KR960008481B1 - Coating composition - Google Patents

Abstract

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Description

Paint Composition

The present invention relates to a paint composition composed of a fluoroalkyl group-containing copolymer.

Compounds containing fluoroalkyl groups in organic compounds have recently been noted as showing useful properties such as weather resistance, water and oil repellency or physiological activity. In particular, the fluoroalkyl group-containing copolymer having a fluoroalkyl group introduced into the organic compound has excellent properties such as low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, mold release property, and chemical resistance. Therefore, in various fields, for example, surface treatment agents, biomaterials, pharmaceuticals, raw materials for pesticides, etc. for imparting water and oil repellency and antifouling properties on surfaces of optical lenses, eyeglass lenses, glassware, paints, etc. Or it is considered useful in the field | area, such as a material which gives a mold release property. However, conventional fluoroalkyl group-containing copolymers are those in which a fluoroalkyl group is introduced to an acrylic acid or methacrylic acid via an ester bond or an amino bond [for example, a fluorine-containing fluoroalkyl group is introduced via an amino bond] Epoxy compound; J. Fluorine chem, 551 (1991)], and generally has a problem with a disadvantage such as low weather resistance. In the acrylic resin containing a fluoroalkyl group, since the fluoroalkyl group is introduced as an ester bond, there is a problem that the fluoroalkyl group is easily detached by furniture decomposition and the water / oil repellency is lowered. There is also a problem that this is insufficient. Fluorine resins using chlorotrifluoroethylene developed for the purpose of improving weather resistance [Japan Organic Synthetic Chemical Association, 42, 841 (1992)] have weather resistance, but have low water and oil repellency, and also pollution resistance. There was a problem that this was insufficient.

Fluorine resins having fluoroalkyl groups, such as fluoroacrylate polymers in which fluoroalkyl groups are introduced by ester bonds, also form a coating on the surface of the substrate to protect the substrate, to have plasticity, water and oil repellency, insulation, release property, It has been used as a surface treatment agent for imparting antifouling properties. However, the fluorine resin has problems such as poor adhesion to inorganic materials such as metals, glass and cement, organic materials such as various plastics and substrates, and fluoroalkyl groups are introduced into the molecules by ester bonds. As a result, there is also a problem that the safety against acids and alkalis is poor.

On the other hand, in order to improve the said adhesiveness, JP-A-59-10280 grade | etc., Etc. restrict | limit the fluoroalkyl-containing silicone type compound. However, in the said silicone type compound, there exists a fault that a sufficient adhesiveness is not yet acquired and a water and oil repellency falls further.

Moreover, in recent years, in the fluorine compound used for SR processing agent, sugar-proofing agent, surfactant, and various surface treatments, amphiphilic material which shows hydrophilicity like the fluoroalkyl group which shows water- and oil-repellent property in the same molecule | numerator I) Surfactants or surface treatment agents having high performance are considered to be useful, attracting attention, and their development is strongly desired. Therefore, there is a strong demand for development of a material having high weather resistance or high water / oil repellency in which a fluoroalkyl group is directly bonded to a carbon-carbon bond.

An object of the present invention is to provide low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, mold release property, water repellent oil repellency and antifouling and chemical resistance on the surface of optical lens, glassware, paint, etc. The present invention provides a coating composition comprising a fluoroalkyl group-containing polymer in which a fluoroalkyl group introduced at a carbon-carbon bond has excellent properties such as a biomaterial or is useful as a raw material for medicines and pesticides.

That is, this invention is the following general formula (VII)

Wherein R ^F is-(CF ₂ ) n ₁ X,- - -OC ₃ F ₇ , N1 is an integer from 1 to 10,

X represents a fluorine atom, a chlorine atom, a hydrogen atom, n2 represents an integer of 0 to 8), and a fluoroalkane peroxide represented by the following general formula (VIII)

[Wherein, Z ¹ represents a hydrogen atom or a methyl group, Z ² and Z ³ are the same or different groups and represent an alkyl, alkoxy or alkylcarbonyloxy group having 1 to 10 carbon atoms and m ₈ represents 1; Display. Provided that when m ₉ = 0, Z ¹ is a hydrogen atom. Silicone monomers represented by] and / or the following general formula (IX)

[Wherein, R ²⁰ represents a hydrogen atom, a halogen atom, a carboxylic acid group or an alkyl group having 1 to 5 carbon atoms, and R ²¹ represents a hydrogen atom, a halogen atom, a saano group, a carboxylic acid group, a phenyl group, a polmiloxy group, a hydroxyl group, C1-C20 alkyloxycarbonyl group, C1-C4 hydroxyalkyloxycarbonyl group, C1-C18 alkylcarbonyloxy group, C1-C18 hydroxyalkylcarbonyloxy group, C1-C8 Alkyl ether group, C1-C18 alkyl sulfonic acid group, C1-C4 amide alkyl sulfonic acid group, C1-C18 hydroxyalkyl ether group, midalkyl sulfonic acid group, C1-C18 hydroxyalkyl ether group,

—CO ₂ CHCH ₃ OR ¹⁴ or —CO ₂ (CH ₂ ) ₁ —CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) s CHR ¹⁷ (CH ₂ ) t CHR ¹⁸ O] u − H, denotes R ¹¹ Silver represents an alkylene group having 1 to 10 carbon atoms or-(CH ₂ CH ₂ ) pCH _2- , R ¹² and R ¹³ are the same or different, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ¹⁴ represents an alkyl group of 1 to 18, m ₈ represents an integer of 0 to 5, P represents an integer of 1 to 10, and R ¹⁵ , R ¹⁶ , R ^17, and R ¹⁸ are the same or different groups As a hydrogen atom or a methyl group, r represents an integer of 0 to 2, s and t represent an integer of 0 to 3, and μ represents an integer of 1 to 5. Containing from 0.01 to 100% by weight of the total polymer component, a fluoroalkyl group-containing copolymer having a number average molecular weight of 500 to 1 million obtained by reacting a raw material component containing a radical synthetic monomer represented by It relates to a paint composition, characterized in that.

Hereinafter, the present invention will be described in more detail.

The fluoroalkyl group-containing polymer used as an essential polymer component in the coating composition of the present invention is a fluoroalkyl group-containing polymer obtained by reacting a specific difluoroalkane oil with a specific raw material monomer.

In the fluoroalkyl group-containing polymer, the specific difluoroalkanoyl peroxide used as a raw material component is represented by the following general formula (VII),

Wherein R ^F is-(CF ₂ ) n ₁ X,- - OC ₃ F ₇ , n ₁ represents an integer of 1 to 10, X represents a fluorine atom, a chlorine atom, a hydrogen atom, and n ₂ represents an integer of 0 to 8). to be.

In the above general formula (VIII), the applicable fluoroalkali group (R _F ), namely-(CF ₂ ) n ₁ X,- - -OC ₃ F ₇ is specifically,

-CF ₃ , F (CF ₂ ) _2- , F (CF ₂ ) _3- , F (CF ₂ ) ₄ , F (CF ₂ ) _5- , F (CF ₂ ) _6- , F (CF ₂ ) _7- , F (CF ₂ ) _8- , F (CF ₂ ) _9- , F (CF ₂ ) _10- , HCF ₂ -,-H (CF ₂ ) ₂ , -H (CF ₂ ) _3- , H (CF ₂ ) _4- , H (CF ₂ ) _5- , H (CF ₂ ) _6- , H (CF ₂ ) _7- , H (CF ₂ ) _8- , H (CF ₂ ) _9- , H (CF ₂ ) ₁₀ -, CℓCF _2- , Cℓ (CF ₂ ) _2- , Cℓ (CF ₂ ) _3- , Cℓ (CF ₂ ) _4- , Cℓ (CF ₂ ) _5- , Cℓ (CF ₂ ) _6- , Cℓ (CF ₂ ) _7- , Cl (CF ₂ ) _8- , Cl (CF ₂ ) _9- , Cl (CF ₂ ) _10- .

to be. At this time, when carbon number, ie, n ₁ and n ₂ of R ^F exceeds 10 and 8, the solubility in a solvent decreases, which is not preferable.

Specific examples of the difluoroalkanoyl peroxide include, for example, diperfluoro-2 -methyl-3 -hexane oil peroxide, perfluoro-2,5-dimethyl-3,6-dioxane onanoyl, Diperfluoro peroxide-2,5,8, -trimethyl-3,6,9-trioxadodecane oil, diperfluoro butylyl peroxide, diperfluoroheptano peroxide etc. are mentioned preferably.

Moreover, the said specific raw material monomer is a monomer represented by the following general formula (VIII) and / or the following general formula (IX), and can use 1 type (s) or 2 or more types. That is, general formula (VIII)

[Wherein, Z ¹ represents a hydrogen atom or an ethyl group, Z ² and Z ³ are the same or different groups and represent an alkyl group, an alkoxy group or an alkylcarbonyloxy group having 1 to 10 carbon atoms and m ₈ is 0 or 1 is displayed. Provided that when m ₉ = 0 Z ¹ is a hydrogen atom. ]

Silicone monomer represented by and / or general formula (IX)

[Wherein, R ²⁰ represents a hydrogen atom, a halogen atom, a carboxylic acid group or an alkyl group having 1 to 5 carbon atoms, and R ²¹ represents a hydrogen atom, a halogen atom, a saano group, a carboxylic acid group, a phenyl group, a polmiloxy group, a hydroxyl group, C1-C20 alkyloxycarbonyl group, C1-C4 hydroxyalkyloxycarbonyl group, C1-C18 alkylcarbonyloxy group, C1-C18 hydroxyalkylcarbonyloxy group, C1-C8 alkyl An ether group, an alkyl sulfonic acid group having 1 to 18 carbon atoms, an amide alkyl sulfonic acid group having 1 to 4 carbon atoms, a hydroxyalkyl ether group having 1 to 18 carbon atoms,

-CO ₂ (CH ₂ CH (R ⁸ ) O) m _4- (CH ₂ CH (R ⁹ ) O) m ₅ [CH ₂ CH ₂ (CH ₂ ) m ₇ O] m ₆ (R ¹⁰ ), CO ₂ R ^11- -CO ₂ ((CH ₂ ) ₆ CO ₂ ) m ₈ CH ₂ , -CO ₂ CHCH ₃ OR ¹⁴ or -CO ₂ (CH ₂ ) -CHR ¹⁵ CHR ¹⁶ O [O (CH ₂ ) _s CHR ¹⁷ (CH ₂ ) tCHR ¹⁸ O] uH, and R ¹⁴ represents 1-C An alkyl group of 18, m ₈ represents an integer of 0-5, P represents an integer of 1-10, R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are the same or different groups and represent a hydrogen atom Or a methyl group, γ represents an integer of 0-2, s and t represent an integer of 0-3, and μ represents an integer of 1-5.). to be.

Silicone monomer represented by general formula (VIII)

[Wherein, Z ¹ represents a hydrogen atom or a methyl group, Z ² and Z ³ represent the same or different groups and represent an alkyl group, an alkoxy group or an alkylcarbonyloxy group having 1 to 10 carbon atoms and m ₉ represents 0 or 1 is displayed. Provided that when m ₉ = 0, Z ¹ is a hydrogen atom. Specific examples thereof include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, diacetyloxymethylvinylsilane, diethoxymethylvinylsilane, triacetyloxyvinylsilane, triisopropoxyvinylsilane and trimethylvinyl. Silane, tri-t-butoxyvinylsilane, ethoxydiethylvinylsilane, diethylmethylvinylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxy Propyldiacetyloxymethylsilane, 3-methacryloxypropyldiethoxymethylsilane, 3-methacryloxypropyltriacetyloxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropyltrimethylsilane, 3-methacryloxypropyl tri-t-buroxysilane, 3-methacryloxypropyl ethoxy diethyl silane, 3-methacryloxypropyl diethyl methyl silane, 3-acryloxypropyl trimethoxy silane, 3-acryl Roxypropyltriethoxysil , 3-acryloxypropyldiacetyloxymethylsilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, 3-acryloxypropyldiacetyloxymethylsilane, 3-acryloxypropyldiethoxy Methylsilane, 3-acryloxypropyltriacetyloxysilane, 3-acryloxypropyltrisoftoxysilane, 3-acryloxypropyltrimethylsilane, 3-acryloxypropyltri-t-butoxysilane, 3-acryloxyproe Oxydiethylsilane, 3-acryloxypropyldiethylmethylsilane, etc. are mentioned preferably.

Wherein R ²⁰ and R ²¹ are the same as defined above.

As specific examples of, for example, vinyl chloride, vinylene chloride, vinyl fluoride, vinylidene fluoride, acrylonitrile, vinyl acetate, vinyl propionate, vinyl butylate, (meth) acrylic acid, methyl (meth) acrylate, ( Meta) acrylic acid-t-butyl, (meth) acrylic acid-n-butyl, (meth) acrylic acid-2-ethylhexyl, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate,

Etc. are mentioned preferably. In the above formula, q ¹ represents an integer of 1 to 10, q ² represents an integer of 1 to 20, q ³ represents an integer of 0 to 20, respectively, and when used alone or q ¹ , q ² or a mixture in which q ³ is a different integer.

The method for producing a fluoroalkyl-containing copolymer according to the present invention is characterized by reacting a specific difluoroalkane oil with a specific raw material monomer.

Difluoroalkanoyl peroxide used for this invention is represented by the said General formula (VII). In difluoroalkanoyl peroxide represented by the general formula (VII), when n ₁ is 11 or more or m ₂ is 9 or more, the reaction of difluoroalkanoyl peroxide when reacting in the presence of a solvent It cannot be used because solubility is degraded. In the present invention, when reacting the difluoroalkanoyl peroxide with the monomer represented by the general formula (IX) and / or the general formula (VIII), the monomer represented by the general formula (IX) and the salt The mixing molar ratio with the monomer represented by the general formula (VIII) can be any ratio, but is preferably in the range of 1: 1.01 to 100, and is represented by the peroxide perfluoroalkane oil and the general formula (IX). In the case of reacting a monomer (or a monomer represented by general formula (VIII)), the insertion molar ratio is preferably in the range of 1:01 to 5000, and particularly preferably in the range of 1:05 to 100. Do. When the molar ratio of the raw material monomer is less than 0.1, a large amount of the product due to the self-decomposition of the peroxide is produced, and when the molar ratio exceeds 5000, the yield of the desired fluoroalkyl group-containing copolymer is lowered. not. In addition, it is possible to control the total molecular weight obtained by controlling the molar molar ratio of the difluoroalkanoyl peroxide. In other words, when the molar ratio of the difluoroalkanoyl peroxide is increased, a low molecular weight aggregate can be obtained, and a low molecular weight aggregate can be obtained. The reaction can be carried out at normal pressure, and the reaction temperature is usually in the range of -20 to 150 ° C, preferably 0 to 100 ° C. If the reaction temperature is less than -20 DEG C, the reaction time tends to be long. On the contrary, if the reaction temperature exceeds 150 DEG C, the pressure during the reaction becomes high and the reaction operation becomes difficult. Moreover, although reaction time can be normally performed in 30 minutes-20 hours, it is preferable to set conditions so that it may become 1 to 10 hours practically.

In the production method of the present invention, under the various reaction conditions, the desired fluoroalkyl group-containing complex is directly obtained by one-step reaction while reacting the fluoroalkanoyl peroxide and the monomers. It is preferable to use a solvent in order to carry out the handling and reaction of rhoalkan oil more smoothly.

As the solvent, a halogenated aliphatic solvent is particularly preferable, and for example, methylene chloride, chloroform, 2-chloro-1,2-dibromo-1,1,2-trifluoroethane, 1,2-di Bromohexafluoropropane, 1,2-dibromotetrafluoroethane, 1,1-difluorotetrachloroethane, 1,2-difluorotetrachloroethane, fluorotrichloromethane, heptafluoro -2,3,3, -trichlorobutane, 1,1,1,3-tetrachlorotetrafluoropropane, 1,1,1-trichloropentafluoropropane, 1,1,2-trichlorotrifluoro Ethane, 1,1,1,2,2-pentafluoro-3,3, -dichloropropane, 1,1,2,2,3-pentafluoro-1,3-dichloropropane and the like can be used, Especially industrially 1,1,2-trichlororifluoroethane, 1,1,1,2,2-pentafluoro-3,3-dichloropropane, 1,1,2,2,3-pentafluoro Examples thereof include solvents such as 1,3-dichloropropane. When using the said solvent, it is preferable that the density | concentration of the said fluoroalkanoyl peroxide in a solvent is about 0.1-30 weight% normally. Although the said aggregate is obtained by the said manufacturing method, this aggregate may contain the aggregate in which R <^F> group was introduce | transduced only in the superposition | polymerization fragment end.

The reaction product obtained by the manufacturing method of this invention can be refine | purified by well-known methods, such as distillation, a reprecipitation method, column chromatography.

As said fluoroalkyl group containing polymer which is an essential polymer component of the coating composition of this invention, following General formula (X)

[Wherein, R ²⁰ represents a hydrogen atom, a halogen atom, a carboxylic acid group or an alkyl group having 1 to 5 carbon atoms, and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, a carboxylic acid group, a phenyl group, a polmiloxy group, a hydroxyl group, C1-C20 alkyloxycarbonyl group, C1-C4 hydroxyalkyloxycarbonyl group, C1-C18 alkylcarbonyloxy group, C1-C18 hydroxyalkylcarbonyloxy group, C1-C8 alkyl An ethyr group, a C1-C18 alkyl sulfonic acid group, a C1-C4 amide alkyl sulfonic acid group, a C1-C18 hydroxyalkyl ether group,

-CO ₂ (CH ₂ CH (R ⁸ ) O) m _4- (CH ₂ CH (R ⁹ ) O) m ₅ [CH ₂ CH ₂ (CH ₂ ) m ₇ O] m ₆ (R ¹⁰ ),

-CO ₂ R ^11- -CO ₂ ((CH ₂ ) ₆ CO ₂ ) m ₈ CH _2-

-CO ₂ CHCH ₃ OR ¹⁴ or

—CO ₂ (CH ₂ ) r—CHR ¹⁵ CHR ¹⁶ O [CO (CH ₂ ) _s CHR ¹⁷ (CH ₂ ) tCHR ¹⁸ O] uH, and R ¹¹ represents an alkylene group having 1 to 10 carbon atoms or-( CH ₂ CH ₂ O) pCH _2- , R ¹² and R ¹³ are the same or different groups, and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, and R ¹⁴ represents an alkyl group having 1 to 18 tano numbers. M ₈ represents an integer of 0 to 5, P represents an integer of 1 to 10, and R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ represent the same or different groups and represent a hydrogen atom or a methyl group. , r represents an integer from 0 to 2, s and t represent an integer from 0 to 3, and μ represents an integer from 1-5.)]

In the above substituents and addition letters, R ²⁰ is preferably a hydrogen atom, a halogen atom or a methyl group, and R ²¹ is preferably R ²¹ excluding cyano group, phenyl group and amide alkyl sulfonic acid group having 1 to 4 carbon atoms, Preferred R ¹¹ is an alkylene group having 1 to 5 carbon atoms or — (CH ₂ CH ₂ O) pCH ₂ —, a preferred group of R ¹² and R ¹³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, preferably a R ¹⁴ an alkyl group having 1 to 8 carbon atoms, the preferred range of ₈ m is an integer from 0 to 2, and a preferred range of p is an integer from 1-5. Or the following general formula (XI)

[Wherein, Z ¹ represents a hydrogen atom or a methyl group, and Z ² and Z ³ are the same or different groups and include a C 1-10 alkyl group, a C 1-10 alkoxy group or a C 1-10 alkylcarbonyl An oxy group and m ₉ represents 0 or 1. Provided that when m ₉ = 0, Z ¹ is a hydrogen atom. ]

In the above substituents and addition letters, Z ² and Z ³ are preferably an alkoxy or alkylcarbonyloxy group having 1 to 10 carbon atoms, particularly preferably an alkoxy or alkylcarbonyloxy group having 1 to 6 carbon atoms.]

It is a polymer which forms a main chain skeletal structure by 1 type, or 2 or more types of the polymer represented by the formula, and which has the R ^F group specifically listed in the said difluoroalkanoyl peroxide, and a R ^F group is introduce | transduced only at the superposition | polymerization terminal end. The polymer may be contained. In the substituent and the addition letter of the R ^F group, X is preferably a fluorine atom, a preferable range of n ₁ is 3 to 8, and a preferable range of n ₂ is 0 to 5. At this time, the number average molecular weight of the polymer having General Formula (X) or (XI) as a repeating unit is in the range of 500 to 1000000, preferably in the range of 500 to 100000. When the said number average molecular weight is out of the said range, it exists in the tendency which becomes difficult to express the outstanding characteristic resulting from a fluoroalkyl group in a coating composition.

In the coating composition of the present invention, the above-mentioned fluorokill group-containing polymer may be used alone as a polymer component as an essential polymer component, but another binder polymer may be used in combination. The other binder polymer is not particularly limited as long as it is an ordinary coating polymer, but specifically, for example, acrylic resin, polyester resin, alkyd resin, silicone resin, fluorine resin, epoxy resin, vinyl chloride resin, and fibrin series Resin, phenol resin, xylene resin, toluene resin, amino resin, polyisocyanate compound, etc. are mentioned preferably, A commercial item can also be used. In addition, it can also be used individually or as a mixture about use.

In the coating composition of the present invention, the fluoroalkyl group-containing polymer used as an essential polymer component is 0.01% to 100% by weight based on the entire polymer component. When the said content is less than 0.01%, water repellency and oil repellency are inadequate and the contamination resistance of a to-be-coated object falls.

Although the coating composition of this invention can be used only with the said polymer component, you may add the paint adjuvant, additive, etc. which are normally used, such as a pigment, dye, a dispersing agent, a hardening accelerator, a labeling agent, as needed.

Although the coating composition of this invention can be used only with the said polymer component, it can also be used by melt | dissolving in a solvent and diluting. As a solvent which can be used at this time, toluene, xylene, a solvent, Aromatic hydrocarbon solvents such as 100 (exon Chemical Co., Ltd. product name), fluorine-containing aromatic hydrocarbon solvents such as benzotrifluoride, hexafluoroxylene, hexafluorobenzene, ethyl acetate, butyl acetate, ethylene acetate Ester solvents such as monoethyl ether, propylene glycol monomethyl ether, ketone solvents such as methyl isobutyl ketone, methyl amyl ketone, alcohol solvents such as butyl alcohol, amyl alcohol, ether alcohols such as ethylene glycol monobutyl ether A system solvent etc. are mentioned preferably.

In order to apply | coat using the coating composition of this invention, it can coat by well-known coating methods, such as spray coating and brushing, and drying is normal temperature It can carry out in the temperature range of 200 degreeC.

Specific examples of the fluoroalkyl group-containing polymer in the coating composition of the present invention include the following general formulas:

Etc. are mentioned preferably.

In the fluoroalkyl group-containing polymer used in the present invention, since the fluoroalkyl group is bonded by a direct carbon-carbon bond rather than an ester bond, it is possible to maintain the properties attributable to the fluoroalkyl group over a long period of time. This is a high compound. Therefore, as a compound having properties such as low surface tension, low refractive index, heat resistance, cold resistance, oil resistance, electrical insulation, water repellency, and chemical resistance, in particular, a surface treatment agent or paint for imparting water / oil repellency and antifouling properties It can be used for materials on the surface of optical lenses, eyeglass lenses, glassware, biomaterials, and raw materials such as medicines and pesticides. In particular, in the fluoroalkyl group-containing polymer having functional groups such as silyl group, hydroxyl group, epoxy group or carboxylic acid group in the present invention, it is also effective for increasing adhesion to the base or as a curing site. In addition, the fluoroalkyl group-containing polymer used in the present invention can be produced in one step in a short time with good yield and easily, without using a reaction catalyst and a special apparatus.

The coating composition of the present invention contains a fluoroalkyl group-containing polymer as an essential polymer component, and is excellent in water repellency, oil repellency, stain resistance of the coating film surface, and the like. In the fluoroalkyl group-containing polymer, since the fluoroalkyl group is introduced by a carbon-carbon bond, the above effects can be maintained for a long time without being detached by hydrolysis, and in the present invention, In a fluoroalkyl group-containing polymer, since it has functional groups, such as a silyl group, a hydroxyl group, an epoxy group, or a carboxylic acid group, these functional groups are effective also as a hardening site | part or in order to improve adhesiveness with respect to a coating film, and to improve coating film performance. Therefore, it is also useful as a coating material for automobile exterior plates, home appliances, furniture, building exterior agents, or as a raw material for water-soluble paints and powder coatings.

EXAMPLES Hereinafter, although an Example, a comparative example, and a synthesis example demonstrate this invention in detail, this invention is not limited to these.

Synthesis Example 1

1,1,2-trichloro containing 7 · 5 g of methyl ketacrylate and 37 · 2 g of 3-methacryloxypropyltrimethoxysilane, containing 16 · 5 g of diperfluoro-2-methyl-3oxahexanoyl peroxide 1500g of fluoroethane solutions were added, and reaction was performed at 30 degreeC under nitrogen atmosphere for 5 hours. After completion of the reaction, the reaction solvent was removed, and then dried under vacuum to yield a fluoroalkyl-containing silicone polymer represented by the following formula at a yield of 50 g. The weight average molecular weight of the obtained polymer was measured by gel permeation chromatography. The results are shown in Table 1.

Synthesis Example 2-4

The reaction was carried out in the same manner as in Synthesis Example 1, except that the raw material compound shown in Table 1 and the preparation ratio shown in Table 1 were used, and a fluoroalkyl group-containing silicone polymer was obtained in the amounts shown in Table 1, respectively. The weight average molecular weight is shown in Table 1.

Synthesis Example 5

50 parts by weight of xylene and 30 parts by weight of butyl acetate were mixed and heated to 100 ° C. while stirring, followed by 30 parts by weight of 3-methacryloxypropyltris (trimethylsiloxy) silane, 12 parts by weight of 2-hydroxyethyl methacrylate, The monomer mixture consisting of 30 parts by weight of styrene, 26 parts by weight of n-butyl methacrylate, 2 parts by weight of acrylic acid and 3 parts by weight of azobisisobutylonitrile was added dropwise over 2 hours.

After completion of the dropwise addition, the reaction was carried out at 100 ° C for 2 hours. After completion of the reaction, the reaction system was cooled to obtain a solution, and to the obtained solution, 23 parts by weight of butyl acetate was added to obtain 206 parts by weight of a solution of an alkylsilane-containing vinyl polymer (weight average molecular weight 14600) of 50% by weight of a heated residue.

Synthesis Example 6

30 parts by weight of 1H, 1H, 2h, 2H-heptadecafluorodecyl methacrylate, 12 parts by weight of 2-hydroxyethyl methacrylate, 30 parts by weight of styrene 10, and 26 parts by weight of n-butyl methacrylate The reaction was carried out in the same manner as in Synthesis example 5 except for changing to 2 parts by weight of acrylic acid to obtain 206 parts by weight of a fluoroalkoxy group-containing vinyl polymer (weight average molecular weight 15300) having a heated residue of 50 · 2% by weight.

Synthesis Example 7

2,8 g (20 mmol) of butyl methacrylate and 2,6 g (20 mmol) of hydroxyethyl methacrylate, containing 4,0 g (6 mmol) of perfluoro-2-methyl-3-oxahexane oil, 40 g of a 1,1,2-trichlorotrifluoroethane solution was added and reacted under a nitrogen stream at 30 ° C. for 6 hours to obtain a fluoroalkyl group-containing polymer represented by the following formula. The number average molecular weight of the obtained polymer was 1200 (Mw / Mn = 1 * 40), and m: m of the food flow was 1: 2.

Synthesis Example 8

The reaction was carried out in Synthesis Example 7 except that the molar ratio of 4 · 0 g (6 mmol) of perfluoro-2-methyl-3-oxahexane oil was changed to 2 · 0 g (3 mmol). A low alkyl group-containing polymer was obtained. The number average molecular weight of the obtained polymer, 2520 (Mw / Mn = 1 · 90), wherein m _1: m ₂ is 1: was 1.

Synthesis Example 9

The reaction was carried out in accordance with Synthesis Example 7 except that the amount of butyl methacrylate was changed to 8 · 4 g (6 mmol). Thus, a fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer, 1200 (Mw / Mn = 1 · 40), wherein m _1: m ₂ is 1: 3 yiyeotda.

Synthesis Example 10

The reaction was carried out in Synthesis Example 7 except that perfluoro-2-methyl-3-oxahexaneoil was replaced with perfluoro-2.5-demethyl-3.6-dioxane onoyl peroxide. A fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained composite material is, 1200 (Mw / Mn = 1.00 ), wherein m _1: m ₂ is 1: was 1.

Synthesis Example 11

The reaction mole ratio of butyl methacrylate was changed to 19 · 6 g (140 mmol) except that the reaction was carried out in accordance with Synthesis Example 7, whereby a fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer, 1200 (Mw / Mn = 1.00 ), wherein m _1: m ₂ is 1: 6 yiyeotda.

Synthesis Example 12

1.5 g (10 mmol) of trimethoxyvinylsilane, 2.0 g (10 mmol) of 2-hydroxyethyl methacrylate, 9,9 g (10 mmol) of perfluoro-2,5-dimethyl-3,6-dioxane onionyl peroxide 124 g of 1,1,2-trichlorofluoroethane containing was added and reacted under a nitrogen stream at 30 ° C. for 6 hours to obtain a fluoroalkyl group-containing polymer represented by the following formula. The number average molecular weight of the obtained polymer was 1990 (Mw / Mn = 1 * 11), and m <_1> : m <_2> in the formula was 1: 1.

Synthesis Example 13

The reaction was carried out in accordance with Synthesis Example 12, except that perfluorofluoro-2,5-dimethyl-3,6-dioxane onanoyl peroxide was replaced with perfluoro-2-methyl-3-oxanoonyl peroxide. A fluoroalkyl group-containing polymer represented by the formula was obtained. The number average molecular weight of the obtained polymer was 2030 (Mw / Mn = 1.12), and m <_1> : m <_2> in the formula was 1: 1.

Synthesis Example 14

The reaction was carried out in accordance with Synthesis Example 12, except that 2-ethylhexyl methacrylate was changed to butyl methacrylate, whereby a fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer was 1850 (Mw = Mn = 1.07), and m <_1> : m <_2> in the formula was 1: 1.

Synthesis Example 15

Perfluorofluoro-2,5-dimethyl-3,6-dioxane onoyl peroxide was replaced with 5.3 g (8 mmol) of perfluoro-2-methyl-3-oxahexane oil, and 2-ethylhexyl methacrylate was replaced with The reaction was carried out in accordance with Synthesis Example 12 except for changing to butyl methacrylate to obtain a fluoroalkyl group-containing polymer represented by the following formula. The number average molecular weight of the obtained polymer was 1770 (Mw / Mn = 1.15), and m <_1> : m <_2> was 1: 1.

Synthesis Example 16

Instead of 2-hydroxyethylmethacrylate, CH = CCH ₃ -CO ₂ -CH _2- The reaction was carried out in accordance with Synthesis Example 7, except that the fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer was 2590 (Mw / Mn = 1.62), and m <_1> : m <_2> was 1: 1.

Synthesis Example 17

Instead of 2-hydroxyethyl methacrylate,

The reaction was carried out in accordance with Synthesis Example 7, except that the fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer was 2990 (Mw / Mn = 1.71), wherein m ₁ : m ₂ =, 1: 1.

Synthesis Example 18

Instead of 2-ethylhexyl methacrylate,

Was reacted according to Synthesis Example 12 except that perfluoro-2-methyl-3-oxahexaneoil was used instead of perfluoro-2,5-dimethyl-3,6-dioxane onoyl peroxide. The fluoroalkyl group-containing polymer represented by the following formula was obtained. The number average molecular weight of the obtained polymer was 1720 (Mw / Mn = 1.14).

Synthesis Example 19

Into a 2-liter four-necked flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel, 599.6 g of a brand name "Solbet # 100" (manufactured by Exxon Chemical Co., Ltd.) was added and kept warm at 130 ° C. 214.8 g of ethyl methacrylate, 139.05 g of methyl methacrylate, 471.3 g of 2-ethylhexyl methacrylate, and 20.7 g of the trade name "Perbutyl O" (manufactured by Nippon Yushi Co., Ltd., Japan) were purchased. Reaction was performed at 130 degreeC for 3.5 hours, and 1460 g of polyol resins of 55.7 weight% of solid content were obtained (weight average molecular weight 12300).

Synthesis Example 20

Glycidyl methacrylate instead of 2-hydroxyethyl methacrylate (CH ₂ = CCH ₃ CO ₂ CH ₂ The reaction was carried out in the same manner as in Synthesis example 19 except for using), whereby an epoxy resin (weight average molecular weight 11300) having a solid content of 55.7% was obtained.

Examples 1-8, Comparative Examples 1-3

The polymers obtained in Synthesis Examples 1 to 6 and the compounds shown in Table 2 were mixed at the blending ratios shown in Table 2, and the coating solution was mixed using a xylene / butyl acetate mixed solution (weight ratio 6: 4). Aude Cup NO. It diluted to 4 at the viscosity of 25 second (20 degreeC), and prepared the coating solution. Subsequently, the high epico NO. 100 white (brand name, Nippon Yushi Co., Ltd. product) were coated, and the coating solution was spray-coated on the coating film obtained by drying at 140 ° C. for 20 minutes, and then dried under the drying conditions shown in Table 2, respectively. A test piece was obtained. The physical tactile and dodecane contact angles of the obtained test pieces were measured. Furthermore, after immersing the test piece in 40 degreeC warm water for 24 hours, the water contact angle, the dodecane contact angle, and contamination resistance were measured again. In addition, the stain resistance was contaminated by artificial mud (including soil, mineral oil, clay, carbon black), magic ink, and lip paper after the test piece was immersed in hot water at 40 ° C. for 24 hours. Subsequently, drain water for artificial mud, and use a mixed solvent of petroleum benzine / ethanol (weight ratio 90:10) for magic ink and lip balm to determine the condition of cracking with a cloth. (Double-circle), (triangle | delta) and (triangle | delta) and (complete | finish mark) of what left a considerable trace remain as (circle).

Examples 9-17

To 16.7 g of the polyol resin synthesized in Synthesis Example 19, 4 g of the brand name "Cymel 301" (manufactured by Mitsui Cycamide Co., Ltd., Japan) was added, and the total weight of the polyol resin and the curing agent is shown in Table. The fluoroalkyl group-containing polymer synthesized in Synthesis Examples 7 to 15 was added so that the compounding amount shown in 3. Next, dodecylbenzenesulfonic acid was added to the total weight of the polyol resin and the curing agent by 1% by weight of the dodecylbenzenesulfonic acid as a catalyst. 9 ml of was added and stirred sufficiently to prepare a coating solution.

Subsequently, after coating the coating solution obtained on the steel plate, it dried at 140 degreeC for 30 minutes, and created the test piece. The presence or absence of frying on the surface of the coated test piece was visually observed, and the same test as in Examples 1 to 8 was conducted. The results are shown in Table 3.

Examples 18-20

Epoxy resin synthesized in Synthesis Example 20 was used instead of the polyol resin synthesized in Synthesis Example 19, adipic acid was used in place of the curing agent "Cyamel 301" used in Synthesis Example 19, and a catalyst used in Synthesis Example 19: Spray coating was carried out in accordance with Example 9 except that tetrabutylphosphonium bromide was used instead of dodecylbenzene sulfonic acid. Table 3 shows the results of the test method as in Example 9.

Comparative Example 4

Except not using the fluoroalkyl group-containing polymer synthesized in Synthesis Examples 7 to 8, a test piece was prepared and tested in the same manner as in Examples 9 to 20. The results are shown in Table 3.

Tables 2 and 3 show that the coating composition of the present invention is superior in water repellency and oil repellency and its sustainability is superior to the coating composition of Comparative Example. Therefore, it is apparent that the coating film formed by the coating composition of the present invention has excellent stain resistance.

Claims (4)

General formula (VII) Where R ^F is-(CF ₂ ) _{n 1} X, _-CF- n ₁ represents an integer of 1 to 10, X represents a fluorine atom, a chlorine atom and a hydrogen atom, n ₂ represents an integer of 0 to 8, and the following general formula (VIII) ) [Wherein, Z ¹ represents a hydrogen atom or a methyl group, Z ² and Z ³ represent the same or different groups and represent an alkyl, alkoxy or alkylcarbonyloxy group having 1 to 10 carbon atoms and m ₈ represents 0 or 1 Is displayed. Provided that when m ₉ = 0, Z ¹ is a hydrogen atom. ] Silicone monomers represented by and or the following general formula (IX) [Wherein, R ²⁰ represents a hydrogen atom, a halogen atom, a carboxylic acid group or an alkyl group having 1 to 5 carbon atoms, and R ²¹ represents a hydrogen atom, a halogen atom, a cyano group, a carboxylic acid group, a phenyl group, a polmiloxy group, a hydroxyl group, C1-C20 alkyloxycarbonyl group, C1-C4 hydroxyalkyloxycarbonyl group, C1-C18 alkylcarbonyloxy group, C1-C18 hydroxyalkylcarbonyloxy group, C1-C8 Alkyl ether group, C1-C18 alkyl sulfonic acid group, C1-C4 amide alkyl sulfonic acid group, C1-C18 hydroxyalkyl ether group -CO ₂ CHCH ₃ OR ¹⁴ or -CO ₂ (CH ₂ ) r-CHR ¹⁵ CHR | ¹⁶ O [CO (CH ₂ ) sCHR ¹⁷ (CH ₂ ) t CHR ¹⁸ O] u-H is represented, and R ¹¹ represents an alkylene group having 1 to 10 carbon atoms or-(CH ₂ CH ₂ O) p CH ₂ -Represent, R ¹² and R ¹³ are the same or different groups and represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, R ¹⁴ represents an alkyl group having 1 to 18 carbon atoms, and m ₈ is 0 to 5 An integer, P represents an integer from 1 to 10, and R ¹⁵ , R ¹⁶ , R | ¹⁷ and R ¹⁸ are the same or different groups and represent a hydrogen atom or a methyl group, r represents an integer of 0 to 2, s and t represent an integer of 0 to 3, and u represents an integer of 1 to 5 It is a paint composition obtained by reacting the raw material component containing the radical synthesis monomer represented by] as a polymer component containing the number average molecular weight 500-1 million fluoroalkyl group containing compound and binder polymer, A coating composition comprising 0.01 to 100% by weight of the fluoroalkyl-containing polymer relative to the entire polymer component. The method of claim 1, wherein the binder polymer is acrylic resin, polyester resin, alkyd resin, silicone resin, fluorine resin, epoxy resin, vinyl chloride resin, fibrin resin, phenol resin, alkylene resin, toluene resin, amino resin, A coating composition, characterized in that the polyisocyanato compound, one selected from the group consisting of block isocyanate compounds. A method of coating the coating composition of claim 1 on a coating object. Article coated by the coating method of claim 3.