Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – At least one aryl ring which is part of a fused or bridged...
Reexamination Certificate
1998-11-10
2001-05-29
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
At least one aryl ring which is part of a fused or bridged...
C524S555000, C430S536000, C526S201000, C526S298000, C526S312000, C526S315000, C526S316000
Reexamination Certificate
active
06239207
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a latex and a sheet material comprising a hydrophilic colloidal layer using the same, which exhibits improvement in the physical properties of layers.
BACKGROUND OF THE INVENTION
In conventional silver halide light-sensitive photographic material, gelatin is widely employed as a binder.
Gelatin exhibits high swelling and gelling capabilities and is easily subjected to cross linking reaction employing various types of hardening agents. In addition, gelatin is a binder which exhibits extremely excellent properties to uniformly coat, over a wide area, a material such as light-sensitive silver halide which is to be protected from high temperatures by adjusting the physical properties of the coating composition.
On the other hand, a technique is known in which the layer physical properties of the light-sensitive material are improved by incorporating a polymer latex comprising a cross linking group with gelatin into a silver halide emulsion layer. However, the latex prepared by copolymerization with the monomer having such cross linking group exhibits low polymerization stability and low compatibility with gelatin. Accordingly, improved effects due to the cross linking group have not been fully exhibited.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a latex and a sheet material using the same, which exhibits excellent physical properties of the layers, especially, strength of layers on the support at wet state, high flexibility of swelled layers on the support.
The present invention will now be described.
The latex of the present invention is prepared by polymerizing a polymerizable monomer having an active methylene group in the presence of a hydrophilic copolymer comprising isoprene sulfonic acid or salts thereof as a monomer unit.
A sheet material is comprised of a support having thereon at least one hydrophilic colloidal layer which is provided by coating composition containing the above-mentioned latex and drying.
In the sheet material mentioned above solid portion of the latex is preferably 1 to 50 percent in terms of weight ratio for the whole hydrophilic colloidal layer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is explained in detail below.
The latex is prepared by copolymerising a polymerizable monomer having an active methylene group in the presence of a hydrophilic copolymer comprising isoprene sulfonic acid or salts thereof as a monomer unit.
The polymerizing is conducted by means of usual way.
The hydrophilic copolymer used for preparation of the latex preferably comprises a water solubilising group such as a sulfonic acid-base, carboxylic acid-base or an acid neutralized group of amine group, and in a certain case, comprises another functional group forming bridge such as a group having an unsaturated double bond.
It is preferably contains unit of isoprene sulfonic acid or salts thereof not less than 30 molar %, more preferably not less than 50 molar %, in the polymer.
Examples of the hydrophilic copolymer are illustrated below.
The hydrophilic polymer is preferably soluble not less than 1 g in 100 ml of water at room temperature.
The molecular weight of the hydrophilic polymer is preferably 3,000-200,000, more preferably 10,000-100,000 in terms of weight average molecular weight.
Polymerizable monomers having an active methylene group is explained.
The active methylene monomers which are preferably employed in the present invention are compounds represented by the general formula (1) described below.
General formula (1)
wherein R
1
represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms (for example, each of a methyl, ethyl, n-propyl, n-butyl group, etc.), or a halogen atom (for example, a chlorine atom, a bromine atom), and preferably represents a hydrogen atom, a methyl group, and a chlorine atom, and L represents a single bond or divalent linkage group. Specifically, the latter are represented by the following formula.
&Parenopenst;L
1
&Parenclosest;
m
&Parenopenst;L
2
&Parenclosest;
n
wherein L
1
represents —CON(R
2
)— (R
2
represents a hydrogen atom, an alkyl group having from 1 to 4 carbon atoms, or a substituted alkyl group having from 1 to 6 carbon atoms), —COO—, —NHCO—, —OCO—,
wherein R
3
and R
4
each independently represents a hydrogen atom, a hydroxyl group, a halogen atoms, a substituted or unsubstituted alkyl, alkoxy, or aryloxy group;
L
2
represents a linkage group to link L
1
with X, and m represents 0 or 1; and n represents 0 or 1. The linkage groups represented by L
2
are specifically represented by the general formula (2) described below.
General formula (2)
&Brketopenst;X
1
&Parenopenst;J
1
—X
2
&Parenclosest;
p
&Parenopenst;J
2
—X
3
&Parenclosest;
q
&Parenopenst;J
3
&Parenclosest;
r
&Brketclosest;
s
wherein J
1
, J
2
, and J
3
are the same or different and each represents —CO—, —SO
2
—, —CON(R
5
)— (R
5
represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms), a substituted alkyl group having from 1 to 6 carbon atoms, —SO
2
N(R
5
) (R
5
is the same as above), —N(R
5
)—R
6
— (R
5
is the same as above, and R
6
represents an alkylene group having from 1 to 4 carbon atoms), —N(R
5
)—R
6
—N(R
7
)— (R
5
and R
6
are the same as above, R
7
represents a hydrogen atom, an alkyl group having from 1 to 6 carbon atoms), a substituted alkyl group having from 1 to 6 carbon atoms), —O—, —S—, —N(R
5
)—CO—N(R
7
)— (R
5
and R
7
are the same as above), —N(R
5
)—SO
2
—N(R
7
)— (R
5
and R
7
are the same as above), —COO—, —OCO—, —N(R
5
)CO— (R
5
is the same as above), —N(R
5
)CO— (R
5
is the same as above), etc.
p, q, r, and s each represents 0 or 1.
X
1
, X
2
, and X
3
may be the same or different, and each represents an alkylene group having from 1 to 10 carbon atoms, an alalkylene group or a phenylene group, each of which group may be substituted or unsubstituted, and the alkylene group may be a straight or branched chain. As the alalkylene groups, can be listed, for example, each of a methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene group, etc. As the alalkylene groups, can be listed, for example, each of a D-phenylene, m-phenylene, methylphenylene group, etc.
X represents a monovalent group comprising an active methylene group. As specific preferred examples, can be listed R
8
—CO—CH
2
—COO—, NC—CH
2
—COO—, R
8
—CO—CH
2
—CO—, R
8
—CO—CH
2
—CON(R
5
)—, etc., wherein R
5
is the same as described above, R
8
represents a substituted or unsubstituted alkyl group (for example, a methyl, ethyl, n-propyl, n-butyl, t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl group, etc.), a substituted or unsubstituted aryl group (for example, each of a phenyl, p-methylphenyl, p-methoxyphenyl, p-chlorophenyl group, etc.), an alkoxy group (for example, each of a methoxy, ethoxy, methoxyethoxy, n-butoxy group, etc.), a cycloalkyloxy group (for example, a cyclohexyloxy group, etc.), an aryloxy group (for example, each of a phenoxy, D-methylphenoxy, o-chlorophenoxy, p-cyanophenoxy group, etc.), an amino group, a substituted amino group (for example, each of a methylamino, ethylamino, dimethylamino, butylamino group, etc.).
Following are exemplified polymerizable monomers having an active methylene group of the present invention.
M-1 2-acetoacetoxyethylmethacrylate
M-2 2-acetoacetoxyethylacrylate
M-3 2-acetoacetoxypropylmethacrylate
M-4 2-acetoacetoxypropylacrylate
M-5 2-acetoacetamidoethylmethacrylate
M-6 2-acetoacetamidoethylacrylate
M-7 2-cyanoacetoxyethylmethacrylate
M-8 2-cyanoacetoxyethylacrylate
M-9 N-2(cyanoacetoxyethyl)acrylate
M-10 2-propionylacetoxyethylacrylate
M-11 N(2-propionylacetoxyethyl)methacrylamide
M-12 N-4-(acetoxybenzyl)phenylacrylamide
M-13 ethylacryloylacetate
M-14 acryloylmethylacetate
M-15 N-methacryloyloxymethylacetoacetamide
M-16 ethylmethacryloylacetoacetate
M-17 N-allylcyanoacetamide
M-18 methylacryloylacetoacetate
M-19 N-(2-methacryloloxymethyl)cyanoacetamide
Kubo Nobuo
Nagaike Chiaki
Ueda Eiichi
Bierman Jordan B.
Bierman, Muserlian and Lucas
Egwim K C
Konica Corporation
Wu David W.
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