JP2023077878A - Additive for dispersing fluoropolymer - Google Patents

Abstract

To provide an additive for dispersing a fluoropolymer, which is added to a non-aqueous composition or coating agent comprising a fluoropolymer to maintain a state where the fluoropolymer is sufficiently dispersed in a non-aqueous liquid medium for a long period, which does not generate a harmful perfluoroalkyl-containing residue even when cured films of the non-aqueous dispersion or the coating agent are burned and decomposed, and which, due to their dispersing property and precipitation preventing property, provide the fluoropolymer with dispersibility and an orientation property on the coating surface and, thereby, make the coating film exhibit water-repellant, oil-repellant, and antifouling properties.SOLUTION: Provided is an additive for dispersing a fluoropolymer, comprising a copolymer which is obtained by copolymerizing 5-40 parts of a fluorine-containing (meth)acrylate monomer (a) represented by CH2=C(-R1)-CO-O-R2-RF, 20-45 parts of a (meth)acrylate monomer (b), and 15-75 parts of a macromonomer (c) containing a nonpolymerizable repeating structure and a terminal (meth)acryloyl group, the macromonomer having a solubility parameter value of 9.0-10.3 and a weight average molecular weight of 3000-100000, and which has a solubility parameter value of 8.5-12.0 and a weight average molecular weight of 10000 to 1000000.SELECTED DRAWING: None

Description

The present invention provides high anti-settling properties and uniform dispersion of the fluoropolymer by stabilizing the uniform dispersion of the fluoropolymer in a non-aqueous liquid medium, which is added to a non-aqueous composition or coating agent containing the fluoropolymer. The present invention relates to an additive for dispersing a fluoropolymer that efficiently orients a fluoropolymer on the surface of a cured non-aqueous composition or coating agent to develop excellent water repellency, oil repellency, and antifouling properties.

Fluoropolymer powder such as polytetrafluoroethylene (PTFE), which is a fluoropolymer, and fluoropolymer oil (PFPE), such as fluoropolymer oil, have low surface energy, are water and oil repellent, and have a specific gravity. Due to their large size, they were very difficult to disperse in non-aqueous liquid media such as organic solvents.

Therefore, conventionally, a compound having a long-chain perfluoroalkyl group having 8 or more carbon atoms, such as a perfluorooctyl group, has been used as a dispersing agent for a fluoropolymer.

However, in recent years, compounds having long-chain perfluoroalkyl groups with 8 or more carbon atoms are oxidized and decomposed by combustion or the like. It has been found that long-chain perfluoroalkyl-containing residues such as PFOS) can be produced.

Since these PFOA and PFOS have poor reactivity of long-chain perfluoroalkyl groups, they are difficult to decompose in the natural environment and are difficult to be metabolized in vivo. There are concerns about its toxicity, and its use is regulated in many countries. Therefore, instead of a compound having a long-chain perfluoroalkyl group having 8 or more carbon atoms, a compound that can be used as a dispersant for a fluoropolymer and that does not generate PFOA, PFOS, etc. even when decomposed will be used. It's becoming

Among them, as a dispersant in place of a compound having a perfluoroalkyl group having 8 or more carbon atoms, for example, Patent Document 1 discloses a fluorine-containing aliphatic polymer ester having a perfluoroalkyl group having 8 or less carbon atoms. A system polymer fine particle dispersion composition is disclosed, and in Patent Document 2, a (meth) acryloyl group-containing fluorine compound having a perfluoroalkyl group having 6 or less carbon atoms and a polyoxyalkylene chain-containing ethylenically unsaturated monomer Dispersants for fluoropolymer particles composed of copolymers have been disclosed, and Patent Document 3 discloses a PTFE dispersant containing a fluorine-containing oligomer having a branched perfluoroalkenyl group. When these dispersants are used, the fluoropolymer has insufficient dispersion stability even though it has dispersibility. Patent Document 4 discloses a dispersing agent for a fluoropolymer having a perfluoroalkyl group having 6 or less carbon atoms and containing a macromonomer. When these dispersants are used, even though the fluoropolymer has dispersion stability, the anti-settling property is insufficient, and the fluoropolymer is effectively oriented on the surface of the cured coating film, resulting in water and oil repellency. is insufficient to obtain

Japanese Patent Application Laid-Open No. 2003-213062 JP 2010-090338 A JP 2011-074129 A JP 2015-110697 A

The present invention has been made to solve the above-mentioned problems, and is added to a non-aqueous composition or coating agent containing a fluoropolymer, and has excellent dispersibility to sufficiently disperse the fluoropolymer in a non-aqueous liquid medium. Excellent anti-settling property that maintains for a long period of time, does not have a perfluoroalkyl group having 8 or more carbon atoms such as a perfluorooctyl group, and is formed by curing this non-aqueous composition or coating agent. Even if it is oxidized and decomposed by combustion, etc., it does not generate harmful perfluoroalkyl-containing residues, and its dispersibility and anti-settling properties make the fluoropolymer uniformly dispersible on the coating surface and highly oriented, making it water repellent. - An object of the present invention is to provide a fluoropolymer-dispersing additive that exhibits oil repellency and antifouling properties, a fluoropolymer-dispersed composition and a coating agent containing the same, and a coating film thereof.

A fluoropolymer dispersing additive for achieving the above object comprises a fluorine-containing (meth)acrylate monomer (a), a (meth)acrylate monomer (b), and a repeating structure terminal (meth)acryloyl group-containing With respect to a total of 100 parts by weight with the macromonomer (c), the following chemical formula (1)
CH ₂ =C(-R ¹ )-CO-OR ² -R ^F (1)
(In formula (1), —R ¹ is a hydrogen atom or a methyl group, —R ² — is a group represented by —(CH ₂ ) _n — in which n is 1 to 12, —R ^F is a carbon number of 2 to 6 5 parts by weight or more and less than 40 parts by weight of the fluorine-containing (meth)acrylate monomer (a) represented by a linear, branched, and / or alicyclic perfluoroalkyl group), and the (meth) 20 parts by weight or more and less than 45 parts by weight of the acrylate monomer (b), the repeating structure terminal (meta ) 15 parts by weight or more and 75 parts by weight or less of the acryloyl group-containing macromonomer (c) are copolymerized with each (meth)acryloyl group, and the solubility parameter value obtained by the Fedors method is 8.5 to 12.0 and a weight average molecular weight of 10,000 to 1,000,000.

This fluoropolymer dispersing additive comprises a main chain portion obtained by copolymerizing the copolymer with the respective (meth)acryloyl groups, and a side chain portion having the repeating structure extending from the middle of the main chain portion. It may be a graft polymer having

In this fluoropolymer dispersing additive, for example, the fluorine-containing (meth)acrylate monomer (a) is at least one selected from perfluorobutylethyl (meth)acrylate and perfluorohexylethyl (meth)acrylate, It is preferable that the (meth)acrylate monomer (b) is at least one selected from an alkyl (meth)acrylate containing an alkyl group having 1 to 12 carbon atoms and an amino group-containing (meth)acrylic monomer.

In this fluoropolymer dispersing additive, for example, the repeating structure terminal (meth)acryloyl group-containing macromonomer (c) is a polyalkyl (meth)acrylate macromonomer, a polyalkenyl (meth)acrylate macromonomer, or a polyester macromonomer. , and polystyrene macromonomers.

In this fluoropolymer dispersing additive, the copolymer comprises the fluorine-containing (meth)acrylate monomer (a), the (meth)acrylate monomer (b), and the repeating structure terminal (meth)acryloyl group-containing macro Monomer (c) and not more than 10 parts by weight, relative to their total 100 parts by weight, (meth)acrylate monomers, (meth)acrylamide monomers, aromatic vinyl monomers, linear or cyclic carbon With a diluted monomer selected from an alkyl vinyl ether monomer having an alkyl number of 1 to 12, a vinyl ester monomer, an amino group-containing (meth)acrylic monomer, a carboxyl group-containing (meth)acrylic monomer, and a nonionic acrylic monomer It may be a polymerized copolymer.

This fluoropolymer dispersing additive is for dispersing the fluoropolymer in the fluoropolymer dispersion composition containing the fluoropolymer and the non-aqueous liquid medium so that the fluoropolymer does not settle in the non-aqueous liquid medium.

The fluoropolymer-dispersing additive comprises a fluoropolymer-dispersed composition containing a fluoropolymer and a non-aqueous liquid medium, and a coating agent containing a coating component. It is for dispersing without settling in the coating components.

A fluoropolymer dispersion composition made to achieve the above objects comprises this fluoropolymer dispersing additive and thereby a fluoropolymer dispersed in a non-aqueous liquid medium.

In this fluoropolymer dispersion composition, for example, the fluoropolymer is fluororesin powder or fluororesin oil.

A coating agent designed to achieve the above object comprises a fluoropolymer dispersion composition and a coating component.

This coating agent is such that the fluoropolymer is dispersed by an additive for dispersing the fluoropolymer so that it does not settle.

The coating film made to achieve the above object is formed by coating and curing this coating agent.

It is said that this coating film has at least one of water repellency, oil repellency, and antifouling property because the fluoropolymer is dispersed by the fluoropolymer dispersing additive and oriented on the coating film surface. It is.

The fluoropolymer dispersing additive of the present invention converts the fluoropolymer contained in the non-aqueous composition or coating agent into a non-aqueous liquid state by a copolymer such as a graft polymer having only perfluoroalkyl groups of 2 to 6 carbon atoms. Medium can be dispersed. Since such a copolymer does not produce harmful and highly persistent long-chain perfluoroalkyl-containing residues such as PFOA and PFOS even when oxidized by combustion or the like, this fluoropolymer dispersing additive is , it does not burden the environment and is safe for humans, animals and plants.

When the additive for dispersing the fluoropolymer is contained in the non-aqueous liquid medium together with the fluoropolymer powder or the fluoropolymer oil in the non-aqueous composition, the fluoropolymer powder or the fluoropolymer powder or the fluoropolymer oil is quickly and uniformly dispersed in the non-aqueous liquid medium. While being dispersed, the dispersed state can be maintained for a long period of time without sedimentation.

A coating agent containing a fluoropolymer dispersion composition and a coating component needs to be frequently stirred or shaken before use because the fluoropolymer dispersion composition has excellent fluoropolymer dispersibility and dispersion stability. do not have.

When a coating agent containing a fluoropolymer dispersion composition and a coating component is applied, the fluoropolymer dispersion composition, especially the fluoropolymer dispersion additive, does not agglomerate the fluoropolymer and the coating components, so uneven coating and color separation are prevented. does not occur.

Furthermore, the coating film formed by applying the coating agent to the base material and curing it is homogeneous, has a clean and smooth finish, and makes the appearance of the base material beautiful.

Furthermore, the coating film formed by coating the base material with the coating agent and curing the coating exhibits water repellency, oil repellency, and antifouling properties. Above all, when both water repellency and oil repellency are excellent, the antifouling property is excellent and the coating performance is improved.

Preferred embodiments for carrying out the present invention will be described in detail below, but the scope of the present invention is not limited to these embodiments.

An example of the fluoropolymer dispersing additive of the present invention is a fluorine-containing (meth)acrylate monomer (a), a (meth)acrylate monomer (b), and a macromonomer having a (meth)acryloyl group at the end of the macromonomer repeating structure. Fluorine having a main chain polymer portion in which the monomer (c) is copolymerized with each (meth)acryloyl group, and a side chain portion in which the macromonomer repeating structure derived from the macromonomer (c) extends from the main chain polymer portion. The content (meth)acrylic graft polymer is included as an active ingredient for dispersion of the fluoropolymer.

Such a fluorine-containing (meth)acrylic graft polymer is obtained by adding fluorine-containing (meth)acrylate monomer (a) forming the main chain polymer portion to a total of 100 parts by mass of each monomer (a), (b), and (c). 5 parts by weight or more and less than 40 parts by weight, 20 parts by weight or more and less than 45 parts by weight of the (meth)acrylate monomer (b), and 15 parts by weight or more and 75 parts by weight of the macromonomer (c) having a (meth)acryloyl group at the end. It is preferably copolymerized together with the following parts.

If the amount of the macromonomer (c) having a (meth)acryloyl group at its end is less than 15 parts by weight, the dispersibility and dispersion stability of the fluoropolymer will deteriorate.

On the other hand, if the amount of the macromonomer (c) having a (meth)acryloyl group at its end exceeds 75 parts by weight, the reactivity of the graft polymer will deteriorate, making its production difficult.

The fluorine-containing (meth)acrylic graft polymer may be random copolymerized or block copolymerized.

The fluorine-containing (meth)acrylic graft polymer has a repeating unit derived from the fluorine-containing (meth)acrylate monomer (a), a repeating unit derived from the (meth)acrylate monomer (b), and a terminal (meth) It has a repeating unit derived from the macromonomer (c) having an acryloyl group. Each (meth)acryloyl group of the fluorine-containing (meth)acrylate monomer (a) and the (meth)acrylate monomer (b) is copolymerized with the macromonomer (c) having a (meth)acryloyl group at the terminal. are doing.

The fluorine-containing (meth)acrylic graft polymer preferably has a weight average molecular weight of 10,000 to 1,000,000. If the weight average molecular weight is less than 10,000, the dispersion stability of the fluoropolymer may deteriorate. On the other hand, when the weight-average molecular weight exceeds 1,000,000, the fluoropolymer dispersion composition and the coating agent containing the same have too high a viscosity and are difficult to handle. More preferably, the weight average molecular weight is 20,000 to 200,000, and even more preferably 40,000 to 150,000.

The solubility parameter value is used as a way of expressing the polarity of the active polymer in the dispersant. The solubility parameter value can be estimated from the molecular structure, and various methods have been proposed. Among them, the theoretical solubility parameter value by the Fedors method is often used because it can be obtained relatively easily because the density parameter value of the polymer is not required.

（数式（１）中Δｅｉ、Δｖｉは、それぞれの原子又は原子団の蒸発エネルギー及びモル体積を表す。） The Fedors theoretical solubility parameter value can be obtained from the following formula (1).

(Δei and Δvi in formula (1) represent the vaporization energy and molar volume of each atom or atomic group.)

The fluorine-containing (meth)acrylic graft polymer preferably has a solubility parameter value of 8.5 to 12.0, more preferably 9.0 to 11.5, according to the Fedors method.

If the solubility parameter value of the fluorine-containing (meth)acrylic graft polymer is less than 8.5, the solubility of the fluorine-containing (meth)acrylic graft polymer in the reaction solvent is poor during the polymerization reaction. If the meth)acrylic graft polymer precipitates and is difficult to generate, or even if it can be generated, the fluorine-containing (meth)acrylic graft polymer aggregates due to too poor solubility, which may damage the appearance of the coating film. .

On the other hand, when the solubility parameter value exceeds 12.0, the fluorine-containing (meth)acrylic graft polymer has poor compatibility with water-insoluble solvents, and sufficient dispersion stability of the fluoropolymer cannot be obtained. .

When the fluorine-containing (meth)acrylate monomer (a), which is the raw material monomer forming the fluorine-containing (meth)acrylic graft polymer, is less than 5 parts by weight, the fluorine-containing (meth)acrylic graft polymer is oriented to the fluoropolymer interface. Due to the low force, the fluoropolymer dispersing additive cannot have sufficient dispersing effect.

On the other hand, when the fluorine-containing (meth)acrylate monomer (a) is 40 parts by weight or more, the solubility in an inert solvent becomes poor, making it difficult to produce a fluorine-containing (meth)acrylic graft polymer.

The fluorine-containing (meth)acrylate monomer (a) has the following chemical formula (1)
CH ₂ =C(-R ¹ )-CO-OR ² -R ^F (1)
(In formula (1), —R ¹ is a hydrogen atom or a methyl group, —R ² — is a group represented by —(CH ₂ ) _n — in which n is 1 to 12, —R ^F is a carbon number of 2 to 6 is a fluorine-containing acrylate or fluorine-containing methacrylate represented by a linear, branched, and/or alicyclic perfluoroalkyl group).

-R ^F preferably has 2 to 6 carbon atoms. Among them, the fluorine-containing (meth)acrylate monomer (a) is particularly preferably perfluorohexylethyl (meth)acrylate. The perfluorohexyl group may be a linear perfluoro-n-hexyl group, a branched chain, or an alicyclic group.

A fluoropolymer dispersing additive containing a graft polymer using a fluorine-containing (meth)acrylate having a perfluoromethyl group, which is a perfluoroalkyl group having 1 carbon atom in R ^F , has a weak affinity with the fluoropolymer. and the fluoropolymer cannot be completely dispersed.

On the other hand, a fluoropolymer dispersing additive containing a graft polymer using a fluorine-containing (meth)acrylate having a perfluoroalkyl group having 7 or more carbon atoms in -R ^F , when added to the fluoropolymer, reacts with the fluoropolymer. Because of its high affinity, the dispersing effect is high. However, since this fluoropolymer dispersing additive has poor compatibility with solvents and coating agents, it aggregates over time, resulting in poor dispersion stability. Furthermore, since the fluorine-containing (meth)acrylate having a perfluoroalkyl group having 7 or more carbon atoms in -R ^F has a strong cohesive force, the fluorine-containing (meth)acrylate monomer (a) of the present invention can be produced by dissolution. Even if it has a property parameter value, it does not dissolve in an inert solvent during the polymerization reaction, making it difficult to produce.

In addition, fluoropolymer dispersing additives containing graft polymers using fluorine-containing (meth)acrylates having perfluoroalkyl groups with 8 or more carbon atoms in —R ^F have increased persistence in the environment and effects on living organisms. Long-chain perfluoroalkyl-containing residues such as PFOA and PFOS, which are of concern for accumulation and toxicity, can be produced.

Examples of the fluorine-containing (meth)acrylate monomer (a) include perfluoroethylmethyl (meth)acrylate, perfluoropropylmethyl (meth)acrylate, perfluorobutylmethyl (meth)acrylate, and perfluoropentylmethyl (meth)acrylate. , perfluorohexylmethyl (meth)acrylate, perfluoroiso-propylmethyl (meth)acrylate, perfluoroiso-butylmethyl (meth)acrylate, perfluorotert-butylmethyl (meth)acrylate, perfluorosec-butylmethyl (meth)acrylate , perfluoroiso-pentylmethyl (meth)acrylate, perfluoroiso-hexylmethyl (meth)acrylate, perfluorocyclopentylmethyl (meth)acrylate, perfluorocyclohexylmethyl (meth)acrylate, perfluoroethylethyl (meth)acrylate, perfluoropropylethyl (meth)acrylate, perfluorobutylethyl (meth)acrylate, perfluoropentylethyl (meth)acrylate, perfluorohexylethyl (meth)acrylate, perfluoroiso-propylethyl (meth)acrylate, perfluoroiso - butyl ethyl (meth) acrylate, perfluoro tert-butyl ethyl (meth) acrylate, perfluoro sec-butyl (meth) ethyl acrylate, perfluoro iso-pentyl ethyl (meth) acrylate, perfluoro iso-hexyl ethyl (meth) acrylate, perfluorocyclopentylethyl (meth)acrylate, perfluorocyclohexylethyl (meth)acrylate, perfluoroethylpropyl (meth)acrylate, perfluoropropylpropyl (meth)acrylate, perfluorobutylpropyl (meth)acrylate, perfluoropentylpropyl ( meth)acrylate, perfluorohexylpropyl (meth)acrylate, perfluoroiso-propyl (meth)acrylate, perfluoroiso-butylpropyl (meth)acrylate, perfluorotert-butylpropyl (meth)acrylate, perfluorosec-butyl Propyl (meth)acrylate, perfluoroiso-pentylpropyl (meth)acrylate, perfluoroiso-hexylpropyl (meth)acrylate, perfluorocyclopentylpropyl (meth)acrylate, perfluorocyclohexylpropyl (meth)acrylate, perfluoroethylbutyl (meth)acrylate, perfluoropropylbutyl (meth)acrylate, perfluorobutylbutyl (meth)acrylate, perfluoropentylbutyl (meth)acrylate, perfluorohexylbutyl (meth)acrylate, perfluoroiso-propylbutyl (meth)acrylate Acrylate, perfluoroiso-butylbutyl (meth)acrylate, perfluorotert-butylbutyl (meth)acrylate, perfluorosec-butylbutyl (meth)acrylate, perfluoroiso-pentylbutyl (meth)acrylate, perfluoroiso-hexylbutyl ( meth)acrylate, perfluorocyclopentylbutyl (meth)acrylate, perfluorocyclohexylbutyl (meth)acrylate, perfluoroethylpentyl (meth)acrylate, perfluoropropylpentyl (meth)acrylate, perfluorobutylpentyl (meth)acrylate, perfluorobutylpentyl (meth)acrylate fluoropentylpentyl (meth)acrylate, perfluorohexylpentyl (meth)acrylate, perfluoroiso-propylpentyl (meth)acrylate, perfluoroiso-butylpentyl (meth)acrylate, perfluorotert-butylpentyl (meth)acrylate, perfluoro sec-butylpentyl (meth)acrylate, perfluoroiso-pentylpentyl (meth)acrylate, perfluoroiso-hexylpentyl (meth)acrylate, perfluorocyclopentylpentyl (meth)acrylate, perfluorocyclohexylpentyl (meth)acrylate , perfluoroethylhexyl (meth)acrylate, perfluoropropylhexyl (meth)acrylate, perfluorobutylhexyl (meth)acrylate, perfluoropentylhexyl (meth)acrylate, perfluorohexylhexyl (meth)acrylate, perfluoroiso-propyl hexyl (meth)acrylate, perfluoroiso-butylhexyl (meth)acrylate, perfluorotert-butylhexyl (meth)acrylate, perfluorosec-butylhexyl (meth)acrylate, perfluoroiso-pentylhexyl (meth)acrylate, perfluoro iso-hexylhexyl (meth)acrylate, perfluorocyclopentylhexyl (meth)acrylate, perfluorocyclohexylhexyl (meth)acrylate, perfluoroethylheptyl (meth)acrylate, perfluoropropylheptyl (meth)acrylate, perfluorobutyl Heptyl (meth)acrylate, perfluoropentylheptyl (meth)acrylate, perfluorohexylheptyl (meth)acrylate, perfluoroiso-propylheptyl (meth)acrylate, perfluoroiso-butylheptyl (meth)acrylate, perfluoro tert- Butylheptyl (meth)acrylate, perfluoro sec-butylheptyl (meth)acrylate, perfluoroiso-pentylheptyl (meth)acrylate, perfluoroiso-hexylheptyl (meth)acrylate, perfluorocyclopentylheptyl (meth)acrylate, perfluorocyclopentylheptyl (meth)acrylate, Fluorocyclohexylheptyl (meth)acrylate, perfluoroethyloctyl (meth)acrylate, perfluoropropyloctyl (meth)acrylate, perfluorobutyloctyl (meth)acrylate, perfluoropentyloctyl (meth)acrylate, perfluorohexyloctyl (meth)acrylate ) acrylate, perfluoroiso-propyloctyl (meth)acrylate, perfluoroiso-butyloctyl (meth)acrylate, perfluorotert-butyloctyl (meth)acrylate, perfluorosec-butyloctyl (meth)acrylate, perfluoroiso - pentyloctyl (meth)acrylate, perfluoroiso-hexyloctyl (meth)acrylate, perfluorocyclopentyloctyl (meth)acrylate, perfluorocyclohexyloctyl (meth)acrylate, perfluoroethylnonyl (meth)acrylate, perfluoropropylnonyl (meth) acrylate, perfluorobutyl nonyl (meth) acrylate, perfluoropentyl nonyl (meth) acrylate, perfluorohexyl nonyl (meth) acrylate, perfluoro iso-propyl nonyl (meth) acrylate, perfluoro iso-butyl nonyl (meth) ) acrylate, perfluoro tert-butyl nonyl (meth) acrylate, perfluoro sec-butyl nonyl (meth) acrylate, perfluoro iso-pentyl nonyl (meth) acrylate, perfluoro iso-hexyl nonyl (meth) acrylate, perfluorocyclopentyl nonyl ( meth)acrylate, perfluorocyclohexyl nonyl (meth)acrylate, perfluoroethyldecyl (meth)acrylate, perfluoropropyldecyl (meth)acrylate, perfluorobutyldecyl (meth)acrylate, perfluoropentyldecyl (meth)acrylate, perfluoropentyldecyl (meth)acrylate fluorohexyldecyl (meth)acrylate, perfluoroiso-propyldecyl (meth)acrylate, perfluoroiso-butyldecyl (meth)acrylate, perfluorotert-butyldecyl (meth)acrylate, perfluorosec-butyldecyl (meth)acrylate, perfluorosec-butyldecyl (meth)acrylate, fluoroiso-pentyldecyl (meth)acrylate, perfluoroiso-hexyldecyl (meth)acrylate, perfluorocyclopentyldecyl (meth)acrylate, perfluorocyclohexyldecyl (meth)acrylate, perfluoroethylundecyl (meth)acrylate, perfluoroethylundecyl (meth)acrylate, Fluoropropylundecyl (meth)acrylate, perfluorobutylundecyl (meth)acrylate, perfluoropentylundecyl (meth)acrylate, perfluorohexylundecyl (meth)acrylate, perfluoroiso-propylundecyl (meth)acrylate , perfluoro iso-butyl undecyl (meth) acrylate, perfluoro tert-butyl undecyl (meth) acrylate, perfluoro sec-butyl undecyl (meth) acrylate, perfluoro iso-pentyl undecyl (meth) acrylate, perfluoro fluoro iso-hexyl undecyl (meth) acrylate, perfluorocyclopentyl undecyl (meth) acrylate, perfluorocyclohexyl undecyl (meth) acrylate, perfluoroethyl dodecyl (meth) acrylate, perfluoropropyl dodecyl (meth) acrylate, perfluoro Fluorobutyldodecyl (meth)acrylate, perfluoropentyldodecyl (meth)acrylate, perfluorohexyldodecyl (meth)acrylate, perfluoroiso-propyldodecyl (meth)acrylate, perfluoroiso-butyldodecyl (meth)acrylate, perfluoro tert-butyldodecyl (meth)acrylate, perfluorosec-butyldodecyl (meth)acrylate, perfluoroiso-pentyldodecyl (meth)acrylate, perfluoroiso-hexyldodecyl (meth)acrylate, perfluorocyclopentyldodecyl (meth)acrylate , and perfluorocyclohexyl dodecyl (meth)acrylate.

The fluorine-containing (meth)acrylate monomer (a) may be used alone or in combination.

If the (meth)acrylate monomer (b) is less than 20 parts by weight, the elongation of the polymer by radical polymerization is poor, and the molecular weight distribution of the fluorine-containing (meth)acrylic graft polymer is biased, resulting in the desired performance. I can't do it anymore.

On the other hand, when the (meth)acrylate monomer (b) is 45 parts by weight or more, the blending amounts of the fluorine-containing (meth)acrylate monomer (a) and the macromonomer (c) having a (meth)acryloyl group at the end are reduced. Therefore, the dispersibility and dispersion stability of the fluoropolymer become insufficient.

The (meth)acrylate monomer (b) is, for example, a (meth)acrylate having 1 to 12 carbon atoms and a linear, branched, and/or cyclic alkyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-, iso-propyl (meth)acrylate, n-, iso-, sec-, or tert-butyl (meth)acrylate, n-amyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, dodecyl (meth)acrylate, iso-propyl (meth)acrylate, iso-amyl (meth)acrylate , iso-hexyl (meth)acrylate, iso-heptyl (meth)acrylate, iso-octyl (meth)acrylate, iso-nonyl (meth)acrylate, iso-decyl (meth)acrylate, iso-undecyl (meth)acrylate, iso -dodecyl (meth)acrylate, neopentyl (meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate. Also, amino group-containing (meth)acrylic monomers may be mentioned, for example, aminomethyl (meth)acrylate, aminoethyl (meth)acrylate, etc., primary amino group-containing (meth)acrylates such as aminoalkyl (meth)acrylates, Secondary amino group-containing (meth)acrylates such as t-butylaminoethyl (meth)acrylate, ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylamino (meth)acrylate tertiary amino group-containing (meth)acrylates such as dialkylaminoalkyl (meth)acrylates, (meth)acryloylmorpholine, and the like.

The (meth)acrylate monomer (b) may be used alone or in combination. Among them, alkyl (meth)acrylate, dimethylaminoethyl (meth)acrylate and (meth)acryloylmorpholine having an alkyl group having 1 to 4 carbon atoms are preferred. Among them, methyl (meth)acrylate is still more preferable.

Macromonomers (c) having a (meth)acryloyl group at the terminal include polyalkyl (meth)acrylate macromonomers, polyalkenyl (meth)acrylate macromonomers, polyester macromonomers and polystyrene macromonomers. More specifically, macromonomer AA-6 (terminal group: methacryloyl group, segment: methyl methacrylate, number average molecular weight: 6000; trade name of Toagosei Chemical Industry Co., Ltd.), macromonomer AW-6S (terminal group : methacryloyl group, segment: isobutyl methacrylate, number average molecular weight: 6000; trade name of Toagosei Chemical Industry Co., Ltd.), macromonomer AB-6 (terminal group: methacryloyl group, segment: butyl acrylate, number average molecular weight: 6000 ; trade name manufactured by Toagosei Chemical Industry Co., Ltd.), macromonomer AS-6 (terminal group: methacryloyl group, segment: number average molecular weight in terms of styrene: 6000; trade name manufactured by Toagosei Chemical Industry Co., Ltd.) mentioned.

In addition, a copolymer obtained by copolymerizing with other monomer (e) may be included as long as it does not inhibit dispersibility and dispersion stability. Other monomers (e) include methyl (meth)acrylate, ethyl (meth)acrylate, n-, iso-propyl (meth)acrylate, n-, iso-, sec-, or tert-butyl (meth)acrylate, styrene , cyclohexyl (meth) acrylate, tetrahydrofurifyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyethyl acrylamide, isopropyl acrylamide, 2-hydroxyethyl (meth) acrylate, polyethylene glycol (meth) acrylate mentioned.

The macromonomer (c) having a (meth)acryloyl group at its terminal preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 6,000 to 50,000. If the molecular weight is lower than 3,000, the physical properties of the coating film may deteriorate. If it is higher than 100,000, the viscosity of the fluorine-containing (meth)acrylic graft polymer may become too high, making handling difficult.

The solubility parameter value of the macromonomer (c) having a (meth)acryloyl group at the terminal is 9.0 to 10.3 when determined by the Fedors method according to the above formula (1).

It is preferable that the repeating structure of the side chain polymer portion of the macromonomer (c) having a (meth)acryloyl group at its terminal consists only of repeating units derived from the macromonomer repeating structure monomer (d). Further, when the repeating structure consists only of repeating units derived from the macromonomer repeating structure monomer (d), the macromonomer repeating structure monomer (d) has a smaller structure than other (meth)acrylate monomers ( That is, the alkyl portion is short) and the steric hindrance is small, so the molecular weight can be easily increased. By lengthening the side chain polymer portion of the macromonomer (c) having a (meth)acryloyl group at the terminal, the steric repulsion between particles can be further increased, which is more preferable.

The macromonomer (c) having a (meth)acryloyl group at the terminal preferably has an unsaturated group such as an acryloyl group bonded directly or via a spacer structure to the terminal of the repeating structure.

More specifically, the macromonomer (c) having a (meth)acryloyl group at the terminal is directly attached to the terminal of the polymer of methyl methacrylate monomer, or with a spacer structure derived from a chain transfer agent such as β-mercaptoethanol, It may be a compound in which a (meth)acryloyl group is bonded via an ester bond and/or a urethane bond spacer structure. In addition, a commercially available macromonomer, for example, macromonomer AA-6 (Toa Synthetic Co., Ltd.; trade name), macromonomer AB-6 (a macromonomer having a methacryloyl group as a terminal group of a butyl acrylate homopolymer (molecular weight (Mw) = 6000, solubility parameter value = 9.9) ( manufactured by Toagosei Co., Ltd.; trade name). These macromonomers may be used alone or in combination.

The macromonomer (c) having a (meth)acryloyl group at its terminal may be a graft polymer copolymerized with another monomer (e) as long as it does not inhibit the dispersion of the fluoropolymer.

The other monomer (e) is a fluorine-containing (meth)acrylate monomer (a), a (meth)acrylate monomer (b), and a macromonomer (c) having a (meth)acryloyl group at its end, based on a total of 100 parts by weight. , preferably from 0 to less than 10 parts by weight, more preferably from 0 to less than 5 parts by weight.

Other monomers (e) include, for example, aromatic vinyl monomers such as styrene and vinyltoluene, linear or cyclic alkyls having 1 to 12 carbon atoms such as normal butyl vinyl ether, isobutyl vinyl ether, dodecyl vinyl ether and cyclohexyl vinyl ether. vinyl ether monomers, vinyl ester monomers such as vinyl acetate, vinyl propionate, vinyl laurate; (meth)acrylamide monomers such as aminomethyl (meth)acrylate; acryloylmorpholine; Methoxypolyethylene glycol acrylate is mentioned.

A macromonomer method is preferred for synthesizing the macromonomer (c) having a (meth)acryloyl group at the terminal. In the macromonomer method, a fluorine-containing (meth)acrylate monomer (a) and an alkyl (meth)acrylate monomer (b), and a macromonomer (c) having a (meth)acryloyl group at the end are combined with each unsaturated group. By polymerizing, a main chain is formed in the presence of a polymer for side chain formation.

One example is the following method. First, a methyl methacrylate monomer and β-mercaptoethanol are dropped into an inert solvent in the presence of a radical polymerization initiator, and heated to polymerize. Karenz MOI (2-isocyanatoethyl methacrylate: manufactured by Showa Denko Co., Ltd.; trade name, Karenz MOI is a registered trademark) or Karenz AOI (2-isocyanatoethyl acrylate: manufactured by Showa Denko K.K.; trade name; Karenz AOI is a registered trademark) as a catalyst TN-12 (dibutyltin laurate: manufactured by Sakai Chemical Industry Co., Ltd.; product name) to synthesize a macromonomer of a methyl methacrylate monomer, which is a side chain forming polymer for forming a side chain polymer portion. Then, the macromonomer of the synthesized methyl methacrylate monomer, the fluorine-containing (meth)acrylate monomer (a), and the (meth)acrylate monomer (b) are dropped into an inert solvent in the presence of a radical polymerization initiator, When heated and polymerized, a macromonomer (c) having a (meth)acryloyl group at its end is prepared.

Moreover, the macromonomer used in the macromonomer method may be synthesized by a known method other than the above.

Although the macromonomer method has been described as a method for synthesizing the macromonomer (c) having a (meth)acryloyl group at the end, other initiators such as benzoyl peroxide and α,α'-azobisisobutyronitrile may be used. A chain transfer method may also be used in which hydrogen and halogen are abstracted from the main chain polymer portion to form polymer radicals, and other monomers are graft-polymerized thereon.

In addition, a main chain polymer for forming a main chain polymer portion constituting a macromonomer (c) having a (meth)acryloyl group at its end and a side chain forming polymer for forming a side chain polymer portion are prepared in advance. A method of synthesizing them separately and combining the two polymers later may also be used. Specifically, a main chain polymer for forming a main chain polymer portion having a group reactive with active hydrogen such as an isocyanate group, and a side chain polymer having an active hydrogen group such as a hydroxyl group at one end. A method of reacting with a polymer for forming a side chain for forming a part to bond the two polymers may be mentioned. A known method other than the above may be used to bond the side chain-forming polymer and the main chain polymer.

When preparing the main chain polymer, the side chain forming polymer, the macromonomer, and the graft polymer by polymerization/copolymerization, it is preferable to use a radical polymerization initiator. The radical polymerization initiator is not particularly limited as long as it is an initiator that is generally used for radical polymerization. For example, peroxides, azo compounds and the like are used. More specifically, V-60 (AIBN) (trade name of Wako Pure Chemical Industries, Ltd.), V-65 (trade name of Wako Pure Chemical Industries, Ltd.), V-601 (trade name of Wako Pure Chemical Industries, Ltd.) trade name), Perbutyl D, Perbutyl O (trade name of NOF Corporation, Perbutyl is a registered trademark), and Perocta O (trade name of NOF Corporation, Perocta is a registered trademark).

This fluoropolymer dispersing additive is for dispersing the fluoropolymer in a non-aqueous liquid medium.

The fluoropolymer dispersing additive may consist of this graft polymer alone, or may contain an inert solvent and other additive components, if necessary. The fluoropolymer dispersing additive may be a graft polymer dissolved or suspended in an inert solvent.

The inert solvent in the additive for dispersing the fluoropolymer is not particularly limited as long as it can dissolve or suspend the graft polymer to dilute it. Specific examples thereof include hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; ether solvents such as methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, and propylene glycol monomethyl ether; ethyl acetate, n-butyl acetate , isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, ester solvents such as 3-methoxybutyl acetate; n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3 alcohol solvents such as -methyl-3-methoxybutanol. These solvents may be used alone or as a mixture of two or more.

The fluoropolymer dispersion composition of the present invention comprises a fluoropolymer dispersing additive and thereby a fluoropolymer dispersed in a non-aqueous liquid medium.

When preparing the fluoropolymer dispersion composition, the dosage of the fluoropolymer dispersing additive is preferably 0.01 to 40 parts by weight with respect to 100 parts by weight of the fluoropolymer. If the amount is less than 0.01 parts by weight, the fluoropolymer cannot be sufficiently dispersed, and if it exceeds 40 parts by weight, the properties of the fluoropolymer, such as slipperiness, are adversely affected. More preferably the dose is 0.1 to 20 parts by weight, even more preferably 0.2 to 10 parts by weight.

The fluoropolymer dispersion composition is diluted with a non-aqueous liquid medium so that the fluoropolymer is 0.1 to 60% by weight.

The fluoropolymer is preferably a solid such as fluoropolymer powder. The average particle size of the fluoropolymer powder is preferably between 0.01 μm and 100 μm, even more preferably between 0.01 μm and 10 μm. The fluoropolymer may be a liquid such as a fluoropolymer oil. The fluoropolymer oil is dispersed to form a suspension dispersion with an average particle size of 0.01-100 μm.

Fluoropolymers are homopolymers or copolymers of fluorine-containing monomers. Specific examples of fluorine monomers include tetrafluoroethylene, hexafluoropropylene, perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoropropyl vinyl ether, perfluorobutyl vinyl ether, perfluoroisobutyl vinyl ether, perfluoropentyl vinyl ether, perfluoro Hexyl vinyl ether, chlorotrifluoroethylene, hexafluoropropylene oxide, perfluoroalkyl (meth)acrylate and the like. Tetrafluoroethylene is particularly preferred.

Specific examples of liquid fluoropolymers such as fluoropolymer oils include those containing perfluoropolyether (PFPE) as a main component. PFPE is represented by the _general formula: RfO( _{CF2O ) p} ( _C2F4O ) _q ( _C3F6O ) _rRf (Rf: perfluoro lower alkyl group, p, q, r: integers). It is a compound that is

Non-aqueous liquid media include, for example, hydrocarbon solvents such as xylene, toluene, and cyclohexane; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methyl isobutyl ketone; methyl cellosolve, cellosolve, butyl cellosolve, methyl carbitol, carbitol, and butyl carbitol. , diethyl carbitol, propylene glycol monomethyl ether and other ether solvents; ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other ester solvents; n -butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol, 3-methyl-3-methoxybutanol and other alcohol solvents. These solvents may be used alone or as a mixture of two or more.

The fluoropolymer dispersion composition is prepared by mixing the fluoropolymer, the non-aqueous liquid medium, and the fluoropolymer dispersing additive, and then using a dispersing device such as a paint shaker, bead mill, ball mill, various mixers, or various high-pressure wet dispersers. can be carried out by dispersing the fluoropolymer. A fluoropolymer dispersion composition cannot disperse a fluoropolymer with excellent water and oil repellency and low surface energy in a non-aqueous liquid medium alone. It is endowed with a dispersibility that allows the dispersion to continue and a dispersion stability that allows the dispersion state to continue stably. Therefore, the fluoropolymer is easily dispersed in a dispersing device and does not agglomerate or sediment once dispersed.

The coating agent of the present invention contains the fluoropolymer-dispersed composition of the present invention and coating agent components commonly used for preparation of coating agents.

The coating agent is prepared by mixing the coating agent components in advance, adding the fluoropolymer dispersion composition, and mixing. They may be mixed simultaneously or in any order.

Coating agent components include, but are not limited to, coloring agents such as pigments and dyes, resins, diluents, catalysts, functional additives, and the like.

Resins include acrylic polyol resins, acrylic melamine resins, polyester resins, urethane resins, alkyd resins, epoxy resins, and acrylic resins. These resins are, for example, heat-curable, isocyanate-curable, UV-curable, electron beam-curable, oxidation-curable, photo-cation-curable, peroxide-curable, acid/epoxy-curable, and have the presence of a catalyst. or in the absence of a catalyst.

The diluting solvent is not particularly limited as long as it is a commonly used organic solvent. Examples include hydrocarbon solvents such as xylene, toluene and cyclohexane; ketone solvents such as cyclohexanone and methyl isobutyl ketone; methyl cellosolve, cellosolve, butyl cellosolve; Ether solvents such as methyl carbitol, carbitol, butyl carbitol, diethyl carbitol, propylene glycol monomethyl ether; n-butyl acetate, isobutyl acetate, n-amyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl ester solvents such as acetate; alcohol solvents such as n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexanol, 2-ethylhexanol and 3-methyl-3-methoxybutanol; These solvents may be used alone, mixed and used, or mixed with water and used.

In addition to the above components, the coating agent may contain optional functional additives such as sensitizers, antistatic agents, leveling agents, wetting agents, antifoaming agents, dispersants, viscosity modifiers, etc. may be added in an appropriate amount depending on the

The coating film of the present invention is obtained by applying this coating agent on a substrate and curing the coating.

The base material is not particularly limited, but is formed of materials such as plastic, rubber, paper, wood, glass, metal, stone material, cement material, mortar material, ceramics, etc. Examples include daily necessities and building materials.

Application of the coating agent is preferably carried out by known methods such as spin coating, spray coating, dip coating, bar coating, doctor blade, roll coating and flow coating.

Although the mechanism by which such an additive for fluoropolymer dispersing provides the fluoropolymer with excellent dispersibility and dispersion stability is not necessarily clear, it is presumed to be as follows.

General polymer-type dispersants have both an adsorption part (affinity part) to resin particles and a compatible part to resin in the molecule contained in the dispersant, and increase the repulsive force between particles due to steric hindrance. This creates a dispersing effect. It is believed that the fluorine-containing (meth)acrylic graft polymer in the additive for dispersing the fluoropolymer of the present invention also exerts a dispersing effect by a similar mechanism. The fluorine-containing (meth)acrylate monomer (a) in the main chain polymer portion having the same fluorine portion as the fluorine polymer acts as an adsorption portion (affinity portion). Since the adsorption part (affinity part) is a polymer, it can be entangled in the fluoropolymer and strongly and continuously adsorbed. Excellent.

In addition, since the methacrylate monomer in the side chain polymer portion acts as a resin-compatible portion and has a hard polymer skeleton, the steric hindrance is increased to suppress aggregation of particles.

By using a (meth)acrylate monomer (b) having a hard skeleton in the main chain polymer portion, the structure of the fluoropolymer dispersant is made rigid, thereby increasing steric hindrance and suppressing aggregation of particles.

If the side chain polymer part has an adsorption part (affinity part) to the fluoropolymer, there are many side chain polymer parts in one molecule, so the particles will be adsorbed to each side chain polymer part. The distance becomes shorter, causing agglomeration. Therefore, the repeating structure derived from the fluorine-substituted alkyl group-containing (meth)acrylate monomer (a), which is the adsorption portion (affinity portion) to the fluoropolymer, must be in the main chain polymer portion having only one chain in one molecule. There is

When the fluorine-containing (meth)acrylate monomer (a) acting as a pigment adsorption group in the fluoropolymer dispersant is present in the main chain polymer portion, the compatibility of the fluorine portion with the solvent or resin when the distance is close deteriorating, adversely affecting the adsorption and dispersibility of the fluoropolymer. Therefore, in order to improve the compatibility and dispersibility of the fluoropolymer dispersant, the fluorine-containing (meth)acrylate monomer (a) in the main chain polymer portion must be kept at a constant distance by the (meth)acrylate monomer (b). There is

When used in a resin composition, if the content of the macromonomer (c) having a (meth)acryloyl group at the end acting as a resin-affinitive moiety in the fluoropolymer dispersant is high, the fluoropolymer dispersant will be dispersed in the resin. It dissolves uniformly, does not align to the surface after curing of the resin, and adversely affects the development of water and oil repellency of the fluoropolymer. Therefore, in order to obtain appropriate solubility in resins and solvents, the (meth)acryloyl group-terminated macromonomer (c) must be contained in an appropriate ratio with respect to the fluoropolymer dispersant.

An additive for fluoropolymer dispersion to which the present invention is applied, a fluoropolymer-dispersed composition containing the dispersant, a coating agent containing the composition, and an example of trial production of a coating film formed from the coating agent, and application of the present invention Comparative examples of trial production of other dispersants, compositions, coating agents, and coating films are shown.

First, a macromonomer (c) having a (meth)acryloyl group at the terminal for forming the side chain polymer portion of the fluorine-containing (meth)acrylic graft polymer contained in the fluoropolymer dispersion additive of the present invention was produced. Examples are shown in Production Examples 1 and 2, macromonomers having a (meth)acryloyl group at the terminal for forming the side chain polymer portion of the fluorine-containing (meth)acrylic graft polymer used in the dispersant that is not applicable to the present invention. Examples of producing (c) are shown in Comparative Production Examples 1 and 2.

(Production example 1)
In a 1000 mL reaction vessel equipped with a stirrer, a reflux condenser, a dropping funnel, a thermometer and a nitrogen gas inlet, a repeating structure of a side chain forming polymer forming a side chain polymer portion was formed as shown in Table 1 below. To do so, 400 parts by weight of methyl methacrylate, which is a macromonomer repeating structure monomer (d), 1.56 parts by weight of β-mercaptoethanol, which is a terminal hydroxyl group-introducing agent that is also a chain transfer agent, and an inert solvent A raw material mixture (A-1) containing 100 parts by weight of n-butyl acetate was added, and the temperature was raised to 85° C. under a nitrogen gas atmosphere. The solution temperature in the reaction vessel was maintained at 85° C., and a dropwise solution of 1 part by weight of Perocta O as a polymerization initiator and 300 parts by weight of n-butyl acetate as an inert solvent as shown in Table 1 below ( B-1) was added dropwise at a constant speed over 3 hours using a dropping funnel. After completion of dropping, the solution in the reaction vessel was heated to 100° C. and reacted for 2 hours to synthesize a copolymer having terminal hydroxyethylmercapto groups. After that, the solution in the reaction vessel was cooled to 80° C., nitrogen gas blowing was switched to air blowing, and 3.72 parts by weight of Karenz MOI, which is an isocyanate group-containing monomer, and TN, which is a catalyst, were mixed as shown in Table 1 below. 0.05 parts by weight of -12 and additional raw material (C-1) were charged, reacted at 80 ° C. for 3 hours, and diluted with n-butyl acetate so that the residue was 40%. A macromonomer (c) having a (meth)acryloyl group at the terminal of was obtained.

Gel permeation chromatography capable of separating molecules of different molecular weights (the column is manufactured by Tosoh Corporation under the product name TSKGEL SUPERMULTIPORE HZ-M, the elution solvent is tetrahydrofuran (THF)), the side chain-forming polymer is eluted by molecular weight, A molecular weight distribution was obtained. A calibration curve was obtained in advance from a polystyrene standard substance with a known molecular weight, and compared with the molecular weight distribution of the side chain forming polymer of Production Example 1, the weight average molecular weight of the side chain forming polymer of Production Example 1 was determined. As a result, the weight-average molecular weight of the macromonomer (c) having a (meth)acryloyl group at the terminal in Production Example 1 was 30,000 in terms of polystyrene.

(Production example 2)
In the same reaction vessel as in Production Example 1, the same method as in Production Example 1 was used, except that the raw material mixture, the dropping solution, and the additional raw material mixture were changed as shown in Table 1 below. A macromonomer (c) having a (meth)acryloyl group was obtained. As with the macromonomer (c) having a (meth)acryloyl group at the end of Production Example 1, the molecular weight distribution of the side chain-forming polymer of each Production Example was determined by gel permeation chromatography. The weight average molecular weight in terms of polystyrene obtained from the molecular weight distribution is shown in Table 1 below.

(Production Comparative Example 1)
In the same reaction vessel as in Production Example 1, the same method as in Production Example 1 was used, except that the raw material mixture, the dropping solution, and the additional raw material mixture were changed as shown in Table 1 below. A chain-forming polymer was obtained. As with the side chain-forming polymer of Production Example 1, the molecular weight distribution of the side chain-forming polymer of each production example was determined by gel permeation chromatography. The weight average molecular weight in terms of polystyrene obtained from the molecular weight distribution is shown in Table 1 below.

(Production Comparative Example 2)
In the same reaction vessel as in Production Example 1, the same method as in Production Example 1 was used, except that the raw material mixture, the dropping solution, and the additional raw material mixture were changed as shown in Table 1 below. A chain-forming polymer was obtained. As with the side chain-forming polymer of Production Example 1, the molecular weight distribution of the side chain-forming polymer of each production example was determined by gel permeation chromatography. The weight average molecular weight in terms of polystyrene obtained from the molecular weight distribution is shown in Table 1 below.

In Synthesis Examples 1 to 7, a commercially available product or a macromonomer (c) having a (meth)acryloyl group at the end obtained in Production Examples 1 and 2 was used as the macromonomer, and the fluoropolymer dispersion additive of the present invention contained Comparative Synthesis Examples 1 to 7 show examples of preparing a fluorine-containing (meth)acrylic graft polymer, and Comparative Synthesis Examples 1 to 7 are commercially available products as macromonomers or have a (meth)acryloyl group at the end obtained in Comparative Production Examples 1 and 2. An example of preparing a fluorine-containing (meth)acrylic graft polymer contained in a fluoropolymer dispersing additive to which the present invention is not applied using the macromonomer (c) is shown.

(Synthesis example 1)
60 parts by weight of n-butyl acetate was placed in a 1000 mL reaction vessel equipped with a stirrer, reflux condenser, dropping funnel, thermometer and nitrogen gas inlet, and the temperature was raised to 100° C. under a nitrogen gas atmosphere. The solution temperature in the reaction vessel was maintained at 100° C., and 20 parts by weight of perfluorohexylethyl acrylate, which is a fluorine-containing (meth)acrylate monomer (a), and a (meth)acrylate monomer (b) as shown in Table 2 below. ), 35 parts by weight of methyl methacrylate, 45 parts by weight of macromonomer AA-6 as a macromonomer (c) having a (meth)acryloyl group at the end, 1 part by weight of perbutyl O as a polymerization initiator, and A mixed dropwise solution (D-1) containing 60 parts by weight of n-butyl acetate as an active solvent was dropped at a constant speed over 2 hours using a dropping funnel. After completion of dropping, the reaction was allowed to proceed for 2 hours while maintaining the solution in the reaction vessel at 100° C. to obtain a fluorine-containing (meth)acrylic graft polymer.

Gel permeation chromatography capable of separating molecules of different molecular weights (the column is manufactured by Tosoh Corporation under the product name TSKGEL SUPERMULTIPORE HZ-M, the elution solvent is THF), fluorine-containing (meth)acrylic graft of this fluoropolymer dispersion additive The polymer was eluted for each molecular weight, and the molecular weight distribution was determined. A calibration curve was obtained in advance from a polystyrene standard substance with a known molecular weight, and compared with the molecular weight distribution of this fluorine-containing (meth)acrylic graft polymer, the weight average molecular weight of the fluorine-containing (meth)acrylic graft polymer was determined. As a result, the weight average molecular weight of the fluorine-containing (meth)acrylic graft polymer used as the fluoropolymer dispersing additive was 60,000 in terms of polystyrene, and the solubility parameter value determined by the Fedors method was 9.5.

(Synthesis Examples 2-7 and Comparative Synthesis Examples 1-7)
Fluorine-containing (meth)acrylic graft polymers were obtained in the same manner as in Synthesis Example 1, except that Synthesis Examples 2 to 7 and Comparative Synthesis Examples 1 to 7 were changed as shown in Tables 2 and 3 below. The weight average molecular weights of these fluorine-containing (meth)acrylic graft polymers determined by gel permeation chromatography in the same manner as in Synthesis Example 1, and the solubility parameter values determined by the Fedors method are summarized in Tables 2 and 3 below.

(Preparation of Example 1)
40 parts by weight of tetrafluoroethylene resin powder KTL-8N (trade name of Kitamura Co., Ltd.), 58 parts by weight of n-butyl acetate, and a fluorine-containing (meth)acrylic graft polymer as an additive for dispersing the fluorine polymer. 2 parts by weight of Synthesis Examples 1 to 7 and Fluorine-containing (meth)acrylic graft polymer synthesis Comparative Examples 1 to 7 were stirred at 1500 rpm for 10 minutes in a lab disper, and a test resin using a fluoropolymer dispersing additive. A composition was obtained.

(Examples 2-6 and Comparative Examples 1-7)
The fluorine-containing (meth)acrylic graft polymer of Production Example 1 in Example 1 was added to the fluorine-containing (meth)acrylic graft polymer of Production Examples 2 to 7 and Comparative Production Examples 1 to 7 as shown in Table 4 below. Test resin compositions of Examples 2 to 7 and Comparative Examples 1 to 7 were obtained in the same manner as in Example 1, except that the prepared fluoropolymer dispersing additive was used instead.

(Preparation of blank)
A blank sample was obtained in the same manner as in Example 1, except that the fluorine-containing (meth)acrylic graft polymer in Example 1 was not used.

The test resin compositions of Examples 1 to 7, Comparative Examples 1 to 7, and a blank were subjected to the following dispersibility evaluation test.

(Initial visual evaluation)
After the test resin compositions of Examples 1 to 7 and Comparative Examples 1 to 7 were prepared, they were placed in a 60φ glass bottle at a height of 50 mm, left to stand at 25 ° C. in a horizontal place for 1 hour, and then visually checked for a dispersed state. confirmed.

The initial visual evaluation was evaluated on a two-point scale, with ◯ indicating no precipitate and x indicating the presence of precipitate. Table 4 shows the results.

The sedimentation prevention rate is determined by visually checking the glass bottle containing the test resin composition 1 from the side after standing at 25 ° C. in a horizontal place for 1 hour after standing. By measuring the height up to the cloudy part of composition 1, it can be obtained from the following formula (2). Table 4 shows the test results.
Anti-settling rate =
(Height of the entire liquid (mm) / Height from the bottom of the glass bottle to the cloudy part (mm)) x 100
... (2)

The glass bottle containing the test resin composition 1 after standing was stirred by hand for 1 minute. The presence or absence of hard caking in the solid portion, which does not become liquid by manual stirring, was visually confirmed.

Confirmation evaluation of hard caking was evaluated on a two-point scale of ◯ when a solid portion not dispersed in the test resin composition 1 was confirmed at the bottom of the glass bottle, and x when it was not confirmed.

As is clear from Table 4, the test resin composition 1 of the example prepared using the fluoropolymer dispersing additive containing the fluorine-containing (meth)acrylic graft polymer of the synthesis example to which the present invention is applied is The initial visual evaluation confirmed the absence of sediment from the comparative example and the blank test resin composition 1 without the application. In addition, no sediment was observed over time, and no hard caking was observed. Therefore, it was confirmed that the fluoropolymer dispersing additives of the present invention obtained in the examples are excellent in dispersibility and dispersion stability as dispersants for fluoropolymers.

<Preparation of coated plate for evaluation>
To a prepared resin composition prepared in advance, the fluorine-containing (meth)acrylic graft polymer Synthesis Examples 1 to 7 and fluorine-containing (meth)acrylic graft polymer synthesis comparative examples 1 to 7 were added to disperse the fluoropolymers. The agents were blended to obtain a test resin composition as a coating agent. A cured film obtained by applying this test resin composition to a substrate was evaluated for properties.

(Preparation of test resin composition 2)
30 parts by weight of urethane acrylate UA-306I (trade name of Kyoeisha Chemical Co., Ltd.), 10 parts by weight of tetrafluoroethylene resin powder KTL-8N (trade name of Kitamura Co., Ltd.), and n-butyl acetate. 59 parts by weight and 1 part by weight of Synthesis Examples 1 to 7 of fluorine-containing (meth)acrylic graft polymer and 1 part by weight of Comparative Examples 1 to 7 of fluorine-containing (meth)acrylic graft polymer as an additive for dispersing fluorine polymer were prepared in a laboratory. Stirring was performed with a disper at 500 rpm for 5 minutes to obtain a tetrafluoroethylene resin powder dispersion using the fluoropolymer dispersing additive.

(Preparation of blank 1)
Blank 1 was prepared in the same manner as Test Resin Composition 2, except that the fluorine-containing (meth)acrylic graft polymer in Preparation Example 1 was not used to obtain a blank 1 sample.

(Adjustment of blank 2)
Blank 2 was prepared in the same manner as Test Resin Composition 2, except that the tetrafluoroethylene resin powder in Preparation Example 1 was not used.

(Working Preparation Example 1)
To the tetrafluoroethylene resin powder dispersion liquid of test resin composition 2, 3 parts by weight of Irgacure 184 (hydroxycyclohexylphenyl ketone; manufactured by Ciba Specialty Co., Ltd.), which is a photopolymerization initiator, was added, dissolved in a paint shaker, and coated. formulations were prepared.

(Preparation of coated plate for evaluation)
The resulting test resin composition 2 was immediately applied onto an aluminum substrate with a 50 μm applicator, immediately after drying the solvent at 80° C. for 5 minutes, and then irradiated with a UV irradiation machine at a dose of 600 mJ/cm ^{2 .} to obtain a coating film.

(Water contact angle measurement of cured film)
A water droplet of 2 μL was dropped on the surface of the cured film immediately after curing, and the water contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 5 below.

Immediately after curing, 1 μL of oleic acid was dropped on the surface of the cured film, and the oil contact angle was measured using a contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.). The results are shown in Table 5 below.

As is clear from Table 5, the coating agent was applied to the example prepared using the fluoropolymer dispersing additive containing the fluorine-containing (meth)acrylic graft polymer of the synthesis example to which the present invention was applied. The coating film exhibited excellent water and oil repellency as compared with the comparative example to which the present invention was not applied and the blank coating film.

The fluoropolymer dispersing additive of the present invention is a tetrafluoropolymer that is added to plastics, paints, and greases for the purposes of slidability, non-adhesiveness, lubricity, antifouling properties, chemical resistance, insulation resistance, and the like. It is used as a dispersing agent that exhibits excellent effects in uniformly dispersing fluoropolymers such as ethylene resins. A fluoropolymer dispersion composition containing this fluoropolymer dispersing additive and a dispersed fluoropolymer is a coating agent used for coating substrates such as home appliances, automobile parts, exterior materials, daily necessities, and building materials. It is added to and used. A coating film obtained by applying and curing this coating agent is used to coat a base material cleanly and smoothly, thereby imparting antifouling properties.

Claims (13)

The following chemical formula ( 1)
CH ₂ =C(-R ¹ )-CO-OR ² -R ^F (1)
(In formula (1), —R ¹ is a hydrogen atom or a methyl group, —R ² — is a group represented by —(CH ₂ ) _n — in which n is 1 to 12, —R ^F is a carbon number of 2 to 6 5 parts by weight or more and less than 40 parts by weight of the fluorine-containing (meth)acrylate monomer (a) represented by a linear, branched, and / or alicyclic perfluoroalkyl group), and the (meth) 20 parts by weight or more and less than 45 parts by weight of the acrylate monomer (b), the repeating structure terminal (meta ) 15 parts by weight or more and 75 parts by weight or less of the acryloyl group-containing macromonomer (c) are copolymerized with each (meth)acryloyl group, and the solubility parameter value obtained by the Fedors method is 8.5 12.0 to 12.0 and a weight average molecular weight of 10,000 to 1,000,000. The copolymer is a graft polymer having a main chain portion obtained by copolymerizing each of the (meth)acryloyl groups and a side chain portion having the repeating structure extending from the middle of the main chain portion. The fluoropolymer dispersing additive according to claim 1. The fluorine-containing (meth)acrylate monomer (a) is at least one selected from perfluorobutylethyl (meth)acrylate and perfluorohexylethyl (meth)acrylate,
The (meth)acrylate monomer (b) is at least one selected from alkyl (meth)acrylates containing alkyl groups having 1 to 12 carbon atoms and amino group-containing (meth)acrylic monomers. Item 2. The additive for dispersing the fluoropolymer according to item 1. The repeating structure terminal (meth)acryloyl group-containing macromonomer (c) is at least one selected from polyalkyl (meth)acrylate macromonomers, polyalkenyl (meth)acrylate macromonomers, polyester macromonomers, and polystyrene macromonomers. The fluoropolymer dispersing additive according to claim 1, characterized in that The copolymer comprises the fluorine-containing (meth)acrylate monomer (a), the (meth)acrylate monomer (b), the repeating structure terminal (meth)acryloyl group-containing macromonomer (c), and a total thereof (Meth)acrylate monomers, (meth)acrylamide monomers, aromatic vinyl monomers, linear or cyclic alkyls having 1 to 12 carbon atoms, not exceeding at most 10 parts by weight per 100 parts by weight It is a copolymer obtained by copolymerizing with a diluent monomer selected from vinyl ether monomers, vinyl ester monomers, amino group-containing (meth)acrylic monomers, carboxyl group-containing (meth)acrylic monomers, and nonionic acrylic monomers. Fluoropolymer dispersing additive according to claim 1. 2. The composition according to claim 1, which is for dispersing the fluoropolymer in a fluoropolymer dispersion composition containing the fluoropolymer and the non-aqueous liquid medium so that the fluoropolymer does not settle in the non-aqueous liquid medium. Fluoropolymer dispersion additive. To disperse the fluoropolymer in a coating agent containing a fluoropolymer dispersion composition containing a fluoropolymer and a non-aqueous liquid medium and a coating component so as not to precipitate the fluoropolymer in the non-aqueous liquid medium and/or the coating component. 2. The fluoropolymer dispersing additive according to claim 1, characterized by: A fluoropolymer dispersion composition comprising the fluoropolymer dispersing additive according to any one of claims 1 to 7 and a fluoropolymer dispersed thereby in a non-aqueous liquid medium. 9. The fluoropolymer dispersion composition according to claim 8, wherein the fluoropolymer is fluororesin powder or fluororesin oil. A coating agent comprising the fluoropolymer dispersion composition according to any one of claims 8 and 9 and a coating component. 11. The coating agent according to claim 10, wherein the fluoropolymer is dispersed by the fluoropolymer dispersing additive so as not to settle. A coating film characterized by being formed by coating and curing the coating agent according to any one of claims 10 to 11. (12) having at least one of water repellency, oil repellency, and antifouling property by dispersing the fluoropolymer and orienting it on the coating film surface by the fluoropolymer dispersing additive; The coating film described in .