Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2002-03-13
2004-05-11
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C525S329400, C525S509000, C525S412000, C525S443000
Reexamination Certificate
active
06734255
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a graft polymer, a process for preparing the same, and a solvent-based water- and oil-repellent composition comprising the same.
RELATED ART
In view of regulation of fluorocarbons and environmental problems, solvents for water- and oil-repellent products, for example, halogen solvents such as R113 are being replaced by petroleum solvents. However, problems such as solidification or deposition of products at low temperature arise even if the solvent is merely replaced. When the water- and oil-repellent product is diluted-with the petroleum solvent having low solubility such as solvent having a small content of an aromatic compound, problems such as deposition or concentration distribution arise.
When the fluorine concentration in an active component of the water- and oil-repellent agent is reduced to impart high product stability and high dilution stability to the water- and oil-repellent composition, the water- and oil-repellency is lowered.
Japanese Patent Kokoku Publication No. 50082/1986 discloses a water- and oil-repellent comprising a graft copolymer obtained by the graft copolymerization which utilizes the reactivity of an OH group. However, the graft copolymer is insufficient in water repellency because a hydroxyl group is remained in the polymer.
Japanese Patent Kokai Publication No. 228534/1994 discloses a water- and oil-repellent comprising a fluorine-containing graft copolymer. However, the fluorine-containing graft copolymer is insufficient in solubility in the petroleum solvent because its trunk polymer is a fluorine-containing polymer.
SUMMARY OF THE INVENTION
An object of the present invention is to give a graft copolymer which has high water- and oil-repellency regardless of a small fluorine content, and also has both a solubility in a petroleum solvent and a repellency effect.
The present inventors have discovered that a graft polymer, wherein a branch polymer is a fluorine-containing polymer and a trunk polymer contains, a fluorine-free (hydrocarbon) polymer as a main component, has high water-repellency and good solubility in a petroleum solvent.
The present invention provides a graft copolymer wherein a branch polymer having a fluoroalkyl group is bonded to a trunk polymer through a linkage having a —C(═O)NH— group.
The present invention also provides a solvent-based water- and oil-repellent composition comprising the graft copolymer.
The graft polymer of the present invention is a graft polymer wherein a branch polymer is grafted at an isocyanate group moiety of a trunk polymer.
The trunk polymer has a repeating unit derived from an isocyanate group-containing vinyl monomer and a repeating unit derived from the other copolymerizable monomer.
The isocyanate group, which exists in the repeating unit derived from the isocyanate group-containing vinyl monomer, reacts with an active hydrogen group of the branch polymer, thereby to bond to the branch polymer.
The term “isocyanate group-containing vinyl monomer” means a compound having a carbon-carbon double-bond and an isocyanate group. The numbers of the carbon-carbon double bond and of the isocyanate group in the isocyanate group-containing vinyl monomer are generally 1. A molecule of the isocyanate group-containing vinyl monomer usually has a carbon-carbon double bond at one terminal of the molecule and an isocyanate group at the other terminal of the molecule.
The isocyanate group-containing vinyl monomer includes, for example,
(i) an isocyanate group-containing (meth)acrylate ester,
(ii) a vinyl isocyanate represented by the formula:
H
2
C═C(R
11
)—A
1
—NCO
wherein R
11
is H or a linear, branched or cyclic hydrocarbon group (for example, an alkyl group) having 1 to 20 (for example, 1 to 10) carbon atoms and A
1
is a direct bond or a hydrocarbon group having 1 to 20 carbon atoms, and
(iii) a reaction product of (iii-1) a compound having two isocyanate groups and (iii-2) a compound having a carbon-carbon double bond- and an active hydrogen.
Examples of the isocyanate group-containing (meth)acrylate ester (i) include:
H
2
C═C(R
12
)COO(CH
2
CH
2
O)
n
(CH
2
)
m
—NCO
wherein R
12
is H or CH
3
, n is from 0 to 20, and m is from 1 to 20 (for example, 2-isocyanatoethyl (meth)acrylate).
Examples of the vinyl isocyanate (ii) include:
H
2
C═C(R
13
)—NCO
wherein R
13
is a linear, branched or cyclic hydrocarbon group (for example, an alkyl group or a cycloalkyl group) having 1 to 20 (for example, 1 to 10) carbon atoms,
H
2
C═C(R
14
)—(CH
2
)
n
—NCO
wherein R
14
is H or a linear, branched or cyclic hydrocarbon group (for example, an alkyl group or a cycloalkyl group) having 1 to 20 (for example, 1 to 10) carbon atoms, and n is from 2 to 20, and
H
2
C═C(R
15
)—Ph—C(R
16
)
2
—NCO
wherein R
15
is H or CH
3
, R
16
is H or CH
3
, and Ph is a phenylene group.
Examples of the compound having two isocyanate groups (iii-1) include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, and isophorone diisocyanate.
Examples of the compound having a carbon-carbon double bond and an active hydrogen (iii-2) (hereinafter referred to as a “monomer having an active hydrogen”) include:
hydroxyethyl (meth)acrylate,
HO(CH
2
CH
2
O)
n
COC(R
17
)C═CH
2
wherein R
17
is H or CH
3
and n is from 2 to 20, and aminoethyl (meth)acrylate.
The reactin between the compound having two isocyanate groups (iii-1) and the monomer having active hydrogen (iii-2) may be conducted in a solvent (especially, an aprotic solvent, for example, an ester solvent) optionally using a catalyst such as dibutyltin dilaurate. The amount of the monomer having active hydrogen (iii-2) in the reaction may be from 1.0 to 2.0 equivalents, and preferably from 1.0 to 1.7 equivalents, based on the compound having two isocyanate groups (iii-1).
The amount of the isocyanate group-containing vinyl monomer is from 1 to 30% by weight, and preferably from 2 to 10% by weight, based on the trunk polymer.
The other copolymerizable monomer constituting the trunk polymer may be any one as far as it is an addition-polymerizable monomer (namely, a compound having a carbon-carbon double bond), and may be either of a fluorine-free monomer and a fluorine-containing monomer. The amount of the fluorine-containing monomer is at most 50% by weight, and preferably at most 10% by weight, based on the trunk polymer. The fluorine-containing monomer may not exist in the trunk polymer.
The fluorine-free monomer includes, for example, a (meth)acrylate ester. The (meth)acrylate ester may be an ester of (meth)acrylic acid and an aliphatic alcohol, for example, a monohydric alcohol or a polyhydric alcohol (for example, a dihydric alcohol).
Examples of the fluorine-free monomer include:
(meth)acrylates such as 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, hydroxyalkyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, polyoxyalkylene (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, benzyl (meth)acrylate glycidyl methacrylate, hydroxypropyl monomethacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxyethyl acrylate, glycerol monomethacrylate, &bgr;-acryloyloxyethyl hydrogen-succinate, &bgr;-methacryloyloxyethyl hydrogen-phthalate, 2-acryloyloxyethylhexahydrophthalic acid, 2-acryloyloxy-ethylphthalic acid, 2-acryloyloxyethyl-2-hydroxyethyl-phthalic acid, methacrylic acid hydroxypropyltrimethyl-ammonium chloride, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-acryloyloxyethyl acid phosphate, glycosyl ethyl methacrylate, methacrylamide, 2-hydroxy-3-acryloyloxypropyl methacrylate, 2-methacryloyloxyethyl acid phosphate, and hydroxypivalic acid neopentyl glycol diacrylate; styrenes such as styrene and p-isopropylstyrene; (meth)acrylamides such as (meth)acrylamide, diacetone(meth)acrylamide, N-methylol(meth)acrylamide, N-butoxymethy
Hanazawa Makoto
Hayashi Kazunori
Yamaguchi Fumihiko
Asinovsky Olga
Daikin Industries Ltd.
Seidleck James J.
Sughrue & Mion, PLLC
LandOfFree
Graft polymer, process for the production thereof and... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Graft polymer, process for the production thereof and..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Graft polymer, process for the production thereof and... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3231079