WO2014034607A1 - Fluorine-containing hyperbranched polymer and unsaturated polyester resin composition containing same - Google Patents

Abstract

[Problem] To provide a fluorine-containing hyperbranched polymer and an unsaturated polyester resin composition which contains the fluorine-containing hyperbranched polymer. [Solution] A fluorine-containing hyperbranched polymer which is obtained by polymerizing a monomer (A) that has two or more radically polymerizable double bonds in each molecule, a monomer (B) that has a fluoroalkyl group and at least one radically polymerizable double bond in each molecule, and a monomer (C) that has a cyclic acid anhydride structure or a cyclic imide structure and at least one radically polymerizable double bond in each molecule in the presence of a polymerization initiator (D) that is in an amount of 5-200% by mole relative to the number of moles of the monomer A.

Description

Fluorine-containing hyperbranched polymer and unsaturated polyester resin composition containing the same

The present invention relates to a fluorine-containing highly branched polymer and an unsaturated polyester resin composition containing a fluorine-containing highly branched polymer.

Polymer (polymer) materials are increasingly used in many fields in recent years. Accordingly, the characteristics of the surface and interface of the polymer as a matrix are important as well as the properties of the polymer according to each field. For example, by using a fluorine-based compound with low surface energy as a surface modifier, water and oil repellency, antifouling properties, non-adhesiveness, peelability, release properties, slipperiness, abrasion resistance, antireflection properties Various improvements relating to surface / interface control such as chemical resistance are expected and various proposals have been made.

Unsaturated polyester resin, which is one of thermosetting resins, is used for artificial marble that has various marble fillers and pigments, and has a natural marble appearance. It is often used for toilets, floors and walls of unit baths, countertops, sanitary applications, furniture, and interior materials. These artificial marbles are generally made of resin, inorganic filler, low shrinkage agent, catalyst, cross-linking agent, pigment, etc., and are molded by casting method, heat press method, etc. It has excellent properties, warm water resistance, strength, weathering resistance, etc., has an appearance close to natural marble, and has a high-class feel and is often used.

However, on the other hand, since the unsaturated polyester resin has excellent affinity with water and oil, there is a problem that the appearance of the artificial marble is impaired by scale or oil stain. In particular, since bathtubs, kitchens, and washrooms are frequently used, a function that the surface has antifouling properties and the dirt can be easily wiped off has been desired.

In order to form such a surface function, a double bond is formed in the molecule on the resin composition for artificial marble (Patent Document 1) blended with fluorine powder and the material for forming the outermost surface layer (gel coat layer) of artificial marble. The composition (patent document 2) which mix | blended the modified silicone oil containing this, or the composition (patent document 3) which mix | blended the fluorine-type polymer with this gel coat layer forming material is disclosed.

JP 2001-207065 A JP 2001-131383 A JP-A-6-154118

However, the antifouling measures taught in these patent documents cannot provide oil repellency, leaving a problem that it is difficult to remove oil stains. Further, the fluorine-based polymer has poor dispersibility in the unsaturated polyester resin, and therefore, the problem is that the glossiness and transparency after curing are impaired.
That is, the object of the present invention is to impart water and oil repellency and antifouling properties without impairing the high-quality feeling of the base material, particularly when applied as a gel coat layer to the surface of the base material such as artificial marble. It is an object of the present invention to provide a fluorinated hyperbranched polymer, a varnish containing it, a curable composition of an unsaturated polyester resin containing the fluorinated hyperbranched polymer, a cured product thereof, and a cured film thereof.

As a result of intensive studies in order to achieve the above object, the inventors of the present invention have made the side chain in the fluorine-containing hyperbranched polymer highly soluble in organic solvents and highly dispersible in the resin, and reactive with unsaturated polyester. When the cyclic acid anhydride structure or the cyclic imide structure having the polymer is introduced, the cured product and the cured film obtained by curing the unsaturated polyester composition containing the polymer have a water-repellent and water-repellent surface without impairing the transparency. The present inventors have found that oiliness can be improved and completed the present invention.
That is, the first aspect of the present invention is a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. And a monomer C having a cyclic acid anhydride structure or a cyclic imide structure and at least one radical polymerizable double bond in the molecule in an amount of 5 to 200 mol% relative to the number of moles of the monomer A. The present invention relates to a fluorine-containing hyperbranched polymer obtained by polymerization in the presence of an agent D.
As a 2nd viewpoint, the said monomer C is related with the fluorine-containing highly branched polymer as described in a 1st viewpoint which is a compound represented by following formula [1].

Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halogen atom or 1 to 6 carbon atoms. Represents a benzyl group which may be substituted with an alkyl group of the above, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ , R ² and the bond thereof A carbon atom and an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may contain a hetero atom, together with a carbon atom, represents an oxygen atom or NR ³ (where R ³ is a hydrogen atom, Represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms).
As a third aspect, the present invention relates to the fluorine-containing highly branched polymer according to the second aspect, in which the monomer C is maleic anhydride.
As a fourth aspect, the fluorine-containing hyperbranched structure according to any one of the first to third aspects, wherein the monomer A is a compound having either one or both of a vinyl group and a (meth) acryl group. Relates to polymers.
As a 5th viewpoint, the said monomer A is related with the fluorine-containing highly branched polymer as described in a 4th viewpoint which is a divinyl compound or a di (meth) acrylate compound.
As a sixth aspect, the fluorine-containing hyperbranched structure according to any one of the first to third aspects, wherein the monomer B is a compound having at least one of a vinyl group and a (meth) acryl group. Relates to polymers.
As a seventh aspect, the present invention relates to the fluorine-containing highly branched polymer according to the sixth aspect, in which the monomer B is a compound represented by the following formula [2].

(Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a fluoroalkyl group having 2 to 12 carbon atoms which may be substituted with a hydroxy group.)
As an eighth aspect, the present invention relates to the fluorine-containing highly branched polymer according to the seventh aspect, wherein the monomer B is a compound represented by the following formula [3].

(Wherein R ⁴ represents the same meaning as defined in the above formula [2], X represents a hydrogen atom or a fluorine atom, p represents an integer of 1 or 2, and q represents an integer of 0 to 5). )
As a ninth aspect, the present invention relates to the fluorine-containing highly branched polymer according to any one of the first aspect to the eighth aspect, in which the polymerization initiator D is an azo polymerization initiator.
As a tenth aspect, the first to ninth aspects are obtained by polymerizing 5 to 300 mol% of the monomer B and 5 to 300 mol% of the monomer C with respect to the number of moles of the monomer A. The fluorine-containing hyperbranched polymer according to any one of the above.
As an 11th viewpoint, it is related with the varnish containing the fluorine-containing hyperbranched polymer as described in any one of a 1st viewpoint thru | or a 10th viewpoint.
As a twelfth viewpoint,
(A) 0.01 to 20 parts by mass of the fluorine-containing highly branched polymer according to any one of the first to tenth aspects;
The present invention relates to a curable composition containing (b) 100 parts by mass of an unsaturated polyester resin and (c) 0.05 to 10 parts by mass of a thermal polymerization initiator.
As a 13th viewpoint, it is related with the hardened | cured material obtained from the curable composition as described in a 12th viewpoint.
As a 14th viewpoint, it is related with the cured film obtained from the curable composition as described in a 12th viewpoint.
As a fifteenth aspect, the present invention relates to the cured film according to the fourteenth aspect, which has a film thickness of 0.01 to 5000 μm.

Since the fluorine-containing hyperbranched polymer of the present invention has positively introduced a branched structure, it has less entanglement between molecules compared to a linear polymer, exhibits fine particle behavior, solubility in an organic solvent, and resin. Is highly dispersible. For this reason, when the fluorine-containing hyperbranched polymer of the present invention is blended with a curable composition to form a cured film, the finely branched hyperbranched polymer easily moves to the interface (cured film surface), and the resin surface This leads to improved surface modification.
In particular, the fluorine-containing highly branched polymer of the present invention has a polymer side chain having a cyclic acid anhydride structure or a cyclic imide structure having reactivity with an unsaturated polyester. When the composition blended in the saturated polyester composition is applied to a base material such as artificial marble and cured, the water and oil repellency is imparted to the base material such as artificial marble without impairing its luxury feeling. Can do.
By using the varnish of the present invention, a thin film containing the fluorine-containing highly branched polymer can be suitably obtained.
By using the curable composition of this invention, the cured | curing material and cured film of unsaturated polyester resin containing the said fluorine-containing hyperbranched polymer are obtained suitably.
Since the cured product of the present invention has a large amount of the above-mentioned fluorine-containing highly branched polymer on its surface, various machines such as a mixing / molding machine used in the production of the cured product, releasability to molds, films, etc. It is excellent in releasability from other resin molded products, water / oil repellency, and antifouling properties.
Since the cured film of the present invention is in a state where a large amount of the above-mentioned fluorine-containing highly branched polymer is present on the surface thereof, it is excellent in releasability from the base material used at the time of forming the cured film, and further in water / oil repellency and antifouling properties.

1 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 1 obtained in Example 1. FIG. 2 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 2 obtained in Example 2. FIG. FIG. 3 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 3 obtained in Example 3. 4 is a diagram showing a ¹³ C NMR spectrum of the hyperbranched polymer 4 obtained in Comparative Synthesis Example 1. FIG.

<Fluorine-containing highly branched polymer>
The fluorine-containing highly branched polymer of the present invention comprises a monomer A having two or more radical polymerizable double bonds in the molecule, and a monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule. And a monomer C having a cyclic acid anhydride structure or a cyclic imide structure and at least one radical polymerizable double bond in the molecule in an amount of 5 to 200 mol% relative to the number of moles of the monomer A. It is obtained by polymerizing in the presence of agent D. The fluorine-containing highly branched polymer of the present invention is a so-called initiator-fragment incorporation type fluorine-containing highly branched polymer, and has a fragment of the polymerization initiator D used for polymerization at the terminal.
Furthermore, the fluorine-containing hyperbranched polymer of the present invention may copolymerize the monomer A, the monomer B, and other monomers that do not belong to the monomer C as necessary, as long as the effects of the present invention are not impaired. .

[Monomer A]
In the present invention, the monomer A having two or more radically polymerizable double bonds in the molecule preferably has one or both of a vinyl group and a (meth) acryl group, and in particular, a divinyl compound or di (meta). ) An acrylate compound is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

Examples of such a monomer A include organic compounds shown in the following (A1) to (A7).
(A1) Vinyl hydrocarbons:
(A1-1) Aliphatic vinyl hydrocarbons; isoprene, butadiene, 3-methyl-1,2-butadiene, 2,3-dimethyl-1,3-butadiene, 1,2-polybutadiene, pentadiene, hexadiene, octadiene etc;
(A1-2) Alicyclic vinyl hydrocarbons; cyclopentadiene, cyclohexadiene, cyclooctadiene, norbornadiene, etc .;
(A1-3) Aromatic vinyl hydrocarbons; divinylbenzene, divinyltoluene, divinylxylene, trivinylbenzene, divinylbiphenyl, divinylnaphthalene, divinylfluorene, divinylcarbazole, divinylpyridine and the like;
(A2) Vinyl esters, allyl esters, vinyl ethers, allyl ethers, vinyl ketones:
(A2-1) Vinyl esters; divinyl adipate, divinyl maleate, divinyl phthalate, divinyl isophthalate, divinyl itaconate, vinyl (meth) acrylate and the like;
(A2-2) allyl esters; diallyl maleate, diallyl phthalate, diallyl isophthalate, diallyl adipate, allyl (meth) acrylate, etc.
(A2-3) Vinyl ethers; divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and the like;
(A2-4) allyl ethers; diallyl ether, diallyloxyethane, triallyloxyethane, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, tetramethallyloxyethane and the like;
(A2-5) Vinyl ketones; divinyl ketone, diallyl ketone, etc .;
(A3) (Meth) acrylic acid esters:
Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) Acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, alkoxytitanium tri (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) ) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decanedimethanol di ( ) Acrylate, dioxane glycol di (meth) acrylate, 2-hydroxy-1-acryloyloxy-3-methacryloyloxypropane, 2-hydroxy-1,3-di (meth) acryloyloxypropane, 9,9-bis [4 -(2- (meth) acryloyloxyethoxy) phenyl] fluorene, undecyleneoxyethylene glycol di (meth) acrylate, bis [4- (meth) acryloylthiophenyl] sulfide, bis [2- (meth) acryloylthioethyl] sulfide 1,3-adamantanediol di (meth) acrylate, 1,3-adamantane dimethanol di (meth) acrylate, etc .;
(A4) Vinyl compound having a polyalkylene glycol chain:
Polyethylene glycol (molecular weight 300) di (meth) acrylate, polypropylene glycol (molecular weight 500) di (meth) acrylate, etc .;
(A5) Nitrogen-containing vinyl compound:
Diallylamine, diallyl isocyanurate, diallyl cyanurate, methylenebis (meth) acrylamide, bismaleimide, etc .;
(A6) Silicon-containing vinyl compound:
Dimethyldivinylsilane, divinylmethylphenylsilane, diphenyldivinylsilane, 1,3-divinyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3-tetraphenyldisilazane , Dietodivinylsilane, etc .;
(A7) Fluorine-containing vinyl compound:
1,4-divinylperfluorobutane, 1,6-divinylperfluorohexane, 1,8-divinylperfluorooctane and the like.

Of these, preferred are the above-mentioned aromatic vinyl hydrocarbons of group (A1-3), vinyl esters of group (A2), allyl esters, vinyl ethers, allyl ethers and vinyl ketones, group (A3) (Meth) acrylic acid esters, vinyl compounds having a polyalkylene glycol chain of group (A4), and nitrogen-containing vinyl compounds of group (A5). Particularly preferred are divinylbenzene belonging to group (A1-3), diallyl phthalate belonging to group (A2), ethylene glycol di (meth) acrylate belonging to group (A3), 1,3-adamantane dimethanol di (meta). ) Acrylate, tricyclo [5.2.1.0 ^2,6 ] decandimethanol di (meth) acrylate, and methylenebis (meth) acrylamide belonging to group (A5). Of these, divinylbenzene is particularly preferred.

[Monomer B]
In the present invention, the monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule preferably has at least one of either a vinyl group or a (meth) acryl group, In particular, the compound represented by the formula [2] is preferable, and the compound represented by the formula [3] is more preferable.

Examples of such a monomer B include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, and 2- (perfluorobutyl) ethyl. (Meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, 2- (perfluoro- 3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-5-methylhexyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H- Tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-Octaf Olopentyl (meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, 1H, 1H, 9H-hexadecafluorononyl (meth) acrylate, 1H-1- (trifluoromethyl) trifluoroethyl (meth) Acrylate, 1H, 1H, 3H-hexafluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluoro Octyl-2-hydroxypropyl (meth) acrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) Acryle DOO, 3- (perfluoro-7-methyl-octyl) -2-hydroxypropyl (meth) acrylate.

In the present invention, the monomer B is used in an amount of 5 to 300 mol%, preferably 10 to 200 mol%, more preferably 20 with respect to the number of moles of the monomer A used from the viewpoint of reactivity and surface modification effect. An amount of ˜100 mol%.

[Monomer C]
In the present invention, the monomer C having a cyclic acid anhydride structure or a cyclic imide structure and at least one radical polymerizable double bond in the molecule is preferably a vinyl group, an internal olefin, or a (meth) acryl group. It is preferable to have at least one, and particularly a compound having an internal olefin in the cyclic acid anhydride structure or cyclic imide structure is preferable, and a compound represented by the formula [1] is more preferable. In the present invention, the internal olefin refers to a carbon-carbon double bond in which each carbon atom constituting the carbon-carbon double bond is substituted with at least one group.

In the formula [1], R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halogen atom or the number of carbon atoms. Represents a benzyl group optionally substituted with 1 to 6 alkyl groups, or a phenyl group optionally substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ , R ² and Together with the carbon atom to which is bonded represents an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may contain a hetero atom, and A represents an oxygen atom or NR ³ . R ³ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms.

Here, examples of the halogen atom represented by R ¹ and R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-hexyl and cyclohexyl. Groups and the like.
Examples of the haloalkyl group having 1 to 6 carbon atoms include difluoromethyl group, trifluoromethyl group, bromodifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 1,1-difluoroethyl group, 2,2,2- Trifluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3-bromopropyl group, 2,2,3, 3-tetrafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, 1,1,1,3,3,3-hexafluoropropan-2-yl group, 3-bromo-2 -Methylpropyl group, 4-bromobutyl group, perfluoropentyl group, 2- (perfluorobutyl) ethyl group, perfluorohexyl group and the like.
In addition, examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms that may include a heteroatom represented by R ¹ , R ² and a carbon atom to which they are bonded include a cyclopropene ring, Cyclobutene ring, cyclopentene ring, cyclohexene ring, cyclohexadiene ring, tetrahydropyrazine ring, dihydrodioxin ring, dihydrodithiin ring, dihydrooxazine ring, dihydrothiazine ring, dihydrooxathiin ring, norbornene ring, bicyclo [2.2.2 ] An octene ring etc. are mentioned.

Examples of the aryl group having 6 to 14 carbon atoms represented by R ³ include a phenyl group, a naphthyl group, and a pyrenyl group.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ³ include the same groups as those exemplified for R ¹ and R ² above.

Examples of such monomer C include maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, maleimide, N-methylmaleimide, N-ethylmaleimide, N-tert-butylmaleimide, N- Examples include cyclohexylmaleimide, N-phenylmaleimide, N- (4-aminophenyl) maleimide, N- (1-pyrenyl) maleimide and the like. Of these, maleic anhydride is preferred.

In the present invention, the amount of monomer C used is from 5 to 300 mol%, preferably from 10 to 200 mol%, more preferably from 20 mol% based on the number of moles of monomer A used from the viewpoint of reactivity and surface modification effect. An amount of ˜100 mol%.

[Polymerization initiator D]
As the polymerization initiator D in the present invention, an azo polymerization initiator is preferably used. Examples of the azo polymerization initiator include compounds shown in the following (1) to (5).
(1) Azonitrile compound:
2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 1,1′-azobis ( 1-cyclohexanecarbonitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2- (carbamoylazo) isobutyronitrile and the like;
(2) Azoamide compound:
2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- ( 1-hydroxybutyl)] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis [N- (2-propenyl) -2- Methylpropionamide], 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) and the like;
(3) Cyclic azoamidine compound:
2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] disulfate dihydrate, 2,2′-azobis [2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane] dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) Propane], 2,2′-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, etc .;
(4) Azoamidine compound:
2,2′-azobis (2-methylpropionamidine) dihydrochloride, 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] tetrahydrate, etc .;
(5) Other:
2,2′-azobis (methyl isobutyrate), 4,4′-azobis (4-cyanopentanoic acid), 2,2′-azobis (2,4,4-trimethylpentane), 1,1′-azobis ( 1-acetoxy-1-phenylethane), 1,1′-azobis (methyl 1-cyclohexanecarboxylate), 4,4′-azobis (2- (trifluoromethyl) ethyl 4-cyanopentanoate), 4,4 '-Azobis (2-cyanopentanoic acid 2- (perfluorobutyl) ethyl), 4,4'-azobis (2-cyanopentanoic acid 2- (perfluorohexyl) ethyl) and the like.

Among the azo polymerization initiators, 2,2'-azobis (methyl isobutyrate) or 2,2'-azobis (2-methylbutyronitrile) is preferable from the viewpoint of surface modification.

In the present invention, the polymerization initiator D is used in an amount of 5 to 200 mol%, preferably 20 to 200 mol%, based on the number of moles of the monomer A used (the total number of moles when a plurality of types of monomers A are used in combination). More preferably, the amount is 20 to 100 mol%.

[Other monomer E]
The other monomer E in the present invention is a known radical polymerizable monomer used for general purposes, and a monomer not corresponding to the above-mentioned monomers A to C can be used. Examples of these monomers include, but are not limited to, ethylene, propylene, styrene, methyl (meth) acrylate, (meth) acrylic acid, and the like. These monomers may be used individually by 1 type, and may use 2 or more types together.
In the present invention, the total amount of other monomers used is from 5 to 300 mol%, preferably from 10 to 200 mol%, more preferably from the number of moles of monomer A used, from the viewpoint of reactivity and surface modification effect. Is an amount of 20 to 100 mol%.

<Method for producing fluorine-containing highly branched polymer>
The fluorine-containing hyperbranched polymer of the present invention is obtained by polymerizing the aforementioned monomer A, monomer B and monomer C in the presence of a predetermined amount of polymerization initiator D with respect to the monomer A.

Examples of the polymerization method in the presence of the polymerization initiator D of the monomer A, the monomer B and the monomer C include known methods such as solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization and the like. Or precipitation polymerization is preferred. In particular, it is preferable to carry out the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.

Examples of the organic solvent used here include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and tetralin; aliphatic or alicyclic hydrocarbons such as n-hexane, n-heptane, mineral spirit, and cyclohexane. Halogens such as methyl chloride, methyl bromide, methyl iodide, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, orthodichlorobenzene; ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate , Ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA) and other esters or ester ethers; diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, methyl cellosol Ethers such as ethyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether (PGME); ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), di-n-butyl ketone, cyclohexanone; methanol, ethanol, n- Alcohols such as propanol, isopropanol, n-butanol, isobutanol, tert-butanol, 2-ethylhexyl alcohol, benzyl alcohol, ethylene glycol; N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl Amides such as -2-pyrrolidone (NMP); sulfoxides such as dimethyl sulfoxide (DMSO). These organic solvents may be used individually by 1 type, and 2 or more types of organic solvents may be mixed and used for them.

Of these, aromatic hydrocarbons, halides, esters, ethers, ketones, alcohols, amides and the like are preferable, and benzene, toluene, xylene, orthodichlorobenzene, acetic acid are particularly preferable. Ethyl, butyl acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), tetrahydrofuran (THF), 1,4-dioxane, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), methanol, ethanol, n -Propanol, isopropanol, n-butanol, isobutanol, tert-butanol, N, N-dimethylformamide (DMF), N, N-dimethylacetamide, N-methyl-2-pyrrolidone NMP), and the like.

When the polymerization reaction is performed in the presence of an organic solvent, the mass of the organic solvent relative to 1 part by mass of the monomer A is usually 5 to 120 parts by mass, preferably 10 to 110 parts by mass.

The polymerization reaction is carried out under normal pressure, under pressure and under pressure, or under reduced pressure, and is preferably carried out under normal pressure in view of simplicity of the apparatus and operation. Moreover, it is preferable to carry out in inert gas atmosphere, such as nitrogen.
The polymerization temperature is arbitrary as long as it is not higher than the boiling point of the reaction mixture, but is preferably 50 to 200 ° C., more preferably 80 to 150 ° C., and more preferably 80 to 130 ° C. from the viewpoint of polymerization efficiency and molecular weight control. More preferred.
The reaction time varies depending on the reaction temperature, the types and ratios of the monomer A, the monomer B, the monomer C and the polymerization initiator D, the type of polymerization solvent, etc., but cannot be specified unconditionally, but preferably 30 to 720 minutes More preferably, it is 40 to 540 minutes.
After completion of the polymerization reaction, the obtained fluorine-containing hyperbranched polymer is recovered by an arbitrary method, and post-treatment such as washing is performed as necessary. Examples of a method for recovering the polymer from the reaction solution include a method such as reprecipitation.

The weight average molecular weight (Mw) measured in terms of polystyrene by gel permeation chromatography of the fluorine-containing highly branched polymer of the present invention is 1,000 to 400,000, preferably 2,000 to 200,000.

<Varnish and thin film>
The present invention also relates to a varnish containing the fluorine-containing hyperbranched polymer.
The organic solvent used in the form of the varnish is not particularly limited as long as it dissolves the fluorine-containing highly branched polymer. For example, aromatic hydrocarbons such as toluene; ethyl acetate, butyl acetate, isobutyl acetate, ethyl lactate, γ -Esters or ester ethers such as butyrolactone, propylene glycol monomethyl ether acetate (PGMEA); tetrahydrofuran (THF), butyl cellosolve, diethylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, hexafluoropropyl = Ethers such as hexafluoro-2-pentyl ether; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone Down like; alcohols such as methanol and ethanol; N, such as N- dimethylformamide (DMF) amides and the like. These organic solvents may be used individually by 1 type, and 2 or more types of organic solvents may be mixed and used for them.

The concentration of the fluorine-containing highly branched polymer dissolved or dispersed in the organic solvent is arbitrary, but the concentration of the fluorine-containing highly branched polymer is 0 with respect to the total mass (total mass) of the fluorine-containing highly branched polymer and the organic solvent. 0.001 to 90% by mass, preferably 0.002 to 80% by mass, and more preferably 0.005 to 70% by mass.

Then, the varnish is coated on a substrate by a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an ink jet method, a printing method (a relief plate, an intaglio plate, a lithographic plate, a screen printing method). Etc.), a coating film can be obtained by applying by a spray coating method, a curtain coating method or the like. The obtained coating film may be dried by a hot plate, an oven or the like as necessary.
Among these coating methods, the spin coating method is preferable. In the case of using the spin coating method, since it can be applied in a single time, even a highly volatile solution can be used, and there is an advantage that highly uniform application can be performed.
In addition, it is preferable to use for the application | coating, after filtering the said varnish beforehand using the filter etc. with a hole diameter of about 0.2 micrometer.

Examples of the substrate include polyesters such as plastic (polycarbonate, polymethacrylate, polystyrene, PET (polyethylene terephthalate), polyolefin, polyamide, polyimide, polyamideimide, epoxy, melamine, triacetylcellulose, ABS (acrylonitrile-butadiene-). Styrene copolymer), AS (acrylonitrile-styrene copolymer), norbornene resin, etc.), FRP, metal, wood, paper, glass, slate and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The thickness of the thin film made of the fluorine-containing highly branched polymer is not particularly limited, but is usually 0.01 to 50 μm, preferably 0.05 to 20 μm.

<Curable composition>
The present invention also relates to a curable composition containing (a) the fluorine-containing hyperbranched polymer, (b) an unsaturated polyester resin, and (c) a thermal polymerization initiator.

[(B) Unsaturated polyester resin]
As unsaturated polyester resin used for the curable composition of this invention, the well-known thing used for general purpose can be used.
Examples of such unsaturated polyester resins include orthophthalic polyesters, isophthalic unsaturated polyesters, terephthalic unsaturated polyesters, heptanoic unsaturated polyesters, bisphenol unsaturated polyesters, vinyl ester unsaturated polyesters. , Novolak unsaturated polyesters, and modified products thereof. These unsaturated polyester resins may be used individually by 1 type, and may use 2 or more types together.

[(C) Thermal polymerization initiator]
As a thermal-polymerization initiator used for the curable composition of this invention, the well-known thing used for hardening of unsaturated polyester resin can be used. Examples of such thermal polymerization initiators (curing agents) include hydroperoxides such as tert-butyl hydroperoxide, cumene hydroperoxide, and diisopropylpyrobenzene hydroperoxide; methyl ethyl ketone peroxide, acetylacetone peroxide, and the like. Ketone peroxides; diacyl peroxides such as diacetyl peroxide, diisobutyryl peroxide, dilauroyl peroxide, dibenzoyl peroxide; di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide Dialkyl peroxides such as 1,3-bis (tert-butylperoxyisopropyl) benzene; peroxyketals such as 1,1-di-tert-butylperoxycyclohexane; tert-butyl = Peroxyacetate, tert-butyl = peroxyisobutyrate, tert-butyl = peroxypivalate, 1,1,3,3-tetramethylbutyl = peroxy-2-ethylhexanoate, tert-amyl = peroxy Alkyl peresters such as -2-ethylhexanoate, tert-butyl = peroxy-2-ethylhexanoate, tert-amyl = peroxy-3,5,5-trimethylhexanoate, tert-butyl = peroxybenzoate Bis (2-ethylhexyl) = peroxydicarbonate, bis (4-tert-butylcyclohexyl) = peroxydicarbonate, 1,6-bis (tert-butylperoxycarbonyloxy) hexane, O-isopropyl = OO -Tert-butyl = Organic peroxides such as peroxycarbonates such as noperoxycarbonate and azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (2-methylbutyronitrile) Can be mentioned. These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
Among these, organic peroxides having a low decomposition temperature are preferable from the viewpoint of curability, and specifically, methyl ethyl ketone peroxide, dibenzoyl peroxide, and dilauroyl peroxide are preferably used.

In the curable composition of the present invention, the content of the (a) fluorine-containing highly branched polymer is 0.01 to 20 parts by mass with respect to 100 parts by mass of the total mass of the (b) unsaturated polyester resin. The amount is preferably 0.1 to 10 parts by mass.
Further, the content of (c) the thermal polymerization initiator is 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total mass of (b) unsaturated polyester resin. Part by mass.

[Other additives]
Furthermore, additives that are generally added as necessary to the curable composition of the present invention, for example, a low shrinkage agent, an internal mold release agent, a thickener, and coloring, unless the effects of the present invention are impaired. Agent, reinforcing agent, antibacterial agent, antifungal agent, curing catalyst, curing accelerator, hydrolysis inhibitor, leveling agent, surfactant, adhesion promoter, plasticizer, ultraviolet absorber, antioxidant, light stabilizer , Heat stabilizers, storage stabilizers, antistatic agents, lubricants, flame retardants, inorganic fillers, pigments, dyes and the like may be appropriately blended. Moreover, you may mix an organic solvent as needed.

<Hardened product and cured film>
The curable composition of the present invention can obtain a cured product by, for example, thermal polymerization (curing) after filling a predetermined mold. When obtaining an FRP molded product containing a reinforcing material such as glass fiber, a conventional molding method such as a hand lay-up (HL) method, a SMC (Sheet Molding Compound) method, a BMC (Bulk Molding Compound) method, RTM (Resin Transfer Molding) method, spray-up method and the like can be arbitrarily used.

The curable composition of the present invention can be applied to, for example, part or all of the substrate surface, and then thermally polymerized (cured) to obtain a film-like cured product, that is, a cured film.
Examples of the base material in this case include the same base materials as those exemplified above in <Varnish and thin film>.
Examples of the coating method on the substrate include the same coating methods as those exemplified in the above <Varnish and thin film>. Among these coating methods, it is desirable to use a spin coat method or a spray coat method. In addition, it is preferable to use for the application | coating, after filtering the said curable composition beforehand using the filter etc. with a hole diameter of about 0.2 micrometer.
In application, an organic solvent may be added to the curable composition as necessary to form a varnish. Examples of the organic solvent in this case include the same organic solvents as those exemplified above in <Varnish and thin film>.
The thickness of the formed cured film is not particularly limited, but is usually 0.01 to 5000 μm, preferably 0.1 to 500 μm.
In addition, when molding using a mold, or when removing from the substrate after molding on the substrate, a release agent having a low surface energy on the mold or substrate used from the viewpoint of mold release and surface modification. Is preferably applied.

As the heating conditions in the thermal polymerization (curing), a temperature and time appropriately selected from the range of 40 to 300 ° C. and 0.3 to 600 minutes are employed. Further, the curable composition of the present invention is a gel-like molded product, so-called semi-cured, by adjusting the content of the curing agent (thermal polymerization initiator) and the heating conditions in the same manner as general-purpose unsaturated polyester resins. It can be a thing. Since this semi-cured product is easy to release and process, it can be made a semi-cured material if necessary, and after various processing, it can be further cured by heating.

As described above, the cured product of the present invention is in a state where more of the fluorine-containing highly branched polymer is present on the cured product surface (interface) than in the cured product (deep part). For this reason, for various machines such as mixing / molding machines used in the production of cured products and mold releasability, releasability from other resin molded products such as films, and water / oil repellency and antifouling properties. An excellent cured product can be obtained.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) Gel permeation chromatography (GPC)
Equipment: HLC-8220GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC K-804L, GPC K-805L manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: RI
(2) ¹³ C NMR spectrum apparatus: JNM-ECA700 manufactured by JEOL Datum Co., Ltd.
Solvent: CDCl ₃
Reference peak: CDCl ₃ (77.0 ppm)
(3) F quantitative analysis (ion chromatography)
Equipment: ICS-1500 manufactured by Nippon Dionex Co., Ltd.
Solvent: (2.7 mmol / L sodium carbonate, 0.3 mmol / L baking soda) aqueous solution Detector: Electrical conductivity (4) Glass transition temperature (Tg) measurement Device: Photo-DSC 204 F1 Phoenix (registered trademark) manufactured by NETZSCH
Measurement conditions: Under nitrogen atmosphere Temperature rising rate: 5 ° C / min (25-200 ° C)
(5) 5% weight loss temperature (Td _5% ) measurement device: Bruker AXS Co., Ltd. Differential thermal and thermogravimetric simultaneous measurement device TG-DTA2000SA
Measurement conditions: In air atmosphere Temperature rising rate: 10 ° C / min (25-400 ° C)
(6) Turbidity (HAZE) measurement device: Nippon Denshoku Industries Co., Ltd. Haze meter NDH5000
(7) Contact angle measurement device: DropMaster DM-501, manufactured by Kyowa Interface Chemical Co., Ltd.
Measurement temperature: 25 ° C
(8) Hot plate equipment: MH-180CS, MH-3CS manufactured by AS ONE Corporation

Abbreviations represent the following meanings.
C6FA: 2- (perfluorohexyl) ethyl acrylate [FAAC-6 manufactured by Unimatec Co., Ltd.]
DVB: Divinylbenzene [DVB-960, manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.]
MA: Maleic anhydride [manufactured by Pure Chemical Co., Ltd.]
St: Styrene [manufactured by Tokyo Chemical Industry Co., Ltd.]
MAIB: 2,2′-azobis (methyl isobutyrate) [MAIB manufactured by Otsuka Chemical Co., Ltd.]
UP-1: Unsaturated polyester resin [Clear gel coat 3Z-0006PI for artificial marble, manufactured by Toago Material Technology Co., Ltd.]
TI-1: methyl ethyl ketone peroxide [Kayamek (registered trademark) M manufactured by Kayaku Akzo Co., Ltd.]
DMF: N, N-dimethylformamide MEK: methyl ethyl ketone MIBK: methyl isobutyl ketone THF: tetrahydrofuran

[Example 1] Synthesis of hyperbranched polymer 1 having acid anhydride group In a 200 mL reaction flask, 78 g of MIBK was charged, nitrogen was flowed for 5 minutes with stirring, and the mixture was heated until the internal liquid was refluxed (approximately 116 ° C).
In a separate 100 mL reaction flask, 2.6 g (20 mmol) DVB as monomer A, 4.2 g (10 mmol) C6FA as monomer B, 1.0 g (10 mmol) MA as monomer C, 4.6 g (20 mmol) MAIB as initiator D, and MIBK78g was prepared, nitrogen was poured for 5 minutes, stirring, and nitrogen substitution was performed.
The contents were added dropwise from the 100 mL reaction flask charged with DVB, C6FA, MA and MAIB into the refluxed MIBK in the 200 mL reaction flask using a dropping pump over 60 minutes. After completion of dropping, the mixture was further stirred for 1 hour.
Next, 135 g of MIBK was distilled off from this reaction solution using a rotary evaporator, and then added to 195 g of hexane cooled in an ice bath to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum-dried to obtain 8.1 g of the desired product (highly branched polymer 1) as a white powder.
The ¹³ C NMR spectrum of the obtained hyperbranched polymer 1 is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 1 represented by the following structural formula calculated from the ¹³ C NMR spectrum is DVB unit [A]: C6FA unit [B]: MA unit [C]: MAIB unit [D]. = 1.0: 0.4: 0.5: 0.6 Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of this polymer was 8,400, and dispersion degree (Mw (weight average molecular weight) / Mn (number average molecular weight)) was 2.2.

In the formula, a black dot represents a coupling end.

[Example 2] Synthesis of hyperbranched polymer 2 having an acid anhydride group The same operation as in Example 1 was performed except that St 1.0 g (10 mmol) was added as monomer E together with monomer A, monomer B and monomer C. 7.7 g of the desired product (hyperbranched polymer 2) was obtained as a white powder.
The ¹³ C NMR spectrum of the obtained hyperbranched polymer 2 is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 2 represented by the following structural formula calculated from the ¹³ C NMR spectrum is DVB unit [A]: C6FA unit [B]: MA unit [C]: St unit [E]. : MAIB unit [D] = 1.0: 0.2: 0.5: 0.2: 0.5. Moreover, the weight average molecular weight Mw measured by poly conversion by GPC of this polymer was 9,000, and dispersion degree (Mw / Mn) was 2.1.

In the formula, a black dot represents a coupling end.

[Example 3] Synthesis of hyperbranched polymer 3 having acid anhydride group Example 2 except that the amount of C6FA used was changed to 5.0 g (12 mmol) and the amount of MAIB used was changed to 5.5 g (24 mmol). In the same manner as described above, 5.4 g of the target product (highly branched polymer 3) as a white powder was obtained.
The ¹³ C NMR spectrum of the obtained hyperbranched polymer 3 is shown in FIG. The unit structure composition (molar ratio) of the hyperbranched polymer 3 represented by the following structural formula calculated from the ¹³ C NMR spectrum is DVB unit [A]: C6FA unit [B]: MA unit [C]: St unit [E]. : MAIB unit [D] = 1.0: 0.3: 0.6: 0.4: 0.6. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of this polymer was 9,200, and dispersion degree (Mw / Mn) was 1.6.

In the formula, a black dot represents a coupling end.

[Comparative Synthesis Example 1] Synthesis of hyperbranched polymer 4 having no acid anhydride group Into a 2 L reaction flask, 521 g of MIBK was charged, and nitrogen was allowed to flow for 5 minutes with stirring until the internal solution was refluxed (approximately 116 ° C). Heated.
In a separate 1 L reaction flask, 26 g (0.2 mol) of DVB as monomer A, 42 g (0.1 mol) of C6FA as monomer B, 55 g (0.24 mol) of MAIB as initiator D, and 521 g of MIBK were charged and stirred for 5 minutes with nitrogen. Was purged with nitrogen and cooled to 0 ° C. in an ice bath.
The contents were added dropwise from the 1 L reaction flask charged with DVB, C6FA and MAIB into the refluxed MIBK in the 2 L reaction flask using a dropping pump over 60 minutes. After completion of dropping, the mixture was further stirred for 1 hour.
Next, this reaction solution was added to 1300 g of hexane to precipitate the polymer in a slurry state. This slurry was filtered under reduced pressure and vacuum dried to obtain 44 g of the desired product (highly branched polymer 4) as a white powder.
The ¹³ C NMR spectrum of the obtained hyperbranched polymer 4 is shown in FIG. The unit structure composition (molar ratio) of hyperbranched polymer 4 represented by the following structural formula calculated from ¹³ C NMR spectrum is DVB unit [A]: C6FA unit [B]: MAIB unit [D] = 1.0: 0. 4: 0.9. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC of this polymer was 8,800, and dispersion degree (Mw / Mn) was 1.5.

In the formula, a black dot represents a coupling end.

The amount of monomer B introduced from the weight average molecular weight, dispersity, and ¹³ C NMR spectrum of the hyperbranched polymers 1 to 3 obtained in Examples 1 to 3 and the hyperbranched polymer 4 obtained in Comparative Synthesis Example 1, Table 1 shows the F atom content, glass transition temperature (Tg), and 5% weight loss temperature (Td _5% ) determined from the F quantitative analysis.

[Example 4] Solvent solubility of hyperbranched polymers 1 to 3 The solubilities of the hyperbranched polymers 1 to 3 obtained in Examples 1 to 3 in each solvent shown in Table 2 were evaluated. In the test, the hyperbranched polymer was mixed with each solvent so as to have a concentration of 10% by mass, stirred at 25 ° C. for 1 minute, and then visually evaluated according to the following criteria. The results are also shown in Table 2.
[Evaluation criteria]
○: Completely dissolved and transparent solution ×: Undissolved residue

[Examples 5 to 8] Surface Modification of Unsaturated Polyester Resin Cured Film A surface modifying agent of the type and addition amount shown in Table 3 was added to 100 parts by mass of UP-1 which is an unsaturated polyester resin, and about 40 The mixture was heated and stirred at 0 ° C. and mixed uniformly. After this mixture was cooled to room temperature (approximately 25 ° C.), 0.1 part by mass of curing agent TI-1 was added to prepare a curable composition.
The obtained curable composition was poured into a 5 mm square x 1 mm thick silicone mold placed on a 50 x 50 mm glass substrate subjected to a release coating treatment. Further, another 50 × 50 mm glass substrate was covered and sealed thereon. The curable composition in the mold was cured by heating on a hot plate at 60 ° C. for 5 hours. The cured product was removed from the substrate and the mold to obtain a cured film.
The turbidity (HAZE) of the obtained cured film was measured and the transparency was evaluated. Moreover, the contact angle of water and oleic acid on the lower surface of the obtained cured film (the surface in contact with the glass substrate subjected to the release coating treatment) was measured to evaluate the water and liquid repellency. The results are also shown in Table 3.

[Comparative Example 1] Surface Properties of Unsaturated Polyester Resin Cured Film without Addition of Surface Modifier Operations and evaluations were performed in the same manner as in Example 5 except that no surface modifier was added. The results are also shown in Table 3.

[Comparative Example 2] Surface Modification of Unsaturated Polyester Resin Cured Film with Hyperbranched Polymer Having No Acid Anhydride Group Except that the hyperbranched polymer 4 obtained in Comparative Synthesis Example 1 was used as a surface modifier. Operation and evaluation were performed in the same manner as in Example 5. The results are also shown in Table 3.

As shown in Table 3, the unsaturated polyester resin cured films to which the fluorine-containing highly branched polymer having an acid anhydride group was added (Examples 5 to 8) had a HAZE of 40 to 59, and contact angles of water and oleic acid. Are 88.4 to 106.2 degrees and 43.3 to 57.4 degrees, respectively, while maintaining a HAZE equal to or higher than that of a cured film to which no surface modifier is added (Comparative Example 1). It had exceptional water and liquid repellency. On the other hand, the unsaturated polyester resin cured film to which a fluorine-containing highly branched polymer having no acid anhydride group is added (Comparative Example 2) has contact angles of water and oleic acid of 100.9 degrees and 34.0 degrees, respectively. Although the water and liquid repellency was improved, the HAZE was 84 and the transparency was greatly lowered.
From the above results, by adding the fluorine-containing hyperbranched polymer having an acid anhydride group of the present invention to the unsaturated polyester resin, the cured film obtained from the resin can be obtained without losing transparency. It was confirmed that water and liquid repellency can be imparted.

The fluorine-containing hyperbranched polymer of the present invention can be suitably used as a material in which an unsaturated polyester resin composition containing the polymer forms a gel coat layer that imparts water / oil repellency to artificial marble and the like.

Claims (15)

1. Monomer A having two or more radical polymerizable double bonds in the molecule, monomer B having a fluoroalkyl group and at least one radical polymerizable double bond in the molecule, and a cyclic acid anhydride structure in the molecule Alternatively, by polymerizing the monomer C having a cyclic imide structure and at least one radical polymerizable double bond in the presence of a polymerization initiator D in an amount of 5 to 200 mol% based on the number of moles of the monomer A. Obtained fluorine-containing hyperbranched polymer.
2. The fluorine-containing highly branched polymer according to claim 1, wherein the monomer C is a compound represented by the following formula [1].
   

   

   Wherein R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a halogen atom or 1 to 6 carbon atoms. Represents a benzyl group which may be substituted with an alkyl group of the above, or a phenyl group which may be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms, or R ¹ , R ² and the bond thereof A carbon atom and an alicyclic hydrocarbon group having 3 to 12 carbon atoms which may contain a hetero atom, together with a carbon atom, represents an oxygen atom or NR ³ (where R ³ is a hydrogen atom, Represents a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 14 carbon atoms).
3. The fluorine-containing highly branched polymer according to claim 2, wherein the monomer C is maleic anhydride.
4. The fluorine-containing highly branched polymer according to any one of claims 1 to 3, wherein the monomer A is a compound having one or both of a vinyl group and a (meth) acryl group.
5. The fluorine-containing highly branched polymer according to claim 4, wherein the monomer A is a divinyl compound or a di (meth) acrylate compound.
6. The fluorine-containing highly branched polymer according to any one of claims 1 to 3, wherein the monomer B is a compound having at least one of a vinyl group and a (meth) acryl group.
7. The fluorine-containing highly branched polymer according to claim 6, wherein the monomer B is a compound represented by the following formula [2].
   

   

   (Wherein R ⁴ represents a hydrogen atom or a methyl group, and R ⁵ represents a fluoroalkyl group having 2 to 12 carbon atoms which may be substituted with a hydroxy group.)
8. The fluorine-containing highly branched polymer according to claim 7, wherein the monomer B is a compound represented by the following formula [3].
   

   

   (Wherein R ⁴ represents the same meaning as defined in the above formula [2], X represents a hydrogen atom or a fluorine atom, p represents an integer of 1 or 2, and q represents an integer of 0 to 5). )
9. The fluorine-containing highly branched polymer according to any one of claims 1 to 8, wherein the polymerization initiator D is an azo polymerization initiator.
10. 10. The method according to claim 1, wherein the monomer B is obtained by polymerizing 5 to 300 mol% of the monomer B and 5 to 300 mol% of the monomer C with respect to the number of moles of the monomer A. The fluorine-containing highly branched polymer according to item.
11. A varnish containing the fluorine-containing highly branched polymer according to any one of claims 1 to 10.
12. (A) 0.01 to 20 parts by mass of the fluorine-containing highly branched polymer according to any one of claims 1 to 10;
    A curable composition comprising (b) 100 parts by mass of an unsaturated polyester resin and (c) 0.05 to 10 parts by mass of a thermal polymerization initiator.
13. A cured product obtained from the curable composition according to claim 12.
14. A cured film obtained from the curable composition according to claim 12.
15. The cured film according to claim 14, which has a film thickness of 0.01 to 5000 μm.

Images