JP5854998B2 - Hydrophilic treatment agent - Google Patents

Description

  The present invention relates to a hydrophilic treatment agent. More specifically, the present invention relates to a hydrophilic treatment agent and a coating resin composition containing the hydrophilic treatment agent. The coating resin composition of the present invention can be suitably used for, for example, a substrate made of a material such as metal, glass, concrete, or resin, and an application in which the substrate is used. The coating resin composition of the present invention can be suitably used for surface finishing of a base material made of a material such as metal, glass, concrete, or resin. The said base material can be used for uses, such as a motor vehicle, a building, a civil engineering structure, a ceramic industry type | system | group inorganic building material, for example. The hydrophilization treatment agent of the present invention can be used alone for imparting hydrophilicity (water wettability) to a substrate, and can also be used for coatings and the like by being contained in a coating resin composition. Can be used.

  In general, a hydrophilicity-imparting agent is used to impart hydrophilicity to the surface of a metal substrate or a resin substrate. For example, as a hydrophilicity imparting agent for imparting hydrophilicity to the surface of an aluminum substrate or the like, a hydrophilicity imparting agent composed of a water-soluble polymer containing colloidal silica and a carboxylic acid polymer and water has been proposed ( For example, see Patent Document 1). However, although this hydrophilicity imparting agent is excellent in hydrophilicity and blocking resistance, it does not sufficiently exhibit water resistance because it requires colloidal silica and a carboxylic acid polymer as active ingredients.

  Further, as a hydrophilization treatment agent, a hydrophilization treatment agent containing a tetraalkoxysilane, a metal compound capable of interacting with a silanol group, a nonionic surfactant, acidic colloidal silica, etc. (see, for example, Patent Document 2), a block co-polymer A hydrophilic treatment agent containing a polymer and polyacrylic acid (for example, see Patent Document 3) has been proposed. However, none of these hydrophilic treatment agents exhibit sufficient water resistance like the hydrophilicity imparting agent.

  Further, a hydrophilic treatment agent containing a specific compound such as polyoxyethylene lauryl ether carboxylic acid has been proposed as a hydrophilic treatment agent that hydrophilizes a solid surface and makes it easy to wet with water (for example, patent document). 4). However, since the specific compound is a surfactant, this hydrophilic treatment agent is excellent in hydrophilicity, but it is easily released when moisture adheres, so that it is inferior in water resistance.

  Therefore, in recent years, development of a hydrophilic treatment agent that imparts excellent hydrophilicity and water resistance to a substrate and a resin composition for coatings containing the hydrophilic treatment agent has been awaited.

Japanese Patent Laid-Open No. 10-30069 JP 2006-052352 A JP 2009-126948 A JP 2009-227705 A

  The present invention has been made in view of the above prior art, and it is possible to provide water without using a hydrophilic treatment agent that imparts excellent hydrophilicity (water wettability) and water resistance to a substrate, and a water-soluble resin. It is an object of the present invention to provide a coating resin composition that forms a coating having excellent wettability and water resistance.

The present invention
(1) A hydrophilic treatment agent for imparting hydrophilicity to a base material, which has two or more hydroxyl groups and has a molecular weight of 500 or less and a polymerizable double bond-containing monomer and the polymerizable two A polymer obtained by polymerizing a monomer component containing a copolymerizable monomer having a copolymerizability with a heavy bond-containing monomer , wherein the copolymerizable monomer is a (meth) acrylic acid cyclohexane (Meth) acrylic acid alkyl ester having an alkyl ester and an alkyl group having 1 to 4 carbon atoms in the ester part is contained in a total content of 50 to 100% by mass, and (meth) acrylic acid cycloalkyl ester and 1 to 1 carbon atom. (Meth) acrylic acid alkyl ester having 4 alkyl groups in the ester part [(meth) acrylic acid cycloalkyl ester / (meth) acrylic having 1 to 4 carbon atoms in the ester part Acid alkyl ester] is 15/85 to 90/10 ,
(2) The emulsion particles containing a polymer obtained by emulsion polymerization of a monomer component containing a polymerizable double bond-containing monomer having two or more hydroxyl groups and a molecular weight of 500 or less. (1) the hydrophilic treatment agent according to
(3) A polymerizable double bond-containing monomer having two or more hydroxyl groups and having a molecular weight of 500 or less is represented by the formula (I):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having two or more hydroxyl groups)
The hydrophilic treatment agent according to (1) or (2), which is a monomer represented by:
(4) In the formula (I), R ² is —COOR ³ group, —OCOR ³ group, —OR ³ group, —CONHR ³ group, —CH ₂ OR ³ group, —CH ₂ OCOR ³ group, —CONHR ³ The hydrophilizing agent according to (3), which is a group, -CON (R ³ ) ₂ group or -NHCOR ³ group (R ³ represents an organic group having two or more hydroxyl groups),
(5) In the above (3) or (4), the monomer represented by the formula (I) is a (meth) acrylic acid ester having two or more hydroxyl groups in the ester portion and a molecular weight of 500 or less. The hydrophilic treatment agent according to the description,
(6) A (meth) acrylic acid ester having two or more hydroxyl groups in the ester moiety and a molecular weight of 500 or less is represented by the formula (II):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms)
The hydrophilizing agent according to (5), which is a (meth) acrylic acid ester represented by:
(7) the glass transition temperature of the polymer constituting the error Marushon particles are -30~80 ℃ (1) hydrophilic treatment agent according to any one of the - (6),
( 8 ) A hydrophilic base material in which a coating film comprising the hydrophilic treatment agent according to any one of (1) to ( 7 ) is formed on the surface,
( 9 ) A coating resin composition containing the hydrophilic treatment agent according to any one of (1) to ( 8 ), and ( 10 ) a coating resin composition according to ( 9 ). The present invention relates to a hydrophilic substrate having a film formed on the surface.

  In the present specification, “(meth) acrylic acid” means “acrylic acid” and / or “methacrylic acid”. “(Meth) acrylate” means “acrylate” and / or “methacrylate”. The “(meth) acrylic acid (cyclo) alkyl ester compound” means a (meth) acrylic acid alkyl ester compound and / or a (meth) acrylic acid cycloalkyl ester compound.

  According to the hydrophilization treatment agent of the present invention, there is an effect that excellent hydrophilicity (water wettability) and water resistance can be imparted to the substrate. Moreover, according to the resin composition for coatings of this invention, the effect that the film excellent in water wettability and water resistance can be formed, without using water-soluble resin is show | played.

  The hydrophilic treatment agent of the present invention is a hydrophilic treatment agent for imparting hydrophilicity (water wettability) to a substrate, and has a polymerizable double having two or more hydroxyl groups and a molecular weight of 500 or less. It contains a polymer obtained by polymerizing a monomer component containing a bond-containing monomer. The resin composition for coatings of the present invention is obtained by emulsion polymerization of a monomer component containing a polymerizable double bond-containing monomer having two or more hydroxyl groups and a molecular weight of 500 or less. Emulsion particles containing the prepared polymer.

  The hydrophilic treatment agent and coating resin composition of the present invention thus comprise a monomer component containing a polymerizable double bond-containing monomer having two or more hydroxyl groups and a molecular weight of 500 or less. One major feature is that it contains a polymer obtained by polymerization. Since the hydrophilization treatment agent of the present invention contains the polymer, an exceptionally excellent effect that excellent hydrophilicity (water wettability) and water resistance can be imparted to the substrate is exhibited. Further, since the resin composition for coatings of the present invention contains the polymer, it can be remarkably excellent that a film excellent in water wettability and water resistance can be formed without using a water-soluble resin. The effect is played.

  The polymer can be used as emulsion particles containing a polymer obtained by emulsion polymerization of the monomer component. In this case, the emulsion particles may be composed only of the polymer, and within the range in which the object of the present invention is not hindered, in addition to the polymer, a layer made of another polymer is present inside or outside. It may be formed.

  A polymerizable double bond-containing monomer having two or more hydroxyl groups and having a molecular weight of 500 or less (hereinafter simply referred to as “polymerizable double bond-containing monomer”) is used only in one type. Two or more types may be used in combination. The reason why the molecular weight of the polymerizable double bond-containing monomer is 500 or less is to improve hydrophilicity (water wettability).

  Examples of the polymerizable double bond-containing monomer include, for example, formula (I):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ² represents an organic group having two or more hydroxyl groups)
And the like. These monomers may be used alone or in combination of two or more.

In the formula (I), R ² is an organic group having two or more hydroxyl groups. Among them, from the viewpoint of improving hydrophilicity (water wettability) and water resistance, —COOR ³ group, —OCOR ³ group, —OR ³ group, —CONHR ³ group, —CH ₂ OR ³ group, —CH ₂ OCOR ³ group, —CONHR ³ group, —CON (R ³ ) ₂ group or —NHCOR ³ group (R ³ represents an organic group having two or more hydroxyl groups) is preferable. These monomers may be used alone or in combination of two or more.

R ³ is an organic group having two or more hydroxyl groups, but from the viewpoint of improving hydrophilicity (water wettability) and water resistance, preferably an organic group having 1 to 30 carbon atoms having two or more hydroxyl groups. And more preferably an organic group having 1 to 20 carbon atoms having two or more hydroxyl groups. Examples of the organic group include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a polyoxyalkylene group having 4 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms. . When two or more R ³ are contained in one molecule, each R ³ may be the same or different. R ³ may contain, for example, a halogen atom such as a fluorine atom or a chlorine atom, a nitrogen atom, or a functional group other than a hydroxyl group within a range that does not impair the object of the present invention.

  Representative examples of the polymerizable double bond-containing monomer include, for example, an ester of a polyhydric alcohol having three or more hydroxyl groups and (meth) acrylic acid, an ester of a saccharide and (meth) acrylic acid, an amino group Examples include esters of saccharides having (meth) acrylic acid and the like, but the present invention is not limited to such examples. These esters may be prepared not only by an esterification reaction but also by a transesterification reaction or a ring-opening reaction of (meth) acrylic acid glycidyl ester.

  Examples of the polyhydric alcohol having 3 or more hydroxyl groups include glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, pentaerythritol, 1,2,6-hexanetriol, and 2-hydroxymethyl-2. -Methyl-1,3-propanediol, 2-ethyl-2-hydroxymethyl-1,3-propanediol and the like can be mentioned, but the present invention is not limited to such examples. Examples of the saccharide include monosaccharides such as glucose, mannose, galactose, growth, fructose, D-ribose, glucosides derived from the monosaccharide, galactoside, fructoside and the like, dimers, trimers thereof, and the like. However, the present invention is not limited to such examples. Examples of the saccharide having an amino group include D-glucosamine, but the present invention is not limited to such examples.

  Among the polymerizable double bond-containing monomers, from the viewpoint of improving hydrophilicity (water wettability) and water resistance, the ester portion has two or more hydroxyl groups and a molecular weight of 500 or less (meth). Acrylic esters are preferred and have the formula (II):

(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms)
(Meth) acrylic acid ester represented by is more preferable, and glycerin mono (meth) acrylate is more preferable from the viewpoint of further improving hydrophilicity (water wettability).

  The content of the polymerizable double bond-containing monomer in the monomer component is preferably 3% by mass or more, more preferably 5% by mass from the viewpoint of improving hydrophilicity (water wettability) or film flexibility. % Or more, more preferably 10% by mass or more, and from the viewpoint of improving water resistance, it is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

  When the polymer is used as emulsion particles obtained by emulsion polymerization of monomer components, the emulsion particles may have one layer or a plurality of layers. When the emulsion particles are formed of a plurality of layers, the polymerizable double bond-containing single amount in the monomer component used as a raw material of the polymer forming at least one of the plurality of layers The content of the polymer, preferably the content of the polymerizable double bond-containing monomer in the monomer component used as a raw material for the polymer forming the outermost layer, improves hydrophilicity (water wettability). From the viewpoint of improving the water resistance, it is preferably 10% by mass or more, and more preferably 15% by mass or more. % Or less.

  In order to make the total amount of the monomer component 100 mass%, the monomer component contains the polymerizable double bond as the remainder of the monomer component in addition to the polymerizable double bond-containing monomer. It is preferable that a monomer that can be copolymerized with the bond-containing monomer (hereinafter referred to as “copolymerizable monomer”) is included. The copolymerizable monomer is used in an amount necessary for the total amount of the monomer components to be 100% by mass.

  The content of the copolymerizable monomer in the monomer component is preferably 70% by mass or more, more preferably 75% by mass or more, and further preferably 80% by mass or more from the viewpoint of improving water resistance. From the viewpoint of improving the property (water wettability) or the flexibility of the coating, it is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

  In the present invention, a monomer component containing a polymerizable double bond-containing monomer is used. From the viewpoint of improving the water resistance of the coating, the monomer component is (meth) acrylic acid (cyclohexane). ) It preferably contains an alkyl ester. Among copolymerizable monomers, it has a substituent from the viewpoint of improving hydrophilicity (water wettability), water resistance or light resistance by using in combination with a polymerizable double bond-containing monomer. (Meth) acrylic acid cycloalkyl ester (hereinafter simply referred to as “(meth) acrylic acid cycloalkyl ester”) having an cycloalkyl group which may be present in the ester part, and having an alkyl group having 1 to 4 carbon atoms in the ester part Preference is given to at least one copolymerizable monomer selected from the group consisting of alkyl (meth) acrylates, UV-stable monomers and UV-absorbing monomers. These copolymerizable monomers may be used alone or in combination of two or more.

  Among the copolymerizable monomers, from the viewpoint of improving water resistance, (meth) acrylic acid cycloalkyl ester and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester moiety. It is preferable to contain at least one kind. The (meth) acrylic acid cycloalkyl ester can be preferably used from the viewpoint of improving water resistance. These monomers may be used alone or in combination of two or more. In addition, it is preferable from a viewpoint of improving water resistance that the copolymerizable monomer contains (meth) acrylic acid cycloalkyl ester as an essential component.

  The cycloalkyl group of the (meth) acrylic acid cycloalkyl ester is preferably a cycloalkyl group having 4 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 10 carbon atoms, from the viewpoint of improving water resistance. It is a group.

  The (meth) acrylic acid cycloalkyl ester may have a substituent as long as the object of the present invention is not inhibited. Examples of the substituent that the (meth) acrylic acid cycloalkyl ester may have include, for example, an alkyl group such as a methyl group and a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, and a hydroxyl group. Examples include a group and a halogen atom, but the present invention is not limited to such examples.

  Examples of (meth) acrylic acid cycloalkyl esters include cycloalkyl (meth) acrylate and cycloalkylalkyl (meth) acrylate, and these monomers may be used alone or in combination of two or more. May be used in combination.

  As the cycloalkyl (meth) acrylate, for example, a cycloalkyl group such as isobornyl (meth) acrylate, cyclohexyl (meth) acrylate and the like preferably has 4 to 20 carbon atoms, more preferably 4 to 10 cycloalkyl (meth) acrylates. These cycloalkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the cycloalkylalkyl (meth) acrylate include carbon numbers of cycloalkyl groups such as cyclohexylmethyl (meth) acrylate, cyclohexylethyl (meth) acrylate, cyclohexylpropyl (meth) acrylate, and 4-methylcyclohexylmethyl (meth) acrylate. Is preferably 4 to 20, more preferably 4 to 10, and examples thereof include cycloalkylalkyl (meth) acrylates in which the number of carbon atoms of the alkyl group bonded to the cycloalkyl group is preferably 1 to 4, and these These cycloalkylalkyl (meth) acrylates may be used alone or in combination of two or more.

  Among the (meth) acrylic acid cycloalkyl esters, a cycloalkyl (meth) acrylate having a cycloalkyl group having 4 to 20 carbon atoms is preferable, and a cycloalkyl (meth) having a cycloalkyl group having 4 to 10 carbon atoms. Acrylates are more preferred, isobornyl (meth) acrylate and cyclohexyl (meth) acrylate are more preferred, and cyclohexyl (meth) acrylate is particularly preferred.

  When (meth) acrylic acid cycloalkyl ester is used as the copolymerizable monomer, the content of (meth) acrylic acid cycloalkyl ester in the monomer component is preferably 10 from the viewpoint of improving water resistance. From the viewpoint of improving hydrophilicity (water wettability), preferably 97% by mass or less, more preferably 95% by mass or less, more preferably 20% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more. More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 70 mass% or less. Further, from the viewpoint of improving the flexibility of the film, the content of the (meth) acrylic acid cycloalkyl ester in the monomer component is preferably 60% by mass or less, more preferably 50% by mass or less. When (meth) acrylic acid cycloalkyl ester is used as the copolymerizable monomer, the content of the polymerizable double bond-containing monomer in the monomer component improves hydrophilicity (water wettability). From a viewpoint, Preferably it is 3 mass% or more, More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, From a viewpoint of improving water resistance, Preferably it is 30 mass% or less, More preferably, it is 25 mass% or less. More preferably, it is 20 mass% or less.

  When (meth) acrylic acid cycloalkyl ester is used as the copolymerizable monomer, if necessary, the monomer component includes the (( Copolymerizable monomers other than (meth) acrylic acid cycloalkyl ester may be contained. The copolymerizable monomer other than the (meth) acrylic acid cycloalkyl ester is used in an amount necessary for the total amount of the monomer components to be 100% by mass.

  When the polymer is used as emulsion particles obtained by emulsion polymerization of monomer components, (meth) acrylic acid (cyclo) in all monomer components used as a raw material for the polymer constituting the emulsion particles From the viewpoint of improving water resistance, the alkyl ester content is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more, and further preferably 30% by mass or more. From the viewpoint of improving the property (water wettability) or the flexibility of the coating, it is preferably 97% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, and still more preferably 80% by mass or less. is there.

  Further, when the emulsion particles are formed of a plurality of layers, (meth) acrylic acid ((meth) acrylic acid () in the monomer component used as a raw material of the polymer forming at least one of the plurality of layers. The content of cyclo) alkyl ester, preferably the content of (meth) acrylic acid (cyclo) alkyl ester in the monomer component used as a raw material for the polymer forming the outermost layer improves the water resistance. From the viewpoint, it is preferably 50% by mass or more, more preferably 60% by mass or more, and preferably 90% by mass or less, more preferably 85% from the viewpoint of improving hydrophilicity (water wettability) or film flexibility. It is below mass%.

  The (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion can be suitably used from the viewpoint of improving water resistance.

  Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) acrylate. , N-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, etc., and these monomers may be used alone, Two or more kinds may be used in combination. Among the (meth) acrylic acid alkyl esters, from the viewpoint of improving water resistance, an alkyl group having 4 carbon atoms is preferable, and n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, and tert-butyl methacrylate are more preferable.

  When the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester part is used as the copolymerizable monomer, the ester part has an alkyl group having 1 to 4 carbon atoms in the monomer component ( The content of the (meth) acrylic acid alkyl ester is preferably 10% by mass or more, more preferably 15% by mass or more from the viewpoint of improving water resistance, and preferably from the viewpoint of improving hydrophilicity (water wettability). Is 97% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, further preferably 80% by mass or less, and still more preferably 75% by mass or less. Moreover, from the viewpoint of improving the flexibility of the coating, the content of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the monomer component in the ester portion is preferably 70% by mass or less. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less. Moreover, when using the (meth) acrylic-acid alkylester which has a C1-C4 alkyl group in an ester part as a copolymerizable monomer, the content rate of the polymerizable double bond containing monomer in a monomer component Is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 10% by mass or more from the viewpoint of improving hydrophilicity (water wettability), preferably from the viewpoint of improving water resistance. It is 30 mass% or less, More preferably, it is 25 mass% or less, More preferably, it is 20 mass% or less.

  When a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester part is used as a copolymerizable monomer, the total amount of monomer components is 100% by mass as necessary. In order to do so, the monomer component may contain a copolymerizable monomer other than the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion. The copolymerizable monomer other than the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion is used in an amount required for the total amount of the monomer components to be 100% by mass. .

  In this invention, it is preferable to use together (meth) acrylic-acid alkylester which has a C1-C4 alkyl group in an ester part from a viewpoint of improving water resistance. At this time, from the viewpoint of improving water resistance, the ratio of (meth) acrylic acid cycloalkyl ester and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester moiety [(meth) acrylic acid cyclohexane The lower limit of the alkyl ester / (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion: mass ratio] is preferably 15/85 or more, more preferably 20/80 or more, and still more preferably. The upper limit is preferably 90/10 or less, more preferably 85/15 or less, and still more preferably 80/20 or less.

  From the viewpoint of improving water resistance, the total content of the (meth) acrylic acid cycloalkyl ester and the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion in the copolymerizable monomer is as follows. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 80 mass% or more, The upper limit is 100 mass%. Therefore, the content of the copolymerizable monomer other than the (meth) acrylic acid cycloalkyl ester and the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion in the copolymerizable monomer is From the viewpoint of improving water resistance, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, and the lower limit is 0% by mass.

  Examples of UV-stable monomers include 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine. 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4- (meth) acryloyl-1-methoxy-2,2,6,6-tetramethylpiperidine, 4-cyano- 4- (meth) acryloyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-croto Noylamino-2,2,6,6-tetramethylpiperidine, 4- (meth) acryloylamino-1,2,2,6,6-pentamethylpiperidine, 4-sia -4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4-cyano- Examples include 4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine, 1-crotonoyl-4-crotonoyloxy-2,2,6,6-tetramethylpiperidine and the like. However, the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  When using an ultraviolet stable monomer as the copolymerizable monomer, the content of the ultraviolet stable monomer in the monomer component is preferably 0.1% by mass from the viewpoint of improving light resistance. From the viewpoint of improving the water resistance, preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 80% by mass or less. Still more preferably, it is 70 mass% or less, Most preferably, it is 60 mass% or less. The content of the UV-stable monomer in the monomer component is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass from the viewpoint of improving the flexibility of the coating. It is as follows.

  When using a UV-stable monomer as the copolymerizable monomer, the UV-stable monomer is included in the monomer component, if necessary, so that the total amount of the monomer component is 100% by mass. A copolymerizable monomer other than the polymerizable monomer may be contained. The copolymerizable monomer other than the UV-stable monomer is used in an amount necessary for the total amount of the monomer components to be 100% by mass.

  Examples of the UV-absorbing monomer include benzotriazole-based UV-absorbing monomers and benzophenone-based UV-absorbing monomers, but the present invention is not limited to such examples. These monomers may be used alone or in combination of two or more.

  Examples of the benzotriazole-based UV-absorbing monomer include 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -2H-benzotriazole and 2- [2′-hydroxy-5′-. (Meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxymethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2 ′ -Hydroxy-5 '-(meth) acryloylaminomethyl-5'-tert-octylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxypropylphenyl] -2H-benzo Triazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyhex Ruphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3′-tert-butyl-5 ′-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2′-hydroxy-3 ′ -Tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2'-hydroxy-5'-tert-butyl-3'-(meth) acryloyloxyethyl Phenyl] -2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(meta ) Acrylyloxyethylphenyl] -5-cyano-2H-benzotriazole, 2- [2'-hydride Xyl-5 ′-(meth) acryloyloxyethylphenyl] -5-tert-butyl-2H-benzotriazole, 2- [2′-hydroxy-5 ′-(β- (meth) acryloyloxyethoxy) -3′- tert-butylphenyl] -4-tert-butyl-2H-benzotriazole, and the like, but the present invention is not limited to such examples. These benzotriazole-based UV-absorbing monomers may be used alone or in combination of two or more.

  Examples of the benzophenone-based UV-absorbing monomer include 2-hydroxy-4- (meth) acryloyloxybenzophenone, 2-hydroxy-4- [2-hydroxy-3- (meth) acryloyloxy] propoxybenzophenone, 2- Hydroxy-4- [2- (meth) acryloyloxy] ethoxybenzophenone, 2-hydroxy-4- [3- (meth) acryloyloxy-2-hydroxypropoxy] benzophenone, 2-hydroxy-3-tert-butyl-4- Examples include [2- (meth) acryloyloxy] butoxybenzophenone, but the present invention is not limited to such examples. These benzophenone-based ultraviolet absorbing monomers may be used alone or in combination of two or more.

  When an ultraviolet absorbing monomer is used as the copolymerizable monomer, the content of the ultraviolet absorbing monomer in the monomer component is preferably 0.1 mass from the viewpoint of improving ultraviolet absorption. % Or more, more preferably 1% by mass or more, and further preferably 3% by mass or more. From the viewpoint of improving water resistance, it is preferably 97% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass. % Or less, more preferably 80% by mass or less, and still more preferably 70% by mass or less. Further, from the viewpoint of improving the flexibility of the coating, the content of the UV-absorbing monomer in the monomer component is preferably 60% by mass or less, more preferably 50% by mass or less, and further preferably 40% by mass. It is as follows.

  When using an ultraviolet-absorbing monomer as the copolymerizable monomer, if necessary, the monomer component contains the UV-absorbing monomer so that the total amount of the monomer component is 100% by mass. A copolymerizable monomer other than the polymerizable monomer may be contained. The copolymerizable monomer other than the ultraviolet absorbing monomer is used in an amount necessary for the total amount of the monomer components to be 100% by mass.

  As the copolymerizable monomer, in addition to the above-described monomers, for example, other than (meth) acrylic acid cycloalkyl ester and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion. (Meth) acrylic acid alkyl ester [hereinafter referred to as “other (meth) acrylic acid alkyl ester”], aromatic monomer, (meth) acrylate having one hydroxyl group, carboxyl group-containing monomer, oxo group In the range in which the object of the present invention is not inhibited, such as a monomer containing a fluorine atom, a monomer containing a fluorine atom, a monomer containing an epoxy group, an alkoxyalkyl (meth) acrylate, a monomer containing a silane group, a monomer containing an aziridinyl group Can be used. These monomers may be used alone or in combination of two or more. Among these monomers, styrenic monomers, carboxyl group-containing monomers, epoxy group-containing monomers and silane group-containing monomers are preferred, carboxyl group-containing monomers, epoxy group-containing monomers And silane group-containing monomers are more preferred.

  As other (meth) acrylic acid alkyl ester, for example, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, tridecyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, Although alkyl (meth) acrylate etc. whose carbon number of ester groups, such as stearyl (meth) acrylate, is 5-18 are mentioned, this invention is not limited only to this illustration. These alkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of aromatic monomers include styrene monomers and aralkyl (meth) acrylates, but the present invention is not limited to such examples.

  Examples of the styrenic monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene, and the like, but the present invention is limited only to such examples. is not. These monomers may be used alone or in combination of two or more. Styrene monomers have functional groups such as alkyl groups such as methyl and tert-butyl groups, nitro groups, nitrile groups, alkoxyl groups, acyl groups, sulfone groups, hydroxyl groups, and halogen atoms in the benzene ring. May be. Among the styrene monomers, styrene is preferable from the viewpoint of improving water resistance.

  Examples of the aralkyl (meth) acrylate include aralkyl having 7 to 18 carbon atoms such as benzyl (meth) acrylate, phenylethyl (meth) acrylate, methylbenzyl (meth) acrylate, naphthylmethyl (meth) acrylate and the like. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These aralkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the (meth) acrylate having one hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, Examples of the hydroxyl group-containing (meth) acrylate having 1 to 18 carbon atoms in the ester group such as 4-hydroxybutyl (meth) acrylate are given, but the present invention is not limited to such examples. These (meth) acrylates having one hydroxyl group may be used alone or in combination of two or more.

  Examples of the carboxyl group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, and itaconic acid monomethyl. Examples thereof include carboxyl group-containing aliphatic monomers such as esters, itaconic acid monobutyl ester, and vinyl benzoic acid, but the present invention is not limited to such examples. These carboxyl group-containing monomers may be used alone or in combination of two or more. Among these carboxyl group-containing monomers, acrylic acid, methacrylic acid and itaconic acid are preferable, and acrylic acid and methacrylic acid are more preferable from the viewpoint of improving the dispersion stability of the emulsion particles.

  Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) (meta) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. ) Acrylate and the like, but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.

  Examples of the fluorine atom-containing monomer include fluorine atom-containing alkyl having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Although (meth) acrylate etc. are mentioned, this invention is not limited only to this illustration. These fluorine atom-containing monomers may be used alone or in combination of two or more.

  Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and glycidyl allyl ether. It is not limited to only. These epoxy group-containing monomers may be used alone or in combination of two or more.

  Examples of the alkoxyalkyl (meth) acrylate include methoxyethyl (meth) acrylate, methoxybutyl (meth) acrylate, ethoxybutyl (meth) acrylate, and trimethylolpropane tripropoxy (meth) acrylate. However, the present invention is not limited to such examples. These alkoxyalkyl (meth) acrylates may be used alone or in combination of two or more.

  Examples of the silane group-containing monomer include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (methoxyethoxy) silane, γ- (meth) acryloyloxypropyltrimethoxysilane, 2-styrylethyltrimethoxysilane, vinyltri Examples include chlorosilane, γ- (meth) acryloyloxypropylhydroxysilane, and γ- (meth) acryloyloxypropylmethylhydroxysilane, but the present invention is not limited to such examples. These silane group-containing monomers may be used alone or in combination of two or more.

  Examples of aziridinyl group-containing monomers include (meth) acryloylaziridine and 2-aziridinylethyl (meth) acrylate, but the present invention is not limited to such examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

  Examples of the method for polymerizing the monomer component include a solution polymerization method, an emulsion polymerization method, a bulk polymerization method, a suspension polymerization method, and the like, but the present invention is not limited to such a polymerization method. Among these polymerization methods, the emulsion polymerization method is preferable from the viewpoint of improving hydrophilicity (water wettability) and water resistance, and emulsification without using an organic solvent from the viewpoint of prevention of environmental pollution and the health of workers. A polymerization method is more preferable.

  When the monomer component is polymerized by a solution polymerization method, examples of the solvent include aromatic solvents such as benzene, toluene, xylene; n-butyl alcohol, propylene glycol methyl ether, diacetone alcohol, ethyl cellosolve, and the like. Alcohol solvents; ester solvents such as ethyl acetate, butyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; dimethylformamide and the like, but the present invention is limited only to such examples. It is not something. The amount of the solvent is preferably appropriately determined according to the concentration of the monomer component, the molecular weight of the target acrylic polymer, and the like.

  Examples of the method of polymerizing the monomer component by the solution polymerization method include a method of mixing a monomer component, a solvent and a polymerization initiator, but the present invention is not limited to such a method. Absent. The amount of the solvent may be appropriately set in consideration of the viscosity and the nonvolatile content in the resulting hydrophilization treatment agent.

  Examples of a method for polymerizing the monomer component by emulsion polymerization include, for example, an aqueous medium containing a water-soluble organic solvent such as lower alcohol such as methanol and water, and an emulsifier dissolved in a medium such as water and stirring. Examples include a method of dropping a monomer component and a polymerization initiator under pressure, a method of dropping a monomer component previously emulsified with an emulsifier and water in water or an aqueous medium, and the like. The method is not limited to such a method. In addition, the amount of the medium may be appropriately set in consideration of the viscosity and the nonvolatile content in the obtained hydrophilic treatment agent. The medium may be charged in the reaction vessel in advance or used as a pre-emulsion. The medium may be used when a resin emulsion is produced by emulsion polymerization of monomer components as required.

  When the monomer component is emulsion-polymerized, the monomer component, the emulsifier and the medium may be mixed and then emulsion polymerization may be performed. The emulsion polymerization may be carried out after preparing the emulsion, or the emulsion polymerization may be carried out by mixing at least one of the monomer component, the emulsifier and the medium and the remaining pre-emulsion. The monomer component, the emulsifier, and the medium may be added all at once, dividedly, or continuously dropped.

  In the case of preparing a resin emulsion containing emulsion particles having an inner layer, a resin emulsion containing emulsion particles forming an inner layer is prepared by emulsion polymerization of the monomer component in the same manner as described above. By emulsion polymerization of the monomer component that forms the outer layer in the resin emulsion, the outer layer can be formed on the emulsion particles that form the inner layer. Further, when preparing emulsion particles having a multilayer structure, one or more stages of emulsion polymerization may be performed before emulsion polymerization for forming the inner layer, and emulsion polymerization for forming the inner layer and emulsification for forming the intermediate layer. One-stage or multiple-stage emulsion polymerization may be performed between the polymerizations.

  From the viewpoint of improving the storage stability of the emulsion particles, the average particle size of the emulsion particles contained in the resin emulsion obtained by emulsion polymerization of the monomer component is preferably 30 nm or more, more preferably 50 nm or more. Further, it is preferably 70 nm or more, and preferably 250 nm or less, more preferably 200 nm or less, from the viewpoint of improving water resistance.

  In the present specification, the average particle size of the emulsion particles is measured using a particle size distribution measuring instrument (particle size systems manufactured by Particle Sizing Systems, trade name: NICOMP Model 380) by a dynamic light scattering method. It means the volume average particle diameter.

  Examples of the emulsifier include an anionic emulsifier, a nonionic emulsifier, a cationic emulsifier, an amphoteric emulsifier, and a polymer emulsifier. These emulsifiers may be used alone or in combination of two or more.

  Examples of the anionic emulsifier include alkyl sulfate salts such as ammonium dodecyl sulfate and sodium dodecyl sulfate; alkyl sulfonate salts such as ammonium dodecyl sulfonate and sodium dodecyl sulfonate; alkyl aryl sulfonate salts such as ammonium dodecyl benzene sulfonate and sodium dodecyl naphthalene sulfonate; Examples include polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl sulfate salts; dialkyl sulfosuccinates; aryl sulfonic acid-formalin condensates; fatty acid salts such as ammonium laurate and sodium stearate. It is not limited to illustration only.

  Nonionic emulsifiers include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, ethylene oxide and aliphatic Although the condensation product with an amine etc. are mentioned, this invention is not limited only to this illustration.

  Examples of the cationic emulsifier include alkylammonium salts such as dodecylammonium chloride, but the present invention is not limited to such examples.

  Examples of amphoteric emulsifiers include betaine ester type emulsifiers, but the present invention is not limited to such examples.

  Examples of the polymer emulsifier include poly (meth) acrylates such as sodium polyacrylate; polyvinyl alcohol; polyvinyl pyrrolidone; polyhydroxyalkyl (meth) acrylates such as polyhydroxyethyl acrylate; single polymers constituting these polymers. Although the copolymer etc. which use 1 or more types of a monomer as a copolymerization component are mentioned, this invention is not limited only to this illustration.

  Further, as the emulsifier, an emulsifier having a polymerizable group, that is, a so-called reactive emulsifier is preferable from the viewpoint of improving water resistance, and a non-nonylphenyl emulsifier is preferable from the viewpoint of environmental protection.

  As the reactive emulsifier, for example, propenyl-alkylsulfosuccinic acid ester salt, (meth) acrylic acid polyoxyethylene sulfonate salt, (meth) acrylic acid polyoxyethylene phosphonate salt [for example, manufactured by Sanyo Chemical Industries, Ltd., Product name: Eleminol RS-30, etc.], polyoxyethylene alkylpropenyl phenyl ether sulfonate salt [for example, product name: Aqualon HS-10, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.], allyloxymethylalkyloxypolyoxyethylene Sulfonate salt [for example, product name: Aqualon KH-10 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.], sulfonate salt of allyloxymethylnonylphenoxyethylhydroxypolyoxyethylene [for example, product name: ADEKA manufactured by ADEKA Corporation Rear soap SE-10 etc.), Ryloxymethylalkoxyethylhydroxypolyoxyethylene sulfate ester salt (for example, manufactured by ADEKA, trade name: Adekaria soap SR-10, SR-30, etc.), bis (polyoxyethylene polycyclic phenyl ether) methacrylated sulfonate Salts (for example, Nippon Emulsifier Co., Ltd., trade name: Antox MS-60, etc.), allyloxymethylalkoxyethylhydroxypolyoxyethylene [eg, ADEKA Corporation, trade name: Adeka Soap ER-20, etc. ], Polyoxyethylene alkylpropenyl phenyl ether [for example, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon RN-20, etc.], allyloxymethylnonylphenoxyethyl hydroxypolyoxyethylene [for example, manufactured by ADEKA Corporation, Product Name: Adekaria Soap E-10, etc.) and the like, the present invention is not limited only to those exemplified.

  The amount of the emulsifier is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 2 parts by mass or more, particularly preferably from the viewpoint of improving the polymerization stability per 100 parts by mass of the monomer component. Is 3 parts by mass or more, and from the viewpoint of improving water resistance, it is preferably 10 parts by mass or less, more preferably 6 parts by mass or less, still more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less.

  A polymerization initiator can be used when the monomer component is polymerized. Examples of the polymerization initiator include azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2,4-dimethylvaleronitrile), 2,2-azobis ( Azo compounds such as 2-diaminopropane) hydrochloride, 4,4-azobis (4-cyanovaleric acid), 2,2-azobis (2-methylpropionamidine); persulfates such as potassium persulfate; hydrogen peroxide , Benzoyl peroxide, parachlorobenzoyl peroxide, lauroyl peroxide, peroxides such as ammonium peroxide, and the like, but the present invention is not limited to such examples. These polymerization initiators may be used alone or in combination of two or more.

  The amount of the polymerization initiator is preferably 0.05 parts by mass or more, more preferably 0 from the viewpoint of increasing the polymerization rate and reducing the residual amount of the unreacted monomer component per 100 parts by mass of the monomer component. From the viewpoint of improving water resistance, it is preferably 1 part by mass or less, and more preferably 0.5 part by mass or less.

  The method for adding the polymerization initiator is not particularly limited. Examples of the addition method include batch charging, divided charging, and continuous dripping. From the viewpoint of advancing the completion time of the polymerization reaction, a part of the polymerization initiator may be added before or after the monomer component is added to the reaction system.

  In order to accelerate the decomposition of the polymerization initiator, for example, a reducing agent such as sodium bisulfite and a polymerization initiator decomposition agent such as transition metal salt such as ferrous sulfate are added in an appropriate amount to the reaction system. Also good.

  Further, if necessary, additives such as chain transfer agents such as compounds having a thiol group such as tert-dodecyl mercaptan, pH buffering agents, chelating agents, and film-forming aids may be added to the reaction system. Good. Since the amount of the additive varies depending on the type, it cannot be determined unconditionally, but usually, it is preferably about 0.01 to 5 parts by weight, more preferably 0.1 to 100 parts by weight per 100 parts by weight of the monomer component. About 3 parts by mass.

  The atmosphere for polymerizing the monomer component is not particularly limited, but is preferably an inert gas such as nitrogen gas from the viewpoint of improving the efficiency of the polymerization initiator.

  Although the polymerization temperature at the time of polymerizing the monomer component is not particularly limited, it is usually preferably 50 to 100 ° C, more preferably 60 to 95 ° C. The polymerization temperature may be constant or may be changed during the polymerization reaction.

  The polymerization time for polymerizing the monomer component is not particularly limited and may be appropriately set according to the progress of the polymerization reaction, but is usually about 2 to 9 hours.

  In addition, when polymerizing a monomer component, you may make it neutralize part or all of the acidic group which the obtained polymer has with a neutralizing agent. The neutralizing agent may be used after the monomer component is added in the final stage. For example, the neutralizing agent may be used between the first stage polymerization reaction and the second stage polymerization reaction. It may be used at the end of the reaction.

  Examples of the neutralizing agent include alkali metal and alkaline earth metal hydroxides such as sodium hydroxide; alkali metal and alkaline earth metal carbonates such as calcium carbonate; and organic amines such as ammonia and monomethylamine. Although an alkaline substance is mentioned, this invention is not limited only to this illustration. Among these neutralizing agents, volatile alkaline substances such as ammonia are preferable from the viewpoint of improving water resistance.

  When the monomer component is polymerized, a silane coupling agent may be used in an appropriate amount from the viewpoint of improving hydrophilicity (water wettability) and water resistance. Examples of the silane coupling agent include a silane coupling agent having a polymerizable unsaturated bond such as a (meth) acryloyl group, a vinyl group, an allyl group, and a propenyl group. It is not limited.

  A polymer is obtained by polymerizing the monomer component as described above, but the polymer may have a crosslinked structure.

  In the case where an outer layer is formed on the emulsion particles contained in the resin emulsion obtained above, the emulsion particles are obtained by emulsion polymerization of the monomer component in the resin emulsion in the same manner as described above. An outer layer can be formed thereon. Moreover, when forming an outer layer further on the emulsion particle | grains in which the said outer layer was formed, an outer layer is further formed on the said emulsion particle | grain by carrying out the emulsion polymerization of the monomer component in a resin emulsion like the above. Can be made. Thus, a resin emulsion containing emulsion particles having a multilayer structure can be prepared by a multistage emulsion polymerization method.

  When preparing emulsion particles having a multilayer structure, one or a plurality of stages of emulsion polymerization may be performed before the emulsion polymerization for forming the inner layer. The emulsion polymerization for forming the inner layer and the emulsion polymerization for forming the intermediate layer One stage or a plurality of stages of emulsion polymerization may be carried out between the two. Moreover, you may perform one step or multiple steps | paragraphs of emulsion polymerization between the emulsion polymerization which forms an intermediate | middle layer, and the emulsion polymerization which forms an outer layer. Furthermore, after the emulsion polymerization for forming the outer layer, one or more stages of emulsion polymerization may be performed.

  The weight average molecular weight of the polymer is preferably 100,000 or more, more preferably from the viewpoint of improving water resistance, regardless of whether the polymer has a crosslinked structure or not. 300,000 or more, more preferably 550,000 or more, particularly preferably 600,000 or more. The upper limit of the weight average molecular weight of the polymer is not particularly limited because it is difficult to measure the weight average molecular weight when it has a crosslinked structure, but when it does not have a crosslinked structure, it should be 5 million or less. Is preferred.

  In addition, in this specification, the weight average molecular weight uses gel permeation chromatography [manufactured by Tosoh Corporation, product number: HLC-8120GPC, column: TSKgel G-5000HXL and TSKgel GMHXL-L used in series]. The weight average molecular weight (in terms of polystyrene) measured by

  The upper limit of the glass transition temperature of the polymer is preferably 80 ° C. or less, more preferably 75 ° C. or less, further preferably 60 ° C. or less, and still more preferably 50 ° C. or less, from the viewpoint of improving water resistance. The lower limit is preferably −30 ° C. or higher, more preferably −20 ° C. or higher, and still more preferably −10 ° C. or higher, from the viewpoint of improving water resistance. The glass transition temperature of the polymer can be easily adjusted by adjusting the composition of the monomer used for the monomer component.

In the present specification, the glass transition temperature of the polymer is expressed by the following formula: the glass transition temperature of the homopolymer of the monomer used in the monomer component constituting the polymer.
1 / Tg = Σ (Wm / Tgm) / 100
[Wherein Wm represents the content (% by mass) of the monomer m in the monomer component constituting the polymer, and Tgm represents the glass transition temperature (absolute temperature: K) of the homopolymer of the monomer m. ]
The temperature calculated | required based on the Formula of Fox (Fox) represented by these.

  The glass transition temperature of the polymer is, for example, -11 ° C. for a homopolymer of glycerol monoacrylate, 55 ° C. for a homopolymer of glycerol monomethacrylate, 105 ° C. for a homopolymer of methyl methacrylate, and for a homopolymer of cyclohexyl methacrylate. 83 ° C., 20 ° C. for n-butyl methacrylate homopolymer, −70 ° C. for 2-ethylhexyl acrylate homopolymer, −56 ° C. for n-butyl acrylate homopolymer, 95 ° C. for acrylic acid homopolymer , A homopolymer of methacrylic acid at 130 ° C., a homopolymer of γ-methacryloyloxypropyltrimethoxysilane (TMSMA) at 70 ° C., a homopolymer of 2-hydroxyethyl methacrylate at 55 ° C., and a homopolymer of cyclohexyl acrylate 16 ° C, 4-metac 130 ° C. for the homopolymer of Royloxy-1,2,2,6,6-pentamethylpiperidine, 74 for the homopolymer of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole ° C.

  The glass transition temperature of the polymer is a value obtained based on the Fox equation, but the measured value of the glass transition temperature of the polymer was obtained based on the Fox equation. The value is preferably the same. The actual measured value of the glass transition temperature of the polymer can be obtained, for example, by measuring the differential scanning calorific value.

  Examples of the differential scanning calorimeter measuring device include Seiko Instruments Inc., product number: DSC220C. Further, when measuring the differential scanning calorific value, a method of drawing a differential scanning calorific value (DSC) curve, a method of obtaining a first derivative curve from the differential scanning calorific value (DSC) curve, a method of performing a smoothing process, and a method of obtaining a target peak temperature There is no limitation in particular. For example, when the measuring device is used, the drawing may be performed from data obtained by using the measuring device. At that time, analysis software capable of performing mathematical processing can be used. Examples of the analysis software include analysis software [manufactured by Seiko Instruments Inc., product number: EXSTAR6000], but the present invention is not limited to such examples. In addition, the peak temperature obtained in this way may include an error due to plotting of about 5 ° C. up and down.

  When emulsion particles having an inner layer and an outer layer are used, the solubility parameter (hereinafter also referred to as SP value) of the polymer constituting the outer layer may be higher than the SP value of the polymer constituting the inner layer. From the viewpoint of forming a layer separation structure in the emulsion particles. The difference between the SP value of the polymer constituting the inner layer and the SP value of the polymer constituting the outer layer is preferably large from the viewpoint of forming a layer separation structure in the emulsion particles.

  The SP value is a value defined by the regular solution theory introduced by Hildebrand, and is also a measure of the solubility of the binary solution. In general, substances having similar SP values tend to be mixed with each other. Therefore, the SP value is also a measure for judging the ease of mixing of the solute and the solvent.

  The hydrophilic treatment agent of the present invention contains the polymer prepared as described above. Moreover, the resin composition for coatings of this invention contains the said hydrophilic treatment agent. More specifically, the resin composition for coatings of the present invention contains a resin emulsion containing emulsion particles prepared as described above.

  Since the non-volatile content in the hydrophilic treatment agent and paint resin composition of the present invention varies depending on the type of polymerization method of the monomer component, it cannot be determined unconditionally. It is preferable to adjust according to the type. For example, when the monomer component is polymerized by a solution polymerization method, the resulting polymer solution contains the solvent used in the polymerization, and this polymer solution is treated with a hydrophilizing agent or When used in a coating resin composition, the solvent contained in the polymer solution is contained. Further, when the monomer component is polymerized by an emulsion polymerization method, the obtained resin emulsion contains an emulsifier and a medium used in the polymerization. When used in a resin composition for paint, the emulsifier and medium contained in the resin emulsion are contained. From the viewpoint of improving productivity, the non-volatile content in the hydrophilic treatment agent or paint resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and improves handling properties. From the viewpoint, it is preferably 70% by mass or less, more preferably 60% by mass or less.

In the present specification, the non-volatile content in the hydrophilizing agent and the non-volatile content in the coating resin composition are each 1 g of the hydrophilizing agent weighed and dried for 1 hour at a temperature of 110 ° C. with a hot air dryer. The resulting residue is non-volatile and has the formula:
[Non-volatile content in hydrophilizing agent (% by mass)]
= ([Mass of residue] ÷ [Hydrophilic treatment agent 1 g]) × 100
Means the value obtained based on

  Crosslinking property can be imparted to the hydrophilic treatment agent and coating resin composition of the present invention by further containing a crosslinking agent. As a crosslinking agent, a crosslinking reaction may be started at room temperature, or a crosslinking reaction may be initiated by heat. Water resistance can be further improved by adding a crosslinking agent to the hydrophilic treatment agent and the resin composition for coatings of the present invention.

  Suitable cross-linking agents include, for example, oxazoline group-containing compounds, isocyanate group-containing compounds, aminoplast resins, and the like. These crosslinking agents may be used alone or in combination of two or more. Among these crosslinking agents, an oxazoline group-containing compound is preferable from the viewpoint of improving water resistance.

  The oxazoline group-containing compound is a compound having in the molecule two or more oxazoline groups that can react with the carboxyl group that the carboxyl group-containing monomer used as the monomer component has as a functional group.

  Examples of the oxazoline group-containing compound include 2,2′-bis (2-oxazoline), 2,2′-methylene-bis (2-oxazoline), 2,2′-ethylene-bis (2-oxazoline), 2 , 2'-trimethylene-bis (2-oxazoline), 2,2'-tetramethylene-bis (2-oxazoline), 2,2'-hexamethylene-bis (2-oxazoline), 2,2'-octamethylene -Bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene-bis (2-oxazoline), 2,2'- m-phenylene-bis (2-oxazoline), 2,2′-m-phenylene-bis (4,4′-dimethyl-2-oxazoline), bis (2-oxazolinylcyclohexane) sulfi , Bis (2-oxazolinyl sulfonyl norbornane) sulfide, but like oxazoline ring-containing polymer, the present invention is not limited only to those exemplified. These oxazoline group-containing compounds may be used alone or in combination of two or more. Among the oxazoline group-containing compounds, from the viewpoint of improving the reactivity, an oxazoline group-containing compound is preferable, an oxazoline ring-containing polymer is more preferable, and these compounds and polymers preferably have water solubility.

  The oxazoline ring-containing polymer contains an addition-polymerizable oxazoline as an essential component, and can be easily prepared by polymerizing a monomer component containing a monomer copolymerizable with the addition-polymerizable oxazoline as necessary. Can do.

  Examples of the addition polymerizable oxazoline include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Examples include 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, and 2-isopropenyl-5-ethyl-2-oxazoline. It is not limited to only. These addition polymerizable oxazolines may be used alone or in combination of two or more. Among these addition-polymerizable oxazolines, 2-isopropenyl-2-oxazoline is preferable because it is easily available.

  Examples of monomers copolymerizable with the addition polymerizable oxazoline include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl (meth) acrylate. , Cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxypropyl (meth) acrylate, monoesterified product of (meth) acrylic acid and polyethylene glycol, 2-aminoethyl (meth) acrylate and its salt, caprolactone modified product of (meth) acrylic acid, (meth) acrylic -(2,2,6,6-tetramethylpiperidine, (meth) acrylic acid-1, methacrylic acid esters such as 1,2,2,6,6-pentamethylpiperidine; sodium (meth) acrylate, (meta ) (Meth) acrylates such as potassium acrylate and ammonium (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; (meth) acrylamide, N-methylol (meth) acrylamide, N- (2-hydroxyethyl) ) Unsaturated amides such as (meth) acrylamide; Vinyl esters such as vinyl acetate and vinyl propionate; Vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; α-olefins such as ethylene and propylene; Vinyl chloride, vinylidene chloride, vinyl fluoride, etc. Halogen-containing α, β-unsaturated fat Hydrocarbon compounds; styrene, alpha-methyl styrene, alpha such as sodium styrene sulfonate, beta-although such unsaturated aromatic hydrocarbon compounds, the present invention is not limited only to those exemplified. These monomers copolymerizable with the addition-polymerizable oxazoline may be used alone or in combination of two or more.

  Oxazoline group-containing compounds are easily commercially available as, for example, Nippon Shokubai Co., Ltd., trade names: Epocross WS-500, Epocross WS-700, Epocross K-2010, Epocross K-2020, Epocross K-2030, etc. can do. Among these, from the viewpoint of improving reactivity, water-soluble oxazoline group-containing compounds such as Nippon Shokubai Co., Ltd., trade names: Epocross WS-500 and Epocross WS-700 are preferable.

  The isocyanate group-containing compound is a compound containing an isocyanate group that can react with a hydroxyl group that the hydroxyl group-containing monomer used as the monomer component has as a functional group.

  Examples of the isocyanate group-containing compound include water-dispersed (block) polyisocyanate. In addition, (block) polyisocyanate means polyisocyanate and / or block polyisocyanate.

  Examples of the water-dispersed polyisocyanate include those obtained by dispersing polyisocyanate imparted with hydrophilicity (water wettability) with a polyethylene oxide chain in water with an anionic dispersant or a nonionic dispersant.

  Examples of the polyisocyanate include diisocyanates such as hexamethylene diisocyanate and isophorone diisocyanate; and polyisocyanate derivatives (modified products) of these diisocyanates such as trimethylolpropane adduct, burette, and isocyanurate. The present invention is not limited to such examples. These polyisocyanates may be used alone or in combination of two or more.

  Water-dispersed polyisocyanates are, for example, Nippon Polyurethane Industry Co., Ltd., trade names: Aquanate 100, Aquanate 110, Aquanate 200, Aquanate 210, etc .; Sumika Bayer Urethane Co., Ltd., trade name: Bihijoule TPLS-2032, SUB-isocyanate L801, etc .; manufactured by Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WD-720, Takenate WD-725, Takenate WD-220, etc .; It can be easily obtained commercially as D-56 or the like.

  The water-dispersed block polyisocyanate is obtained by blocking the isocyanate group of the water-dispersed polyisocyanate with a blocking agent. Examples of the blocking agent include diethyl malonate, ethyl acetoacetate, ε-caprolactam, butanone oxime, cyclohexanone oxime, 1,2,4-triazole, dimethyl-1,2,4-triazole, and 3,5-dimethylpyrazole. , Imidazole and the like can be mentioned, but the present invention is not limited to such examples. These blocking agents may be used alone or in combination of two or more. Among these blocking agents, those that cleave at a temperature of 160 ° C. or lower, preferably 150 ° C. or lower are desirable. Suitable blocking agents include, for example, butanone oxime, cyclohexanone oxime, 3,5-dimethylpyrazole and the like. Of these, butanone oxime is more preferred.

  The water-dispersed block polyisocyanate is, for example, manufactured by Mitsui Takeda Chemical Co., Ltd., trade names: Takenate WB-720, Takenate WB-730, Takenate WB-920, etc .; manufactured by Sumika Bayer Urethane Co., Ltd. BL116, Bihijoule BL5140, Bihijoule BL5235, Bihijoule TPLS2186, Death Module VPLS2310, etc. can be easily obtained commercially.

  The functional groups of the polymer contained in the emulsion particles (functional group for the oxazoline group-containing compound: carboxyl group, functional group for the isocyanate group-containing compound: hydroxyl group) and crosslinking agents such as oxazoline group-containing compounds and isocyanate group-containing compounds Equivalent ratio [functional group of polymer (II) / functional group of cross-linking agent] with functional group (functional group of oxazoline group-containing compound: oxazoline group, functional group of isocyanate group-containing compound: isocyanate group) is usually preferably Is 0.1 to 2.5, more preferably 0.2 to 2, and still more preferably 0.3 to 1.8.

  The aminoplast resin is an addition condensate of a compound having an amino group such as melamine or guanamine with formaldehyde, and is also called an amino resin.

  Examples of aminoplast resins include dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, hexamethylol melamine, fully alkyl methylated melamine, fully alkyl butylated melamine, fully alkyl isobutylated melamine, completely Melamine resins such as alkyl mixed etherified melamine, methylol group methylated melamine, imino group methylated melamine, methylol group mixed etherified melamine, imino group mixed etherified melamine; butylated benzoguanamine, methyl / ethyl mixed alkyl Benzoguanamine, methyl / butyl mixed alkylated benzoguanamine, guanamine resins such as butylated glycoluril, and the like, but the present invention is limited only to such examples. Not to. These aminoplast resins may be used alone or in combination of two or more.

  Aminoplast resin is, for example, manufactured by Mitsui Cytec Co., Ltd., trade names: My Coat 506, My Coat 1128, Cymel 232, Cymel 235, Cymel 254, Cymel 303, Cymel 325, Cymel 370, Cymel 771, Cymel 1170, etc. It can be easily obtained commercially.

  The amount of aminoplast resin is usually such that the mass ratio of the solid content of the polymer contained in the emulsion particles to the solid content of the aminoplast resin (solid content of polymer / solid content of aminoplast resin) is 60/40. It is preferable to adjust so that it may be set to -99/1.

  In the present invention, in addition to the above-described crosslinking agent, for example, a polyfunctional hydrazine compound, a carbodiimide compound; a crosslinking agent such as a polyvalent metal compound represented by a zirconium compound, a zinc compound, a titanium compound, an aluminum compound, or the like. It can be used as long as the object of the present invention is not inhibited.

  The hydrophilic treatment agent and paint resin composition of the present invention can contain a pigment as necessary. Examples of the pigment include organic pigments and inorganic pigments, and these may be used alone or in combination of two or more.

  Examples of organic pigments include azo pigments such as benzidine and hansa yellow, azomethine pigments, methine pigments, anthraquinone pigments, phthalocyanine pigments such as phthalocyanine blue, perinone pigments, perylene pigments, diketopyrrolopyrrole pigments, thioindigo pigments, and iminoisoindoline. Pigments, iminoisoindolinone pigments, quinacridone pigments such as quinacridone red and quinacridone violet, flavantron pigments, indanthrone pigments, anthrapyrimidine pigments, carbazole pigments, monoarylide yellow, diaryride yellow, benzimidazolone yellow, tolyl orange , Naphthol orange, quinophthalone pigment, and the like, but the present invention is not limited to such examples. These organic pigments may be used alone or in combination of two or more.

  Examples of inorganic pigments include titanium dioxide, antimony trioxide, zinc white, lithopone, lead white, red iron oxide, black iron oxide, iron oxide, chromium oxide green, carbon black, yellow lead, molybdenum red, ferrocyanide Pigment with flat shape such as ferric (Prussian blue), ultramarine, lead chromate, mica, clay, aluminum powder, talc, aluminum silicate, calcium carbonate, magnesium hydroxide, aluminum hydroxide And extender pigments such as barium sulfate and magnesium carbonate, but the present invention is not limited to such examples. These inorganic pigments may be used alone or in combination of two or more.

  From the viewpoint of improving water resistance, the lower limit of the amount of pigment per 100 parts by mass of the nonvolatile content of the resin emulsion is preferably 10 parts by mass or more, more preferably 25 parts by mass or more, and the upper limit is water resistance. From the viewpoint of improving the amount, it is preferably 100 parts by mass or less.

  The hydrophilic treatment agent and the coating resin composition of the present invention are, for example, an ultraviolet absorber, an ultraviolet stabilizer, a filler, a leveling agent, a dispersant, a thickener, within a range that does not impair the object of the present invention. Additives such as wetting agents, plasticizers, stabilizers, dyes and antioxidants may be contained in appropriate amounts.

  The hydrophilic treatment agent and paint resin composition of the present invention may contain a polymer other than the above polymer as long as the object of the present invention is not impaired. In addition, the resin composition for paints of the present invention may contain other resin emulsions other than the resin emulsions within the range in which the object of the present invention is not hindered. May be adjusted so that the average particle diameter of the whole emulsion particles contained in is within the above range.

  The hydrophilic treatment agent of the present invention can be applied to a substrate as it is. When the hydrophilic treatment agent of the present invention is applied to a substrate, the hydrophilic treatment agent may be applied in one layer, or may be applied in two or more layers. When two or more layers are overcoated, only a part of the layers may be formed by the hydrophilic treatment agent of the present invention, or all the layers may be formed by the hydrophilic treatment agent of the present invention.

  The coating resin composition of the present invention may be applied alone as a single layer, or may be applied by recoating two or more layers. When the coating is performed by recoating two or more layers, only some of the layers may be formed by the coating resin composition of the present invention, and all the layers are formed by the coating resin composition of the present invention. May be. For overcoating, for example, a first layer (for example, undercoat layer) coating is applied to an object that has been subjected to primer treatment or sealer treatment, and then dried, and then for the second layer (for example, topcoat layer). Although the method of overcoating and drying a paint is mentioned, this invention is not limited by this method.

  When applying the hydrophilic treatment agent or paint resin composition of the present invention, for example, spray, roller, brush, iron or the like can be used.

  The hydrophilic treatment agent and coating resin composition of the present invention can be suitably used for the surface finishing of a substrate made of a material such as metal, glass, concrete, or resin. Examples of applications in which the base material is used include automobiles, inorganic building materials that constitute the exterior of buildings, civil engineering structures, ceramic building materials, and the like, but the present invention is limited to such examples only. is not. As an inorganic building material which comprises the exterior of a building, a flexible board, a calcium silicate board, a gypsum slag perlite board, a piece of wood cement board, a precast concrete board, an ALC board, a gypsum board etc. are mentioned, for example. A top coating material (water-based paint) is usually applied to the surface of such building materials in order to impart a desired design. The hydrophilic treatment agent and coating resin composition of the present invention can be suitably used for this top coating material (aqueous coating). Examples of ceramic building materials include tiles and outer wall materials. Ceramic building materials are obtained by adding inorganic fillers, fibrous materials, etc. to hydraulic glue that is the raw material of inorganic hardened bodies, molding the resulting mixture, curing the resulting molded body, and curing it. can get.

  According to the present invention, the film made of the hydrophilic treatment agent or paint resin composition of the present invention is formed on the surface of the substrate, whereby the film made of the hydrophilic treatment agent or paint resin composition is surfaced. A hydrophilic substrate formed thereon is obtained. The thickness of the formed coating after drying is not particularly limited, and may be appropriately set depending on the application, but is usually about 1 to 1000 μm. As described above, this hydrophilic substrate can be suitably used for various applications such as automobiles, buildings, civil engineering structures, and ceramics-based inorganic building materials.

  EXAMPLES Next, although this invention is demonstrated further in detail based on an Example, this invention is not limited only to this Example. In the following Examples, “part” means “part by mass” and “%” means “mass%” unless otherwise specified.

Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria soap SR-10], 180 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, methyl A pre-emulsion for dripping consisting of 610 parts of methacrylate, 100 parts of glycerol monomethacrylate and 10 parts of acrylic acid is prepared, of which 85 parts, which is 6% of the total amount of all polymerizable monomer components, are added to the flask and gently nitrogen is added. The temperature was raised to 80 ° C. while blowing gas, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekari Soap SR-10], 150 parts of methyl methacrylate, 350 parts of cyclohexyl methacrylate, 200 of n-butyl methacrylate Part, 2-ethylhexyl acrylate 90 parts, n-butyl acrylate 100 parts, glycerin monomethacrylate 100 parts and acrylic acid 10 parts, a pre-emulsion for dropping is prepared, which corresponds to 6% of the total amount of all polymerizable monomer components 85 parts were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 3
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 70 parts of methyl methacrylate, 350 parts of cyclohexyl methacrylate, 200 of n-butyl methacrylate Parts, 2-ethylhexyl acrylate 70 parts, n-butyl acrylate 100 parts, glycerin monomethacrylate 200 parts and acrylic acid 10 parts, a pre-emulsion for dropping is prepared, which corresponds to 6% of the total amount of all polymerizable monomer components 85 parts were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 4
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: ADEKA rear soap SR-10], 600 parts of cyclohexyl methacrylate, 80 parts of n-butyl methacrylate, 2-ethylhexyl A pre-emulsion for dripping consisting of 110 parts of acrylate, 100 parts of n-butyl acrylate, 100 parts of glycerin monomethacrylate and 10 parts of acrylic acid is prepared, of which 85 parts corresponding to 6% of the total amount of all polymerizable monomer components are contained in the flask. The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 5
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: ADEKA rear soap SR-10], 350 parts of cyclohexyl methacrylate, 200 parts of n-butyl methacrylate, 2-ethylhexyl A pre-emulsion for dropping comprising 330 parts of acrylate, 100 parts of glycerin monomethacrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid and 10 parts of γ-methacryloxypropyltrimethoxysilane was prepared, of which the total amount of all polymerizable monomer components Was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle diameter of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 0 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 6
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a lower funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 95 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl methacrylate, A pre-emulsion for first stage dropping consisting of 150 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate and 5 parts of acrylic acid was prepared, and 85 parts corresponding to 6% of the total amount of all polymerizable monomer components were added to the flask. The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Soap SR-10], n-butyl acrylate 100 parts, 95 parts of n-butyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of glyceryl monomethacrylate and 5 parts of acrylic acid, a pre-emulsion of the second stage, 21.5 parts of an aqueous 3.5% ammonium persulfate solution and 2.5% 20 parts of an aqueous sodium hydrogen sulfite solution was uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 7
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In the lower funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 95 parts of 2-ethylhexyl acrylate, 110 parts of n-butyl methacrylate, A pre-emulsion for first stage dropping consisting of 135 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate and 10 parts of acrylic acid is prepared, and 85 parts corresponding to 6% of the total amount of all polymerizable monomer components are added to the flask, The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Soap SR-10], n-butyl acrylate A second pre-emulsion comprising 100 parts, n-butyl methacrylate 80 parts, cyclohexyl methacrylate 200 parts, glycerin monomethacrylate 100 parts and 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 20 parts 21.5 parts of a 3.5% aqueous solution of ammonium persulfate and 20 parts of a 2.5% aqueous solution of sodium hydrogen sulfite were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 8
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a lower funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 95 parts of 2-ethylhexyl acrylate, 95 parts of n-butyl methacrylate, A pre-emulsion for first-stage dripping consisting of 145 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 5 parts of acrylic acid and 10 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole was prepared. Of these, 85 parts corresponding to 6% of the total amount of the polymerizable monomer components were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added. The polymerization was started. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Soap SR-10], n-butyl acrylate 100 parts, 85 parts of n-butyl methacrylate, 200 parts of cyclohexyl methacrylate, 100 parts of glycerol monomethacrylate, 5 parts of acrylic acid and 10 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole The second stage pre-emulsion, 21.5 parts of 3.5% ammonium persulfate aqueous solution and 20 parts of 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 9
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a lower funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 95 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl methacrylate, A pre-emulsion for first-stage dropping comprising 135 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, 10 parts of acrylic acid and 10 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole was prepared. Of these, 85 parts corresponding to 6% of the total amount of the polymerizable monomer components were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added. The polymerization was started. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adeka Soap SR-10], n-butyl acrylate 110 parts, n-butyl methacrylate 60 parts, cyclohexyl methacrylate 200 parts, glycerol monomethacrylate 100 parts, 4-methacryloyloxy-1,2,2,6,6-pentamethylpiperidine 20 parts and 2- [2′-hydroxy- 5′-methacryloyloxymethylphenyl] -2H-benzotriazole, a second stage pre-emulsion, 21.5 parts of 3.5% aqueous ammonium persulfate solution and 20 parts of 2.5% aqueous sodium hydrogen sulfite solution for 120 minutes It was dripped uniformly over the entire area.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 10
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a lower funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 50 parts of glycerin monoacrylate, 150 parts of methyl methacrylate, 150 cyclohexyl methacrylate Part, n-butyl methacrylate 55 parts, 2-ethylhexyl acrylate 90 parts and acrylic acid 5 parts pre-emulsion for the first drop is prepared, of which 85 parts corresponding to 6% of the total amount of all polymerizable monomer components The mixture was added to the flask, heated to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Soap SR-10), 50 of glycerin monoacrylate Part, 200 parts of cyclohexyl methacrylate, 210 parts of n-butyl methacrylate, 35 parts of n-butyl acrylate and 5 parts of acrylic acid, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 2.5% 20 parts of an aqueous sodium hydrogen sulfite solution was uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh metal-mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle diameter of the emulsion particles was 150 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 11
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, Inc., trade name: ADEKA rear soap SR-10], 300 parts of glycerol monomethacrylate, 600 parts of cyclohexyl methacrylate, 2-ethylhexyl acrylate A pre-emulsion for dropping consisting of 80 parts, 10 parts acrylic acid and 10 parts γ-methacryloxypropyltrimethoxysilane was prepared, and 85 parts corresponding to 6% of the total amount of all polymerizable monomer components were added to the flask. The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 150 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 55 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Example 12
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: ADEKA rear soap SR-10], 200 parts of glycerol monomethacrylate, 70 parts of methyl methacrylate, 350 parts of cyclohexyl methacrylate , 200 parts of n-butyl methacrylate, 70 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, and 10 parts of acrylic acid were prepared, which corresponds to 6% of the total amount of all polymerizable monomer components. 85 parts were added into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% ammonium persulfate aqueous solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, 25 parts of an oxazoline polymer [manufactured by Nippon Shokubai Co., Ltd., trade name: Epocross (registered trademark) WS-700] was added, and 300 mesh (JIS mesh, the same applies hereinafter) A resin emulsion was prepared by filtering through a wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C.

Example 13
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 100 parts of glycerol monomethacrylate, 350 parts of cyclohexyl methacrylate, n-butyl methacrylate 200 parts, 330 parts of 2-ethylhexyl acrylate, 5 parts of acrylic acid, 5 parts of methacrylic acid and 10 parts of γ-methacryloxypropyltrimethoxysilane are prepared, and the total amount of all polymerizable monomer components is prepared. Was added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous ammonium persulfate solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction solution to room temperature, 100 parts of polyvinylpyrrolidone polymer [manufactured by Nippon Shokubai Co., Ltd., product number: K30] is added, and filtered through a wire mesh of 300 mesh (JIS mesh, the same shall apply hereinafter), A resin emulsion was prepared. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle diameter of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 0 ° C.

Example 14
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a full funnel, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, Inc., trade name: ADEKA rear soap SR-10], 150 parts of methyl methacrylate, 150 parts of cyclohexyl methacrylate, n-butyl methacrylate 100 parts, 95 parts of 2-ethylhexyl acrylate and 5 parts of acrylic acid are prepared as a first drop pre-emulsion, of which 85 parts corresponding to 6% of the total amount of all polymerizable monomer components are added to the flask, The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 20 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 120 minutes.

  After completion of dropping, the mixture is maintained at 80 ° C. for 60 minutes. Subsequently, 145 parts of deionized water, 60 parts of a 25% aqueous solution of an emulsifier (manufactured by ADEKA, trade name: Adeka Soap SR-10), 100 of glycerol monomethacrylate Part, 200 parts of cyclohexyl methacrylate, 95 parts of n-butyl methacrylate, 100 parts of n-butyl acrylate and 5 parts of acrylic acid, 21.5 parts of a 3.5% aqueous ammonium persulfate solution and 2.5% 20 parts of an aqueous sodium hydrogen sulfite solution was uniformly added dropwise over 120 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, 50 parts of polyethylene glycol [manufactured by ADEKA, trade name: PEG6000] was added, and the mixture was filtered through a 300-mesh wire mesh to prepare a resin emulsion. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C.

Example 15
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria Soap SR-10], 100 parts of glycerol monomethacrylate, 600 parts of cyclohexyl methacrylate, n-butyl methacrylate A pre-emulsion for dropping composed of 80 parts, 110 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate and 10 parts of acrylic acid was prepared, and 85 parts corresponding to 6% of the total amount of all polymerizable monomer components were contained in the flask. The temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the resulting reaction solution to room temperature, 50 parts of a polycarboxylic acid polymer [manufactured by Nippon Shokubai Co., Ltd., product number: DL-40S] is added and filtered through a 300 mesh (JIS mesh, the same applies hereinafter) wire mesh. Thus, a resin emulsion was prepared. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C.

Example 16
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekari Soap SR-10], 600 parts of glycerol monomethacrylate, 310 parts of methyl methacrylate, 30 parts of acrylic acid , 30 parts of γ-methacryloxypropyltrimethoxysilane and 30 parts of 2- [2′-hydroxy-5′-methacryloyloxyethylphenyl] -2H-benzotriazole. 85 parts corresponding to 6% of the total amount of the monomer components were added to the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, 50 parts of an oxazoline polymer [manufactured by Nippon Shokubai Co., Ltd., trade name: Epocross (registered trademark) WS-700] was added, and 300 mesh (JIS mesh, the same applies hereinafter) A resin emulsion was prepared by filtering through a wire mesh. The non-volatile content in the obtained resin emulsion was 30% by mass, the average particle size of the emulsion particles was 130 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 71 ° C.

Comparative Example 1
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: ADEKA rear soap SR-10], 200 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, methyl A pre-emulsion for dropping consisting of 690 parts of methacrylate and 10 parts of acrylic acid was prepared, of which 85 parts corresponding to 6% of the total amount of all polymerizable monomer components were added into the flask, and 80 ° C. while gently blowing nitrogen gas. Then, 43 parts of a 3.5% aqueous ammonium persulfate solution was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Comparative Example 2
In a flask equipped with a dropping funnel, a stirrer, a nitrogen gas inlet tube, a thermometer, and a reflux condenser, 1040 parts of deionized water was charged. In a dropping funnel, 290 parts of deionized water, 120 parts of a 25% aqueous solution of an emulsifier [manufactured by ADEKA, trade name: Adekaria soap SR-10], 180 parts of 2-ethylhexyl acrylate, 100 parts of n-butyl acrylate, methyl A pre-emulsion for dripping consisting of 610 parts of methacrylate, 100 parts of 2-hydroxyethyl methacrylate and 10 parts of acrylic acid is prepared, of which 85 parts corresponding to 6% of the total amount of all polymerizable monomer components are added into the flask and gently The temperature was raised to 80 ° C. while blowing nitrogen gas, and 43 parts of a 3.5% aqueous solution of ammonium persulfate was added to initiate polymerization. Next, the remainder of the dropping pre-emulsion, 43 parts of a 3.5% aqueous ammonium persulfate solution and 40 parts of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 240 minutes.

  After completion of the dropwise addition, the temperature was maintained at 80 ° C. for 60 minutes, and the pH was adjusted to 9 by adding 25% aqueous ammonia to complete the polymerization. After cooling the obtained reaction liquid to room temperature, the resin emulsion was prepared by filtering with a 300 mesh (JIS mesh, the same hereafter) wire mesh. The non-volatile content in the obtained resin emulsion was 40% by mass, the average particle size of the emulsion particles was 170 nm, and the glass transition temperature of the entire polymer constituting the emulsion particles was 30 ° C. This resin emulsion was used as a hydrophilic treatment agent and a resin composition for paints.

Experimental example 1
In order to be able to accurately evaluate hydrophilicity (water wettability) and water resistance with respect to 100 parts of the hydrophilization treatment agent obtained in each example or each comparative example, Add 10 parts of a mixed solution obtained by mixing 2,4-trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] and butyl cellosolve in equal mass. Test samples were prepared by curing at room temperature for 1 day.

(1) Application to acrylic resin plate or metal plate Black acrylic resin plate obtained by molding the test sample obtained above by extrusion molding methyl methacrylate according to JIS K6717 (2006) [Japan Test Panel Co., Ltd., length: 75 mm, width: 150 mm, thickness: 3 mm] or an aluminum plate as a metal plate [manufactured by Japan Test Panel Co., Ltd., product number: A1050P (length: 75 mm, width: 150 mm, thickness: 0.3 mm)] with a 5 mil applicator and dried with a hot air dryer at 100 ° C. for 10 minutes to prepare a test plate on which a film (thickness of the film: about 40 μm) was formed.

(2) Application to slate plate Dispersant [Kao Co., Ltd., trade name: Demol EP] 60 parts, Dispersant [Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N-14] 50 parts, Wetting agent [manufactured by Kao Corporation, trade name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, 210 parts of deionized water, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts, A white paste was prepared by dispersing 10 parts of a foam suppressor [manufactured by San Nopco, trade name: Nopco 8034L] and 500 parts of glass beads (diameter: 1 mm) with a homodisper at a rotational speed of 3000 min ^{-1 for} 60 minutes. did.

  Next, 300 parts of an acrylic resin emulsion [made by Nippon Shokubai Co., Ltd., trade name: Acryset EX-41], 135 parts of the white paste obtained above, film forming aid (15 parts of butyl cellosolve, 2, 2, 4 -Trimethyl-1,3-pentanediol monoisobutyrate [manufactured by Chisso Corporation, product number: CS-12] 15 parts], black paste [manufactured by Yokohama Kasei Co., Ltd., trade name: Unilant 88] and 10 parts A base coat paint was prepared by mixing 1.5 parts of a foaming agent (manufactured by San Nopco Co., Ltd., trade name: Nopco 8034L).

In accordance with JIS A5430 (2004), a slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm], solvent-based sealer [manufactured by SK Kaken Co., Ltd., trade name: EX Sealer] was applied by air spray so that the dry weight was 20 g / m ² , dried at 23 ° C. for 24 hours, and then the base coat paint obtained above was applied with a 5 mil applicator, and 100 ° C. The substrate was prepared by drying with a hot air dryer for 10 minutes.

  A test plate on which a film (film thickness: about 40 μm) was formed by applying a test sample to the substrate obtained above with a 5 mil applicator and drying it with a hot air dryer at 100 ° C. for 10 minutes was produced. did.

  The following physical properties were examined using each test plate obtained above. The results are also shown in Table 1. In addition, a thing with one evaluation of "x" in a physical property is determined to be disqualified.

[Hydrophilicity (water wettability)]
The test plate was sprayed with a shower for 10 seconds, and when 10 seconds passed, the state of the coating surface of the test plate was evaluated based on the following evaluation criteria.
[Evaluation criteria]
A: The entire surface of the coating is completely wet with water.
○: Almost the entire surface of the coating is wet with water.
Δ: A part of the film repels water.
X: The entire surface of the coating repels water.

〔water resistant〕
The L value (L ₀ ) of the test plate was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name: spectroscopic color difference meter SE-2000), and this test plate was further heated to 60 ° C. After being immersed for 240 hours, it was lifted from warm water, wiped with Kim Towel (manufactured by Nippon Paper Crecia Co., Ltd.), and the L value (L ₁ ) was measured with the color difference meter within 1 minute.

Next, the change value of the L value is expressed by the formula:
ΔL = (L ₁ ) − (L ₀ )
And evaluated based on the following evaluation criteria.
[Evaluation criteria]
◎: ΔL is less than 5 ○: ΔL is 5 or more and less than 7 Δ: ΔL is 7 or more and less than 10 ×: ΔL is 10 or more

Experimental example 2
Dispersant [Kao Co., Ltd., trade name: Demol EP] 60 parts, Dispersant [Daiichi Kogyo Seiyaku Co., Ltd., trade name: DISCOAT N-14] 50 parts, Wetting agent [Kao Co., Ltd. , Trade name: Emulgen LS-106] 10 parts, propylene glycol 60 parts, deionized water 210 parts, titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., product number: CR-95] 1000 parts, foam suppressor [San Nopco Corporation] Manufactured, trade name: Nopco 8034L] and 500 parts of glass beads (diameter: 1 mm) were dispersed with a homodisper at a rotational speed of 3000 min ^{-1 for} 60 minutes to prepare a white paste.

  Next, 300 parts of the resin emulsion obtained in each example or each comparative example, 135 parts of the white paste obtained above, film forming aid (15 parts of butyl cellosolve, 2,2,4-trimethyl-1,3- Pentanediol monoisobutyrate [manufactured by Chisso Co., Ltd., product number: CS-12] 15 parts], black paste [manufactured by Yokohama Kasei Co., Ltd., trade name: Unirant 88] and foam suppressor [San Nopco Co., Ltd.] Manufactured, trade name: Nopco 8034L] by mixing 1.5 parts, a test paint was prepared.

In accordance with JIS A5430 (2004), a slate plate [manufactured by Nippon Test Panel Co., Ltd., length: 70 mm, width: 150 mm, thickness: 6 mm], solvent-based sealer [manufactured by SK Kaken Co., Ltd., trade name: EX Sealer] was applied by air spray so that the dry weight was 20 g / m ² , dried at 23 ° C. for 24 hours, and then the test paint obtained above was applied with a 5 mil applicator, at room temperature. A test plate on which a film (thickness of the film: about 40 μm) was formed by drying for 1 week was produced.

  The hydrophilicity (water wettability) and water resistance were evaluated in the same manner as in Experimental Example 1 using the test plate obtained above. The results are also shown in Table 1.

〔Comprehensive evaluation〕
In each evaluation, ◎ was 4 points, ○ was 2 points, Δ was 0 points, and × was -4 points, and the total score was obtained by totaling the scores of each evaluation. The results are also shown in Table 1.

  From the results shown in Experimental Example 1 of Table 1, the hydrophilic treatment agent and the resin composition for paint obtained in each example were excellent in hydrophilicity with respect to the resin plate, metal plate and slate plate. It can be seen that (water wettability) and water resistance are imparted. Furthermore, from the results shown in Experimental Example 2 of Table 1, the base coat paints prepared using the paint resin compositions obtained in the respective examples all have excellent hydrophilicity with respect to the slate plate. It can be seen that (water wettability) and water resistance are imparted.

  The hydrophilic treatment agent and coating resin composition of the present invention can be suitably used, for example, for surface finishing of a base material made of a material such as metal, glass, concrete, or resin. Moreover, the hydrophilic base material on which the coating film formed of the hydrophilic treatment agent and the resin composition for paints of the present invention is formed is used for applications such as automobiles, buildings, civil engineering structures, ceramics-based inorganic building materials, and the like. It can be used suitably.

Claims (7)

A hydrophilic treatment agent for imparting hydrophilicity to a substrate, comprising 2 to 30% by weight of a polymerizable double bond-containing monomer having two or more hydroxyl groups and a molecular weight of 500 or less and the polymerization And emulsion particles containing a polymer obtained by emulsion polymerization of a monomer component containing 70 to 97% by mass of a copolymerizable monomer having a copolymerizable property with a polymerizable double bond-containing monomer, The polymerizable monomer contains (meth) acrylic acid cycloalkyl ester and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester portion at a total content of 50 to 100% by mass ( Mass ratio of (meth) acrylic acid cycloalkyl ester and (meth) acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms in the ester moiety [(meth) acrylic acid cycloalkyl ester / C1-1 Hydrophilization treatment agent characterized in that having an alkyl group in ester moiety (meth) acrylic acid alkyl ester] is 15 / 85-90 / 10. A polymerizable double bond-containing monomer having two or more hydroxyl groups and a molecular weight of 500 or less is a (meth) acrylic acid ester having two or more hydroxyl groups in the ester portion and a molecular weight of 500 or less. The hydrophilic treatment agent according to claim 1 . A (meth) acrylic acid ester having two or more hydroxyl groups in the ester portion and a molecular weight of 500 or less is represented by the formula (II):
(Wherein R ¹ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkylene group having 1 to 4 carbon atoms)
The hydrophilizing agent according to claim 2 , which is a (meth) acrylic acid ester represented by: The hydrophilicity treating agent according to any one of claims 1 to 3 , wherein the polymer constituting the emulsion particles has a glass transition temperature of -30 to 80 ° C. The hydrophilic base material by which the film which consists of a hydrophilic treatment agent in any one of Claims 1-4 is formed on the surface. The resin composition for coating materials containing the hydrophilic treatment agent in any one of Claims 1-4 . The hydrophilic base material by which the film which consists of the resin composition for coating materials of Claim 6 is formed on the surface.