JPWO2015056751A1 - Fluoroolefin copolymer-containing solution composition, method for producing the same, and coating composition - Google Patents

Abstract

Solution composition containing fluoroolefin copolymer which is difficult to cause gelation of solution during polymerization of monomer and after polymerization, increase of molecular weight of copolymer, and discoloration of solution; method for producing the solution composition; Disclosed is a coating composition that can form a coating film that does not easily turn yellow, has good gloss, boiling water resistance, alkali resistance, and moisture resistance and does not easily discolor. A fluoroolefin copolymer (A) comprising a structural unit based on a fluoroolefin, a structural unit based on a monomer having a crosslinkable group, and a structural unit based on a monomer having no fluorine atom and a crosslinkable group; A solution composition comprising a compound (B) having a 2,2,6,6-tetrasubstituted piperidyl group and an organic solvent (D); a method for producing the solution composition using hydrotalcite; Coating composition containing a product and a specific curing agent (E).

Description

  The present invention relates to a solution composition containing a fluoroolefin copolymer, a method for producing the same, and a coating composition using the fluoroolefin copolymer-containing solution composition.

A solution in which a fluoroolefin copolymer having a crosslinkable group (such as a hydroxyl group) is dissolved in an organic solvent is used, for example, as a raw material for a paint.
For example, the fluoroolefin copolymer-containing solution contains a monomer mixture composed of a fluoroolefin, a monomer having a crosslinkable group, and a monomer having no fluorine atom and no crosslinkable group in an organic solvent. It is obtained by polymerizing.
However, when the fluoroolefin copolymer-containing solution is produced, the solution is generated during or after the polymerization of the monomer due to an inorganic acid component (hydrofluoric acid or the like) generated during the polymerization of the monomer mixture. The stability of the polymer is impaired, the solution is likely to gel, and the molecular weight of the copolymer is likely to increase.

The following method has been proposed as a method for producing a solution containing a fluoroolefin copolymer in which the solution is difficult to gel.
Polymerization of a monomer mixture consisting of a fluoroolefin, a vinyl ether having a hydroxyl group and, if necessary, other monomers in an organic solvent in the presence of a compound having a 2,2,6,6-tetrasubstituted piperidyl group To obtain a fluoroolefin copolymer-containing solution (Patent Document 1).

  However, the fluoroolefin copolymer-containing solution obtained by this method is likely to change color (yellowing or cloudiness) during storage or increase the molecular weight of the copolymer. Further, when a curing agent (isocyanate-based curing agent, blocked isocyanate-based curing agent or amino resin) is blended with the fluoroolefin copolymer-containing solution obtained by the above method to form a one-component coating composition, the coating composition The product is yellowed during storage, the gloss of the coating film formed from the coating composition after long-term storage is insufficient, the coating film is discolored, or formed from the coating composition immediately after compounding Even a coating film has insufficient boiling water resistance, alkali resistance, and moisture resistance.

JP 62-292814 A

The present invention provides a fluoroolefin copolymer-containing solution composition that does not easily cause gelation of the solution, increase in the molecular weight of the copolymer, or discoloration of the solution during storage. Moreover, this invention provides the fluoroolefin copolymer containing solution composition which can obtain the coating composition which has the following effect.
The present invention also provides a method for producing a fluoroolefin copolymer-containing solution composition that hardly causes gelation of the solution during polymerization of the monomer or after polymerization, increases in the molecular weight of the copolymer, and does not cause discoloration of the solution. Moreover, this invention provides the method of manufacturing the fluoroolefin copolymer containing solution composition which can obtain the coating composition which has the following effect.
In addition, the present invention provides a coating composition that can form a coating film that does not easily yellow during storage, has good gloss, boiling water resistance, alkali resistance, and moisture resistance and is not easily discolored.

  The solution composition of the present invention comprises a fluoroolefin copolymer comprising a structural unit based on a fluoroolefin, a structural unit based on a monomer having a crosslinkable group, and a structural unit based on a monomer having no fluorine atom and no crosslinkable group. A homogenous solution comprising a polymer, a compound having a 2,2,6,6-tetrasubstituted piperidyl group, and an organic solvent, the solution composition having a pH of 4.0 to 8.0 It is characterized by that.

The pH of the solution composition is preferably 5.0 to 7.0.
The amount of the compound having a 2,2,6,6-tetrasubstituted piperidyl group in the solution composition is 0.01 to 15.0 parts by mass with respect to 100 parts by mass of the fluoroolefin copolymer. preferable.

  The solution composition of the present invention is obtained by removing insoluble components from a composition containing a fluoroolefin copolymer, a compound having a 2,2,6,6-tetrasubstituted piperidyl group, hydrotalcite and an organic solvent. The obtained solution composition is preferable. The amount of the hydrotalcite in the solution composition is preferably 0.01 to 10.0 parts by mass with respect to 100 parts by mass of the fluoroolefin copolymer.

The method for producing a solution composition of the present invention comprises a monomer mixture containing a fluoroolefin, a monomer having a crosslinkable group, and a monomer having no fluorine atom and no crosslinkable group. In the presence of a compound having a 6-tetrasubstituted piperidyl group, it is polymerized in an organic solvent to produce a fluoroolefin copolymer, and then adsorbed by adding hydrotalcite, and then insoluble components are removed. It is characterized by that.
The amount of the compound having a 2,2,6,6-tetrasubstituted piperidyl group in the production method is preferably 0.01 to 15.0 parts by mass with respect to 100 parts by mass of the monomer mixture.
It is preferable that the addition amount of the hydrotalcite in the said manufacturing method is 0.01-10.0 mass parts with respect to 100 mass parts of a fluoro olefin copolymer. Moreover, it is preferable that pH of the said solution composition exists in the range of 4.0-8.0.

In the second production method of the solution composition of the present invention, a monomer mixture containing a fluoroolefin, a monomer having a crosslinkable group, and a monomer having no fluorine atom and no crosslinkable group is obtained. , 6,6-tetra-substituted piperidyl group-containing compound and hydrotalcite are polymerized in an organic solvent to form a fluoroolefin copolymer, and then insoluble components are removed.
In the second production method, the mass ratio represented by the compound having a 2,2,6,6-tetrasubstituted piperidyl group / the hydrotalcite is preferably 5/95 to 95/5.
The total mass of the compound having a 2,2,6,6-tetrasubstituted piperidyl group and the hydrotalcite in the second production method is 0.01 to 15 with respect to 100 parts by mass of the monomer mixture. It is preferable that it is a mass part. Moreover, it is preferable that pH of the said solution composition exists in the range of 4.0-8.0.

  The coating composition of the present invention comprises at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin, and the solution composition of the present invention. And

The solution composition containing the fluoroolefin copolymer of the present invention is less prone to gelation of the solution, increase in the molecular weight of the copolymer, and discoloration of the solution during storage. Moreover, according to the solution composition of this invention, the coating composition which has the following effect can be obtained.
In the method for producing a solution composition containing the fluoroolefin copolymer of the present invention, gelation of the solution during polymerization of the monomer or after polymerization, increase in the molecular weight of the copolymer, and discoloration of the solution are unlikely to occur. . Moreover, according to the manufacturing method of the solution composition of this invention, the solution composition which can obtain the coating composition which has the following effect can be manufactured.
In addition, according to the coating composition of the present invention, it is possible to form a coating film that is hardly yellowed during storage, has good gloss, boiling water resistance, alkali resistance, and moisture resistance and is not easily discolored.

The following definitions of terms apply throughout this specification and the claims.
“Monomer” means a compound having a polymerization-reactive carbon-carbon double bond.
“Structural unit” means a unit derived from a monomer formed by polymerization of the monomer. The structural unit may be a unit directly formed by a monomer polymerization reaction, or may be a unit in which a part of the unit is converted to another structure by treating the polymer.
“Fluoroolefin” means a compound in which part or all of the hydrogen atoms bonded to the carbon atoms of the olefin hydrocarbon are substituted with fluorine atoms. You may have a substituent atom or substituent other than a fluorine atom. However, those having a crosslinkable group are excluded.
The “crosslinkable group” means a functional group that does not substantially react during the production of the fluoroolefin copolymer and causes cross-linking between molecules of the fluoroolefin copolymer by reacting with a curing agent or the like.
“Hydrotalcite” means a layered double hydroxide represented by the following formula.
[Mg ²⁺ _1-x Al ³⁺ _x (OH) ₂ ] ^{x +} [CO ₃ ²⁻ _{x / 2} · mH ₂ O] ^x−
However, x is 0.2-0.33 and m is 0-2.
“(Meth) acrylic acid” means acrylic acid or methacrylic acid.
The “ether ester solvent” means a compound having both an ether bond and an ester bond in the molecule.

<Solution composition>
The solution composition of the present invention is a homogeneous solution containing a fluoroolefin copolymer, a compound having a 2,2,6,6-tetrasubstituted piperidyl group, and an organic solvent, and has a pH of 4.0-8. .0.
The fluoroolefin copolymer in the present invention is hereinafter also referred to as “copolymer (A)”, and a compound having a 2,2,6,6-tetrasubstituted piperidyl group is hereinafter referred to as “compound (B)”. Also called.

  The solution composition of the present invention being a “homogeneous solution” means a solution substantially free of insoluble components. In the process of producing the solution composition of the present invention, hydrotalcite is used to adsorb and remove the acid component. Hydrotalcite is insoluble in an organic solvent, and after adsorption treatment with hydrotalcite, the solution containing hydrotalcite is filtered, and is a homogeneous solution substantially free of insoluble components. A solution composition is obtained.

The pH of the solution composition of the present invention is in the range of 4.0 to 8.0. If the pH is 4.0 or more, in the one-component coating composition containing the blocked isocyanate curing agent, there is no difference in the curing rate between the coating film surface layer and the coating film, and it is derived from wrinkles on the coating film surface layer. It is difficult for the gloss of the coating film to decrease. When the pH is 8.0 or less, the coating film is unlikely to be hardened, and the durability of the coating film, such as acid resistance, alkali resistance, and solvent resistance, is unlikely to decrease.
The pH of the solution composition of the present invention is preferably 4.5 to 7.5, and more preferably 5.0 to 7.0.
The pH of the solution composition of the present invention is such that a 6-fold mass of methyl isobutyl ketone is added to the solution composition to make a homogeneous solution, and then ion-exchanged water of the same mass as methyl isobutyl ketone is added to obtain a solution and water. It is a numerical value obtained by sufficiently contacting and then allowing to stand to separate the solution and water and measuring the pH of the separated water. For details, refer to the section (Measurement of pH) in the Examples described later.

  The solid content concentration in the solution composition is not particularly limited. When used in a paint, it preferably has an appropriate viscosity according to the coating method, for example, 40 to 80% by mass.

(Fluoroolefin copolymer)
The copolymer (A) comprises a structural unit based on a fluoroolefin, a structural unit based on a monomer having a crosslinkable group, and a structural unit based on a monomer having no fluorine atom and no crosslinkable group.
Hereinafter, the monomer having a crosslinkable group is also referred to as a monomer (a2), and the monomer having no fluorine atom and a crosslinkable group is also referred to as a monomer (a3).

The number average molecular weight of the copolymer (A) is not particularly limited. When using the solution composition containing a copolymer (A) for a coating material, it is preferable that the number average molecular weights of a copolymer (A) are 3,000-100,000. If the number average molecular weight of a copolymer (A) is 3,000 or more, it is excellent in the weather resistance of the coating film obtained. If the number average molecular weight of the copolymer (A) is 100,000 or less, sufficient solubility can be achieved even in a high concentration of the copolymer (A) in the copolymer (A) solution or coating composition. And low viscosity can be realized.
The number average molecular weight of the copolymer (A) is measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

Fluoroolefin:
The number of fluorine atoms contained in the fluoroolefin is preferably 2 or more, more preferably 2 to 6, and still more preferably 3 to 4. When the number of fluorine atoms is 2 or more, the resulting coating film has excellent weather resistance.

Examples of the fluoroolefin include tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, hexafluoropropylene, and the like, and tetrafluoroethylene and chlorotrifluoroethylene are preferable.
A fluoro olefin may be used individually by 1 type, and may be used in combination of 2 or more type.

Monomer (a2):
The monomer (a2) is a monomer having a crosslinkable group.
As the crosslinkable group, a functional group having active hydrogen (hydroxyl group, carboxyl group, amino group, etc.), hydrolyzable silyl group (alkoxysilyl group, etc.) and the like are preferable.

As the monomer (a2), a monomer represented by the following formula is preferable.
^{_{CH 2 = CX 1 (CH 2}} ) n1 -Q 1 -R 1 -Y
However, ^{X 1} is hydrogen atom or a methyl group, n1 is 0 or 1, ^{Q 1} represents an oxygen atom, -C (O) O-or -O (O) a C-, ^{R 1} Is an alkylene group having 2 to 20 carbon atoms which may have a branched structure or a ring structure, and Y is a crosslinkable functional group.

Y is preferably a hydroxyl group, a carboxyl group or an amino group, more preferably a hydroxyl group.
R ¹ is preferably a linear alkylene group. 1-10 are preferable, as for carbon number of this alkylene group, 1-6 are more preferable, and 2-4 are more preferable.
Q ¹ is preferably an oxygen atom.

  Examples of the monomer (a2) include hydroxyalkyl vinyl ethers, hydroxyalkyl vinyl esters, hydroxyalkyl allyl ethers, hydroxyalkyl allyl esters, and (meth) acrylic acid hydroxyalkyl esters. The hydroxyalkyl and hydroxyallyl groups in the hydroxyalkyl vinyl esters and hydroxyalkyl allyl esters are each preferably bonded to the carbon atom of the carbonyl group of the ester bond.

Monomers (a2) include hydroxyalkyl vinyl ethers (2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ether, 4-hydroxybutyl vinyl ether, etc.), hydroxyalkyl allyl ethers (hydroxyethyl allyl ether, etc.), (meth) acrylic acid Hydroxyalkyl esters (hydroxyethyl (meth) acrylate, etc.) are preferred, and from the viewpoint of excellent copolymerizability and excellent weather resistance of the formed coating film, hydroxyalkyl vinyl ethers are more preferred, and 4-hydroxybutyl vinyl ether Is particularly preferred.
A monomer (a2) may be used individually by 1 type, and may be used in combination of 2 or more type.

Monomer (a3):
A monomer (a3) is a monomer which does not have a fluorine atom and a crosslinkable group.
As the monomer (a3), a monomer represented by the following formula is preferable.
^{_{CH 2 = CX 2 (CH 2}} ) n2 -Q 2 -R 2
However, ^{X 2} is a hydrogen atom or a methyl group, n2 is 0 or 1, ^{Q 2} represents an oxygen atom, -C (O) O-or -O (O) a C-, ^{R 2} Is an alkyl group having 2 to 20 carbon atoms which may have a branched structure or a ring structure.

  Examples of the monomer (a3) include alkyl vinyl ethers, alkyl vinyl esters, alkyl allyl ethers, alkyl allyl esters, and (meth) acrylic acid esters. The alkyl group in the alkyl vinyl esters and alkyl allyl esters is preferably bonded to the carbon atom of the carbonyl group of the ester bond.

As the monomer (a3), ethyl vinyl ether, cyclohexyl vinyl ether, and 2-ethylhexyl vinyl ether are preferable. When the fluoroolefin copolymer (A) has high rigidity, is soluble in an organic solvent, and applied to a coating material. Cyclohexyl vinyl ether is particularly preferred because it is easy to apply and provides a hard coating.
A monomer (a3) may be used individually by 1 type, and may be used in combination of 2 or more type.

Composition unit ratio:
The proportion of the structural unit based on the fluoroolefin is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, and more preferably 45 to 55 mol, of all the structural units (100 mol%) of the copolymer (A). % Is more preferable. If the ratio of the structural unit based on fluoroolefin is 30 mol% or more, the weather resistance of the coating film obtained will be excellent. If the ratio of the structural unit based on a fluoro olefin is 70 mol% or less, it is excellent in the solubility to an organic solvent or a diluent.

The total proportion of the structural unit based on the monomer (a2) and the structural unit based on the monomer (a3) is 70 to 30 moles among all the structural units (100 mol%) of the copolymer (A). % Is preferable, 60 to 40 mol% is more preferable, and 55 to 45 mol% is more preferable.
Therefore, when the structural unit other than the structural unit based on the fluoroolefin is only the structural unit based on the monomer (a2) and the structural unit based on the monomer (a3), the structural unit based on the monomer (a2) The total proportion of the structural units based on the monomer (a3) is preferably 70 to 30 mol%, more preferably 60 to 40 mol%, of all the structural units (100 mol%) of the copolymer (A). More preferably, it is 55 to 45 mol%.

  The proportion of the structural unit based on the monomer (a2) is preferably from 5 to 40 mol%, more preferably from 8 to 35 mol%, based on the total structural units (100 mol%) of the copolymer (A). If the proportion of the structural unit based on the monomer (a2) is 5 mol% or more, a sufficient amount of crosslinkable groups are introduced into the copolymer (A) to obtain a coating film having high hardness. If the proportion of the structural unit based on the monomer (a2) is 40 mol% or less, even if it is a high solid content type, a sufficiently low viscosity as the copolymer (A) solution can be maintained.

  The proportion of the structural unit based on the monomer (a3) is preferably more than 0 mol% and 45 mol% or less, and 3 to 35 mol% of all the structural units (100 mol%) of the copolymer (A). More preferably, 5-30 mol% is further more preferable. By having a structural unit based on the monomer (a3), the hardness and flexibility of the obtained coating film can be appropriately adjusted. When the proportion of the structural unit based on the monomer (a3) is 45 mol% or less, a sufficient amount of crosslinkable groups are obtained in the copolymer (A) to obtain a coating film having excellent weather resistance and high hardness. To be introduced.

  When having a structural unit based on a monomer other than a structural unit based on fluoroolefin, a structural unit based on monomer (a2), and a structural unit based on monomer (a3) Is preferably 20 mol% or less, more preferably 10 mol% or less, of all the structural units (100 mol%) of the copolymer (A).

(Compound (B))
The compound (B) is a compound having a 2,2,6,6-tetrasubstituted piperidyl group. A compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type.
Examples of the compound (B) include a compound represented by the following formula.

R ^{11 to} R ¹⁴ are each independently an alkyl group having 1 to 18 carbon atoms (methyl group, ethyl group, propyl group, dodecyl group, stearyl group, etc.), cycloalkyl group (cyclopentyl group, cyclohexyl group, etc.), substituted An alkyl group (2-hydroxyethyl group, 2-methoxycarbonylethyl group, 3-hydroxypropyl group, etc.), aryl group (phenyl group, naphthyl group, etc.) or aralkyl group (phenethyl group, benzyl group, etc.); R ¹¹ And R ¹² , or R ¹³ and R ¹⁴ may form an aliphatic ring having 3 to 6 carbon atoms. As R < ¹¹ > -R < ¹⁴ >, a C1-C18 alkyl group is preferable from the point of a price and availability, and a methyl group is especially preferable.

R ¹⁵ represents a hydrogen atom, an alkyl group (methyl group, ethyl group, propyl group, butyl group, dodecyl group, stearyl group, etc.), substituted alkyl group (2-hydroxyethyl group, 2-methoxycarbonylethyl group, 2-acetoxy group). Ethyl group, 2- (3-methoxycarbonylpropionyloxy) ethyl group, 3-hydroxypropyl group, etc.), aryl group (phenyl group, naphthyl group, hydroxyphenyl group, etc.), aralkyl group (phenethyl group, benzyl group, hydroxyphenyl) An alkyl group or the like) or a cycloalkyl group (such as a cyclohexyl group).

R ¹⁶ represents a hydrogen atom, a hydroxyl group, an alkyl group (methyl group, ethyl group, propyl group, butyl group, dodecyl group, stearyl group, etc.), substituted alkyl group (2-hydroxyethyl group, 2-methoxycarbonylethyl group, 2 -Acetoxyethyl group, 2- (3-methoxycarbonylpropionyloxy) ethyl group, 3-hydroxypropyl group, etc.), aryl group (phenyl group, naphthyl group, etc.), aralkyl group (phenethyl group, benzyl group, etc.), ester bond Containing group (acetoxy group, propionyloxy group, butyryloxy group, lauroyloxy group, substituted alkylcarbonyloxy group, benzoyloxy group, substituted benzoyloxy group, etc.), amino group containing group (alkoxycarbonylamino group, N-monoalkylcarbamoylamino) Group, N, N-dialkylcarbamoy Or a 2,2,6,6-tetrasubstituted piperidyl group-containing group.

  Specific examples of the compound (B) include 2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethylpiperidine, 4-hydroxy-2,2,6,6-tetramethyl. Piperidine, 4-hydroxy-1,2,2,6,6-pentamethylpepyridine, 1-ethyl-2,2,6,6-tetramethylpiperidine, 1-ethyl-4-hydroxy-2,2,6 , 6-tetramethylpiperidine, 1-butyl-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-dodecyl-2,2,6,6-tetramethylpiperidine, 1-phenyl-2,2 , 6,6-tetramethylpiperidine, 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpipericin, 1- (6-hydroxyethyl) -4-hydroxy-2,2,6, 6-Tetrame Lupiperidine, 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-acetoxy-1,2,2,6,6-pentamethylpiperidine, 1- (2-acetoxyethyl) -4-acetoxy-2 , 2,6,6-tetramethylpiperidine, 1- (2-benzoyloxyethyl) -4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-ethyl-2,2,6,6- Tetramethylpiperidine, 4-ethyl-1,2,2,6,6-pentamethylpiperidine, 4-butyl-2,2,6,6-tetramethylpiperidine, 4-octyl-2,2,6,6- Tetramethylpiperidine, 4-dodecyl-2,2,6,6-tetramethylpiperidine, 4-stearyl-2,2,6,6-tetramethylpiperidine, 4-stearyl-1,2,2 6,6-penta-methylpiperidine, and the like.

Examples of the compound (B) in which R ¹⁶ is a 2,2,6,6-tetrasubstituted piperidyl group-containing group include 2,2,6,6-tetramethylpiperidines having a hydroxyl group (4-hydroxy-2,2, 6,6-tetramethylpiperidine, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidine and the like) and polybasic acids (succinic acid, adipic acid, sebacic acid, azelaic acid, decane-1,0-dicarboxylic acid, Phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, malonic acid, substituted malonic acid, etc.) obtained by reaction with two or more 2,2,6,6-tetramethylpiperidini per molecule And a compound (B1) containing a sulfur group.
Examples of the compound (B1) include those represented by the following formula. However, n3 is an integer of 1-20.

  0.01-15.0 mass parts is preferable with respect to 100 mass parts of a copolymer (A), and, as for the quantity of a compound (B), 0.05-10.0 mass parts is more preferable. When the amount of the compound (B) is 0.01 parts by mass or more, the fluoroolefin copolymer (A) solution becomes more difficult to gel during or after polymerization of the monomer. When the amount of the compound (B) is 15.0 parts by mass or less, the discoloration (yellowing, cloudiness) of the solution during storage and the increase in the molecular weight of the copolymer are further suppressed.

(Organic solvent (D))
The organic solvent (D) includes at least one organic solvent selected from the group consisting of aromatic hydrocarbon solvents, ketone solvents, ester solvents, and third organic solvents in the Industrial Safety and Health Act (hereinafter referred to as organic solvents). (Referred to as (D1)). When the organic solvent (D) is the organic solvent (D1), the copolymer (A) solution is likely to be discolored, and thus the effect of the present invention is particularly great.

  As the organic solvent (D), a solvent corresponding to the PRTR method and HAPs regulations, that is, an organic solvent having no aromatic ring is preferable from the viewpoint of reducing the environmental load. Moreover, the organic solvent classified into the 3rd type organic solvent in the classification of the organic solvent by the occupational safety and health law is also preferable. Specifically, ketone solvents, ether ester solvents that do not comply with the PRTR method and HAPs regulations; paraffinic solvents or naphthenic solvents classified as the third organic solvents in the Industrial Safety and Health Act are preferable.

Examples of the aromatic hydrocarbon solvent include toluene, xylene, ethylbenzene, aromatic petroleum naphtha, tetralin, turpentine oil, Solvesso (registered trademark) # 100 (manufactured by Exxon Chemical), Solvesso (registered trademark) # 150 (Exxon Chemical) Product).
As the ketone solvent, acetone, methyl ethyl ketone, methyl amyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, diisobutyl ketone, cyclohexanone, and isophorone are preferable.
As the ester solvent, methyl acetate, ethyl acetate, n-propyl acetate, isobutyl acetate, and tert-butyl acetate are preferable.

Class 3 organic solvents in the Industrial Safety and Health Act are gasoline, coal tar naphtha (including solvent naphtha), petroleum ether, petroleum naphtha, petroleum benzine, turpentine oil, mineral spirit (mineral thinner, petroleum spirit, white spirit and A solvent consisting of one or more selected from the group consisting of mineral terpenes).
As the third type organic solvent in the Industrial Safety and Health Law, mineral spirits (including mineral thinner, petrolium spirit, white spirit and mineral turpentine) are preferable because the flash point is room temperature or higher.

The organic solvent (D) may contain an organic solvent other than the organic solvent (D1). Other organic solvents are preferably alcohol solvents and ether ester solvents.
As the alcohol solvent, those having 4 or less carbon atoms are preferable, and specifically, ethanol, tert-butyl alcohol, and iso-propyl alcohol are preferable.
As the ether ester solvent, ethyl 3-ethoxypropionate, propylene glycol monomethyl ether acetate, and methoxybutyl acetate are preferable.
As other organic solvents, ethanol, tert-butyl alcohol and the like are more preferable.

An organic solvent (D) may be used individually by 1 type, and may be used in combination of 2 or more type.
The organic solvent (D) may be the same organic solvent as the organic solvent (D) used as the polymerization solvent, or may be a different organic solvent.

The amount of the organic solvent (D) is preferably such that the solid content concentration in the copolymer (A) solution is within the above-described range.
10-100 mass% is preferable among organic solvents (D) (100 mass%), and, as for the ratio of an organic solvent (D1), 30-95 mass% is more preferable. When the proportion of the organic solvent (D1) is 10% by mass or more, the solubility of the fluoroolefin copolymer (A) in the organic solvent (D) becomes good. When the proportion of the organic solvent (D1) is 100% by mass or less, in the coating composition containing an isocyanate curing agent, the curing rate does not become slow and the problem of poor curing of the coating film hardly occurs.

(Hydrotalcite)
It is preferable that the solution composition before removal of insoluble components contains hydrotalcite. A solution composition having a high pH can be obtained by mixing hydrotalcite at the time of polymerization or after polymerization to adsorb the acid component.
As hydrotalcite, those capable of sufficiently adsorbing acid components (hydrogen chloride and the like) are preferable.
As hydrotalcite, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O (x = 0.25, m = 0.5) from the point that it can sufficiently adsorb the acid component and is easily available. , or _{Mg 4.5 Al 2 (OH) 13} CO 3 · 3.5H 2 O (x = 0.308, m = 0.538) is preferred.
A hydrotalcite may be used individually by 1 type, and may be used in combination of 2 or more type.

The particle size of the hydrotalcite is preferably 5 to 500 μm, more preferably 5 to 110 μm. If the hydrotalcite particle size is 5 μm or more, removal by filtration becomes easy. When the hydrotalcite particle size is 500 μm or less, the surface area per unit mass is large, and the effect of hydrotalcite is sufficiently exhibited.
The particle size of hydrotalcite is measured in accordance with JIS K 0069 “Chemical product screening test method”.

  The amount of hydrotalcite is preferably 0.01 to 10.0 parts by mass, more preferably 0.05 to 5.0 parts by mass, with respect to 100 parts by mass of the copolymer (A). 2.0 parts by mass is more preferable. When the amount of hydrotalcite is 0.01 parts by mass or more, an increase in the molecular weight of the copolymer (A) during the polymerization of the monomer or after the polymerization, and a discoloration of the copolymer (A) solution are further unlikely to occur. . If the amount of hydrotalcite is 10.0 parts by mass or less, acid components such as hydrogen fluoride and hydrogen chloride generated from the copolymer (A) solution can be sufficiently removed, and the pH variation of the solution can be reduced. Can be reduced. When the pH fluctuation of the solution is reduced, in the one-component coating composition containing the blocked isocyanate curing agent, there is no difference in the curing rate between the coating surface layer and the coating film, and the coating film is derived from wrinkles on the coating surface layer. It is difficult to cause a decrease in gloss. When it is 2.0% or less, there is little clogging of the filter medium when removing the insoluble matter.

Further, when copolymerizing monomers such as fluoroolefin in the presence of hydrotalcite, the total mass of compound (B) and hydrotalcite is 0.01% with respect to 100 parts by mass of the monomer mixture. -15 mass parts is preferable, and 0.05-10 mass parts is more preferable. If the total mass of the compound (B) and hydrotalcite is 0.01 parts by mass or more, an increase in the molecular weight of the fluoroolefin copolymer (A) during or after polymerization of the monomer, A) Discoloration of the solution is less likely to occur. If the total mass of the compound (B) and hydrotalcite is 15 parts by mass or less, acid components such as hydrogen fluoride and hydrogen chloride generated from the solution of the fluoroolefin copolymer (A) can be sufficiently removed. The pH fluctuation of the solution can be reduced.
In order to exhibit the same effect as described above, the mass ratio of the compound (B) to hydrotalcite (hereinafter, the mass ratio of the compound (B) / hydrotalcite is represented by (B) / (C). ) Is preferably 5/95 to 95/5, and more preferably 20/80 to 80/20.

(Use)
The solution composition of the present invention can be suitably used as a raw material for paints. In particular, since the discoloration of the copolymer (A) solution is suppressed, it is suitable for clear paints, light color paints, and the like.

(Function and effect)
Since the solution composition of the present invention described above contains the compound (B), gelation of the solution composition is unlikely to occur during storage.
Further, since the solution composition of the present invention described above temporarily contains hydrotalcite, the copolymer (A) solution may be discolored (yellowing, clouded) or stored during storage. Components that increase the molecular weight of the polymer (A) (acid components (hydrogen chloride and the like)) are adsorbed and removed by hydrotalcite. As a result, increase in the molecular weight of the copolymer (A) and discoloration of the solution composition hardly occur.

<Method for producing solution composition>
The method for producing the solution composition of the present invention includes the following method (1) and method (2).
Method (1): A monomer mixture containing a fluoroolefin, a monomer (a2), and a monomer (a3) is polymerized in an organic solvent (D) in the presence of the compound (B) to co-polymerize. A method in which the coalescence (A) is generated, and then hydrotalcite is added and adsorbed, and then insoluble components are removed.
Method (2): A monomer mixture containing a fluoroolefin, a monomer (a2) and a monomer (a3) is polymerized in an organic solvent (D) in the presence of the compound (B) and hydrotalcite. To produce a copolymer (A) and then to remove insoluble components.

The monomer mixture is polymerized by a so-called solution polymerization method.
Specific examples of the solution polymerization method include the following methods.
(I) A method in which a monomer mixture, a compound (B), an organic solvent (D), and a polymerization initiator are collectively charged into a reactor for polymerization. The order of preparation can be set as appropriate.
(Ii) Monomer (a2), monomer (a3) and polymerization initiator are added continuously or in portions to a reactor charged with fluoroolefin, compound (B) and organic solvent (D). Method. The monomer (a2), the monomer (a3) and the polymerization initiator may be mixed with the organic solvent (D) and added together, and the charging order can be appropriately set.
(Iii) A method in which a monomer mixture and a polymerization initiator are added continuously or dividedly to a reactor charged with the compound (B) and the organic solvent (D). The monomer mixture and the polymerization initiator may be mixed with the organic solvent (D) and added together, and the charging order can be appropriately set.
(Vi) A compound (B) and an organic solvent (D) are charged, and further, a part or all of one or two of fluoroolefin (a1), monomer (a2) and monomer (a3), or a single amount A method in which the remainder of the monomer and the polymerization initiator are added continuously or divided into a reaction vessel charged with a part of the body mixture. The remainder of the monomer and the polymerization initiator may be mixed with the organic solvent (D) and added together, and the charging order can be appropriately set.

Monomer mixture:
A monomer mixture consists of a fluoro olefin, a monomer (a2), and a monomer (a3).
Examples of the fluoroolefin, monomer (a2) and monomer (a3) include those described above.

Compound (B):
Examples of the compound (B) include the same compounds as those contained in the above-described solution composition.

Organic solvent (D):
As an organic solvent (D), the thing similar to what is contained in the solution composition mentioned above is mentioned.
The organic solvent (D) may be the same organic solvent as the organic solvent (D) contained in the solution composition, or may be a different organic solvent.

Polymerization initiator:
As polymerization initiators, azo initiators (2,2′-azobisisobutyronitrile, 2,2′-azobiscyclohexane carbonate nitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), peroxide initiators (ketone peroxides (cyclohexanone peroxide, etc.), hydroperoxides (tert-butyl hydroperoxide, etc.), diacyl peroxides (benzoyl) Peroxides), dialkyl peroxides (di-tert-butyl peroxide, etc.), peroxyketals (2,2-di- (tert-butylperoxy) butane, etc.), alkyl peresters (tert-butyl peroxypivalate, etc.) ), Percarbonates (diisopropylperoxy Dicarbonate etc.)}.

Charge amount:
The amount of the fluoroolefin is preferably 30 to 70 mol%, more preferably 40 to 60 mol%, still more preferably 45 to 55 mol% in the monomer mixture (100 mol%). When the amount of the fluoroolefin is 30 mol% or more, the weather resistance of the resulting coating film is excellent. When the amount of the fluoroolefin is 70 mol% or less, the resulting copolymer (A) is excellent in solubility in an organic solvent or a diluent.

The total amount of the monomer (a2) and the monomer (a3) is preferably 70 to 30 mol%, more preferably 60 to 40 mol% in the monomer mixture (100 mol%), and 55 to 55 mol%. More preferably, it is 45 mol%.
Therefore, when the monomer other than the fluoroolefin is only the monomer (a2) and the monomer (a3), the total amount of the monomer (a2) and the monomer (a3) is the monomer mixture. Among (100 mol%), 70 to 30 mol% is preferable, 60 to 40 mol% is more preferable, and 55 to 45 mol% is more preferable.

  The amount of the monomer (a2) is preferably 5 to 40 mol% and more preferably 8 to 35 mol% in the monomer mixture (100 mol%). When the amount of the monomer (a2) is 5 mol% or more, a sufficient amount of crosslinkable groups is introduced into the fluoroolefin copolymer (A) to obtain a coating film having high hardness. If the amount of the monomer (a2) is 40 mol% or less, even if it is a high solid content type, a sufficiently low viscosity can be maintained as the fluoroolefin copolymer (A) solution.

  The amount of the monomer (a3) is preferably more than 0 mol% and 45 mol% or less, more preferably 3 to 35 mol%, and further preferably 5 to 30 mol% in the monomer mixture (100 mol%). . By including the monomer (a3), the hardness and flexibility of the obtained coating film can be appropriately adjusted. When the amount of the monomer (a3) is 45 mol% or less, a sufficient amount of crosslinkable groups are introduced into the copolymer (A) to obtain a coating film having excellent weather resistance and high hardness. .

  When a monomer other than the fluoroolefin, monomer (a2) and monomer (a3) is further used, the amount of the other monomer is 20 mol% in the monomer mixture (100 mol%). The following is preferable, and 10 mol% or less is more preferable.

  0.01-15.0 mass parts is preferable with respect to 100 mass parts of a monomer mixture, and, as for the quantity of a compound (B), 0.05-10.0 mass parts is more preferable. If the amount of the compound (B) is 0.01 parts by mass or more, the solution composition is more difficult to gel during or after polymerization of the monomer. When the amount of the compound (B) is 15.0 parts by mass or less, discoloration (yellowing, cloudiness) of the solution composition during storage and increase in the molecular weight of the copolymer (A) can be further suppressed.

The amount of the organic solvent (D) is preferably such that the solid content concentration in the solution composition is within the above-described range.
10-100 mass% is preferable among organic solvents (D) (100 mass%), and, as for the ratio of an organic solvent (D1), 30-95 mass% is more preferable. If the ratio of an organic solvent (D1) is 10 mass% or more, the solubility to the organic solvent (D) of a copolymer (A) will become favorable. When the proportion of the organic solvent (D1) is 100% by mass or less, in the coating composition containing an isocyanate curing agent, the curing rate does not become slow and the problem of poor curing of the coating film hardly occurs.

  In the method (1), hydrotalcite is added to a solution containing the copolymer (A) obtained by polymerization to perform an adsorption treatment.

  The amount of hydrotalcite is preferably 0.01 to 10.0 parts by mass and more preferably 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the copolymer (A) as described above.

After the adsorption treatment with hydrotalcite, insoluble components such as hydrotalcite are removed from the copolymer solution containing hydrotalcite.
Specifically, a solid-liquid separation such as filtration is performed to remove hydrotalcite and the like that are present as an insoluble component, and a homogeneous product containing the copolymer (A), the compound (B), and the organic solvent (D). Obtain a solution.

In the method (2), the monomer mixture is polymerized in the organic solvent (D) in the presence of the compound (B) and hydrotalcite to produce a copolymer (A). By polymerizing in the presence of hydrotalcite, the acid component by-produced during the polymerization is quickly adsorbed on the hydrotalcite. After the copolymer (A) is formed, insoluble components such as hydrotalcite are removed from the copolymer solution containing hydrotalcite. As in the case of the method (1), specifically, hydrotalcite existing as an insoluble component is removed by performing solid-liquid separation such as filtration, and the copolymer (A), compound (B) and A homogeneous solution containing the organic solvent (D) is obtained.
As described above, the total mass of the compound (B) and hydrotalcite in the method (2) is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the monomer mixture, and 0.05 to 10 Part by mass is more preferable. Moreover, (B) / (C) is preferably 5/95 to 95/5, and more preferably 20/80 to 80/20.

(Function and effect)
In the method for producing the solution composition of the present invention described above, since the monomer mixture is polymerized in the presence of the compound (B) having a 2,2,6,6-tetrasubstituted piperidyl group, Gelation of the fluoroolefin copolymer (A) solution hardly occurs during or after polymerization of the monomer mixture.
Further, in the method for producing the solution composition of the present invention described above, since the hydrotalcite is added after the polymerization or the polymerization is performed in the presence of the hydrotalcite, the polymerization of the monomer is performed. Hydrotalcite is a component (acid component (hydrogen chloride, etc.)) that changes the color of the copolymer (A) -containing solution during or after polymerization (yellowing, cloudiness) or increases the molecular weight of the copolymer (A). Adsorbed and removed. As a result, the increase in the molecular weight of the copolymer (A) and the discoloration of the copolymer (A) solution are unlikely to occur.

<Coating composition>
The coating composition of the present invention comprises at least one curing agent selected from the group consisting of the solution composition of the present invention, an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin (hereinafter referred to as curing agent (E )))). You may further mix | blend another coating compounding component (henceforth a compounding agent (F)) as needed.
Moreover, the coating composition of this invention mix | blends a hardening | curing agent (E) and a compounding agent (F) before the removal of an insoluble component in the method of manufacturing the solution composition of the said invention, and an insoluble component is added after that. It can also be removed and manufactured. In this case, the curing agent (E) and the compounding agent (F) to be blended must be soluble in the organic solvent (D). Those that are insoluble or hardly soluble in the organic solvent (D) need to be blended in the solution composition of the present invention.

(Curing agent)
The curing agent (E) is at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent, and an amino resin.

As the isocyanate curing agent, non-yellowing isocyanates (hexamethylene diisocyanate, isophorone diisocyanate, etc.) are preferable.
As the blocked isocyanate curing agent, those obtained by blocking the isocyanate group of the isocyanate curing agent with caprolactam, isophorone, β-diketone or the like are preferable.

  An amino resin is a resin obtained by polycondensation of amines (melamine, methylolmelamine, guanamine, urea, etc.) and aldehydes (formaldehyde, etc.). Examples of amino resins include melamine resins, guanamine resins, urea resins, sulfoamide resins, and aniline resins.

  1-100 mass parts is preferable with respect to 100 mass parts of the copolymer (A) in a coating composition, and, as for the quantity of a hardening | curing agent, 1-50 mass parts is more preferable. When the curing agent is 1 part by mass or more, the solvent resistance of the coating film is excellent and the hardness is sufficient. If a hardening | curing agent is 100 mass parts or less, it is excellent in workability and is excellent in impact resistance.

(Compounding agent (F))
As the compounding agent (F), other curing agents other than the curing agent (E), organic solvents, colorants, resins other than the copolymer (A), silane coupling agents, ultraviolet absorbers, curing accelerators, light Stabilizers, matting agents and the like can be mentioned. Two or more of these may be used in combination.

Organic solvent:
When preparing the coating composition, an organic solvent may be further added to the solution composition. The organic solvent may be the same organic solvent as the organic solvent (D) used as the polymerization solvent, or may be a different organic solvent. For example, the organic solvent (D1) may be used, and other organic solvents (xylene, toluene, etc.) other than the organic solvent (D1) may be used.

Colorant:
Examples of the colorant include inorganic pigments (carbon black, titanium oxide, etc.) having good weather resistance, organic pigments (phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, isoindolinone yellow, etc.), dyes, and the like. .

Resins other than copolymer (A):
Examples of the resin other than the copolymer (A) include known resins blended in the paint.
For example, cellulose acetate butyrate, nitrocellulose, or the like may be blended in order to improve the drying properties of the coating film. Moreover, in order to improve the glossiness, hardness, and workability of the coating film, a polymer made of (meth) acrylic acid or an ester thereof, polyester, or the like may be blended.

(Function and effect)
In the coating composition of the present invention described above, since the solution composition of the present invention is blended, a specific curing agent (isocyanate curing agent, blocked isocyanate system) is added to the copolymer (A) solution. Even when it is a one-component coating composition by blending a curing agent or amino resin), it is difficult to yellow during storage, and the gloss, boiling water resistance, alkali resistance, and moisture resistance of the coating film are good. It is possible to form a coating that hardly changes color.

<Coated article>
A coated article is obtained by applying the coating composition of the present invention to the surface of the article and drying it.
Examples of the coating method include spray coating, air spray coating, brush coating, dipping method, roll coating, and flow coating.

  Materials to be painted include inorganic substances (concrete, natural stone, glass, metal (iron, stainless steel, aluminum, copper, brass, titanium, etc.)), organic substances (plastic, rubber, adhesive, wood, etc.), organic Examples thereof include inorganic composite materials (fiber reinforced plastic, resin reinforced concrete, fiber reinforced concrete, and the like).

  Articles to be painted include transportation equipment (automobiles, trains, aircraft, etc.), civil engineering members (bridge members, steel towers, etc.), industrial equipment (waterproofing sheets, tanks, pipes, etc.), building materials (building exteriors, doors, Window gate members, monuments, poles, etc.), road members (road median strips, guardrails, noise barriers, etc.), communication equipment, electrical parts, electronic parts, solar cell module surface sheets, solar cell module back sheets, etc. Can be mentioned.

EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following description, “%” is “mass%” unless otherwise specified.
Examples 1-4 and 6-9 are examples, and examples 5 and 10 are comparative examples.

(Solid content concentration of solution composition)
The solid content concentration of the solution composition was determined by measuring the heating residue according to JIS K 5601-1-2 (established in 2009).

(Number average molecular weight of copolymer (A))
The number average molecular weight of the copolymer (A) was measured by GPC (manufactured by Tosoh Corporation, HLC-8220). Tetrahydrofuran was used as a developing solvent, and polystyrene was used as a standard substance.

(Measurement of pH)
The pH of the solution composition was measured as follows.
By filtering diatomaceous earth as a filter medium, 10 g of the homogeneous solution composition after removing insoluble components and 30 g of methyl isobutyl ketone were put into a 100 mL glass container and dissolved until uniform. Next, this dissolved solution was charged into a 300 mL separatory funnel, and 30 g of methyl isobutyl ketone was further charged. Thereafter, 60 g of ion-exchanged water was added, and the separatory funnel was manually shaken for 1 minute, and then allowed to stand until it became two layers. The aqueous layer was separated, and the pH of the aqueous layer was measured to obtain the pH of the solution composition.

(Storage stability of solution composition)
The storage stability of the solution composition was evaluated as follows.
100 g of the solution composition was put in a heat-resistant container, left in a thermostat bath at 70 ° C. and RH 50%, and the number average molecular weight after 14 days was measured with GPC (manufactured by Tosoh Corporation, HLC-8220).
The increase rate of the number average molecular weight after 14 days with respect to the initial number average molecular weight was determined. Further, the degree of discoloration of the solution composition after 14 days with respect to the initial solution composition was visually evaluated.
Based on the increase rate of the number average molecular weight and the degree of discoloration, the following criteria were used for evaluation.

A: The increase rate of the number average molecular weight after 14 days was less than 150%, and no significant discoloration (yellowing or cloudiness) was observed.
B: The increase rate of the number average molecular weight after 14 days was less than 150%, but significant discoloration (yellowing or cloudiness) was confirmed.
C: The increase rate of the number average molecular weight after 14 days was 150% or more, but no significant discoloration (yellowing or cloudiness) was confirmed.
D: The increase rate of the number average molecular weight after 14 days was 150% or more, and significant discoloration (yellowing or cloudiness) was also confirmed.

(Storage stability of coating composition)
100 g of the coating composition was placed in a heat-resistant container and left in a thermostatic bath at 50 ° C. for 1 month. The degree of discoloration of the coating composition after one month relative to the initial coating composition was evaluated visually according to the following criteria.
A: Significant discoloration (yellowing or cloudiness) was not confirmed.
B: Significant discoloration (yellowing or cloudiness) was confirmed.

(Glossiness of coating film: 1)
The paint composition immediately after blending is applied to one surface of the chromate-treated aluminum plate so that the film thickness becomes 40 μm, and dried and cured in a hot air drying oven at 230 ° C. for 2 minutes. A test piece with a film was obtained.
About the test piece with a coating film, the gloss value of the coating film was measured and evaluated on the following reference | standard.
○ (Good): The gloss was 100 or more, and no significant discoloration (yellowing or cloudiness) was observed in the coating film.
X (defect): Gloss was less than 100, and significant discoloration (yellowing or cloudiness) was confirmed in the coating film.

(Glossiness of coating film: 2)
On one surface of the aluminum plate subjected to the chromate treatment, a coating composition which was left in a thermostatic bath at 50 ° C. for 1 month after blending was applied to a film thickness of 40 μm, and a hot air drying oven at 230 ° C. And dried and cured for 2 minutes to obtain a test piece with a coating film.
About the test piece with a coating film, the gloss value of the coating film was measured and evaluated on the following reference | standard.
○ (Good): The gloss was 100 or more, and no significant discoloration (yellowing or cloudiness) was observed in the coating film.
X (defect): Gloss was less than 100, and significant discoloration (yellowing or cloudiness) was confirmed in the coating film.

(Boiling water resistance)
The test piece with a coating film prepared in “Glossiness of coating film: 1” was immersed in ion-exchanged water (95 ± 5 ° C.) for 24 hours. After water cooling, it was dried and the adhesion of the coating film was evaluated according to the following criteria by a method based on JIS K 5600-5-6 (cross-cut method).
○ (Good): No peeling of the coating film was confirmed.
X (defect): Peeling of the coating film was confirmed.

(Alkali resistance)
Ten drops of a 10% aqueous sodium hydroxide solution were placed on the surface of the coating film of the test piece with a coating film prepared in “Glossiness of coating film: 1”, covered with a watch glass, and allowed to stand for one week. It was washed with ion-exchanged water and dried, and the state of the coating film was visually evaluated according to the following criteria.
○ (Good): No swelling or disappearance of the coating was confirmed. That is, the base material was not corroded.
X (defect): Swelling or disappearance of the coating film was confirmed. That is, the base material was corroded.

(Moisture resistance)
The test piece with a coating film prepared in “Glossiness of coating film: Part 1” was allowed to stand in a high humidity environment of 50 ° C. and 95 RH% for 3,000 hours, washed with ion-exchanged water, allowed to cool, and dried. Then, the state of the coating film was visually evaluated according to the following criteria.
○ (Good): No swelling or change in the color of the coating film was confirmed.
X (defect): The swelling and the change of the color of the coating film were confirmed.

(Example 1)
A stainless steel pressure resistant reactor with an internal volume of 2500 ml equipped with a stirrer was charged with bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl). ) -4-Hydroxyphenyl] methyl] butyl malonate (BASF, trade name: TINUVIN 144) 12.43 g, xylene 929 g, ethyl vinyl ether 212 g, 4-hydroxybutyl vinyl ether 132 g, cyclohexyl vinyl ether 214 g The dissolved oxygen in the liquid was removed by deaeration with nitrogen. 677 g of chlorotrifluoroethylene is introduced into the reactor and the temperature is gradually raised. When the temperature reaches 65 ° C., 12.14 g of tert-butyl peroxypivalate as a polymerization initiator is intermittently added. The polymerization was allowed to proceed.
After 10 hours, the reaction was stopped by cooling the reactor with water. After the reaction solution was cooled to room temperature, unreacted monomers were purged, and the concentration of the resulting reaction solution was adjusted to obtain a base solution having a solid content concentration of 60.0%. The number average molecular weight of the fluoroolefin copolymer was 21,000.

  In the base solution, hydrotalcite (Kyowa Chemical Industry Co., Ltd., KW500, particle size: 45 μm or less 38%, 45 to 74 μm 35%, 75 to 106 μm 21%, 106 to 500 μm 6 with respect to 100 parts by mass of the fluoroolefin copolymer. %) Was added and mixed for about 1 hour to obtain a solution composition (1) before removing insoluble components. Table 1 shows the storage stability of the solution composition (1) before removing insoluble components.

(Example 2)
Except for changing hydrotalcite (KW500) to hydrotalcite (KW2000, manufactured by Kyowa Chemical Industry Co., Ltd., particle size: 45% or less 25%, 45-74 μm 31%, 75-105 μm 35%, 105-149 μm 9%) In the same manner as in Example 1, a solution composition (2) before removing insoluble components was obtained. Table 1 shows the storage stability of the solution composition (2) before removing insoluble components.

(Example 3)
The solution composition (1) obtained in Example 1 was filtered using diatomaceous earth as a filter medium to remove insoluble components to obtain a solution composition (3). Table 1 shows the storage stability of the solution composition (3).

(Example 4)
The solution composition (2) obtained in Example 2 was filtered using diatomaceous earth as a filter medium to remove insoluble components to obtain a solution composition (4). Table 1 shows the storage stability of the solution composition (4).

(Example 5)
A solution composition (5) was obtained in the same manner as in Example 1 except that hydrotalcite was not added. Table 1 shows the storage stability of the solution composition (5).

(Example 6)
In place of Tinuvin 144, a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidyl) separate and methyl 1,2,2,6,6-pentamethyl-4-piperidylsepacate (mass ratio 3: 1) A copolymer was produced in the same manner as in Example 1 except that (trade name: TINUVIN292, manufactured by BASF) was used, and then the same treatment as in (Example 3) was performed to obtain a solution composition (6). . Table 1 shows the storage stability of the solution composition (6).
Hereinafter, in the table, the compound (B) is represented by “(B)” and the hydrotalcite is represented by “(C)”.

(Example 7)
72.3 g of the solution composition (1) containing hydrotalcite obtained in Example 1 and 14.1 g of a blocked isocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur (registered trademark) BL-3175) Then, 12.2 g of xylene and dibutyltin dilaurate as a curing catalyst (diluted 10,000 times with xylene to 1.4 g) were added and mixed. A coating composition (1) was obtained by removing insoluble components with a membrane filter (manufactured by Yamato Scientific Co., Ltd.). The evaluation results are shown in Table 2.

(Example 8)
A coating composition (2) was obtained in the same manner as in Example 7 except that the solution composition (1) was changed to the solution composition (2). The evaluation results are shown in Table 2.

(Example 9)
A coating composition (3) was obtained in the same manner as in Example 7 except that the solution composition (1) was changed to the solution composition (3). The evaluation results are shown in Table 2.

(Example 10)
A coating composition (4) was obtained in the same manner as in Example 7, except that the solution composition (1) was changed to the solution composition (4). The evaluation results are shown in Table 2.

(Example 11)
A coating composition (5) was obtained in the same manner as in Example 7 except that the solution composition (1) was changed to the solution composition (5). The evaluation results are shown in Table 2.

(Example 12)
A coating composition (6) was obtained in the same manner as in Example 7 except that the solution composition (1) was changed to the solution composition (6). The evaluation results are shown in Table 2.

The coating compositions (1) to (4) and (6) of Examples 7 to 10 and Example 12 are excellent in storage stability as a one-pack type coating composition, and the coating composition after storage can be used without any problem. did it.
On the other hand, as the coating composition (5) of Example 11, the coating composition immediately after blending can be used without any problem, but the coating composition after storage has been confirmed to have a problem that the gloss of the coating film is insufficient, Further, even a coating composition immediately after blending was not satisfactory with respect to the physical properties of the coating film.

(Example 13)
Into a stainless steel pressure resistant reactor with an internal volume of 2500 mL equipped with a stirrer, 12.43 g of TINUVIN 144, hydrotalcite (Kyowa Chemical Industries, KW500, particle size: 45 μm or less 38%, 45-7 μm 35%, 75 -106 μm 21%, 106-500 μm 6%) 6.2 g, xylene 929 g, ethyl vinyl ether 212 g, 4-hydroxybutyl vinyl ether 132 g, cyclohexyl vinyl ether 214 g, and dissolved oxygen in the liquid removed by deaeration with nitrogen did. 677 g of chlorotrifluoroethylene is introduced into the reactor and the temperature is gradually raised. When the temperature reaches 65 ° C., 12.14 g of tert-butyl peroxypivalate as a polymerization initiator is intermittently added. The polymerization was allowed to proceed.
After 10 hours, the reaction was stopped by cooling the reactor with water. After cooling the reaction solution to room temperature, the unreacted monomer is purged, and the resulting reaction solution is filtered using diatomaceous earth as a filter medium to remove insoluble components, so that the solid content concentration is 60.0%. A solution composition (7) was obtained. The number average molecular weight of the fluoroolefin copolymer was 14,200. Table 3 shows the storage stability of the solution composition (7). In Table 3, “(B) + (C)” represents the total amount of the compound (B) and hydrotalcite.

(Example 14)
Into a stainless steel pressure resistant reactor with an internal volume of 2500 mL equipped with a stirrer, 12.43 g of TINUVIN 144, hydrotalcite (Kyowa Chemical Industries, KW2000, particle size: 45 μm or less 25%, 45 to 74 μm 31%, 75 -105 μm 35%, 105-149 μm 9%) 6.2 g, xylene 929 g, ethyl vinyl ether 212 g, 4-hydroxybutyl vinyl ether 132 g, cyclohexyl vinyl ether 214 g, and dissolved oxygen in the liquid removed by degassing with nitrogen did. 677 g of chlorotrifluoroethylene is introduced into the reactor and the temperature is gradually raised. When the temperature reaches 65 ° C., 12.14 g of tert-butyl peroxypivalate as a polymerization initiator is intermittently added. The polymerization was allowed to proceed.
After 10 hours, the reaction was stopped by cooling the reactor with water. After cooling the reaction solution to room temperature, the unreacted monomer is purged, and the resulting reaction solution is filtered using diatomaceous earth as a filter medium to remove insoluble components, so that the solid content concentration is 60.0%. A solution composition (8) was obtained. The number average molecular weight of the fluoroolefin copolymer was 13,900. Table 3 shows the storage stability of the solution composition (8).

(Example 15)
A solution composition (9) having a solid content concentration of 60.0% was obtained in the same manner as in Example 13 except that hydrotalcite was not added. The number average molecular weight of the fluoroolefin copolymer was 13,900. Table 3 shows the storage stability of the solution composition (9).

(Example 16)
72.3 g of the solution composition (7) obtained in Example 13, 14.1 g of a blocked isocyanate curing agent (manufactured by Sumika Bayer Urethane Co., Ltd., Desmodur (registered trademark) BL-3175), and 12.1 g of xylene. 2 g of dibutyltin dilaurate as a curing catalyst (diluted 10,000 times with xylene to give 1.4 g) was mixed to obtain a coating composition (7). The evaluation results are shown in Table 4.

(Example 17)
A coating composition (8) was obtained in the same manner as in Example 16 except that the solution composition (7) was changed to the solution composition (8). The evaluation results are shown in Table 4.

(Example 18)
A coating composition (9) was obtained in the same manner as in Example 4 except that the solution composition (7) was changed to the solution composition (9). The evaluation results are shown in Table 4.

The coating compositions (7) and (8) of Examples 16 and 17 were excellent in storage stability as a one-component coating composition, and the coating compositions after storage could be used without any problem.
On the other hand, as the coating composition (9) of Example 18, the coating composition immediately after blending can be used without any problem, but the coating composition after storage has been confirmed to have a problem that the gloss of the coating film is insufficient, Further, even a coating composition immediately after blending was not satisfactory with respect to the properties of the coating film.

The solution composition containing the fluoroolefin copolymer of the present invention is useful as a raw material for paints.
The specification, claims and abstract of Japanese Patent Application No. 2013-216477 filed on October 17, 2013 and Japanese Patent Application No. 2013-235103 filed on November 13, 2013 are as follows. The contents of which are hereby incorporated herein by reference.

Claims (14)

A fluoroolefin copolymer comprising a structural unit based on a fluoroolefin, a structural unit based on a monomer having a crosslinkable group, and a structural unit based on a monomer having no fluorine atom and a crosslinkable group;
A compound having a 2,2,6,6-tetrasubstituted piperidyl group;
A solution composition comprising an organic solvent and a pH of 4.0 to 8.0.   The solution composition according to claim 1, wherein the pH of the solution composition is 5.0 to 7.0.   The amount of the compound having the 2,2,6,6-tetra-substituted piperidyl group is 0.01 to 15.0 parts by mass with respect to 100 parts by mass of the fluoroolefin copolymer. 3. The solution composition according to 2.   It was obtained by removing insoluble components from a composition containing the fluoroolefin copolymer, the 2,2,6,6-tetrasubstituted piperidyl group-containing compound, hydrotalcite, and the organic solvent. The solution composition as described in any one of 1-3.   The solution composition of Claim 4 whose quantity of the said hydrotalcite in the said solution composition is 0.01-10.0 mass parts with respect to 100 mass parts of the said fluoro olefin copolymer. Existence of a compound having a 2,2,6,6-tetra-substituted piperidyl group by mixing a monomer mixture containing a fluoroolefin, a monomer having a crosslinkable group and a fluorine atom and a monomer having no crosslinkable group Under polymerization in an organic solvent to produce a fluoroolefin copolymer,
Next, the manufacturing method of the solution composition characterized by adding hydrotalcite and carrying out adsorption treatment, and removing an insoluble component after that.   The amount of the compound having the 2,2,6,6-tetra-substituted piperidyl group is 0.01 to 15.0 parts by mass with respect to 100 parts by mass of the monomer mixture. A method for producing a solution composition of   The manufacturing method of the solution composition of Claim 6 or 7 whose addition amount of the said hydrotalcite is 0.01-10.0 mass parts with respect to 100 mass parts of the said fluoro olefin copolymer.   The manufacturing method of the solution composition as described in any one of Claims 6-8 whose pH of the said solution composition exists in the range of 4.0-8.0.   A monomer mixture containing a fluoroolefin, a monomer having a crosslinkable group, and a monomer having no fluorine atom and no crosslinkable group is converted into a compound having a 2,2,6,6-tetrasubstituted piperidyl group and hydro A method for producing a solution composition comprising polymerizing in an organic solvent in the presence of talcite to form a fluoroolefin copolymer and then removing insoluble components.   The production of the solution composition according to claim 10, wherein a mass ratio represented by the compound having the 2,2,6,6-tetra-substituted piperidyl group / the hydrotalcite is 5/95 to 95/5. Method.   The total mass of the compound having the 2,2,6,6-tetrasubstituted piperidyl group and the hydrotalcite is 0.01 to 15 parts by mass with respect to 100 parts by mass of the monomer mixture. Item 12. A method for producing a solution composition according to Item 10 or 11.   The manufacturing method of the solution composition as described in any one of Claims 10-12 whose pH of the said solution composition exists in the range of 4.0-8.0.   A paint comprising at least one curing agent selected from the group consisting of an isocyanate curing agent, a blocked isocyanate curing agent and an amino resin, and the solution composition according to any one of claims 1 to 5. Composition.