KR20130072254A - Acryl-fluorine composite polymer particles - Google Patents

Abstract

Provided are acrylic-fluorine composite polymer particles and water-based coating compositions using the particles, which can ensure water resistance even by a forced drying method, and can reduce the amount of fluorine resin while maintaining weather resistance and chemical resistance. (A) Vinylidene fluoride system containing at least one fluoroolefin unit and vinylidene fluoride unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units (B) compatible with the polymer, (B) the vinylidene fluoride polymer (A), (meth) acrylic acid ester unit (b1), the incompatible (meth) acrylic acid ester unit (b2), and It is an acryl-fluorine composite polymer particle containing the crosslinkable acrylic polymer (B) containing the (meth) acrylic-type monomer unit (b3) which has a crosslinkable group which can be bridge | crosslinked by heating, and a vinylidene fluoride-type polymer (A) / crosslinkable Acrylic-fluorine composite polymer particles whose acrylic polymer (B) is 10/90 to 90/10 by mass ratio.

Description

ACRYL-FLUORINE COMPOSITE POLYMER PARTICLES

This invention relates to the novel fluorine-containing copolymer particle suitable for the binder of the coating composition for coatings of various base materials, the aqueous dispersion containing the said fluorine-containing copolymer particle, and the aqueous coating composition containing the said aqueous dispersion. will be.

As the coating composition for coating, in addition to the organic solvent-based paint, an aqueous coating which uses water as a dispersion medium in consideration of the natural environment and improvement of the painting work environment is known. In addition, in terms of the coating of building materials, especially roofing materials and exterior walls, it is required to have excellent weather resistance, and in particular, an aqueous coating composition having a fluororesin as a binder having excellent weather resistance, water resistance, chemical resistance, film forming properties, and the like is developed. have.

However, since the fluorine resin is inherently inferior in adhesion with other materials, various improvements have been made in adhesion with the substrate. For example, in patent document 1, when seed-polymerizing the vinylidene fluoride (VDF) system fluororesin in the presence of a seed particle, the monomer mixture containing a (meth) acrylic acid ester and an ethylenically unsaturated monomer is carried out in a monomer mixture, By containing 0.5-45 mass% of monomers which have a cyclohexyl group, and making a monomer mixture 50 mass% or less with respect to a fluororesin, it is described that the obtained fluorine-containing polymer aqueous dispersion liquid provides the coating film excellent in adhesiveness. .

Japanese Patent Application Laid-Open No. 08-259773

Since an aqueous coating composition requires time for drying compared with a solvent-based coating composition, it is forcibly dried. Forced drying is generally performed for 3 seconds to 10 minutes at 60-200 degreeC (temperature of a base material), As a result, since the film formation becomes inadequate depending on resin composition, the strength of a coating film falls and water resistance is It may fall and the interface adhesion with a base material may be damaged.

Moreover, although the viewpoint which reduces the ratio of a fluororesin is also performed from another viewpoint, especially the viewpoint of reducing an expensive fluororesin, there exists a limit in order to exhibit the characteristic of a fluororesin, and the ratio of a fluororesin at least 50 mass% or more is practical. The phase needed to be 60-70 mass%.

From these viewpoints, the fluorine-containing polymer aqueous dispersion liquid of patent document 1 has room for improvement in the adhesive fall by forced drying, and it is necessary to also increase the ratio of acrylic resin.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve such a subject, the inventors studied the composition of the crosslinkable acrylic polymer which comprises a particle | grain in the acryl-fluorine composite polymer particle of a fluorine-containing polymer and an acryl-type monomer, and ensures water resistance also by the forced drying method. Furthermore, it was found out that the amount of fluorine resin can be reduced while maintaining weather resistance and chemical resistance, and completed the present invention.

That is,

(A) Vinylidene fluoride system containing at least one fluoroolefin unit and vinylidene fluoride unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units Polymers,

(B) Compatibility with the vinylidene fluoride polymer (A) (in) (meth) acrylic acid ester unit (b1), incompatible with the vinylidene fluoride polymer (A), and heating It is an acryl-fluorine composite polymer particle containing the crosslinkable acrylic polymer (B) containing the (meth) acrylic-type monomer unit (b3) which has a crosslinkable crosslinkable group, and a vinylidene fluoride polymer (A) / crosslinkable acrylic polymer ( B) relates to acrylic-fluorine composite polymer particles having a mass ratio of 10/90 to 90/10.

The present invention also relates to an aqueous dispersion containing the acrylic-fluorine composite polymer particles of the present invention, and further to an aqueous coating composition containing the aqueous dispersion.

According to the present invention, it is possible to provide acryl-fluorine composite polymer particles which can ensure water resistance even by a forced drying method and can reduce the amount of fluorine resin while maintaining weather resistance and chemical resistance.

Acrylic-fluorine composite polymer particles of the present invention,

(A) at least one fluoroolefin unit and vinyl fluoride selected from the group consisting of tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) units and chlorotrifluoroethylene (CTFE) units as structural units; A VDF-based polymer comprising a lidene (VDF) unit,

(B) Compatibility with the said VDF-type polymer (A) (meth) acrylic acid ester unit (b1), Incompatible with the said VDF-type polymer (A) (meth) acrylic acid ester unit (b2), and a crosslinkable group which can be bridge | crosslinked by heating. Acrylic fluorine composite polymer particles comprising a crosslinkable acrylic polymer (B) containing a (meth) acrylic monomer unit (b3) having a VDF-based polymer (A) / crosslinkable acrylic polymer (B) in a mass ratio of 10 / 90 to 90/10 acrylic-fluorine composite polymer particles.

The VDF-based polymer (A) and the crosslinkable acrylic polymer (B) are present in a single particle. The VDF polymer (A) and the crosslinkable acrylic polymer (B) may or may not be bonded chemically. The mass ratio of the VDF polymer (A) and the crosslinkable acrylic polymer (B) is the mass ratio of single particles of the VDF polymer (A) and the crosslinkable acrylic polymer (B) constituting the single particles.

Each component will be described below.

As the VDF polymer (A) in the present invention, a structural unit other than VDF is selected from the group consisting of tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) units, and chlorotrifluoroethylene (CTFE) units. At least one fluoroolefin unit selected. As the VDF-based polymer (A) in the present invention, it is preferable to include a tetrafluoroethylene unit and a chlorotrifluoroethylene unit.

Particularly preferred VDF polymers as the VDF polymer (A) include VDF / TFE copolymers, VDF / TFE / CTFE copolymers, VDF / HFP copolymers, VDF / TFE / HFP copolymers, VDF / CTFE copolymers, and the like. Can be.

In summary, the structural unit derived from the other fluoroolefin and the non-fluorine-type monomer copolymerizable with a fluoroolefin may be included.

Other fluoroolefins include, for example, perfluoro (alkyl vinyl ethers), perfluoro

≪ Formula 1 >

Perfluoroolefins, such as these; Vinyl fluoride, trifluoroethylene, trifluoropropylene, pentafluoropropylene, tetrafluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoropropene, 1,3,3,3 And non-perfluoro olefins such as tetrafluoropropene and 1,1,3,3,3-pentafluoropropene. As perfluoro (alkyl vinyl ether), perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), etc. are mentioned.

Moreover, a functional group containing fluoroolefin can also be used. As a functional group containing fluoroolefin, For example, Formula (1):

(Wherein Y ¹ is —OH, —COOH, —SO ₂ F, —SO ₃ M ² (M ² is a hydrogen atom, an NH ₄ group or an alkali metal), a carboxylate, a carboxyester group, an epoxy group, or a cyano group; X ¹ and X ² are the same or different, or both a hydrogen atom or a fluorine atom; Rf is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms or an ether bond having 2 to 40 carbon atoms. The divalent fluorine-containing alkylene group containing m is a compound represented by 0 or 1).

As a specific example, for example

<Formula 2>

<Formula 3>

And the like.

The polymer (A) may contain the repeating unit based on an iodine containing monomer. As an iodine containing monomer, the perfluoro (6,6-dihydro-6-iodo-3-oxa) described in Unexamined-Japanese-Patent No. 5-63482 and Unexamined-Japanese-Patent No. 62-12734, for example. Iodides of perfluoro vinyl ether, such as -1-hexene) and perfluoro (5-iodo-3-oxa-1-pentene), can also be used.

The polymer (A) may contain the repeating unit based on the non-fluorine-type monomer copolymerizable with a fluoroolefin.

As for fluorine element content of a VDF-type polymer, 50-76 mass%, Furthermore, 60-70 mass% is preferable.

The manufacturing method of a VDF-type polymer (A) is not specifically limited, It can carry out by a conventionally well-known emulsion polymerization method.

The crosslinkable acrylic polymer (B) in the present invention is compatible with the VDF polymer (A) (meth) acrylic acid ester unit (b1), the VDF polymer (A) and the incompatible (meth) acrylic acid ester unit (b2). ) And a (meth) acrylic monomer unit (b3) having a crosslinkable group crosslinkable by heating.

(b1) VDF-type polymer (A) and compatibility (meth) acrylic acid ester (Hereinafter, it may be called "compatibility (meth) acrylic acid ester.).)

The compatibility (meth) acrylic acid ester (b1) enhances the compatibility of the VDF polymer (A) and the crosslinkable acrylic polymer (B), increases the unity of the acrylic-fluorine composite polymer, and is dried at room temperature. The film formation of the city is improved.

As a specific example of compatible (meth) acrylic acid ester (b1), C1-C4 linear alkyl ester, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acryl 1 type, or 2 or more types, such as a rate, a methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, can be illustrated. Among them, methyl methacrylate (MMA), ethyl methacrylate (EMA), n-butyl methacrylate (n-MBA), n-butyl acrylate (n- One kind or two or more kinds such as BA), ethyl acrylate (EA) and methyl acrylate are preferable.

As for content of compatible (meth) acrylic acid ester (b1), 10-90 mass% of crosslinkable acrylic polymer (B) is preferable, Furthermore, 20-75 mass% is preferable at the transparency of a coating film.

(b2) VDF-type polymer (A) and incompatible (meth) acrylic acid ester (Hereinafter, it may be called "incompatible (meth) acrylic acid ester.).)

Incompatible (meth) acrylic acid ester (b2) improves the film forming property of the acrylic-fluorine composite polymer during forced drying, improves the adhesion to the substrate, and improves the water resistance of the coating film.

In addition, "compatibility with a VDF-type polymer (A)" and "incompatibility with a VDF-type polymer (A)", when mixing a VDF-type polymer (A) with a monomer, the case where it is transparent is "VDF-type polymer (A) And compatibility ", and the case where it becomes cloudy at the time of mixing is called" incompatibility with VDF polymer (A). "

As a specific example of incompatible (meth) acrylic acid ester (b2), a C6-C20 linear alkyl ester, a C6-C20 alicyclic structure, or a C6-C20 aryl ester is mentioned. For example, hexyl acrylate, 2-ethylhexyl acrylate, 2-hydroxy acrylate, 2-hydroxypropyl acrylate, n-propyl acrylate, isopropyl acrylate, isobutyl acrylate, Acrylate, 2-methoxyethyl acrylate, 2-methoxyethyl acrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxymethacrylate, Propyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, lauryl methacrylate, tri Chain alkyl esters such as decyl methacrylate, stearyl methacrylate, 2-ethoxyethyl methacrylate, and 2-methoxyethyl methacrylate; Alicyclic alkyl esters such as cyclohexyl acrylate, isobornyl acrylate, cyclohexyl methacrylate and isobornyl methacrylate; 1 type, or 2 or more types of aryl ester, such as benzyl acrylate and benzyl methacrylate, can be illustrated. Especially, since the weather resistance of a coating film is favorable, the C6-C20 linear alkyl ester and / or the alkyl ester which has a C6-C20 alicyclic structure, especially 2-ethylhexyl acrylate (2-EHA) and / or cyclo Hexyl methacrylate (CHMA) is preferred.

The content of the incompatible (meth) acrylic acid ester (b2) is preferably from 5 to 85% by mass of the crosslinkable acrylic polymer (B), and more preferably from 15 to 70% by mass, in terms of good film forming properties and adhesion.

(b3) (meth) acrylic-type monomer which has a crosslinkable group which can be bridge | crosslinked by heating (Hereinafter, it may be called "crosslinkable group containing (meth) acrylic-type monomer.")

The crosslinkable group-containing (meth) acrylic monomer (b3) is an incompatible (meth) acrylic acid ester unit (b2) and a VDF polymer (A) in the acrylic polymer (B) at the time of film formation of the acrylic-fluorine composite polymer during forced drying. The adhesion to the substrate is improved while the action of suppressing the separation of the c) and the turbidity of the membrane is suppressed.

The crosslinkable group which a crosslinkable group containing (meth) acrylic-type monomer (b3) has is a functional group which can be bridge | crosslinked by heating. Therefore, crosslinkable groups, such as the nonblock type isocyanate group which bridge | crosslinks normal temperature, are not the crosslinkable group of the crosslinkable group containing (meth) acrylic-type monomer (b3) in this invention.

As a crosslinkable group which can be bridge | crosslinked by heating, an epoxy group, a carboxyl group, a hydroxyl group, an amino group, a methylolamide group, a silyl group, a carbodiimide group, an oxazoline group, a block isocyanate group, an ethylene imine group, etc. are mentioned, for example, Emulsion Epoxy group and carboxyl group are preferable at the point which the stability of is good.

As a crosslinkable group containing (meth) acrylic-type monomer which has an epoxy group, glycidyl compounds, such as glycidyl acrylate and glycidyl methacrylate (GMA), are mentioned, for example. 1 type, or 2 or more types of glycidyl acrylate and glycidyl methacrylate are preferable. When a crosslinkable group containing (meth) acrylic-type monomer contains an epoxy group, the film forming property between particle | grains at the time of coating, and adhesiveness with a base material become further more favorable.

As a crosslinkable group containing (meth) acrylic-type monomer which has a carboxyl group, For example, acrylic acid, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl hexahydrophthalic acid, methacrylic acid, 2-methacryloyloxy phthalate 1 type, or 2 or more types, such as ethyl and hexahydrophthalic acid 2-methacryloyloxyethyl, etc. are mentioned, 1 or 2 types of acrylic acid (AA) and methacrylic acid (MAA) from the point of which emulsion stability is favorable. Species or more are preferred. When a crosslinkable group containing (meth) acrylic-type monomer contains a carboxyl group, the film forming property between particle | grains at the time of coating, and adhesiveness with a base material become further more favorable.

As a crosslinkable group containing (meth) acrylic-type monomer which has a hydroxyl group, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, etc. 1 type, or 2 or more types of is mentioned.

As a crosslinkable group containing (meth) acrylic-type monomer which has an amino group, for example, aminoethyl acrylate, dimethylaminoacrylate, diethylaminoethyl acrylate, aminoethyl methacrylate, dimethylamino methacrylate, diethylaminoethyl meth 1 type (s) or 2 or more types, such as a acrylate and 2- (O- [1'-methylpropylidene amino] carboxyamino) ethyl methacrylate, are mentioned.

As a crosslinkable group containing (meth) acrylic-type monomer which has a methylolamide group, 1 type, or 2 or more types, such as methylolated acrylamide and alkoxy methyl acrylamide, are mentioned, for example.

As a crosslinkable group containing (meth) acrylic-type monomer which has a silyl group, it is, for example,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ,

CH ₂ = CHCOO (CH ₂ ) ₃ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OC ₂ H ₅ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₂ (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) COO (CH ₂ ) ₁₁ Si (CH ₃ ) (OCH ₃ ) ₂ ,

, And the like.

These crosslinkable group containing (meth) acrylic-type monomers (b3) are not limited to the kind of crosslinkable group, You may use 2 or more types together. For example, an epoxy group containing acrylic monomer and a carboxyl group containing acrylic monomer, an epoxy group containing acrylic monomer and a hydroxyl group containing acrylic monomer, an epoxy group containing acrylic monomer and an amino group containing acrylic monomer, an epoxy group containing acrylic monomer and a methylolamide group containing acrylic monomer, and a carboxyl group containing acrylic type Monomers and carbodiimide group-containing acrylic monomers, carboxyl group-containing acrylic monomers and oxazoline group-containing acrylic monomers, hydroxyl group-containing acrylic monomers and block isocyanate group-containing acrylic monomers, hydroxyl group-containing acrylic monomers and ethyleneimine group-containing acrylic monomers, hydroxyl group-containing acrylic monomers, Carboxyl group-containing acrylic monomer, hydroxyl group-containing acrylic monomer and methylolamide group-containing acrylic monomer, methylolamide-containing Combination of a krill-based monomer, an ethyleneimine group-containing acrylic monomer, a methylolamide group-containing acrylic monomer and a carboxyl group-containing acrylic monomer, an amino group-containing acrylic monomer and an ethyleneimine group-containing acrylic monomer, and the like, among others, an epoxy group-containing acrylic monomer and a carboxyl group When using together an acryl-type monomer, stability of an emulsion becomes especially excellent.

As for content of a crosslinkable group containing (meth) acrylic-type monomer (b3), 1-20 mass% of crosslinkable acrylic polymer (B) is preferable, Furthermore, 1-5 mass% is preferable at the point of stability of emulsion. In addition, what is necessary is just to select suitably the total amount in the said range, when containing 2 or more types of crosslinkable group containing (meth) acrylic-type monomeric units (b3). For example, when using together an epoxy group containing acrylic monomer and a carboxyl group containing acrylic monomer, the range of 70/30-30/70 is preferable at a mass ratio.

The crosslinkable acrylic polymer (B) may contain, in addition to the above (b1) to (b3), other structural units other than the above (b1) to (b3) within the range not to impair the effect of the present invention. As another structural unit, for example, an aromatic vinyl monomer unit, an epoxy group containing monomer unit other than the said (b3), an unsaturated carboxylic acid type monomer unit other than the said (b3), a vinyl ether monomer, an olefin monomer, and a hydrolyzable silyl group Containing vinyl monomers, vinyl ester monomers, and the like.

As an aromatic vinyl monomer, styrene, such as styrene and (alpha) -methylstyrene, can be illustrated. As an epoxy group containing monomer, allyl glycidyl ether etc. can be illustrated.

Examples of the unsaturated carboxylic acid monomer include vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-aryloxyethoxycarbonyl) propionic acid, itaconic acid, itaconic acid monoester, maleic acid, Maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, undecylenic acid, and the like.

Examples of the vinyl ether monomers include alkyl vinyl ethers and hydroxyl group-containing vinyl ethers. Examples of the hydroxyl group-containing vinyl ethers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, and 2-hydroxypropyl vinyl. Ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, glycerol monoallyl ether, etc. are mentioned.

As an olefin monomer, ethylene, propylene, n-butene, isobutene, styrene, etc. are mentioned, for example.

As the hydrolyzable silyl group-containing vinyl monomer, for example,

CH ₂ = CHSi (OCH ₃ ) ₃ ,

CH ₂ = CHSi (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = C (CH ₃ ) Si (OCH ₃ ) ₃ ,

CH ₂ = C (CH ₃ ) Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = CHSi (OC ₂ H ₅ ) ₃ ,

CH ₂ = CHSi (OC ₃ H ₇ ) ₃ ,

CH ₂ = CHSi (OC ₄ H ₉ ) ₃ ,

CH ₂ = CHSi (OC ₆ H ₁₃ ) ₃ ,

CH ₂ = CHSi (OC ₈ H ₁₇ ) ₃ ,

CH ₂ = CHSi (OC ₁₀ 0H ₂₁ ) ₃ ,

CH ₂ = CHSi (OC ₁₂ H ₂₅ ) ₃ ,

CH ₂ = CHCH ₂ OCO (oC ₆ H ₄ ) COO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCH ₂ OCO (oC ₆ H ₄ ) COO (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ ,

CH ₂ = CH (CH ₂ ) ₄ Si (OCH ₃ ) ₃ ,

CH ₂ = CH (CH ₂ ) ₈ Si (OCH ₃ ) ₃ ,

CH ₂ = CHO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCH ₂ O (CH ₂ ) ₃ Si (OCH ₃ ) ₃ ,

CH ₂ = CHCH ₂ OCO (CH ₂ ) ₁₀ Si (OCH ₃ ) ₃

And the like.

Examples of the vinyl ester monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate and vinyl cyclohexyl carboxylate, Carboxylic acid vinyl esters, such as vinyl benzoate and vinyl para-t- butylbenzoate, etc. are mentioned.

Although content in the crosslinkable acrylic polymer (B) of monomers other than said (b1)-(b3) is based also on a kind of monomer, 10 mass% or less is preferable.

In the present invention, as a preferable specific composition of the crosslinkable acrylic polymer (B), for example, MMA / 2-EHA / MAA / GMA (60 to 80/10 to 30 / 0.5 to 5 / 0.5 to 10 mass ratio), n -BA / CHMA / MAA / GMA (10 to 30/55 to 80 / 0.5 to 10 / 0.5 to 5 mass ratios), MMA / n-BA / CHMA / MAA / GMA (1 to 50/5 to 40/1 to 70 /0.5 to 5 / 0.5 to 10 mass ratio) and the like, but are not limited thereto.

The ratio of the VDF-based polymer (A) and the crosslinkable acrylic polymer (B) in the acrylic-fluorine composite polymer of the present invention is 10/90 to VDF-based polymer (A) / crosslinkable acrylic-based polymer (B) in a mass ratio. It is 90/10, and it is preferable that it is 10/90-70/30. For example, when (A) / (B) becomes larger than 70/30, that is, when VDF polymer (A) exceeds 70 mass%, the advantage of the film forming property at the time of coating, and adhesiveness to a base material will be impaired. More preferably, (A) / (B) is 20/80-50/50. More preferably, (A) / (B) is 30/70-40/60.

As the polymerization method used for producing the acrylic-fluorine composite polymer particles of the present invention, a conventionally known polymerization method, in particular, an emulsion polymerization method may be employed, and for example, a seed polymerization method may be particularly preferably employed. The seed polymerization method is not particularly limited and can be carried out by conventionally known methods and conditions.

For example, seed polymerization of an acryl-type monomer mixture is a method of putting all the amounts of an acryl-type monomer mixture into a reaction system collectively in the presence of VDF polymer particle, a part of an acryl-type monomer mixture is made to react, and the remainder is continuous or It can carry out by the method of dividing and injecting, the method of continuously adding the whole quantity of an acryl-type monomer mixture, etc.

In addition, the polymerization conditions of this seed polymerization are the same as that of normal emulsion polymerization. For example, an emulsifier, a polymerization initiator, a chain transfer agent, optionally a chelating agent, a pH adjuster, and the like are added to an aqueous medium containing VDF polymer particles, and the reaction is carried out at a temperature of 10 to 90 ° C. for 0.5 to 6 hours. It can superpose | polymerize by performing.

As an emulsifier, a reactive emulsifier, a non-reactive emulsifier, or those combinations may be used. As a non-reactive emulsifier, a conventionally well-known anionic emulsifier and a nonionic emulsifier are used individually or in combination of these. In some cases, amphoteric emulsifiers may be used.

As a polymerization initiator used at the time of seed polymerization, if it can provide to a free radical reaction in an aqueous medium, it will not specifically limit, In some cases, it can also be used in combination with a reducing agent. As a water-soluble polymerization initiator which can be used, a persulfate, a hydrogen peroxide, and a reducing agent can be mentioned sodium pyro sulfite, sodium hydrogen sulfite, sodium L-ascorbate, rongalit, etc., for example. As an oil-soluble polymerization initiator, diisopropyl peroxydicarbonate (IPP), benzoyl peroxide, dibutyl peroxide, azobisisobutyronitrile (AIBN) etc. are mentioned, for example. The usage-amount of a polymerization initiator is 0.05-2.0 mass parts normally per 100 mass parts of acryl-type monomer mixture.

As a chain transfer agent which may be used at the time of seed polymerization, For example, Halogenated hydrocarbons, such as chloroform and carbon tetrachloride; mercaptans, such as n-dodecyl mercaptan, tert- dodecyl mercaptan, and n-octyl mercaptan, etc. are mentioned. The usage-amount of a chain transfer agent is 0-5.0 mass parts normally per 100 mass parts of acryl-type monomer mixture.

 In the production of the acrylic-fluorine composite polymer particles of the present invention, the ratio of the VDF polymer particles and the acrylic monomer mixture including the b1 to b3 is 100 parts by mass or more based on 100 parts by mass of the VDF polymer particles. to be. Furthermore, since the film forming property at the time of coating is favorable, it is 110 mass parts or more, especially 150 mass parts or more of an acryl-type monomer mixture with respect to 100 mass parts of VDF type polymer particles.

The present invention is also an aqueous dispersion containing the above-described acrylic-fluorine composite polymer particles. In the present invention, the particle diameter of the acrylic-fluorine composite polymer particles in the aqueous dispersion is preferably from 50 to 300 nm. More preferably, it is 50-250 nm. If the particle diameter is less than 50 nm, the viscosity of the aqueous dispersion may increase remarkably at 30 mass% or more, where the concentration of the acrylic-fluorine composite polymer particles of the aqueous dispersion is in a practical range, which may cause a problem in the coating operation. On the other hand, when it exceeds 300 nm, the sedimentation stability of the aqueous dispersion obtained tends to fall, and also raises the minimum film-forming temperature of an acryl- fluorine composite polymer particle.

It is preferable that solid content concentration of the aqueous dispersion of the acryl-fluorine composite polymer particle of this invention is 30-65 mass% from a coating use viewpoint, More preferably, it is 35-50 mass%.

The aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention can be used for various applications in various forms.

For example, an adhesive composition, an ink composition, etc. can be illustrated other than the coating film formation component of various coating compositions, the molding material of a film, a sheet, etc., It is not limited to these. When using as a composition for water-based coatings, even when it forms into a film by forced drying, adhesiveness with a base material improves.

The aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention can be produced by the seed polymerization method described above.

The aqueous dispersion of the acrylic-fluorine composite polymer particles of the present invention is compatible with the VDF-based polymer (A) and the (meth) acrylic acid ester (b1), in an aqueous dispersion containing the particles containing the VDF-based polymer (A), A step of adding a VDF polymer (A), an incompatible (meth) acrylic acid ester (b2), a (meth) acrylic monomer (b3) having a crosslinkable group crosslinkable by heating, and a polymerization initiator, and a (meth) acrylic acid ester ( It can manufacture more suitably by the manufacturing method containing the process of making b1), (meth) acrylic acid ester (b2) and (meth) acrylic-type monomer (b3) react.

This invention is also the composition for aqueous coatings containing the above-mentioned aqueous dispersion. The composition for aqueous coatings of this invention can employ | adopt a conventionally well-known additive and a compounding ratio except using the acryl-fluorine composite polymer particle mentioned above as a film forming material. For example, what is necessary is just to select in the range of about 10-60 mass% as a density | concentration of acryl- fluorine composite polymer particle.

Moreover, when manufacturing the composition for aqueous coatings containing a pigment, water, pigments, such as a titanium oxide, an antifoamer, a pigment dispersing agent, a pH adjuster, etc. beforehand into pigment dispersions, such as a sand mill, to the aqueous dispersion of acryl- fluorine composite polymer particle | grains, etc. After stirring and mixing the predetermined amount of the pigment dispersion which disperse | distributed and the predetermined amount of film-forming auxiliary agent, the predetermined amount of a thickener is added and mixed, and other necessary additives may be added suitably. When manufacturing the composition for aqueous coatings which do not add a pigment, water, a film auxiliary agent, an antifoamer, a thickener, a pH adjuster, and other necessary additives are added to the aqueous dispersion of acryl-fluorine composite polymer particle as needed, and it is well-known. What is necessary is just to mix by stirring.

As additives for coating applications, a film forming aid, a cryoprotectant, a pigment, a filler, a pigment dispersant, an antifoaming agent, a leveling agent, a rheology modifier, a preservative, a ultraviolet absorber, an antioxidant, a quencher, a lubricant, a vulcanizing agent, and the like are added. You may.

The base material to which the composition for water-based coating of this invention is applied is not specifically limited, Metal-based base materials, such as a hot dip galvanized steel plate, a stainless steel plate, and an aluminum steel plate; Slate, ceramic sizing materials such as industrial sizing materials, foamed concrete, and glass; It is applicable to plastic base materials, such as a vinyl chloride sheet, PET film, polycarbonate, and an acrylic film. As a hot-dip galvanized steel plate, a hot-dip galvanized steel plate, a hot-dip zinc-aluminum-magnesium alloy plated steel plate, a hot-dip aluminum-galvanized steel plate, a hot-dip aluminum plated steel plate, etc. are mentioned, for example.

As a method of coating the various coating materials for the aqueous coating composition of the present invention, conventionally known methods and conditions can be adopted. For example, a coating method such as spray coating, roll coating, flow coating, roller, or painting with a brush can be adopted for the substrate.

The method of drying after coating is not particularly limited, and may be natural drying at ambient temperature, and drying at low temperature (5 to 60 ° C.) that takes a drying time may be used, but the coating composition of the present invention is a room temperature to 200 ° C. Also in forced drying at 60-200 degreeC (substrate temperature), the coating film excellent in weather resistance, water resistance, strength, base material adhesiveness, and film forming property can be formed. The time required for forced drying is usually 3 seconds to 10 minutes.

As the composition for paints, a composition for weathering paints, in particular, a composition for weathering paints for building and building materials, a composition for paints for interior and exterior of automobiles, a composition for paints for interior and exterior paints of electric products, a composition for paints for office equipment or kitchen appliances, etc. It can illustrate, and it is especially applicable to the composition for weatherable coating materials for building materials from a point with favorable weather resistance and durability.

Example

Next, although this invention is demonstrated based on an Example, this invention is not limited only to these Examples.

Example 1

[Production of Aqueous Dispersion of VDF-Based Polymer (A)]

65.2 g of aqueous dispersion (solid content concentration 45.5 mass%) of particles of VdF / TFE / CTFE copolymer (= 72.1 / 14.9 / 13 (mol%)) (VTC) as VDF-based polymer particles Into this, 37.1 g of New Cole 707 SF (manufactured by Nippon New Kazai Co., Ltd.) and 56.8 g of water were added thereto as an emulsifier, and the mixture was sufficiently mixed to prepare an aqueous dispersion.

Into a 1.0 L volume glass flask, 185.2 g (71.2 mass%) of methyl methacrylate (MMA), 49.9 g (19.2 mass%) of 2-ethylhexyl acrylate (2EHA), and glycidyl methacrylate (GMA) ) 14.3 g (5.5 mass%) and methacrylic acid (MAA) 10.7 g (4.1 mass%) were added, and the monomer solution was prepared.

The internal temperature of the separable flask was raised to 80 ° C., and the entire amount of the monomer solution was added to the aqueous dispersion of the VDF / TFE / CTFE copolymer particles over 3 hours. At the same time as the monomer solution was added dropwise, polymerization was carried out while adding 41.1 g of ammonium persulfate (APS) (1% by mass aqueous solution) in 7 portions every 30 minutes. After 5 hours from the start of the polymerization, the reaction solution was cooled to room temperature to complete the reaction to obtain an aqueous dispersion of acryl-fluorine composite polymer particles (solid content concentration of 52.0 mass%). The composition of the acrylic polymer part in the obtained acrylic fluorine composite polymer was MMA / 2EHA / MAA / GMA = 71.2 / 19.2 / 4.1 / 5.5 (mass% ratio). In addition, the mass ratio (VDF / acrylic) of the VDF type polymer part and the acrylic polymer part in the obtained acrylic fluorine composite polymer particles was 50/50.

(Production of water-based paint)

The aqueous dispersion of the obtained acrylic-fluorine composite polymer was used to neutralize to triethylamine to pH7.5. 5 mass% / solid content of film-forming adjuvant (diethyl adipic acid) was added to the aqueous dispersion liquid, and it stirred for 30 minutes with a three-one motor, and prepared the composition for aqueous coating materials for clear paints.

(Production of one coat painting and a test piece)

The obtained aqueous coating composition was coated on a galvalume steel sheet (manufactured by Nippon Testo Paneru Co., Ltd.) with a bar coater, dried at 140 ° C. for 7 seconds to prepare a test piece having a clear coating film having a thickness of 4 μm.

The following characteristic was evaluated using the obtained test piece. The results are shown in Table 1.

(Jointness)

(Evaluation standard)

20 microliters of 10 mass% sodium hydroxide aqueous solution was dripped at the test piece. After dripping, time to bubble generation was evaluated in the following five steps. 1: occurs within 2 minutes after dropping, 2: occurs between 2 to 5 minutes after dropping, 3: occurs between 5 to 10 minutes after dropping, 4: occurs between 10 to 15 minutes after dropping, 5: 15 after dropping Occurs or does not occur more than minutes later.

(Exterior)

(Evaluation standard)

Visually judge whether the fabricated specimen has aggregates, swelling, cracks or not. (Circle) means that there is no expansion, a crack, etc. at all, (triangle | delta) is one or more and five or less things, and x is expansion, a crack, etc. are more than five.

(Initial adhesion)

After leaving the coating film for 24 hours, the test piece eye tape peeling test is performed on the test piece in accordance with JIS D0202-1988. The cellophane tape ("CT24", Nichiban Co., Ltd.) is used to adhere to the film with a finger and then peeled off. The determination is expressed by the number of grid patterns that are not peeled out of the 25 masses.

(Weather resistance)

(Test Methods)

The prepared test piece is put into an accelerated weather resistance tester, and the infrared spectral spectrum after 322 hours is measured using the ATR method (damping total reflection method). Weather resistance is evaluated by the absorption attenuation rate of CH stretching vibration (near 1700 cm <^-1> ) derived from an acrylate.

Accelerated weathering tester (SUV): Super UV tester, manufactured by Iwasaki Electric Co., Ltd.

Test cycle: Pure water spray (every 10 seconds) 1 hour → exposure 11 hours (black panel temperature 63 ° C., relative humidity 70%) → condensation 11 hours (black panel temperature 30 ° C., relative humidity 100%). Let this cycle be 1 cycle (23 hours).

Test time: 322 hours (14 cycles)

(Evaluation standard)

An infrared spectral spectrum is measured using the ATR method (damping total reflection method) after a test piece surface part. Compare the specimen before the accelerated weathering test and the specimen after the test (after 322 hours). The absorption of CF stretching vibration around 1150 cm ⁻¹ is normalized and it is confirmed whether absorption of CH stretching vibration derived from acrylate from around 1700 cm ⁻¹ is not attenuated before or after the test. (Circle) is attenuation of absorption of CH stretching vibration derived from an acrylate of 1700cm <^-1> vicinity less than 10%, (triangle | delta) is attenuation greater than 10%, less than 25%, and x is attenuation compared with before the test. It is larger than%.

ATR measurement: We use FT-IR Spectrometer Spectorum 100 made by Perkin Elmer

(Production of top clear painting and test piece)

Initially apply the obtained aqueous coating composition to a galvalume steel sheet (manufactured by Nippon Testo Paneru Co., Ltd.): Daikin Co., Ltd. It coated using the coater, dried for 1 day, and produced the test piece which has a clear coating film of 10 micrometers in thickness.

(Initial adhesion test)

The test piece eye tape peeling test is performed in accordance with JIS D0202-1988. Using cellophane tape ("CT24", Nichiban Co., Ltd.), the film is adhered to the film with a finger and then peeled off. The determination is expressed by the number of grid patterns that are not peeled out of the 25 masses.

(Initial domestic test)

The obtained test piece was treated with water for 1 day at 23 ° C, and the grades of expansion (JIS K5600-8-2), cracking (JIS K5600-8-4) and peeling (JIS K5600-8-5) immediately after taking out were evaluated. .

(2nd adhesion test)

Moreover, it extracts after a water condensation process, and dries at 23 degreeC for 1 day, and performs the board | substrate eye tape peeling test based on JISD0202-1988. The cellophane tape ("CT24", Nichiban Co., Ltd. product) is used, and it sticks to a film with a finger, and peels off. The determination is expressed by the number of grid patterns that are not peeled out of the 25 masses.

(expansion)

Criteria for evaluation of expansion (JIS K5600-8-2)

The density is divided into grades 0 to 5 (small side is 0), and the size is divided into grades S1 to S5 (S1 side is small), and is described as 2 (S1), for example.

(fracture)

Criteria for the Grade of Cracking (JIS K5600-8-4)

The density is divided into grades 0 to 5 (smaller side is 0), the size is divided into grades S0 to S5 (S0 is smaller), and depth is divided into grades a to c (a side is shallower), for example, 2 ( It describes as S1) b.

(Peeling)

Evaluation standard of grade of peeling (JIS K5600-8-5)

The density is divided into grades 0 to 5 (smaller side is 0), the size is divided into grades S1 to S5 (S1 side is smaller), and depth is divided into grades a to b (the side a is shallower), for example, 2 ( It describes as S1) a.

(General domestic test)

The specimens were forfeited for 6 days at 23 ° C, and the grades of expansion (JIS K5600-8-2), cracking (JIS K5600-8-4), and peeling (JIS K5600-8-5) immediately after taking out were evaluated.

(2nd adhesion test)

Moreover, after taking out a water | moisture treatment and drying for 1 week at 23 degreeC, the board | substrate eye tape peeling test is done based on JISD0202-1988. Using cellophane tape ("CT24", Nichiban Co., Ltd.), the film is adhered to the film with a finger and then peeled off. The determination is expressed by the number of grid patterns that are not peeled out of the 25 masses.

(Weather resistance)

The produced test piece is put into an accelerated weather resistance tester, and the gloss value, L value, a value, and b value are measured every constant cycle. Glossiness retention is computed from the result, and the weather resistance of a coating film is evaluated.

Accelerated weathering tester (SUV): Super UV tester, manufactured by Iwasaki Electric Co., Ltd.

Test cycle: Pure water spray (every 10 seconds) 1 hour → exposure 11 hours (black panel temperature 63 ° C, relative humidity 70%) → condensation 11 hours (black panel temperature 30 ° C, relative humidity 100%). This cycle is referred to as one cycle (23 hours).

Test time: 966 hours (42 cycles) to 1610 hours (70 cycles)

Examples 2 to 4

As the acrylic monomer mixture for the acrylic polymer, seed polymerization was carried out in the same manner as in Example 1 except that the monomer mixture shown in Table 1 was used to obtain an acrylic-fluorine composite polymer, respectively.

Using the aqueous dispersion liquid of the obtained acrylic-fluorine composite polymer particle, it carried out similarly to Example 1, and prepared the composition for aqueous coating materials for clearing paints, the coating film was formed like Example 1, the test piece was produced, and the various characteristics were investigated. The results are shown in Table 1.

Comparative Example 1

As the acrylic monomer mixture for the acrylic polymer, seed polymerization was carried out in the same manner as in Example 1 except that a comparative monomer mixture of MMA / n-BA / AA = 98.0 / 1.0 / 1.0 (mass% ratio) was used, and a comparative acrylic- A fluoropolymer was obtained. The composition of the acrylic polymer part was MMA / n-BA / AA = 98.0 / 1.0 / 1.0 (mass% ratio). In addition, the mass ratio (VDF / acrylic) of the VDF type polymer part and the acrylic type polymer part in the obtained acrylic fluorine composite polymer particles was 70/30.

Using the aqueous dispersion of the obtained acrylic-fluorine composite polymer particles, a composition for aqueous paint for clear paint was prepared in the same manner as in Example 1, a coating film was formed in the same manner as in Example 1, and test pieces were prepared to investigate various properties. The results are shown in Table 1.

The symbol of the monomer in Table 1 shows the following compounds.

MMA: methyl methacrylate

n-BA: n-butyl acrylate

CHMA: cyclohexyl methacrylate

2-EHA: 2-ethylhexyl acrylate

GMA: glycidyl methacrylate

MAA: methacrylic acid

AA: Acrylic acid

MPTES: 3-methacryloxypropyltriethoxysilane

From Table 1, it turns out that the acryl-fluorine composite polymer containing a component (b1), a component (b2), and a component (b3) improves adhesiveness with a base material.

Example 5

Seed polymerization was carried out in the same manner as in Example 3, except that an aqueous dispersion (solid content concentration of 10.0% by mass) of the particles of the VdF / TFE copolymer [= 80/20 (mol%)] (VT) was used as the VDF polymer particles. An acrylic-fluorine composite polymer was obtained.

Using the aqueous dispersion of the obtained acrylic-fluorine composite polymer particles, a composition for water-based coating for clear paint was prepared in the same manner as in Example 1, and a coating film was formed in the same manner as in Example 1 to prepare a test piece, and various properties were investigated. . The results are shown in Table 2.

Example 6

Seed polymerization was carried out in the same manner as in Example 3, except that an aqueous dispersion (solid content concentration of 10.0% by mass) of the particles of the VdF / HFP copolymer [= 91/9 (mol%)] (VH) was used as the VDF polymer particles. An acrylic-fluorine composite polymer was obtained.

Using the aqueous dispersion of the obtained acrylic-fluorine composite polymer particles, a composition for water-based coating for clear paint was prepared in the same manner as in Example 1, and a coating film was formed in the same manner as in Example 1 to prepare a test piece, and various properties were investigated. . The results are shown in Table 2.

From Table 2, it turns out that the acryl- VDF type fluoropolymer containing a component (b1), a component (b2), and a component (b3) improves adhesiveness with a base material.

Claims (9)

(A) Vinylidene fluoride system containing at least one fluoroolefin unit and vinylidene fluoride unit selected from the group consisting of tetrafluoroethylene units, hexafluoropropylene units and chlorotrifluoroethylene units as structural units Polymers,
(B) Compatibility with the vinylidene fluoride polymer (A) (in) (meth) acrylic acid ester unit (b1), incompatible with the vinylidene fluoride polymer (A), and heating Crosslinkable acrylic polymer (B) containing the (meth) acrylic-type monomer unit (b3) which has a crosslinkable crosslinkable group
An acryl-fluorine composite polymer particle comprising an acryl-fluorine composite polymer particle, wherein the vinylidene fluoride polymer (A) / crosslinkable acrylic polymer (B) is 10/90 to 90/10 by mass ratio. The acryl-fluorine composite polymer particle according to claim 1, wherein the vinylidene fluoride polymer (A) contains a tetrafluoroethylene unit and a chlorotrifluoroethylene unit. The acryl-fluorine composite polymer particles according to claim 1, wherein the vinylidene fluoride polymer (A) is a vinylidene fluoride / tetrafluoroethylene copolymer. The acryl-fluorine composite polymer particles according to claim 1, wherein the vinylidene fluoride polymer (A) is a vinylidene fluoride / tetrafluoroethylene / hexafluoropropylene copolymer. The acryl-fluorine composite polymer particles according to claim 1, wherein the vinylidene fluoride polymer (A) is a vinylidene fluoride / hexafluoropropylene copolymer. The acryl-fluorine composite polymer particle according to any one of claims 1 to 5, wherein the compatible (meth) acrylic acid ester unit (b1) is a linear alkyl ester unit having 1 to 4 carbon atoms of (meth) acrylic acid. . The acryl- in any one of Claims 1-6 whose incompatible (meth) acrylic acid ester unit (b2) is a C6-C20 alkylester unit which may have an alicyclic structure of (meth) acrylic acid. Fluoropolymer Polymer Particles. An aqueous dispersion comprising the acrylic-fluorine composite polymer particles according to any one of claims 1 to 7. The aqueous coating composition containing the aqueous dispersion of Claim 8.