Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2000-01-21
2003-11-25
Mulcahy, Peter D. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S221000, C524S224000, C524S220000, C524S157000, C524S158000, C524S101000, C524S166000, C524S380000, C524S386000, C524S388000, C524S370000, C524S372000
Reexamination Certificate
active
06653376
ABSTRACT:
BACKGROUND OF THE INVENTION
Technical Field
The present invention relates to a water dispersion type water and oil repellent composition which is capable of imparting durability excellent in water and oil repellency and water resistance against washing, abrasion, etc. of clothing, etc., and a method for its production. Further, it relates to a water dispersion type water and oil repellent composition excellent in water and oil repellency performance in various papers, and a method for its production.
Heretofore, a technique has been known to treat e.g. a fiber product with a polymer having polymer units of an addition polymerizable monomer containing a polyfluoroalkyl group (hereinafter referred to as a R
f
group) or a compound having a R
f
group in the form of an organic solvent solution or an aqueous solvent dispersion to impart water and oil repellency to its surface. The addition polymerizable monomer will hereinafter be referred to simply as a monomer.
Improvement of the water and oil repellency has been accomplished to some extent by forming a copolymer by employing a monomer having a bonding group together with a monomer having a R
f
group, by blending a polymer having R
f
groups with a polymer having a high coating film strength, or by modifying the polymerization method, for the purpose of improving the durability against washing, abrasion, etc.
A method of coating a polyurethane resin or an acrylic resin is known in order to improve the durability of water resistance as higher water and oil repellency, but there has been a problem that the hand and feel of the fabric tend to be hard. Further, a method is also known to apply water repellency treatment to a high a density fabric employing extremely fine fibers to improve the water resistance, but no adequate water resistance has been obtained with conventional water dispersion type water and oil repellent treating agents.
Further, a method is also known wherein a fabric once treated with a water and oil repellent, is further treated with a water and oil repellent of a solvent type, but the treating process is cumbersome, and there has been a problem such as environmental pollution by the organic solvent.
On the other hand, as a water and oil repellent for paper, a phosphoric acid ester having a perfluoroalkyl group or the like is known. However, for the treatment by a post treating method wherein a treating agent is impregnated or coated on base paper, a sizing press or a coater is employed, and treatment is carried out at a high speed, whereby there has been a problem that with a conventional water and oil repellent, inadequate oil repellency tends to result frequently.
With conventional water and oil repellent compositions and water and oil repellent treatments, the durability of water resistance has been inadequate, although the durability against washing, abrasion, etc. of the water and oil repellency imparted to common clothing, has been at a satisfactory level.
Especially when fibers, etc., having a special surface shape, employing very fine high density synthetic fibers, new synthetic fibers (a general term for fabrics employing very fine fibers or processed yarns (such as split yarns), for example “relanche”, trade name, manufactured by Toray Corporation), etc., are treated for water and oil repellency, there has been a practical problem that the water and oil repellency or the water resistance tends to be remarkably decreased by abrasion during wearing and by washing a few times.
Further, the method by coating or the like of a resin, has had a problem of hardening of the hand and feel. On the other hand, the application to paper has had a problem of inadequate oil repellency depending upon the treating method.
An object of the present invention is to provide a water dispersion type water and oil repellent composition which has excellent water resistance against washing, abrasion, etc. and durability of practical water and oil repellency whereby there will be little hardening of the hand and feel, and to provide a water dispersion type water and oil repellent composition for paper, whereby excellent oil repellency can be obtained constantly. A further object is to provide a water dispersion type water and oil repellent composition which can be applied to an article such as a metal, glass or a resin, for which water and oil repellency is required.
DISCLOSURE OF THE INVENTION
The present invention is a water dispersion type In water and oil repellent composition comprising an aqueous medium, the following Polymer A and the following Compound B, as essential components:
Polymer A: a polymer comprising polymer units a of a monomer having a polyfluoroalkyl group and one polymerizable unsaturated group,
Compound B: a monool or polyol having an unsaturated triple bond, or an alkylene oxide adduct thereof.
BEST MODE FOR CARRYING OUT THE INVENTION
Polymer A is a polymer comprising polymer units of a monomer having a R
f
group and only one polymerizable unsaturated group (hereinafter referred to as a R
f
group containing monomer).
The R
f
group is a group having at least two hydrogen atoms in an alkyl group substituted by fluorine atoms. The carbon number of the R
f
group is preferably from 4 to 20, more preferably from 6 to 16, particularly preferably from 9 to 12. The R
f
group may be of a straight chain structure or a branched structure. In the case of a branched structure, it is preferred that the branched moiety is present in the vicinity of a terminal of the R
f
group, and the branched moiety is of a short chain with a carbon number of from about 1 to 4. Further, the R
f
group may have an etheric oxygen atom inserted between a carbon-carbon bond. The R
f
group may contain a halogen atom other than a fluorine atom, and a chlorine atom is preferred as the halogen atom other than a fluorine atom.
The number of fluorine atoms in the R
f
group is preferably at least 60%, particularly preferably at least 80%, when it is represented by [(number of fluorine atoms in the R
f
group)/(number of hydrogen atoms contained in an alkyl group having the same carbon number as in the R
f
group)]×100 (%). Further, the R
f
group is preferably a group having all hydrogen atoms in an alkyl group substituted by fluorine atoms, i.e. a perfluoroalkyl group (hereinafter referred to as a R
f
group) of the formula C
m
F
2m+1
—, wherein m is an integer of from 4 to 20. Particularly preferred is a linear R
f
group wherein the average of m is from 9 to 12.
If m exceeds 20, the R
f
group-containing monomer is solid at room temperature, has a high sublimation property and is difficult to handle. Further, if m is less than 4, the water and oil repellency tends to be low, and the desired functions may not be obtained.
In the R
f
group-containing monomer, the R
f
group and the polymerizable unsaturated group may be bonded directly or indirectly via a connecting group, and they are preferably indirectly bonded. Particularly preferred is a compound of a structure wherein one R
f
group is connected to a polymerizable unsaturated group via a bivalent connecting group.
As the R
f
group-containing monomer, a known compound may be employed, and it can readily be synthesized from a R
f
group-containing alcohol, a R
f
group-containing carboxylic acid or a R
f
group-containing sulfonic acid.
The R
f
group-containing monomer is preferably a compound represented by the following Formula 3.
R
f
—R
1
—X
Formula 3
In the Formula 3, R
f
represents the R
f
group, R
f
represents a single bond or a bivalent connecting group, and X represents a monovalent organic group having one polymerizable unsaturated group. The R
f
group is preferably a group disclosed in the following specific examples and Examples.
The bivalent connecting group represented by R
f
may be an alkylene group, an ester bond, an amide bond, an imino bond, a urethane bond, an etheric oxygen atom, a phenylene oxide group, a sulfonyl group or a connecting group containing such a structure. Specifically, it may, for example, be —(CH
2
)
n&plu
Kaneko Kyouichi
Maekawa Takashige
Shindo Minako
Sugimoto Shuichiro
Asahi Glass Company Ltd.
Mulcahy Peter D.
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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