Stock material or miscellaneous articles – Composite – Of polyester
Reexamination Certificate
1999-07-09
2001-05-01
Michl, Paul R. (Department: 1714)
Stock material or miscellaneous articles
Composite
Of polyester
Reexamination Certificate
active
06224988
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to emulsion type adhesive compositions, and adhesive films and photographic materials by the use thereof, and in particular to adhesive compositions containing a acetoacetoxy group-containing polymer and a sulfonic acid group-containing copolyester, and adhesive films and photographic materials by the use thereof.
BACKGROUND OF THE INVENTION
Adhesives are mainly classified into a solvent type adhesive and a aqueous emulsion type adhesive. Of these, the solvent type adhesive has disadvantages such that the use thereof involves problems such as ignition or fire due to a used solvent and health and environment problems such as environmental pollution. On the contrary, the aqueous emulsion type adhesive has no problem such as above.
Aqueous emulsion type adhesives are comprised of fine water-insoluble resin particles with particle sizes of 0.05 to 10 &mgr;m and dispersed in water as a medium. To disperse the resin particles in water, it is necessary to allow an aqueous component to exist on the particle surface. The method for allowing the aqueous component to exist includes adsorption of a surfactant and copolymerization of an aqueous comonomer. When such an aqueous emulsion type adhesive is used, however, the surfactant or aqueous component remains in the formed adhesive coating or is present largely in the interface of the coating, leading to deterioration in coating strength or strength adhered to material. Specifically, low-polar plastic resin films tend to be hardly adhered. Photographic materials, which are generally provided with a sublayer to perform adhesion between a plastic resin film support such as a polyester and a light-sensitive layer, are processed with a developer at a high pH or heated to form images, so that when applying the aqueous emulsion type adhesive described above to the sublayer, it is needed to have adhesion sufficient for such an image forming treatment with a developer or by heating and therefore, an adhesive with higher adhesion is desired.
Attempts to enhance adhesion of the aqueous emulsion type adhesive include a technique of using an emulsion without using a low molecular weight surfactant, for example, JP-A 5-287248 discloses a technique of using polyvinyl alcohol as a protective colloid and as a adhesive, a latex comprised of copolymer of ethylene, vinyl acetate and acetoacetic acid allyl ester (herein, the term, JP-A means an unexamined and published Japanese Patent Application). However, as a sublayer of the photographic material which is to be subjected to the processing described above is insufficient the adhesion. JP-A 63-218952 discloses a technique of incorporating a polymer latex containing an active methylene group into a sublayer of a polyester support. In this technique, its adhesion property is exhibited to a certain extent, but when subjected to recent rapid processing or an image forming treatment by heating, sufficient adhesion was not obtained. Toku-hyo-hei (PCT Application Publication) No. 8-503687 discloses an aqueous coating composition comprised of a copolymer of vinyl acetate and dialkyl maleate, which is polymerized in a polyester containing a sulfonic acid group and a polymer containing an active methylene group. When this polymer mixture composition is applied to photographic materials, however, sufficient adhesion was not obtained after subjected to an image forming treatment by developing or heating.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide an adhesive composition exhibiting superior adhesion specifically in polyesters and having sufficient adhesion property as a sublayer of photographic materials, an adhesive films and an image forming material.
The object of the invention described above can be accomplished by the following consitution:
an adhesive composition comprising an ethylenic copolymer comprising a repeating unit derived from an ethylenically unsaturated monomer containing an active methylene group and at least a repeating unit derived from an ethylenically unsaturated monomer, and a copolyester containing, as a copolymerizing component, a repeating unit derived from a dicarboxylic acid containing a sulfonate group or a repeating unit derived from a diol containing a sulfonate group.
DETAILED DESCRIPTION OF THE INVENTION
The above-described copolymer, i.e., polymer containing an active methylene group is preferably represented by the following formula (1):
—(
A
)
x
—(
B
)
y
—(
C
)
z—
Formula (1)
wherein A represents a repeating unit derived from an ethylenically unsaturated monomer containing an active methylene group and represented by formula (2) described below, B represents a repeating unit derived from an ethylenically unsaturated monomer selected from the group consisting of a methacrylic acid ester, acrylic acid ester and maleic acid ester, provided that a homopolymer of each of them [i.e., a homopolymer of monomer B, represented by (B)y] exhibits a glass transition temperature of not more than 35° C.; C represents a repeating unit derived from an ethylenically unsaturated monomer, except for A and B described above; x, y and z each are the proportion of each polymeric component, represent in terms of a percentage by weight, provided that 5≦x≦60, 5≦y≦90 and x+y+z=100.
wherein R
1
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a halogen atom; L represents a single bond or a bivalent linkage group, such as one represented by the following formula:
—(
L
1
)
m
—(
L
2
)
n—
wherein L
1
represents —CON(R
2
)—, in which R
2
represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a substituted alkyl group having 1 to 6 carbon atoms, —COO—, —NHCO—, —OCO—,
in which R
3
and R
4
independently represent a hydrogen atom, hydroxy, halogen atom, or an alkyl, alkoxy, acyloxy or aryloxy, each of which may be substituted or unsubstituted; L
2
represent a linkage group linking L
1
and X. The linkage group represented by L2 is preferably represented by the following formula:
—[X
1
—(
J
1
—X
2
)
p
-(
J
2
—X
3
)
q
-(
J
3
)
r]s—
where J
1
, J
2
and J
3
, which may be the same or different, represent —CO—, —SO
2
—, —CON(R
5
)—, —SO
2
N(R
5
)—, —N(R
5
)—R
6
—, —N(R
5
)—R
6
—N(R
7
)—, —O—, —S—, —N(R
5
)—CO—N(R
7
)—, —N(R
5
)—SO
2
N(R
7
)—, —COO—, —OCO—, —N(R
5
)CO
2
—or —N(R
5
)CO—, in which R
5
represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or substituted alkyl group having 1 to 6 carbon atoms; R
6
represents an alkylene group having 1 to 4 carbon atoms and R
7
represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or substituted alkyl group having 1 to 6 carbon atoms); p, q, r and s each 0 or 1; X
1
, X
2
and X
3
, which may be the same or different, each represents a straight-chained or branched alkylene, an aralkylene or a phenylene group, each of which has 1 to 10 carbon atoms and may be substituted or unsubstituted. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene and decylmethylene; Examples of the aralkylene group include benzylidene; and examples of the phenylene group include p-phenylene, m-phenylene and methylphenylene.
X represents a univalent group containing an active methylene group, and preferred examples thereof include R
8
—CO—CH
2
—COO—, CN—CH
2
—COO—, R
8
—CO—CH
2
—CO—or R
8
—CO—CH
2
—CON(R
5
)—, in which R
5
is the same as defined above, R
8
represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (e.g., methyl, ethyl, n-butyl, t-butyl, n-nonyl, 2-methoxyethyl, 4-phenoxybutyl, benzyl, 2-methanesulfonamidoethyl, etc.), substituted or unsubstituted aryl group (e.g., phenyl, p-methylphenyl, p-methoxyphenyl, o-chlorophenyl, etc.), substituted or unsubstituted alkoxy group (e.g., methoxy, ethoxy, methoxyethoxy, n-butoxy, etc.), substituted or unsubstituted cycloalkyloxy group (e.g., cyclohexyloxy), substituted or
Kubo Nobuo
Kurachi Yasuo
Nagaike Chiaki
Nakajima Akihisa
Ueda Eiichi
Frishauf, Holtz Goodman, Langer & Chick, P.C.
Konica Corporation
Michl Paul R.
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