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
• • 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
• • 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
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety

Definitions

• the present invention relates to polymer particles and a dispersion liquid containing the same, and relates to polymer particles and a dispersion liquid containing the same, which can form a coating film having excellent flexibility and chemical resistance.
• Fluorine-containing polymer particles have the advantage of being excellent in properties such as water repellency and chemical resistance, and various fluorine-containing polymer particles have been conventionally proposed. Utilizing the property that the free energy of the fluorine-containing polymer particles is low, that is, it is difficult to adhere to other substances, the fluorine-containing polymer particles are used, for example, as a water-repellent oil-repellent agent and an antifouling agent. (See, for example, Patent Documents 1 to 3). However, if too much fluorine-containing polymer particles are added, the chemical resistance is lowered and the cost is increased, and it is a problem to reduce the manufacturing cost.
• the polymer particles are used for the purpose of improving physical properties such as light diffusivity, blocking resistance and slipperiness of the resin molded product and imparting further characteristics, and are also spacers and electricals between minute parts of electronic devices. It is used as a base particle for conductive fine particles that are responsible for connection. Therefore, polymer particles are required to have various properties depending on the intended use, and various proposals have been made to satisfy such requirements (see, for example, Patent Documents 4 to 6).
• fluorine-containing polymer particles that form a coating film with excellent flexibility and chemical resistance have not yet been established. Further, in order to further improve the battery characteristics, further improvement of the polymer particles containing fluorine is required.
• An object of the present invention is to provide polymer particles and a dispersion containing the same, which can form a coating film having excellent flexibility and chemical resistance by mixing a small amount with the coating film.
• the polymer particles of the present invention contain more than 20% by mass of the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) and the structure derived from the (meth) acrylic acid ester monomer (B). Polymer particles containing 30% by mass or more of the unit (Y) and 2% by mass or more and 30% by mass or less of the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group.
• the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is the following general formula (1)
• the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B) is The following general formula (2)
• the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group is represented by the following formula (3).
• R 1 is a hydrogen or a methyl group
• R 2 is a hydrocarbon group containing fluorine and having 1 to 10 carbon atoms
• R 3 is a benzyl group and a cyclic group having 5 to 10 carbon atoms.
• R 4 is a hydrocarbon group having 1 to 10 carbon atoms including a hydroxyl group
• a, b, and c represent the degree of polymerization.
• the polymer particles of the present invention can be applied to the surface of the coating film while maintaining the characteristics of other particles contained in the coating film. It is possible to express the characteristics of fluorine.
• the polymer particles have a structural unit (X) derived from a fluorine-containing (meth) acrylic acid ester monomer (A) having a low surface free energy, and a (meth) acrylic acid ester monomer (B) having excellent chemical resistance.
• the polymer particles of the present invention are formed of a copolymer composed of a structural unit (X), a structural unit (Y) and a structural unit (Z).
• the structural unit (X), the structural unit (Y), and the structural unit (Z) may be referred to as "polymer particle unit”.
• the structural unit (X) is a repeating unit derived from the fluorine-containing (meth) acrylic acid ester monomer (A) and is represented by the following general formula (1).
• R 1 is a hydrogen or a methyl group
• R 2 is a hydrocarbon group containing fluorine and having 1 to 10 carbon atoms
• a is a degree of polymerization.
• R 1 is a hydrogen or methyl group independent of each other.
• the monomer in which R 1 is hydrogen represents acrylate, and the monomer in which R 1 is a methyl group represents methacrylate.
• R 2 is a hydrocarbon group having 1 to 10 carbon atoms containing fluorine, and preferably a hydrocarbon group having 2 to 10 carbon atoms containing fluorine.
• the hydrocarbon group may have an unsaturated bond, and may be either a linear hydrocarbon group or a branched chain hydrocarbon group.
• at least one hydrogen of the hydrocarbon group is replaced with fluorine.
• all hydrogens in the hydrocarbon group may be replaced with fluorine.
• R 2 for example, -CH 2 CF 3 , -CH 2 CF 2 CF 2 H, -CH 2 CF 2 CF 3 , -CH 2 CF 2 CFHCF 3 , -CH 2 (CF 2 ) 3 CF 2 H,- CH 2 CH 2 (CF 2 ) 3 CF 3 , -CH 2 (CF 2 ) 5 CF 2 H, -CH 2 CH 2 (CF 2 ) 5 CF 3 , -CH 2 CH 2 (CF 2 ) 7 CF 3 , -CH (CF 3 ) 2 , -CH 2 CCH 3 (CF 3 ) 2, etc. may be mentioned.
• the fluorine-containing (meth) acrylic acid ester monomer (A) is a hydrocarbon group (R 2 ) having 1 to 10 carbon atoms whose ester portion contains fluorine.
• R 2 fluorine-containing (meth) acrylic acid ester monomer
• CH 2 CHCOOCH 2 CF 3 (3FA)
• CH 2 CHCOOCH 2 CF 2 CF 2 H (4FA)
• CH 2 CHCOOCH 2 CF 2 CF 3
• CH 2 CHCOOCH 2 CF 2 CFHCF 3 (6FA)
• CH 2 CHCOOCH 2 (CF 2 ) 3 CF 2 H
• CH 2 CHCOOCH 2 (CF 2 ) 3 CF 2 H (8FA)
• CH 2 CHCOOCH 2 CH 2 (CF 2 ) 3 CF 3 (9FA)
• CH 2 CHCOOCH 2 (CF 2 ) 5 CF 2 H (12FA)
• CH 2 CHCOOCH 2 CH 2 (CF 2 ) 5 CF 3 (13FA)
• CH 2 CHCOOCH
• the structural unit (Y) is a repeating unit derived from the (meth) acrylic acid ester monomer (B) and is represented by the following general formula (2).
• R 1 is a hydrogen or methyl group
• R 3 is a group selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms
• b is a degree of polymerization.
• R 1 represents a hydrogen or methyl group.
• R 3 is a group selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms.
• the structural unit having R 3 can be composed of one or more structural units, and preferably has one to three kinds of structural units different from each other.
• the different structural units are those in which R 3 is different from each other and / or those in which acrylate and methacrylate are different.
• Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a monocyclic group, a polycyclic group, and a bridging ring group.
• the cyclic hydrocarbon group may be saturated or unsaturated.
• Examples of the cyclic hydrocarbon group having 5 to 10 carbon atoms include a cyclohexyl group, a t-butylcyclohexyl group, a dicyclopentanyl group, a dicyclopentenyl group, an isovonyl group and the like.
• the (meth) acrylic acid ester monomer (B) is a (meth) acrylate having a group (R 3 ) selected from the group consisting of a benzyl group and a cyclic hydrocarbon group having 5 to 10 carbon atoms.
• the (meth) acrylic acid ester monomer (B) includes benzyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and dicyclopentenyl (meth). It is preferable that it is at least one selected from the group consisting of acrylate and isovonyl (meth) acrylate.
• the structural unit (Z) is a repeating unit derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group, and is represented by the following formula (3).
• R 1 is a hydrogen or a methyl group
• R 4 is a hydrocarbon group having 1 to 10 carbon atoms including a hydroxyl group
• c is a degree of polymerization.
• R 1 represents a hydrogen or methyl group.
• R 4 is a hydrocarbon group having 1 to 10 carbon atoms containing a hydroxyl group, and preferably a hydrocarbon group having 2 to 6 carbon atoms containing a hydroxyl group. Hydrocarbon groups may have unsaturated bonds. Further, either a linear hydrocarbon group or a branched chain hydrocarbon group may be used. In R 4 , at least one of hydrogens in the hydrocarbon group is substituted with a hydroxyl group. Examples of R 4 include hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyhepticyl, hydroxyoctyl, and the like.
• the glass transition temperature (Tg) of the homopolymer composed of the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 70 ° C. or higher, still more preferably ⁇ 50 ° C. or higher. Is.
• the glass transition temperature (Tg) of the homopolymer composed of the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, still more preferably ⁇ 20 ° C. or lower. be.
• glass transition temperature (Tg) is the intermediate point glass transition temperature measured by differential scanning calorimetry (DSC) in accordance with JIS K7121: 2012.
• the midpoint glass transition temperature is the temperature at the intersection of a straight line equidistant from the extended straight line of each baseline in the vertical direction and the curve of the stepwise change portion of the glass transition.
• Examples of the (meth) acrylic acid ester monomer (C) having a hydroxyl group include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxypropyl (meth). ) Acrylate, 4-hydroxybutyl (meth) acrylate, 5-hydroxypentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 7-hydroxyhepticyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, And so on.
• 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, and 2-hydroxypropyl acrylate are preferable.
• the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) exceeds 20% by mass.
• 30% by mass or more of the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B), and 2% by mass of the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group It consists of more than 30% by mass and less than 30% by mass.
• the amount of the structural unit derived from the (meth) acrylic acid ester monomer (B) is the total of the structural units derived from one or more kinds of monomers (B).
• the a, b, and c of the general formulas (1), (2), and (3) are the degree of polymerization of each repeating unit, and are real numbers consistent with the above mass ratio.
• the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is more than 20% by mass, preferably 22% by mass or more, more preferably 25% by mass in 100% by mass of the polymer particle unit. , More preferably 30% by mass or more.
• the structural unit (X) derived from the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 50% by mass, based on 100% by mass of the polymer particle unit. It is 40% by mass or less, more preferably 35% by mass or less.
• the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B) is 30% by mass or more, preferably more than 30% by mass, more preferably 35% by mass or more in 100% by mass of the polymer particle unit. It is more preferably 40% by mass or more, further preferably 45% by mass or more, and particularly preferably 50% by mass or more.
• the structural unit (Y) derived from the (meth) acrylic acid ester monomer (B) is preferably 75% by mass or less, more preferably 70% by mass or less, still more preferably 68% by mass in 100% by mass of the polymer particle unit. % Or less, more preferably 66% by mass or less, still more preferably 64% by mass or less, and particularly preferably 62% by mass or less.
• the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group is more than 2% by mass, preferably 2.5% by mass or more, based on 100% by mass of the polymer particle unit. It is preferably 4% by mass or more, more preferably 6% by mass or more, still more preferably 10% by mass or more, still more preferably more than 10% by mass, particularly preferably 12% by mass or more, and most preferably 14% by mass or more.
• the structural unit (Z) derived from the (meth) acrylic acid ester monomer (C) having a hydroxyl group is 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass in 100% by mass of the polymer particle unit. It should be less than%. By containing the structural unit (Z) in the above range, polymer particles having excellent stability after particle formation can be obtained. In addition, polymer particles having excellent adhesiveness and chemical resistance can be obtained.
• the total of the structural unit (X), the structural unit (Y), and the structural unit (Z) is preferably 70% by mass or more, more preferably more than 70% by mass, and further preferably 72% by mass in 100% by mass of the polymer particle unit. % Or more, more preferably 74% by mass or more, still more preferably 76% by mass or more, and particularly preferably 78% by mass or more.
• the total of the structural unit (X), the structural unit (Y) and the structural unit (Z) is preferably less than 97% by mass, more preferably less than 95% by mass, still more preferably 90% by mass in 100% by mass of the polymer particle unit. % Or less, more preferably less than 90% by mass.
• the polymer particles containing the structural unit (X), the structural unit (Y), and the structural unit (Z) were further polymerized by using the monomer (D) having two or more reactive groups per molecule.
• a crosslinked structure can be formed.
• the monomer (D) having two or more reactive groups per molecule is a monofunctional monomer having a thermally crosslinkable crosslinkable group and one olefinic double bond per molecule. Examples include a metric and a polyfunctional monomer having two or more olefinic double bonds per molecule.
• the thermally crosslinkable group contained in the monofunctional monomer include an epoxy group, an N-methylolamide group, an oxetanyl group, an oxazoline group, and a combination thereof.
• crosslinkable monomer having an epoxy group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include vinyl glycidyl ether, allyl glycidyl ether, butenyl glycidyl ether, and o-allyl phenyl glycidyl.
• Unsaturated glycidyl ethers such as ethers; butadiene monoepoxides, chloroprene monoepoxides, 4,5-epoxide-2-pentene, 3,4-epoxy-1-vinylcyclohexene, 1,2-epoxide-5,9-cyclododecadiene Diene or polyene monoepoxides such as; alkenyl epoxides such as 3,4-epoxy-1-butene, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene; and glycidyl acrylates, glycidyl methacrylates, etc.
• Examples thereof include glycidyl esters of unsaturated carboxylic acids.
• crosslinkable monomer having an N-methylolamide group as a thermally crosslinkable crosslinkable group and having an olefinic double bond it has a methylol group such as N-methylol (meth) acrylamide (meth).
• a methylol group such as N-methylol (meth) acrylamide (meth).
• Acrylamides can be mentioned.
• crosslinkable monomer having an oxetanyl group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include 3-((meth) acryloyloxymethyl) oxetane and 3-((meth)). Acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-phenyloxetane, 2-((meth) acryloyloxymethyl) oxetane, and 2-((meth) acryloyloxymethyl) ) -4-Trifluoromethyloxetane.
• crosslinkable monomer having an oxazoline group as a thermally crosslinkable crosslinkable group and having an olefinic double bond examples include 2-vinyl-2-oxazoline and 2-vinyl-4-methyl-2-.
• polyfunctional monomers having two or more olefinic double bonds per molecule examples include allyl (meth) acrylate, ethylene di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di (meth).
• the glass transition temperature (Tg) or the monomer (D) of the homopolymer composed of the monomer (D) is selected from the viewpoint of flexibility.
• the monomer (D) having two or more reactive groups per molecule having a glass transition temperature (Tg) of ⁇ 50 ° C. or higher and 0 ° C. or lower can be preferably used.
• the glass transition temperature (Tg) of the monomer (D) or the homopolymer composed of the monomer (D) having two or more reactive groups per molecule is preferably ⁇ 50 ° C. or higher, more preferably ⁇ 45. ° C. or higher, more preferably ⁇ 40 ° C. or higher.
• the glass transition temperature (Tg) of the monomer (D) or the homopolymer composed of the monomer (D) having two or more reactive groups per molecule is preferably 0 ° C. or lower, more preferably ⁇ 5 ° C. Below, it is more preferably ⁇ 10 ° C. or lower.
• polyalkylene glycol di (meth) acrylate and urethane acrylate can be particularly preferably used.
• the monomer (D) having two or more reactive groups per molecule is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass in 100% by mass of the polymer particle unit. As mentioned above, it is particularly preferably 6% by mass or more.
• the monomer (D) having two or more reactive groups per molecule is preferably 10% by mass or less, more preferably 9% by mass or less, still more preferably 8% by mass, based on 100% by mass of the monomer unit. It should be as follows. By containing the monomer (D) having two or more reactive groups per molecule in the above range, polymer particles having excellent flexibility and chemical resistance can be obtained.
• the copolymer forming the polymer particles can contain a repeating unit derived from a radically polymerizable compound as a structural unit other than the structural unit (X), the structural unit (Y), and the structural unit (Z). ..
• a radically polymerizable compound that can be another structural unit include (meth) acrylic acid esters and vinyl compounds excluding the above-mentioned (meth) acrylic acid ester monomers (A) to (C).
• Examples of the radically polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, isopropyl (meth) acrylate, and -n-butyl (meth) acrylate, (.
• the softening start temperature of the polymer particles is preferably 20 ° C. or higher, more preferably 20 ° C. or higher, still more preferably 22 ° C. or higher, and even more preferably 25 ° C. or higher.
• the softening start temperature of the polymer particles is preferably 45 ° C. or lower, more preferably less than 45 ° C., still more preferably 40 ° C. or lower, still more preferably 35 ° C. or lower.
• the "softening start temperature of the polymer particles” is the temperature at which the glass transition starts (external glass transition start temperature) measured by differential scanning calorimetry (DSC) in accordance with JIS K7121: 2012. be.
• the supplementary glass transition start temperature is the temperature of the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the gradient of the curve of the stepped change part of the glass transition is maximized. do.
• the surface free energy of the particle film made of polymer particles can be obtained, for example, as follows. A dispersion liquid in which the polymer particles are dispersed in water so that the solid content concentration becomes 10% by mass is prepared. This dispersion is applied onto a PET substrate with a bar coater (# 3) and dried at 60 ° C. for 10 minutes to form a coating film layer, and the coating film layer is measured at a contact angle using a known solvent. -The surface free energy of the particle film made of polymer particles is obtained from the Drying equation.
• the surface free energy of the particle film is preferably 30 mN / m or more, more preferably 35 mN / m or more, still more preferably 36 mN / m or more, still more preferably 38 mN / m or more.
• the surface free energy of the particle film is preferably 50 mN / m or less, more preferably less than 50 mN / m, still more preferably 48 mN / m or less, still more preferably 46 mN / m or less, and particularly preferably 44 mN / m or less.
• the surface free energy of the particle film made of polymer particles can be adjusted by changing the type and composition ratio of the monomers of the polymer particles.
• Gel fraction (XY) / X
• X Area strength of polymer particles containing no monomer (D) having two or more reactive groups per molecule ( ⁇ total amount)
• Y Area strength of GPC ( ⁇ dissolved content) of the filtrate of the polymer particles containing the monomer (D) having two or more reactive groups per molecule.
• XY Area strength corresponding to the filtration residue containing the monomer (D) having two or more reactive groups per molecule ⁇ (insoluble content, gel content)
• the gel fraction of the polymer particles is preferably 0.7 or more, more preferably more than 0.7, still more preferably 0.8 or more.
• the gel fraction of the polymer particles is preferably 1.0 or less, more preferably less than 1.0, and even more preferably 0.9 or less.
• the volume average particle size of the polymer particles is preferably 100 to 500 nm, and the particle size distribution (volume average particle size / number average particle size) is preferably 1.5 or less.
• the volume average particle size of the polymer particles is preferably 100 nm or more, more preferably 120 nm or more, and further preferably 150 nm or more.
• the volume average particle size of the polymer particles is preferably 500 nm or less, more preferably 450 nm or less, and further preferably 400 nm or less.
• the volume average particle diameter is less than 100 nm, the viscosity of the dispersion liquid in which the polymer particles are dispersed in water increases, and there is a possibility that it becomes difficult to obtain an aqueous dispersion liquid having a high solid content. Further, when mixed with other particles, it becomes difficult to unevenly distribute the polymer particles on the surface of the dispersion liquid. Further, if the volume average particle diameter exceeds 500 nm, the storage stability of the aqueous dispersion of the polymer particles may decrease, which further causes the uniformity of the formed coating film to decrease.
• the volume average particle size of the polymer particles can be adjusted by changing the type and composition ratio of the emulsifier.
• the particle size distribution (volume average particle size / number average particle size) of the polymer particles is preferably 1.5 or less, more preferably 1.4 or less, still more preferably 1.3 or less, still more preferably 1.2 or less. It is preferably 1.1 or less. If the particle size distribution exceeds 1.5, it causes a decrease in the uniformity of the coating film containing the polymer particles, and it becomes difficult to bring out the performance peculiar to fluorine.
• the particle size distribution of the polymer particles can be adjusted by changing the monomer, the type of emulsifier, the composition ratio and the polymerization conditions.
• the average particle size and particle size distribution of the polymer particles can be measured by using a particle size distribution measuring device based on a dynamic light scattering method.
• a particle size distribution measuring device examples include HORIBA LB-550, SZ-100 series (all manufactured by HORIBA, Ltd.), FPAR-1000 (manufactured by Otsuka Electronics Co., Ltd.) and the like.
• the polymer particles can be mixed with water to prepare a dispersion liquid.
• this dispersion can also be mixed with inorganic particles such as alumina and titania.
• the pH of the dispersion is preferably 5 to 10, more preferably 6 to 9.5. By keeping the pH of the dispersion in such a range, the dispersion stability can be improved.
• the dispersion liquid containing the polymer particles can be used for a film, that is, the surface characteristics of the film can be modified by applying the dispersion liquid to the film to form a coating film.
• the film is not particularly limited, and examples thereof include a plastic film, a metal film, paper, a porous film, a porous substrate, a conductive film, and the like.
• the polymer particles are a fluorine-containing (meth) acrylic acid ester monomer (A), a (meth) acrylic acid ester monomer (B), and a (meth) acrylic acid ester monomer having a hydroxyl group. Obtained by emulsion polymerization of the body (C), optionally, a monomer mixture consisting of a monomer (D) having two or more reactive groups per molecule, and other radically polymerizable compounds in an aqueous medium. Be done.
• the fluorine-containing (meth) acrylic acid ester monomer (A) is preferably more than 20% by mass, and the (meth) acrylic acid ester monomer (B) is preferably 30% by mass or more.
• the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably more than 2% by mass to 30% by mass or less, and the fluorine-containing (meth) acrylic acid ester monomer (A), (meth).
• the total of the acrylic acid ester monomer (B) and the (meth) acrylic acid ester monomer (C) having a hydroxyl group is preferably 70% by mass or more, more preferably 70% by mass or more and less than 90% by mass. It is good.
• the monomer (D) having two or more reactive groups per molecule is contained, it is preferably 1% by mass or more and 10% by mass or less in 100% by mass of the monomer mixture.
• the conditions for emulsion polymerization of the monomer mixture are not particularly limited.
• the temperature is preferably about 50 to 100 ° C. for about 1 to 30 hours. You just have to react. If necessary, a chain transfer agent, a chelating agent, a pH adjuster, a solvent and the like may be added.
• an anionic surfactant As the emulsifier, an anionic surfactant, a nonionic surfactant, a combination of an anionic surfactant and a nonionic surfactant, etc. are used, and in some cases, an amphoteric surfactant and a cationic surfactant. Can also be used.
• anionic surfactant examples include alkyl sulfate ester sodium salt, alkylbenzene sulfonic acid sodium salt, succinic acid dialkyl ester sulfonic acid sodium salt, alkyldiphenyl ether disulfonic acid sodium salt, polyoxyethylene alkyl ether sulfate sodium salt, and polyoxyethylene.
• Alkylphenyl ether sodium sulfate and the like can be mentioned. Among these, sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium lauryl sulfate and the like are preferable.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester and the like.
• polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether and the like are used.
• amphoteric tenside examples include lauryl betaine, hydroxyethyl imidazoline sulfate sodium salt, imidazoline sulfonic acid sodium salt and the like.
• cationic surfactant examples include alkylpyridinium chloride, alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, alkyldimethylbenzylammonium chloride and the like.
• a fluorine-based surfactant such as perfluoroalkyl carboxylate, perfluoroalkyl sulfonate, perfluoroalkyl phosphate ester, perfluoroalkyl polyoxyethylene, perfluoroalkyl betaine, perfluoroalkoxyfluorocarboxylate ammonium, etc.
• Activators can also be used.
• reactive emulsifiers that can be copolymerized with the above-mentioned monomers, such as styrene sulfonic acid sodium salt, allylalkyl sulfonic acid sodium salt, polyoxyethylene alkyl allylphenyl ether ammonium sulfate, polyoxyethylene alkyl allylphenyl ether and the like.
• a combination of 2- (1-allyl) -4-nonylphenoxypolyethylene glycol sulfate ester ammonium salt and 2- (1-allyl) -4-nonylphenoxypolyethylene glycol is preferable.
• the amount of the emulsifier used is preferably about 0.05 to 10 parts by mass per 100 parts by mass of the total amount of the monomer mixture.
• a water-soluble polymerization initiator such as sodium persulfate, potassium persulfate, ammonium persulfate, or hydrogen peroxide, or a redox-based polymerization initiator that combines these water-soluble polymerization initiators and a reducing agent is used.
• a reducing agent include sodium pyrobisulfite, sodium hydrogen sulfite, sodium sulfite, sodium thiosulfate, L-ascorbic acid or a salt thereof, sodium formaldehyde sulfoxylate, ferrous sulfate, glucose and the like.
• L-ascorbic acid or a salt thereof is preferable.
• oil-soluble polymerization initiator can also be used by dissolving it in a monomer or a solvent.
• examples of the oil-soluble polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis- (4-methoxy-2,4-dimethylvaleronitrile), and 2,2'-azobis.
• 2,2'-azobisisobutyronitrile benzoyl peroxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide, t-butyl hydroperoxide, 3,5,5- Trimethylhexanol peroxide and t-butylperoxy (2-ethylhexanoate) are preferred.
• the amount of the polymerization initiator used is preferably about 0.1 to 3 parts by mass per 100 parts by mass of the monomer mixture.
• chain transfer agent examples include halogenated hydrocarbons (eg, carbon tetrachloride, chloroform, bromoform, etc.), mercaptans (eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.), xantogen.
• halogenated hydrocarbons eg, carbon tetrachloride, chloroform, bromoform, etc.
• mercaptans eg, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, n-hexadecyl mercaptan, etc.
• Classes eg, dimethylxanthogen disulfide, diethylxantogen disulfide, diisopropylxantogen disulfide, etc.
• terpenes eg, dipentene, turpinolene, etc.
• thiuram sulfides eg, tetramethylthium monosulfide, tetraethylthiuram disulfide, tetrabutylthium disulfide, dipentamethyl, etc.
• Thiuram disulfide etc.
• the amount of the chain transfer agent used is preferably about 0 to 10 parts by mass per 100 parts by mass of the monomer mixture.
• Examples of the pH adjuster include sodium carbonate, potassium carbonate, sodium hydrogencarbonate, ammonia and the like.
• the amount of the pH adjuster used is preferably about 0 to 3 parts by mass per 100 parts by mass of the monomer mixture.
• the monomer mixture can be added by various methods.
• a method of adding the entire amount of the monomer mixture at a time a method of charging a part of the monomer mixture and reacting it, and then continuously or dividing the remaining monomer mixture, and a reaction.
• the method of charging is preferable.
• volume average particle size and particle size distribution The volume average particle size and number average particle size of the polymer particles were measured using a particle size distribution measuring device (HORIBA LB-550, manufactured by HORIBA, Ltd.). The particle size distribution was obtained from the obtained values.
• a dispersion liquid in which polymer particles are dispersed in water so that the solid content concentration becomes 10% by mass is applied on a PET substrate with a bar coater (# 3 count) and dried at 60 ° C. for 10 minutes.
• a coating layer (particle film composed of polymer particles) was formed. The contact angle was measured using water, ethylene glycol, methylene iodide, and formamide as a solvent in the coating film layer, and the surface free energy of the particle film composed of polymer particles was determined from the Young-Dupre formula.
• XY Area strength corresponding to the filtration residue containing the monomer (D) having two or more reactive groups per molecule ⁇ (insoluble content, gel content)
• the monomer (D) having two or more reactive groups per molecule is polyalkylene glycol dimethacrylate (Blemmer (registered trademark) PDE-600 (manufactured by NOF CORPORATION)). ..
• Flexibility A dispersion was prepared by dispersing the polymer particles in water so that the solid content concentration was 10% by mass. This dispersion is applied on a PET substrate with a bar coater (# 3) and dried at 60 ° C. for 10 minutes to form a coating film layer, and the surface elastic modulus of the coating film layer is measured with an atomic force microscope (AFM). The elastic modulus of the particle film made of the polymer particles was determined. If the elastic modulus of the obtained particle film is less than 1.0 GPa, it is "excellent", if it is 1.0 GPa or more and 1.7 GPa or less, it is “good”, and if it is more than 1.7 GPa and 3.0 GPa or less, it is “slightly inferior”. , If it exceeds 3.0 GPa, it is evaluated as “inferior”, and if it is 1.7 GPa or less, it is judged that the flexibility is good.
• rate of change volume average particle diameter of the sample immersed in DEC / volume average particle diameter of the sample not immersed in DEC] was calculated. If the rate of change is 1.0 or more and less than 2.0, it is “excellent”, if the rate of change is 2.0 or more and less than 4.0, it is “good”, and if the rate of change is 4.0 or more and less than 6.0, it is “good”. If it is “slightly inferior” and the rate of change is 6.0 or more (including the case where the particles are dissolved in DEC and the particle size cannot be measured), it is evaluated as “inferior”, and when the rate of change is less than 4.0, it is good. Judged as chemical resistant.
• Example 1 120 parts of ion-exchanged water and 1 part of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Corporation) were charged into the reactor, and stirring was started. To this, 0.4 part of 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (manufactured by Wako Pure Chemical Industries, Ltd.) was added under a nitrogen atmosphere, and 2,2,2- 30 parts of trifluoroethyl methacrylate (3FMA), 49 parts of cyclohexyl acrylate (CHA), 14 parts of 4-hydroxybutyl acrylate (4HBA), polyalkylene glycol dimethacrylate (Blemmer (registered trademark) PDE-600 (manufactured by Nichiyu Co., Ltd.) ), 7 parts of this homopolymer made of Blemmer (registered trademark) PDE-600 (Tg: -34 ° C), 9 parts of Adecaria Sorb SR-1025 (e
• the mixture was continuously added dropwise at 60 ° C. over 2 hours, and the polymerization treatment was carried out for 4 hours after the completion of the addition.
• the obtained polymer particles were as shown in Table 1.
• the composition ratio of the monomers shown in Table 1 is the ratio of each component to the total amount of the monomer components.
• the abbreviations of each component in Table 1 have the following meanings.
• 3FMA 2,2,2-trifluoroethyl methacrylate (in the above formula (1), R 1 : -CH 3 , R 2 : -CH 2 CF 3 )
• CHA Cyclohexyl acrylate (R 1 : ⁇ H, R 3 : Cyclohexyl group in the above formula (2))
• 4HBA 4-hydroxybutyl acrylate (R 1 : ⁇ H, R 4 : 4-hydroxybutyl group in the above formula (3))
• Example 2 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 3 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 4 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 5 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 6 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 7 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 8 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 1. The obtained polymer particles were as shown in Table 1.
• Example 9 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The obtained polymer particles were as shown in Table 2.
• Example 10 The monomer (D) having two or more reactive groups per molecule was changed to urethane acrylate UF-C052 (manufactured by Kyoeisha Chemical Co., Ltd.), and the composition ratio of the monomer mixture was shown in Table 2. Polymer particles were obtained in the same manner as in Example 1 except that the above was changed to. The obtained polymer particles were as shown in Table 2.
• Example 11 Polymer particles were obtained in the same manner as in Example 10 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The obtained polymer particles were as shown in Table 2.
• Comparative Example 1 120 parts of ion-exchanged water and 1 part of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Corporation) were charged into the reactor, and stirring was started. To this, 0.4 part of 2,2'-azobis (2- (2-imidazolin-2-yl) propane) (manufactured by Wako Pure Chemical Industries, Ltd.) was added under a nitrogen atmosphere, and 2,2,2- From 30 parts of trifluoroethyl methacrylate (3FMA), 68 parts of cyclohexyl acrylate (CHA), 2 parts of 4-hydroxybutyl acrylate (4HBA), 9 parts of Adecaria Sorb SR-1025 (emulsifier manufactured by Adeca Co., Ltd.), 115 parts of ion-exchanged water. The monomer mixture was continuously added dropwise at 60 ° C. over 2 hours, and the polymerization treatment was carried out for 4 hours after the completion of the addition. The obtained polymer particles were as shown in Table
• Comparative Example 2 The composition ratio of the monomer mixture was the same as that of Comparative Example 1 except that the composition was changed to the composition shown in Table 2, but stable emulsification was not possible and particles could not be obtained.
• Comparative Example 3 Polymer particles were obtained in the same manner as in Comparative Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The obtained polymer particles were as shown in Table 2.
• Comparative Example 4 Polymer particles were obtained in the same manner as in Example 1 except that the composition ratio of the monomer mixture was changed to the composition shown in Table 2. The obtained polymer particles were as shown in Table 2.
• the polymer particles of the present invention were added in a small amount to the coating film on the film to maximize the low surface free energy of fluorine itself, thereby retaining the characteristics of other particles contained in the coating film on the film. As it is, the characteristics of fluorine can be expressed on the surface of the coating film.
• the particles are fused by heat to form a film and have adhesion to other materials due to the anchor effect, a film that forms a coating film with excellent flexibility and chemical resistance can be produced with high productivity. It will be possible to provide. As a result, its application is progressing as a coating agent that modifies the surface of separator films used in lithium-ion batteries in particular, and it is expected to contribute to the reduction of greenhouse gas emissions by promoting the spread of EV / PHEV.

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)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78708620

Family Applications (1)

Country Status (2)

Cited By (1)

Citations (5)

• 2021
  • 2021-05-21 WO PCT/JP2021/019321 patent/WO2021235540A1/ja not_active Ceased
  • 2021-05-21 JP JP2021539409A patent/JPWO2021235540A1/ja active Pending

Patent Citations (5)

Also Published As

Similar Documents

Legal Events