Stock material or miscellaneous articles – Composite – Of polyamide
Reexamination Certificate
2001-08-06
2003-07-01
Hampton-Hightower, P. (Department: 1711)
Stock material or miscellaneous articles
Composite
Of polyamide
C428S412000, C428S478800, C428S480000, C428S515000, C428S516000, C428S411100, C427S372200, C427S384000, C427S393100, C427S407100, C264S129000, C264S289300
Reexamination Certificate
active
06586106
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a thermoplastic resin film, and particularly to a thermoplastic resin film excellent in printability, which is obtained by conducting a specific oxidation treatment on a surface of a polyolefin film formed, and then, forming a coating film, the film having ink transfer, adhesion and aging stability, and being satisfactory in back ghost when offset printing using oxidation polymerization type ink is performed on both faces.
BACKGROUND ART
As stickers for outdoor advertisements and labels stuck on containers for frozen food, there has previously been used coated paper for paper for the stickers and the labels. However, the coated paper is poor in water resistance, so that one in which a surface of the coated paper is further covered with a polyester film has been used for reinforcing it.
In recent years, for applications requiring water resistance like this, synthetic paper of the polyolefin family satisfactory in water resistance has attracted attention as a hopeful material substituted for the above-mentioned polyester film-covered coated paper.
However, such synthetic paper of the polyolefin family is not necessarily satisfactory in printability and processability because of non-polarity of the polyolefin resin, a raw material therefor. It is therefore generally used after appropriate surface treatments have been conducted.
As one of such surface treatments, a method of applying a coating solution after an oxidation treatment has been conducted on a surface of a resin sheet is known, and as such an oxidation treatment method, a corona discharge treatment or a flame treatment is known. As the coating solution, specifically, the use of a cationic antistatic agent or an amphoteric antistatic agent is disclosed in JP-A-50-161478 (the term “JP-A” as used herein means an “unexamined published Japanese patent application”), JP-B-59-27769 (the term “JP-B” as used herein means an “examined Japanese patent publication”), JP-B-2-2910, etc. For example, JP-B-2-2910 discloses a water-soluble coating solution comprising a water-soluble polymer obtained by making quaternary a tertiary nitrogen atom of a polymer formed by CH
2
═CR
1
—COOANR
3
R
4
, CH
2
═CR
1
—COOR
2
and another hydrophobic vinyl monomer (in each formula, R
1
is a hydrogen atom or a methyl group, R
2
is an alkyl group having from 1 to 8 carbon atoms, R
3
and R
4
are each a hydrogen atom or an alkyl group having from 1 to 2 carbon atoms, and A is an alkylene group having from 2 to 6 carbon atoms) with a cationizing agent to convert it to a quaternary compound, a water-soluble polyaminepolyamide-epichlorohydrin adduct and a polyethyleneimine.
On the other hand, in JP-A-53-8380, there is described a conductive agent having an antistatic performance comprising a polymer having repeating units represented by the following general formula (II):
(in the formula, R represents a hydrogen atom or a methyl group, R
1
and R
2
each represents a methyl group or an ethyl group, R
3
and R
4
each represents a methyl group, an ethyl group, —(—CH
2
—CH
2
—O—)
m
—H (m is an integer of from 1 to 4) or a benzyl group, R
5
represents an alkyl group having from 1 to 18 carbon atoms, an alkenyl group or —(—CH
2
—CH
2
—O—)
p
—H (p is an integer of from 1 to 4), X
−
represents a halogen ion, A represents an alkylene group which may be substituted, and n usually represents an integer of from 10
1
to 10
4
.)
Further, in each of JP-B-40-12302, JP-B-53-6676 and JP-A-57-149363, it is described that polyethyleneimine or an ethyleneimine-ethyleneurea copolymer is applied as a primer (coating agent). In particular, in JP-A-1-141736, it is disclosed that modified polyethyleneimine as represented by the following chemical formula is applied for obtaining transfer stability of ultraviolet curing type ink for a long period of time:
(in the formula, A represents —NHR
4
or a polyaminepolyamide residue, R
1
to R
4
are each independently a hydrogen atom, an alkyl or alkenyl group having from 1 to 24 carbon atoms, an aliphatic cyclic hydrocarbon group or a benzyl group, but at least one thereof is a group other than a hydrogen atom, m is from 0 to 300, and n, p and q are each from 1 to 300.)
However, such a surface oxidation treatment and the coating of the antistatic agent or the primer, particularly the above-mentioned alkyl, alkenyl and aliphatic hydrocarbon, or benzyl-modified polyethyleneimine provides printed matter which sufficiently fit for practical applications in printing using ultraviolet curing type ink. However, when offset printing using oxidation polymerization type ink is performed on both faces, printing of a back face several days after printing of a front face causes the occurrence of poor ink transfer from a pattern of the front face to a pattern of the back face, which sometimes exerts on the pattern of the back face such an influence that printed matter is difficult to fit for practical applications. This phenomenon is called back ghost.
An object of the invention is to provide a thermoplastic resin film excellent in printability, which has antistatic properties and water resistance, and generates no back ghost when double-face offset printing with oxidation polymerization type ink is performed.
DISCLOSURE OF THE INVENTION
The invention has discovered that the generation of the above-mentioned back ghost is improved by forming a specific hydroxy-modified imine polymer on a surface of a thermoplastic resin film.
That is to say, there is provided a thermoplastic resin film satisfactory in printability characterized by having on a surface thereof a hydroxy-modified imine polymer containing repeating units represented by the following general formula (I) in an amount of 5 mol % or more based on the total of repeating units:
(in the formula, R
1
and R
2
are each independently a hydrogen atom, or a straight chain or branched alkyl group within the range of 1 to 10 carbon atoms, an alkyl group having an alicyclic structure or an aryl group, R
3
, R
4
, R
5
, R
6
, R
7
, R
8
and R
9
are each independently a hydrogen atom, or an alkyl group within the range of 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, an alkylaryl group, groups each alternately forming bonds to form a cyclic structure, an alkyloxyalkyl group having a straight chain, branched or alicyclic structure within the range of 1 to 20 carbon atoms, an alkylaryloxyalkyl group, a hydroxyalkyl group having a straight chain, branched or alicyclic structure within the range of 1 to 20 carbon atoms or an aryl group-containing hydroxyalkyl group, h is an integer ranging from 0 to 4, i is an integer ranging from 1 to 4, j is an integer ranging from 0 to 4, k is an integer ranging from 0 to 4 and m is an integer ranging from 2 to 6.)
In the film having the hydroxyimine copolymer on the surface thereof like this, volatile components generated in a drying process of ink after printing of the front face are poorly adsorbed by the back face of the sheet, when offset printing using oxidation polymerization type ink is performed, compared with a film obtained by coating and drying an aqueous solution containing the above-mentioned conventional alkyl-modified polyethyleneimine, and the ink transfer thereof is uniform in printing of the back face, which causes generation of no ghost. It becomes therefore possible to provide good printed matter.
BEST MODE FOR CARRYING OUT THE INVENTION
The invention is described in more detail below.
(I) Thermoplastic Resin Film Layers
(1) Raw Materials
Thermoplastic resins used include polyolefin resins such as ethylene resins such as high density polyethylene and intermediate density polyethylene, polypropylene resins, polymethyl-1-pentene resins or ethylene-cyclic olefin copolymers, polyamide resins such as nylon-6, nylon-6,6, nylon-6,10 and nylon-6,12, thermoplastic polyester resins such as polyethylene terephthalate and its copolymers, polyethylene naphthalate and aliphatic polyesters, and thermoplastic resins such as polycarbonates, atactic polystyrene, syn
Hayama Kazuhide
Kitamura Kazuhisa
Kitani Yasuo
Shibata Ayako
Shibuya Nobuhiro
Hampton-Hightower P.
Yupo Corporation
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