Stock material or miscellaneous articles – Composite – Of addition polymer from unsaturated monomers
Reexamination Certificate
1999-07-28
2003-04-15
Wilson, D. R. (Department: 1713)
Stock material or miscellaneous articles
Composite
Of addition polymer from unsaturated monomers
C428S507000, C524S522000, C524S512000, C524S507000
Reexamination Certificate
active
06548182
ABSTRACT:
BACKGROUND OF THE INVENTION
A. Technical Field
The present invention relates to an ink jet recording material and a coating agent therefor, more particularly, relates to: an ink jet recording material which displays sufficient water resistance and further, excellent definition of initial images; and a coating agent therefor to give such an ink jet recording material.
B. Background Art
Ink jet recording apparatuses are machines such as printers, facsimile machines, and copiers. For the ink jet recording apparatus, U.S. Pat. No. 5,486,854 issued Jan. 23, 1996 is hereby incorporated by reference. The ink jet recording apparatus is to make a recording by jetting ink from a recording means (i.e. a recording head which is a part of the ink jet recording apparatus) onto a recording material, wherein the recording material is, for example, a paper sheet, or a plastic sheet such as transparent PET sheet.
The ink jet recording material, generally, suffers from a lack of water resistance. That is, an exposure to water usually will dissolve and destroy the image (the imaged ink). To prevent this, the image must be rendered water-resistant, and further, if the ink is, for example, an organic dye, then the image must also be fixed. Examples of known methods of giving the image the water resistance to thereby fix the image include arts to fix dyes with mordants and arts involving the use of adsorptive pigments. However, operations thereof are complicated, or the optimal method is different according to the composition of the ink, so the above known methods are not commonly usable means.
In comparison, JP-A-035090/1998 discloses a water-resistant composition for ink jet recording sheets, comprising a polymer containing an amino group (and/or quaternary ammonium salt) and a carboxyl group (and/or acid anhydride) and a crosslinking agent containing at least two oxazoline groups, as a method of not giving the image the water resistance, but carrying out a water-resisting pretreatment for the recording material. However, as to this technique, not only is the resultant water-resistification insufficient, but also there are problems on the definition of initial images.
SUMMARY OF THE INVENTION
A. Objects of the Invention
An object of the present invention is to provide: an ink jet recording material which displays sufficient water resistance and further, excellent definition of initial images; and a coating agent therefor to give such an ink jet recording material.
B. Disclosure of the Invention
To solve the above problems, the present invention provides the following:
A first coating agent for ink jet recording materials, according to the present invention, comprises: an aqueous polymer having a carboxyl group; and a water-soluble polymer having an oxazoline group as a crosslinking agent.
A second coating agent for ink jet recording materials, according to the present invention, comprises a polymer and a crosslinking agent, wherein the polymer has both a structural unit, as formed by ring-opening polymerization of an oxazoline compound, and a carboxyl group.
An ink jet recording material, according to the present invention, has on at least one face thereof a coated and cured layer of the above present invention first coating agent and/or a coated and cured layer of the above present invention second coating agent.
These and other objects and the advantages of the present invention will be more fully apparent from the following detailed disclosure.
DETAILED DESCRIPTION OF THE INVENTION
The first coating agent, according to the present invention, comprises: an aqueous polymer having a carboxyl group; and a water-soluble polymer having an oxazoline group as a crosslinking agent.
The aqueous polymer having a carboxyl group is not especially limited if it is a polymer that has a carboxyl group and further is aqueous (that is, water-soluble or water-dispersible). To obtain the polymer having a carboxyl group, a monomer having a carboxyl group is, for example, polymerized as a raw material, or a carboxyl group is introduced into a polymer (as prepared beforehand) by denaturation. To obtain the aqueous polymer, a hydrophilic monomer (available whether it has a carboxyl group or not) is, for example, used in the ratio of preferably 10 mol % or higher, more preferably 50 mol % or higher, to the entire monomer component.
Examples of the monomer having a carboxyl group include: unsaturated monocarboxylic acids, such as acrylic acid, methacrylic acid, and crotonic acid; unsaturated dicarboxylic acids, such as maleic acid, itaconic acid, citraconic acid, and fumaric acid; and unsaturated dicarboxylic anhydrides, such as maleic anhydride, itaconic anhydride, and citraconic anhydride.
Examples of the method, in which a carboxyl group is introduced into a polymer (as prepared beforehand) by denaturation, include a method including the step of jumping up a polymer, having an OH group in opposite terminal portions, with pyromellitic dianhydride.
Examples of the hydrophilic monomer include: monomers having a carboxyl group; and other monomers, such as hydroxyethyl acrylate, hydroxyethyl methacrylate, vinylpyrrolidone, dimethylaminoethyl acrylate, and chloridized-triaminoethyl methacrylate.
Examples of the aqueous polymer having a carboxyl group, as preferably usable in the present invention, include: polyvinyl alcohols having a carboxyl group (for example, anionic KEPS series made by Dai-ichi Kogyo Seiyaku Co., Ltd., and K Polymer made by Kuraray Co., Ltd.); (meth)acrylic ester copolymers (for example, Arolon made by Nippon Shokubai Co., Ltd.); vinyl ether-maleic anhydride copolymers (Gantrez AN series made by ISP); and aqueous polymers having both a structural unit, as formed by ring-opening polymerization of an oxazoline compound, and a carboxyl group. Particularly preferable ones are the aqueous polymers having both a structural unit, as formed by ring-opening polymerization of an oxazoline compound, and a carboxyl group.
Examples of the above aqueous polymer having both a structural unit, as formed by ring-opening polymerization of an oxazoline compound, and a carboxyl group include a polymer having a structural unit of general formula (1) below:
wherein: each of R
1
and R
2
, independently of each other, denotes a
hydrogen atom or a methyl group;
R
3
denotes a divalent organic residue;
R
4
denotes a monovalent organic residue;
Z denotes a halogen atom;
a denotes an integer of 1~1,000;
b denotes an integer of 3~110,000; and
n denotes an integer of 3~5,000.
This polymer can be synthesized by carrying out cationic polymerization of an oxazoline compound in the presence of an unsaturated halide to synthesize a polyoxazoline macromonomer having a radical-polymerizable double bond at a polymerization-initiating terminal, and then copolymerizing this polyoxazoline macromonomer and a monomer having a carboxyl group, as is illustrated by the following chemical reaction formula:
wherein R
1
, R
2
, R
3
, R
4
, Z, a, b, and n are the same as those in general formula (1).
Examples of the oxazoline compound, as usable in the above cationic polymerization, include 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-(n-propyl)-2-oxazoline, 2-(i-propyl)-2-oxazoline, 2-(n-butyl)-2-oxazoline, 2-(i-butyl)-2-oxazoline, and 2-(t-butyl)-2-oxazoline. Preferable ones among them are compounds with not more than 3 carbon atoms in R
4
, of which specific examples include 2-ethyl-2-oxazoline.
Examples of the above unsaturated halide include chloromethylstyrene, allyl chloride, epichlorohydrin, and chloroethyl vinyl ether. A preferable one among them is chloromethylstyrene.
As to the monomer having a carboxyl group, compounds in which R
2
is a hydrogen atom or a methyl group are preferable among the above-exemplified monomers having a carboxyl group. Specific examples of such compounds include acrylic acid and methacrylic acid.
Therefore, preferable examples of the aqueous polymer having both a structural unit, as formed by ring-opening polymerization of an oxazoline compound, and a carboxyl group include poly(2-methyl-2-oxazoline)/(meth)ac
Arita Yoshihiro
Field Dana D.
Wakao Norihiro
Yamamoto Yoshinobu
Esprit Chemical Co.
Haugen Law Firm PLLP
Wilson D. R.
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