WO2018174292A1 - Résine pour revêtement d'apprêt aqueux - Google Patents

Résine pour revêtement d'apprêt aqueux Download PDF

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Publication number
WO2018174292A1
WO2018174292A1 PCT/JP2018/011926 JP2018011926W WO2018174292A1 WO 2018174292 A1 WO2018174292 A1 WO 2018174292A1 JP 2018011926 W JP2018011926 W JP 2018011926W WO 2018174292 A1 WO2018174292 A1 WO 2018174292A1
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mass
monomer
resin
parts
meth
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PCT/JP2018/011926
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English (en)
Japanese (ja)
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清水　亮
芳峰 坂元
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株式会社日本触媒
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Priority to JP2019507049A priority Critical patent/JP6869329B2/ja
Publication of WO2018174292A1 publication Critical patent/WO2018174292A1/fr

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  • the present invention relates to a resin (emulsion) useful as a primer (sealer) or the like, a paint containing the resin (emulsion), and the like.
  • Coatings of base materials are roughly classified into undercoats and overcoats (further, middle coats).
  • the base coat (sealer) is further roughly divided into the coating (first sealer) of the surface (surface to be coated) of the substrate and the coating (back sealer) of the back surface of the substrate.
  • the coating films adhere to each other when water resistance and / or building materials are laminated to prevent water from entering the substrate. It is required to have performance such as blocking resistance for prevention.
  • sealers conventionally, solvent-based (organic solvent-based) sealers have been mainly used. However, since solvent-based sealers contain a large amount of organic solvents, water-based (water-based) sealers are used from the viewpoint of environmental protection. Is required.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 201-180398 is a resin emulsion containing emulsion particles having an inner layer and an outer layer, wherein the inner layer is styrene 85. It is formed of a polymer (I) obtained by emulsion polymerization of a monomer component A containing 1 to 100% by weight and 0 to 15% by weight of monomers other than styrene, and the outer layer is a carboxyl group-containing monomer A polymer having a glass transition temperature of 40 ° C.
  • An object of the present invention is to provide a resin (emulsion) useful as a primer (for primer coating) and the like.
  • Another object of the present invention is to provide a resin capable of reducing variation in coating film performance (for example, water permeability) in a ceramic base material.
  • Another object of the present invention is to provide a resin capable of realizing sufficient reduction in coating film performance and variations thereof even in roller coating and factory coating.
  • the present inventors have been required to reduce the acid group (such as carboxyl group) -containing monomer constituting the resin contained in the emulsion to a predetermined ratio (further, the resin has an acid group). Not be able to reduce variations in coating film performance such as water permeability in ceramic-based building materials), and also to reduce such coating film performance and variations in rollers, etc., in the factory. It has been found that it can be realized even in a coating film formed under severe conditions such as painting.
  • the acid group such as carboxyl group
  • the carboxyl group-containing monomer is considered to contribute to the mechanical stability of the resin (emulsion) in the coating film, and the mechanical stability is impaired by reducing the proportion of the carboxyl group-containing monomer.
  • coating film defects would occur due to aggregation of the resin at the time of coating, and the like.
  • a coating film having sufficient coating film performance is formed, and in particular, high load by roller coating, not brush coating at the time of application, etc. -It was surprising that a good coating film with excellent stability in quality with little blurring in the coating film performance such as water permeation resistance can be obtained even through factory coating where high pressure acts.
  • the inventors of the present invention have found that the decrease in coating film performance such as water permeability is due to the chemical stability of the resin emulsion due to the interaction between the alkali component and the metal component contained in the ceramic building material and the carboxyl group monomer. It was estimated that the decrease was due to the decrease of the Therefore, the variation of the permeability resistance varies depending on the location of the ceramic building materials and the amount of alkali components and metal components among the ceramic building materials, and the variation in the degree of chemical stability of the emulsion resin also occurs accordingly. Although it was presumed that the cause was caused and attempts were made to reduce the proportion of carboxyl group-containing monomers, it is possible to sufficiently enhance the chemical stability while sufficiently securing the mechanical stability even by such a reduction. did it. Thus, the finding that the mechanical stability and the chemical stability can be compatible at a high level, which is presumed to be in a trade-off relationship, is extremely surprising.
  • the inventors of the present invention obtained various new findings as described below in addition to the above, and conducted extensive studies to complete the present invention.
  • the resin of the present invention is a resin having a monomer component (a) as a polymerization component, and the ratio of the acid group-containing monomer (a1) in the monomer component (a) is a predetermined ratio (for example, 4 .5 mass% or less).
  • Such resins may usually constitute an emulsion (aqueous emulsion). Therefore, the present invention also includes emulsions of such resins (resin emulsions, emulsions containing resins).
  • the monomer component (a) may usually contain a hydrophilic monomer (a2) in such a resin (or a resin emulsion, hereinafter, these may be simply referred to as a resin, etc.). .
  • such a resin may be a resin for a paint, in particular, a primer (for a primer) for a ceramic base material.
  • the primer may be a roller coating and / or a back sealer (such as a factory-painted back sealer), in particular a roller coated back sealer.
  • the proportion of the acid group-containing monomer (a1) may be 3.5% by mass or less (for example, 3.0% by mass or less).
  • the proportion of a2) may be 1.2% by mass or more (eg, 1.5 to 8.0% by mass).
  • the resin of the present invention may constitute an emulsion (in particular, an aqueous emulsion).
  • Representative resins (emulsions) of the present invention include the following resins (emulsions).
  • the hydrophilic monomer (a1) contains a hydroxy group-containing (meth) acrylate
  • the monomer component (a) contains a hydrophobic monomer (a3) containing a styrenic monomer (and, if necessary, a (meth) acrylic monomer),
  • the proportion of the hydrophobic monomer (a3) is 50% by mass or more (for example, in the monomer component (a), the proportion of the acid group-containing monomer (a1) is 3% by mass
  • the resin in which the proportion of the hydrophilic monomer (a2) is 1.5% by mass or more and the proportion of the hydrophobic monomer (a3) is 50% by mass or more).
  • the resin may be a resin in which the ratio of the acid group-containing monomer (a1) to 1 part by mass of the hydrophilic monomer (a2) is 1.8 parts by mass or less.
  • the resin may have a multilayer structure.
  • the proportion of the acid group-containing monomer (a1) contained in the outer layer is 1.5% by mass or less, and the hydrophilic monomer contained in the outer layer ( It may be a resin in which the proportion of a2) is 1.2% by mass or more (for example, 1.8 to 10% by mass).
  • the resin may contain relatively low molecular weight components (eg, components having a weight average molecular weight of 10,000 to 80,000).
  • the ratio of low molecular weight components [components of weight average molecular weight 10,000 to 80,000 (polymer, polymer component)] to the whole resin is 5 to 50% in area ratio in gel permeation chromatography It may be an extent.
  • such a low molecular weight component may be possessed by the outer layer (particularly, the outermost layer) particularly in a resin having a multilayer structure.
  • the present invention also includes a paint containing the resin (or an emulsion of the resin).
  • a paint may be, in particular, a sealer (primer, primer) of ceramic base material.
  • a sealer primer
  • Such a sealer (priming paint) may also be for roller coating and / or back sealer (such as factory-coated back sealer), in particular for roller coated back sealer.
  • the present invention also includes a coating film formed of the coating material and a substrate having the coating film.
  • a substrate coated substrate
  • a coated (undercoated) substrate in which a subbing layer is formed on a substrate (particularly a ceramic base material), and the subbing layer is the above-mentioned sealer (paint).
  • a coated substrate formed of Such a coated substrate is typically a coated (undercoated) substrate having a back sealer layer (subbing layer) formed on the back surface (one surface) of a ceramic base material, which is a back sealer. It may be a coated substrate in which the layer is formed of the sealer (primer).
  • the present invention also includes a method of producing a coated substrate using the paint.
  • a method may be a method of coating the coating material on a substrate (in particular, a ceramic base material) to produce the coated base material, typically, the back surface of the ceramic base material
  • the sealer may be roller coated to produce the coated substrate.
  • it may be factory-painted with a roller and dried under heating (for example, a drying temperature of 60 ° C. or more).
  • a resin useful as a primer or the like can be provided.
  • variation eg, water resistance
  • coating film performance for example, water permeability
  • a ceramic base material for example, outer wall or building material such as siding
  • the resin of the present invention (and the coating or coating containing the resin or the emulsion of the resin) maintains good coating performance (water resistance, blocking resistance, particularly water resistance) over a long period of time It is extremely useful because the quality stability of the coating is high.
  • Another aspect of the present invention can also provide a resin emulsion excellent in viscosity response. Therefore, according to such a resin emulsion, even if the amount of the thickener component is small, the viscosity can be adjusted to a desired or desired viscosity.
  • the resin of the present invention has a monomer component (a) as a polymerization component.
  • the proportion of the acid group-containing monomer is relatively small, for example, less than 5% by mass (based on the entire monomer component (a))
  • it can be selected from the range of 4.7% by mass or less, and is 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)
  • it may be 3.5% by mass or less (eg, 3.2% by mass or less), particularly preferably 3% by mass or less (eg, 2.9% by mass or less), and 2.8% by mass or less (eg, , 2.6% by mass or less, 2.5% by mass or less (eg, 2.4% by mass or less), 2.2% by mass or less (eg, 2.1% by mass or less), 2% by mass or less (eg, 1.8 mass% or less), 1.5 mass% or less, etc. may be sufficient.
  • the lower limit value of the ratio of the acid group-containing monomer may be 0 mass% with respect to the whole monomer component (a), but a finite value (for example, 0.1 mass%, 0.2 mass%, 0) .3 mass%, 0.4 mass%, 0.5 mass%, 0.6 mass%, 0.7 mass%, 0.8 mass%, etc.). These lower limits can be set in combination with the above-mentioned proportions arbitrarily (0 to 4% by mass, 0.3 to 2.8% by mass, 0.5 to 3% by mass, etc.). And so on).
  • the above range may be satisfied in the entire multilayer structure, but preferably the ratio of the acid group-containing monomer in the outer layer also satisfies the above range (for example, 1.5 It is preferable that the content is not more than% by mass etc. (hereinafter, the same applies to hydrophilic monomers etc.).
  • 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, and may have different acid groups.
  • acid group-containing monomer for example, a carboxylic acid group or an acid anhydride group-containing monomer [for example, unsaturated monocarboxylic acid (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] and the like can be mentioned.
  • unsaturated dicarboxylic acids for example, aliphatic unsaturated monocarboxylic acids such as maleic acid and fumaric acid
  • acid anhydrides thereof for example, maleic anhydride etc.
  • sulfonic acids Group-containing monomers for example, styrene-based monomers (for example, styrene sulfonic acid etc.) and the like] and the like can be mentioned.
  • Representative acid group-containing monomers include acrylic acid, methacrylic acid and the like.
  • the monomer component (a) contains an acid group-containing monomer, it may contain one or more acid group-containing monomers in combination.
  • monomer component (a) contains the monomer (acid-group non-containing monomer) which does not contain an acid group.
  • acid group non-containing monomers examples include hydrophilic monomers (sometimes referred to as hydrophilic monomers containing no acid group, monomers (a2), etc.), hydrophobic monomers (hydrophobic monomers containing no acid group, monomers (a3), etc. And so on).
  • the monomer component (a) may suitably contain a hydrophilic monomer (monomer (a2)).
  • a hydrophilic monomer even if the proportion of the acid group-containing monomer is reduced, it is easy to make the mechanical and chemical stability of the resin in the coating film compatible, and, consequently, the coating performance such as water resistance It is also advantageous in point.
  • hydrophilic monomers examples include monomers having a hydroxyl group (hydroxyl group), nitrogen-containing monomers, and monomers having an oxyalkylene group.
  • the hydrophilic monomer may be a monomer that does not belong to the category of the acid group-containing monomer.
  • 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), poly
  • the monomers having a hydroxyl group may be used alone or in combination of two or more.
  • nitrogen-containing monomers include lactam monomers (eg, N-vinylpyrrolidone, N-vinylcaprolactam), (meth) acrylamide compounds ⁇ eg, (meth) acrylamide, N-substituted (meth) acrylamide [eg, N -Alkyl (meth) acrylamide (eg, N, N-di C 1-4 alkyl (meth) acrylamide such as N, N-dimethyl (meth) acrylamide, etc .; N, N-dimethylaminopropyl (meth) acrylamide etc.) , Polyalkylene glycol mono (meth) acrylamides (compounds described later, etc.), nitrogen atom-containing (meth) acrylate compounds ⁇ eg, N-substituted aminoalkyl (meth) acrylates [eg, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (Meta
  • the nitrogen-containing monomers may be used alone or in combination of two or more.
  • Examples of the monomer having an oxyalkylene group include polyalkylene glycol mono (meth) acrylate ⁇ or poly (oxyalkylene) mono (meth) acrylate, such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, poly (oxyethylene / oxypropylene) poly C 2-4 alkylene glycol mono (meth) acrylates such as 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) acrylamide, poly (oxyethylene /
  • 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) For example, 3 to 100 (eg, 3 to 50), 4 to 40 (eg, 5 to 30), etc. may be used.
  • 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.
  • the hydrophilic monomer may contain at least one selected from monomers having at least a hydroxyl group and monomers having an oxyalkylene group.
  • 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), and more preferably 30% by mass or more (eg, 40% by mass or more) And particularly preferably about 50% by mass or more (for example, 60% by mass or more), and may be 70% by mass or more (for example, 80% by mass or more).
  • hydroxyalkyl (meth) acrylate eg, 2-hydroxyethyl (meth) acrylate etc.
  • the monomer having a hydroxyl group may contain at least 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 (eg, 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.
  • the proportion of the hydrophilic monomer in the monomer component (a) is, for example, 0.1% by mass or more (for example, 0.2% by mass or more) ) Can be selected from the range of about 0.3% by mass (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 (for example, 1.2% by mass or more), particularly preferably 1.5% by mass or more (for example, 1.6% by mass or more), particularly preferably 1.8% by mass or more (for example, 1.9% by mass or more) 2 mass% or more (for example, 2.5 mass% or more, 3 mass% or more, 3.5 mass% or more, 4 mass% or more, 4.5 mass% or more, 5 mass% or more, etc.) It may be.
  • the upper limit value of the ratio of the hydrophilic monomer (a2) is not particularly limited, but for example, with respect to the entire monomer component (a) 90 mass%, 80 mass%, 70 mass%, 60 mass%, 50 mass%, 40 mass%, 30 mass%, 25 mass%, 20 mass%, 15 mass%, 12 mass%, 10 mass%, 8 mass %, Etc.
  • the ratio of the acid group-containing monomer (a1) to 1 part by mass of the hydrophilic monomer (a2) 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
  • it may be 1.9 parts by mass or less, more preferably 1.8 parts by mass or less (e.g., 1.7 parts by mass or less, 1.6 parts by mass or less, 1.5 parts by mass or less, 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 Below 0.5 mass part etc.
  • the ratio of the acid group-containing monomer (a1) to the above-described ratio (for example, 2 parts by mass or less) to 1 part by mass of the hydrophilic monomer (a2) variation in coating film performance such as water resistance is obtained. It can be suppressed efficiently.
  • Monomer component (a) includes other monomers or hydrophobic monomers (or monomers which do not belong to any category of monomer (a1) and monomer (a2), monomers (a3), etc.) It may be
  • hydrophobic monomers examples include styrene-based monomers, (meth) acrylic-based monomers, carbonyl-containing monomers, fluorine-containing monomers ⁇ eg, fluorine-containing acrylic monomers [eg, fluoroalkyl Meta) 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 monosilane such as vinyltrichlorosilane) To trihalosilane), alkoxysilane having a vinyl group [vinylalkoxysilane (eg, vinyltrimethoxysilane, vinyltriethoxysilane, etc.)], alkoxysilyl group-containing radically polymerizable monomer [eg, (meth) acryloyl group-containing] Alkoxysilanes (eg,
  • the hydrophobic monomers may be used alone or in combination of two or more.
  • the monomer component (a) may or may not contain an alkoxysilyl group-containing radically polymerizable monomer.
  • the proportion of the hydrophobic monomer in the monomer component (a) is, for example, selected from the range of about 1% by mass or more (for example, 3% by mass or more) 5% by mass or more (eg, 10% by mass or more), preferably 20% by mass or more (eg, 25% by mass or more), more preferably 30% by mass or more (eg, 35% by mass or more), particularly 40% by mass Or more (for example, 45% by mass or more), particularly preferably 50% by mass or more (for example, 55% by mass or more), 60% by mass or more (for example, 65% by mass or more, 70% by mass or more) It may be.
  • the monomer component (a) or the hydrophobic monomer is at least one selected from styrenic monomers, (meth) acrylic monomers, and carbonyl group-containing monomers, in particular styrenic monomers and (meth) acrylic resins It may contain at least one selected from monomers.
  • styrene-based monomer examples include styrene, ⁇ -alkylstyrene (eg, ⁇ -C 1-4 alkylstyrene such as ⁇ -methylstyrene), alkylstyrene (eg, C 1-4 alkylstyrene such as vinyl toluene), Halostyrene (eg, chlorostyrene etc.) and the like can be mentioned.
  • ⁇ -alkylstyrene eg, ⁇ -C 1-4 alkylstyrene such as ⁇ -methylstyrene
  • alkylstyrene eg, C 1-4 alkylstyrene such as vinyl toluene
  • Halostyrene eg, chlorostyrene etc.
  • the styrenic monomers may be used alone or in combination of two or more.
  • Preferred styrenic monomers include styrene. Therefore, the styrenic monomer may contain at least styrene.
  • the ratio of styrene to the entire styrene-based 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
  • 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% by mass or more (eg, 10% by mass or more), preferably 20% by mass or more (eg, 25% by mass or more), more preferably 30% by mass or more (eg, 35% by mass or more), particularly 40% by mass or more (For example, 45% by mass or more), particularly preferably 50% by mass or more (for example, 55% by mass or more), or 60% by mass or more (for example, 65% by mass or more, 70% by mass or more) May be By setting the ratio of the styrenic monomer in the above range, it is easy to suppress the decrease in water resistance of the coating film, and it is easy to efficiently maintain the water permeability of the coating film.
  • the upper limit of the ratio of the styrene-based monomer is not particularly limited, but for example, 95% by mass, 90% by mass with respect to the entire monomer component (a) %, 85 mass%, 80 mass%, etc. may be sufficient.
  • ((Meth) acrylic monomers) As a (meth) acrylic-type monomer, aliphatic (meth) acrylate, aromatic (meth) acrylate, etc. are mentioned.
  • aliphatic (meth) acrylates include linear aliphatic (meth) acrylates ⁇ eg, alkyl (meth) acrylates [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) acryl
  • aromatic (meth) acrylate for example, 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) acrylates such as phenethyl (meth) acrylate, aryloxyalkyl methacrylates (eg, C 6-10 aryloxy C 1-4 alkyl methacrylates such as phenoxyethyl methacrylate), etc.
  • aryl (meth) acrylate for example, C 6-10 aryl (meth) acrylate such as phenyl (meth) acrylate
  • aralkyl (meth) acrylate for example, benzyl (meth) acrylate
  • the (meth) acrylic monomers may be used alone or in combination of two or more.
  • 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.
  • 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.
  • the (meth) acrylic monomer may contain at least a linear aliphatic (meth) acrylate (in particular, an alkyl (meth) acrylate).
  • the (meth) acrylic monomer may not generally belong to the category of the acid group-containing monomer and the hydrophilic monomer.
  • the acid group such as a carboxyl group
  • the hydrophilic group may be used.
  • it may be a monomer that does not contain a hydrophilic moiety (eg, hydroxyl group, oxyalkylene group and nitrogen).
  • the ratio of the linear aliphatic (meth) acrylate to the entire (meth) acrylic monomer is, for example, 10% by mass or more (for example, 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 50% by mass or more (eg, 60% by mass or more) Or the like, or 70% by mass or more (for example, 80% by mass or more).
  • 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.
  • the upper limit of the ratio of the (meth) acrylic monomer is not particularly limited, but for example, with respect to the entire monomer component (a), It may be 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 35% by mass or the like.
  • the monomer component (a) contains a hydrophilic monomer and a (meth) acrylic monomer
  • 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, methacryl) Oxyalkylpropenal), formylstyrene, etc.], unsaturated ketones ⁇ eg, alkenones (eg, methyl vinyl ketone, ethyl vinyl ketone, vinyl butyl ketone etc.), (meth) acryloyloxyalkanones (eg, acetonyl acrylate, aceto) Nil methacrylate etc., acetoacetoxy group-containing ethylenic unsaturated monomer [eg acetoacetoxy alkyl (meth) acrylate (eg 2- (acetoacet
  • the carbonyl group-containing monomers may be used alone or in combination of two or more.
  • the proportion of the carbonyl group-containing monomer in the monomer component (a) is, for example, about 50% by mass or less (eg, 45% by mass or less) 40 mass% or less (eg, 35 mass% or less), preferably 30 mass% or less (eg, 25 mass% or less), more preferably 20 mass% or less (eg, 15 mass% or less), particularly 10 mass% % Or less, or 5% by mass or less.
  • the monomer component (a) may be substantially free of the acetoacetoxy group-containing ethylenically unsaturated monomer.
  • the ratio of the acetoacetoxy group-containing ethylenically unsaturated monomer in the monomer component (a) can be selected, for example, from the range of about 5% by mass or less (for example, 4% by mass or less) % By mass or less (eg, 2.5% by mass or less), preferably 2% by mass or less (eg, 1.5% by mass or less), more preferably 1% by mass or less (eg, 0.8% by mass or less), particularly It may be 0.5% by mass or less, and may be 0.1% by mass or less.
  • the carbonyl group-containing monomer (or acetoacetoxy group-containing ethylenic unsaturated monomer) in the monomer component (a) contains a carbonyl group-containing monomer (or an acetoacetoxy group-containing ethylenic unsaturated monomer)
  • the lower limit value of the ratio of the unsaturated monomer is not particularly limited, but for example, 0.01% by mass, 0.03% by mass, 0.05% by mass, based on the whole of the monomer component (a). 0.1 mass%, 0.2 mass%, 0.3 mass%, 0.5 mass%, etc. may be sufficient.
  • the resin may have a monomer component (a) as a polymerization component, and may constitute an emulsion (or may be in an emulsion state). Therefore, the emulsion may be composed of a resin (particles) and an emulsifier (an emulsifier that coats the resin particles).
  • the emulsion may be a resin (resin particles) [or the resin (or resin particles)] containing the monomer component (a) as a polymerization component dispersed in a solvent.
  • the present invention also encompasses emulsions (or emulsions of resins, resin compositions, resin emulsions, emulsion compositions, resin compositions for paints) containing such resins.
  • the emulsion may usually be an aqueous emulsion. Even if the resin or emulsion of the present invention is aqueous, it can efficiently form a coating film as described above.
  • Such an emulsion may generally be obtained by emulsion polymerization (polymerization in the presence of an emulsifier) of the monomer component (a) in a solvent.
  • the solvent generally include aqueous solvents (water-based 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.)], particularly water.
  • aqueous solvents water-based solvents
  • solvents containing water mixed solvents of water and alcohol (such as C 1-4 alcohol such as methanol and ethanol, etc.)
  • alcohol such as C 1-4 alcohol such as methanol and ethanol, etc.
  • the emulsifier (dispersant, surfactant) is not particularly limited, and examples thereof include anionic emulsifiers, nonionic emulsifiers, cationic emulsifiers, and amphoteric emulsifiers.
  • the emulsifier may be a polymeric emulsifier or a reactive emulsifier.
  • 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, still more preferably 5 parts by mass or less.
  • the polymerization initiator is not particularly limited, and a conventional polymerization initiator can be used.
  • the emulsion polymerization may be carried out in the presence of a chain transfer agent such as a compound having a thiol group, a pH buffer, a chelating agent, a coalescent agent and the like.
  • a chain transfer agent such as a compound having a thiol group, a pH buffer, a chelating agent, a coalescent agent and the like.
  • emulsion polymerization conditions temperature, time, etc. can be selected appropriately.
  • the resin (or emulsion) of the present invention may have a single layer structure (or may be composed of only one layer) or a multilayer structure (or core-shell structure) (even if the inner layer is formed, It may be composed of an outer layer and an inner layer).
  • the multilayer structure (core-shell structure) may be advantageous in terms of the physical properties of the coating film and the like.
  • the number of outer layers may be one or more, for example, 1 to 5, preferably 1 to 4, and more preferably 1 to 3 (for example, 1 or 2). In particular, it may be two.
  • 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.
  • the multilayer structure may be configured (relatively configured) by a hard layer (hard layer) and a soft layer (soft layer).
  • a hard layer hard layer
  • a soft layer soft layer
  • 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. It may be.
  • the outer layer is formed of a plurality of layers
  • the hard layer and the soft layer may be formed between the plurality of outer layers.
  • the inner layer is preferably a hard layer
  • the outer layer is preferably a soft layer, from the viewpoint of improving water permeability and blocking resistance.
  • the mass ratio of the inner layer to the outer layer is not particularly limited, and is, for example, 95/5 to 3/97 (eg, 90/10 to 4/96), preferably It may be about 85/15 to 5/95 (e.g. 80/20 to 6/94), more preferably 75/25 to 7/93 (e.g. 70/30 to 8/92), 65/35 ⁇ 3/97 (e.g. 60/40 to 4/96, 55/45 to 5/95, 52/48 to 7/93, 50/50 to 8/92, 49/51 to 10/90 etc) And may be 95/5 to 30/70 (eg, 90/10 to 50/50, 85/15 to 60/40, etc.).
  • the mass of the first layer (inner layer) is 1
  • the mass of the second layer (outer layer) is 0.1 to 10
  • the mass of the third to fifth layer (the outermost layer among the outer layers) may be 0.1 to 10 (eg, 0.5 to 5).
  • the resin or emulsion of the present invention uses the specific monomer component (a) as the polymerization component as described above, the aspect such as the acid group-containing monomer or the hydrophilic monomer has an outer layer of multilayer structure It is preferable to satisfy also in the outer layer).
  • 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 the monomers may satisfy the above proportion (eg, a range of, for example, 1.2% by mass or more, 1.8 to 10% by mass, etc.).
  • the ratio of the acid group-containing monomer in the resin of multilayer structure is 4% by mass or less, not only 4% by mass or less is satisfied in the entire multilayer structure, but also in the outer layer.
  • the proportion of the monomer having an acid group may also satisfy 4% by mass or less.
  • the outer layer is composed of a plurality of layers
  • the plurality of layers may satisfy an aspect such as an acid group-containing monomer or a hydrophilic monomer, and at least the outermost layer (for example, only the outermost layer) You may satisfy aspects, such as a containing monomer and a hydrophilic monomer.
  • the ratio of the hydrophilic monomer contained in the outer layer to the entire monomer component contained in the outer layer may also satisfy the ratio (range).
  • the proportion of the hydrophilic monomer contained in the outer layer (or the outermost layer) is 0.1% by mass or more (for example, 0.2 mass%) with respect to the monomer component (monomer) contained in the outer layer (the outermost layer) % Or more, 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), particularly preferably 1.8% by mass or more (eg, 1.8 to 10% by mass) %, And may be 1.9% by mass or more, and 2% by mass or more (for example, 2.5% by mass or more, 3% by mass or more, 3.5% by mass or more, 4% by mass or more, 4.5% by mass % Or more
  • the ratio of the acid group-containing monomer contained in the outer layer to the entire monomer component contained in the outer layer may also satisfy the ratio (range).
  • the ratio of the acid group-containing monomer contained in the outer layer (or the outermost layer) is less than 5% by mass (for example, 4.7% by mass) with respect to the monomer component (monomer) contained in the outer layer (the outermost layer) Or less, and is 4.5 mass% or less (eg, 4.2 mass% or less), preferably 4 mass% or less (eg, 3.8 mass% or less), more preferably 3.5 mass% Or less (eg, 3.2% by mass or less), particularly preferably 3% by mass or less (eg, 2.9% by mass or less), or 2.8% by mass or less (eg, 2.6% by mass or less) 2.5% by mass or less (eg, 2.4% by mass or less), 2.2% by mass or less (eg, 2.1% by mass or less), 2% by mass or less (eg, 1.8% by mass or less) Or 1.5 mass% or less.
  • the ratio of the acid group-containing monomer contained in the inner layer is, for example, 200 parts by mass or less (for example, 100 parts by mass of the acid group-containing monomer contained in the outer layer (or outermost layer) 150 parts by weight or less, 100 parts by weight or less, 80 parts by weight or less), 50 parts by weight or less (for example, 0 to 40 parts by weight), preferably 30 parts by weight or less (for example, 25 or less) It may be 20 parts by mass or less (eg, 18 parts by mass or less), and may be 15 parts by mass or less (eg, 12 parts by mass or less).
  • the proportion of the hydrophilic monomer contained in the inner layer is, for example, 200 parts by mass or less (e.g. 150 parts by mass) with respect to 100 parts by mass of the hydrophilic monomer contained in the outer layer (or the outermost layer). Or less, 100 parts by weight or less, 80 parts by weight or less), and may be selected from 50 parts by weight or less (eg, 0 to 40 parts by weight), preferably 30 parts by weight or less (eg, 25 parts by weight or less) And more preferably 20 parts by mass or less (e.g., 18 parts by mass or less) or 15 parts by mass or less (e.g., 12 parts by mass or less).
  • the ratio of the acid group-containing monomer to the hydrophilic monomer can be selected from the above-mentioned range, but for example, the acid group-containing monomer (outer layer) to 1 part by mass of the hydrophilic monomer (hydrophilic monomer contained in the outer layer)
  • the ratio of the acid group-containing monomer) is 2 parts by mass or less (e.g., 1.5 parts by mass or less), 1 part by mass or less (e.g., 0.9 parts by mass or less, 0.8 parts by mass or less, 0.. It may be 7 parts by mass or less.
  • the weight average molecular weight of the resin or resin constituting the emulsion may be, for example, selected from the range of 50,000 or more, preferably 100,000 or more, preferably 200,000 or more, and more preferably 300,000 in terms of coating film performance etc. The above (for example, 500,000 or more) may be sufficient.
  • the resin constituting the resin or the emulsion may contain relatively low molecular weight components (low molecular weight polymers, low molecular weight polymer components).
  • a low molecular weight component for example, a component having a weight average molecular weight of 80,000 or less (for example, a weight average molecular weight of 70,000, 60,000 or less, 50,000 or less, etc.) may be used.
  • the lower limit value of the weight average molecular weight of the low molecular weight component is not particularly limited, but may be, for example, 10,000, 20,000, 30,000 or 40,000.
  • 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%, etc.
  • the resin constituting the resin or the emulsion contains such low molecular weight components, in terms of coating film performance (for example, water resistance, blocking resistance, impregnation adhesion, frost resistance, etc.). May be
  • the measuring method of the ratio of the component of a weight average molecular weight or a low molecular weight is not specifically limited, For example, you may measure by the below-mentioned method etc.
  • the weight average molecular weight (weight average molecular weight of the entire resin) of the resin or the resin constituting the emulsion is selected according to the proportion of the low molecular weight component in the entire resin. And may be in the same range as above (eg, 100,000 or more, 200,000 or more), relatively low molecular weight, for example, 600,000 or less (eg, 50,000 to 500,000), preferably 450,000 or less (eg, , 100,000 to 400,000, and more preferably 350,000 or less (eg, 150,000 to 350,000).
  • the resin constituting the resin or the emulsion has a low molecular weight component
  • the form of its presence is not particularly limited.
  • 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.
  • 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.
  • the outer layer is composed of a plurality of layers
  • 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.
  • a resin component having a weight average molecular weight of more than 80,000 may be present.
  • the proportion of the low molecular weight component in the outer layer may be selected from the same range as described above, or may be relatively large.
  • the proportion of low molecular weight components is 5% or more (for example, 10% or more) in area ratio in gel permeation chromatography (chart) 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.).
  • each layer may be made of a resin having a different molecular weight (such as weight average molecular weight), and in particular, the molecular weight of the resin constituting the outer layer is from the molecular weight of the resin constituting the inner layer You may also lower it.
  • the use of such a multilayer resin may be advantageous in terms of water resistance and blocking resistance.
  • the outer layer is two or more layers (in the case of having the intermediate layer)
  • the molecular weight of the resin constituting the outermost layer is particularly lower than the molecular weight of the resin constituting the inner layer. Good.
  • the weight average molecular weight of the low molecular weight resin 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) Is, for example, 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), particularly preferably 100,000. It may be about (for example, 1 to 80,000) or less.
  • 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).
  • 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 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.
  • the use of a chain transfer agent and the amount thereof used It may be manufactured by adjustment of.
  • 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.
  • the chain transfer agent is not particularly limited.
  • a thiol compound for example, aliphatic thiol [eg alkanethiol (eg octyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan)] , C 1-20 alkanethiols such as decanetrithiol), mercaptoalkanols (eg, mercaptoethanol, 3-mercapto-1-propanol, etc.), mercaptoalkanepolyols (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 mer
  • the chain transfer agent (in particular, the thiol compound) may be used alone or in combination of two or more.
  • chain transfer agents octyl thioglycolate, 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 thioglycolate Is more preferred.
  • 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).
  • the amount may be, more preferably, 0.8 parts by mass or less, and even more preferably 0.5 parts by mass or less.
  • 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.
  • the resin When a chain transfer agent is used, the resin usually contains a chain transfer agent (or a residue or a decomposition product thereof). Therefore, when the resin constituting the resin or the emulsion has a multilayer structure, at least a low molecular weight resin (or a layer composed of a resin, in particular, an outer layer or the outermost layer) is a chain transfer agent (especially a thiol compound) or a chain transfer It may have (or contain) a structure derived from an agent.
  • a chain transfer agent especially a thiol compound
  • the glass transition temperature (Tg) of the resin (or the entire resin in the case of a multilayer structure) constituting the resin or the emulsion is preferably ⁇ 20 ° C. or more, more preferably ⁇ 10 ° C. or more, from the viewpoint of coating film properties and the like. More preferably, it may be 0 ° C. or more, particularly 20 ° C. or more.
  • the upper limit of the glass transition temperature is not particularly limited, and may be, for example, 100 ° C., 80 ° C., 60 ° C., or the like.
  • the glass transition temperature may be determined, for example, by the method described in the below-mentioned example [Formula of Fox].
  • resin which comprises resin or an emulsion when resin which comprises resin or an emulsion has multilayer structure, it may be a different glass transition temperature by an inner layer and an outer layer, for example, is a multilayer by the layer of high glass transition temperature, and the layer of low glass transition temperature. It may form a structure.
  • 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)
  • Tg 1 may be higher than Tg 2 (Tg 1 > Tg 2 ).
  • the glass transition temperature of the inner layer is preferably, for example, about 20 ° C. to 150 ° C.
  • the glass transition temperature of the outer layer is preferably, for example, about 0 ° C. to 50 ° C., from the viewpoint of improving water permeability and blocking resistance.
  • the difference between the glass transition temperature Tg 2 of the outer layer is not particularly limited, from the range of about -20 ° C. or higher (for example, -18 ° C. or higher) For example, -15 ° C. or higher (eg, -12 ° C. to 200 ° C.), preferably -10 ° C. or higher (eg, -5 ° C. to 180 ° C.), more preferably 0 ° C. or higher (eg, 0 to It may be 150 ° C., more than 0 ° C. [eg 1 to 200 ° C., 5 ° C.
  • the amount of resin (or solid content or non-volatile content) in the 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 resin (or emulsion, hereinafter the same) of the present invention can be suitably used for coating or coating, particularly for primer coating or primer coating (or sealer).
  • the present invention also includes a paint (paint composition, resin composition for paint) containing the above-mentioned resin.
  • the paint may contain conventional additives depending on the application of the paint, etc., as long as it contains the resin of the present invention (included as a film forming or film forming component).
  • Additives are not particularly limited, and, for example, pigments (such as calcium carbonate), dispersants, antifoaming agents, thickeners / viscosity modifiers, film-forming assistants (film-forming assistants), light (climate) stability Agents, pH adjusters, etc.
  • additives may be used alone or in combination of two or more.
  • 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 a coating film may be performed through the drying process accompanied by heat, a wind, etc.
  • two or more glycol ethers glycol ethers (glycol ether (A)) and an ester (ester (B)
  • the specific film forming aid will be described in detail.
  • the film forming aid 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
  • 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).
  • the solubility (solubility at 20 ° C.) in 100 g of water may be selected, for example, from the range of about 20 g (20 g / 100 g water) or more, preferably 25 g or more (eg, 25 to 100 g), preferably May be 30 to 80 g.
  • the solubility (solubility at 20 ° C.) in 100 g of water can be selected, for example, from the range of less than 20 g, and may be 0.1 g or more and less than 20 g, preferably 0.15 g or more and less than 15 g .
  • the difference (absolute value) between the solubility (solubility at 20 ° C.) of glycol ether (A1) in 100 g of water and the solubility (solubility at 20 ° C.) of glycol ether (A2) in water is, for example, 5 g or more, preferably It may be 10 g or more.
  • the solubility in water is low, it is usually easy to migrate to a film forming component (such as resin particles), and while it is expected that the function as a film forming aid is likely to be achieved, It tends to remain and may reduce the blocking resistance.
  • a film forming component such as resin particles
  • the function as a film forming aid is likely to be achieved, It tends to remain and may reduce the blocking resistance.
  • the present invention by combining the film forming aids having different water solubility, it is surprisingly easy to balance the function as the film forming aid and the blocking resistance with good balance.
  • glycol ether (A1) and glycol ether (A2) When combining glycol ether (A1) and glycol ether (A2), one or more kinds of each may be selected from (A1) and (A2), and glycol ethers (A1) and (A2) may be each alone or Two or more may be used in combination.
  • the glycol ether (A) may be solid or liquid at normal temperature (eg, 15 to 30 ° C.), and in particular may be liquid.
  • 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 ethylene glycol mono C such as ethylene glycol
  • glycol ethers (A1) may be used alone or in combination of two or more.
  • glycol ether (A1) ethylene glycol monobutyl ether, diethylene glycol monobutyl ether and the like may be suitably used as the glycol ether (A1).
  • 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.
  • the substrate in particular, ceramic base material
  • an impregnation effect can also be expected.
  • glycol ether (A2) for example, Ethylene glycol monoether ⁇ eg, ethylene glycol monoalkyl ether [eg 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.
  • ethylene glycol monoalkyl ether eg ethylene glycol mono C 6-12 alkyl ether such as hexyl glycol (ethylene glycol monohexyl ether), 2-ethylhexyl glycol (ethylene glycol mono
  • 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), etc.], phenyl diethylene glycol 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 monoether ⁇
  • glycol ethers (A2) may be used alone or in combination of two or more.
  • propylene glycol (A2) butyl propylene glycol, butyl propylene diglycol and the like may be suitably used.
  • the use of the glycol ether (A2) as described above may improve the volatilization rate within a limited drying time, or may reduce the amount of the film forming aid remaining after drying.
  • the substrate in particular, ceramic base material
  • an impregnation effect can also be expected.
  • ester (B) is not particularly limited as long as it can be used as a film forming aid in paints, etc. in combination with the above glycol ether (A), but in particular, hydrophobic or poorly water-soluble esters are preferably used. Good.
  • 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 (eg, 0.0001 to 0.1 g).
  • the ester (B) may be solid or liquid at normal temperature (eg, 15 to 30 ° C.), and in particular may be liquid.
  • Ester (B) for example, Polyol esters ⁇ eg, esters of aliphatic polyols [eg, alkane polyol acylates (eg, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, 2,2,4-trimethyl-1,3 C 2-10 alkanepolyols such as pentanediol diisobutyrate C 1-20 acylates, 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, diethyl adipate (eg diethyl adipate, diisobutyl adipate, bis (2
  • 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 C 10-30 aliphatic monocarboxylic acid ester, etc. ⁇ Etc.
  • esters (B) may be used alone or in combination of two or more.
  • ester (B) 2,2,4-trimethyl-1,3-pentane from the viewpoint of moderate volatility (eg, low volatility compared to glycol ether (A)), etc.
  • Diol monoisobutyrate, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and the like may be suitably used.
  • the paint of the present invention may usually be a water-based paint (or a water-based paint, especially a water-based base paint).
  • 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, it may be water.
  • the proportion of the resin of the present invention may be, for example, about 3 to 80% by mass (for example, 6 to 80% by mass), preferably 8 to 70% by mass, and more preferably about 10 to 60% by mass. .
  • the proportion of the pigment is, for example, 1 to 70% by mass (eg, 1 to 65% by mass), preferably 3 to 60% by mass (eg, 3 to 55% by mass), more preferably 4 It may be about 50 to 50% by mass (for example, 4 to 45% by mass).
  • the ratio of solid content (or non-volatile content) may be, for example, about 5 to 80% by mass, preferably about 15 to 70% by mass, and more preferably about 20 to 60% by mass.
  • 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 amount 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).
  • 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). And particularly preferably 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), Preferably, it may be about 40 parts by mass or less (eg, about 0.5 to 45 parts by mass).
  • the proportion of the glycol ether (A) is, for example, 1 to 80 parts by mass, preferably 1 to 70 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). And particularly preferably about 2 to 55 parts by mass.
  • 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 forming component (resin).
  • the amount may be about 40 parts by mass, more preferably about 0.5 to 35 parts by mass, and particularly preferably about 0.5 to 30 parts by mass.
  • 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.
  • the proportion of the ester (B) is, for example, 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0. 1 to 100 parts by mass of the film forming component (resin). It may be about 1 to 10 parts by mass.
  • the viscosity of the coating is, for example, about 10 to 10000 mPa ⁇ s (eg, 20 to 9000 mPa ⁇ s), preferably 30 to 8000 mPa ⁇ s, and more preferably about 50 to 5000 mPa ⁇ s (eg, 100 to 4000 mPa ⁇ s). It may be 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.
  • a film-forming adjuvant contains 2 or more types of glycol ether (A) and ester (B)
  • the mixing method (order) to these coating materials is not specifically limited.
  • a film forming aid prepared in advance that is, a film forming aid containing glycol ether (A) and ester (B)
  • a paint or another component (for example, a film forming component) constituting the paint]
  • the film forming aid may be formed (in the paint) during preparation of the paint.
  • 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].
  • glycol ether (A) and the mixing order of glycol ether (A) and ester (B) are not specifically limited.
  • glycol ether (A1), glycol ether (A2), and ester (B) may be mixed in any order, and mixtures of glycol ether (A1) and glycol ether (A2), ester (B), etc. may be mixed in this order.
  • the base material to which the paint or the paint is applied is not particularly limited, but in the present invention, particularly, a ceramic base material (ceramic base material) can be suitably used.
  • Ceramic base examples 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 Therefore, the ceramic base usually contains an alkali component derived from cement and a metal component (a metal ion component such as a calcium ion component).
  • the ceramic base include calcium silicate board, pulp cement board, gypsum slag board, wood piece cement board, ALC board and the like.
  • a base coat (or a sealer, a post-cure sealer) is further applied to the base material [the base material after curing, in particular, the ceramic base material (post-cured ceramic base material)].
  • the base coat is roughly classified into a surface sealer [or a sealer on a surface to be coated with a first sealer and a coat (and an inner coat)] and a back sealer (a second sealer, a base coat on the back surface of the substrate (a surface opposite to the surface to be coated)).
  • the paint of the present invention can be applied to any primer, but in particular it may be used at least in back sealers.
  • 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.
  • the paint of the present invention may be suitably used for roller coating.
  • a roll coater is, for example, a direct roll coater, a reverse roll coater, etc., and is not particularly limited.
  • Undercoating may be performed at the time of construction, but in the present invention, it may be performed before construction, especially in a plant (plant coating).
  • Pre-priming such as factory coating
  • it is performed under an environment [or under pressure (further, under heating)] in which load and high pressure (or even high temperature) act using a roller or the like.
  • the pressure or load (roller pressure etc.) acting on the paint (coating film) is, for example, 4 g / cm 2 or more, preferably 8 g / cm 2 or more, and more preferably 10 g / cm 2 or more. It may be.
  • the coating amount is not particularly limited, but may be, for example, about 5 g / m 2 or more, preferably about 10 g / m 2 or more, and more preferably about 15 g / m 2 or more.
  • the paint (coating film) may be dried naturally, but in roller coating, factory coating, etc., usually under heating, for example, 40 ° C. or more (eg 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 is, for example, 120 minutes or less (eg, 1 to 120 minutes), preferably 60 minutes or less (eg, 1 to 60 minutes), more preferably 30 minutes or less (eg, 1 30 30 minutes). In the present invention, even with such limited drying time, a good coating can be efficiently obtained.
  • the resin (paint) of the present invention seems to be relatively high in mechanical stability and chemical stability, and even if it is applied under such severe conditions, it is also applied to ceramic base materials. Also, the excellent stability of the resin in the coating can be realized.
  • Example 1 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), 711 parts of styrene, 2-ethylhexyl acrylate A dropping pre-emulsion consisting of 197 parts, 20 parts of n-butyl acrylate, 6 parts of acrylic acid, 6 parts of methacrylic acid and 60 parts of 2-hydroxyethyl methacrylate was prepared.
  • an emulsifier Disaiichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08
  • 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.
  • the ratio of monomers having an acid group in this example, acrylic acid and methacrylic acid
  • the ratio of hydrophilic monomers containing no acid group in this example, 2-hydroxyethyl methacrylate
  • the solid content ratio in the obtained emulsion, was 43%, and the glass transition temperature was 41 ° C.
  • the solid content ratio (non-volatile content) in the emulsion was determined by weighing 1 g of the emulsion, drying it at 110 ° C. for 1 hour with a hot-air dryer, and using the obtained residue as non-volatile content.
  • [Non-volatile content (mass%)] ([Mass of residue] / [resin emulsion 1 g for sealer]) x 100 (Based on the same below).
  • Tg glass transition temperature of the monomer component which comprises a polymer from the formula of FOX including this example.
  • Methyl methacrylate (MMA) 105 ° C Styrene (St): 100 ° C.
  • 2-ethylhexyl acrylate (2EHA) -70 ° C
  • Butyl acrylate (BA) -56 ° C
  • Acrylic acid (AA) 95 ° C Methacrylic acid (MAA): 130 ° C.
  • HEMA 2-hydroxyethyl methacrylate
  • t-BMA t-Butyl methacrylate
  • IBXMA 180 ° C
  • TMSMA ⁇ -Methacryloxypropyltrimethoxysilane
  • Examples 2 to 4 and Reference Example 1 A resin emulsion was obtained in the same manner as in Example 1 except that the components used in the dropping pre-emulsion and the ratio thereof were changed to those shown in Table 1 below.
  • Example 5 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), 355 parts of styrene, 2-ethylhexyl acrylate A dropping pre-emulsion (first stage pre-emulsion) consisting of 98 parts, 10 parts of n-butyl acrylate and 1 part of acrylic acid was prepared.
  • first stage pre-emulsion consisting of 98 parts, 10 parts of n-butyl acrylate and 1 part of acrylic acid was prepared.
  • the temperature was maintained at 80 ° C. for 120 minutes.
  • 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.
  • the ratio of monomers having an acid group (in this example, acrylic acid and methacrylic acid) is 0.7% (the ratio of monomers having an acid group contained in the inner layer is 0.1%, which is included in the outer layer)
  • the proportion of monomers having an acid group is 0.6%
  • the proportion of hydrophilic monomers containing no acid group (2-hydroxyethyl methacrylate in this example) is 6.0% (the proportion of hydrophilic monomers contained in the inner layer is 0%, the proportion of hydrophilic monomers contained in the outer layer is 6.0%).
  • the proportion of monomers having an acid group is 0.2%
  • the proportion of hydrophilic monomers is 0%
  • the proportion of monomers having an acid group is 1.
  • the proportion of hydrophilic monomer is 1% and 11.2%.
  • the solid content ratio is 43%
  • the mass ratio of the inner layer to the outer layer is 46/54
  • the glass transition temperature is 41 ° C. (the glass transition temperature of the inner layer is 40 ° C., the glass transition temperature of the outer layer is 42) ° C).
  • Examples 6 to 13 and Reference Example 2 A resin emulsion was obtained in the same manner as in Example 5 except that the proportions of the components used in the second stage pre-emulsion in Example 5 were changed to those shown in Tables 2 and 3 below.
  • Example 14 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), 319 parts of styrene, n-butyl acrylate A dropping pre-emulsion (first stage pre-emulsion) consisting of 20 parts and 1 part of acrylic acid was prepared.
  • an emulsifier Diichi Kogyo Seiyaku Co., Ltd., trade name: Hytenol NF-08
  • the temperature was maintained at 80 ° C. for 120 minutes.
  • 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.
  • the ratio of monomers having an acid group is 0.7% [The ratio of monomers having an acid group contained in the inner layer is 0.1%, the outer layer (or The ratio of the monomer having an acid group contained in the outer layer is 0.6%], the ratio of a hydrophilic monomer containing no acid group (2-hydroxyethyl methacrylate in this example) is 2.0% [the hydrophilicity contained in the inner layer The proportion of the sex monomer is 0%, and the proportion of the hydrophilic monomer contained in the outer layer (or the outermost layer) is 2.0%].
  • the proportion of monomers having an acid group is 0.3%
  • the proportion of hydrophilic monomers is 0%
  • the proportion of monomers having an acid group is 0.
  • the proportion of hydrophilic monomers is 9% and the proportion of hydrophilic monomers is 3.0%
  • the proportion of monomers having an acid group is 0% and the proportion of hydrophilic monomers is 0%
  • the ratio of the monomer having an acid group is 1.8%
  • the ratio of the hydrophilic monomer is 6.0%.
  • the solid content ratio is 43%
  • the mass ratio of the inner layer to the outer layer is 34/66 [of the outer layer
  • the mass ratio of the second layer to the third layer (the outermost layer) is 325/335
  • Glass transition temperature is 44 ° C. [The glass transition temperature of the inner layer is 85 ° C., the glass transition temperature of the outer layer is 26.5 ° C. (of the outer layers, the glass transition temperature of the second layer is 28 ° C., the third layer (outmost layer) The glass transition temperature of) was 25 ° C)].
  • Example 15 A resin emulsion was obtained in the same manner as in Example 14 except that the components used in the third stage pre-emulsion and the proportions thereof were changed to those shown in Table 4 below.
  • Example 14 is the same as Example 14 except that the components used in the dropping pre-emulsion, the second stage pre-emulsion, and the third stage pre-emulsion and the proportions thereof are changed to those shown in Table 4 below.
  • the resin emulsion was obtained.
  • Example 16 to 17 A resin emulsion was obtained in the same manner as in Example 1 except that the components used in the dropping pre-emulsion and the ratio thereof were changed to those shown in Table 5 below.
  • Example 18 A resin emulsion was obtained in the same manner as in Example 5, except that the proportions of the components used in the first and second pre-emulsions were changed to those shown in Table 6 below.
  • a thickener (UH-420 manufactured by Adeka Co., Ltd.) is added so that the viscosity at a rotational speed of 30 rpm is BM type viscometer, and the paint for sealer is stirred for 15 minutes with homodisper 1000 rpm.
  • a composition (priming paint) was obtained. The sample after 1 day progress was used for evaluation.
  • the paint composition for sealer is applied to a test plate (calcium silicate plate, manufactured by Nippon Test Panel, 12 mm in thickness) with a small roller (manufactured by TRUSCO NAKAYAMA) so that the applied amount is 100 g / m 2, and dried.
  • the coating was dried at 100 ° C. for 10 minutes with a press to form a coating.
  • the coating was carried out under such conditions that a roller pressure of 15 g / cm 2 was applied. That is, it simulates and reproduces the roller coating (base coating) in a factory where high pressure (and high temperature drying) acts.
  • a funnel (inner diameter: 35 mm) is placed on the coating film formed on the test plate, the contact portion between the two is sealed with a silicone based bus bond (manufactured by Konishi Co., Ltd.), and the “Rot method” defined in JIS A 5422 The amount of water reduction after 24 hours (the difference between the height of the water surface at the start and after 24 hours) was measured. In this test sheet, the test was carried out a total of five times using five test plates of different lots, and the average value was taken as the amount of water reduction, and the standard deviation of the amount of water reduction was calculated, and the results were Variation)).
  • the weight average molecular weight was measured by gel permeation chromatography (GPC) under the following conditions.
  • the proportion of the low molecular weight component (polymer with a weight average molecular weight of 10,000 to 80,000) was determined as follows. From the results of measuring the standard substance for calibration curve by gel permeation chromatography (GPC), a calibration curve (a graph in which the molecular weight is plotted on the vertical axis and the outflow time is plotted on the horizontal axis) is created, and the weight average molecular weight is determined from the calibration curve. The outflow time (ta) corresponding to the upper limit (in this case, 80,000) and the outflow time (tb) corresponding to the lower limit of the weight average molecular weight (in this case, 10,000) were determined.
  • GPC gel permeation chromatography
  • the area of the entire GPC chart (the area of the portion surrounded by the chart and the baseline, the area S1), and the upper limit of the weight average molecular weight determined from the calibration curve From the outflow time (ta) corresponding to the value (in this case 80,000) to the outflow time (tb) corresponding to the lower limit value (in this case 10,000) of the weight average molecular weight determined from the calibration curve
  • composition (feed) of the resin emulsion and the evaluation results are shown in the following table.
  • Brenmer PE-200 (Repetition number of oxyethylene chain: about 4.5), "OTG” is octyl thioglycollate, “TMSMA” is ⁇ -methacryloxypropyltrimethoxysilane, “Tg” is glass transition Indicates the temperature.
  • the “acid group-containing monomer (%)” in the inner layer or the outer layer is the ratio (%) of the acid group-containing monomer contained in the inner layer or the outer layer to the entire monomer component constituting the resin
  • the “acid group-containing monomer (% in layer)” in the inner layer or the outer layer is the ratio (%) of the acid group-containing monomer contained in the inner layer or the outer layer to the entire monomer component constituting the inner layer or the outer layer
  • the “acid group-containing monomer (% in two layers)” or “acid group-containing monomer (% in three layers)” in the outer layer is a monomer component constituting two or three layers (the outermost layer) of the outer layer It is the ratio (%) of the acid group-containing monomer contained in two layers or three layers with respect to the whole, and the same applies to hydrophilic monomers.

Landscapes

  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne une émulsion de résine qui est utile pour des produits d'étanchéité arrière pour des substrats en céramique ou similaires. Selon la présente invention, une émulsion de résine qui contient un composant monomère (a) en tant que composant de polymérisation est configurée de telle sorte que : le rapport d'un monomère contenant un groupe acide (a1) dans le composant monomère (a) est de 4,5 % en masse ou moins ; et un monomère hydrophile (a2) est contenu dans le composant monomère (a). Pour cette résine, le rapport du monomère contenant un groupe acide (a1) dans le composant monomère (a) peut être de 3,5 % en masse ou moins ; et le rapport du monomère hydrophile (a2) dans le composant monomère (a) peut être de 1,2 % en masse ou plus.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000160097A (ja) * 1998-11-30 2000-06-13 Kansai Paint Co Ltd 水性塗料及びこれを用いた塗装仕上げ工法
JP2000204285A (ja) * 1999-01-14 2000-07-25 Kansai Paint Co Ltd 水性シ―ラ―及び窯業系基材のインライン塗装方法
JP2002309160A (ja) * 2001-02-08 2002-10-23 Kansai Paint Co Ltd 水性塗料組成物及びこれを用いた塗装仕上げ方法
JP2003096390A (ja) * 2001-09-27 2003-04-03 Dainippon Ink & Chem Inc 水性被覆組成物
JP2004002749A (ja) * 2002-04-23 2004-01-08 Nippon Shokubai Co Ltd 乳化重合樹脂組成物
JP2008150401A (ja) * 2006-12-14 2008-07-03 Nippon Paint Co Ltd 無機質系窯業建材用バックシーラーおよび無機質系窯業建材
JP2011111487A (ja) * 2009-11-25 2011-06-09 Nippon Shokubai Co Ltd シーラー用樹脂エマルション

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3375699B2 (ja) * 1993-11-17 2003-02-10 昭和高分子株式会社 無機板用プライマー組成物
JP2005272619A (ja) * 2004-03-24 2005-10-06 Daicel Chem Ind Ltd 水分散性樹脂組成物
JP5530156B2 (ja) * 2008-11-26 2014-06-25 株式会社日本触媒 シーラー用樹脂エマルションおよびその製造方法
JP6044067B2 (ja) * 2011-12-09 2016-12-14 三菱レイヨン株式会社 重合体エマルションの製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000160097A (ja) * 1998-11-30 2000-06-13 Kansai Paint Co Ltd 水性塗料及びこれを用いた塗装仕上げ工法
JP2000204285A (ja) * 1999-01-14 2000-07-25 Kansai Paint Co Ltd 水性シ―ラ―及び窯業系基材のインライン塗装方法
JP2002309160A (ja) * 2001-02-08 2002-10-23 Kansai Paint Co Ltd 水性塗料組成物及びこれを用いた塗装仕上げ方法
JP2003096390A (ja) * 2001-09-27 2003-04-03 Dainippon Ink & Chem Inc 水性被覆組成物
JP2004002749A (ja) * 2002-04-23 2004-01-08 Nippon Shokubai Co Ltd 乳化重合樹脂組成物
JP2008150401A (ja) * 2006-12-14 2008-07-03 Nippon Paint Co Ltd 無機質系窯業建材用バックシーラーおよび無機質系窯業建材
JP2011111487A (ja) * 2009-11-25 2011-06-09 Nippon Shokubai Co Ltd シーラー用樹脂エマルション

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