WO2014034607A1 - Polymère hyper-ramifié contenant du fluor et composition de résine polyester insaturée le contenant - Google Patents

Polymère hyper-ramifié contenant du fluor et composition de résine polyester insaturée le contenant Download PDF

Info

Publication number
WO2014034607A1
WO2014034607A1 PCT/JP2013/072738 JP2013072738W WO2014034607A1 WO 2014034607 A1 WO2014034607 A1 WO 2014034607A1 JP 2013072738 W JP2013072738 W JP 2013072738W WO 2014034607 A1 WO2014034607 A1 WO 2014034607A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer
fluorine
group
highly branched
branched polymer
Prior art date
Application number
PCT/JP2013/072738
Other languages
English (en)
Japanese (ja)
Inventor
元信 松山
将幸 原口
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2014532994A priority Critical patent/JP6331026B2/ja
Publication of WO2014034607A1 publication Critical patent/WO2014034607A1/fr

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen

Definitions

  • 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.
  • Patent Document 1 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.
  • blended the fluorine-type polymer with this gel coat layer forming material is disclosed.
  • the antifouling measures taught in these patent documents cannot provide oil repellency, leaving a problem that it is difficult to remove oil stains.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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].
  • 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.
  • the present invention relates to the fluorine-containing highly branched polymer according to the second aspect, in which the monomer C is maleic anhydride.
  • 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.
  • 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.
  • 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.
  • 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].
  • 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].
  • 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
  • q represents an integer of 0 to 5).
  • 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.
  • 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.
  • it is related with the varnish containing the fluorine-containing hyperbranched polymer as described in any one of a 1st viewpoint thru
  • 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.
  • a 13th viewpoint it is related with the hardened
  • a 14th viewpoint it is related with the cured film obtained from the curable composition as described in a 12th viewpoint.
  • the present invention relates to the cured film according to the fourteenth aspect, which has a film thickness of 0.01 to 5000 ⁇ m.
  • the fluorine-containing hyperbranched polymer of the present invention 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.
  • 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.
  • 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.
  • a thin film containing the fluorine-containing highly branched polymer can be suitably obtained.
  • the curable composition of this invention the cured
  • 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.
  • FIG. 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. 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.
  • 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. .
  • 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.
  • the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound.
  • (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,
  • 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).
  • divinylbenzene is particularly preferred.
  • 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,
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • haloalkyl group having 1 to 6 carbon atoms examples 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, perfluorohex
  • 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.
  • 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%.
  • an azo polymerization initiator is preferably used as the polymerization initiator D in the present invention.
  • the azo polymerization initiator include compounds shown in the following (1) to (5).
  • 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;
  • 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-N
  • 2,2'-azobis methyl isobutyrate
  • 2,2'-azobis (2-methylbutyronitrile) is preferable from the viewpoint of surface modification.
  • 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%.
  • 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.
  • 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.
  • 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%.
  • 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.
  • organic solvent used here examples 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.
  • 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-but
  • aromatic hydrocarbons halides, esters, ethers, ketones, alcohols, amides and the like are preferable, and benzene, toluene, xylene, orthodichlorobenzene, acetic acid are particularly preferable.
  • PMEA propylene glycol monomethyl ether acetate
  • PGME propylene glycol monomethyl ether
  • THF tetrahydrofuran
  • MEK methyl ethyl ketone
  • MIBK methyl isobutyl ketone
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • the spin coating method is preferable.
  • 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 ⁇ m, preferably 0.05 to 20 ⁇ m.
  • 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.
  • unsaturated polyester resin used for the curable composition of this invention the well-known thing used for general purpose can be used.
  • 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.
  • 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.
  • thermal polymerization initiators 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
  • diacyl peroxides such as diacetyl peroxide, diisobutyryl peroxide, dilauroyl peroxide, dibenzoyl peroxide; di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide
  • thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
  • 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.
  • 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.
  • 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.
  • 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.
  • the curable composition of the present invention can obtain a cured product by, for example, thermal polymerization (curing) after filling a predetermined mold.
  • 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.
  • the base material in this case include the same base materials as those exemplified above in ⁇ Varnish and thin film>.
  • 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
  • an organic solvent may be added to the curable composition as necessary to form a varnish.
  • 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 ⁇ m, preferably 0.1 to 500 ⁇ m.
  • 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.
  • the heating conditions in the thermal polymerization a temperature and time appropriately selected from the range of 40 to 300 ° C. and 0.3 to 600 minutes are employed.
  • 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.
  • 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.
  • 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.
  • 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-dimethylform
  • Example 1 Synthesis of hyperbranched polymer 1 having acid anhydride group
  • 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).
  • 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 13 C NMR spectrum of the obtained hyperbranched polymer 1 is shown in FIG.
  • 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.
  • 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 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.
  • 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.
  • Mw measured by polystyrene conversion by GPC of this polymer was 9,200, and dispersion degree (Mw / Mn) was 1.6.
  • a black dot represents a coupling end.
  • 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.
  • a black dot represents a coupling end.
  • 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.
  • 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.
  • ⁇ Completely dissolved and transparent solution
  • ⁇ Undissolved residue
  • 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.
  • the contact angle of water and oleic acid on the lower surface of the obtained cured film was measured to evaluate the water and liquid repellency. The results are also 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 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.
  • 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne un polymère hyper-ramifié contenant du fluor et une composition de résine polyester insaturée contenant le polymère hyper-ramifié contenant du fluor. La présente invention concerne un polymère hyper-ramifié contenant du fluor qui est obtenu par polymérisation d'un monomère (A) qui présente deux liaisons doubles polymérisables par radicaux ou plus dans chaque molécule, un monomère (B) qui possède un groupe fluoroalkyle et au moins une liaison double polymérisable par radicaux dans chaque molécule, et un monomère (C) qui présente une structure d'anhydride acide cyclique ou une structure d'imide cyclique et au moins une liaison double polymérisable par radicaux dans chaque molécule en présence d'un initiateur de polymérisation (D) qui est présent en quantité de 5 à 200 % par mole par rapport au nombre de moles du monomère A.
PCT/JP2013/072738 2012-08-30 2013-08-26 Polymère hyper-ramifié contenant du fluor et composition de résine polyester insaturée le contenant WO2014034607A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2014532994A JP6331026B2 (ja) 2012-08-30 2013-08-26 含フッ素高分岐ポリマー及びそれを含む不飽和ポリエステル樹脂組成物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012190234 2012-08-30
JP2012-190234 2012-08-30

Publications (1)

Publication Number Publication Date
WO2014034607A1 true WO2014034607A1 (fr) 2014-03-06

Family

ID=50183419

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/072738 WO2014034607A1 (fr) 2012-08-30 2013-08-26 Polymère hyper-ramifié contenant du fluor et composition de résine polyester insaturée le contenant

Country Status (2)

Country Link
JP (1) JP6331026B2 (fr)
WO (1) WO2014034607A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016092844A1 (fr) * 2014-12-12 2016-06-16 富士フイルム株式会社 Polymère, composition, film optique, dispositif d'affichage à cristaux liquides
WO2019189628A1 (fr) * 2018-03-30 2019-10-03 株式会社大阪ソーダ Composition de résine thermodurcissable

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5529501A (en) * 1978-08-04 1980-03-01 Daikin Ind Ltd Water- and oil-repellent copolymer and its use
JPS61236806A (ja) * 1985-03-20 1986-10-22 ソシエテ　アトケム フルオロコポリマーおよびその種々の基材の疎水性並びに疎油性処理での使用
JPH04272986A (ja) * 1991-02-27 1992-09-29 Asahi Glass Co Ltd 耐久性の優れた撥水撥油剤および撥水撥油剤組成物
WO2001019884A1 (fr) * 1999-09-14 2001-03-22 Daikin Industries, Ltd. Polymere greffe, procede de production dudit polymere, et compositions hydrofuges et oleofuges solubles contenant ledit polymere
WO2010137724A1 (fr) * 2009-05-29 2010-12-02 日産化学工業株式会社 Polymère fluoré fortement ramifié et composition de résine contenant celui-ci

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3603480B2 (ja) * 1995-07-27 2004-12-22 旭硝子株式会社 撥水撥油剤組成物
JP2001158811A (ja) * 1999-12-02 2001-06-12 Daikin Ind Ltd グラフト共重合体およびそれを用いた溶液型撥水撥油剤組成物
JP2007231160A (ja) * 2006-03-01 2007-09-13 Dainippon Ink & Chem Inc ラジカル硬化型粉体塗料の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5529501A (en) * 1978-08-04 1980-03-01 Daikin Ind Ltd Water- and oil-repellent copolymer and its use
JPS61236806A (ja) * 1985-03-20 1986-10-22 ソシエテ　アトケム フルオロコポリマーおよびその種々の基材の疎水性並びに疎油性処理での使用
JPH04272986A (ja) * 1991-02-27 1992-09-29 Asahi Glass Co Ltd 耐久性の優れた撥水撥油剤および撥水撥油剤組成物
WO2001019884A1 (fr) * 1999-09-14 2001-03-22 Daikin Industries, Ltd. Polymere greffe, procede de production dudit polymere, et compositions hydrofuges et oleofuges solubles contenant ledit polymere
WO2010137724A1 (fr) * 2009-05-29 2010-12-02 日産化学工業株式会社 Polymère fluoré fortement ramifié et composition de résine contenant celui-ci

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016092844A1 (fr) * 2014-12-12 2016-06-16 富士フイルム株式会社 Polymère, composition, film optique, dispositif d'affichage à cristaux liquides
WO2019189628A1 (fr) * 2018-03-30 2019-10-03 株式会社大阪ソーダ Composition de résine thermodurcissable

Also Published As

Publication number Publication date
JPWO2014034607A1 (ja) 2016-08-08
JP6331026B2 (ja) 2018-05-30

Similar Documents

Publication Publication Date Title
US10227457B2 (en) Fluorine-containing highly branched polymer and resin composition containing the same
JP6093744B2 (ja) 有機無機複合体及びその製造方法、有機無機複合膜及びその製造方法、フォトニック結晶、コーティング材、熱可塑性組成物、微細構造体、光学材料、反射防止部材、並びに、光学レンズ
JP6385274B2 (ja) 含ケイ素高分岐ポリマー及びそれを含む硬化性組成物
TWI615410B (zh) 親油性高分支聚合物及含其之光聚合性組成物
JP5542371B2 (ja) 含フッ素高分岐ポリマーを用いた界面接着性制御
WO2014054698A1 (fr) Composition durcissable comprenant un polymère très ramifié contenant du silicium
JP5920590B2 (ja) 含フッ素高分岐ポリマー及びそれを含む光カチオン重合性組成物
JP6331026B2 (ja) 含フッ素高分岐ポリマー及びそれを含む不飽和ポリエステル樹脂組成物
JP2009108211A (ja) 硬化性組成物および硬化物
WO2012074055A1 (fr) Film moulé par extrusion et modifié en surface
JP6210233B2 (ja) 含フッ素高分岐ポリマー及びそれを含むポリカーボネート樹脂組成物
JP6217935B2 (ja) 含フッ素高分岐ポリマー及びそれを含むエポキシ樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13833634

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2014532994

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13833634

Country of ref document: EP

Kind code of ref document: A1