U.S. patent application number 17/456739 was filed with the patent office on 2022-03-17 for oil-resistant agent for paper.
This patent application is currently assigned to DAIKIN INDUSTRIES, LTD.. The applicant listed for this patent is DAIKIN INDUSTRIES, LTD.. Invention is credited to Michio MATSUDA, Daisuke NOGUCHI, Hirotoshi SAKASHITA, Tetsuya UEHARA, Yuuki YAMAMOTO.
Application Number | 20220081842 17/456739 |
Document ID | / |
Family ID | 1000006052538 |
Filed Date | 2022-03-17 |
United States Patent
Application |
20220081842 |
Kind Code |
A1 |
UEHARA; Tetsuya ; et
al. |
March 17, 2022 |
OIL-RESISTANT AGENT FOR PAPER
Abstract
A paper oil-resistant agent which is added to the interior of
paper and includes (1) a non-fluorine polymer and (2) at least one
type of particles selected from inorganic particles or organic
particles, the amount of the particles (2) being 1-99.9 wt % of the
total weight of the non-fluorine polymer (1) and the particles (2).
Also disclosed is an oil-resistant paper including the paper
oil-resistant agent and a method for producing the oil-resistant
paper.
Inventors: |
UEHARA; Tetsuya; (Osaka,
JP) ; MATSUDA; Michio; (Osaka, JP) ;
SAKASHITA; Hirotoshi; (Osaka, JP) ; YAMAMOTO;
Yuuki; (Osaka, JP) ; NOGUCHI; Daisuke; (Osaka,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
DAIKIN INDUSTRIES, LTD. |
Osaka |
|
JP |
|
|
Assignee: |
DAIKIN INDUSTRIES, LTD.
Osaka
JP
|
Family ID: |
1000006052538 |
Appl. No.: |
17/456739 |
Filed: |
November 29, 2021 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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PCT/JP2020/020972 |
May 27, 2020 |
|
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17456739 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D21H 17/74 20130101;
D21H 17/28 20130101; D21H 17/37 20130101; D21H 17/675 20130101;
D21H 23/04 20130101 |
International
Class: |
D21H 17/37 20060101
D21H017/37; D21H 17/67 20060101 D21H017/67; D21H 17/28 20060101
D21H017/28; D21H 17/00 20060101 D21H017/00 |
Foreign Application Data
Date |
Code |
Application Number |
May 28, 2019 |
JP |
2019-099463 |
Claims
1. A paper oil-resistant agent which is added to interior of paper,
comprising: (1) a fluorine-free polymer, and (2) at least one type
of particles selected from inorganic particles or organic
particles, wherein an amount of the particles (2) is 1 to 99.9% by
weight, based on the total weight of the fluorine-free polymer (1)
and the particles (2).
2. The paper oil-resistant agent according to claim 1, wherein the
fluorine-free polymer (1) is an acrylic polymer.
3. The paper oil-resistant agent according to claim 1, wherein the
fluorine-free polymer has a repeating unit formed from (a) an
acrylic monomer having a long-chain hydrocarbon group, and the
acrylic monomer having a long-chain hydrocarbon group (a) is a
monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.1)--C(.dbd.O)--Y.sup.1(R.sup.1).sub.k
wherein R.sup.1 each is independently a hydrocarbon group having 7
to 40 carbon atoms, X.sup.1 is a hydrogen atom, a monovalent
organic group, or a halogen atom, Y.sup.1 is a divalent to a
tetravalent group composed of at least one selected from a
hydrocarbon group having one carbon atom, --C.sub.6H.sub.4--,
--O--, --C(.dbd.O)--, --S(.dbd.O).sub.2--, or --NH--, provided that
a hydrocarbon group is excluded, and k is 1 to 3.
4. The paper oil-resistant agent according to claim 3, wherein, in
the acrylic monomer having a long-chain hydrocarbon group (a),
X.sup.1 is a hydrogen atom or a methyl group.
5. The paper oil-resistant agent according to claim 3, wherein, in
the acrylic monomer having a long-chain hydrocarbon group (a), the
long-chain hydrocarbon group has 18 or more carbon atoms.
6. The paper oil-resistant agent according to claim 3, wherein the
acrylic monomer having a long-chain hydrocarbon group (a) is: (a1)
an acrylic monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.4)--C(.dbd.O)--Y.sup.2--R.sup.2 wherein
R.sup.2 is a hydrocarbon group having 7 to 40 carbon atoms, X.sup.4
is a hydrogen atom, a monovalent organic group, or a halogen atom,
and y.sup.2 is --O-- or --NH--, and/or (a2) an acrylic monomer
represented by formula:
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--Y.sup.3--Z(--Y.sup.4--R.sup.3).sub.-
n wherein R.sup.3 each is independently a hydrocarbon group having
7 to 40 carbon atoms, X.sup.5 is a hydrogen atom, a monovalent
organic group, or a halogen atom, Y.sup.3 is --O-- or --NH--,
Y.sup.4 each is independently a group composed of at least one
selected from a direct bond, --O--, --C(.dbd.O)--,
--S(.dbd.O).sub.2--, or --NH--, Z is a direct bond or a divalent or
trivalent hydrocarbon group having 1 to 5 carbon atoms, and n is 1
or 2.
7. The paper oil-resistant agent according to claim 3, wherein the
acrylic monomer having a hydrophilic group (b) is at least one
oxyalkylene (meth)acrylate represented by formula:
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--X.sup.3 (b1)
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--C(.dbd.O)CX.sup.2.dbd.CH.s-
ub.2 (b2), or
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--NH--(RO).sub.n--X.sup.3 (b3)
wherein X.sup.2 is a hydrogen atom or a methyl group, X.sup.3 is a
hydrogen atom or an unsaturated or saturated hydrocarbon group
having 1 to 22 carbon atoms, R each is independently an alkylene
group having 2 to 6 carbon atoms, and n is an integer of 1 to
90.
8. The paper oil-resistant agent according to claim 3, wherein the
fluorine-free polymer further comprises a repeating unit formed
from (c) a monomer having an olefinic carbon-carbon double bond and
having an anion donating group or a cation donating group, other
than the monomers (a) and (b).
9. The paper oil-resistant agent according to claim 8, wherein the
anion donating group is a carboxyl group, or the cation donating
group is an amino group.
10. The paper oil-resistant agent according to claim 3, wherein an
amount of the repeating unit formed from the acrylic monomer having
a long-chain hydrocarbon group (a) is 30 to 90% by weight, based on
a copolymer, and an amount of the repeating unit formed from the
acrylic monomer having a hydrophilic group (b) is 5 to 70% by
weight, based on the copolymer.
11. The paper oil-resistant agent according to claim 1, wherein the
inorganic particles are made of at least one selected from calcium
carbonate, talc, kaolin, clay, mica, aluminum hydroxide, barium
sulfate, calcium silicate, calcium sulfate, silica, zinc carbonate,
zinc oxide, titanium oxide, bentonite, and white carbon, and the
organic particles are made of at least one selected from
polysaccharides and thermoplastic resins.
12. The paper oil-resistant agent according to claim 1, wherein the
organic particles are insoluble in water at 40.degree. C.
13. The paper oil-resistant agent according to claim 1, wherein the
inorganic particles are calcium carbonate, and the organic
particles are starch.
14. The paper oil-resistant agent according to claim 1, wherein the
particles (2) comprises the organic particles.
15. The paper oil-resistant agent according to claim 1, further
comprising a liquid medium which is water or a mixture of water and
an organic solvent.
16. Oil-resistant paper comprising the paper oil-resistant agent
according to claim 1, in interior of the paper.
17. The oil-resistant paper according to claim 16, which is a
molded pulp product.
18. The oil-resistant paper according to claim 16, which is a food
packaging material or a food container.
19. A method for producing oil-resistant paper, comprising:
preparing a formulated pulp slurry by adding the oil-resistant
agent according to claim 1 to a slurry in which pulp is dispersed
in an aqueous medium, making an oil-resistant paper intermediate,
followed by dehydrating and then drying to obtain the oil-resistant
paper.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Rule 53(b) Continuation of
International Application No. PCT/JP2020/020972 filed May 27, 2020,
claiming priority based on Japanese Patent Application No.
2019-099463 filed May 28, 2019, the respective disclosures of which
are incorporated herein by reference in their entirety.
TECHNICAL FIELD
[0002] The present disclosure relates to an oil-resistant agent for
paper, and paper treated with the oil-resistant agent for
paper.
BACKGROUND ART
[0003] Paper may be required to have oil resistance.
[0004] For example, food packaging and food containers which are
made of paper are required to prevent water and oil contained in
food from oozing out. Accordingly, an oil-resistant agent is
internally or externally applied to the paper.
[0005] Several proposals have been made to impart oil resistance to
paper.
[0006] Patent Literature 1 (JP 2015-129365 A) discloses a method of
forming a cellulose article, comprising: attaching cellulose fibers
to a compound comprising an aqueous dispersion comprising at least
one polymer selected from the group consisting of an ethylene
thermoplastic polymer, a propylene thermoplastic polymer, and a
mixture thereof; at least one polymer stabilizer; and water.
[0007] Patent Literature 2 (WO 2015/008868 A1) discloses a fine
cellulose fiber sheet comprising fine cellulose fibers having an
average fiber diameter of 2 nm or more and 1,000 nm or less,
wherein a weight ratio of the fine cellulose fibers is 50% to 99%
by weight, and the block polyisocyanate aggregate is contained in a
weight ratio of 1 to 100% by weight, based on the fine cellulose
fiber weight.
[0008] Patent Document 3 (JP 2004-148307 A) discloses a method for
producing a coated support comprising: a) forming a composite
multilayer free-flowing curtain comprising at least two layers
imparting barrier functionalities, and b) bringing the curtain into
contact with a continuous web support to give a coated support.
CITATION LIST
Patent Literature
Patent Literature 1
[0009] JP 2015-129365 A
Patent Literature 2
[0010] WO 2015/008868 A1
Patent Literature 3
[0011] JP 2004-148307 A
SUMMARY OF INVENTION
Technical Problem
[0012] An object of the present disclosure is to provide an
oil-resistant agent capable of imparting excellent oil resistance
to paper.
Solution to Problem
[0013] The present disclosure relates to an oil-resistant agent
comprising (1) a fluorine-free polymer and (2) particles selected
from inorganic particles and/or organic particles. In the treatment
of the paper, the oil-resistant agent may be externally or
internally added, and preferably the oil-resistant agent is
internally added.
[0014] Preferable embodiments of the present disclosure are as
follows:
[1]
[0015] A paper oil-resistant agent which is added to interior of
paper, comprising: [0016] (1) a fluorine-free polymer, and [0017]
(2) at least one type of particles selected from inorganic
particles or organic particles,
[0018] wherein an amount of the particles (2) is 1 to 99.9% by
weight, based on the total weight of the fluorine-free polymer (1)
and the particles (2).
[2]
[0019] The paper oil-resistant agent according to [1], wherein the
fluorine-free polymer (1) is an acrylic polymer.
[3]
[0020] The paper oil-resistant agent according to [1] or [2],
wherein the fluorine-free polymer has a repeating unit formed from
an acrylic monomer having a long-chain hydrocarbon group (a),
and
[0021] the acrylic monomer having a long-chain hydrocarbon group
(a) is a monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.1)--C(.dbd.O)--Y.sup.1(R.sup.1).sub.k
wherein
[0022] R.sup.1 each is independently a hydrocarbon group having 7
to 40 carbon atoms,
[0023] X.sup.1 is a hydrogen atom, a monovalent organic group, or a
halogen atom,
[0024] Y.sup.1 is a divalent to a tetravalent group composed of at
least one selected from a hydrocarbon group having one carbon atom,
--C.sub.6H.sub.4--, --O--, --C(.dbd.O)--, --S(.dbd.O).sub.2--, or
--NH--, provided that a hydrocarbon group is excluded, and
[0025] k is 1 to 3.
[4]
[0026] The paper oil-resistant agent according to [3], wherein, in
the acrylic monomer having a long-chain hydrocarbon group (a),
X.sup.1 is a hydrogen atom or a methyl group.
[5]
[0027] The paper oil-resistant agent according to any one of [1] to
[4], wherein, in the acrylic monomer having a long-chain
hydrocarbon group (a), the long-chain hydrocarbon group has 18 or
more carbon atoms.
[6]
[0028] The paper oil-resistant agent according to any one of [3] to
[5], wherein
the acrylic monomer having a long-chain hydrocarbon group (a) is:
(a1) an acrylic monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.4)--C(.dbd.O)--Y.sup.2--R.sup.2
wherein
[0029] R.sup.2 is a hydrocarbon group having 7 to 40 carbon
atoms,
[0030] X.sup.4 is a hydrogen atom, a monovalent organic group, or a
halogen atom, and
[0031] Y.sup.2 is --O-- or --NH--, and/or
(a2) an acrylic monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--Y.sup.3--Z(--Y.sup.4--R.sup.3).sub-
.n
wherein
[0032] R.sup.3 each is independently a hydrocarbon group having 7
to 40 carbon atoms,
[0033] X.sup.5 is a hydrogen atom, a monovalent organic group, or a
halogen atom,
[0034] Y.sup.3 is --O-- or --NH--,
[0035] Y.sup.4 each is independently a group composed of at least
one selected from a direct bond, --O--, --C(.dbd.O)--,
--S(.dbd.O).sub.2--, or --NH--,
[0036] Z is a direct bond or a divalent or trivalent hydrocarbon
group having 1 to 5 carbon atoms, and
[0037] n is 1 or 2.
[7]
[0038] The paper oil-resistant agent according to any one of [3] to
[6], wherein
the acrylic monomer having a hydrophilic group (b) is at least one
oxyalkylene (meth)acrylate represented by formula:
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--X.sup.3 (b1),
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--C(.dbd.O)CX.sup.2.dbd.CH.-
sub.2 (b2), or
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--NH--(RO).sub.n--X.sup.3 (b3)
wherein
[0039] X.sup.2 is a hydrogen atom or a methyl group,
[0040] X.sup.3 is a hydrogen atom or an unsaturated or saturated
hydrocarbon group having 1 to 22 carbon atoms,
[0041] R each is independently an alkylene group having 2 to 6
carbon atoms, and
[0042] n is an integer of 1 to 90.
[8]
[0043] The paper oil-resistant agent according to any one of [3] to
[7], wherein the fluorine-free polymer further comprises a
repeating unit formed from (c) a monomer having an olefinic
carbon-carbon double bond and having an anion donating group or a
cation donating group, other than the monomers (a) and (b).
[9]
[0044] The paper oil-resistant agent according to [8], wherein the
anion donating group is a carboxyl group, or the cation donating
group is an amino group.
[10]
[0045] The paper oil-resistant agent according to any one of [3] to
[9], wherein an amount of the repeating unit formed from the
acrylic monomer having a long-chain hydrocarbon group (a) is 30 to
90% by weight, based on a copolymer, and an amount of the repeating
unit formed from the acrylic monomer having a hydrophilic group (b)
is 5 to 70% by weight, based on the copolymer.
[11]
[0046] The paper oil-resistant agent according to any one of [1] to
[10], wherein the inorganic particles are made of at least one
selected from calcium carbonate, talc, kaolin, clay, mica, aluminum
hydroxide, barium sulfate, calcium silicate, calcium sulfate,
silica, zinc carbonate, zinc oxide, titanium oxide, bentonite, and
white carbon, and
the organic particles are made of at least one selected from
polysaccharides and thermoplastic resins. [12]
[0047] The paper oil-resistant agent according to any one of [1] to
[11], wherein the organic particles are insoluble in water at
40.degree. C.
[13]
[0048] The paper oil-resistant agent according to any one of [1] to
[12], wherein the inorganic particles are calcium carbonate, and
the organic particles are starch.
[14]
[0049] The paper oil-resistant agent according to any one of [1] to
[13], wherein the particle (2) comprises the organic particles.
[15]
[0050] The paper oil-resistant agent according to any one of [1] to
[14], further comprising a liquid medium which is water or a
mixture of water and an organic solvent.
[16]
[0051] Oil-resistant paper comprising the paper oil-resistant agent
according to any one of [1] to [15] inside the paper.
[17]
[0052] The oil-resistant paper according to [16], which is a molded
pulp product.
[18]
[0053] The oil-resistant paper according to [16] or [17], which is
a food packaging material or a food container.
[19]
[0054] A method for producing oil-resistant paper, comprising:
preparing a formulated pulp slurry by adding the oil-resistant
agent according to any one of [1] to [15] to a slurry in which pulp
is dispersed in an aqueous medium, making an oil-resistant paper
intermediate, followed by dehydrating and then drying to obtain the
oil-resistant paper.
Advantageous Effects of Invention
[0055] In the oil-resistant agent, the fluorine-free polymer is
favorably dispersed in an aqueous medium, particularly water.
[0056] The oil-resistant agent imparts high oil resistance to
paper. The oil-resistant agent can impart high water resistance and
high gas barrier properties.
DESCRIPTION OF EMBODIMENT
[0057] The oil-resistant agent comprises (1) a fluorine-free
polymer, and (2) particles. The oil-resistant agent may be a one-,
two-, or three-part liquid. The one-part liquid is a liquid
comprising the fluorine-free polymer (1) and the particles (2). The
two-part liquid (two components) is a combination of a liquid
comprising fluorine-free polymer (1) and a liquid comprising the
particles (2) (or only particles (2)). In the three-part liquid
(three components), a liquid comprising an additive for paper is
added for use. The liquid comprising the particles (2) may be a
solid (for example, particles only).
(1) Fluorine-Free Polymer
[0058] The fluorine-free polymer may be, for example, an acrylic
polymer, polyester polymer, polyether polymer, silicone polymer, or
urethane polymer. A polymer having an ester bond, an amide bond,
and/or a urethane bond is preferable. Particularly, an acrylic
polymer (i.e., a fluorine-free acrylic polymer) is preferable. The
acrylic polymer preferably has an ester bond and/or an amide
bond.
[0059] The fluorine-free polymer may be a homopolymer or a
copolymer. The fluorine-free polymer is preferably a copolymer.
[0060] A homopolymer has only a repeating unit formed from one
monomer. The homopolymer is preferably formed only from an acrylic
monomer having a long-chain hydrocarbon group having 7 to 40 carbon
atoms.
[0061] A copolymer has repeating units formed from two or more
monomers.
[0062] The fluorine-free polymer preferably has:
(a) a repeating unit formed from an acrylic monomer having a
long-chain hydrocarbon group having 7 to 40 carbon atoms, and (b) a
repeating unit formed from an acrylic monomer having a hydrophilic
group.
[0063] Moreover, the fluorine-free polymer preferably has a
repeating unit formed of (c) a monomer having an ion donating group
in addition to the monomers (a) and (b).
[0064] The fluorine-free polymer may have a repeating unit formed
from (d) another monomer, in addition to the monomers (a), (b), and
(c).
(a) Acrylic Monomer Having Long-Chain Hydrocarbon Group
[0065] The acrylic monomer having a long-chain hydrocarbon group
(a) has a long-chain hydrocarbon group having 7 to 40 carbon atoms.
The long-chain hydrocarbon group having 7 to 40 carbon atoms is
preferably a linear or branched hydrocarbon group having 7 to 40
carbon atoms. The number of carbon atoms of the long-chain
hydrocarbon group is preferably 10 to 40, such as 12 to 30,
particularly 15 to 30. Alternatively, the number of carbon atoms of
the long-chain hydrocarbon group may be 18 to 40 carbon atoms.
[0066] The acrylic monomer having a long-chain hydrocarbon group
(a) is preferably a monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.1)--C(.dbd.O)--Y.sup.1(R.sup.1).sub.k
wherein
[0067] R.sup.1 each is independently a hydrocarbon group having 7
to 40 carbon atoms,
[0068] X.sup.1 is a hydrogen atom, a monovalent organic group, or a
halogen atom,
[0069] Y.sup.1 is a divalent to tetravalent group composed of at
least one selected from a hydrocarbon group having one carbon atom
(particularly, --CH.sub.2--, --CH.dbd.), --C.sub.6H.sub.4--, --O--,
--C(.dbd.O)--, --S(.dbd.O).sub.2--, or --NH--, provided that a
hydrocarbon group is excluded, and
[0070] k is 1 to 3.
[0071] X.sup.1 may be a hydrogen atom, a methyl group, halogen
excluding a fluorine atom, a substituted or unsubstituted benzyl
group, or a substituted or unsubstituted phenyl group. Examples of
X.sup.1 include a hydrogen atom, a methyl group, a chlorine atom, a
bromine atom, an iodine atom, and a cyano group. X.sup.1 is
preferably a hydrogen atom, a methyl group, or a chlorine atom.
X.sup.1 is particularly preferably a hydrogen atom.
[0072] Y.sup.1 is a divalent to tetravalent group. Y.sup.1 is
preferably a divalent group.
[0073] Y.sup.1 is preferably a group composed of at least one
selected from a hydrocarbon group having one carbon atom,
--C.sub.6H.sub.4--, --O--, --C(.dbd.O)--, --S(.dbd.O).sub.2--, or
--NH--, provided that a hydrocarbon group is excluded. Examples of
the hydrocarbon group having one carbon atom include --CH.sub.2--,
--CH.dbd. having a branched structure, and --C.dbd. having a
branched structure.
[0074] Y.sup.1 may be --Y'--, --Y'--Y'--, --Y'--C(.dbd.O)--,
--C(.dbd.O)--Y'--, --Y'--C(.dbd.O)--Y'--, --Y'--R'--,
--Y'--R'--Y'--, --Y'--R'--Y'--C(.dbd.O)--,
--Y'--R'--C(.dbd.O)--Y'--, --Y'--R'--Y'--C(.dbd.O)--Y'--, or
--Y'--R'--Y'--R'-- wherein
[0075] Y' is a direct bond, --O--, --NH--, or --S(.dbd.O).sub.2--,
and
[0076] R' is --(CH.sub.2).sub.m-- wherein m is an integer of 1 to
5, or --C.sub.6H.sub.4-- (a phenylene group)
[0077] Specific examples of Y.sup.1 include --O--, --NH--,
--O--C(.dbd.O)--, --C(.dbd.O)--NH--, --NH--C(.dbd.O)--,
--O--C(.dbd.O)--NH--, --NH--C(.dbd.O)--O--, --NH--C(.dbd.O)--NH--,
--O--C.sub.6H.sub.4--, --O--(CH.sub.2).sub.m--O--,
--NH--(CH.sub.2).sub.m--NH--, --O--(CH.sub.2).sub.m--NH--,
--NH--(CH.sub.2).sub.m--O--, --O--(CH.sub.2).sub.m--O--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--C(.dbd.O)--O--,
--NH--(CH.sub.2).sub.m--O--C(.dbd.O)--,
--NH--(CH.sub.2).sub.m--C(.dbd.O)--O--,
--O--(CH.sub.2).sub.m--O--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--O--,
--O--(CH.sub.2).sub.m--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--O--C.sub.6H.sub.4--,
--O--(CH.sub.2).sub.m--NH--S(.dbd.O).sub.2--,
--O--(CH.sub.2).sub.m--S(.dbd.O).sub.2--NH--,
--NH--(CH.sub.2).sub.m--O--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--NH--C(.dbd.O)--O--,
--NH--(CH.sub.2).sub.m--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--NH--C(.dbd.O)--,
--NH--(CH.sub.2).sub.m--NH--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--O--C.sub.6H.sub.4--,
--NH--(CH.sub.2).sub.m--NH--C.sub.6H.sub.4--,
--NH--(CH.sub.2).sub.m--NH--S(.dbd.O).sub.2--, or
--NH--(CH.sub.2).sub.m--S(.dbd.O).sub.2--NH--, wherein m is 1 to 5,
particularly 2 or 4.
[0078] Y.sup.1 is preferably --O--, --NH--,
--O--(CH.sub.2).sub.m--O--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--O--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--O--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--S(.dbd.O).sub.2--,
--O--(CH.sub.2).sub.m--S(.dbd.O).sub.2--NH--,
--NH--(CH.sub.2).sub.m--NH--S(.dbd.O).sub.2--, or
--NH--(CH.sub.2).sub.m--S(.dbd.O).sub.2--NH-- wherein m is an
integer of 1 to 5, particularly 2 or 4. Y.sup.1 is more preferably
--O-- or --O--(CH.sub.2).sub.m--NH--C(.dbd.O)--, particularly
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--.
[0079] R.sup.1 is preferably a linear or branched hydrocarbon
group. The hydrocarbon group may be particularly a linear
hydrocarbon group. The hydrocarbon group is preferably an aliphatic
hydrocarbon group, particularly a saturated aliphatic hydrocarbon
group, and especially an alkyl group. The number of carbon atoms of
the hydrocarbon group is preferably 12 to 30, such as 16 to 26 or
15 to 26, particularly 18 to 22 or 17 to 22.
[0080] Examples of the acrylic monomer having a long-chain
hydrocarbon group (a) include:
(a1) an acrylic monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.4)--C(.dbd.O)--Y.sup.2--R.sup.2
wherein
[0081] R.sup.2 is a hydrocarbon group having 7 to 40 carbon
atoms,
[0082] X.sup.4 is a hydrogen atom, a monovalent organic group, or a
halogen atom, and
[0083] Y.sup.2 is --O-- or --NH--, and
(a2) an acrylic monomer represented by formula:
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--Y.sup.3--Z(--Y.sup.4--R.sup.3).sub-
.n
wherein
[0084] R.sup.3 each is independently a hydrocarbon group having 7
to 40 carbon atoms,
[0085] X.sup.5 is a hydrogen atom, a monovalent organic group, or a
halogen atom,
[0086] Y.sup.3 is --O-- or --NH--,
[0087] Y.sup.4 each is independently a group composed of at least
one selected from a direct bond, --O--, --C(.dbd.O)--,
--S(.dbd.O).sub.2--, or --NH--,
[0088] Z is a divalent or trivalent hydrocarbon group having 1 to 5
carbon atoms, and
[0089] n is 1 or 2.
(a1) Acrylic Monomer
[0090] The acrylic monomer (a1) is a compound represented by
formula:
CH.sub.2.dbd.C(--X.sup.4)--C(.dbd.O)--Y.sup.2--R.sup.2
wherein
[0091] R.sup.2 is a hydrocarbon group having 7 to 40 carbon
atoms,
[0092] X.sup.4 is a hydrogen atom, a monovalent organic group, or a
halogen atom, and
[0093] Y.sup.2 is --O-- or --NH--.
[0094] The acrylic monomer (a1) is a long-chain acrylate ester
monomer wherein Y.sup.2 is --O-- or a long-chain acrylamide monomer
wherein Y.sup.2 is --NH--.
[0095] R.sup.2 is preferably an aliphatic hydrocarbon group,
particularly a saturated aliphatic hydrocarbon group, and
especially an alkyl group. In R.sup.2, the number of carbon atoms
of the hydrocarbon group is preferably 12 to 30, such as 16 to 26,
particularly 18 to 22.
[0096] X.sup.4 may be a hydrogen atom, a methyl group, halogen
excluding a fluorine atom, a substituted or unsubstituted benzyl
group, or a substituted or unsubstituted phenyl group, and is
preferably a hydrogen atom, a methyl group, or a chlorine atom.
[0097] Preferable specific examples of the long-chain acrylate
ester monomer include lauryl (meth)acrylate, stearyl
(meth)acrylate, icosyl (meth)acrylate, behenyl (meth)acrylate,
stearyl .alpha.-chloroacrylate, icosyl .alpha.-chloroacrylate, and
behenyl .alpha.-chloroacrylate.
[0098] Preferable specific examples of the long-chain acrylamide
monomer include stearyl (meth)acrylamide, icosyl (meth)acrylamide,
and behenyl (meth)acrylamide.
(a2) Acrylic Monomer
[0099] The acrylic monomer (a2) is a monomer different from the
acrylic monomer (a1). The acrylic monomer (a2) is (meth)acrylate or
(meth)acrylamide having a group composed of at least one selected
from --O--, --C(.dbd.O)--, --S(.dbd.O).sub.2--, or --NH--.
[0100] The acrylic monomer (a2) may be a compound represented by
formula:
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--Y.sup.3--Z(--Y.sup.4--R.sup.3).sub-
.n
wherein
[0101] R.sup.3 each is independently a hydrocarbon group having 7
to 40 carbon atoms,
[0102] X.sup.5 is a hydrogen atom, a monovalent organic group, or a
halogen atom,
[0103] Y.sup.3 is --O-- or --NH--,
[0104] Y.sup.4 each is independently a group composed of at least
one selected from a direct bond, --O--, --C(.dbd.O)--,
--S(.dbd.O).sub.2--, or --NH--,
[0105] Z is a direct bond or a divalent or trivalent hydrocarbon
group having 1 to 5 carbon atoms, and
[0106] n is 1 or 2.
[0107] R.sup.3 is preferably an aliphatic hydrocarbon group,
particularly a saturated aliphatic hydrocarbon group, and
especially an alkyl group. In R.sup.3, the number of carbon atoms
of the hydrocarbon group is preferably 12 to 30, such as 16 to 26
or 15 to 26, particularly 18 to 22 or 17 to 22.
[0108] X.sup.5 may be a hydrogen atom, a methyl group, halogen
excluding a fluorine atom, a substituted or unsubstituted benzyl
group, or a substituted or unsubstituted phenyl group, and is
preferably a hydrogen atom, a methyl group, or a chlorine atom.
[0109] Y.sup.4 may be --Y'--, --Y'--Y'--, --Y'--C(.dbd.O)--,
--C(.dbd.O)--Y'--, --Y'--C(.dbd.O)--Y'--, --Y'--R'--,
--Y'--R'--Y'--, --Y'--R'--Y'--C(.dbd.O)--,
--Y'--R'--C(.dbd.O)--Y'--, --Y'--R'--Y'--C(.dbd.O)--Y'--, or
--Y'--R'--Y'--R'-- wherein
[0110] Y' each is independently a direct bond, --O--, --NH--, or
--S(.dbd.O).sub.2--, and
[0111] R' is --(CH.sub.2).sub.m-- wherein m is an integer of 1 to
5, a linear hydrocarbon group having 1 to 5 carbon atoms and an
unsaturated bond, a hydrocarbon group having 1 to 5 carbon atoms
and a branched structure, or
--(CH.sub.2).sub.l--C.sub.6H.sub.4--(CH.sub.2).sub.l-- wherein l
each is independently an integer of 0 to 5, and --C.sub.6H.sub.4--
is a phenylene group.
[0112] Specific examples of Y.sup.4 include a direct bond, --O--,
--NH--, --O--C(.dbd.O)--, --C(.dbd.O)--O--, --C(.dbd.O)--NH--,
--NH--C(.dbd.O)--, --NH--S(.dbd.O).sub.2--,
--S(.dbd.O).sub.2--NH--, --O--C(.dbd.O)--NH--,
--NH--C(.dbd.O)--O--, --NH--C(.dbd.O)--NH--, --O--C.sub.6H.sub.4--,
--NH--C.sub.6H.sub.4--, --O--(CH.sub.2).sub.m--O--,
--NH--(CH.sub.2).sub.m--NH--, --O--(CH.sub.2).sub.m--NH--,
--NH--(CH.sub.2).sub.m--O--, --O--(CH.sub.2).sub.m--O--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--C(.dbd.O)--O--,
--NH--(CH.sub.2).sub.m--O--C(.dbd.O)--,
--NH--(CH.sub.2).sub.m--C(.dbd.O)--O--,
--O--(CH.sub.2).sub.m--O--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--O--,
--O--(CH.sub.2).sub.m--C(.dbd.O)--NH--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--,
--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--NH--, --O--
(CH.sub.2).sub.m--O--C.sub.6H.sub.4--,
--NH--(CH.sub.2).sub.m--O--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--NH--C(.dbd.O)--O--,
--NH--(CH.sub.2).sub.m--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--NH--C(.dbd.O)--,
--NH--(CH.sub.2).sub.mNH--C(.dbd.O)--NH--,
--NH--(CH.sub.2).sub.m--O--C.sub.6H.sub.4--,
--NH--(CH.sub.2).sub.m--NH--C.sub.6H.sub.4-- wherein m is an
integer of 1 to 5.
[0113] Y.sup.4 is preferably --O--, --NH--, --O--C(.dbd.O)--,
--C(.dbd.O)--O--, --C(.dbd.O)--NH--, --NH--C(.dbd.O)--,
--NH--S(.dbd.O).sub.2--, --S(.dbd.O).sub.2--NH--,
--O--C(.dbd.O)--NH--, --NH--C(.dbd.O)--O--, --NH--C(.dbd.O)--NH--,
or --O--C.sub.6H.sub.4--. Y.sup.4 is more preferably
--NH--C(.dbd.O)--, --C(.dbd.O)--NH--, --O--C(.dbd.O)--NH--,
--NH--C(.dbd.O)--O--, or --NH--C(.dbd.O)--NH--.
[0114] Z is a direct bond or a divalent or trivalent hydrocarbon
group having 1 to 5 carbon atoms, and may have a linear structure
or a branched structure. The number of carbon atoms of Z is
preferably 2 to 4, particularly 2. Specific examples of Z include a
direct bond, --CH.sub.2--, --CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2--, --CH.sub.2CH.sub.2CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.sub.2--, --CH.sub.2CH.dbd.
having a branched structure, --CH.sub.2(CH--)CH.sub.2-- having a
branched structure, --CH.sub.2CH.sub.2CH.dbd. having a branched
structure, --CH.sub.2CH.sub.2CH.sub.2CH.sub.2CH.dbd. having a
branched structure, --CH.sub.2CH.sub.2(CH--)CH.sub.2-- having a
branched structure, and --CH.sub.2CH.sub.2CH.sub.2CH.dbd. having a
branched structure.
[0115] Z is preferably not a direct bond, and Y.sup.4 and Z are
simultaneously not direct bonds.
[0116] The acrylic monomer (a2) is preferably
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--O--(CH.sub.2).sub.m--NH--C(.dbd.O)--
-R.sup.3,
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--O--(CH.sub.2).sub.m--O--C(-
.dbd.O)--NH--R.sup.3,
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--O--(CH.sub.2).sub.mNH--C(.dbd.O)--O-
--R.sup.3, or
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--O--(CH.sub.2).sub.mNH--C(.dbd.O)--N-
H--R.sup.3,
wherein R.sup.3 and X.sup.5 are as defined above.
[0117] The acrylic monomer (a2) is particularly preferably
CH.sub.2.dbd.C(--X.sup.5)--C(.dbd.O)--O--(CH.sub.2).sub.mNH--C(.dbd.O)--R-
.sup.3.
[0118] The acrylic monomer (a2) can be produced by reacting
hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with
long-chain alkyl isocyanate. Examples of the long-chain alkyl
isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl
isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl
isocyanate.
[0119] Alternatively, the acrylic monomer (a2) can also be produced
by reacting (meth)acrylate having an isocyanate group in a side
chain, such as 2-methacryloyloxyethyl methacrylate, with long-chain
alkylamine or long-chain alkyl alcohol. Examples of the long-chain
alkylamine include laurylamine, myristylamine, cetylamine,
stearylamine, oleylamine, and behenylamine. Examples of the
long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol,
cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl
alcohol.
[0120] Preferable examples of the long-chain hydrocarbon
group-containing acrylic monomer are as follows:
[0121] stearyl (meth)acrylate, behenyl (meth)acrylate, stearyl
.alpha.-chloroacrylate, behenyl .alpha.-chloroacrylate;
[0122] stearyl (meth)acrylamide, behenyl (meth)acrylamide;
##STR00001## ##STR00002##
wherein n is a number of 7 to 40, and m is a number of 1 to 5.
[0123] The compounds of the above chemical formulae are acrylic
compounds in which the .alpha.-position is a hydrogen atom, and
specific examples may be methacrylic compounds in which the
.alpha.-position is a methyl group and .alpha.-chloroacrylic
compounds in which the .alpha.-position is a chlorine atom.
[0124] The melting point of the acrylic monomer having a long-chain
hydrocarbon group (a) is preferably 10.degree. C. or higher, and
more preferably 25.degree. C. or higher.
[0125] The acrylic monomer having a long-chain hydrocarbon group
(a) is preferably an acrylate in which X.sup.1, X.sup.4, and
X.sup.3 are hydrogen atoms.
[0126] The acrylic monomer (a2) is preferably an amide
group-containing monomer represented by formula:
[0127] R.sup.12--C(.dbd.O)--NH--R.sup.13--O--R.sup.11 wherein
[0128] R.sup.11 is an organic residue having an ethylenically
unsaturated polymerizable group,
[0129] R.sup.12 is a hydrocarbon group having 7 to 40 carbon atoms,
and
[0130] R.sup.13 is a hydrocarbon group having 1 to 5 carbon
atoms.
[0131] R.sup.11 is an organic residue having an ethylenically
unsaturated polymerizable group, and is not limited as long as
there is a carbon-carbon double bond. Specific examples include
organic residues having an ethylenically unsaturated polymerizable
group such as --C(.dbd.O)CR.sup.14.dbd.CH.sub.2,
--CHR.sup.14.dbd.CH.sub.2, and --CH.sub.2CHR.sup.14.dbd.CH.sub.2,
and R.sup.14 is a hydrogen atom or an alkyl group having 1 to 4
carbon atoms. R.sup.11 may have various organic groups other than
the ethylenically unsaturated polymerizable group, e.g., organic
groups such as chain hydrocarbons, cyclic hydrocarbons,
polyoxyalkylene groups, and polysiloxane groups, and these organic
groups may be substituted with various substituents. R.sup.11 is
preferably --C(.dbd.O)CR.sup.14.dbd.CH.sub.2.
[0132] R.sup.12 is a hydrocarbon group having 7 to 40 carbon atoms
and preferably an alkyl group, such as a chain hydrocarbon group or
a cyclic hydrocarbon group. Among them, a chain hydrocarbon group
is preferable, and a linear saturated hydrocarbon group is
particularly preferable. The number of carbon atoms of R.sup.12 is
7 to 40, preferably 11 to 27, and particularly preferably 15 to
23.
[0133] R.sup.13 is a hydrocarbon group having 1 to 5 carbon atoms,
and preferably an alkyl group. The hydrocarbon group having 1 to 5
carbon atoms may be either linear or branched, may have an
unsaturated bond, and is preferably linear. The number of carbon
atoms of R.sup.13 is preferably 2 to 4, and particularly preferably
2. R.sup.13 is preferably an alkylene group.
[0134] The amide group-containing monomer may be a monomer having
one type of R.sup.12 (for example, a compound in which R.sup.12 has
17 carbon atoms) or a monomer having a combination of multiple
types of R.sup.12 (for example, a mixture of a compound in which
R.sup.12 has 17 carbon atoms and a compound in which R.sup.12 has
15 carbon atoms)
[0135] An example of the amide group-containing monomer is
carboxylic acid amide alkyl (meth)acrylate.
[0136] Specific examples of the amide group-containing monomer
include palmitic acid amide ethyl (meth)acrylate, stearic acid
amide ethyl (meth)acrylate, behenic acid amide ethyl
(meth)acrylate, myristic acid amide ethyl (meth)acrylate, lauric
acid amide ethyl (meth)acrylate, isostearic acid ethylamide
(meth)acrylate, oleic acid ethylamide (meth)acrylate,
tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate,
adamantanecarboxylic acid ethylamide (meth)acrylate,
naphthalenecarboxylic acid amide ethyl (meth)acrylate,
anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid
amide propyl (meth)acrylate, stearic acid amide propyl
(meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid
amide ethyl vinyl ether, palmitic acid amide ethyl allyl ether,
stearic acid amide ethyl allyl ether, and mixtures thereof.
[0137] The amide group-containing monomer is preferably stearic
acid amide ethyl (meth)acrylate. The amide group-containing monomer
may be a mixture comprising stearic acid amide ethyl
(meth)acrylate. In a mixture comprising stearic acid amide ethyl
(meth)acrylate, the amount of stearic acid amide ethyl
(meth)acrylate is, for example, 55 to 99% by weight, preferably 60
to 85% by weight, and more preferably 65 to 80% by weight, based on
the weight of the entirety of the amide group-containing monomer,
and the remainder of the monomer may be, for example, palmitic acid
amide ethyl (meth)acrylate.
(b) Acrylic Monomer Having Hydrophilic Group
[0138] The acrylic monomer having a hydrophilic group (b) is a
monomer different from the monomer (a), and is a hydrophilic
monomer. The hydrophilic group is preferably an oxyalkylene group
(the number of carbon atoms of the alkylene group is 2 to 6).
Particularly, the acrylic monomer having a hydrophilic group (b) is
preferably polyalkylene glycol mono(meth)acrylate, polyalkylene
glycol di(meth)acrylate, and/or polyalkylene glycol
mono(meth)acrylamide. Polyalkylene glycol mono(meth)acrylate,
polyalkylene glycol di(meth)acrylate, and polyalkylene glycol
mono(meth)acrylamide are preferably those represented by general
formulae:
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--X.sup.3 (b1),
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--O--(RO).sub.n--C(.dbd.O)CX.sup.2.dbd.CH.-
sub.2 (b2), or
CH.sub.2.dbd.CX.sup.2C(.dbd.O)--NH--(RO).sub.n--X.sup.3 (b3)
wherein,
[0139] X.sup.2 each is independently a hydrogen atom or a methyl
group,
[0140] X.sup.3 each is independently is a hydrogen atom or an
unsaturated or saturated hydrocarbon group having 1 to 22 carbon
atoms,
[0141] R each is independently an alkylene group having 2 to 6
carbon atoms, and
[0142] n is an integer of 1 to 90. n may be, for example, 1 to 50,
particularly 1 to 30, and especially 1 to 15 or 2 to 15.
Alternatively, n may be, for example, 1.
[0143] R may be a linear or branched alkylene group such as a group
represented by formula --(CH.sub.2).sub.x-- or
--(CH.sub.2).sub.x1--(CH(CH.sub.3)).sub.x2-- wherein x1 and x2 are
0 to 6 such as 2 to 5, and the sum of x1 and x2 is 1 to 6; and the
order of --(CH.sub.2).sub.x1-- and --(CH(CH.sub.3)).sub.x2-- is not
limited to the formula shown, and may be random.
[0144] In --(RO).sub.n--, there may be two or more types (such as 2
to 4 types, particularly 2 types) of R, and thus --(RO).sub.n-- may
be a combination of, for example, --(R.sup.1O).sub.n1-- and
--(R.sup.2O).sub.n2-- wherein R.sup.1 and R.sup.2 are mutually
different and an alkylene group having 2 to 6 carbon atoms, n1 and
n2 are a number of 1 or more, and the sum of n1 and n2 is 2 to
90.
[0145] R in general formulae (b1), (b2), and (b3) is particularly
preferably an ethylene group, a propylene group, or a butylene
group. R in general formulae (b1), (b2), and (b3) may be a
combination of two or more types of alkylene groups. In this case,
at least one R is preferably an ethylene group, a propylene group,
or a butylene group. Examples of the combination of R include a
combination of an ethylene group/a propylene group, a combination
of an ethylene group/a butylene group, and a combination of a
propylene group/a butylene group. The monomer (b) may be a mixture
of two or more types. In this case, in at least one monomer (b), R
in general formula (b1), (b2), or (b3) is preferably an ethylene
group, a propylene group, or a butylene group. Polyalkylene glycol
di(meth)acrylate represented by general formula (b2) is not
preferably used solely as the monomer (b), and is preferably used
in combination with the monomer (b1). In this case as well, the
compound represented by general formula (b2) is preferably less
than 30% by weight in the monomer (b) used.
[0146] Specific examples of the acrylic monomer having a
hydrophilic group (b) include, but are not limited to, the
following.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.CHCOO--CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH(CH.sub.3) CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH.sub.2CH(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.CHCOO--CH.sub.2C(CH.sub.3).sub.2O--H
CH.sub.2.dbd.CHCOO--CH(CH.sub.2CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CHCOO--C(CH.sub.3).sub.2CH.sub.2O--H
CH.sub.2.dbd.CHCOO--CH(CH.sub.3) CH(CH.sub.3)O--H
CH.sub.2.dbd.CHCOO--C(CH.sub.3)(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.2--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.4--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O) s-H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.6--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.5--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.9--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.23--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.90--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH(CH.sub.3)O).sub.9--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH(CH.sub.3)O).sub.9--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH(CH.sub.3)O).sub.12--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH.sub.3)O).su-
b.2--H
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH.sub.3-
)O).sub.3--CH.sub.3
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH.sub.3)O).su-
b.6--CH.sub.2CH(C.sub.2H.sub.5) C.sub.4H.sub.9
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.23--OOC(CH.sub.3)
C.dbd.CH.sub.2
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.20--(CH.sub.2CH(CH.sub.3)O)
s-CH.sub.2--CH.dbd.CH.sub.2
CH.sub.2.dbd.CHCOO--(CH.sub.2CH.sub.2O).sub.9--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH(CH.sub.3) CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2C(CH.sub.3).sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH(CH.sub.2CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--C(CH.sub.3).sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)COO--CH(CH.sub.3) CH(CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)COO--C(CH.sub.3)(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.2--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.4--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.5--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.6--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.9--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.5--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.9--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.23--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.90--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH(CH.sub.3)O).sub.9--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH(CH.sub.3)O).sub.9--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH(CH.sub.3)O).sub.12--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH.su-
b.3)O).sub.2--H
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH.su-
b.3)O).sub.3--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.8--(CH.sub.2CH(CH.su-
b.3)O).sub.6--CH.sub.2CH(C.sub.2H.sub.5) C.sub.4H.sub.9
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.23--OOC(CH.sub.3)
C.dbd.CH.sub.2
CH.sub.2.dbd.C(CH.sub.3)COO--(CH.sub.2CH.sub.2O).sub.20--(CH.sub.2CH(CH.s-
ub.3)O) s-CH.sub.2--CH.dbd.CH.sub.2
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH(CH.sub.3) CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH.sub.2C(CH.sub.3).sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH(CH.sub.2CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--C(CH.sub.3).sub.2CH.sub.2O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--CH(CH.sub.3)CH(CH.sub.3)O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--C(CH.sub.3)(CH.sub.2CH.sub.3)O--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.2--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.4--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.6--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.9--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.9--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.23--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.90--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub.9--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub.9--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub.12--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH-
.sub.3)O).sub.2--H
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--(CH.sub.2CH(CH-
.sub.3)O).sub.3--CH.sub.3
CH.sub.2.dbd.CH--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.8--(CH.sub.2CH(CH-
.sub.3)O).sub.6--CH.sub.2CH(C.sub.2H.sub.5) C.sub.4H.sub.9
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH(CH.sub.3) CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH.sub.2CH.sub.2-
O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH.sub.2CH(CH.sub.3)-
O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.3)CH.sub.2-
O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH(CH.sub.3)CH.sub.2CH.sub.2-
O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2CH(CH.sub.2CH.sub.3)-
O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH.sub.2C(CH.sub.3).sub.2O---
H CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH(CH.sub.2CH.sub.3)
CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--C(CH.sub.3).sub.2CH.sub.2O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--CH(CH.sub.3)CH(CH.sub.3)O--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--C(CH.sub.3)(CH.sub.2CH.sub.3)O---
H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.2--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.4--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.6--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.9--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--CH.su-
b.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.9--C-
H.sub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.-
23--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.90--CH.s-
ub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub-
.9--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub-
.9--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH(CH.sub.3)O).sub.12---
CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub-
.5--(CH.sub.2CH(CH.sub.3)O).sub.2--H
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.5--(CH.s-
ub.2CH(CH.sub.3)O).sub.3--CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)--C(.dbd.O)--NH--(CH.sub.2CH.sub.2O).sub.8--(CH.s-
ub.2CH(CH.sub.3)O).sub.6--CH.sub.2CH(C.sub.2H.sub.5)
C.sub.4H.sub.9
[0147] The monomer (b) is preferably acrylate or acrylamide in
which X.sup.2 is a hydrogen atom. Particularly, hydroxyethyl
acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, or
hydroxyethyl acrylamide is preferable.
(c) Monomer Having Ion Donating Group
[0148] The monomer having an ion donating group (c) is a monomer
different from the monomer (a) and the monomer (b). The monomer (c)
is preferably a monomer having an olefinic carbon-carbon double
bond and an ion donating group. The ion donating group is an anion
donating group and/or a cation donating group.
[0149] Examples of the monomer having an anion donating group
include monomers having a carboxyl group, a sulfonic acid group, or
a phosphoric acid group. Specific examples of the monomer having an
anion donating group include (meth)acrylic acid, crotonic acid,
maleic acid, fumaric acid, itaconic acid, citraconic acid, vinyl
sulfonic acid, (meth)allylsulfonic acid, styrenesulfonic acid,
phosphoric acid (meth)acrylate, vinylbenzenesulfonic acid,
acrylamide tert-butyl sulfonic acid, and salts thereof.
[0150] Examples of salts of the anion donating group include alkali
metal salts, alkaline earth metal salts, and ammonium salts, such
as a methyl ammonium salt, an ethanol ammonium salt, and a
triethanol ammonium salt.
[0151] In the monomer having a cation donating group, examples of
the cation donating group include an amino group and preferably a
tertiary amino group and a quaternary amino group. In the tertiary
amino group, two groups bonded to the nitrogen atom are the same or
different and are preferably an aliphatic group having 1 to 5
carbon atoms (particularly an alkyl group), an aromatic group
having 6 to 20 carbon atoms (an aryl group), or an araliphatic
group having 7 to 25 carbon atoms (particularly an aralkyl group
such as a benzyl group (C.sub.6H.sub.5--CH.sub.2--)). In the
quaternary amino group, three groups bonded to the nitrogen atom
are the same or different and are preferably an aliphatic group
having 1 to 5 carbon atoms (particularly an alkyl group), an
aromatic group having 6 to 20 carbon atoms (an aryl group), or an
araliphatic group having 7 to 25 carbon atoms (particularly an
aralkyl group such as a benzyl group (C.sub.6H.sub.5--CH.sub.2--)).
In the tertiary and quaternary amino groups, the remaining one
group bonded to the nitrogen atom may have a carbon-carbon double
bond. The cation donating group may be in the form of a salt.
[0152] A cation donating group which is a salt is a salt formed
with an acid (an organic acid or an inorganic acid). Organic acids
such as carboxylic acids having 1 to 20 carbon atoms (particularly,
monocarboxylic acids such as acetic acid, propionic acid, butyric
acid, and stearic acid) are preferable. Dimethylaminoethyl
(meth)acrylate, diethylaminoethyl (meth)acrylate, and salts thereof
are preferable.
[0153] Specific examples of the monomer having a cation donating
group are as follows.
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2--N(CH.sub.3).sub.2 and salts
thereof (such as acetate)
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2--N(CH.sub.2CH.sub.3).sub.2 and
salts thereof (such as acetate)
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N(CH.sub.3).sub.2
and salts thereof (such as acetate)
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N(CH.sub.2CH.sub.3).sub.2
and salts thereof (such as acetate) CH.sub.2.dbd.CHC(O)
N(H)--CH.sub.2CH.sub.2CH.sub.2--N(CH.sub.3).sub.2 and salts thereof
(such as acetate)
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2--N(--CH.sub.3)
(--CH.sub.2--C.sub.6H.sub.5) and salts thereof (such as acetate)
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N(--CH.sub.2CH.sub.3)
(--CH.sub.2--C.sub.6H.sub.5) and salts thereof (such as acetate)
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3).sub.3Cl.sup.-
CH.sub.2.dbd.CHCOO--CH.sub.2CH.sub.2--N.sup.+(--CH.sub.3).sub.2
(--CH.sub.2--C.sub.6H.sub.5) Cl.sup.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3).sub.3Cl.-
sup.- CH.sub.2.dbd.CHCOO--CH.sub.2CH(OH)
CH.sub.2--N.sup.+(CH.sub.3).sub.3Cl.sup.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH(OH)
CH.sub.2--N.sup.+(CH.sub.3).sub.3Cl.sup.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH(OH)
CH.sub.2--N.sup.+(--CH.sub.2CH.sub.3).sub.2
(--CH.sub.2--C.sub.6H.sub.5) Cl.sup.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3)-
.sub.3Br.sup.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3).sub.3I.s-
up.-
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3).sub.-
3O.sup.-SO.sub.3CH.sub.3
CH.sub.2.dbd.C(CH.sub.3)COO--CH.sub.2CH.sub.2--N.sup.+(CH.sub.3)
(--CH.sub.2--C.sub.6H.sub.5).sub.2Br.sup.-
[0154] The monomer having an ion donating group (c) is preferably
methacrylic acid, acrylic acid, and dimethylaminoethyl
methacrylate, and more preferably methacrylic acid and
dimethylaminoethyl methacrylate.
(d) Another Monomer
[0155] Another monomer (d) is a monomer different from the monomers
(a), (b), and (c). Examples of the other monomer include ethylene,
vinyl acetate, vinyl chloride, vinyl fluoride, halogenated vinyl
styrene, .alpha.-methylstyrene, p-methylstyrene, polyoxyalkylene
mono(meth)acrylate, (meth)acrylamide, diacetone (meth)acrylamide,
methylollated (meth)acrylamide, N-methylol (meth)acrylamide, alkyl
vinyl ether, halogenated alkyl vinyl ether, alkyl vinyl ketone,
butadiene, isoprene, chloroprene, glycidyl (meth)acrylate,
aziridinyl (meth)acrylate, benzyl (meth)acrylate, isocyanate ethyl
(meth)acrylate, cyclohexyl (meth)acrylate, isobornyl
(meth)acrylate, short-chain alkyl (meth)acrylate, maleic anhydride,
(meth)acrylate having a polydimethylsiloxane group, and
N-vinylcarbazole.
[0156] The amount of the repeating unit formed from the monomer (a)
may be 30 to 95% by weight, preferably 40 to 88% by weight, and
more preferably 50 to 85% by weight, based on the fluorine-free
polymer (particularly, an acrylic polymer).
[0157] The amount of the repeating unit formed from the monomer (b)
may be 5 to 70% by weight, preferably 8 to 50% by weight, and more
preferably 10 to 40% by weight, based on the fluorine-free
polymer.
[0158] The amount of the repeating unit formed from the monomer (c)
may be 0.1 to 30% by weight, preferably 0.5 to 20% by weight, and
more preferably 1 to 15% by weight, based on the fluorine-free
polymer.
[0159] The amount of the repeating unit formed from the monomer (d)
may be 0 to 20% by weight, such as 1 to 15% by weight, particularly
2 to 10% by weight, based on the fluorine-free copolymer.
[0160] The weight-average molecular weight of the fluorine-free
polymer may be 1,000 to 10,000,000, preferably 5,000 to 8,000,000,
and more preferably 10,000 to 4,000,000. The weight-average
molecular weight is a value obtained in terms of polystyrene by gel
permeation chromatography.
[0161] Herein, "(meth)acryl" means acryl or methacryl. For example,
"(meth)acrylate" means acrylate or methacrylate.
[0162] From the viewpoint of oil resistance, the fluorine-free
polymer (particularly, an acrylic polymer) is preferably a random
copolymer rather than a block copolymer.
[0163] Polymerization for the fluorine-free polymer is not limited,
and various polymerization methods can be selected, such as bulk
polymerization, solution polymerization, emulsion polymerization,
and radiation polymerization. For example, in general, solution
polymerization involving an organic solvent, and emulsion
polymerization involving water or involving an organic solvent and
water in combination, are selected. The fluorine-free copolymer
after polymerization is diluted with water to be emulsified in
water and thus formed into a treatment liquid.
[0164] Herein, it is preferable that after polymerization (for
example, solution polymerization or emulsion polymerization,
preferably solution polymerization), water is added, and then the
solvent is removed to disperse the polymer in water. An emulsifier
does not need to be added, and a self-dispersive product can be
produced.
[0165] Examples of organic solvents include ketones such as acetone
and methyl ethyl ketone, esters such as ethyl acetate and methyl
acetate, glycols such as propylene glycol, dipropylene glycol
monomethyl ether, N-methyl-2-pyrrolidone (NMP), dipropylene glycol,
tripropylene glycol, and low molecular weight polyethylene glycol,
and alcohols such as ethyl alcohol and isopropanol.
[0166] For example, peroxide, an azo compound, or a persulfate
compound can be used as a polymerization initiator. The
polymerization initiator is, in general, water-soluble and/or
oil-soluble.
[0167] Specific examples of the oil-soluble polymerization
initiator preferably include 2,2'-azobis(2-methylpropionitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile),
1,1'-azobis(cyclohexan-1-carbonitrile), dimethyl
2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile),
benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene
hydroperoxide, t-butyl peroxypivalate, diisopropyl
peroxydicarbonate, and t-butyl perpivalate.
[0168] Specific examples of the water-soluble polymerization
initiator preferably include 2,2'-azobisisobutylamidine
dihydrochloride, 2,2'-azobis(2-methylpropionamidine) hydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate,
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride,
potassium persulfate, barium persulfate, ammonium persulfate, and
hydrogen peroxide.
[0169] The polymerization initiator is used in the range of 0.01 to
5 parts by weight, based on 100 parts by weight of the
monomers.
[0170] In order to regulate the molecular weight, a chain transfer
agent such as a mercapto group-containing compound may be used, and
specific examples thereof include 2-mercaptoethanol, thiopropionic
acid, and alkyl mercaptan. The mercapto group-containing compound
is used in the range of 10 parts by weight or less, or 0.01 to 5
parts by weight, based on 100 parts by weight of the monomers.
[0171] Specifically, the fluorine-free polymer can be produced as
follows.
[0172] In solution polymerization, a method is employed that
involves dissolving the monomers in an organic solvent, performing
nitrogen purge, then adding a polymerization initiator, and heating
and stirring the mixture, for example, in the range of 40 to
120.degree. C. for 1 to 10 hours. The polymerization initiator may
be, in general, an oil-soluble polymerization initiator.
[0173] The organic solvent is inert to and dissolves the monomers,
and examples include ketones such as acetone and methyl ethyl
ketone, esters such as ethyl acetate and methyl acetate, glycols
such as propylene glycol, dipropylene glycol monomethyl ether,
N-methyl-2-pyrrolidone (NMP), dipropylene glycol, tripropylene
glycol, and low molecular weight polyethylene glycol, alcohols such
as ethyl alcohol and isopropanol, and hydrocarbon solvents such as
n-heptane, n-hexane, n-octane, cyclohexane, methylcyclohexane,
cyclopentane, methylcyclopentane, methylpentane, 2-ethylpentane,
isoparaffin hydrocarbon, liquid paraffin, decane, undecane,
dodecane, mineral spirit, mineral turpen, and naphtha. Preferable
examples of the solvent include acetone, chloroform, HCHC 225,
isopropyl alcohol, pentane, hexane, heptane, octane, cyclohexane,
benzene, toluene, xylene, petroleum ether, tetrahydrofuran,
1,4-dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl
acetate, butyl acetate, 1,1,2,2-tetrachloroethane,
1,1,1-trichloroethane, trichloroethylene, perchloroethylene,
tetrachlorodifluoroethane, trichlorotrifluoroethane,
N-methyl-2-pyrrolidone (NMP), and dipropylene glycol monomethyl
ether (DPM). The organic solvent is used in the range of 50 to
2,000 parts by weight, such as 50 to 1,000 parts by weight, based
on total 100 parts by weight of the monomers.
[0174] In emulsion polymerization, a method is employed that
involves emulsifying the monomers in water in the presence of an
emulsifier, performing nitrogen purge, then adding a polymerization
initiator, and stirring the mixture in the range of 40 to
80.degree. C. for 1 to 10 hours for polymerization. As the
polymerization initiator, a water-soluble polymerization initiator
such as 2,2'-azobisisobutylamidine dihydrochloride,
2,2'-azobis(2-methylpropionamidine) hydrochloride.
2,2'-azobis[2-(2-imidazolin-2-yl)propane] hydrochloride,
2,2'-azobis[2-(2-imidazolin-2-yl)propane] sulfate hydrate,
2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] hydrochloride,
potassium persulfate, barium persulfate, ammonium persulfate, or
hydrogen peroxide; or an oil-soluble polymerization initiator such
as 2,2'-azobis(2-methylpropionitrile),
2,2'-azobis(2-methylbutyronitrile),
2,2'-azobis(2,4-dimethylvaleronitrile),
2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile),
1,1'-azobis(cyclohexan-1-carbonitrile), dimethyl
2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-isobutyronitrile),
benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene
hydroperoxide, t-butyl peroxypivalate, diisopropyl
peroxydicarbonate, or t-butyl perpivalate is used. The
polymerization initiator is used in the range of 0.01 to 10 parts
by weight, based on 100 parts by weight of the monomers.
[0175] In order to obtain a water dispersion of the polymer, that
has excellent stability when being left to stand, it is desirable
that the monomers are formed into particles in water by using an
emulsifying apparatus capable of applying strong crushing energy
such as a high-pressure homogenizer or an ultrasonic homogenizer,
and polymerized by using an oil-soluble polymerization initiator.
Various anionic, cationic, or nonionic emulsifiers can be used as
emulsifiers, and are used in the range of 0.5 to 20 parts by
weight, based on 100 parts by weight of the monomers. An anionic
and/or nonionic and/or cationic emulsifier is preferably used. When
the monomers are not completely compatible, a compatibilizer such
as a water-soluble organic solvent or a low molecular weight
monomer that causes the monomers to be sufficiently compatible is
preferably added. By adding a compatibilizer, emulsifiability and
copolymerizability can be increased.
[0176] Examples of the water-soluble organic solvent include
acetone, propylene glycol, dipropylene glycol monomethyl ether
(DPM), dipropylene glycol, tripropylene glycol, ethanol,
N-methyl-2-pyrrolidone (NMP), 3-methoxy-3-methyl-1-butanol, or
isoprene glycol, and the water-soluble organic solvent may be used
in the range of 1 to 50 parts by weight, such as 10 to 40 parts by
weight, based on 100 parts by weight of water. By adding NMP or DPM
or 3-methoxy-3-methyl-1-butanol or isoprene glycol (a preferable
amount is, for example, 1 to 20% by weight, and particularly 3 to
10% by weight, based on the composition), the stability of the
composition (particularly, the emulsion) is increased. Examples of
the low molecular weight monomer include methyl methacrylate,
glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate, and
the low molecular weight monomer may be used in the range of 1 to
50 parts by weight, such as 10 to 40 parts by weight, based on
total 100 parts by weight of the monomers.
[0177] The amount of the fluorine-free polymer (1) is 0.1 to 99% by
weight, based on the total weight of the fluorine-free polymer (1)
and the particles (2). The lower limit of the amount of the
fluorine-free polymer (1) may be 1% by weight, such as 5% by
weight, particularly 10% by weight, and especially 20% by weight or
30% by weight. The upper limit of the amount of the fluorine-free
polymer (1) may be 90% by weight, such as 70% by weight,
particularly 60% by weight, and especially 50% by weight or 40% by
weight.
(2) Particle
[0178] The particles (2) comprise at least one type of inorganic
particles or organic particles. The particles (2) preferably
comprise organic particles. The particles (2) more preferably
comprise both inorganic particles and organic particles.
[0179] The inorganic particles are particles made of inorganic
materials. Examples of the inorganic materials constituting the
inorganic particles include calcium carbonate, talc, kaolin (and
calcined kaolin), clay (and calcined clay), mica, aluminum
hydroxide, barium sulfate, calcium silicate, calcium sulfate,
silica, zinc carbonate, zinc oxide, titanium oxide, bentonite, and
white carbon. Calcium carbonate, silica, and calcined clay are
preferable. Calcium carbonate is particularly preferable.
[0180] The organic particles are particles made of organic
materials. Examples of the organic materials constituting the
organic particles include polysaccharides and thermoplastic resins
(such as polyvinyl alcohol, polyolefin, polystyrene). The organic
particles (such as particles of polysaccharides and particles of
thermoplastic resins) may be modified (for example, cation-modified
or anion-modified). Polysaccharides are preferable.
[0181] The polysaccharides are biopolymers synthesized in
biological systems by the condensation and polymerization of
various monosaccharides, including those that have been chemically
modified (denatured). Examples of polysaccharides include starch,
cellulose, modified cellulose, amylose, amylopectin, pullulan,
curdlan, xanthan, chitin, and chitosan. Examples of modified
cellulose include hydroxymethyl cellulose, hydroxyethyl cellulose,
and carboxymethyl cellulose.
[0182] The polysaccharides are preferably starch. Starch particles
have excellent dispersibility in the pulp slurry. The starch may be
an undenatured starch. Examples of the starches include rice flour
starch, wheat starch, corn starch, potato starch, tapioca starch,
sweet potato starch, adzuki bean starch, mung bean starch, kudzu
starch, and dogtooth violet starch. The starch may be those that
have been denatured, such as enzymatic denaturation, thermochemical
denaturation, acetate esterification, phosphate esterification,
carboxy etherification, hydroxy etherification, and cationic
denaturation. Since it gives high air permeability and high oil
resistance, the starch is preferably amphoterized starch (starch
having a cation group and an anion group) or cationized starch
(starch having a cation group). A combination of amphoterized
starch and cationized starch (at a preferred weight ratio of
0.1:9.9 to 4:6 or 0.5:9.5 to 2:8) is preferable since it also
increases water resistance.
[0183] In the particles (2), the cation group (particularly, the
cation group in the amphoterized starch or the cationized starch)
may be a cation group similar to the cation group in the monomer
having the ion donating group (c), such as an amino group, and the
anion group (particularly, the anion group in the amphoterized
starch) may be an anion group similar to the anion group in the
monomer having the ion donating group (c), such as a carboxyl
group, a sulfonic acid group, and a phosphoric acid group.
[0184] The particles (2) may have a powdery, granular, fibrous,
flaky, or a like form.
[0185] The particles (inorganic particles and organic particles)
are preferably insoluble in water at 40.degree. C. Insoluble in
water means that the solubility in 100 g of water at 40.degree. C.
is 1 g or less, such as 0.5 g or less.
[0186] The average particle size of the particles may be 0.01 to
100 .mu.m, such as 0.1 to 50 .mu.m, particularly 1.0 to 20
.mu.m.
[0187] The average particle size can be measured by a laser
diffraction particle size distribution measurement apparatus
(applying light scattering theory) using a water dispersion of the
particles.
[0188] The dissolution temperature of organic particles in water is
preferably about 55.degree. C. or more (for example, 60.degree. C.
to 100.degree. C.). The "dissolution temperature" means the highest
temperature at which the appearance of the liquid changes from
cloudy to transparent after adding 5 parts by weight of organic
particles based on 100 parts by weight of water maintained at the
target temperature with stirring by visual observation under
atmospheric pressure (the liquid might be cloudy at the time of
addition), and maintaining the liquid at the temperature for 30
minutes with continuous stirring.
[0189] Examples of such organic particles that can be dissolved in
water are undenatured starch, denatured starch (such as cationized
starch), locust bean gum, carboxymethyl cellulose, and polyvinyl
alcohol.
[0190] The organic particles may be ionic or nonionic. If the pulp
is ionic, the organic particles are preferably ionic, more
specifically anionic, cationic, or amphoteric organic particles, so
that they can be easily anchored to the pulp in the pulp slurry and
the product. Particularly, if the pulp is ionic, it is preferable
to use organic particles having the opposite ionic part to the
pulp, so that the organic particles can be effectively anchored to
the pulp (preferably together with an oil-resistant agent) and the
gas barrier properties of the finally obtained molded pulp
container can be enhanced. Pulps are usually anionic, and for such
pulps, it is preferable that the organic particles have a cationic
moiety, or more particularly are cationized or amphoterized.
[0191] Organic particles having cation moieties include cationized
starch, amphoteric starch, and cation-modified polyvinyl
alcohol.
[0192] The amount of the particles (2) is 1 to 99.9% by weight,
based on the total weight of the fluorine-free polymer (1) and the
particles (2). The lower limit of the amount of the particles (2)
may be 10% by weight, such as 30% by weight or 40% by weight,
particularly 50% by weight or 60% by weight, and especially 65% by
weight or 70% by weight. The upper limit of the amount of the
particles (2) may be 99% by weight or 98% by weight, such as 97% by
weight or 95% by weight, particularly 90% by weight, and especially
80% by weight or 70% by weight. Alternatively, the amount of the
particles (2) may be 60 to 99% by weight, such as 65 to 98% by
weight, particularly 70 to 97% by weight, based on the total weight
of the fluorine-free polymer (1) and the particles (2).
(3) Another Component
[0193] The oil-resistant agent may comprise another component (3)
other than the fluorine-free polymer (1) and the particles (2).
Examples of the other component (3) include an aqueous medium and
an emulsifier.
[0194] The aqueous medium is water or a mixture of water and an
organic solvent (an organic solvent miscible with water). The
amount of the aqueous medium may be 50% by weight to 99.99% by
weight, based on the total amount of the fluorine-free polymer (1)
(and the particles (2), if necessary) and the aqueous medium.
[0195] The amount of the emulsifier may be 0 to 30 parts by weight,
such as 0.1 to 10 parts by weight, based on 100 parts by weight of
the fluorine-free polymer (1).
[Oil-Resistant Agent]
[0196] The oil-resistant agent may be in the form of a solution, an
emulsion, or an aerosol. The oil-resistant agent may comprise the
fluorine-free polymer (1) and a liquid medium. The liquid medium
is, for example, an organic solvent and/or water, and preferably an
aqueous medium. The aqueous medium is water or a mixture of water
and an organic solvent (such as polypropylene glycol and/or a
derivative thereof).
[0197] In the case of a dispersion (emulsion) form, the
fluorine-free polymer is a water dispersion type which is dispersed
in an aqueous medium, and the fluorine-free polymer (1) may be
self-emulsified, dispersed in the aqueous medium in the form of a
neutralized salt, or emulsified using an emulsifier.
[0198] The particles (2) may be used in the form of solid or
dispersed in a liquid medium. The fluorine-free polymer (1) and the
particles (2) may be dispersed in the same liquid medium or may be
dispersed in different liquid media. In the oil-resistant agent,
the concentration of the fluorine-free polymer may be, for example,
0.01 to 50% by weight. The oil-resistant agent may either comprise
or not comprise an emulsifier, but it is preferable not to comprise
an emulsifier.
[0199] The oil-resistant agent can be used to treat a paper
substrate. The "treatment" means that the oil-resistant agent is
applied to interior and/or exterior of paper.
[0200] The oil-resistant agent can be applied to the substrate by a
conventionally known method. The oil-resistant agent is mainly
present inside the paper through internal treatment.
[0201] Examples of the paper substrate to be treated include paper,
a container made of paper, and a molded article made of paper (for
example, molded pulp).
[0202] The fluorine-free polymer favorably adheres to the paper
substrate.
[0203] The oil-resistant agent should be used such that the amount
of fluorine-free polymer (1) and the particles (2) is 0.01 to 75
parts by weight, such as 0.1 to 60 parts by weight, based on 100
parts by weight of pulp solids.
[Papermaking]
[0204] Paper can be produced by a conventionally known papermaking
method. An internal treatment method in which the oil-resistant
agent is added to a pulp slurry before papermaking, or an external
treatment method in which the oil-resistant agent is applied to
paper after papermaking, can be used. The method of treatment with
the oil-resistant agent in the present disclosure is preferably an
internal treatment method. Even if the oil-resistant agent of the
present disclosure is used in the internal treatment, no new
equipment is required.
[0205] In the internal treatment method, paper treated by the
oil-resistant agent may be produced by mixing the oil-resistant
agent with pulp slurry and paper making. The paper treated by the
oil-resistant agent is oil-resistant paper having oil resistance.
The oil-resistant paper can be thin or thick, or molded pulp.
[0206] Paper thus treated, after rough drying at room temperature
or high temperature, is optionally subjected to a heat treatment
that can have a temperature range of up to 300.degree. C., such as
up to 200.degree. C., particularly 80.degree. C. to 180.degree. C.,
depending on the properties of the paper, and thus shows excellent
oil resistance and water resistance.
[0207] The present disclosure can be used in gypsum board base
paper, coated base paper, wood containing paper, commonly used
liner and corrugating medium, neutral machine glazed paper, neutral
liner, rustproof liner and metal laminated paper, kraft paper, and
the like. The present disclosure can also be used in neutral
printing writing paper, neutral coated base paper, neutral PPC
paper, neutral heat sensitive paper, neutral pressure sensitive
base paper, neutral inkjet paper, and neutral communication
paper.
[0208] A pulp (pulp raw material) may be any of bleached or
unbleached chemical pulp such as kraft pulp or sulfite pulp,
bleached or unbleached high yield pulp such as ground pulp,
mechanical pulp, or thermomechanical pulp, waste paper pulp such as
waste newspaper, waste magazine, waste corrugated cardboard, or
waste deinked paper, and non-wood pulp such as bagasse pulp, kenaf
pulp, or bamboo pulp. The pulp raw material may be a combination of
one or more of these. A mixture of the above pulp raw material and
one or more of synthetic fiber of asbestos, polyamide, polyimide,
polyester, polyolefin, or the like can be used as well.
[0209] In the internal treatment, a pulp slurry having a pulp
concentration of 0.5 to 5.0% by weight (such as 2.5 to 4.0% by
weight) is preferably formed into paper. An additive (such as a
sizing agent, a paper strengthening agent, a flocculant, a
retention aid, or a coagulant) and the fluorine-free polymer can be
added to the pulp slurry. Since the pulp is generally anionic, at
least one of the additive and the fluorine-free polymer is
preferably cationic or amphoteric such that the additive and the
fluorine-free polymer are favorably anchored to paper. A
combination of a cationic or amphoteric additive and an anionic
fluorine-free polymer, a combination of an anionic additive and a
cationic or amphoteric fluorine-free polymer, and a combination of
a cationic or amphoteric additive and fluorine-free polymer are
preferably used.
[0210] Other components (additives) may be used in addition to the
oil-resistant agent. Examples of the other components are cationic
coagulants, water-resistant agents, paper strength additives,
flocculants, fixing agents, and yield improvers.
[0211] Cationic coagulants, paper strength additives, flocculants,
fixing agents, and yield improvers can be polymers or inorganic
materials which are cationic or amphoteric. The cationic
coagulants, paper strength additives, flocculants, fixing agents,
and yield improvers can effectively anchor the oil-resistant agent
consisting of the fluorine-free polymer (1) and the particles (2)
to the pulp, which is generally anionic, and the gas barrier
properties and/or water resistance and oil resistance of the
finally obtained molded pulp container can be enhanced.
[0212] Examples of cationic coagulants, paper strength additives,
flocculants, fixing agents, and yield improvers include a polyamine
epichlorohydrin resin, a polyamide epichlorohydrin resin, cationic
polyacrylamide (an acrylamide-allylamine copolymer, an
acrylamide-dimethylaminoethyl (meth)acrylate copolymer, an
acrylamide-diethylaminoethyl (meth)acrylate copolymer, an
acrylamide-quaternized dimethylaminoethyl (meth)acrylate copolymer,
an acrylamide-quaternized diethylaminoethyl (meth)acrylate
copolymer, or the like), polydiallyldimethylammonium chloride,
polyallylamine, polyvinylamine, polyethyleneimine, an
N-vinylformamide-vinylamine copolymer, a melamine resin, a
polyamide epoxy resin, sulfate band, PAC (polyaluminum chloride),
aluminum chloride, and ferric chloride. Particularly,
polyamidepolyamine-epichlorohydrin (PAE),
polydiallyldimethylammonium chloride (poly-DADMAC), polyacrylamide
(PAM), and the like can be used.
[0213] A water-resistant agent may be used in addition to the
oil-resistant agent. In the present disclosure, the
"water-resistant agent" refers to a component that, when added to
the pulp slurry, is capable of increasing the water resistance of a
molded pulp product as compared to the case where it is not added
(provided that the above-described oil-resistant agent is
excluded). Due to the water-resistant agent, the water resistance
of the finally obtained molded pulp container can be increased. The
above-described cationic coagulant is generally incapable of
increasing water resistance by itself and can be understood as
being different from the water-resistant agent.
[0214] A sizing agent or the like used in ordinary papermaking is
usable as a water-resistant agent. Examples of the water-resistant
agent include cationic sizing agents, anionic sizing agents, and
rosin-based sizing agents (such as acidic rosin-based sizing agents
or neutral rosin-based sizing agents), and cationic sizing agents
are preferable. Particularly, a styrene-containing polymer such as
a styrene-(meth)acrylate copolymer, an alkenyl succinic anhydride,
and an alkyl ketene dimer are preferable.
[0215] If necessary, a dye, a fluorescent dye, a slime control
agent, an antislip agent, an antifoaming agent, and a pitch control
agent which are usually used as paper making chemicals in paper
treatment agents may also be used.
[0216] Paper is preferably a molded pulp product. The molded pulp
product can be produced by a producing method comprising: preparing
a formulated pulp slurry by adding an oil-resistant agent to a
slurry in which pulp is dispersed in an aqueous medium, making a
molded pulp intermediate, followed by dehydrating and then at least
drying to obtain a molded pulp product.
[0217] The preparation of the formulated pulp slurry is preferably
performed such that the organic particles remain in a solid state.
For example, the formulated pulp slurry is prepared at a
temperature lower than, for example, a temperature at least
5.degree. C. lower than the dissolution temperature of the organic
particles. In the formulated pulp slurry prepared, the organic
particles remain in a solid state (powdery, granular, fibrous,
flaky, or the like depending on the organic particles used as a raw
material), and for example, when starch powder is used as a raw
material, the starch powder may remain dispersed in an aqueous
medium.
[0218] The oil-resistant agent and the organic particles, and
optionally the cationic coagulant and/or the water-resistant agent
or the like may be added to the pulp slurry in any order as long as
the organic particles remain in a solid state.
[0219] The content of each component in the formulated pulp slurry
(based on all components) can be suitably selected so as to attain
a high freeness suitable for papermaking and dehydrating and the
physical properties desired of a molded pulp product, and, for
example, can be as follows.
[0220] Aqueous medium: 89.5 to 99.89% by weight, particularly 94.5
to 99.69% by weight
[0221] Pulp: 0.1 to 5% by weight, particularly 0.3 to 2.5% by
weight
[0222] Oil-resistant agent (solids): 0.00001 to 1% by weight,
particularly 0.0001 to 0.5% by weight
[0223] Cationic coagulant (solids): 0 to 1% by weight, particularly
0 to 0.5% by weight (when added, for example, 0.00005% by weight or
more)
[0224] Water-resistant agent (solids): 0 to 1% by weight,
particularly 0 to 0.5% by weight (when added, for example, 0.00005%
by weight or more)
[0225] When each component is in the form of, for example, a
dispersion, the above content indicates the solid content (based on
all components) of each component in the formulated pulp
slurry.
[0226] From another viewpoint, the content of each of the pulp and
the oil-resistant agent based on the aqueous medium in the
formulated pulp slurry can be suitably selected so as to attain a
high freeness suitable for papermaking and dehydrating, and for
example, can be as follows.
[0227] Pulp: 0.1 to 5.58% by weight, particularly 0.3 to 2.64% by
weight
[0228] Oil-resistant agent (solids): 0.001 to 2.79% by weight,
particularly 0.005 to 1.05% by weight
[0229] When the organic particles are dissolved in the aqueous
medium (or when an aqueous solution in which the organic particles
such as starch are dissolved in advance in the aqueous medium is
added to a pulp slurry), the resulting aqueous composition has a
reduced freeness. On the other hand, in the formulated pulp slurry,
the organic particles remain in a solid state without being
dissolved in the aqueous medium, and therefore, as compared to the
case where the organic particles are dissolved in the aqueous
medium, a larger amount of the organic particles can be added while
maintaining the high freeness of the formulated pulp slurry.
[0230] Next, the formulated pulp slurry prepared above is made to
form a molded pulp intermediate, the molded pulp intermediate is
dehydrated and then at least dried to obtain a molded pulp
product.
[0231] Papermaking, dehydrating, and drying can be performed
according to conventionally known methods concerning molded
pulp.
[0232] For example, by straining the formulated pulp slurry to
dehydrate it (for example, by suction and/or pressure reduction)
using a mold which has a desired shape and which is provided with
numerous holes (and that may be equipped with a filter as
necessary), the aqueous medium can be at least partially removed
from the formulated pulp slurry, and a molded pulp intermediate
having a shape that corresponds to the mold can be obtained.
[0233] The process from the preparation to the dehydration of the
formulated pulp slurry is performed, with the organic particles
remaining in a solid state. For example, after preparation,
dehydrating is performed at a temperature lower than, such as a
temperature at least 5.degree. C. lower than the dissolution
temperature of the organic particles. As for papermaking and
dehydrating, the aqueous medium is removed from the formulated pulp
slurry through a mold (and optionally a filter), and therefore, an
excessively lowered freeness of the formulated pulp slurry due to
dissolution of the organic particles makes it substantially
impossible to perform papermaking and dehydrating and is thus not
preferable. On the other hand, with the organic particles remaining
in a solid state, the freeness of the formulated pulp slurry is not
lowered, and papermaking and dehydrating can be appropriately
performed.
[0234] After dehydrating, in the resulting molded pulp
intermediate, the organic particles remain in a solid state
(powdery, granular, fibrous, flaky, or the like depending on the
organic particles used as raw materials) and, for example, when
starch powder is used as a raw material, the starch powder may be
dispersed in the pulp.
[0235] Drying does not need to be performed such that the organic
particles remain in a solid state, and can be performed at a
temperature at which the remaining aqueous medium can be
effectively removed (if applicable, it can be a temperature equal
to or higher than the dissolution temperature of the organic
particles), for example, 90 to 250.degree. C., particularly 100 to
200.degree. C. The drying time is not limited, and can be selected
such that the aqueous medium remaining in the molded pulp
intermediate is substantially removed. The drying atmosphere is not
limited, and may be conveniently an ambient atmosphere (air under
normal pressure).
[0236] During and/or after drying, other steps which are
conventionally known concerning molded pulp, for example, press
molding (including heat pressing), may be performed if
necessary.
[0237] During drying and/or press molding, causing the organic
particles to at least partially dissolve makes it possible to
obtain even higher gas barrier properties. The organic particles do
not need to dissolve entirely, and the organic particles may
partially remain in a solid state.
[0238] Thus, a molded pulp product can be produced. This molded
pulp product comprises a pulp, an oil-resistant agent, and can
achieve high gas barrier properties and excellent water resistance
and oil resistance.
[0239] In the molded pulp product of the present disclosure, the
content of the organic particles based on the pulp is 0.0001 to 75%
by weight, such as 0.1 to 60% by weight, particularly 2 to 50% by
weight.
[0240] When a molded pulp product is obtained by adding an aqueous
solution in which organic particles such as starch are dissolved in
advance in an aqueous medium to a pulp slurry to increase strength,
a sufficient strength improving effect can be obtained even when
the content of organic particles based on the pulp is low, and it
was thus not required to increase the content of the organic
particles based on the pulp.
[0241] In the present disclosure, the content of the organic
particles based on the pulp is preferably high, and the lower limit
of the content of the organic particles based on the pulp may be 3%
by weight or 5% by weight, such as 8% by weight or 10% by weight,
particularly 15% by weight. The upper limit of the content of the
organic particles based on the pulp may be 60% by weight, such as
50% by weight or 40% by weight, particularly 30% by weight or 20%
by weight. The content of the organic particles based on the pulp
may be 3 to 70% by weight or 5 to 60% by weight, such as 8 to 50%
by weight or 8 to 40% by weight. In other words, the content of the
organic particles may be 3 to 70 parts by weight or 5 to 60 parts
by weight, such as 8 to 50 parts by weight or 8 to 40 parts by
weight, based on the 100 parts by weight of the pulp. With such a
high content of the organic particles, it is possible to not only
obtain high gas barrier properties but also further increase water
resistance and oil resistance.
[0242] In the molded pulp product, the organic particles may be
derived from starch powder dispersed in the aqueous medium (in the
formulated pulp slurry).
[0243] The proportions of the pulp, the organic particles, the
oil-resistant agent, and optionally the cationic coagulant and/or
the water-resistant agent contained in the molded pulp product can
be considered substantially the same as the solid contents of these
components used as raw materials (usually, the aqueous medium and,
if present, other liquid media can be removed by drying and press
molding, but the solids can remain without being removed or
decomposed).
[0244] In the molded pulp product, the content of each component (a
component that can remain in the molded pulp product) based on the
pulp (solids) can be suitably selected according to the physical
properties desired of the molded pulp product, and, for example,
can be as follows.
[0245] Oil-resistant agent (solids): 0.01 to 50% by weight or 0.01
to 20% by weight, particularly 0.05 to 10% by weight
[0246] Cationic coagulant (solids): 0 to 20% by weight,
particularly 0 to 10% by weight (if present, such as 0.001% by
weight or more)
[0247] water-resistant agent (solids): 0 to 20% by weight,
particularly 0 to 10% by weight (if present, such as 0.001% by
weight or more)
[0248] The oil-resistant agent are internally added to the molded
pulp product (they are added to a pulp slurry, and the molded pulp
product is produced by a pulp molding method). Accordingly, after
the molded pulp product is used, the entirety of the product can be
crushed to bring it back to the original raw materials, and is thus
suitable for recycle use. Furthermore, it is possible to utilize
the intrinsic biodegradability of the pulp, the molded pulp product
can extremely reduce and preferably can substantially eliminate the
environmental burden. Also, with the molded pulp product, the
texture of the pulp can be maintained on the front side of the
product, and the appearance is not impaired unlike when the front
side is laminated with a plastic film and becomes glossy.
[0249] The molded pulp product can be suitably used as food
containers (including trays and the like), for example, storage
containers for frozen food and chilled food.
[0250] Since the molded pulp product of the present disclosure has
excellent water resistance and oil resistance, moisture and oil
derived from food do not impregnate the molded pulp product (a
container), and it is thus possible to prevent deterioration of
container strength resulting from impregnation with water and oil
and prevent staining of the table surface or the like facing the
bottom surface of the container with moisture and oil permeated
through the container. Also, the molded pulp product of the present
disclosure has high gas barrier properties and unlikely allows gas
and water vapor to permeate, and thus, when accommodating hot and
wet food or when heated in a microwave with food being accommodated
therein, it is possible to prevent the problem that gas and water
vapor derived from food permeate through the container and leak to
the outside and, particularly, condense on the table surface or the
like facing the bottom surface of the container. Further, the
molded pulp product of the present disclosure has high gas barrier
properties and unlikely allow gas and water vapor (or moisture) to
permeate, and thus, when refrigerating accommodated food,
evaporation of water from food and exposure of food to oxygen can
be effectively reduced, freezer burn resulting therefrom can be
effectively prevented, and the flavor of food can be maintained for
a long period of time.
[0251] Embodiments have been described above, but it will be
understood that various changes to form and detail can be made
without departing from the spirit and scope of the claims.
EXAMPLES
[0252] Next, the present disclosure will now be described in detail
by way of Examples, Comparative Examples, and Test Examples.
However, the description of these does not limit the present
disclosure.
[0253] Below, a part, %, and a ratio indicate a part by weight, %
by weight, and a weight ratio, respectively, unless otherwise
specified.
[0254] The test methods used below are as follows.
[High-Temperature Oil Resistance]
[0255] First, 100 ml of an evaluation liquid (corn oil) at
90.degree. C. was poured into a molded pulp product molded into a
container shape, the molded pulp product was left to stand still
for 30 minutes, then the evaluation liquid was discarded, and the
extent of impregnation of the molded pulp product (the container)
with the evaluation liquid was visually evaluated according to the
following criteria.
[0256] 4: Almost no oil stains observed in the interior of the
bottom of the molded pulp container
[0257] 3: No oil stains observed on the exterior of the bottom of
the molded pulp container
[0258] 2: Oil stains observed on less than 5% of the exterior area
of the bottom of the molded pulp container
[0259] 1: Oil stains observed on 5% or more and less than 50% of
the exterior area of the bottom of the molded pulp container
[0260] 0: Oil stains observed on 50% or more of the exterior area
of the bottom of the molded pulp container
[High-Temperature Water Resistance]
[0261] First, 100 ml of an evaluation liquid (tap water) at
90.degree. C. was poured into a molded pulp product molded into a
container shape, the molded pulp product was left to stand still
for 30 minutes, then the evaluation liquid was discarded, and the
extent of impregnation of the molded pulp product (the container)
with the evaluation liquid was visually evaluated according to the
following criteria.
[0262] 4: Almost no water stains observed in the interior of the
bottom of the molded pulp container
[0263] 3: No water stains observed on the exterior of the bottom of
the molded pulp container
[0264] 2: Water stains observed on less than 5% of the exterior
area of the bottom of the molded pulp container
[0265] 1: Water stains observed on 5% or more and less than 50% of
the exterior area of the bottom of the molded pulp container
[0266] 0: Water stains observed on 50% or more of the exterior area
of the bottom of the molded pulp container
[Air Permeance]
[0267] The air permeance (air resistance) at the bottom part of a
molded pulp product molded into a container shape was measured in
accordance with JIS P 8117 (2009) using an automatic Gurley
densometer manufactured by YASUDA SEIKI SEISAKUSHO, LTD. (Product
No. 323-AUTO, vent hole diameter 28.6.+-.0.1 mm). The measured
value of air permeance was evaluated according to the following
criteria.
Evaluation Criteria
[0268] Excellent: 500 seconds or more
[0269] Good: 300 seconds or more
[0270] Fair: 100 seconds or more
[0271] Poor: less than 100 seconds
Synthesis Example 1
[0272] A reactor having a volume of 500 ml and equipped with a
stirrer, a thermometer, a reflux condenser, a dropping funnel, a
nitrogen inlet, and a heater was provided, and 100 parts of a
methyl ethyl ketone (MEK) solvent was added. Subsequently, while
the solvent is stirred, a monomer composed of 78 parts of stearyl
acrylate (StA, melting point: 30.degree. C.), 16 parts of
hydroxyethyl acrylate (HEA), and 6 parts of methacrylic acid (MAA)
(the monomer being 100 parts in total) as well as 1.2 parts of a
perbutyl PV (PV) initiator were added in this order, and the
mixture was mixed by being stirred for 12 hours in a nitrogen
atmosphere at 65 to 75.degree. C. to carry out copolymerization.
The solid content concentration of the resulting
copolymer-containing solution was 50% by weight. When the molecular
weight of the resulting copolymer was analyzed by gel permeation
chromatography, the weight-average molecular weight in terms of
polystyrene was 230,000.
[0273] As a post-treatment, 142 g of a 0.3% aqueous NaOH solution
was added to 50 g of the resulting copolymer solution and
dispersed, then MEK was distilled off under reduced pressure while
heating the mixture by using an evaporator, and thus a milky white
water dispersion of a copolymer was obtained (the content of the
volatile organic solvent was 1% by weight or less). Moreover,
ion-exchanged water was added to the water dispersion, and thus a
water dispersion having a solid content concentration of 15% by
weight was obtained.
[0274] The melting point of the copolymer was 48.degree. C.
Synthesis Example 2
[0275] A reactor having a volume of 500 ml and equipped with a
stirrer, a thermometer, a reflux condenser, a dropping funnel, a
nitrogen inlet, and a heater was provided, and 100 parts of a
methyl ethyl ketone (MEK) solvent was added. Subsequently, while
the solvent is stirred, a monomer composed of 78 parts of stearic
acid amide ethyl acrylate (C18AmEA, melting point: 70.degree. C.),
16 parts of hydroxybutyl acrylate (HBA, Tg: -40.degree. C.), and 6
parts of dimethylaminoethyl methacrylate (DM) (the monomer being
100 parts in total) as well as 1.2 parts of a perbutyl PV (PV)
initiator were added in this order, and mixed by being stirred for
12 hours in a nitrogen atmosphere at 65 to 75.degree. C. to carry
out copolymerization. The solid content concentration of the
resulting copolymer-containing solution was 50% by weight.
[0276] As a post-treatment, 142 g of a 0.4% aqueous acetic acid
solution was added to 50 g of the resulting copolymer solution and
dispersed, then the mixture was heated by using an evaporator to
distill off MEK under reduced pressure, and thus a light brown
copolymer-water dispersion liquid (the content of the volatile
organic solvent was 1% by weight or less) was obtained. Moreover,
ion-exchanged water was added to the water dispersion, and thus a
water dispersion having a solid content concentration of 15% by
weight was obtained.
Example 1
[0277] 2,400 g of a 0.5% by weight of the water dispersion of a
mixture of 70 parts of leaf bleached kraft pulp and 30 parts of
needle bleached kraft pulp beaten to a freeness (Canadian Freeness)
of 550 cc, was added with contiguous stirring. Next, 1.2 g of
calcium carbonate was added and kept stirring for 1 minute, and 2.4
g of a 5% solid aqueous solution of amphoterized starch was added
and kept stirring for 1 minute. Then, 0.72 g of a 5% solid aqueous
solution of alkyl ketene dimer (AKD) was added and kept stirring
for 1 minute, and subsequently 3.6 g of the water dispersion of the
fluorine-free copolymer of Synthesis Example 2 diluted with water
to a solid content of 10% was added and kept stirring for 1
minute.
[0278] The above pulp slurry was placed in a metal tank. In the
lower part of the tank, a metal pulp mold with many suction holes
was present with a reticular body placed on top of the mold. From
the side opposite to the side where the reticular body of the pulp
mold was placed, the pulp-containing aqueous composition was
suctioned and dehydrated through the pulp mold and the reticular
body using a vacuum pump, and the solids (such as a pulp) contained
in the pulp-containing aqueous composition were deposited on the
reticular body to obtain a molded pulp intermediate. Next, the
resulting molded pulp intermediate was dried by applying pressure
from top and bottom with metal male and female molds heated to 60
to 200.degree. C. As a result, a molded pulp product molded into a
container shape was produced. Table 1 shows the results of
evaluating the content of each component based on the pulp in the
resulting molded pulp product, as well as high-temperature
oil-resistant characteristics, high-temperature water-resistant
characteristics, and air permeance.
Example 2
[0279] 2,400 g of a 0.5% by weight of the water dispersion of a
mixture of 70 parts of leaf bleached kraft pulp and 30 parts of
needle bleached kraft pulp beaten to a freeness (Canadian Freeness)
of 550 cc, was added with contiguous stirring. Next, 0.6 g of
calcium carbonate was added and kept stirring for 1 minute, and 1.2
g of cationized starch powder was added and kept stirring for 1
minute. Then, 2.4 g of a 5% solid aqueous solution of amphoterized
starch was added and kept stirring for 1 minute, and 0.72 g of a 5%
solid aqueous solution of alkyl ketene dimer (AKD) was added and
kept stirring for 1 minute. Subsequently, 3.6 g of the water
dispersion of the fluorine-free copolymer of Synthesis Example 2
diluted with water to a solid content of 10% was added and kept
stirring for 1 minute.
[0280] Thereafter, molded pulp products were produced in the same
manner as in Example 1, except that the above pulp slurry was used.
Table 1 shows the results of evaluating the content of each
component based on the pulp in the resulting molded pulp product,
as well as high-temperature oil-resistant characteristics,
high-temperature water-resistant characteristics, and air
permeance.
Example 3
[0281] The experiment was performed in the same manner as in
Example 1, except that 1.2 g of calcium carbonate in Example 2 was
added, and 2.4 g of cationized starch powder was added. Table 1
shows the results of evaluating the content of each component based
on the pulp in the resulting molded pulp product, as well as
high-temperature oil-resistant characteristics, high-temperature
water-resistant characteristics, and air permeance.
Example 4
[0282] The experiment was performed in the same manner as in
Example 1, except that 2.4 g of the water dispersion of the
fluorine-free copolymer of Synthesis Example 2 in Example 3 diluted
with water to a solid content of 10% was added. Table 1 shows the
results of evaluating the content of each component based on the
pulp in the resulting molded pulp product, as well as
high-temperature oil-resistant characteristics, high-temperature
water-resistant characteristics, and air permeance.
Example 5
[0283] The experiment was performed in the same manner as in
Example 1, except that 4.8 g of cationized starch powder in Example
4 was added. Table 1 shows the results of evaluating the content of
each component based on the pulp in the resulting molded pulp
product, as well as high-temperature oil-resistant characteristics,
high-temperature water-resistant characteristics, and air
permeance.
Example 6
[0284] The experiment was performed in the same manner as in
Example 1, except that calcium carbonate in Example 5 was not
added, and 3.6 g of the water dispersion of the fluorine-free
copolymer of Synthesis Example 2 diluted with water to a solid
content of 10% was added. Table 1 shows the results of evaluating
the content of each component based on the pulp in the resulting
molded pulp product, as well as high-temperature oil-resistant
characteristics, high-temperature water-resistant characteristics,
and air permeance.
Example 7
[0285] The experiment was performed in the same manner as in
Example 1, except that a 5% solid aqueous solution of amphoterized
starch in Example 5 was not added, and a 5% solid aqueous solution
of alkyl ketene dimer (AKD) was not added. Table 1 shows the
results of evaluating the content of each component based on the
pulp in the resulting molded pulp product, as well as
high-temperature oil-resistant characteristics, high-temperature
water-resistant characteristics, and air permeance.
Example 8
[0286] The experiment was performed in the same manner as in
Example 1, except that 0.6 g of calcium carbonate in Example 1 was
added. Table 1 shows the results of evaluating the content of each
component based on the pulp in the resulting molded pulp product,
as well as high-temperature oil-resistant characteristics,
high-temperature water-resistant characteristics, and air
permeance.
Example 9
[0287] The experiment was performed in the same manner as in
Example 1, except that 3.6 g of the water dispersion of the
fluorine-free copolymer of Synthesis Example 2 in Example 8 diluted
with water to a solid content of 10% was added and kept stirring
for 1 minute, and then 6.0 g of the water dispersion of the
fluorine-free copolymer of Synthesis Example 1 diluted with water
to a solid content of 10% was added and kept stirring for 1 minute.
Table 1 shows the results of evaluating the content of each
component based on the pulp in the resulting molded pulp product,
as well as high-temperature oil-resistant characteristics,
high-temperature water-resistant characteristics, and air
permeance.
Example 10
[0288] The experiment was performed in the same manner as in
Example 1, except that a 5% solid aqueous solution of the alkyl
ketene dimer (AKD) in Example 3 was not added. Table 1 shows the
results of evaluating the content of each component based on the
pulp in the resulting molded pulp product, as well as
high-temperature oil-resistant characteristics, high-temperature
water-resistant characteristics, and air permeance.
Comparative Example 1
[0289] The experiment was performed in the same manner as in
Example 1, except that calcium carbonate in Example 1 was not
added, and 3.6 g of styrene-butadiene latex diluted with water to a
solid content of 10% was added in place of the water dispersion of
the fluorine-free copolymer of Synthesis Example 2 diluted with
water to a solid content of 10%. Table 1 shows the results of
evaluating the content of each component based on the pulp in the
resulting molded pulp product, as well as high-temperature
oil-resistant characteristics, high-temperature water-resistant
characteristics, and air permeance.
Comparative Example 2
[0290] The experiment was performed in the same manner as in
Example 1 except that 3.6 g of styrene-butadiene latex diluted with
water to a solid content of 10% was added in place of the water
dispersion of the fluorine-free copolymer of Synthesis Example 2 in
Example 2 diluted with water to a solid content of 10%. Table 1
shows the results of evaluating the content of each component based
on the pulp in the resulting molded pulp product, as well as
high-temperature oil-resistant characteristics, high-temperature
water-resistant characteristics, and air permeance.
TABLE-US-00001 TABLE 1 Ex. Ex. Ex. Ex. Ex. Com. Com. Ex. 1 Ex. 2
Ex. 3 Ex. 4 Ex. 5 6 7 8 9 10 Ex. 1 Ex. 2 Particles Inorganic
Calcium solid %/ 10% 5% 10% 10% 10% 10% 5% 5% 10% 5% Particles
carbonate pulp Organic Cationized solid %/ 10% 20% 20% 40% 40% 40%
20% 10% Particles starch pulp Aqueous starch Amphoterized solid %/
1% 1% 1% 1% 1% 1% 1% 1% 1% 1% 1% solution starch pulp Water- Alkyl
ketene dimer solid %/ 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3%
0.3% resistant (AKD) pulp agent Treatment Acrylic Syn. Ex. 1 solid
%/ 5% agent polymer pulp Syn. Ex. 2 solid %/ 3% 3% 3% 2% 2% 2% 2%
3% 3% 3% pulp Styrene-butadiene latex solid %/ 3% 3% pulp
High-temp. oil- Corn oil 90.degree. C. .times. 30 min. 3 3 4 3 4 4
4 2 3 4 0 0 resistance High-temp. water- Tap water 90.degree. C.
.times. 30 3 3 3 3 3 3 1 3 3 1 4 4 resistance min. Air permeance
Evaluation Poor Fair Ex- Ex- Ex- Ex- Ex- Poor Poor Ex- Poor Fair
cellent cellent cellent cellent cellent cellent Measured value
(sec.) 37 161 701 718 801 797 783 30 33 687 42 177
INDUSTRIAL APPLICABILITY
[0291] The oil-resistant agent of the present disclosure is
applicable to a variety of paper, particularly paper for use in a
food container and a food packaging material. The oil-resistant
agent is externally or internally, particularly internally
incorporated into the paper.
* * * * *