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JP-7854866-B2 - Fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles

JP7854866B2JP 7854866 B2JP7854866 B2JP 7854866B2JP-7854866-B2

Inventors

  • 西井 健太郎

Assignees

  • 株式会社ネオス

Dates

Publication Date
20260507
Application Date
20220615
Priority Date
20210830

Claims (8)

  1. (i) Repeating units derived from monomer (A) and (ii) Repeating units derived from monomer (B) , wherein the mass ratio of monomer (A) to monomer (B) {mass of monomer (B) / mass of monomer (A)} is 1 to 20 , is a fluorine-containing copolymer: (A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I) (In the formula, R1 represents a hydrogen atom or a methyl group. Y1 represents a divalent linking group. Rf is either formula (1) or formula (2) below.) (This represents a perfluoroalkyl group represented by [the symbol].) (B) (meth)acrylamide monomer represented by the following formula (II), (In the formula, R2 represents a hydrogen atom or a methyl group. R3 and R4 are the same or different alkyl groups having 1 to 6 carbon atoms. )
  2. (i) Repeating units derived from the monomer (A) below (ii) Repeating units derived from monomer (B) (iii) Fluorine-containing copolymers containing repeating units derived from monomer (C): (A) Fluorine-containing (meth)acrylate monomers represented by the following formula (I) (In the formula, R 1 Y represents a hydrogen atom or a methyl group. 1 represents a divalent linking group. Rf is represented by the following formula (1) or formula (2). (This represents a perfluoroalkyl group represented by [the symbol].) (B) (meth)acrylamide monomer represented by the following formula (II), (In the formula, R 2 R represents a hydrogen atom or a methyl group. 3 , R 4 (These represent alkyl groups having 1 to 6 carbon atoms, which are the same or different.) (C) A hydrophobic monomer represented by the following formula (III). (In the formula, R 5 R represents a hydrogen atom or a methyl group. 6 This represents an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted cycloalkyl group having 3 to 30 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, or an optionally substituted aralkyl group having 7 to 30 carbon atoms.
  3. The fluorine-containing copolymer according to claim 2 , wherein the mass ratio of monomer (A) to monomer (B) {mass of monomer (B) / mass of monomer (A)} is 1 to 20.
  4. The fluorine-containing copolymer according to claim 2 , wherein the mass ratio of monomer (C) to monomer (A) {mass of monomer (C) / mass of monomer (A)} is 1 to 20.
  5. A surface modifier comprising a fluorine-containing copolymer according to claim 1 or 2 .
  6. A leveling agent comprising a fluorine-containing copolymer according to claim 1 or 2 .
  7. A coating agent comprising a UV-curing resin, a coating polymer, or a thermosetting resin and the fluorine-containing copolymer described in claim 1 or 2 .
  8. An article comprising a layer formed using the coating agent described in claim 7.

Description

This invention relates to fluorine-containing copolymers, surface modifiers, leveling agents, coating agents, and articles. In image display devices such as plasma displays (PDPs), electroluminescent displays (ELDs), fluorescent display displays (VFDs), field emission displays (FEDs), and liquid crystal displays (LCDs), it is preferable to provide a hard coat layer on the surface to prevent scratches on the display surface. With the diversification of image display devices, such as touch panels, there is a growing demand for laminating (recoating) other functional layers onto the hard coat layer. Therefore, there is a need for a hard coat layer that is easy to laminate with other layers, i.e., has excellent lamination (recoating) properties. When recoating onto a hard coat layer, if the wettability of the hard coat layer surface is not high, uneven coating due to repelling or uneven coating thickness can occur, impairing the surface smoothness. However, on the other hand, hard coat layers typically contain leveling agents such as fluorine-containing polymers to improve the homogeneity of the coating film itself. The hydrophobicity of these leveling agents causes the hard coat surface to become hydrophobic. Thus, a trade-off between the homogeneity of the hard coat layer and its recoatability becomes a problem. Patent Document 1 discloses a fluorine-containing pyrolytic surfactant as a leveling agent that combines recoating properties and homogeneity. However, when using this surfactant, a pyrolysis step of the leveling agent is required to achieve recoating properties, which has the drawback of limiting the use of the leveling agent depending on the heat resistance of the substrate. Patent Document 2 discloses the use of a fluorine-containing polymer, obtained by polymerizing a fluorine-containing monomer and an acrylamide compound, for water-repellent and oil-repellent applications. Patent No. 6025008WO2009/123006 The fluorine-containing copolymer of the present invention comprises the following three fluorine-containing copolymers: (x) to (z): (x) A fluorine-containing copolymer containing repeating units derived from monomer (A) and repeating units derived from monomer (B), (y) A fluorine-containing copolymer containing repeating units derived from monomer (A) and repeating units derived from monomer (C), (z) A fluorine-containing copolymer comprising repeating units derived from monomer (A), repeating units derived from monomer (B), and repeating units derived from monomer (C). Monomer (A) is a fluorine-containing (meth)acrylate monomer represented by the following formula (I). Monomer (A) may be used alone or in combination of two or more types. (In the formula, R 1 represents a hydrogen atom or a methyl group. Y 1 represents a divalent linking group. Rf is either formula (1) or formula (2) below.) (This represents a perfluoroalkyl group.) R1 is a hydrogen atom or a methyl group, preferably a hydrogen atom. Examples of divalent linking groups represented by Y1 include linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms, optionally substituted arylene groups, and optionally substituted aralkylene groups. The two adjacent carbon atoms of the divalent linking group may be interposed by an ether bond (-O-), an ester bond (-COO- or -O-CO-), or an amide bond (-NHCO- or -CONH-). For example, those in which the above bonds are interposed on a butylene group include -CH2CH2 - O-CH2CH2-, -CH2CH2 - O - CO - CH2CH2- , -CH2CH2 - CO-O - CH2CH2- , -CH2CH2 - CONH -CH2CH2- , and -CH2CH2 - NHCO - CH2CH2- . Examples of linear or branched alkylene groups having 1 to 20 carbon atoms include -( CH2 ) m- (where m is an integer from 1 to 20), -CH( CH3 ) CH2- , -CH2CH ( CH3 )-, -CH( CH2CH3 ) CH2- , and -CH2CH ( CH2CH3 ) - . Examples of cyclic alkylene groups having 1 to 20 carbon atoms include cyclopropylene, 1,3-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, and 1,4-cyclohexylene. Examples of allerene groups include phenylene, biphenylene, phenoxyphenylene, naphthylene, anthracenylene, phenantrenylene, and fluorenylene. Examples of aralkylene groups include the bendiylene group and the phenethylene group. The number of substituents on the arylene group and aralkylene group is preferably 1 to 3, more preferably 1 to 2. Examples of substituents include methoxy group, ethoxy group, methyl group, ethyl group, chlorine atom, -CN, -NO₂ , OH, acetyl group, acetylamino group, and carbamoyl group. Preferred divalent linking groups represented by Y1 include the following: -(CH 2 ) n1 -, (n1=2 to 10), -CH( CH3 ) CH2- , -CH2CH ( CH3 )-, -CH(CH 2 CH 3 )CH 2 -, -CH 2 CH(CH 2 CH 3 )-, -(CH 2 CH 2 O) n2 -CH 2 CH 2 -, (n2=1 to 9), -CH 2 CH 2 O-CO-(C 6 H 4 )-, -CH 2 CH 2 -CO-O-(C 6 H 4 )-, -CH 2 CH 2 O-CO-(CH 2 CH 2 )-, -CH 2 CH 2 -CO-O-(CH 2 CH 2 )-, -CH₂CH₂O -CO-( cyclohexylene group)- -CH₂CH₂ - CO-O-(cyclohexylene group)-. The above acrylamide monomer (B) is preferably represented by the following formula (II): (I