, 60% by mass, 50% by mass or the like.
The amount of solid content (nonvolatile content) is not particularly limited, and can be determined by a conventional method, but may be determined by, for example, the method described in the examples below.

  The pH of the resin emulsion is not particularly limited, and may be, for example, 4 to 12 (for example, 5 to 11), 6 to 10 (for example, 7 to 9), and the like.

<Water-soluble polymer (B)>
The water-soluble polymer (B) is not particularly limited. For example, a vinyl alcohol resin (for example, a resin having a vinyl alcohol unit such as polyvinyl alcohol), a vinyl lactam resin [for example, a vinyl lactam (N -Vinyl lactam) as a polymerization component (vinyl lactam resin, vinyl lactam polymer, N-vinyl cyclic lactam polymer)], oxyalkylene resin (for example, resin having an oxyethylene unit such as polyethylene glycol) , Acrylic resins [for example, resins containing (meth) acrylic acid as a polymerization component, such as resins containing polyacrylic acid, (meth) acrylic acid and (meth) acrylate (eg, methyl methacrylate) as polymerization components, etc. ], Aqueous polyol [e.g., acrylic Polyols (for example, polymers having the above-mentioned hydroxyl group-containing (meth) acrylate and (meth) acrylic acid as polymerization components) such as hydroxyalkyl (meth) acrylate), acrylamide resins (for example, polyacrylamide ( (Meth) acrylamide-based monomer as a polymerization component), urethane-based resin (water-soluble urethane-based resin), polyester-based resin (water-soluble polyester-based resin), cellulose-based resin (or aqueous cellulose-based resin such as hydroxyethyl cellulose) Of cellulose ether).

  These water soluble polymers (B) may be used alone or in combination of two or more.

  Representative water-soluble polymers (B) include vinyl alcohol resins, vinyl lactam resins, oxyalkylene resins, acrylic acid resins, aqueous polyols, acrylamide resins and the like, among which vinyl lactam resins For example, N-vinyl cyclic lactam polymer (for example, N-vinyl pyrrolidone polymer)] is preferable.

  The water-soluble polymer may be a polymer which is soluble (eg, optionally dissolved) in water at room temperature.

  The water-soluble polymer (B) may be a polymer of the monomer component (b) (a polymer having the monomer component (b) as a polymerization component).

  The monomer component (b) is not particularly limited as long as it can impart water-solubility to the polymer. In particular, the monomer component (b) may contain a monomer (water-soluble monomer) that can impart water-solubility.

(Water soluble monomer)
Examples of monomers capable of imparting water solubility (water-soluble monomers) include hydrophilic monomers [for example, monomers having a hydroxyl group (hydroxyl group) (for example, hydroxyl group-containing (meth) acrylate as exemplified above such as hydroxyalkyl (meth) acrylate, etc.) And hydrophilic monomers such as lactam monomers (for example, N-vinylpyrrolidone, N-vinylcaprolactam etc.), acid group-containing monomers [for example, monomers having a carboxyl group (for example, acrylic acid, methacrylic acid, And the like) and the like.

  Moreover, the monomer which has the below-mentioned functional group (beta) can also be used as a water-soluble monomer (water-soluble monomer which has functional group (beta)) depending on a kind.

  Among these, the water-soluble monomer may preferably contain a lactam monomer (in particular, an N-vinyl cyclic lactam monomer such as vinyl pyrrolidone). A polymer having a monomer component (b) containing such a lactam monomer as a polymerization component, that is, a lactam polymer (in particular, a vinyl pyrrolidone polymer) is a coating film, particularly a coating film formed as a primer. In many cases, it is excellent in terms of being able to efficiently achieve both adhesion and reinforcement with respect to ceramic base materials, which is preferable.

  The water soluble monomers may be used alone or in combination of two or more.

  When a lactam monomer is used as the water soluble monomer, the water soluble monomer may be composed of only the lactam monomer, and the lactam monomer and another water soluble monomer [water soluble monomer which is not a lactam monomer, for example, A combination of a hydroxyl group-containing monomer (for example, hydroxyalkyl (meth) acrylate and the like) and an acid group-containing monomer (for example, a monomer having a carboxyl group such as acrylic acid and methacrylic acid) May be.

  When a lactam monomer and another water soluble monomer are combined, the ratio of lactam monomer to other water soluble monomer (mass ratio) is, for example, 99.9 / 0.1 to 20/80 (for example, 99.7 / 0.3-30 / 70), preferably 99.5 / 0.5-40 / 60 (e.g. 99.3 / 0.7-50 / 50), more preferably 99 / 1-60. / 40 (for example, 99/1 to 70/30), or 99.9 / 0.1 to 80/20 (for example, 99.8 / 0.2 to 85/15, 99.7 / 0.3-88 / 12, 99.5 / 0.5-90 / 10, 99 / 1-92 / 8, 98.8 / 1.2-95 / 5, 98.5 / 1.5-97 / 3) It may be a grade.

  When the monomer component (b) contains a water-soluble monomer, the content ratio (content ratio) of the water-soluble monomer in the monomer component (b) can be appropriately selected according to the type of the water-soluble monomer, etc. It may be 3% by mass or more, preferably 5% by mass or more, and more preferably 8% by mass or more.

  In particular, when the monomer component (b) contains a lactam monomer as the water soluble monomer, the content ratio (content ratio) of the water soluble monomer in the monomer component (b) is, for example, 20% by mass or more, It may be preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 60% by mass or more, particularly preferably 70% by mass or more (eg, 75% by mass or more, 80% by mass or more).

(Monomer having functional group β)
The monomer component (b) may contain a monomer having a functional group (referred to as a functional group β).
As the functional group β, the same functional group as the functional group α, for example, a carbonyl group (or a carbonyl group-containing group such as a ketone group, an aldehyde group, an acyl group), a carboxyl group, an acid anhydride group, an acid halide Group, carbonate group, isocyanate group, oxazoline group, oxazolidine group, hydrazino group, epoxy group, amino group, hydroxyl group, mercapto group and the like.

  The monomer having the functional group β may have these functional groups singly or in combination of two or more.

  Among these functional groups, a carbonyl group, a carboxyl group, an oxazoline group, a hydrazino group, a hydroxyl group and the like are preferable, and at least one selected from a carbonyl group and a carboxyl group is particularly preferable as a functional group.

  The functional group β may be a functional group that can form a crosslinked structure (or bond) in combination with the functional group α (a monomer having the functional group α). Such a crosslinked structure (or bond) may be formed by a direct reaction of the functional group α and the functional group β, and as described later, the functional group α and the functional group β are linked via a crosslinking agent. A crosslinked structure may be formed.

  Specific examples of the monomer having a functional group β include a carbonyl group-containing monomer, a carboxyl group-containing monomer, and a hydroxyl group-containing monomer.

As the carbonyl group-containing monomer, for example, unsaturated aldehyde [eg, alkenal (eg, C _3-10 alkenal such as acrolein, methacrolein etc.), (meth) acryloxyalkyl alkenal (eg, acroxyalkyl propenal) , Methacryloxyalkylpropenal), formylstyrene, etc.], unsaturated ketones {eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone etc.), (meth) acryloyloxyalkanones (eg, acetonyl acrylate) Acetonyl methacrylate etc., N- (meth) acryloylaminoalkanone (eg diacetone acrylamide, diacetone methacrylamide etc), alkanediol (meth) acrylate acetylene Acetate (for example, C _2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxy group Containing ethylenically unsaturated monomers [eg, acetoacetoxyalkyl (meth) acrylates (eg, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate), acetoacetoxy allyl ester etc.], etc. It can be mentioned.

  As the carboxyl group-containing monomer, acid group-containing monomers of the above-mentioned examples, for example, unsaturated monocarboxylic acid (for example, aliphatic unsaturated monocarboxylic acid such as acrylic acid, methacrylic acid, crotonic acid), unsaturated dicarboxylic acid (For example, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid).

As the oxazoline group-containing monomer, for example, alkenyl oxazoline (for example, C _2-6 alkenyl oxazoline such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, preferably vinyl or isopropenyl oxazoline), Alkenyl-alkyloxazolines (eg 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl- C _2-6 alkenyl-C _1-10 alkyl oxazoline such as 5-ethyl-2-oxazoline, preferably vinyl or isopropenyl-C _1-4 alkyl oxazoline) and the like.

As a hydroxyl group containing monomer, the hydroxyl group containing monomer of the said illustration (for example, hydroxyl group containing (meth) acrylate) etc. are mentioned.
As the carbonyl group-containing monomer, for example, unsaturated aldehyde [eg, alkenal (eg, C _3-10 alkenal such as acrolein, methacrolein etc.), (meth) acryloxyalkyl alkenal (eg, acroxyalkyl propenal) , Methacryloxyalkylpropenal), formylstyrene and the like], unsaturated ketone [eg, alkenone (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone etc.), (meth) acryloyloxyalkanone (eg, acetonyl acrylate) Acetonyl methacrylate etc., N- (meth) acryloylaminoalkanone (eg diacetone acrylamide, diacetone methacrylamide etc), alkanediol (meth) acrylate acetylene Acetate (for example, C _2-6 alkanediol (meth) acrylate acetyl acetate such as 2-hydroxypropyl acrylate acetyl acetate, 2-hydroxypropyl methacrylate acetyl acetate, butanediol-1,4-acrylate acetyl acetate), acetoacetoxyalkyl Examples include (meth) acrylates (eg, 2- (acetoacetoxy) ethyl acrylate, 2- (acetoacetoxy) ethyl methacrylate) and the like] and the like.

  The monomers having the functional group β may be used alone or in combination of two or more.

  Among these, carbonyl group-containing monomers and unsaturated monocarboxylic acids (acrylic acid and the like) are particularly preferable, and carbonyl group-containing monomers (particularly diacetone (meth) acrylamide) are particularly preferable.

  When the monomer component (b) contains a monomer having a functional group β, the content ratio (content ratio) of the monomer having a functional group β in the monomer component (b) is, for example, 50 mass. % Or less (eg, 0.01 to 45% by mass), preferably 40% by mass or less (eg, 0.1 to 35% by mass), more preferably 30% by mass or less (eg, 0.5 to 25% by mass) In particular, it may be about 20% by mass or less (for example, 1 to 18% by mass) or 2% by mass or more (for example, 3% by mass or more, 5% by mass or more).

  In particular, when a carbonyl group-containing monomer is used as a monomer having a functional group β, the content (percentage) of the carbonyl group-containing monomer in the monomer component (b) is 50% by mass or less (Eg, 0.01 to 45% by mass), preferably 40% by mass or less (eg, 0.1 to 35% by mass), more preferably 30% by mass or less (eg, 0.5 to 25% by mass), particularly It may be 20% by mass or less (for example, 1 to 18% by mass), and 2% by mass or more (for example, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass or more, 12% by mass or more). , 15% by mass or more).

  In particular, when a carboxyl group-containing monomer is used as a monomer having a functional group β (further, a water-soluble monomer), the content ratio (content ratio) of the carboxyl group-containing monomer in the monomer component (b) Is 50% by mass or less (eg, 0.01 to 45% by mass), preferably 40% by mass or less (eg, 0.1 to 35% by mass), more preferably 30% by mass or less (eg, 0.5%) To 25% by mass), in particular, 20% by mass or less (for example, 1 to 18% by mass), or 2% by mass or more (for example, 3% by mass or more, 5% by mass or more, 7% by mass or more, 10% by mass). % Or more, 12% by mass or more, etc.).

(Other monomers)
As described above, the monomer component (b) may usually contain a water-soluble monomer, but the water-soluble monomer (furthermore, the functional group β can be used as long as the water-solubility of the water-soluble polymer can be ensured. Other monomers that do not belong to the category of (monomers having) may be included.

  The other monomer is not particularly limited and can be selected according to the type of water-soluble monomer to be combined. For example, the monomer exemplified in the section of the resin emulsion (A), for example, a (meth) acrylic monomer [for example, And (meth) acrylates such as methyl methacrylate], styrene-based monomers, fluorine-containing monomers, silicon-containing monomers, UV-absorbing monomers, UV-stable monomers, and the like.

  You may use another monomer individually or in combination of 2 or more types.

  In addition, when a monomer component (b) contains another monomer, the ratio (upper limit ratio) of the other monomer in a monomer component (b) can be selected according to the kind of water-soluble monomer etc., for example 95% by mass or less, preferably 90% by mass or less, and more preferably 85% by mass or less.

  In particular, when the monomer component (b) contains a lactam monomer as a water-soluble monomer and contains another monomer, the content ratio (content ratio) of the other monomer in the monomer component (b) is For example, it may be 70% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less (for example, 20% by mass or less), and 10% by mass or less (for example, 5% by mass or less). It is also good.

  When the water-soluble polymer (B) is a copolymer (for example, a polymer having as a polymerization component a monomer component (b) containing a lactam monomer and a monomer having a functional group β) The copolymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like, but from the viewpoint of coating film properties and the like, a block copolymer or a graft copolymer (especially, It is preferable that it is a graft copolymer.

  The water-soluble polymer (B) may be nonionic (nonionic or nonionic) or ionic (ionic). A combination of a nonionic water-soluble polymer and an ionic water-soluble polymer. May be included.

  As a nonionic water-soluble polymer, for example, a monomer component containing a nonionic monomer (for example, a monomer having a hydroxyl group, a lactam monomer, a carbonyl group-containing monomer, a (meth) acrylic monomer, etc.) The resin etc. which make (b) a polymerization component are mentioned.

  The ionic water-soluble polymer includes a water-soluble polymer having a cationic group and / or an anionic group, such as a monomer having an ionic group or an ionic monomer (for example, an acid group-containing monomer). Examples include resins having a monomer component (b) as a polymerization component [for example, (meth) acrylic acid-based resins such as polyacrylic acid and (meth) acrylic acid- (meth) acrylate copolymers).

  The nonionic water-soluble polymer may be substantially nonionic, and has a ionic group or an ionic skeleton (for example, a skeleton or an acid group derived from an acid group-containing monomer) in a very small part. It is also good. For example, in the nonionic water-soluble polymer, a monomer having an ionic group or an ionic monomer (for example, an acid group-containing monomer) is 10% by mass or less (eg, 8% by mass or less, 6% by mass or less, 5% by mass) % Or less and 4% by mass or less) may be a resin containing a monomer component (b) as a polymerization component.

  Preferred water-soluble polymers (B) include a resin {or a vinyl lactam resin, for example, a polymer of a lactam monomer; a lactam monomer; and a monomer component (b) containing at least a lactam monomer as a polymerization component. A polymer comprising a monomer component (b) containing a monomer having a functional group β (for example, a carbonyl group-containing monomer such as diacetone (meth) acrylamide) as a polymerization component; a lactam monomer, other Water-soluble monomer (for example, at least one selected from hydroxy group-containing monomer and carboxyl group-containing monomer), and monomer having functional group β (for example, carbonyl group-containing monomer such as diacetone (meth) acrylamide) And the like having a monomer component (b) containing as a polymerization component. Such a resin may usually be nonionic (nonionic).

  The weight average molecular weight of the water-soluble polymer (B) can be appropriately selected according to the type of polymer and is not particularly limited. However, from the viewpoint of physical properties of the coating film, for example, 6000 to 3000000 (for example, 6500 to 1000000), preferably The number may be 7,000 to 500,000 (e.g., 7,500 to 300,000), and more preferably 8,000 to 200,000.

  In particular, the weight average molecular weight of the water-soluble polymer (B) is a relatively low molecular weight [for example, a weight average molecular weight of 200000 or less (for example, 6000 to 18000), 150,000 or less (for example, 7000 to 120,000), or 100,000 or less (for example, 8000 -80000), 70000 or less (for example, 9000-60000), 50000 or less (for example, 10000-45000), 40000 or less (for example, 15000-35000), or about 6000-100,000. . Use of such a relatively low molecular weight water-soluble polymer (B) may be advantageous in terms of adhesion to a substrate, reinforcement of a substrate, and the like.

  The weight average molecular weight is determined using, for example, gel permeation chromatography (for example, manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L used in series). It may be a weight average molecular weight (in terms of polystyrene) that can be measured.

A commercially available product may be used as the water-soluble polymer, and for example, it may be prepared by a polymerization method such as a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or a precipitation polymerization method.
In the polymerization, the polymerization initiator is not particularly limited, and a conventional polymerization initiator (such as the exemplified polymerization initiator) can be used depending on the polymerization method and the like. Further, the polymerization may be performed in the presence of a chain transfer agent (such as the compound having a thiol group exemplified above), a reducing agent, or the like. In addition, polymerization conditions (type and amount of solvent, temperature, atmosphere, time, etc.) can be appropriately selected.

  The molecular weight of the water-soluble polymer can be adjusted by selection of the type of monomer and polymerization conditions.

<Composition>
The composition of the present invention comprises a resin emulsion (A) and a water soluble polymer (B).

  The ratio of the resin emulsion (A) to the water-soluble polymer (B) is, for example, the former / the latter (mass ratio of solid content) = 99.9 / 0.1 to 1/99 (for example, 99.7 / 0 .. 3 to 3/97), preferably 99.5 / 0.5 to 5/95 (e.g. 99/1 to 10/90), more preferably 98/2 to 20/80 (e.g. 97/3 to 30) / 70), particularly 95/5 to 40/60 (eg 93/7 to 45/55), and 99/1 to 50/50 (eg 97/3 to 55/45, 95 / 5 to 60/40).

  The composition of the present invention may form (or be able to form) a crosslinked structure.

For example, the resin emulsion (A) or the water-soluble polymer (B) may form a bond (crosslink) with each other, or may be capable of forming a bond (or a crosslinked structure).
In another aspect, the resin emulsion (A) and the water-soluble polymer (B) may be bonded (crosslinked) to each other.
In the case of bonding, the resin emulsion (A) and the water-soluble polymer (B) may be bonded at least in part.

  In addition, in the composition, even if it is not bonded (or crosslinked), it may form a bonded or crosslinked structure afterward or temporally (for example, in a coating film etc.) afterward. In particular, substantially no bond or crosslinked structure may be formed at the composition (sealer) stage, and the bond or crosslinked structure may be formed along with the formation of the coating film.

  Therefore, in the composition of the present invention, the resin emulsion (A) or the water-soluble polymer (B) may be capable of forming a bond (or a crosslinked structure).

  In particular, in the present invention, at least the water-soluble polymer (B) may form (or be able to form) a bond (or a crosslinked structure). As such an embodiment, for example, an embodiment in which water-soluble polymers (B) form a bond (or a crosslinked structure) (can be formed), a resin emulsion (A) and a water-soluble polymer (B). Examples include a mode in which a bond (or a crosslinked structure) is formed (can be formed), a mode in which these are combined, and the like. In a preferred embodiment, at least the resin emulsion (A) and the water-soluble polymer (B) may form a bond.

  More specifically, when the resin emulsion (A) or the water-soluble polymer (B) is bonded (or can be bonded), the bonding form is not particularly limited, and (i) the resin emulsion ( A) A form in which the water-soluble polymer (B) is directly bonded (forms a crosslinked structure), (ii) The resin emulsion (A) and the water-soluble polymer (B) are bonded through the crosslinking agent (C). (Iii) a form in which the resin emulsion (A) (to each other) and / or the water-soluble polymer (B) (to each other) are bonded (to form a cross-linked structure) via the cross-linking agent (C). And (iv) forms in which these are combined and the like.

  As the form (i), for example, the resin emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the water-soluble polymer (B) is , Composed of a polymer having a monomer component (a) containing a monomer having a functional group β (functional group β that can react and bond with the functional group α) as a polymerization component, the functional group α and the functional group β And forms a bond (or a crosslinked structure) (or may have a bond or a crosslinked structure).

  Further, as the form (ii), the resin emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and the water-soluble polymer (B) is The polymer is composed of a monomer component (b) containing a monomer having a functional group β (a functional group β capable of forming a crosslinked structure via the functional group α and the crosslinking agent (C)) as a polymerization component, An embodiment in which the functional group α and the functional group β are reacted with the crosslinker (C) to form a bond (or a crosslinked structure) (or can take a bonded or crosslinked structure) is included.

  As the form (iii), the resin emulsion (A) is composed of a resin having a monomer component (a) containing a monomer having a functional group α as a polymerization component, and a plurality of functional groups α are cross-linking agents (C And a monomer component in which the water-soluble polymer (B) contains a monomer having a functional group β. Embodiment which is comprised with the polymer which uses (b) as a polymerization component, and several functional groups (beta) react with a crosslinking agent (C), and forms a bond (or crosslinked structure) (or can take a bonded or crosslinked structure) And so on.

  In such forms (i) to (iii), the combination of the functional group α and the functional group β, or the combination of the functional group α and / or the functional group β and the functional group (functional group γ) that the crosslinking agent has , Not particularly limited, for example, epoxy group and hydroxyl group, epoxy group and carboxyl group, epoxy group and amino group, carbonate group and carboxyl group, hydroxyl group and alkoxycarbonyl group, hydroxyl group and isocyanate group, hydroxyl group and carboxylic anhydride group, Examples include acetoacetoxy group and isocyanate group, oxazoline group and carboxyl group, hydroxyl group and carboxylic anhydride group, oxazolidine group and isocyanate group or carboxylic anhydride group, hydrazino group and carbonyl group, amino group or carboxyl group and carbodiimide group. . One or more of these may be used in combination.

  In the form (i), the combination of the representative functional group α and the functional group β is not particularly limited as long as it is a combination capable of forming a crosslinked structure or a bond by reaction with each other. For example, a carboxyl group and an oxazoline group , A combination of a carbonyl group and a hydrazino group, a combination of an isocyanate group and a hydroxy group, a carboxyl group, an amino group or the like.

  In the form (ii), the combination of a typical functional group α and a functional group β can be appropriately selected according to the type of the crosslinking agent (C), and the same functional group may be used. As such a combination, for example, a combination in which both the functional group α and the functional group β are carbonyl groups, a combination in which the functional group α and the functional group β are both carboxyl groups, one of the functional group α and the functional group β Includes a combination in which is an amino group and the other is a carboxyl group. In addition, in such a combination, the below-mentioned hydrazine type crosslinking agent, an oxazoline type crosslinking agent, and a carbodiimide type crosslinking agent can be used suitably as a crosslinking agent (C).

  In the form (iii), the functional group α or the functional group β can be appropriately selected depending on the type of the crosslinking agent (C), and may generally be the same functional group. For example, when the functional group α or the functional group β is a carbonyl group, the hydrazine-based crosslinking agent described later can be used as the crosslinking agent (C). When the functional group α or the functional group β is a carboxyl group, the crosslinking agent ( As C), an oxazoline-based crosslinking agent described later can be used.

  As the cross-linking agent (C), a cross-linking agent capable of reacting between the functional group α and the functional group β or reacting with a plurality of functional groups α and functional groups β to form a bond (or a cross-linked structure) ( It is not particularly limited as long as it is C), and can be appropriately selected according to the type of functional group α or functional group β. However, it is usually a polyfunctional compound (polyfunctional compound having a plurality of functional groups γ). Good. Examples of the functional group γ include the functional groups exemplified as the functional group α and the functional group β, and examples thereof include a carboxyl group, a hydrazino group, an oxazoline group, a carbodiimide group, an epoxy group, an isocyanate group, and an amino group.

  The polyfunctional compound may have the same or different functional groups. In the polyfunctional compound, the number of functional groups (functional group γ) may be two or more. For example, in the case of a low molecular type (non-polymer type or non-resin type) polyfunctional compound, It is 2 to 10, preferably 2 to 6, more preferably 2 to 4, particularly 2.

  Typical crosslinking agents (C) include hydrazine crosslinking agents (compounds having a plurality of hydrazino groups), oxazoline crosslinking agents, carbodiimide crosslinking agents, isocyanate crosslinking agents, amine crosslinking agents, epoxy crosslinking agents, and the like. It can be mentioned. In particular, the crosslinking agent (C) may be water soluble (water soluble crosslinking agent).

Examples of the hydrazine-based crosslinking agent include dicarboxylic acid dihydrazide [for example, alkane dicarboxylic acid dihydrazide (for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid hydride, etc.) _{C 2-20} alkane dicarboxylic acid dihydrazide, preferably _{C 2-10} alkane dicarboxylic acid dihydrazide), alkene dicarboxylic acid dihydrazide (e.g., maleic acid dihydrazide, fumaric acid dihydrazide, _{C 2-10} alkene dicarboxylic acid dihydrazide and itaconic acid dihydrazide Aliphatic dicarboxylic acid dihydrazides such as aromatic dihydrazides such as isophthalic acid dihydrazide, etc.], dihydrazines [eg Ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, aliphatic dihydrazine, such as butylene-1,4-dihydrazine, preferably like _{C 2-4} aliphatic dihydrazine.

  As an oxazoline type crosslinking agent, the polymer etc. which use an oxazoline group containing monomer as a polymerization component are mentioned, for example. Examples of such a polymer include a homopolymer or a copolymer of an oxazoline group-containing monomer, a copolymer of an oxazoline group-containing monomer and another copolymerizable monomer, and the like.

As the oxazoline group-containing monomer, the above-exemplified monomers, for example, alkenyl oxazolines (for example, C _2-6 alkenyl oxazolines such as 2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, etc., preferably Vinyl or isopropenyl oxazoline), alkenyl-alkyl oxazoline (for example, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline) And C _2-6 alkenyl-C _1-10 alkyl oxazolines such as 2-isopropenyl-5-ethyl-2-oxazoline, preferably vinyl or isopropenyl C _1-4 alkyl oxazoline and the like) and the like.

  The other copolymerizable monomer is not particularly limited as long as it is a copolymerizable monomer that does not react with the oxazoline group. For example, (meth) acrylic acid ester [for example, methyl (meth) acrylate , Alkyl (meth) acrylates as exemplified above such as ethyl (meth) acrylate; hydroxy group-containing (meth) acrylates as exemplified above such as hydroxyethyl (meth) acrylate], (meth) acrylic acid amide, vinyl acetate, aromatic Group-based monomers (for example, the above-mentioned styrenic monomers such as styrene and α-methylstyrene).

  In the oxazoline-based crosslinking agent, the oxazoline group equivalent may be, for example, about 200 to 5000 g / equivalent, preferably about 250 to 4000 g / equivalent, and more preferably about 300 to 3000 g / equivalent.

  Such an oxazoline-based crosslinking agent can also be obtained as an Epocross series (for example, Epocross K-2010E, K-2020E, K-2030E, WS-500, etc.) manufactured by Nippon Shokubai Co., Ltd.

The carbodiimide-based crosslinking agent (carbodiimide compound) may be a compound having at least one carbodiimide group [—N═C═N—] in the molecule, may be a monocarbodiimide compound, or may be a polycarbodiimide compound. May be.
In particular, the carbodiimide compound may be water soluble (hydrophilic, aqueous). Such a water-soluble carbodiimide compound may usually have a hydrophilic group (hydrophilic skeleton, hydrophilic segment). The hydrophilic group (hydrophilic skeleton) is not particularly limited, and examples thereof include a hydroxy group, a carbamate group, a (poly) oxyalkylene group, and a substituted amino group (tertiary amino group). The hydrophilic group may form a salt (eg, an amine salt).

  Such hydrophilic groups may, for example, be located at the end of the carbodiimide. In such a water-soluble carbodiimide compound (aqueous carbodiimide compound), for example, the terminal of the carbodiimide compound serving as a base may be blocked with a hydrophilic group (or a hydrophilic skeleton).

  As a typical carbodiimide type crosslinking agent, the polymer etc. which have a carbodiimide group (-N = C = N-) etc. are mentioned.

  The carbodiimide-based cross-linking agent can be easily obtained commercially, and examples thereof include Nisshinbo Chemical Co., Ltd., trade name: Carbodilite V-02, etc., but the present invention is exemplified as such. It is not limited to only.

  Examples of the isocyanate crosslinking agent include polyisocyanates [eg, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, Aliphatic polyisocyanates such as lysine isocyanate; 1,3-diisocyanatecyclohexane, 1,4-diisocyanatecyclohexane, 1,3-bis (isocyanatemethyl) cyclohexane, 1,4-bis (isocyanatemethyl) cyclohexane, dicyclohexylmethane-4 Alicyclic polyisocyanates such as 4,4′-diisocyanate, isophorone diisocyanate, norbornane diisocyanate, etc .; xylylene diisocyanate, tetramethyl Xylylene diisocyanate, 4,4-bis such araliphatic polyisocyanates such as (isocyanatomethyl) diphenylmethane], reaction products of polyisocyanate and polyol.

  Examples of the amine-based crosslinking agent include urea-based resins (for example, urea resins and thiourea resins), triazine-based resins (for example, melamine resins, isomelamine resins, benzoguanamine resins, acetoguanamine resins, guanylmelamine resins) and the like. .

  Examples of the epoxy-based crosslinking agent include polyglycidyl ether, epoxy resin (for example, novolac type epoxy resin, brominated epoxy resin, alicyclic epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, etc.). Be

  The crosslinking agents (C) may be used alone or in combination of two or more.

  Among these crosslinking agents (C), a water-soluble crosslinking agent is preferable. Also preferred are hydrazine-based crosslinking agents, oxazoline-based crosslinking agents, carbodiimide-based crosslinking agents, and the like.

  Such a crosslinking agent is usually stable to water and the crosslinking reaction is mild, so a stable composition can be obtained. In addition, by combining such a crosslinking agent, a resin emulsion, and a water-soluble polymer, a good coating film can be obtained because it is easily cross-linked or bonded together with the formation of the coating film.

  In addition, although the crosslinking agent (C) may contain an isocyanate type crosslinking agent, an epoxy type crosslinking agent, etc. as above-mentioned, the aspect which does not contain such a crosslinking agent substantially is also preferable.

  Representative forms (ii) include the following forms (ii-1) and (ii-2).

  (Ii-1) The resin emulsion (A) is composed of a polymer of a monomer component (a) containing a carbonyl group-containing monomer as a monomer having a functional group α, and the water-soluble polymer (B) is It is composed of a polymer of a monomer component (b) containing a carbonyl group-containing monomer as a monomer having a functional group β, and a resin emulsion (A) and a water-soluble polymer (via a hydrazine-based crosslinking agent (C1)). Form in which (B) and (B) are bonded

  (Ii-2) The resin emulsion (A) is composed of a polymer of a monomer component (a) containing a carboxyl-containing monomer as a monomer having a functional group α, and the water-soluble polymer (B) is functional. It is composed of a polymer of a monomer component (b) containing a carboxyl group-containing monomer as a monomer having a group β, and a resin emulsion (A) and a water-soluble polymer (B) via an oxazoline-based crosslinking agent (C2) Form in which (or can be combined with)

  The representative forms (iii) include the following forms (iii-1) to (iii-4) and the like.

  (Iii-1) The resin emulsion (A) is composed of a polymer of a monomer component (a) containing a carbonyl group-containing monomer as a monomer having a functional group α, and a hydrazine-based crosslinking agent (C1). The form in which the resin emulsion (A) is bonded (or bondable) via

  (Iii-2) The resin emulsion (A) is composed of a polymer of a monomer component (a) containing a carboxyl-containing monomer as a monomer having a functional group α, and via an oxazoline-based cross-linking agent (C2). The resin emulsion (A) is bound (or bindable)

  (Iii-3) The water-soluble polymer (B) is composed of a polymer of a monomer component (b) containing a carbonyl group-containing monomer as a monomer having a functional group β, and a hydrazine-based crosslinking agent (C1) In which the water-soluble polymer (B) is bonded (or bondable) via

  (Iii-4) The water-soluble polymer (B) is composed of a polymer of a monomer component (b) containing a carboxyl-containing monomer as a monomer having a functional group β, and an oxazoline-based crosslinking agent (C2). A form in which the water-soluble polymer (B) is bound (or bindable) via

  The ratio of the monomer having the functional group α to the monomer having the functional group β is, for example, the former / the latter (mass ratio) = 0.1 / 1 to 1000/1, preferably 0.5 / 1 The ratio may be about 500/1, more preferably about 1/1 to 300/1 (e.g., 1/1 to 240/1).

  The ratio of the total amount of the monomer having the functional group α and the monomer having the functional group β to the total amount of the monomer component (a) and the monomer component (b) is, for example, 0. It may be about 01 to 40% by mass, preferably 0.05 to 30% by mass, and more preferably about 0.1 to 20% by mass.

  When the crosslinking agent (C) is used, the proportion of the crosslinking agent (C) is, for example, 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin emulsion (A) (solid content). It may be about 1.5 to 7 parts by mass, more preferably about 2 to 5 parts by mass. .

  When using a crosslinking agent (C), the proportion of the crosslinking agent (C) is, for example, 1 to 25 parts by mass, preferably 2.5 to 20 parts by mass, with respect to 100 parts by mass of the water-soluble polymer (B) More preferably, it may be about 3 to 15 parts by mass, or about 5 to 10 parts by mass.

  When using a crosslinking agent (C), the proportion of the crosslinking agent (C) is, for example, 0.001 to 100 parts by mass relative to the total amount (solid content) of the resin emulsion (A) and the water-soluble polymer (B). It may be about 30 parts by mass, preferably about 0.01 to 20 parts by mass, more preferably about 0.1 to 10 parts by mass (for example, 0.3 to 8 parts by mass), about 0.5 to 5 parts by mass It may be

  When the crosslinking agent (C) is used, the ratio of the crosslinking agent (C) is, for example, 0 with respect to 100 parts by mass of the total amount of the monomer having the functional group α and the monomer having the functional group β. The amount may be about 0.01 to 500 parts by mass, preferably about 0.1 to 300 parts by mass, and more preferably about 1 to 100 parts by mass.

<Sealer>
The composition of the present invention can be suitably used as a paint, in particular, a sealer (primer).

As long as the paint (especially the sealer) contains a resin emulsion (A) and a hydrophilic polymer (B) (and further contains a crosslinking agent (C) as necessary) (including as a film-forming or film-forming component), Optionally, conventional additives may be included.
The additive is not particularly limited, and examples thereof include pigments (eg, calcium carbonate, titanium oxide, talc, kaolin, iron oxide, carbon black), dispersants, antifoaming agents, thickeners / viscosity modifiers, Examples include film assistants (film forming assistants), light resistance (climate stabilizers), pH adjusters, and the like.

  These additives may be used alone or in combination of two or more.

The pigment is not particularly limited, and can be selected according to the purpose of the paint. Such a pigment may be either an inorganic pigment or an organic pigment, and an inorganic pigment may be suitably used. The pigment may be a color pigment or an extender pigment. Specific examples of the pigment include calcium carbonate, titanium oxide, talc, kaolin, iron oxide, carbon black and the like.
The pigments may be used alone or in combination of two or more.

  The paint of the present invention may contain an alkali silicate, but may not contain substantially.

  The film forming aid is not particularly limited, and for example, general-purpose components such as glycol ethers and esters can be used. The film forming aid may be a component that promotes (or assists) film formation, and may be, for example, a component that promotes fusion of a resin (emulsion particles). The film forming aid preferably acts or functions as a plasticizer during film formation, and is preferably removed or eliminated from the coating film after film formation. The removal from the coating film may be performed through a drying process accompanied by heat, wind, or the like.

In particular, two or more glycol ethers (glycol ether (A)) and an ester (ester (B)) may be combined as a film forming aid. By using such a specific film-forming auxiliary, water permeability resistance and blocking resistance may be easily and efficiently compatible.
Hereinafter, the specific film forming aid will be described in detail.

[Filming aid]
The film-forming aid (solvent, solvent composition) contains glycol ether (A) and ester (B).
(Glycol ether (A))
The glycol ether (A) is selected from, but not limited to, glycol ethers (eg, glycol ether (A1) and glycol ether (A2)) belonging to a specific group, as long as at least two types (different glycol ethers) are used. May be.

  For example, the glycol ether (A) may be selected from each of the group (A1) having relatively high solubility in water and the other group (A2). That is, glycol ether (A) may contain glycol ether (A1) and glycol ether (A2).

  In glycol ether (A1), the solubility in 100 g of water (solubility at 20 ° C.) may be selected from a range of, for example, about 20 g (20 g / 100 g water) or more, preferably 25 g or more (for example, 25 to 100 g), preferably May be 30-80 g.

In the glycol ether (A2), the solubility in 100 g of water (solubility at 20 ° C.) can be selected, for example, from a range of less than 20 g, and may be from 0.1 g to less than 20 g, preferably from 0.15 g to less than 15 g. .
The difference (absolute value) between the solubility of glycol ether (A1) in 100 g of water (solubility at 20 ° C.) and the solubility of glycol ether (A2) in 100 g of water (solubility at 20 ° C.) is, for example, 5 g or more, preferably It may be 10 g or more.
If the solubility in water is low, it tends to easily shift to film-forming components (resin particles, etc.), and it is expected to easily achieve the function as a film-forming aid. It tends to remain and may reduce blocking resistance. On the other hand, by combining the film forming aids having different solubility in water, the function as the film forming aid and the blocking resistance can be both balanced in a balanced manner.

  When the glycol ether (A1) and the glycol ether (A2) are combined, one or more types may be selected from (A1) and (A2), and each of the glycol ethers (A1) and (A2) may be used alone or Two or more may be used in combination.

  In addition, glycol ether (A) may be solid or liquid at normal temperature (for example, 15 to 30 ° C.), and may be particularly liquid.

Hereinafter, specific glycol ether (A) is illustrated.
As glycol ether (A1), for example,
Ethylene glycol monoether {eg ethylene glycol mono C such as ethylene glycol monoalkyl ether [eg methyl cellosolve (ethylene glycol monomethyl ether), isopropyl glycol (ethylene glycol monoisopropyl ether), butyl glycol (butyl cellosolve, ethylene glycol monobutyl ether) _1-4 alkyl ether], allyl glycol (ethylene glycol monoallyl ether), etc., propylene glycol monoether {eg, propylene glycol monoalkyl ether [eg, methyl propylene glycol (propylene glycol monomethyl ether), propyl propylene glycol (propylene glycol) Propylene glycol such as monopropyl ether) Alkanediol mono ethers such as _{mono-C 1-2} alkyl ethers], etc.};
Diethylene glycol monoether {eg, diethylene glycol monoalkyl ether [eg methyl diglycol (methyl carbitol, diethylene glycol monomethyl ether), isopropyl diglycol (diethylene glycol monoisopropyl ether), isobutyl diglycol (diethylene glycol monoisobutyl ether), butyl diglycol (eg Diethylene glycol mono C _1-4 alkyl ether such as diethylene glycol monobutyl ether, butyl carbitol], benzyl diglycol (diethylene glycol monobenzyl ether) etc., dipropylene glycol monoether {eg, dipropylene glycol monoalkyl ether [eg, methyl] Propylene diglycol (dipropylene) Dipropylene glycol mono C _1-2 alkyl ether such as glycol monomethyl ether], etc.}, triethylene glycol monoether {eg, triethylene glycol monoalkyl ether [eg methyl triglycol (triethylene glycol monomethyl ether), butyl tri] Triethylene glycol mono C _1-4 alkyl ether such as glycol (triethylene glycol monobutyl ether) etc.}, tripropylene glycol monoether {eg tripropylene glycol monoalkyl ether [eg methyl propylene triglycol (tripropylene glycol monomethyl) polyalkylene glycol mono and tri propylene glycol mono C _1-2 alkyl ether], etc.}, such as ether) Ether;
Alkanediol diethers such as ethylene glycol diether {eg ethylene glycol dialkyl ether [eg ethylene glycol di C _1-12 alkyl ether such as dimethyl glycol (ethylene glycol dimethyl ether) etc] etc;
Diethylene glycol diether {eg, diethylene glycol dialkyl ether [eg, diethylene glycol di C _1-3 alkyl ether such as dimethyl diglycol (diethylene glycol dimethyl ether), diethyl diglycol (diethylene glycol diethyl ether)], etc.}, dipropylene glycol diether {eg, Dipropylene glycol dialkyl ether [eg dipropylene glycol di C _1-12 alkyl ether such as dimethyl propylene diglycol (dipropylene glycol dimethyl ether)] etc.}, triethylene glycol diether {eg triethylene glycol dialkyl ether [eg Dimethyl triglycol (triethylene glycol dimethyl ether) Polyalkylene glycol diethers such as ethylene glycol di C _1-12 alkyl ethers], etc.};
Etc.

  The glycol ethers (A1) may be used alone or in combination of two or more.

Among these, in particular, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the like may be suitably used as the glycol ether (A1).
By using the glycol ether (A1) as described above, the rate of volatilization in a limited drying time can be easily improved, or the amount of a film forming aid remaining after drying can be reduced. In addition, since the surface tension of the paint is lowered, the substrate (in particular, ceramic base material) can be easily wetted, and an impregnation effect can also be expected.

As glycol ether (A2), for example,
Ethylene glycol monoether {for example, ethylene glycol monoalkyl ether [for example, ethylene glycol mono C _6-12 alkyl ether such as hexyl glycol (ethylene glycol monohexyl ether), 2-ethylhexyl glycol (ethylene glycol mono 2-ethylhexyl ether)] , Phenyl glycol (ethylene glycol monophenyl ether), benzyl glycol (ethylene glycol monobenzyl ether), etc.}, propylene glycol monoether {eg, propylene glycol monoalkyl ether [eg, butyl propylene glycol (propylene glycol monobutyl ether), etc. glycol mono _{C 3-12} alkyl ether, phenyl propylene glycol Alkanediol mono ethers such as propylene glycol monophenyl ether), etc.};
Diethylene glycol monoether {eg, diethylene glycol monoalkyl ether [eg, diethylene glycol mono C _6-12 alkyl ether such as hexyl diglycol (diethylene glycol monohexyl ether), 2-ethylhexyl diglycol (diethylene glycol mono 2-ethylhexyl ether)], phenyldi Glycol (diethylene glycol monophenyl ether), etc.}, dipropylene glycol monoether {eg dipropylene glycol monoalkyl ether [eg propylpropyl diglycol (dipropylene glycol monopropyl ether), butyl propylene diglycol (dipropylene glycol monobutyl ether) Etc.) dipropylene glycol mono C _3-12 alkyl Ether]], tripropylene glycol monoether {eg, tripropylene glycol monoalkyl ether [eg, tripropylene glycol mono C _3-12 alkyl ether such as _{butylpropylene triglycol} (tripropylene glycol monobutyl ether)], etc. Polyalkylene glycol monoethers;
Polyalkylene glycol diethers such as diethylene glycol diether {eg diethylene glycol dialkyl ether [eg diethylene glycol di C _4-12 alkyl ether such as dibutyl diglycol (diethylene glycol dibutyl ether) etc] etc;
Etc.

  The glycol ethers (A2) may be used alone or in combination of two or more.

Of these, butyl propylene glycol, butyl propylene diglycol and the like may be suitably used as the glycol ether (A2).
The rate of volatilization within the limited drying time can be easily improved by using the glycol ether (A2) as described above, or the amount of film forming aid remaining after drying can be reduced. In addition, since the surface tension of the paint is lowered, the substrate (in particular, ceramic base material) can be easily wetted, and an impregnation effect can also be expected. Furthermore, even within a limited drying time, it is easy to promote particle fusion and form a stable film, and to easily obtain a coating film having excellent water permeability resistance.

  When combining glycol ether (A1) and glycol ether (A2), the ratio of glycol ether (A1) and glycol ether (A2) is the former / the latter (weight ratio) = 1 / 0.01 to 1/100 ( For example, 1 / 0.1 to 1/50), preferably 1 / 0.3 to 1/40 (eg, 1 / 0.5 to 1/30), more preferably 1 / 0.8 to 1/20. For example, it may be about 1/1 to 1/15, particularly about 1 / 1.5 to 1/10 (for example, 1 / 1.8 to 1/5).

(Ester (B))
The ester (B) is not particularly limited as long as the ester (B) can be used as a film-forming aid in the paint in combination with the glycol ether (A). Good.

  In such ester (B), the solubility (solubility at 20 ° C.) in 100 g of water can be selected, for example, from the range of less than 1 g (eg, 0.5 g or less), 0.3 g or less (eg, 0.2 g) Or less), preferably 0.1 g or less (e.g., 0.0001 to 0.1 g).

  In addition, ester (B) may be solid or liquid at normal temperature (for example, 15 to 30 ° C.), and particularly may be liquid.

As specific ester (B), for example,
Polyol ester {e.g. ester of aliphatic polyol [e.g. alkane polyol acylate (e.g. 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3 C _2-10 alkane polyols C _1-20 acylates such as pentanediol diisobutyrate, preferably C _3-10 alkanediol mono- or di-C _1-12 acylates, more preferably C _4-8 alkanediol mono- or di-C Esters of aliphatic polyols with aliphatic carboxylic acids such as _3-10 acylate), etc.},
Polycarboxylic acid esters {eg, aliphatic dicarboxylic acid esters [eg, adipic acid esters (eg, diethyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (adipate) 2-butoxyethyl) and the like, and sebacic acid esters (for example, dimethyl sebacate, dibutyl sebacate, bis (2-ethylhexyl) sebacate) and the like, preferably C _{4- 10} aliphatic dicarboxylic acid alkyl ester, more preferably such C _4-10 alkane dicarboxylic acid dialkyl ester], aliphatic tricarboxylic acid esters [for example, citric acid esters (e.g., triethyl citrate, acetyl tributyl citrate ethyl Aliphatic tricarboxylic acid esters such as phthalic acid esters (eg bisphthalate), etc .; aliphatic dicarboxylic acid esters [eg phthalic acid esters (eg bisphthalic acid bis) (2-ethylhexyl), diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate, bis (2-butoxyethyl phthalate), etc.], aromatic tricarboxylic acid esters [eg, trimellitic acid ester (eg, trimellitic acid) An aromatic polycarboxylic acid ester} such as tri-2-ethylhexyl, trinormal alkyl trimellitic acid, triisodecyl trimellitic acid, trinormal octyl trimellitic acid, etc.]
Monocarboxylic acid esters {eg, aliphatic monocarboxylic acid esters (eg, isopropyl myristate (eg, isopropyl myristate, octyldodecyl myristate, myristyl myristate, lauryl myristate, etc.) aliphatic monoesters having 6 or more carbon atoms, etc. Carboxylic acid ester, preferably mono-higher fatty acid ester, more preferably _C10-30 aliphatic monocarboxylic acid ester, etc.}
Etc.

  The esters (B) may be used alone or in combination of two or more.

Among them, in particular, as ester (B), 2,2,4-trimethyl-1,3-pentane from the viewpoint of appropriate volatility (for example, low volatility compared to glycol ether (A)) Diol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and the like may be preferably used.
By combining the ester (B) as described above with the glycol ether (A), fusion of resin particles, which are film forming components, is promoted and film formation is stably performed even during a limited drying time. On the other hand, it is easy to volatilize quickly after film formation. As a result, it is easy to efficiently obtain excellent coating film properties (water permeability resistance, frost damage resistance, etc.).

  The ratio of glycol ether (A) to ester (B) is, for example, the former / the latter (weight ratio) = 1 / 0.001 to 1/10 (for example, 1 / 0.002 to 1/5), preferably 1 / 0.005 to 1/3 (e.g., 1 / 0.01 to 1/2), more preferably 1 / 0.02 to 1/1 (e.g., 1 / 0.03 to 1 / 0.8) In particular, it may be about 1 / 0.05 to 1 / 0.5 (for example, 1 / 0.06 to 1 / 0.3).

The paint (in particular the sealer) of the present invention may usually be a water-based paint (or a water-based paint, in particular an aqueous sealer). Examples of the aqueous solvent (or aqueous solvent) constituting the water-based paint generally include water and a solvent containing water [such as a mixed solvent of water and alcohol (such as methanol, C _1-4 alcohol such as ethanol, etc.), In particular, water may be used.

  In the paint, the ratio of the resin emulsion (A) is, for example, 3 to 40% by mass (for example, 4 to 35% by mass), preferably 5 to 5% in terms of solid content (or resin constituting the resin emulsion (A)). It may be about 30% by mass (e.g. 7 to 20% by mass), more preferably 10 to 15% by mass (e.g. 12 to 14% by mass).

  In the paint, the proportion of the water-soluble polymer (B) is, for example, 0.1 to 20% by mass (for example, 1 to 15% by mass), preferably 1 to 10% by mass (for example, 2 to 7% by mass) Preferably, it may be about 3 to 8% by mass (for example, 4 to 6% by mass).

  In the paint, the ratio of the total amount of the resin emulsion (A) and the water-soluble polymer (B) is, for example, 3 to 55% by mass (for example, 5 to 5%) in terms of solid content (or resin constituting the resin emulsion (A)). It may be about 50% by mass, preferably about 6 to 40% by mass (for example, 9 to 27% by mass), and more preferably about 13 to 23% by mass (for example, 16 to 20% by mass).

When the paint contains a pigment, the proportion of the pigment can be selected for the purpose of the paint etc. For example, it is 10% or more, 20% or more, 30% or more, 40% or more, etc. Good.
In particular, in the sealer, the pigment weight concentration may be 50% or more, 55% or more, 60% or more, and the like.
The pigment weight concentration (%) is represented by [(mass of pigment) / (mass of solid content)] × 100.

  In the paint, the ratio of the solid content (or non-volatile content) is, for example, 5 to 90 mass%, preferably 10 to 80 mass%, more preferably 20 to 70 mass% (for example, 30 to 65 mass%, 40 to 60). It may be about mass%).

  In the paint, the proportion of the film forming aid is, for example, 0.4 to 25% by mass (for example, 0.5 to 23% by mass), preferably 0.6 to 20% by mass, and more preferably 0.8 to 15 The content may be, for example, about 0.9 to 13% by mass, and particularly about 1 to 10% by mass (for example, 1.1 to 8% by mass).

  In the paint, the proportion of the film forming aid is, for example, 1 to 100 parts by mass, preferably 1 to 80 parts by mass, and more preferably 1 to 60 parts by mass with respect to 100 parts by mass of the film forming component (resin). Particularly preferably, it may be about 2 to 60 parts by mass, 50 parts by mass or less [eg, 0.1 to 50 parts by mass, preferably 45 parts by mass or less (eg, 0.1 to 45 parts by mass), more preferably May be about 40 parts by mass or less (e.g., about 0.5 to 45 parts by mass).

  When the paint contains a glycol ether (A), the proportion of the glycol ether (A) is, for example, 1 to 80 parts by mass, preferably 1 to 70 parts by mass with respect to 100 parts by mass of the film forming component (resin). More preferably, it may be about 1 to 60 parts by mass, and particularly preferably about 2 to 55 parts by mass.

  When the paint contains a glycol ether (A1), the proportion of the glycol ether (A1) is, for example, 0.1 to 50 parts by mass, preferably 0.1 to 100 parts by mass of the film formable component (resin). -40 mass parts, More preferably, it is 0.5-35 mass parts, Most preferably, about 0.5-30 mass parts may be sufficient.

  When the paint contains glycol ether (A2), the proportion of glycol ether (A2) is, for example, 1 to 60 parts by mass, preferably 1 to 50 parts by mass with respect to 100 parts by mass of the film forming component (resin). More preferably, it may be about 1 to 45 parts by mass, and particularly preferably about 1 to 40 parts by mass.

  When the coating material contains an ester (B), the proportion of the ester (B) is, for example, 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass with respect to 100 parts by mass of the film forming component (resin). It may be about 0.1 to 10 parts by mass, more preferably about 0.1 to 10 parts by mass.

  The viscosity of the paint is, for example, about 10 to 10000 mPa · s (for example, 20 to 9000 mPa · s), preferably 30 to 8000 mPa · s, more preferably 50 to 5000 mPa · s (for example, 100 to 4000 mPa · s). Or about 50 to 3000 mPa · s.

  The viscosity may be measured, for example, using a BM viscometer at a predetermined rotational speed (for example, 30 rpm).

The paint is not particularly limited, and can be obtained by mixing the respective components. In addition, when the film-forming auxiliary contains two or more kinds of glycol ethers (A) and esters (B), the mixing method (order) to these paints is not particularly limited.
For example, a film-forming aid prepared in advance (that is, a film-forming aid containing glycol ether (A) and ester (B)) is applied to a paint [or another component constituting the paint (for example, a film-forming component)]. The film forming aid may be formed during the preparation of the coating material (in the coating material). Specifically, the glycol ether (A) and the ester (B) may be mixed individually or collectively with the paint [or other components (for example, film-forming components) constituting the paint]. When mixing individually, the mixing order of 2 or more types of glycol ether (A) and the mixing order of glycol ether (A) and ester (B) are not specifically limited. For example, glycol ether (A1), glycol ether (A2), ester (B) may be mixed in any order, a mixture of glycol ether (A1) and glycol ether (A2), ester (B), etc. May be.

  Although it does not limit as a base material to which coating or a paint is applied, in this invention, especially a ceramic industry base material (ceramic industry building material) (or inorganic porous base material) can be used conveniently.

  Examples of the ceramic base include tile, outer wall material [(ceramic) siding, siding board] and the like.

  The ceramic base material is usually a base material (building material) containing a hydraulic adhesive (cement) and a fiber (wood-based component), and a hydraulic adhesive (cement) and a fiber (wood-based component) Obtained by curing (curing) a substrate containing For this reason, ceramic-based substrates usually contain cement-derived alkali components and metal components (metal ion components such as calcium ion components).

  Specific examples of the ceramic base material include a calcium silicate board, a pulp cement board, a gypsum slag board, a wood piece cement board, and an ALC board.

  Here, undercoating (or sealer, post-curing sealer) is further applied to the base material [base material after curing, in particular, ceramic base material (ceramic base material after curing)].

  In addition, the base material may be a base material to which a pre-cure sealer is not applied (a base material not to be subjected to a pre-cure sealer treatment).

  The undercoat is roughly classified into a surface sealer [or a post-curing sealer, a sealer on the surface to be coated (and intermediate coating)] and a back sealer [an undercoat on the back surface (the surface opposite to the surface to be coated)].

  Although the paint (sealer) of the present invention can be applied to any primer, it may be used particularly for at least a surface sealer (or a post-cure sealer).

  Examples of the coating method include roll coating (roller coating), flow coating, spray coating, electrostatic coating, vacuum coating, brush coating and the like. The painting may be automatic painting. In particular, the paint of the present invention may be suitably used for flow coating.

  The undercoating (sealer) may be performed at the time of construction, but in the present invention, it may be performed before construction, especially in a factory (factory coating).

In the undercoating, the coating amount is not particularly limited, but may be, for example, about 1 g / m ² or more, preferably 1.5 g / m ² or more, and more preferably about ² g / m ² or more as a nonvolatile content.

The paint (coating film) may be dried naturally, but in roller coating or factory coating, it is usually heated, for example, 40 ° C. or higher (for example, 45 to 180 ° C.), preferably It is often dried at 50 ° C. or more (eg, 60 to 150 ° C.), more preferably 70 ° C. or more (eg, 80 to 130 ° C.).
The drying time depends on the coating method and the like, but is, for example, 120 minutes or less (for example, 1 to 120 minutes), preferably 60 minutes or less (for example, 1 to 60 minutes), more preferably 30 minutes or less (for example, 1 ~ 30 minutes).
In the present invention, even with such limited drying time, a good coating film (such as an undercoat layer) can be efficiently obtained.

According to the paint (sealer, primer) of the present invention, reinforcement of a substrate and formation of a coating can be efficiently performed.
In particular, in the coating material of the present invention, it is possible to realize the reinforcement of the base material and the formation of the coating film, which are difficult to be compatible, at one time or one liquid (one coat). Moreover, because of the high compatibility between the reinforcing part and the coating film part, it is possible to realize excellent adhesion (interlayer adhesion) between the substrate and the coating film.

  Also, the paint of the present invention seems to be relatively high in mechanical stability and chemical stability, and even if it is applied under severe conditions or even when applied to a ceramic base, Excellent stability of the resin in the membrane can be realized. In the case of pre-application coating such as factory coating, after application and after application, it is stored until application, but since the stability of the resin in the coating film is high as described above, coating defect and lamination of base material even after long-term storage Blocking and the like associated with can be suppressed at a high level.

  In addition, on the base material after undercoat, it is possible to carry out overcoating (and intermediate coating).

  The present invention is not limited to the above-described embodiments, and various modifications are possible. Embodiments obtained by appropriately combining technical means disclosed in different embodiments are also included in the present invention. .

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not restrict | limited by the following Example from the first.
In Examples, “part” and “%” mean “mass (weight) part” and “mass%”, respectively, unless otherwise specified.

  Further, various physical properties and the like were measured and evaluated as follows.

[Solid content ratio (nonvolatile content, nonvolatile content)]
1 g of sample was weighed and dried with a hot air dryer at a temperature of 110 ° C. for 1 hour.
[Non-volatile content (% by mass)]
= ([Mass of residue] ÷ [1 g]) × 100
Based on.

[Glass-transition temperature]
The glass transition temperature is calculated using the glass transition temperature of the homopolymer of each monomer:
1 / Tg = Σ (Wm / Tgm) / 100
[Wm represents the content (% by weight) of monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of monomer m]
It calculated | required based on the formula of Fox (Fox) represented by these.

The Tg of the homopolymer used to calculate the glass transition temperature (Tg) of the monomer component constituting the polymer from the formula for FOX is shown below.
Styrene (St): 100 ° C.
2-ethylhexyl acrylate (2EHA): -70 ° C
Butyl acrylate (BA): -56 ° C
Methyl methacrylate (MMA): 105 ° C
Acrylic acid (AA): 95 ° C
Methacrylic acid (MAA): 130 ° C.
2-hydroxyethyl methacrylate (HEMA): 55 ° C.
Diacetone acrylamide (DAAM): 77 ° C
N-vinyl pyrrolidone (VP): 105 ° C.

[Weight average molecular weight]
It measured on the following conditions by the gel permeation chromatography (GPC).

System: Tosoh Co., Ltd. product name: HLC-8320 GPC
・ Developing solvent: Tetrahydrofuran (THF) [Wako Pure Chemical Industries, Ltd., special grade]
・ Solvent flow rate: 0.350 mL / min ・ Standard sample: TSK-GEL standard polystyrene [manufactured by Tosoh Corporation, trade name: PS-oligomer kit, product number: 0005214, 0005202, 0005211, 0005207, 0005205, 0005209 and 0005213]
・ Measurement side column constitution: Tosoh Co., Ltd. product name: TSK-GEL SuperMultipore HZ-M 6.0 × 150 two-piece serial connection • Reference side column configuration: Tosoh Corp. product name: TSK− GEL SuperH-RC 6.0 × 150
・ Column temperature: 40 ° C
・ Detector: Differential refractometer (RI)
Measurement method: The object to be measured was dissolved in tetrahydrofuran so as to have a non-volatile content of about 0.2% by mass, and filtered through a filter, and then the weight average molecular weight was measured using the obtained solution.

[Adhesiveness]
Apply the obtained sample to a slate plate [Nippon Test Panel Co., Ltd. product, length: 70 mm, width: 150 mm, thickness: 6 mm] using a 6 mil applicator and dry it in an oven at 100 ° C. for 10 minutes. Thus, a test plate for evaluation was obtained.
The coating film of the test plate for evaluation was cut with a cutter knife so that 100 squares of 2 mm square were formed, and cellophane adhesive tape [trade name: Cellotape (registered trademark) CT405AP-18, manufactured by Nichiban Co., Ltd.] The laminate was attached to this grid, and a peeling test was conducted according to JIS K5400 to count the number of grids remaining, and the adhesion was evaluated based on the following evaluation criteria.
(Evaluation criteria)
◎: 80 or more remaining grids ○: 79 to 60 remaining grids □: 59 to 40 remaining grids Δ: 39 to 20 remaining grids Number x: 19 or less remaining grids

[Base material reinforcement]
Apply the obtained sample to a slate plate (manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm) using a 4 mil applicator and dry in an oven at 100 ° C. for 10 minutes. Thus, a test plate for evaluation was obtained.
The two supports were spaced 13 cm apart, and the coated side of the test body was upside, and the supports were simply supported on the opposite side. About 500 g of a spherical weight was dropped toward the center of the test body from a height of 25 cm from the test body, and it was confirmed whether or not cracking occurred. Ten test pieces were prepared and ten tests were performed. Evaluation criteria were as follows.
(Evaluation criteria)
◎: No cracked base material ○: One to three base materials with cracks □: Four to six base materials with cracks Δ: Seven base materials with cracks Sheets to 9 sheets x: cracks occurred in all the base materials

Water Permeability
The obtained sample was spray-coated on a test plate (calcium silicate plate, manufactured by Nippon Test Panel Co., Ltd., thickness 12 mm) so that the coating amount was 170 g / m ^2, and dried at 100 ° C. for 10 minutes with a dryer. To form a coating. A test frame was attached to the painted surface of the test body with reference to the surface water absorption test method of JIS A 1414. Water was poured into the test frame so that the water surface height was 20 mm, and left still for 24 hours. After 24 hours, the water in the test frame was discharged, and the presence or absence of water permeation to the back surface of the substrate was visually confirmed. Evaluation criteria were as follows.
(Evaluation criteria)
:: no water permeability to the back surface ○: water permeability range is less than half of the inner surface area of the test frame but there is water permeability Δ: water permeability range is more than half of the inner surface area of the test frame and less than the inner surface area ×: water permeability range is the test More than inside area of frame

Resin emulsion production example
Production Example A1 (One-Step Polymerization)
In a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 800 parts of deionized water was charged.
In a dropping funnel, 270 parts of deionized water, 150 parts of a 20% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08), 150 parts (30 parts of an emulsifier), 700 parts of styrene, 2-ethylhexyl acrylate A dropping pre-emulsion comprising 180 parts, 70 parts of methyl methacrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid, 30 parts of 2-hydroxylethyl methacrylate and 10 parts of octyl thioglycolate was prepared.
Of the obtained pre-emulsion for dropping, 71 parts corresponding to 5% of the total amount of monomer components is added into the flask, and while gradually blowing nitrogen gas, the temperature is raised to 80 ° C., 3.5% ammonium persulfate An aqueous solution of 14 parts was added to the flask to initiate emulsion polymerization.
Next, the remainder of the pre-emulsion for dropping, 87 parts of 3.5% aqueous ammonium persulfate solution and 60 parts of 2.5% aqueous sodium hydrogen sulfite solution were dropped into the flask over 270 minutes. After completion of the addition, the temperature was maintained at 80 ° C. for 120 minutes.
Next, 25% ammonia water was added to adjust the pH to 8, and the emulsion polymerization reaction was completed. The resulting reaction mixture was cooled to room temperature and then filtered through a 100 mesh wire mesh to obtain a resin emulsion A1.

[Production example A2 (two-stage polymerization)]
In a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 800 parts of deionized water was charged.
In a dropping funnel, 90 parts of deionized water, 50 parts of a 20% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08) 50 parts (10 parts of emulsifier), 320 parts of styrene, 2-ethylhexyl acrylate A pre-emulsion for dropping (first-stage pre-emulsion) comprising 10 parts, 5 parts of acrylic acid, 2 parts of methacrylic acid, and 3 parts of octyl thioglycolate was prepared.
Of the obtained pre-emulsion for dropping, 71 parts corresponding to 5% of the total amount of monomer components is added into the flask, and while gradually blowing nitrogen gas, the temperature is raised to 80 ° C., 3.5% ammonium persulfate An aqueous solution of 14 parts was added to the flask to initiate emulsion polymerization.
Next, the remainder of the dropping pre-emulsion, 29 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium bisulfite solution were dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.
Thereafter, 180 parts of deionized water, 100 parts of a 20% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: HITENOL NF-08) (20 parts of emulsifier), 380 parts of styrene, 170 parts of 2-ethylhexyl acrylate Second stage pre-emulsion consisting of 70 parts of methyl methacrylate, 3 parts of methacrylic acid, 30 parts of 2-hydroxyethyl methacrylate, 7 parts of octyl thioglycolate, 58 parts of 3.5% aqueous ammonium persulfate solution and 2.5% hydrogen sulfite 40 parts of an aqueous sodium solution was dropped into the flask over 180 minutes. After completion of the addition, the temperature was maintained at 80 ° C. for 120 minutes.
Next, 25% ammonia water was added to adjust the pH to 8, and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature and then filtered through a 100-mesh wire mesh to obtain a resin emulsion A2.

[Production Examples A3 to A5 (2-stage polymerization)]
Except having changed into the monomer component described in Table 1, it carried out similarly to manufacture example A2, and obtained resin emulsion A3-A5.

[Production Example A6 (three-stage polymerization)]
In a flask equipped with a dropping funnel, a stirrer, a nitrogen inlet tube, a thermometer and a reflux condenser, 800 parts of deionized water was charged.
In a dropping funnel, 90 parts of deionized water, 50 parts of a 20% aqueous solution of an emulsifier (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08) 50 parts (10 parts of an emulsifier), 164 parts of styrene, 2-ethylhexyl acrylate A dropping pre-emulsion (first stage pre-emulsion) consisting of 10 parts and 1 part of acrylic acid was prepared.
Of the obtained pre-emulsion for dropping, 71 parts corresponding to 5% of the total amount of monomer components is added into the flask, and while gradually blowing nitrogen gas, the temperature is raised to 80 ° C., 3.5% ammonium persulfate An aqueous solution of 14 parts was added to the flask to initiate emulsion polymerization.
Next, the remainder of the dropping pre-emulsion, 29 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium bisulfite solution were dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.
Thereafter, 90 parts of deionized water, 50 parts of a 20% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: HITENOL NF-08] (10 parts of emulsifier), 110 parts of styrene, 100 parts of 2-ethylhexyl acrylate A second pre-emulsion consisting of 111 parts of methyl methacrylate, 29 parts of 3.5% aqueous ammonium persulfate solution and 20 parts of 2.5% aqueous sodium bisulfite solution were dropped into the flask over 90 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 60 minutes.
Next, 90 parts of deionized water, 50 parts of a 20% aqueous solution of an emulsifier [Daiichi Kogyo Seiyaku Co., Ltd., trade name: HITENOL NF-08] (10 parts of emulsifier), 105 parts of styrene, 2-ethylhexyl acrylate 92 Third stage pre-emulsion consisting of 95 parts methyl methacrylate, 5 parts methacrylic acid, 30 2-hydroxy ethyl methacrylate, 3 parts octyl thioglycolate, 29 parts 3.5% aqueous ammonium persulfate solution and 2.5% hydrogen sulfite 20 parts of an aqueous sodium solution was dropped into the flask over 90 minutes. After completion of the addition, the temperature was maintained at 80 ° C. for 120 minutes.
Next, 25% ammonia water was added to adjust the pH to 8, and the emulsion polymerization reaction was completed. The resulting reaction mixture was cooled to room temperature and then filtered through a 100 mesh wire mesh to obtain a resin emulsion A6.

Production Example A7 to 10 (Three-Step Polymerization)
Resin emulsions A7 to A10 were obtained in the same manner as in Production Example A6, except that the monomer components described in Table 1 were changed.

Water-soluble polymer production example
[Production Example B1 (nonionic (PVP), DAAM-containing, Mw10000)]
Into a polymerization vessel equipped with a cooling pipe, a nitrogen introduction line and a thermometer, 1295 parts of deionized water was charged. Nitrogen gas was introduced into the flask to make the inside of the flask a nitrogen gas atmosphere.
In the dropping funnel A, 518 parts of N-vinylpyrrolidone and 38 parts of diacetone acrylamide were added to prepare a premix. In the dropping funnel B, 133 parts of deionized water, 17 parts of acrylic acid and 16 parts of 25% aqueous ammonia solution were added. In a dropping funnel C, 258 parts of deionized water and 29 parts of 2,2'-azobis (2-methylpropionamidine) dihydrochloride were added.
The contents of dripping funnel A, dripping funnel B and dripping funnel C were uniformly dropped into the polymerization vessel over 2 hours, respectively, to initiate the polymerization reaction. After the temperature in the polymerization vessel rose due to the heat of polymerization, it was stirred for 2 hours at a temperature of 90 ° C.
Next, each of the dropping funnel A and the dropping funnel B was washed with 10 parts of deionized water, and the obtained washing solution was added to the polymerization vessel, and stirred at a temperature of 80 ° C. for 1 hour. After 1 hour, 0.6 part of a 10% aqueous solution of 2,2′-azobis (2-methylpropionamidine) dihydrochloride dissolved in deionized water was added to the polymerization vessel, and further stirred at a temperature of 90 ° C. for 1 hour. Thus, a water-soluble polymer solution was obtained. The obtained water-soluble polymer solution had a nonvolatile content of 26.0% by mass, and the obtained polymer had a weight average molecular weight of 10,000.

[Production Example B2 (Nonion-based (PVP-based), containing DAAM, Mw 30000)]
Into a polymerization vessel provided with a cooling pipe, a nitrogen introduction line and a thermometer, 602 parts of deionized water were charged, and nitrogen gas was introduced to make the inside of the polymerization vessel a nitrogen gas atmosphere. While stirring the contents in the polymerization vessel at room temperature, 1.7 parts of a 0.02% aqueous solution of copper sulfate was added. To the dropping funnel A was added 186.6 parts of deionized water and 1053 parts of N-vinylpyrrolidone to prepare a premix. To the dropping funnel B were added 74 parts of deionized water and 21.3 parts of 35% hydrogen peroxide water. To the dropping funnel C were added 69 parts of deionized water and 3.3 parts of a 25% aqueous ammonia solution. The contents of dropping funnel A, dropping funnel B and dropping funnel C were uniformly dropped over 3 hours into the polymerization vessel to start the polymerization reaction. After the internal temperature of the polymerization vessel rose due to the heat of polymerization, the contents in the polymerization vessel were stirred at 60 ° C. for 3 hours.
Next, the dropping funnel A, the dropping funnel B and the dropping funnel C were respectively washed with 30 parts of deionized water, and the obtained washing solution was added to the polymerization vessel. After further adding 2.2 parts of a 25% aqueous ammonia solution and 10 parts of a 30% aqueous hydrogen peroxide solution into the polymerization vessel, the contents in the polymerization vessel are stirred at 60 ° C. for 1 hour to obtain a polymer solution. It was. The non-volatile content of the obtained polymer solution B2 was 50.0% by mass, and the weight average molecular weight of the polymer contained in the polymer solution was 25,000.
In a polymerization vessel provided with a cooling pipe, a nitrogen introduction line, and a thermometer, 100 parts of deionized water and 900 parts of the polymer solution B2 obtained in Production Example B2 were added into the polymerization vessel, and nitrogen gas was added into the polymerization vessel. By introducing the nitrogen gas atmosphere. The temperature in the polymerization vessel is raised to 85 ° C. with stirring at room temperature, and when the temperature becomes constant, 100 parts of diacetone acrylamide, 8 parts of acrylic acid, 2 parts of hydroxyethyl methacrylate, 50 parts of deionized water and An aqueous solution obtained by mixing 3.8 parts of a 25% aqueous ammonia solution is added to the polymerization vessel over 120 minutes, and an aqueous solution in which 1.5 parts of ammonium persulfate is dissolved in 48.5 parts of deionized water is polymerized over 120 minutes Added into the container. After completion of the dropwise addition, 200 parts of deionized water was added into the polymerization vessel, and the reaction was completed by stirring at 80 ° C. for 1 hour. The non-volatile content of the obtained water soluble polymer solution was 40.1%, and the weight average molecular weight of the polymer contained in the water soluble polymer solution was 30,000.

[Production example B3 (anionic system, Mw 16000)]
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser, 1200 parts of deionized water was charged.
In a dropping funnel, 234 parts of deionized water, 35 parts of a 20% aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08) (7 parts of emulsifier), 603 parts of methyl methacrylate, 84 parts of methacrylic acid A drop pre-emulsion consisting of 13 parts of octyl thioglycollate was prepared.
Of the obtained pre-emulsion for dropping, 49 parts corresponding to 5% of the total amount of monomer components is added into the flask, and while gradually blowing nitrogen gas, the temperature is raised to 80 ° C., and 5% ammonium persulfate aqueous solution 42 Part was added into the flask and emulsion polymerization was started.
Next, the remainder of the pre-emulsion for dropping was dropped into the flask over 120 minutes. After the addition was completed, the temperature was maintained at 88 ° C. for 30 minutes.
Next, 25% ammonia water was added to adjust the pH to 8, and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature, and then filtered through a 100-mesh wire mesh to obtain a water-soluble polymer. The weight average molecular weight of the obtained water soluble polymer was 16000. The non-volatile content of the obtained water-soluble polymer was 30% by mass.

[Production Example B4 (anionic, containing DAAM, Mw 16000)]
In a flask equipped with a dropping funnel, a stirrer, a nitrogen introducing tube, a thermometer and a reflux condenser, 1200 parts of deionized water was charged.
In a dropping funnel, 234 parts of deionized water, 35 parts of a 20% aqueous solution of an emulsifier (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: HITENOL NF-08) (7 parts of emulsifier), 554 parts of methyl methacrylate, 84 parts of methacrylic acid A dripping pre-emulsion consisting of 13 parts of octyl thioglycollate and 49 parts of diacetone acrylamide was prepared.
Of the obtained pre-emulsion for dropping, 49 parts corresponding to 5% of the total amount of monomer components is added into the flask, and while gradually blowing nitrogen gas, the temperature is raised to 80 ° C., and 5% ammonium persulfate aqueous solution 42 Part was added into the flask and emulsion polymerization was started.
Next, the remainder of the pre-emulsion for dropping was dropped into the flask over 120 minutes. After the addition was completed, the temperature was maintained at 88 ° C. for 30 minutes.
Next, 25% ammonia water was added to adjust the pH to 8, and the emulsion polymerization reaction was completed. The obtained reaction mixture was cooled to room temperature, and then filtered through a 100-mesh wire mesh to obtain a water-soluble polymer. The weight average molecular weight of the obtained water soluble polymer was 16000. The non-volatile content of the obtained water-soluble polymer was 30% by mass.

Example 1: Stepwise polymerization + nonionic (PVP-based, containing DAAM, Mw 10000)
17.1 parts of ion-exchanged water and 350.3 parts of the water-soluble polymer solution obtained in Production Example B1 were added while dispersing 500 parts of the resin emulsion obtained in Production Example A1 with a homodisper at 1000 rpm (Resin emulsion) / Water-soluble polymer (solid content mass ratio) = 70/30).
Ion-exchanged water (adjusting the amount so that the solids content of the sealer before addition of the thickener is 50%) while dispersing 200 parts of the compound of the obtained resin emulsion and water-soluble polymer solution with a homodisper at 1000 rpm 5 parts of butyl cellosolve as a film forming agent, 5.3 parts of butyl propylene diglycol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC, product number: CS-12] 5.3 parts were added.
13.2 parts of a dispersant (Discoat N14, Dai-ichi Kogyo Seiyaku Co., Ltd.), 100 parts of titanium oxide (Ishihara Sangyo Co., Ltd., Taipek R-930), talc (Nippon Talc Co., Ltd., Talc SSS) in the obtained mixture 32 parts were added, and 1 part of a defoaming agent (Sannopco, SN deformer 777) and 21.5 parts of a 5% aqueous solution of adipic acid dihydrazide were further added. After that, a thickener (ADEKA, UH-472) is added so that the viscosity at a rotational speed of 30 rpm is BM type viscometer is 1000 mPa · s, and stirring is carried out for 15 minutes with a homodisper 1000 rpm Paint). The sample after 1 day progress was used for evaluation.

[Example 2: Two-stage polymerization + nonionic system (PVP system, DAAM containing, Mw 10000)]
A sealer (primer) was obtained in the same manner as in Example 1 except that the resin emulsion obtained in Production Example A2 was changed. The sample after 1 day progress was used for evaluation.

[Example 3: Two-stage polymerization + nonionic system (PVP system, DAAM containing, Mw10000)]
A sealer (undercoat paint) was obtained in the same manner as in Example 1 except that the resin emulsion obtained in Production Example A3 was used. The sample after 1 day progress was used for evaluation.

[Example 4: Two-stage polymerization + nonionic system (PVP system, DAAM containing, Mw 30000)]
A sealer was prepared in the same manner as in Example 3, except that 147.4 parts of deionized water, 227.1 parts of the water-soluble polymer solution obtained in Production Example B2, and 31.8 parts of a 5% aqueous solution of adipic acid dihydrazide were used. Got the paint). The sample after 1 day progress was used for evaluation.

[Example 5: Two-stage polymerization (DAAM-containing) + nonionic system (PVP system, DAAM-containing, Mw10000)]
A sealer (undercoat) was obtained in the same manner as in Example 1, except that the resin emulsion obtained in Production Example A4 was changed to 29.2 parts of a 5% aqueous solution of adipic acid dihydrazide. The sample after 1 day progress was used for evaluation.

[Example 6: Two-stage polymerization (containing DAAM) + nonionic system (PVP system, containing DAAM, Mw 30000)]
A sealer was prepared in the same manner as in Example 5 except that 147.4 parts of deionized water, 227.1 parts of the water-soluble polymer solution obtained in Production Example B2, and 39.4 parts of a 5% aqueous solution of adipic acid dihydrazide were used. Got the paint). The sample after 1 day progress was used for evaluation.

[Example 7: Two-stage polymerization (DAAM-containing) + nonionic system (PVP system, DAAM-containing, Mw10000)]
A sealer (undercoat paint) was obtained in the same manner as in Example 5 except that the resin emulsion obtained in Production Example A5 was used. The sample after 1 day progress was used for evaluation.

[Example 8: Three-stage polymerization + nonionic system (PVP system, DAAM content, Mw 30000)]
A sealer (undercoat paint) was obtained in the same manner as in Example 4 except that the resin emulsion obtained in Production Example A6 was used. The sample after 1 day progress was used for evaluation.

[Example 9: Three-stage polymerization (DAAM-containing) + nonionic system (PVP system, DAAM-containing, Mw30000)]
A sealer (primer) was obtained in the same manner as in Example 6, except that the resin emulsion obtained in Production Example A7 was changed. The sample after 1 day progress was used for evaluation.

[Example 10: Three-step polymerization (containing DAAM) + nonionic (PVP-based, containing DAAM, Mw 30000)]
A sealer (primer) was obtained in the same manner as Example 6, except that the resin emulsion obtained in Production Example A8 was changed. The sample after 1 day progress was used for evaluation.

[Example 11: Three-step polymerization (containing DAAM) + nonionic (PVP-based, containing DAAM, Mw 30000)]
A sealer (primer) was obtained in the same manner as Example 6, except that the resin emulsion obtained in Production Example A9 was changed. The sample after 1 day progress was used for evaluation.

[Example 12: Three-stage polymerization (containing DAAM) + nonionic system (PVP system, containing DAAM, Mw30000)]
A sealer (primer) was obtained in the same manner as in Example 6, except that the resin emulsion obtained in Production Example A10 was changed. The sample after 1 day progress was used for evaluation.

[Example 13: Three-step polymerization (containing DAAM) + anion system (Mw 16000)]
59.3 parts of ion-exchanged water, 242.9 parts of the water-soluble polymer obtained in Production Example B3 and 22.4 parts of the cross-linking agent while dispersing 400 parts of the resin emulsion obtained in Production Example A10 with a homodisper at 1000 rpm (Nippon Catalyst, Epocross WS-500) was added.
Ion-exchanged water (adjusting amount so that the solid content of the sealer before addition of the thickener is 50%) while dispersing 200 parts of the obtained composition with a homodisper at 1000 rpm, butyl cellosolve 5 as a coalescent Parts, 5.3 parts of butyl propylene diglycol, and 5.3 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC, product number: CS-12] were added.
13.2 parts of a dispersant (Discoat N14, Dai-ichi Kogyo Seiyaku Co., Ltd.), 100 parts of titanium oxide (Ishihara Sangyo Co., Ltd., Taipek R-930), talc (Nippon Talc Co., Ltd., Talc SSS) in the obtained mixture 32 parts were added, and further 1 part of an antifoamer (San Nopco, SN deformer 777) was added. After that, a thickener (ADEKA, UH-472) is added so that the viscosity at a rotational speed of 30 rpm is BM type viscometer is 1000 mPa · s, and stirring is carried out for 15 minutes with a homodisper 1000 rpm Paint). The sample after 1 day progress was used for evaluation.

[Example 14: Three-stage polymerization (containing DAAM) + anion system (containing DAAM, Mw 16000)]
While dispersing 400 parts of the resin emulsion obtained in Production Example A10 at 1000 rpm with a homodisper, 59.3 parts of ion-exchanged water and 242.9 parts of the water-soluble polymer obtained in Production Example B4 were added.
While dispersing 200 parts of the resulting resin emulsion and water-soluble polymer blend at 1000 rpm with a homodisper, ion-exchanged water (adjusted so that the solid content of the sealer before adding the thickener is 50%), 5 parts of butyl cellosolve, 5.3 parts of butylpropylene diglycol, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC Corporation, product number: CS-12] 5 3 parts were added.
Dispersant (Discoat N14, Daiichi Kogyo Seiyaku Co., Ltd.) 13.2 parts, Titanium oxide (Ishihara Sangyo Co., Ltd., Taipaque R-930) 100 parts, Talc (Nippon Talc Co., Ltd., Talc SSS) 32 parts were added, and further 1 part of an antifoaming agent (San Nopco, SN deformer 777) and 31.7 parts of a 5% adipic acid dihydrazide aqueous solution were added. After that, a thickener (ADEKA, UH-472) is added so that the viscosity at a rotational speed of 30 rpm is BM type viscometer is 1000 mPa · s, and stirring is carried out for 15 minutes with a homodisper 1000 rpm Paint). The sample after 1 day progress was used for evaluation.

[Example 15: one-stage polymerization + nonionic system (PVP system, DAAM contained, Mw 10000)]
A sealer (undercoat paint) was obtained in the same manner as in Example 1 except that the resin emulsion obtained in Production Example A11 was used. The sample after 1 day progress was used for evaluation.

[Example 16: Three-stage polymerization (containing DAAM) + nonionic system (PVP system, containing DAAM, Mw 30000)]
A sealer (undercoat paint) was obtained in the same manner as in Example 6 except that the resin emulsion obtained in Production Example A12 was used. The sample after 1 day progress was used for evaluation.

[Reference example 1: 1 step polymerization, no water soluble polymer]
Ion-exchanged water (adjusting amount so that the solid content of the sealer before addition of the thickener is 50%) while dispersing 200 parts of the resin emulsion obtained in Production Example A1 with a homodisper at 1000 rpm, film-forming aid Parts of butyl cellosolve, 5.3 parts of butyl propylene diglycol as a curing agent, 5.3 parts of 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by JNC, product number: CS-12] Was added.
13.2 parts of a dispersant (Discoat N14, Dai-ichi Kogyo Seiyaku Co., Ltd.), 100 parts of titanium oxide (Ishihara Sangyo Co., Ltd., Taipek R-930), talc (Nippon Talc Co., Ltd., Talc SSS) in the obtained mixture 32 parts were added, and 1 part of a defoaming agent (Sannopco, SN deformer 777) and 21.5 parts of a 5% aqueous solution of adipic acid dihydrazide were further added. After that, a thickener (ADEKA, UH-472) is added so that the viscosity at a rotational speed of 30 rpm is BM type viscometer is 1000 mPa · s, and stirring is carried out for 15 minutes with a homodisper 1000 rpm Paint). The sample after 1 day progress was used for evaluation.

  The composition (preparation) and physical properties of production examples (resin emulsions) A1 to A12 are shown in Table 1 below, and the compositions and physical properties of Examples and Reference Examples are shown in Tables 2 to 6 below.

  In the table, “St” is styrene, “2EHA” is 2-ethylhexyl acrylate, “BA” is butyl acrylate, “MMA” is methyl methacrylate, “AA” is acrylic acid, “MAA” is methacrylic acid, "HEMA" is 2-hydroxyethyl methacrylate, "OTG" is octyl thioglycolate, "DAAM" is diacetone acrylamide, "Tg" is the glass transition temperature, "ADH" is adipic acid dihydrazide, "Epocross" is Japan Corporation The catalyst "Epocross WS-500" [water-soluble polymer containing an oxazoline group (water-soluble oxazoline crosslinking agent), 39% active ingredient] is shown.

  As is clear from the results in the above table, in the examples, a good coating film (undercoat layer) could be formed in terms of adhesion to the base material (ceramic base material) and reinforcement.

  According to the present invention, a paint (paint composition) useful as a sealer or the like can be provided.

Claims (18)

  A sealer comprising a resin emulsion (A) and a water-soluble polymer (B) having a weight average molecular weight of 100,000 or less.   The sealer according to claim 1, wherein the resin constituting the resin emulsion (A) is an acrylic resin.   The resin component constituting the resin emulsion (A) contains a (meth) acrylic monomer and a styrenic monomer, and the monomer component (a) in which the proportion of the styrenic monomer is 15% by mass or more is a polymerization component. Sealer of 1 statement.   The sealer according to any one of claims 1 to 3, wherein the resin constituting the resin emulsion (A) is a resin having as a polymerization component a monomer component (a) containing a styrene-based monomer in a proportion of 55% by mass or more. .   Resin emulsion (A) polymerizes monomer component (a) containing a (meth) acrylic monomer, a styrene monomer, and a monomer having a functional group α, and the proportion of the styrene monomer is 60% by mass or more. The sealer according to any one of claims 1 to 4, wherein the sealer comprises a resin having a weight average molecular weight of 50,000 to 500,000 and a glass transition temperature of 15 ° C or higher.   The sealer according to any one of claims 1 to 5, wherein the water-soluble polymer (B) is nonionic.   The sealer according to any one of claims 1 to 6, wherein the water-soluble polymer (B) contains as a polymerization component a monomer component (b) containing a monomer having a functional group β.   The sealer according to any one of claims 1 to 7, wherein the water-soluble polymer (B) contains a monomer component (b) containing a lactam monomer as a polymerization component.   The water-soluble polymer (B) contains a lactam monomer and a monomer having a functional group β, the ratio of the lactam monomer is 50% by mass or more, and the ratio of the monomer having an ionic group is 10% by mass or less. The sealer according to any one of claims 1 to 8, which is a water-soluble polymer having a certain monomer component (b) as a polymerization component.   The sealer according to any one of claims 1 to 9, further comprising a crosslinking agent (C).   The sealer according to any one of claims 1 to 10, further comprising at least one water-soluble crosslinking agent (C) selected from a hydrazine crosslinking agent, an oxazoline crosslinking agent, and a carbodiimide crosslinking agent.   The sealer according to claim 10 or 11, wherein the water-soluble polymer (B) can form a crosslinked structure via the crosslinking agent (C).   The sealer according to any one of claims 1 to 12, wherein the resin emulsion (A) and the water-soluble polymer (B) can form a crosslinked structure.   Further, a resin that contains a hydrazine-based crosslinking agent and that constitutes the resin emulsion (A) has a monomer component (a) that contains a carbonyl group-containing monomer as a polymerization component, and a resin that constitutes the water-soluble polymer (B). The monomer component (b) containing a carbonyl group-containing monomer is a polymerization component, and the resin emulsion (A) and the water-soluble polymer (B) can form a crosslinked structure via a hydrazine-based crosslinking agent. The sealer in any one of 1-13.   The sealer according to any one of claims 1 to 14, comprising a pigment at a pigment weight concentration (PWC) of 50% or more.   A coated substrate comprising a substrate and an undercoat layer formed on the substrate, wherein the undercoat layer is formed with the sealer according to any one of claims 1 to 15.   The coated substrate according to claim 16, wherein the substrate is a ceramic-based substrate.   The coated substrate according to claim 16 or 17, wherein a coating film is further formed on the undercoat layer.