U.S. patent application number 13/470636 was filed with the patent office on 2012-09-06 for water/oil resistant composition, article treated therewith, and processes for their production.
This patent application is currently assigned to Asahi Glass Company, Limited. Invention is credited to Junsuke KAWANA, Shuichiro Sugimoto.
Application Number | 20120225300 13/470636 |
Document ID | / |
Family ID | 43991696 |
Filed Date | 2012-09-06 |
United States Patent
Application |
20120225300 |
Kind Code |
A1 |
KAWANA; Junsuke ; et
al. |
September 6, 2012 |
WATER/OIL RESISTANT COMPOSITION, ARTICLE TREATED THEREWITH, AND
PROCESSES FOR THEIR PRODUCTION
Abstract
To provide a water/oil resistant composition which can impart a
sufficient water/oil resistance to a base material even though a
fluorinated copolymer having an R.sup.f group with at most 6 carbon
atoms is used, said water/oil resistance being not substantially
influenced by an adjuvant or the pH of dilution water, and which
has little odor; an article treated therewith; and processes for
their production. A water/oil resistant composition having a
fluorinated copolymer dispersed or dissolved in a medium, wherein
the fluorinated copolymer is one having one, some or all of amino
groups in a fluorinated copolymer comprising structural units based
on a monomer (a) having a C.sub.1-6 R.sup.f group and structural
units based on a monomer (b) having an amino group, converted to
form a salt with an organic acid comprising an organic acid having
a pKa of from 2.0 to 4.0.
Inventors: |
KAWANA; Junsuke; (Tokyo,
JP) ; Sugimoto; Shuichiro; (Tokyo, JP) |
Assignee: |
Asahi Glass Company,
Limited
Tokyo
JP
|
Family ID: |
43991696 |
Appl. No.: |
13/470636 |
Filed: |
May 14, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP2010/070142 |
Nov 11, 2010 |
|
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13470636 |
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Current U.S.
Class: |
428/421 ;
526/245 |
Current CPC
Class: |
D21H 19/20 20130101;
D21H 17/34 20130101; Y10T 428/3154 20150401; C08F 220/20 20130101;
C08F 220/24 20130101; D21H 21/16 20130101; C08F 220/36 20130101;
C09K 3/18 20130101; C08F 222/1006 20130101 |
Class at
Publication: |
428/421 ;
526/245 |
International
Class: |
C09D 133/14 20060101
C09D133/14; B32B 27/10 20060101 B32B027/10 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 13, 2009 |
JP |
2009-260164 |
Claims
1. A water/oil resistant composition having a fluorinated copolymer
dispersed or dissolved in a medium, wherein the fluorinated
copolymer is one having some or all of --N(R.sup.5)(R.sup.6) in a
fluorinated copolymer comprising from 50 to 98 mass % of structural
units based on the following monomer (a) and from 2 to 50 mass % of
structural units based on the following monomer (b), converted to
form a salt with an organic acid comprising an organic acid having
a pKa of from 2.0 to 4.0, Monomer (a): a compound represented by
the following formula (1): (Z--Y).sub.nX (1) wherein Z is a
C.sub.1-6 polyfluoroalkyl group or a group represented by the
following formula (2), Y is a bivalent organic group or a single
bond, n is 1 or 2, and X is any one of groups represented by the
following formulae (3-1) to (3-5) when n is 1, or any one of groups
represented by the following formulae (4-1) to (4-4) when n is 2,
C.sub.mF.sub.2m+1O(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)-- (2)
wherein m is an integer of from 1 to 6, and d is an integer of from
1 to 4, --C(R).dbd.CH.sub.2 (3-1) --C(O)OC(R).dbd.CH.sub.2 (3-2)
--OC(O)C(R).dbd.CH.sub.2 (3-3) --OCH.sub.2-.phi.-C(R).dbd.CH.sub.2
(3-4) --OCH.dbd.CH.sub.2 (3-5) wherein R is a hydrogen atom, a
methyl group or a halogen atom, and .phi. is a phenylene group,
--CH[--CH.sub.2).sub.pC(R).dbd.CH.sub.2]-- (4-1)
--CH[--CH.sub.2).sub.pC(O)OC(R).dbd.CH.sub.2]-- (4-2)
--CH[--CH.sub.2).sub.pOC(O)C(R).dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4) wherein R is a hydrogen atom, a
methyl group or a halogen atom, and p is an integer of from 0 to 4,
Monomer (b): a compound represented by the following formula (5):
CH.sub.2.dbd.C(R.sup.4)C(O)O-Q-N(R.sup.5)(R.sup.6) (5) wherein
R.sup.4 is a hydrogen atom or a methyl group, Q is a group having
one, some or all of hydrogen atoms in a C.sub.2-3 alkylene group,
substituted by hydroxy groups, or a C.sub.2-4 alkylene group, and
each of R.sup.5 and R.sup.6 which are independent of each other, is
a benzyl group or a C.sub.1-8 alkyl group, or R.sup.5 and R.sup.6
are bonded to form a morpholino group, a piperidino group or a
pyrrolidinyl group together with the nitrogen atom.
2. The water/oil resistant composition according to claim 1,
wherein the organic acid having a pKa of from 2.0 to 4.0 is at
least one member selected from the group consisting of lactic acid,
citric acid, malic acid and itaconic acid.
3. The water/oil resistant composition according to claim 1, which
further contains an adjuvant.
4. The water/oil resistant composition according to claim 3, which
contains, as the adjuvant, at least one member selected from the
group consisting of an anionic paper strength enhancing agent, an
anionic defoaming agent, an anionic sizing agent and an anionic
chelating agent.
5. The water/oil resistant composition according to claim 1,
wherein the fluorinated copolymer further contains structural units
based on the following monomer (c): Monomer (c): a compound
represented by the following formula (6):
CH.sub.2.dbd.C(R.sup.f)-G-(R.sup.2O).sub.q-R.sup.3 (6) wherein
R.sup.1 is a hydrogen atom or a methyl group, G is a group
represented by the following formula (7-1) or (7-2), R.sup.2 is a
C.sub.2-4 alkylene group and two or more alkylene groups different
in the number of carbon atoms may be contained in one molecule, q
is an integer of from 1 to 50, and R.sup.3 is a hydrogen atom or a
methyl group, --C(O)O--(CH.sub.2).sub.r-- (7-1)
--C(O)O--(CH.sub.2).sub.r--NHC(O)O-- (7-2) wherein r is an integer
of from 0 to 4.
6. The water/oil resistant composition according to claim 1,
wherein the fluorinated copolymer further contains structural units
based on the following monomer (d): Monomer (d): a compound having
a blocked isocyanate group, an alkoxysilyl group, a glycidyl group
or an oxyalkylene group, and a polymerizable unsaturated group, and
not having a polyfluoroalkyl group, and when it has a
polyoxyalkylene group, it has polymerizable unsaturated groups at
both terminals (provided that monomers (a) to (c) are
excluded).
7. Water/oil resistant paper having a base material treated with
the water/oil resistant composition as defined in claim 1.
8. A process for producing a water/oil resistant composition, which
comprises: a step of polymerizing a monomer mixture comprising from
50 to 98 mass % of the following monomer (a) and from 2 to 50 mass
% of the following monomer (b) to obtain a fluorinated copolymer,
and a step of converting some or all of --N(R.sup.5)(R.sup.6) in
the fluorinated copolymer to form a salt with an organic acid
comprising an organic acid having a pKa of from 2.0 to 4.0 and
dispersing or dissolving the fluorinated copolymer in a medium,
Monomer (a): a compound represented by the following formula (1):
(Z--Y).sub.nX (1) wherein Z is a C.sub.1-6 polyfluoroalkyl group or
a group represented by the following formula (2), Y is a bivalent
organic group or a single bond, n is 1 or 2, and X is any one of
groups represented by the following formulae (3-1) to (3-5) when n
is 1, or any one of groups represented by the following formulae
(4-1) to (4-4) when n is 2,
C.sub.mF.sub.2m+1(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)-- (2)
wherein m is an integer of from 1 to 6, and d is an integer of from
1 to 4, --C(R).dbd.CH.sub.2 (3-1) C(O)OC(R).dbd.CH.sub.2 (3-2)
--OC(O)C(R).dbd.CH.sub.2 (3-3) --OCH.sub.2-.phi.-C(R).dbd.CH.sub.2
(3-4) --OCH.dbd.CH.sub.2 (3-5) wherein R is a hydrogen atom, a
methyl group or a halogen atom, and .phi. is a phenylene group,
--CH[--CH.sub.2).sub.pC(R).dbd.CH.sub.2]-- (4-1)
--CH[(CH.sub.2).sub.pC(O)OC(R).dbd.CH.sub.2]-- (4-2)
--CH[(CH.sub.2).sub.pOC(O)C(R).dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O--tm (4-4) wherein R is a hydrogen atom, a
methyl group or a halogen atom, and p is an integer of from 0 to 4,
Monomer (b): a compound represented by the following formula (5):
CH.sub.2.dbd.C(R.sup.4)C(O)O-Q-N(R.sup.5)(R.sup.6) (5) wherein
R.sup.4 is a hydrogen atom or a methyl group, Q is a group having
one, some or all of hydrogen atoms in a C.sub.2-3 alkylene group,
substituted by hydroxy groups, or a C.sub.2-4 alkylene group, and
each of R.sup.5 and R.sup.6 which are independent of each other, is
a benzyl group or a C.sub.1-8 alkyl group, or R.sup.5 and R.sup.6
are bonded to form a morpholino group, a piperidino group or a
pyrrolidinyl group together with the nitrogen atom.
9. The process for producing a water/oil resistant composition
according to claim 8, wherein the organic acid is from 5 to 80
parts by mass per 100 parts by mass of the fluorinated
copolymer.
10. The process for producing a water/oil resistant composition
according to claim 8, wherein the organic acid having a pKa of from
2.0 to 4.0 is at least one member selected from the group
consisting of lactic acid, citric acid, malic acid and itaconic
acid.
11. The process for producing a water/oil resistant composition
according to claim 8, which further contains a step of adding an
adjuvant.
12. The process for producing a water/oil resistant composition
according to claim 11, wherein the adjuvant is at least one member
selected from the group consisting of an anionic paper strength
enhancing agent, an anionic defoaming agent, an anionic sizing
agent and an anionic chelating agent.
13. The process for producing a water/oil resistant composition
according to claim 8, wherein the monomer mixture further contains
the following monomer (c): Monomer (c): a compound represented by
the following formula (6):
CH.sub.2.dbd.C(R.sup.1)-G-(R.sup.2O).sub.q--R.sup.3 (6) wherein
R.sup.1 is a hydrogen atom or a methyl group, G is a group
represented by the following formula (7-1) or (7-2), R.sup.2 is a
C.sub.2-4 alkylene group and two or more alkylene groups different
in the number of carbon atoms may be contained in one molecule, q
is an integer of from 1 to 50, and R.sup.3 is a hydrogen atom or a
methyl group, --C(O)O(CH.sub.2).sub.r-- (7-1)
C(O)O--(CH.sub.2).sub.r--NHC(O)O-- (7-2) wherein r is an integer of
from 0 to 4.
14. The process for producing a water/oil resistant composition
according to claim 8, wherein the monomer mixture further contains
the following monomer (d): Monomer (d): a compound having a blocked
isocyanate group, an alkoxysilyl group, a glycidyl group or an
oxyalkylene group, and a polymerizable unsaturated group, and not
having a polyfluoroalkyl group, and when it has a polyoxyalkylene
group, it has polymerizable unsaturated groups at both terminals
(provided that monomers (a) to (c) are excluded).
15. A process for producing water/oil resistant paper, which
comprises treating a base material with the water/oil resistant
composition obtained by the process as defined in claim 8.
Description
TECHNICAL FIELD
[0001] The present invention relates to a water/oil resistant
composition, an article treated therewith, and processes for their
production.
BACKGROUND ART
[0002] Water/oil resistant paper (hereinafter referred to as
fluorinated water/oil resistant paper) obtained by treating paper
with a water/oil resistant composition containing a fluorinated
copolymer having perfluoroalkyl groups (hereinafter referred to as
R.sup.F groups), has a barrier property against a liquid such as
water or oil and thus is used as e.g. wrapping paper for food
products or a packaging container for food products. Further,
fluorinated water/oil resistant paper has good water resistance and
oil resistance while maintaining air permeability, as different
from water/oil resistant paper other than the fluorinated type, and
thus, it is used also as wrapping paper for fried products which
disfavor moisture remaining inside, as wrapping paper for a
freshness-keeping agent which requires air permeability for its
function, or as wrapping paper for a deoxidant.
[0003] The following two types of methods are available as a method
for treating paper with a water/oil resistant composition.
[0004] (1) A method so-called "internal sizing" wherein a water/oil
resistant composition is added to a pulp slurry before
paper-making.
[0005] (2) A method so-called "external sizing" wherein a water/oil
resistant composition is applied to paper in size press coating
after paper-making, wet pressing and preliminary drying, or a
water/oil resistant composition is applied to paper after
preparation of base paper by means of various coaters or various
printing machines.
[0006] As a water/oil resistant composition containing a
fluorinated copolymer, the following one is, for example,
known.
[0007] A water/oil resistant composition having a fluorinated
copolymer dispersed or dissolved in an aqueous medium, wherein the
fluorinated copolymer is one obtained by converting amino groups
with an acid to form a salt in a fluorinated copolymer obtained by
copolymerizing a (meth)acrylate having a polyfluoroalkyl group
(hereinafter referred to as an R.sup.f group), a
dialkylaminoalkyl(meth)acrylate and a vinyl monomer such as vinyl
acetate (Patent Document 1).
[0008] In such a water/oil resistant composition, as the acid to be
used for conversion of amino groups to form a salt, acetic acid is
employed from the viewpoint of the safety and price.
[0009] However, the water/oil resistant composition obtained by
using acetic acid for conversion of amino groups to form a salt,
has the following problems.
[0010] (i) The fluorinated copolymer having amino groups converted
to form a salt is cationic, and therefore, if an anionic adjuvant
is used at the time of treating paper, not only no adequate
water/oil resistance can be obtainable, but also agglomerates are
likely to be formed thus leading to a trouble in the operation.
[0011] (ii) In the external sizing, there may be a case where water
having a high pH (e.g. water having a pH of at least 8) is used as
dilution water, or in the internal sizing, there may be case where
a pulp having a high pH is used. Also in such a case, not only no
adequate water/oil resistance can be obtainable, but also
agglomerates are likely to be formed, thus leading to a trouble in
the operation.
[0012] (iii) There is an odor specific to acetic acid.
[0013] In recent years, there has been a concern about an
environmental load due to fluorinated compounds having R.sup.E
groups with at least 8 carbon atoms such as perfluorooctanoic acid
and its precursor, analogues, etc., and an attempt is being made by
e.g. US Environmental Protection Agency, to reduce their
accumulation in the environment. Therefore, a substitute water/oil
resistant composition is desired which contains a fluorinated
copolymer having R.sup.F groups with at most 6 carbon atoms or
perfluoropolyether (Patent Document 2).
[0014] However, a substitute water/oil resistant composition
obtained by converting amino groups with acetic acid to form a salt
in a fluorinated copolymer having R.sup.F groups with at most 6
carbon atoms or perfluoropolyether, is inadequate in the water/oil
resistance, as compared with a conventional water/oil resistant
composition obtained by converting amino groups with acetic acid to
form a salt in a fluorinated copolymer having R.sup.F groups with
at least 8 carbon atoms.
PRIOR ART DOCUMENTS
Patent Documents
[0015] Patent Document 1: JP-A-2001-504546
[0016] Patent Document 2: W02005/090423
DISCLOSURE OF INVENTION
Technical Problem
[0017] The present invention is to provide a water/oil resistant
composition which can impart a sufficient water/oil resistance to a
base material even though a fluorinated copolymer having R.sup.f
groups with at most 6 carbon atoms or perfluoropolyether is used,
said water/oil resistance being not substantially influenced by an
adjuvant or the pH of dilution water, and which has little odor; an
article having a sufficient water/oil resistance with a low
environmental load; and processes for their production.
Solution to Problem
[0018] The water/oil resistant composition of the present invention
is a water/oil resistant composition having a fluorinated copolymer
dispersed or dissolved in a medium, wherein the fluorinated
copolymer is one having some or all of --N(R.sup.5)(R.sup.6) in a
fluorinated copolymer comprising from 50 to 98 mass % of structural
units based on the following monomer (a) and from 2 to 50 mass % of
structural units based on the following monomer (b), converted to
form a salt with an organic acid comprising an organic acid having
a pKa of from 2.0 to 4.0,
[0019] Monomer (a): a compound represented by the following formula
(1):
(Z--Y).sub.nX (1)
wherein Z is a C.sub.1-6 R.sup.f group or a group represented by
the following formula (2), Y is a bivalent organic group or a
single bond, n is 1 or 2, and X is any one of groups represented by
the following formulae (3-1) to (3-5) when n is 1, or any one of
groups represented by the following formulae (4-1) to (4-4) when n
is 2,
C.sub.mF.sub.2m+1O(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)--
(2)
wherein m is an integer of from 1 to 6, and d is an integer of from
1 to 4,
--C(R).dbd.CH.sub.2 (3-1)
--C(O)OC(R).dbd.CH.sub.2 (3-2)
--OC(O)C(R).dbd.CH.sub.2 (3-3)
--OCH.sub.2-.phi.-C(R).dbd.CH.sub.2 (3-4)
--OCH.dbd.CH.sub.2 (3-5)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and
.phi. is a phenylene group,
--CH[--CH.sub.2).sub.pC(R).dbd.CH.sub.2]-- (4-1)
--CH[--CH.sub.2).sub.pC(O)OC(R).dbd.CH.sub.2]-- (4-2)
--CH[--CH.sub.2).sub.pOC(O)C(R).dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and
p is an integer of from 0 to 4,
[0020] Monomer (b): a compound represented by the following formula
(5):
CH.sub.2.dbd.C(R.sup.4)C(O)O-Q-N(R.sup.5)(R.sup.6) (5)
wherein R.sup.4 is a hydrogen atom or a methyl group, Q is a group
having one, some or all of hydrogen atoms in a C.sub.2-3 alkylene
group, substituted by hydroxy groups, or a C.sub.2-4 alkylene
group, and each of R.sup.5 and R.sup.6 which are independent of
each other, is a benzyl group or a C.sub.1-8 alkyl group, or
R.sup.5 and R.sup.6 are bonded to form a morpholino group, a
piperidino group or a pyrrolidinyl group together with the nitrogen
atom.
[0021] The organic acid having a pKa of from 2.0 to 4.0 is
preferably at least one member selected from the group consisting
of lactic acid, citric acid, malic acid and itaconic acid.
[0022] The water/oil resistant composition of the present invention
preferably further contains an adjuvant.
[0023] It may contains, as the adjuvant, at least one member
selected from the group consisting of an anionic paper strength
enhancing agent, an anionic defoaming agent, an anionic sizing
agent and an anionic chelating agent.
[0024] The above fluorinated copolymer preferably further contains
structural units based on the following monomer (c):
[0025] Monomer (c): a compound represented by the following formula
(6):
CH.sub.2.dbd.C(R.sup.1)-G-(R.sup.2O).sub.q--R.sup.3 (6)
wherein R.sup.1 is a hydrogen atom or a methyl group, G is a group
represented by the following formula (7-1) or (7-2), R.sup.2 is a
C.sub.2-4 alkylene group and two or more alkylene groups different
in the number of carbon atoms may be contained in one molecule, q
is an integer of from 1 to 50, and R.sup.3 is a hydrogen atom or a
methyl group,
--C(O)O--(CH.sub.2).sub.r (7-1)
--C(O)O--(CH.sub.2).sub.r--NHC(O)O-- (7-2)
wherein r is an integer of from 0 to 4.
[0026] The above fluorinated copolymer preferably further contains
structural units based on the following monomer (d):
[0027] Monomer (d): a compound having a blocked isocyanate group,
an alkoxysilyl group, a glycidyl group or an oxyalkylene group, and
a polymerizable unsaturated group, and not having a polyfluoroalkyl
group, and when it has a polyoxyalkylene group, it has
polymerizable unsaturated groups at both terminals (provided that
monomers (a) to (c) are excluded).
[0028] The water/oil resistant paper of the present invention is
one having a base material treated with the water/oil resistant
composition of the present invention.
[0029] The process for producing a water/oil resistant composition
of the present invention comprises a step of polymerizing a monomer
mixture comprising from 50 to 98 mass % of the above monomer (a)
and from 2 to 50 mass % of the above monomer (b) to obtain a
fluorinated copolymer, and a step of converting some or all of
--N(R.sup.5)(R.sup.6) in the fluorinated copolymer to form a salt
with an organic acid comprising an organic acid having a pKa of
from 2.0 to 4.0 and dispersing or dissolving the fluorinated
copolymer in a medium.
[0030] The above organic acid is preferably from 5 to 80 parts by
mass per 100 parts by mass of the fluorinated copolymer.
[0031] The above organic acid having a pKa of from 2.0 to 4.0 is
preferably at least one member selected from the group consisting
of lactic acid, citric acid, malic acid and itaconic acid.
[0032] The process for producing a water/oil resistant composition
of the present invention preferably further contains a step of
adding an adjuvant.
[0033] The adjuvant may be at least one member selected from the
group consisting of an anionic paper strength enhancing agent, an
anionic defoaming agent, an anionic sizing agent and an anionic
chelating agent.
[0034] The above monomer mixture preferably further contains the
above monomer (c).
[0035] The above monomer mixture preferably further contains the
above monomer (d).
[0036] The process for producing water/oil resistant paper of the
present invention comprises treating a base material with the
water/oil resistant composition obtained by the process of the
present invention.
Advantageous Effects of Invention
[0037] The water/oil resistant composition of the present invention
can impart a sufficient water/oil resistance to a base material
even though a fluorinated copolymer having R.sup.f groups with at
most 6 carbon atoms or perfluoropolyether is used, and the
water/oil resistance is not substantially influenced by the pH of
dilution water or the adjuvant used at the time of treating paper
with the water/oil resistant composition. Further, the composition
has little odor.
[0038] By the process for producing a water/oil resistant
composition of the present invention, it is possible to produce a
water/oil resistant composition, whereby a sufficient water/oil
resistance can be imparted to a base material even though a
fluorinated copolymer having R.sup.f group with at most 6 carbon
atoms or perfluoropolyether is used, and the water/oil resistance
is not substantially influenced by the pH of dilution water or the
adjuvant used at the time of treating paper with the water/oil
resistant composition, and further the odor is little.
[0039] The article of the present invention has a sufficient
water/oil resistance with a low environmental load.
[0040] By the process for producing an article of the present
invention, it is possible to produce an article having a sufficient
water/oil resistance with a low environmental load.
Description of Embodiments
[0041] In this specification, a compound represented by the formula
(1) will be referred to as a compound (1). Compounds represented by
other formulae will also be referred to in the same manner.
Further, in this specification, a group represented by the formula
(2) will be referred to as a group (2). Groups represented by other
formulae will also be referred to in the same manner. Further, a
(meth)acrylate in this specification means an acrylate or a
methacrylate. Further, a monomer in this specification means a
compound having a polymerizable unsaturated group. Further, an
R.sup.f group in this specification is a group having one, some or
all of hydrogen atoms in an alkyl group substituted by fluorine
atoms, and an R.sup.F group is a group having all hydrogen atoms in
an alkyl group substituted by fluorine atoms.
<Water/Oil Resistant Composition>
[0042] A water/oil resistant composition of the present invention
is one having a fluorinated copolymer dispersed or dissolved in a
medium, wherein the fluorinated copolymer is one having some or all
of --N(R.sup.5)(R.sup.6) in a fluorinated copolymer comprising
structural units based on a monomer (a) and structural units based
on a monomer (b), and, as the case requires, structural units based
on a monomer (c), structural units based on a monomer (d) and
structural units based on a monomer (e), converted to form a salt
with a specific organic acid, and, as the case requires, an
adjuvant may be added thereto, or it may be diluted with water.
(Monomer (a))
[0043] Monomer (a) is a compound (1).
(Z--Y).sub.nX (1)
[0044] Z is a C.sub.1-6 R.sup.f group or a group (2).
C.sub.mF.sub.2m+1O(CF.sub.2CF(CF.sub.3)O).sub.dCF(CF.sub.3)--
(2)
wherein m is an integer of from 1 to 6, and d is an integer of from
1 to 4.
[0045] Z and C.sub.mF.sub.2m+.sub.1 may be linear or branched, but
preferably linear. Z is preferably a C.sub.1-6 R.sup.F group, more
preferably a 0.sub.3-6 R.sup.f group, further preferably
F(CF.sub.2).sub.4--, F(CF.sub.2).sub.5-- or
F(CF.sub.2).sub.6--.
[0046] Y is a bivalent organic group or a single bond.
[0047] Y is preferably a bivalent organic group having no fluorine
atom, more preferably a group (8).
--R.sup.M-T-R.sup.N-- (8)
wherein each of R.sup.M and R.sup.N which are independent of each
other, is a single bond or a C.sub.1-22 hydrocarbon group (which
may contain an etheric oxygen atom), T is a single bond,
--OC(O)NH--, --C(O)NH--, --OC(O)O--, --C(O)O--, --SO.sub.2NH--,
--SO.sub.2N(R')-- or --NHCONH--, and R' is a C.sub.1-6 alkyl
group.
[0048] The group (8) is preferably a C.sub.1-10 alkylene group,
--CH.dbd.CHCH.sub.2--, --(CH.sub.2CH(R'')O).sub.jCH.sub.2CH.sub.2--
(wherein j is an integer of from 1 to 10, and R'' is a hydrogen
atom or a methyl group), --C.sub.2H.sub.4OC(O)NHC.sub.2H.sub.4--,
--C.sub.2H.sub.4OC(O)0C.sub.2H.sub.4-- or --C(O)OC.sub.2H.sub.4--,
more preferably a C.sub.1-10 alkylene group, further preferably
-CH.sub.2--, --CH.sub.2CH.sub.2--, --(CH.sub.2).sub.11-- or
--CH.sub.2CH.sub.2CH(CH.sub.3)--.
[0049] n is 1 or 2.
[0050] When n is 2, two (Z--Y) present in one molecule may be the
same or different.
[0051] X is any one of groups (3-1) to (3-5) when n is 1, or any
one of groups (4-1) to (4-4) when n is 2.
--C(R).dbd.CH.sub.2 (3-1)
--C(O)OC(R).dbd.CH.sub.2 (3-2)
--OC(O)C(R).dbd.CH.sub.2 (3-3)
--OCH.sub.2-T-C(R).dbd.CH.sub.2 (3-4)
--OCH.dbd.CH.sub.2 (3-5)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and
.phi. is a phenylene group,
CH[--CH.sub.2).sub.pC(R).dbd.CH.sub.2F (4-1)
--CH[--CH.sub.2).sub.pC(O)OC(R).dbd.CH.sub.2]-- (4-2)
--CH[--CH.sub.2).sub.pOC(O)C(R).dbd.CH.sub.2]-- (4-3)
--OC(O)CH.dbd.CHC(O)O-- (4-4)
wherein R is a hydrogen atom, a methyl group or a halogen atom, and
p is an integer of from 0 to 4.
[0052] X is preferably the group (3-3) or the group (4-4), more
preferably the group (3-3) in that the solubility in a solvent is
thereby excellent, and the solution polymerization can easily be
carried out.
[0053] R is preferably a hydrogen atom, a halogen atom (such as a
fluorine atom or a chlorine atom) or a C.sub.1-3 alkyl group, in
that the polymerizability is thereby excellent. The alkyl group is
more preferably a methyl group.
[0054] The monomer (a) is preferably a compound wherein Z is a
C.sub.1-6 (preferably C.sub.3-6) R.sup.E group, Y is a bivalent
organic group having no fluorine atom, X is the group (3-3) (when n
is 1) or the group (4-4) (when n is 2), and R is a hydrogen atom, a
methyl group or a halogen atom, particularly preferably a compound
(1-1).
F(CF.sub.2).sub.sY.sup.1OC(O)C(R).dbd.CH.sub.2 (1-1)
wherein s is an integer of from 1 to 6 (preferably from 3 to 6), R
is a hydrogen atom, a methyl group or a halogen atom, and Y.sup.1
is a C.sub.1-10 alkylene group.
[0055] As the compound (1-1), the following compounds are
preferred.
F(CF.sub.2).sub.6CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.sub.2,
F(CF.sub.2).sub.6CH.sub.2CH.sub.2OC(O)CH.dbd.CH.sub.2,
F(CF.sub.2).sub.4CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.sub.2.
[0056] As the monomer (a), one type may be used alone, or two or
more types may be used in combination.
(Monomer (b))
[0057] The monomer (b) is a compound (5).
CH.sub.2.dbd.C(R.sup.4)C(O)O-Q-N(R.sup.5)(R.sup.6) (5)
[0058] R.sup.4 is a hydrogen atom or a methyl group.
[0059] Q is a group having one, some or all of hydrogen atoms in a
C.sub.2-3 alkylene group substituted by hydroxy groups, or a
C.sub.2-4 alkylene group.
[0060] Q is preferably a C.sub.2-4 alkylene group.
[0061] Each of R.sup.5 and R.sup.6 which are independent of each
other, is a benzyl group or a C.sub.1-8 alkyl group, or R.sup.5 and
R.sup.6 are bonded to form a morpholino group, a piperidino group
or a pyrrolidinyl group together with the nitrogen atom.
[0062] Each of R.sup.5 and R.sup.6 is preferably a C.sub.1-8 alkyl
group, particularly preferably a methyl group or an ethyl
group.
[0063] The monomer (b) includes acrylates and methacrylates of the
following amino alcohols.
[0064] Dimethylamino-2-ethanol, diethylamino-2-ethanol,
diproyplamino-2-ethanol, diisobutylamino-2-ethanol,
N-tert-butylamino-2-ethanol, N-tert-butyl-N-methylamino-2-ethanol,
morpholino-2-ethanol, N-ethyl-N-(ethyl-2-hexyl)amino-2-ethanol,
piperizino-2-ethanol, (pyrrolidinyl-1)-2-ethanol,
diethylamino-3-propanol-1, diethylamino-2-propanol-1,
dimethylamino-1-propanol-2, diethylamino-4-butanol-1,
diisobutylamino-4-butanol-1, dimethylamino-1-butanol-2, and
dimethylamino-4-butanol-2.
[0065] These esters may be synthesized, for example, by a method
disclosed in U.S. Pat. No. 2,138,763. The monomer (b) is
particularly preferably dimethylaminoethyl methacrylate or
diethylaminoethyl methacrylate.
[0066] As the monomer (b), one type may be used alone, or two or
more types may be used in combination.
(Monomer (c))
[0067] The monomer (c) is a compound (6).
CH.sub.2.dbd.C(R.sup.1)-G-(R.sup.2O).sub.q--R.sup.3 (6)
[0068] R.sup.1 is a hydrogen atom or a methyl group.
[0069] G is a group (7-1) or a group (7-2).
--C(O)O--(CH.sub.1-2).sub.r--tm (7-1)
--C(O)O--(CH.sub.2).sub.r--NHC(O)O-- (7-2)
wherein r is an integer of from 0 to 4.
[0070] G is preferably the group (7-1).
[0071] R.sup.2 is a C.sub.2-4 alkylene group. Two or more alkylene
groups different in the number of carbon atoms may be contained in
one molecule. In such a case, the arrangement of two or more
oxyalkylene groups different in the number of carbon atoms may be
block or random.
[0072] q is an integer of from 1 to 50, preferably from 1 to 9,
more preferably from 1 to 4.
[0073] R.sup.3 is a hydrogen atom or a methyl group.
[0074] R.sup.3 is more preferably a hydrogen atom.
[0075] As the monomer (c), the following compounds are
preferred.
[0076] 2-Hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate,
2-hydroxybutyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,
polyoxyethylene glycol mono(meth)acrylate, polyoxypropylene glycol
mono(meth)acrylate, and methoxypolyoxyethylene
glycol(meth)acrylate.
[0077] The monomer (c) is particularly preferably 2-hydroxyethyl
methacrylate. As the monomer (c), one type may be used alone, or
two or more types may be used in combination.
(Monomer (d))
[0078] The monomer (d) is a compound having a blocked isocyanate
group, an alkoxysilyl group, a glycidyl group or an oxyalkylene
group, and a polymerizable unsaturated group, and not having an
R.sup.t group, and when it has a polyoxyalkylene group, it has
polymerizable unsaturated groups at both terminals (provided that
monomers (a) to (c) are excluded).
[0079] As the compound having a blocked isocyanate group and a
polymerizable unsaturated group, the following compounds may be
mentioned.
[0080] A 2-butanoneoxime adduct of 2-isocyanate
ethyl(meth)acrylate, a pyrazole adduct of 2-isocyanate
ethyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of 2-isocyanate
ethyl(meth)acrylate, a 3-methylpyrazole adduct of 2-isocyanate
ethyl(meth)acrylate, an .epsilon.-caprolactam adduct of
2-isocyanate ethyl(meth)acrylate, a 2-butanoneoxime adduct of
3-isocyanate propyl(meth)acrylate, a pyrazole adduct of
3-isocyanate propyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of
3-isocyanate propyl(meth)acrylate, 3-methylpyrazole adduct of
3-isocyanate propyl(meth)acrylate, an .epsilon.-caprolactam adduct
of 3-isocyanate propyl(meth)acrylate, a 2-butanoneoxime adduct of
4-isocyanate butyl(meth)acrylate, a pyrazole adduct of 4-isocyanate
butyl(meth)acrylate, a 3,5-dimethylpyrazole adduct of 4-isocyanate
butyl(meth)acrylate, a 3-methylpyrazole adduct of 4-isocyanate
butyl(meth)acrylate, and an .epsilon.-caprolactam adduct of
4-isocyanate butyl(meth)acrylate.
[0081] As the compound having an alkoxysilyl group and a
polymerizable unsaturated group, a compound (9) may be
mentioned.
CH.sub.2.dbd.C(R.sup.7)-D-E-Si(R.sup.a)(R.sup.b)(R.sup.c) (9)
wherein D is --C(O)O-- or a single bond, E is a C.sub.1-4 alkylene
group, each of R.sup.a, R.sup.b and R.sup.c which are independent
of one another, is a C.sub.1-6 alkyl group or a C.sub.1-6 alkoxy
group, and R.sup.7 is a hydrogen atom or a methyl group.
[0082] The compound (9) may, for example, be
3-methacryloyloxypropyl trimethoxysilane, 3-methacryloyloxypropyl
dimethoxymethylsilane, 3-methacryloyloxypropyl triethoxysilane,
3-methacryloyloxypropyl diethoxyethylsilane or
allyltrimethoxysilane.
[0083] As the compound having a glycidyl group and a polymerizable
unsaturated group, the following compounds may be mentioned.
[0084] Glycidyl(meth)acrylate, and polyoxyalkylene glycol
monoglycidyl ether(meth)acrylate.
[0085] As the compound having an oxyalkylene group and having
polymerizable unsaturated groups at both terminals, a compound (10)
may be mentioned.
CH.sub.2.dbd.CR'-D-L-D-CR'.dbd.CH.sub.2 (10)
Wherein L is --(C.sub.2H.sub.4O).sub.i--,
--(C.sub.3H.sub.6O).sub.i--, --(C.sub.4H.sub.8O).sub.i,--, a
C.sub.1-15 linear or branched alkylene group, or a group containing
--NHCO--, wherein i is an integer of from 1 to 200.
[0086] Each D is independently --OC(O)--, --C(O)O-- or a single
bond.
[0087] Each R' is independently a hydrogen atom or a methyl
group.
[0088] The compound (10) may be ethylene glycol di(meth)acrylate,
triethylene glycol di(meth)acrylate, tetraethylene glycol
di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene
glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate,
polytetramethylene glycol di(meth)acrylate, 1,6-hexandiol
di(meth)acrylate, neopentyl glycol di(meth)acrylate, poly(ethylene
glycol-propylene glycol) di(meth)acrylate, poly(ethylene
glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene
glycol-tetramethylene glycol) di(meth)acrylate, diethylene glycol
diglycidyl di(meth)acrylate, polyethylene glycol diglycidyl
di(meth)acrylate, propylene glycol diglycidyl di(meth)acrylate,
polypropylene glycol di(meth)acrylate, glycerin diglycidyl ether
di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate,
allyloxypolyethylene glycol mono(meth)acrylate,
allyloxypoly(ethylene glycol-propylene glycol) mono(meth)acrylate,
glycerin di(meth)acrylate, oxyalkylene glycol mono(meth)acrylate
monoisocyanatoethyl(meth)acrylate, or oxyalkylene glycol
diisocyanatoethyl(meth)acrylate. The compound (10) is preferably
triethylene glycol di(meth)acrylate.
[0089] As the monomer (d), one type may be used alone, or two or
more types may be used in combination.
(Monomer (e))
[0090] The monomer (e) is a monomer other than the monomers (a) to
(d).
[0091] The monomer (e) may, for example, be ethylene, vinylidene
chloride, vinyl chloride,(meth)acrylic acid, vinylidene fluoride,
vinyl acetate, vinyl propionate, vinyl isobutanoate, vinyl
isodecanoate, vinyl stearate, cetyl vinyl ether, dodecyl vinyl
ether, isobutyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl
ether, styrene, .alpha.-methylstyrene, p-methylstyrene,
(meth)acrylamide, N,N-dimethyl(meth)acrylamide,
diacetone(meth)acrylamide, methylol-modified
diacetone(meth)acrylamide, vinyl alkyl ketone, butadiene, isoprene,
chloroprene, benzyl(meth)acrylate, a (meth)acrylate having a
polycyloxane, allyl acetate, N-vinylcarbazole, maleimide or
N-methylmaleimide.
(Fluorinated Copolymer)
[0092] The proportion of structural units based on the monomer (a)
is from 50 to 98 mass %, preferably from 60 to 90 mass %, more
preferably from 60 to 80 mass %, in the structural units (100 mass
%) based on all monomers, in view of the water/oil resistance.
[0093] The proportion of structural units based on the monomer (b)
is from 2 to 50 mass %, preferably from 5 to 30 mass %, more
preferably from 5 to 25 mass %, in the structural units (100 mass
%) based on all monomers, from the viewpoint of the dispersibility
or solubility in the medium.
[0094] The proportion of structural units based on the monomer (c)
is preferably from 0 to 30 mass %, in the structural units (100
mass %) based on all monomers, and with a view to improvement of
the affinity with pulp, it is more preferably from 1 to 25 mass %,
particularly preferably from 5 to 20 mass %.
[0095] The proportion of structural units based on the monomer (d)
is preferably from 0 to 5 mass % in the structural units (100 mass
%) based on all monomers, and from the viewpoint of the durability,
it is more preferably from 0 to 4 mass %, particularly preferably
from 0 to 2 mass %.
[0096] The proportion of structural units based on the monomer (e)
is preferably from 0 to 30 mass % in the structural units (100 mass
%) based on all monomers, and from the viewpoint of the
film-forming property and the barrier property, it is more
preferably from 0 to 10 mass %, particularly preferably from 0 to 1
mass %.
[0097] The proportion of structural units based on a monomer is
obtained by an NMR (nuclear magnetic resonance) analysis and an
elemental analysis. Further, in a case where it cannot be obtained
by an NMR analysis or an elemental analysis, it may be calculated
based on the charged amount of the monomer at the time of the
preparation of the fluorinated copolymer.
[0098] The mass average molecular weight of the fluorinated
copolymer is preferably from 5,000 to 100,000, more preferably from
20,000 to 90,000. When the mass average molecular weight is at
least 5,000, the water/oil resistance will be good. When the mass
average molecular weight is at most 100,000, the film-forming
property and liquid stability will be good.
[0099] The mass average molecular weight of the fluorinated
copolymer is a molecular weight calculated as a polymethyl
methacrylate obtained by a measurement by gel permeation
chromatography, using a calibration curve prepared by using a
standard polymethyl methacrylate sample.
(Organic Acid)
[0100] The organic acid in the present invention is an organic acid
which can convert some or all of --N(R.sup.5)(R.sup.6) in a
fluorinated copolymer to form a salt with the organic acid, and it
is preferred that all are converted to form a salt with the organic
acid. The amount of the organic acid is preferably an amount
whereby it is possible to convert all of --N(R.sup.5)(R.sup.6) in
the fluorinated copolymer to form a salt.
[0101] As the organic acid, an organic acid having a pKa (pKa1 in a
case where a plurality of carboxy groups are present in one
molecule) of from 2.0 to 4.0.
[0102] The organic acid having a pKa of from 2.0 to 4.0 may, for
example, be lactic acid (pKa:3.66), citric acid (pKa1:2.87), malic
acid (pKa1:3.24), itaconic acid (pKa:3.85), tartaric acid
(pKa1:2.82), fumaric acid (pKa1:2.85), succinic acid (pKa1:4.00),
or formic acid (pKa:3.55), and from the viewpoint of the safety,
water dispersibility and stability of the salt-form polymer, it is
preferably one member selected from the group consisting of lactic
acid, citric acid, malic acid and itaconic acid. Particularly
preferred is lactic acid or malic acid.
[0103] As the organic acid, other organic acids having a pKa of
less than 2.0 or more than 4.0 may be additionally used within a
range not to impair the effects of the present invention. As such
other organic acids, acetic acid (pKa:4.56), adipic acid (pKa:4.26,
5.03), propionic acid (pKa:4.67), oxalic acid (pKa:1.04, 3.82),
maleic acid (pKa:1.75), etc. may be mentioned. The content of such
other organic acids is preferably at most 40 mass %, more
preferably at most 30 mass %, particularly preferably from 0 to 10
mass %, based on all organic acids.
[0104] The pKa is values disclosed in "Kagaku Binran Kisohen II"
(3rd edition, complied by the Chemical Society of Japan, published
by Maruzen).
(Medium)
[0105] Conversion of --N(R.sup.5)(R.sup.6) in the fluorinated
copolymer to form a salt with an organic acid, can be carried out
by using a medium.
[0106] As the medium to be used for the conversion to form a salt,
an aqueous medium is preferred from the viewpoint of the handling
efficiency and safety.
[0107] As the aqueous medium, water or an azeotropic mixture
containing water may be mentioned, and water is preferred.
[0108] As the azeotropic mixture containing water, a mixture of
water with the following compound is preferred.
[0109] The compound is preferably at least one member selected from
the group consisting of propylene glycol, propylene glycol
monomethyl ether, dipropylene glycol monomethyl ether, dipropylene
glycol, tripropylene glycol and diacetone alcohol.
[0110] The aqueous medium is preferably one wherein the content of
a volatile organic solvent is at most 1 mass %.
[0111] The volatile organic solvent is meant for an organic solvent
which evaporates when stored at room temperature. Specifically, it
is an organic solvent having a boiling point of at most 100.degree.
C. Here, a solvent forming an azeotropic mixture together with
water is considered to be not included in such a volatile organic
solvent.
[0112] The amount of the medium is suitably selected within a range
of from 150 to 100,000 parts by mass, preferably from 150 to 1,000
parts by mass, per 100 parts by mass of the fluorinated
copolymer.
(Adjuvant)
[0113] In the internal sizing, known internal sizing agents to be
used in a common step for preparation of paper making materials,
may be used in combination. Here, there is no particular
restriction with respect to the ionic nature of the internal sizing
agents, the addition order of the internal sizing agents or the
number of the internal sizing agents. As such known internal sizing
agents, a coagulating agent, a retention aid, a sizing agent, a
paper strength enhancing agent, a pigment, a dye, a pH adjusting
agent, etc. may be mentioned.
[0114] Specific examples of the coagulating agent or retention aid
include, for example, aluminum sulfate, polyammonium chloride,
polyammonium nitrate/sulfate, polydiallyldimethyl ammonium
chloride, polyethyleneimine, polyamine, a diallylamine/acrylamide
copolymer, polyamideamine epichlorohydrin, cationic starch,
amphoteric polyacrylamide, anionic polyacrylamide, cationic
polyacrylamide, a polyamide epoxy resin, a polyamine
epichlorohydrin resin, colloidal silica, a polyphenol resin,
polyvinylamine, a phenol/formaldehyde resin, polyethylene oxide,
carboxymethylcellulose, bentonite, etc.
[0115] The adjuvant in the external sizing may, for example, be a
paper strength enhancing agent (various starches, resins, etc.), a
sizing agent, a penetrating agent, a defoaming agent, a chelating
agent, a dye, a pigment, a dyestuff, a binder, an acid, an alkali,
an alginate or aluminum sulfate.
[0116] The resin as an adjuvant may, for example, be polyvinyl
alcohol, a polyamideamine resin, a polyamideamine
epichlorohydrin-modified resin, urea or a melamine formaldehyde
condensate or precondensate, a methylol/dihydroxyethylene/urea or
its derivative, uronate, a methylol/ethylene/urea, a
methylol/propylene/urea, a methylol/triazone, or a
dicyandiamide/formaldehyde condensate.
[0117] The penetrating agent as an adjuvant may, for example, be a
dendrimer alcohol type penetrating agent or an acetylene glycol
type penetrating agent.
[0118] The defoaming agent as an adjuvant may, for example, be a
silicone type defoaming agent, a dendrimer alcohol type defoaming
agent, or an acetylene glycol type defoaming agent.
[0119] In the present invention, an anionic, cationic or nonionic
adjuvant may be used.
[0120] The anionic adjuvant is preferably at least one member
selected from the group consisting of an anionic paper strength
enhancing agent, an anionic defoaming agent, an anionic sizing
agent and an anionic chelating agent.
[0121] The anionic paper strength enhancing agent may, for example,
be a phosphate starch, an oxidized starch, an amphoteric starch, an
enzyme-modified starch, a carboxymethylated guar gum, an oxidized
guar gum, a carboxymethylcellulose NA, an anionic polyvinyl
alcohol, an acrylic resin, an anionic polyacrylamide, an amphoteric
polyacrylamide, an acrylamide/acrylic acid copolymer, a
styrene/butadiene copolymer, a methyl methacrylate/butadiene
copolymer, an acrylonitrile/butadiene copolymer, an acrylate
copolymer, an acrylonitrile/styrene copolymer, a colloidal silica
complex particle emulsion, or an olefin resin emulsion. Further, as
a raw material for the above various starches, corn, potato, wheat,
tapioca, sago palm or rice may, for example, be mentioned.
[0122] The anionic defoaming agent may, for example, be a fatty
acid defoaming agent, a wax defoaming agent or an aliphatic alcohol
derivative.
[0123] The anionic sizing agent may, for example, be a rosin soap
sizing agent, a rosin emulsion sizing agent, a specially modified
rosin sizing agent, an alkenyl succinic acid, an alkenyl succinic
anhydride, an anionic alkyl ketene dimer, an olefin resin, a
styrene resin, a styrene/acrylic resin, a styrene/maleic
acid/acrylic resin, or a wax sizing agent.
[0124] The anionic chelating agent may, for example, be
ethylenediamine tetraacetic acid or its salt, or diethylenetriamine
pentaacetic acid or its salt.
[0125] Other anionic adjuvants include, for example, an anionic
water-dispersed pigment, a pigment (such as kaolin clay, talc,
calcium carbonate, titanium oxide or silica), a scale-preventing
agent, an anticeptic, a release agent (a fatty acid calcium salt,
or polyethylene wax), a coating binder (such as a styrene/butadiene
copolymer, an acrylic acid ester or a polylactic acid), etc.
[0126] The cationic adjuvant may, for example, be a cationic sizing
agent such as wax, AKD, ASA or a styrene resin, or a cationic paper
strength enhancing agent such as a cationic starch, a
cation-modified polyvinyl alcohol, a polyacrylamide, a polyamide
epichlorohydrin resin, a polyamine epichlorohydrin resin, a
melamine resin or a polyamide epoxy resin.
[0127] The nonionic adjuvant may, for example, be a nonionic paper
strength enhancing agent such as polyvinyl alcohol, or a nonionic
defoaming agent.
[0128] The amount of such adjuvant is preferably from 0.001 to 100
parts by mass, more preferably from 0.01 to 10 parts by mass, per
100 parts by mass of the medium.
<Process for Producing Water/Oil Resistant Composition>
[0129] The process for producing a water/oil resistant composition
of the present invention is a process comprising the following
steps (I) to (IV):
[0130] (I) a step of polymerizing the monomers (a) and (b), and, as
the case requires, the monomers (c), (d) and (e) to obtain a
fluorinated copolymer,
[0131] (II) a step of converting some or all of
--N(R.sup.5)(R.sup.6) in the fluorinated copolymer to form a salt
with a specific organic acid, and dispersing or dissolving the
fluorinated copolymer in a medium,
[0132] (III) as the case requires, a step of removing a solvent
used in the step (I), and
[0133] (IV) as a case requires, a step of adding an adjuvant or
diluting the composition with a medium.
(Step (I))
[0134] As the polymerization method, a solution polymerization
method or an emulsion polymerization may, for example, be
mentioned, and from the viewpoint of the polymerization stability,
a solution polymerization method is preferred.
[0135] The solution polymerization method is a method of
polymerizing the monomer mixture in a solvent, if necessary in the
presence of a polymerization initiator or a chain transfer
agent.
[0136] As the solvent, the following compounds may be
mentioned.
[0137] A ketone (such as acetone, methyl ethyl ketone or methyl
isobutyl ketone), an alcohol (such as isopropyl alcohol), a
diacetone alcohol, an ester (such as ethyl acetate or butyl
acetate), an ether (such as diisopropyl ether), an aliphatic
hydrocarbon, an aromatic hydrocarbon, a halogenated hydrocarbon
(such as perchloroethylene, trichloro-1,1,1-ethane,
trichlorotrifluoroethane or dichloropentafluoropropane),
N,N-dimethylformamide, N-methyl-pyrrolidone-2, butyroacetone,
dimethylsulfoxide, glycol ether, water, derivatives thereof,
etc.
[0138] As the solvent, one type may be used alone, or two or more
types may be used in combination.
[0139] As the solvent, from the viewpoint of the operation
efficiency in the step (III), an organic solvent having a
relatively low boiling point, or an organic solvent which forms an
azeotropic mixture with water, is preferred.
[0140] As the organic solvent having a relatively low boiling
point, one having a boiling point under 1.times.10.sup.5 Pa
(hereinafter simply referred to as a boiling point) of at most
80.degree. C. is preferred. Specifically, acetone or methanol may
be mentioned. The organic solvent which forms an azeotropic mixture
with water may, for example, be 2-propyl alcohol, methyl isobutyl
ketone, methyl ethyl ketone, or a mixed solvent thereof.
[0141] As the polymerization initiator, ammonium persulfate,
potassium persulfate, a peroxide (such as benzyl peroxide, lauryl
peroxide, succinyl peroxide or tert-butyl peroxypivalate) or an azo
compound may, for example, be preferred.
[0142] The azo compound may, for example, be
dimethyl-2,2'-azobis(2-methylpropionate),
2,2'-azobis(2-methylbutyronitrile), 4,4'-azobis(4-cyanovaleric
acid), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis[2-(2-imidazolin-2-yl)propane],
2,2'-azobisisobutyronitrile,
1,1'-azobis(2-cyclohexane-1-carbonitrile) or
2,2'-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamid-
e}.
[0143] The polymerization initiator is more preferably ammonium
persulfate, dimethyl-2,2'-azobis(2-methylpropionate) or
4,4'-azobis(4-cyanovaleric acid).
[0144] The chain transfer agent may, for example, be an
alkylmercaptan (such as tert-dodecylmercaptan, n-dodecylmercaptan
or stearyl mercaptan), aminoethanethiol, mercaptoethanol,
thioglycolic acid, 2-mercaptopropionic acid or
2,4-diphenyl-4-methyl-1-pentene.
[0145] The proportion of the monomer (a) is from 50 to 98 mass %,
preferably from 60 to 90 mass %, more preferably from 60 to 80 mass
%, in the monomer mixture (100 mass %) from the viewpoint of the
water/oil resistance.
[0146] The proportion of the monomer (b) is from 2 to 50 mass %,
preferably from 5 to 30 mass %, more preferably from 5 to 25 mass
%, in the monomer mixture (100 mass %), from the viewpoint of the
dispersibility or solubility in the medium.
[0147] The proportion of the monomer (c) is preferably from 0 to 30
mass % in the monomer mixture (100 mass %), and with a view to
improvement of the affinity with pulp, it is more preferably from 1
to 25 mass %, particularly preferably from 5 to 20 mass %.
[0148] The proportion of the monomer (d) is preferably from 0 to 5
mass % in the monomer mixture (100 mass %), and from the viewpoint
of the durability, it is more preferably from 0 to 4 mass %,
particularly preferably from 0 to 2 mass %.
[0149] The proportion of the monomer (e) is preferably from 0 to 30
mass % in the monomer mixture (100 mass %), and from the viewpoint
of the film-forming property and barrier property, it is more
preferably from 0 to 5 mass %, particularly preferably from 0 to 1
mass %.
[0150] The concentration of the monomer mixture is preferably from
5 to 60 mass %, more preferably from 10 to 40 mass %, in 100 mass %
of all materials (including the solvent).
[0151] The amount of the polymerization initiator is preferably
from 0.1 to 1.5 parts by mass, per 100 parts by mass of the monomer
mixture.
[0152] The amount of the chain transfer agent is preferably from 0
to 1 part by mass, per 100 parts by mass of the monomer
mixture.
[0153] The polymerization temperature is preferably within a range
of from room temperature to the boiling point of the solution, and
with a view to efficiently using the polymerization initiator, it
is preferably at least the half-life temperature of the
polymerization initiator, more preferably from 30 to 90.degree.
C.
(Step (II))
[0154] A specific organic acid and a medium are added to the
fluorinated copolymer obtained in the step (I) to convert some or
all of --N(R.sup.5)(R.sup.6) in the fluorinated copolymer to form a
salt and thereby to disperse or dissolve the fluorinated copolymer
in the medium.
[0155] The organic acid and the medium may be added in the order of
the organic acid and then the medium, or the organic acid and the
medium may be added at the same time.
[0156] As the specific organic acid, an organic acid comprising the
above-described organic acid having a pKa of from 2.0 to 4.0 is
used. The amount of the organic acid (including other organic
acids) is preferably from 5 to 80 parts by mass, more preferably
from 10 to 50 parts by mass, particularly preferably from 20 to 40
parts by mass, per 100 parts by mass of the fluorinated
copolymer.
[0157] As the medium, the above-mentioned aqueous medium may be
used in the same manner. The amount of the medium to be used at the
time of the conversion to form a salt (not including the
after-described medium for dilution) is preferably from 200 to 600
parts by mass, more preferably from 200 to 500 parts by mass,
particularly preferably from 250 to 450 parts by mass, per 100
parts by mass of the fluorinated copolymer from the viewpoint of
the dispersibility or solubility of the fluorinated copolymer in
the medium.
(Step (III))
[0158] Removal of the solvent is carried out, for example, by
removing an organic solvent having a low boiling point from the
solvent or the mixture of the solvent with water out of the system
by a known method such as stripping (vaporizing) treatment,
distillation or bubbling.
(Step (IV))
[0159] As the case requires, the above-described adjuvant may be
added, or the composition may be diluted with a medium. The amount
of the adjuvant is preferably from 0.001 to 100 parts by mass, more
preferably from 0.01 to 10 parts by mass, per 100 parts by mass of
the medium.
[0160] As the medium for dilution, the above-described aqueous
medium is preferred, and water is more preferred. The amount of the
medium for dilution is suitably adjusted for the processing within
a range of from 150 to 100,000 parts by mass per 100 parts by mass
of the monomer mixture.
(Advantageous Effects)
[0161] In the water/oil resistant composition of the present
invention and the process for its production as described in the
foregoing, some or all of --N(R.sup.5)(R.sup.6) in the fluorinated
copolymer are converted to form a salt with an organic acid
comprising an organic acid having a pKa of from 2.0 to 4.0, and the
fluorinated copolymer is thereby dispersed or dissolved in a
medium. Therefore, as compared with a conventional case where
conversion to form a salt is carried out solely by acetic acid to
disperse or dissolve the fluorinated copolymer in a medium, it is
possible to impart a sufficient water/oil resistance to a base
material even though a fluorinated copolymer having R.sup.f groups
with at most 6 carbon atoms or perfluoropolyether, is used.
[0162] Further, some or all of --N(R.sup.5)(R.sup.6) in the
fluorinated copolymer are converted to form a salt with an organic
acid having a relatively low pKa thereby to disperse or dissolve
the fluorinated copolymer in a medium, whereby the cationic
fluorinated copolymer is less likely to be agglomerated by an
anionic adjuvant or dilution water having a high pH used at the
time of the treatment. Thus, the water/oil resistance is not
substantially influenced by the adjuvant or the pH of dilution
water used at the time of the treatment.
[0163] Further, no acetic acid is employed, whereby an odor is
less.
<Article>
[0164] The article of the present invention is one having a base
material treated with the water/oil resistant composition of the
present invention.
[0165] Since the water/oil resistant composition of the present
invention is suitable for treatment of paper, the article of the
present invention is preferably water/oil resistant paper having
paper treated with the water/oil resistant composition of the
present invention.
[0166] As the base material, basically, paper, card board, pulp or
related materials thereof may be mentioned.
[0167] As other base materials, for example, woven fabric or
nonwoven fabric using cellulose or regenerated cellulose as the
base, woven fabric or nonwoven fabric using natural or artificial
fibers (such as cotton, cellulose acetate, wool or silk) as the
base, woven fabric or nonwoven fabric using artificial fibers or
synthetic fibers (such as polyamide fibers, polyester fibers,
polyolefin fibers, polyurethane fibers or polyacrylonitrile fibers)
as the base, leather, plastic material, glass, wood, metal,
porcelain, brick, coated surface, etc. may be mentioned.
<Process for Producing Article>
[0168] The process for producing an article of the present
invention is a process which comprises treating a base material
with the water/oil resistant composition of the present
invention.
[0169] The process for treating a base material with the water/oil
resistant composition may, for example, be a process which
comprises coating a base material with the water/oil resistant
composition by means of a coating means or which comprises
impregnating a base material with the water/oil resistant
composition, followed by drying at a temperature of room
temperature or higher, and as the case requires, applying heat
treatment. By carrying out drying, heat treatment, etc. superior
water/oil resistance can be obtained.
[0170] The process for producing an article of the present
invention is suitable for the process for producing water/oil
resistant paper, which comprises treating paper with the water/oil
resistant composition of the present invention, since the water/oil
resistant composition of the present invention is suitable for
treatment of paper. Now, the process for producing water/oil
resistant paper will be described.
[0171] As a method for treating paper with the water/oil resistant
composition, the following two types of methods are available.
[0172] (1) A method so-called "internal sizing" wherein the
water/oil resistant composition is added to a pulp slurry before
paper making.
[0173] (2) A method so-called "external sizing" wherein in size
pressing after paper making, wet pressing and preliminary drying,
the water/oil resistant composition is applied to paper, or after
base paper making, the water/oil resistant composition is applied
to paper by means of various coaters or various printing
machines.
[0174] The internal sizing may be carried out at any stage so long
as it is prior to adding the pulp slurry (paper making material)
onto a wire of a paper making machine, and specifically, it may be
carried out, for example, in a pulp production step or a paper
material preparation step, preferably in a paper material
preparation step.
[0175] Further, the paper making machine may be any machine so long
as it is an apparatus capable of dehydrating the pulp slurry on the
wire, and it includes, in addition to a continuous paper making
machine such as a Foundrinear paper machine, a batch type pulp
molding machine, whereby the pulp slurry is added onto a molding
frame formed by a wire, and then dehydration is carried out below
the wire to produce a molded product.
[0176] As pulp material, in addition to wood, any material may be
used so long as it contains plant cellulose, such as glass, bamboo,
rice straw, reed, bagasse, palm, etc.
[0177] Further, with respect to the pulping method, a known pulping
method may be employed, such as a mechanical pulping method, a
thermomechanical pulping method, a chemithermomechanical pulping
method, a craft pulping method, a sulfite pulping method, a
deinking pulping method or a recycling pulping method, and it is
not particularly limited.
[0178] In the external sizing, any one of a sizing press, a coater
and a printing machine may be used.
[0179] In the sizing press, analogous gate roll coater, two roll
gate roll, metering size press, film size press, etc. may be
utilized.
[0180] The coater may be either on machine or off machine, either
single stage or multi stage, or either one side or both sides. The
coater may, for example, be a blade coater, a rod blade coater, a
bar coater, a cast coater, an air knife coater, a roll coater (such
as a gate roll or a metering size press), a curtain coater, a
gravure coater or a spray coater.
[0181] Further, as other external sizing means, various types of
printing machines such as gravure, flexo, offset, etc., coaters,
varnish-applying devices, sprays, brushing, padding, rollers, rotor
dampening, foams, etc. may, for example, be mentioned.
[0182] In the present invention, it is preferred that after size
pressing and coating, drying is carried out at a temperature of
room temperature or higher, and as the case requires, heat
treatment is applied. By carrying out drying, heat treatment, etc.,
superior water/oil resistance can be obtained.
EXAMPLES
[0183] Now, the present invention will be described in detail with
reference to Examples and Comparative Examples, but it should be
understood that the present invention is by no means limited
thereto.
(Oil Resistance Test)
[0184] A kit test was carried out by the following method in
accordance with TAPPI T559cm-02 method. In the test, a test
solution was used wherein castor oil, toluene and n-heptane were
mixed in a volume ratio as shown in Table 1. A result of the test
is represented by a kit No., and the larger the number, the better
the oil resistance. The kit test is widely used for evaluation of
the oil resistance of paper, since the oil resistance of test paper
can thereby be obtained in a short time (about 20 seconds). The
evaluation result has a meaning as an index against the surface
tension of the surface of paper. An animal or plant oil or fat
usually has a surface tension of at least 25 dyne/cm corresponding
to a kit No. of from 6 to 7.
[0185] Test paper was placed on a clean flat black surface, and one
droplet of a test solution of kit No. 16 was dropped on the test
paper from a height of 13 mm. Upon expiration of 15 seconds from
the dropping (contact time: 15 seconds), the dropped test solution
was removed by a clean absorption paper, whereupon the surface of
the test paper contacted with the test solution was visually
observed. If the color of the surface was found to be dark, the
same operation was carried out by using a test solution of kit No.
15, and the same operation was repeated by sequentially reducing
the kit No. until the kit No. where the color of the surface no
longer became dark. The evaluation is made by the first (largest)
kit No. where the color of the surface no longer became dark.
TABLE-US-00001 TABLE 1 Mixing ratio (vol %) Kit No. Castor oil
Toluene n-Heptane 1 100 0 0 2 90 5 5 3 80 10 10 4 70 15 15 5 60 20
20 6 50 25 25 7 40 30 30 8 30 35 35 9 20 40 40 10 10 45 45 11 0 50
50 12 0 45 55 13 0 35 65 14 0 25 75 15 0 15 85 16 0 0 100
(Monomer (a))
[0186]
C6FMA:F(CF.sub.2).sub.6CH.sub.2CH.sub.2OC(O)C(CH.sub.3).dbd.CH.sub.-
2
(Monomer (b))
[0187] DEAEMA: Diethylaminoethyl methacrylate
(Monomer (c))
[0188] HEMA: Hydroxyethyl methacrylate
(Monomer (d))
[0189] 3ED: Triethylene glycol dimethacrylate
(Polymerization Initiator)
[0190] DAIB: Dimethyl-2,2'-azobisisobutyrate
(Fluorinated Copolymer Solution B)
[0191] Into a 1L glass container, 132.8 g of C6FMA (purity: 99.6%),
15.8 g of HEMA, 26.3 g of DEAEMA, 0.2 g of 3ED, 524.9 g of acetone
and 1.4 g of DAIB were charged, and nitrogen substitution was
repeated three times. Polymerization was carried out at 65.degree.
C. for 20 hours at a stirring rotational speed of 350 rpm, to
obtain a pale yellow fluorinated copolymer solution B having a
solid content concentration of 25.2 mass %.
(Fluorinated Copolymer Solutions A, D and E)
[0192] Fluorinated copolymer solutions A, D and E were obtained in
the same manner as for the fluorinated copolymer solution B except
that the charges were changed as shown in Table 2. The mass average
molecular weight (Mw) of the fluorinated copolymer in the
fluorinated copolymer solution A was 62,000.
TABLE-US-00002 TABLE 2 Fluorinated copolymer solution B A D E
Charges (g) C6FMA 132.8 133.0 133.0 134.6 HEMA 15.8 19.5 15.8 0
DEAEMA 26.3 21.0 26.3 42.0 3ED 0.2 1.5 0 0 Acetone 524.9 525.0
524.9 523.4 DAIB 1.4 1.4 1.4 1.4 Structural Monomer (a) 75.8 76.0
76.0 76.2 units Monomer (b) 15.0 12.0 15.0 23.8 (mass %) Monomer
(c) 9.0 11.15 9.0 0 Monomer (d) 0.1 0.85 0 0
(Water/Oil Resistant Composition 1)
[0193] To 50 g of the fluorinated copolymer solution B, 45 g of
water and 2.1 g of DL-malic acid were added, followed by stirring
for 15 minutes. Under a reduced pressure condition, acetone was
removed at 65.degree. C. to obtain a transparent pale orange
aqueous dispersion. The solid content concentration was adjusted to
be 20 mass % by ion-exchanged water to obtain a water/oil resistant
composition 1.
(Water/Oil Resistant Compositions 2 to 13, W to Z)
[0194] Water/oil resistant compositions 2 to 13, W to Z, were
obtained in the same manner as for the water/oil resistant
composition 1 except that the charged amounts were changed as shown
in Tables 3, 4 and 5.
[0195] Here, in Tables 3, 4 and 5, blank spaces mean that the
charged amount is "0".
TABLE-US-00003 TABLE 3 Water/oil resistant composition 1 2 3 4 5 6
7 Charges Fluorinated B B B B B A A (g) copolymer 50 50 50 50 50 50
50 solution Water 45 43 41 44 44 45 45 Acetic acid 0.7 0.7 Lactic
acid 2.7 1.4 1.1 DL-malic 2.1 4.2 6.2 2.1 1.7 acid Citric acid
Itaconic acid Amount (parts by mass) per 100 parts by mass of
fluorinated copolymer Organic acid 16.8 33.6 49.6 21.6 28 19.2 14.4
medium 360 344 328 352 352 360 360
TABLE-US-00004 TABLE 4 Water/oil resistant composition 8 9 10 11 12
13 Charges Fluorinated B B B B D E (g) copolymer 50 50 50 50 50 50
solution Water 45 41 45 43 43 40 Acetic acid Lactic acid DL-malic
4.2 6.6 acid Citric acid 1.9 5.8 Itaconic 2.0 4.0 acid Amount
(parts by mass) per 100 parts by mass of fluorinated copolymer
Organic acid 15.2 46.4 16 32 33.6 52.8 medium 360 328 360 344 344
320
TABLE-US-00005 TABLE 5 Water/oil resistant composition (Comparative
Examples) W X Y Z Charges Fluorinated A B D E (g) copolymer 50 50
50 50 solution Water 46 46 46 46 Acetic acid 0.7 0.9 0.9 1.5 Lactic
acid DL-malic acid Citric acid Itaconic acid Amount (parts by mass)
per 100 parts by mass of fluorinated copolymer Organic acid 5.6 7.2
7.2 12 medium 368 368 368 368
[0196] In the following Examples, Examples 5 to 17, 19, 21, 23, 24,
26, 27, 29, 30, 32, 33, 35, 36, 38, 39 and 41 are Working Examples
of the present invention, and Examples 1 to 4, 18, 20, 22, 25, 28,
31, 34, 37 and 40 are Comparative Examples.
Example 1
[0197] Into a 500 mL glass container, 30 g of oxidized starch and
270 g of water were charged. The solution was stirred at a stirring
rotational speed of 100 rpm and heated from room temperature to
95.degree. C. over a period of 20 minutes, and then, held for 30
minutes to obtain a semi-transparent aqueous dispersion. Then, the
concentration of oxidized starch was adjusted to 10 mass % by
ion-exchanged water to obtain an oxidized starch dispersion.
[0198] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W, 30 g of the oxidized
starch dispersion obtained as described above, 0.3 g of a nonionic
penetrating agent (acetylene glycol type) and 68.2 g of
ion-exchanged water at 60.degree. C., were added and thoroughly
mixed and then maintained in a 60.degree. C. water bath, and the
mixture thereby obtained was used as a test solution.
[0199] Papers A, B and C having a size of 15 cm.times.25 cm were
treated with the test solution by a size press method. Then, the
papers A, B and C treated with the test solution were heated and
dried at 105.degree. C. for 1 minute to obtain test papers. The
results of oil resistance tests of the test papers are shown in
Table 6.
Examples 5 to 15
[0200] Test solutions were prepared in the same manner as in
Example 1 except that the water/oil resistant composition W was
changed to water/oil resistant compositions 1 to 11, to obtain test
papers. The results of oil resistance tests of the test papers are
shown in Table 6.
Examples 2 to 4, 16 and 17
[0201] Test solutions were prepared in the same manner as in
Example 1 except that the water/oil resistant composition W was
changed to the water/oil resistant compositions X to Z, 12 and 13,
to obtain test papers. The results of oil resistance tests of the
test papers are shown in Table 6.
TABLE-US-00006 TABLE 6 Solid Water/oil content in Oil resistance
test resistant Organic Adjuvant 1 Adjuvant 2 composition Water
Paper Paper Paper Paper composition Polymer acid Type Mass % Type
Mass % Mass % Mass % A B C D Ex. W A Acetic acid Oxidized 3
Penetrating 0.3 0.3 96.4 0.5 2.5 1.5 1 starch agent Ex. X B Acetic
acid Oxidized 3 Penetrating 0.3 0.3 96.4 1 2 starch agent Ex. Y D
Acetic acid Oxidized 3 Penetrating 0.3 0.3 96.4 2.5 3 starch agent
Ex. Z E Acetic acid Oxidized 3 Penetrating 0.3 0.3 96.4 1.5 4
starch agent Ex. 1 B Malic acid Oxidized 3 Penetrating 0.3 0.3 96.4
3 3 5 starch agent Ex. 2 B Malic acid Oxidized 3 Penetrating 0.3
0.3 96.4 3.5 4 6 starch agent Ex. 3 B Malic acid Oxidized 3
Penetrating 0.3 0.3 96.4 3 3 7 starch agent Ex. 4 B Lactic acid
Oxidized 3 Penetrating 0.3 0.3 96.4 3 4.5 8 starch agent Ex. 5 B
Malic acid + Oxidized 3 Penetrating 0.3 0.3 96.4 3.5 4 9 lactic
acid starch agent Ex. 6 A Malic acid + Oxidized 3 Penetrating 0.3
0.3 96.4 2.5 3.5 10 acetic acid starch agent Ex. 7 A Lactic acid +
Oxidized 3 Penetrating 0.3 0.3 96.4 2.5 3.5 11 acetic acid starch
agent Ex. 8 B Citric acid Oxidized 3 Penetrating 0.3 0.3 96.4 3.5
12 starch agent Ex. 9 B Citric acid Oxidized 3 Penetrating 0.3 0.3
96.4 3.5 13 starch agent Ex. 10 B Itaconic Oxidized 3 Penetrating
0.3 0.3 96.4 3 14 acid starch agent Ex. 11 B Itaconic Oxidized 3
Penetrating 0.3 0.3 96.4 3 15 acid starch agent Ex. 12 D Malic acid
Oxidized 3 Penetrating 0.3 0.3 96.4 3.5 16 starch agent Ex. 13 E
Malic acid Oxidized 3 Penetrating 0.3 0.3 96.4 2.5 17 starch
agent
Example 18
[0202] To ion-exchanged water, 0.1 mass % of ethylenediamine
tetrasodium tetraacetate (hereinafter referred to as EDTA-4Na) was
added to adjust the pH to be 10.4 thereby to obtain EDTA-added
water (ion-exchanged water having EDTA-4Na dissolved).
[0203] Into a 500 mL glass container, 30 g of oxidized starch and
270 g of the EDTA-added water obtained as described above, were
charged. The solution was stirred at a stirring rotational speed of
100 rpm and heated from room temperature to 95.degree. C. over a
period of 20 minutes, and then held for 30 minutes to obtain a
semi-transparent aqueous dispersion. Then, the concentration of
oxidized starch was adjusted to be 10 mass % by ion-exchanged water
to obtain an oxidized starch dispersion.
[0204] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W, 30 g of the oxidized
starch dispersion obtained as described above, 0.3 g of a nonionic
penetrating agent (acetylene glycol type) and 68.2 g of the
EDTA-added water at 60.degree. C. obtained as described above, were
added and thoroughly mixed, and then, held in a 60.degree. C. water
bath, and the mixture thereby obtained was used as a test
solution.
[0205] Paper C having a size of 15 cm.times.25 cm was treated with
the test solution by a size press method. Then, the paper C treated
with the test solution was heated and dried at 105.degree. C. for 1
minute to obtain test paper. The result of the oil resistance test
of the test paper is shown in Table 7.
Example 19
[0206] A test solution was prepared, and test paper was obtained in
the same manner as in Example 18 except that the water/oil
resistant composition W was changed to the water/oil resistant
composition 2. The result of the oil resistance test of the test
paper is shown in Table 7.
Example 20
[0207] To ion-exchanged water, 0.1 mass % of EDTA-4Na was added to
adjust the pH to 10.4 to obtain EDTA-added water.
[0208] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W, 0.3 g of a nonionic
penetrating agent (acetylene glycol type) and 98.2 g of the
EDTA-added water at 60.degree. C. obtained as described above, were
added and thoroughly mixed, and then held in a 60.degree. C. water
bath, and the mixture thereby obtained was used as a test
solution.
[0209] Paper C having a size of 15 cm.times.25 cm was treated with
the test solution by a size press method. Then, the paper C treated
with the test solution was heated and dried at 105.degree. C. for 1
minute to obtain test paper. The results of the oil resistance test
of the test paper is shown in Table 7.
Example 21
[0210] A test solution was prepared, and test paper was obtained in
the same manner as in Example 20 except that the water/oil
resistant composition W was changed to the water/oil resistant
composition 2. The result of the oil resistance test of the test
paper is shown in Table 7.
TABLE-US-00007 TABLE 7 Solid Water/oil content in Dilution Oil
resistance test resistant Organic Adjuvant 1 Adjuvant 2 composition
Water water Paper Paper Paper Paper composition Polymer acid Type
Mass % Type Mass % Mass % Mass % pH A B C D Ex. W A Acetic Oxidized
3 Penetrating 0.3 0.3 96.4 10 0 18 acid starch agent Ex. 2 B Malic
Oxidized 3 Penetrating 0.3 0.3 96.4 10 3 19 acid starch agent Ex. W
A Acetic Penetrating 0.3 0.3 99.4 10 0 20 acid agent Ex. 2 B Malic
Penetrating 0.3 0.3 99.4 10 4 21 acid agent
Example 22
[0211] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W and 98.5 g of
ion-exchanged water at 60.degree. C. were added and thoroughly
mixed, and then held in a 60.degree. C. water bath, and the mixture
obtained was used as a test solution.
[0212] Paper D having a size of 15 cm.times.25 cm was treated with
the test solution by a size press method. Then, the paper D treated
with the test solution was heated and dried at 105.degree. C. for 1
minute to obtain test paper. The results of the oil resistance test
of the test paper is shown in Table 8.
Examples 23 and 24
[0213] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 22 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 8.
Example 25
[0214] Into a 500 mL glass container, 30 g of a hydroxyethyl
ether-modified starch (hereinafter referred to as HES) and 270 g of
water were charged. The solution was stirred at a stirring
rotational speed of 100 rpm and heated from room temperature to
95.degree. C. over a period of 20 minutes, and then held for 30
minutes to obtain a semi-transparent aqueous dispersion. Then, the
concentration of HES was adjusted to be 10 mass % by ion-exchanged
water to obtain a HES dispersion.
[0215] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W, 30 g of the HES
dispersion obtained as described above, and 68.5 g ion-exchanged
water at 60.degree. C. were added and then held in a 60.degree. C.
water bath, and the mixture thus obtained was used as a test
solution.
[0216] Paper D having a size of 15 cm.times.25 cm was treated with
the test solution by a size press method. Then, the paper D treated
with the test solution was heated and dried at 105.degree. C. for 1
minute to obtain test paper. The result of the oil resistance test
of the test paper is shown in Table 8.
Examples 26 and 27
[0217] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 25 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 8.
Example 28
[0218] Into a 500 mL glass container, 30 g of a completely
saponified polyvinyl alcohol (hereinafter referred to as PVA) and
270 g of water were charged. The solution was stirred at a stirring
rotational speed of 100 rpm and heated from room temperature to
95.degree. C. over a period of 20 minutes, and then held for 30
minutes to obtain a semi-transparent aqueous dispersion. Then, the
concentration of PVA was adjusted to be 10 mass % by ion-exchanged
water to obtain a PVA dispersion.
[0219] Into a 100 mL glass container to be hermetically sealed, 1.5
g of the water/oil resistant composition W, 30 g of the PVA
dispersion obtained as described above, and 68.5 g ion-exchanged
water at 60.degree. C. were added and thoroughly mixed, and then
held in a 60.degree. C. water bath, and the mixture thus obtained
was used as a test solution.
[0220] Paper D having a size of 15 cm.times.25 cm was treated with
the test solution by a size press method. Then, the paper D treated
with the test solution was heated and dried at 105.degree. C. for 1
minute to obtain test paper. The result of the oil resistance test
of the test paper is shown in Table 8.
Examples 29 and 30
[0221] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 28 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 8.
TABLE-US-00008 TABLE 8 Solid Water/oil content in Oil resistance
test resistant Organic Adjuvant 1 Adjuvant 2 composition Water
Paper Paper Paper Paper composition Polymer acid Type Mass % Type
Mass % Mass % Mass % A B C D Ex. W A Acetic acid 0.3 99.7 4 22 Ex.
2 B Malic acid 0.3 99.7 5 23 Ex. 5 B Malic acid + 0.3 99.7 5.5 24
lactic acid Ex. W A Acetic acid HES 3 0.3 96.7 5 25 Ex. 2 B Malic
acid HES 3 0.3 96.7 6 26 Ex. 5 B Malic acid + HES 3 0.3 96.7 6.5 27
lactic acid Ex. W A Acetic acid PVA 3 0.3 96.7 5.5 28 Ex. 2 B Malic
acid PVA 3 0.3 96.7 7 29 Ex. 5 B Malic acid + PVA 3 0.3 96.7 7 30
lactic acid
Example 31
[0222] Into a 100 mL glass container to be hermetically sealed, 5.0
g of the water/oil resistant composition W, 70 g of ethanol
(hereinafter referred to as EtOH), and 25 g ion-exchanged water
were added and thoroughly mixed to obtain a test solution.
[0223] The test solution was applied to white paper boards A and B
having a size of 15 cm.times.25 cm by means of No. 4 mayerbar.
Then, the white paper boards A and B treated with the test solution
was heated and dried at 105.degree. C. for 1 minute to obtain test
papers. The results of the oil resistance tests of the test papers
are shown in Table 9.
Examples 32 and 33
[0224] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 31 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 9.
Example 34
[0225] Into a 500 mL glass container, 30 g of PVA and 270 g of
water were charged. The solution was stirred at a stirring
rotational speed of 100 rpm and heated from room temperature to
95.degree. C. over a period of 20 minutes, and then held for 30
minutes to obtain a semi-transparent aqueous dispersion. Then, the
concentration of PVA was adjusted to be 10 mass % by ion-exchanged
water to obtain a PVA dispersion.
[0226] Into a 100 mL glass container to be hermetically sealed, 5.0
g of the water/oil resistant composition W, 40 g of EtOH, 10 g of
the PVA dispersion obtained as described above, and 45 g
ion-exchanged water were added and thoroughly mixed to obtain a
test solution.
[0227] The test solution was applied to white boards A and B having
a size of 15 cm.times.25 cm by means of No. 4 mayerbar, and the
white boards A and B treated with the test solution were heated and
dried at 105.degree. C. for 1 minute to obtain test papers. The
results of the oil resistance tests of the test papers are shown in
Table 9.
Examples 35 and 36
[0228] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 34 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 9.
Example 37
[0229] Into a 100 mL glass container to be hermetically sealed, 5.0
g of the water/oil resistant composition W, 5 g of a nonionic
penetrating agent (acetylene glycol type) and 90 g ion-exchanged
water were added and thoroughly mixed to obtain a test
solution.
[0230] The test solution was applied to white boards A and B having
a size of 15 cm.times.25 cm by means of No. 4 mayerbar. Then, the
white boards A and B treated with the test solution were heated and
dried at 105.degree. C. for 1 minute to obtain test papers. The
results of the oil resistance tests of the test papers are shown in
Table 9.
Examples 38 and 39
[0231] Test solutions were prepared, and test papers were obtained
in the same manner as in Example 37 except that the water/oil
resistant composition W was changed to the water/oil resistant
compositions 2 and 5. The results of the oil resistance tests of
the test papers are shown in Table 9.
TABLE-US-00009 TABLE 9 Solid Water/oil content in Oil resistance
test resistant Organic Adjuvant 1 Adjuvant 2 composition Water
White White composition Polymer acid Type Mass % Type Mass % Mass %
Mass % board A board B Ex. W A Acetic acid EtOH 70 1 29.0 5 3.5 31
Ex. 2 B Malic acid EtOH 70 1 29.0 7 7.5 32 Ex. 5 B Malic acid +
EtOH 70 1 29.0 6 6.5 33 lactic acid Ex. W A Acetic acid EtOH 40 PVA
1 1 58.0 6 5 34 Ex. 2 B Malic acid EtOH 40 PVA 1 1 58.0 8 9 35 Ex.
5 B Malic acid + EtOH 40 PVA 1 1 58.0 8 9 36 lactic acid Ex. W A
Acetic acid Penetrating 5 1 94.0 3 3 37 agent Ex. 2 B Malic acid
Penetrating 5 1 94.0 5 4.5 38 agent Ex. 5 B Malic acid +
Penetrating 5 1 94.0 4 4 39 lactic acid agent
Example 40
[0232] By means of a disintegrator, bleached bagasse pulp was
disintegrated under conditions of a pulp concentration of 3 mass %
for 10 minutes to obtain a pulp slurry. The pulp slurry was diluted
with water to 1.2 mass %, and then, with stirring, to the pulp
solid content, 0.03 mass % of a coagulating agent (a polyamine
epichlorohydrin resin) and 0.5 mass % (as solid content) of the
water/oil resistant composition W were added at 3-minute
intervals.
[0233] Then, a handmade paper was prepared in accordance with JIS
P8222. Here, the sheet basis weight was 300 g/m.sup.2, and the seat
drying was carried out under conditions of 170.degree. C. and 80
seconds. The results of the oil resistance test of the handmade
paper is shown in Table 10.
Example 41
[0234] Handmade paper was prepared in the same manner as in Example
40 except that the water/oil resistant composition W was changed to
the water/oil resistant composition 2. The result of the oil
resistance test of the handmade paper is shown in Table 10.
TABLE-US-00010 TABLE 10 Water/oil Solid content resistant Organic
Additive in composition Oil resistance composition Polymer acid
Type Mass % Mass % test Ex. W A Acetic Coagulating 0.03 0.5 3 40
acid agent Ex. 2 B Malic Coagulating 0.03 0.5 3.5 41 acid agent
INDUSTRIAL APPLICABILITY
[0235] Water/oil resistant paper obtained by treating paper with
the water/oil resistant composition of the present invention is
excellent in the water/oil resistance and has little odor, and thus
it is useful for e.g. a packaging container for food products,
wrapping paper for food products, wrapping paper for
freshness-keeping agents, wrapping paper for deoxidants, etc.
[0236] This application is a continuation of PCT Application No.
PCT/JP2010/070142, filed Nov. 11, 2010, which is based upon and
claims the benefit of priority from Japanese Patent Application No.
2009-260164 filed on Nov. 13, 2009. The contents of those
applications are incorporated herein by reference in its
entirety.
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