U.S. patent application number 15/561862 was filed with the patent office on 2018-04-26 for resin for ink and ink.
This patent application is currently assigned to HARIMA CHEMICALS, INCORPORATED. The applicant listed for this patent is HARIMA CHEMICALS, INCORPORATED. Invention is credited to Hiroyuki HISADA, Yasunori OHASHI, Maiko YAMAMOTO, Lin ZHOU.
Application Number | 20180112024 15/561862 |
Document ID | / |
Family ID | 57007034 |
Filed Date | 2018-04-26 |
United States Patent
Application |
20180112024 |
Kind Code |
A1 |
OHASHI; Yasunori ; et
al. |
April 26, 2018 |
RESIN FOR INK AND INK
Abstract
A resin for ink is obtained by reaction of a lignin, phenols,
aldehydes, a rosin-based resin, and polyhydric alcohol.
Inventors: |
OHASHI; Yasunori; (Hyogo,
JP) ; HISADA; Hiroyuki; (Hyogo, JP) ; ZHOU;
Lin; (Hyogo, JP) ; YAMAMOTO; Maiko; (Hyogo,
JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
HARIMA CHEMICALS, INCORPORATED |
Kakogawa-shi, Hyogo |
|
JP |
|
|
Assignee: |
HARIMA CHEMICALS,
INCORPORATED
Kakogawa-shi, Hyogo
JP
|
Family ID: |
57007034 |
Appl. No.: |
15/561862 |
Filed: |
February 29, 2016 |
PCT Filed: |
February 29, 2016 |
PCT NO: |
PCT/JP2016/056023 |
371 Date: |
September 26, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C09D 161/14 20130101;
C08G 8/34 20130101; C09D 11/08 20130101; C09D 11/103 20130101 |
International
Class: |
C08G 8/34 20060101
C08G008/34; C09D 11/103 20060101 C09D011/103; C09D 161/14 20060101
C09D161/14 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 31, 2015 |
JP |
2015-070997 |
Claims
1. A resin for ink obtained by reaction of a lignin, phenols,
aldehydes, a rosin-based resin, and polyhydric alcohol.
2. The resin for ink according to claim 1, obtained by reaction of
a lignin-containing resol-type phenolic resin obtained by reaction
of the lignin, the phenols, and the aldehydes; the rosin-based
resin; and the polyhydric alcohol.
3. The resin for ink according to claim 2, wherein the
lignin-containing resol-type phenolic resin is obtained by allowing
a phenol-modified lignin obtained after allowing the lignin to
react with the phenols under the presence of an acid catalyst to
react with the aldehydes under the presence of an alkali
catalyst.
4. The resin for ink according to claim 1, wherein the lignin is
modified with acetic acid.
5. Ink containing a resin for ink according to claim 1.
Description
TECHNICAL FIELD
[0001] The present invention relates to a resin for ink and ink,
more specifically, a resin for ink and ink containing the resin for
ink.
BACKGROUND ART
[0002] Conventionally, printing ink used in offset printing or the
like contains, for example, a varnish containing a resin for ink
such as a rosin-modified phenolic resin, a rosin ester resin, a
maleic acid resin, a petroleum resin, and an alkyd resin and
colorant (pigment).
[0003] More specifically, a varnish containing a rosin-modified
phenolic resin ("d" component), which is a reaction product of a
resol resin ("a" component) having a phenol average nucleus number
of 6 to 10, a condensation product ("b" component) of rosin and/or
rosin and an unsaturated carboxylic acid, and polyhydric alcohol
("c" component) and has a weight average molecular weight of 40,000
to 200,000, and printing ink containing the varnish have been
proposed (see Patent Document 1).
CITATION LIST
Patent Document
[0004] Patent Document 1: Japanese Unexamined Patent Publication
No. 2002-322411
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0005] Meanwhile, ink is required not to be scattered at the time
of its use, that is, to have misting resistance. Scattering
(misting) at the time of the use usually easily occurs in a case
where the elasticity and the viscosity of ink are low, so that a
certain degree of elasticity and viscosity of the ink are required
in order to obtain excellent misting resistance. There is, however,
a disadvantage that in the case of excessively high viscosity
(tackiness) of the ink, the printing properties (gloss or the like)
are poor.
[0006] An object of the invention is, therefore, to provide a resin
for ink capable of ensuring excellent printing properties and
improving misting resistance and ink containing the resin for
ink.
Means for Solving the Problem
[0007] The invention [1] includes a resin for ink, wherein the
resin for ink is obtained by reaction of a lignin, phenols,
aldehydes, a rosin-based resin, and polyhydric alcohol.
[0008] The invention [2] includes the resin for ink as described in
the above [1], wherein the resin for ink is obtained by reaction of
a lignin-containing resol-type phenolic resin obtained by reaction
of the lignin, the phenols, and the aldehydes; the rosin-based
resin; and the polyhydric alcohol.
[0009] The invention [3] includes the resin for ink as described in
the above [2], wherein the lignin-containing resol-type phenolic
resin is obtained by allowing a phenol-modified lignin obtained
after allowing the lignin to react with the phenols under the
presence of an acid catalyst to react with the aldehydes under the
presence of an alkali catalyst.
[0010] The invention [4] includes the resin for ink as described in
any one of the above [1] to [4], wherein the lignin is modified
with acetic acid.
[0011] The invention [5] includes the ink containing the resin for
ink as described in any one of the above [1] to [4].
Effect of the Invention
[0012] According to the resin for ink and the ink of the invention,
excellent printing properties are ensured and improvement of
misting resistance can be achieved.
EMBODIMENT OF THE INVENTION
[0013] A resin for ink of the invention is obtained by reaction of
a lignin, phenols, aldehydes, a rosin-based resin, and polyhydric
alcohol.
[0014] Lignins are polymeric phenolic compounds having a basic
skeleton such as guaiacyl lignin (G type), syringyl lignin (S
type), p-hydroxyphenyl lignin (H type), or the like, which are
contained in many plants. As such lignins, known are soda lignin,
sulfite lignin, kraft lignin, and the like, which are contained in
a waste liquor (black liquor) discharged during manufacturing pulp
from plant raw materials, for example, through a soda process, a
sulfite process, a kraft process, or the like.
[0015] Specific examples of the lignins include arboreous
plant-derived lignins and herbaceous plant-derived lignins.
[0016] Examples of the arboreous plant-derived lignins include
softwood lignins contained in softwoods (for example, Japanese
cedar) and hardwood lignins contained in hardwoods. Such arboreous
plant-derived lignins do not contain lignin having an H type as a
basic skeleton. For example, softwood lignins have a G type as a
basic skeleton, while hardwood lignins have a G type and an S type
as a basic skeleton.
[0017] Examples of the herbaceous plant-derived lignins include
gramineous lignins contained in gramineous plants (such as wheat
straw, rice straw, corn, and bamboo). These herbaceous
plant-derived lignins have all of an H type, a G type, and an S
type as the basic skeleton thereof.
[0018] These lignins may be used either singly or in combination of
two or more.
[0019] As the lignin, herbaceous plant-derived lignins are
preferred, with herbaceous plant-derived lignins derived from corn
stover (cobs, stalks, leaves, and the like of a maize) being more
preferred.
[0020] As the lignin, from the standpoint of reactivity, that
containing an H type as the basic skeleton thereof in an amount of
3 mass % or more is preferred, with that containing in an amount of
9 mass % or more being more preferred and that containing in an
amount of 14 mass % or more being further more preferred.
[0021] The lignin is preferably modified with a carboxylic acid.
That is, as the lignin, a lignin that is modified with a carboxylic
acid (which may hereinafter be called "carboxylic acid-modified
lignin") is preferably used.
[0022] In the carboxylic acid-modified lignin, examples of the
carboxylic acid include carboxylic acids having one carboxy group
(which may hereinafter be called "monofunctional carboxylic acid").
Specific examples thereof include saturated aliphatic
monofunctional carboxylic acids, unsaturated aliphatic
monofunctional carboxylic acids, and aromatic monofunctional
carboxylic acids.
[0023] Examples of the saturated aliphatic monofunctional
carboxylic acids include acetic acid, propionic acid, butyric acid,
and lauric acid.
[0024] Examples of the unsaturated aliphatic monofunctional
carboxylic acids include acrylic acid, methacrylic acid, and
linoleic acid.
[0025] Examples of the aromatic monofunctional carboxylic acids
include benzoic acid, 2-phenoxybenzoic acid, and 4-methylbenzoic
acid.
[0026] These carboxylic acids may be used either singly or in
combination of two or more.
[0027] The carboxylic acid is preferably a saturated aliphatic
monofunctional carboxylic acid, more preferably acetic acid (in
other words, as a lignin, a lignin modified with acetic acid is
used). Using the above-mentioned carboxylic acid enables easy
preparation of a carboxylic acid-modified lignin. The carboxylic
acid-modified lignin thus obtained has, as described later,
relatively high solubility in an organic solvent. In addition, it
is capable of melting at a relatively low temperature (from about
100 to 200.degree. C.), so that it is also excellent in ease of
handling.
[0028] The carboxylic acid can be also prepared as an aqueous
solution. In such a case, the concentration of the aqueous solution
of the carboxylic acid is not particularly limited and is
determined as needed.
[0029] A production method of a carboxylic acid-modified lignin is
not particularly limited and can be based on a known method.
[0030] Described specifically, a carboxylic acid-modified lignin
can be obtained as a pulp waste liquor by using a carboxylic acid
(preferably, acetic acid) to digest a plant material (for example,
softwood, hardwood, or gramineous plant) which will become a raw
material of a lignin.
[0031] Although the digesting method is not particularly limited,
for example, it is performed by mixing a plant material which will
become a raw material of a lignin, with a carboxylic acid and an
inorganic acid (for example, hydrochloric acid or sulfuric acid) to
allow them to react.
[0032] The mixing ratio of the carboxylic acid (in terms of 100%)
with respect to 100 parts by mass of the plant material which
becomes a raw material of the lignin is, for example, 500 parts by
mass or more, preferably 900 parts by mass or more and for example,
30000 parts by mass or less, preferably 15000 parts by mass or
less.
[0033] The mixing ratio of the inorganic acid (in terms of 100%)
with respect to 100 parts by mass of the plant material which
becomes a raw material of the lignin is, for example, 0.01 part by
mass or more, preferably 0.05 part by mass or more and for example,
10 parts by mass or less, preferably 5 parts by mass or less.
[0034] With regard to reaction conditions, the reaction temperature
is, for example, 30.degree. C. or more, preferably 50.degree. C. or
more and for example, 400.degree. C. or less, preferably
250.degree. C. or less. The reaction time is, for example, 0.5 hour
or more, preferably 1 hour or more and for example, 20 hours or
less, preferably 10 hours or less.
[0035] By such digestion, a pulp can be obtained and also a
carboxylic acid-modified lignin can be obtained as a pulp waste
liquor.
[0036] Next, in this method, the pulp is separated by a known
separation method such as filtration to collect filtrate (pulp
waste liquor) and if necessary, the carboxylic acid which has
remained unreacted is removed (distilled off) by a known method
using, for example, a rotary evaporator or vacuum distillation.
Then, a large excess of water is added to precipitate the
carboxylic acid-modified lignin, followed by filtration to obtain
the carboxylic acid-modified lignin as a solid component.
[0037] The method of obtaining a carboxylic acid-modified lignin is
not limited to the above-mentioned method. For example, a
carboxylic acid-modified lignin can be obtained by allowing a
lignin which is not modified with a carboxylic acid (which will
hereinafter be called "unmodified lignin") to react with a
carboxylic acid.
[0038] In such a method, the unmodified lignin is preferably in
powder form.
[0039] The unmodified lignin powder has an average particle size
of, for example, 0.1 pin or more, preferably 5 .mu.m or more and
for example, 1000 .mu.M or less, preferably 500 .mu.m or less.
[0040] When the unmodified lignin powder has an average particle
size falling within the above-mentioned range, it can be dispersed
well in the carboxylic acid without causing agglomeration.
[0041] The unmodified lignin powder can be obtained by drying and
grinding a massive unmodified lignin in a known manner.
Alternatively, a commercially available unmodified lignin powder
can be used.
[0042] A reaction between the unmodified lignin and the carboxylic
acid is made, for example, by mixing the unmodified lignin with the
carboxylic acid and an inorganic acid (for example, hydrochloric
acid or sulfuric acid) to allow them to react.
[0043] The mixing ratio of the carboxylic acid (in terms of 100%)
with respect to 100 parts by mass of the unmodified lignin is, for
example, 300 parts by mass or more, preferably 500 parts by mass or
more and for example, 15000 parts by mass or less, preferably 10000
parts by mass or less.
[0044] The mixing ratio of the inorganic acid (in terms of 100%)
with respect to 100 parts by mass of the unmodified lignin is, for
example, 0.01 part by mass or more, preferably 0.05 part by mass or
more and for example, 10 parts by mass or less, preferably 5 parts
by mass or less.
[0045] With regard to reaction conditions, the reaction temperature
is, for example, 30.degree. C. or more, preferably 50.degree. C. or
more and for example, 400.degree. C. or less, preferably
250.degree. C. or less. The reaction time is, for example, 0.5 hour
or more, preferably 1 hour or more and for example, 20 hours or
less, preferably 10 hours or less.
[0046] The carboxylic acid-modified lignin thus obtained is
excellent in ease of handling.
[0047] This means that a lignin not modified with a carboxylic acid
has relatively low solubility in an organic solvent and in
addition, it does not melt, so that it is inferior in ease of
handling in some applications.
[0048] The lignin modified with the carboxylic acid as described
above has relatively high solubility in an organic solvent (for
example, esters such as methyl acetate, ethyl acetate, butyl
acetate, and isobutyl acetate; ketones such as acetone, methyl
ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aliphatic
alcohols such as methanol; phenols such as phenol, cresol, and
bisphenol A; ethers such as diethyl ether, tetrahydrofuran, and
dioxane; glycol ether esters such as methyl cellosolve acetate,
ethyl cellosolve acetate, methyl carbitol acetate, ethyl carbitol
acetate, ethylene glycol ethyl ether acetate, propylene glycol
methyl ether acetate, 3-methyl-3-methoxybutyl acetate, and
ethyl-3-ethoxypropionate; nitriles such as acetonitrile; and in
addition, polar solvents such as N-methylpyrrolidone,
N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide,
and hexamethyl phosphonyl amide) and is capable of melting at a
relatively low temperature (from about 100 to 200.degree. C.), so
that it is excellent in ease of handling.
[0049] Thus, the carboxylic acid-modified lignin can be also used
as a solution of the above-mentioned organic solvent. In such a
case, the concentration of the carboxylic acid-modified lignin in
the solution is, for example, 10 mass % or more, preferably 30 mass
% or more.
[0050] The carboxylic acid-modified lignin has an average particle
size of, for example, 0.1 .mu.m or more, preferably 5 .mu.m or more
and for example, 2 cm or less, preferably 1 cm or less.
[0051] The lignin (preferably, carboxylic acid-modified lignin) has
a phenolic hydroxyl group equivalent of, for example, 100 g/eq or
more, preferably 300 g/eq or more and for example, 1700 g/eq or
less, preferably 1350 g/eq or less.
[0052] The phenolic hydroxyl group equivalent is obtained in
conformity with Examples to be described later.
[0053] The carboxylic acid-modified lignin may be obtained as a
mixture of a component (soluble component) capable of being
dissolved with the above-mentioned organic solvent (preferably,
ethyl acetate) and a component (insoluble component) incapable of
being dissolved with the above-mentioned organic solvent.
[0054] In such a case, as the carboxylic acid-modified lignin, a
mixture of the soluble component and the insoluble component (which
will hereinafter be called "crude carboxylic acid-modified lignin")
can be used.
[0055] Also, by separating the soluble component from the insoluble
component, the soluble component only can be used or the insoluble
component only can be used. Furthermore, the soluble component and
the insoluble component, which are separated, can be used by mixing
them.
[0056] As a method for separating the soluble component from the
insoluble component, for example, an extracting method with the
above-mentioned organic solvent is used.
[0057] The extracting conditions are determined as needed in
accordance with an organic solvent to be used and the physical
properties of a crude carboxylic acid-modified lignin or the
like.
[0058] When a carboxylic acid-modified lignin is used as the
lignin, improvement of misting resistance can be achieved and
furthermore, improvement of quick drying properties, abrasion
resistance, and glossiness can be achieved.
[0059] The phenols are phenol and a derivative thereof and examples
thereof include phenol; furthermore, bifunctional phenol
derivatives such as o-cresol, p-cresol, p-tert-butylphenol,
phenylphenol, cumylphenol, octylphenol (p-tert-octylphenol and the
like), nonylphenol, and 2,4- or 2,6-xylenol; trifunctional phenol
derivatives such as m-cresol, resorcinol, and 3,5-xylenol; and
tetrafunctional phenol derivatives such as bisphenol A and
dihydroxydiphenylmethane. Also, examples thereof include
halogenated phenols that are substituted with halogen such as
chlorine and bromine. These phenols may be used either singly or in
combination of two or more.
[0060] As the phenols, p-tert-butylphenol, p-tert-octylphenol, and
nonylphenol are preferred. From the standpoint of glossiness,
single use of nonylphenol is more preferred. Also, from the
standpoint of quick drying properties and misting resistance,
combination of p-tert-butylphenol and nonylphenol and combination
of p-tert-octylphenol and nonylphenol are more preferred.
[0061] Examples of the aldehydes include formaldehyde,
paraformaldehyde, acetaldehyde, propionaldehyde, butylaldehyde
(n-butylaldehyde, isobutylaldehyde), furfural, glyoxal,
benzaldehyde, trioxane, and tetraoxane. A part of aldehyde may be
substituted with furfuryl alcohol or the like. These aldehydes may
be used either singly or in combination of two or more.
[0062] As the aldehydes, formaldehyde and paraformaldehyde are
preferred.
[0063] The aldehydes can be also used as, for example, an aqueous
solution. In such a case, the concentration of the aldehydes is,
for example, 10 mass % or more, preferably 20 mass % or more and
for example, 99 mass % or less, preferably 95 mass % or less.
[0064] Examples of the rosin-based resin include rosins and rosin
derivatives.
[0065] The rosins are tall rosin, gum rosin, and wood rosin and
also the concept thereof including disproportionated rosin,
polymerized rosin, hydrogenated rosin, another chemically modified
rosin, or a refined product thereof.
[0066] Examples of the rosin derivatives include rosin esters,
unsaturated carboxylic acid-modified rosins, unsaturated carboxylic
acid-modified rosin esters, rosin-modified phenols, and rosin
alcohols in which a carboxyl group of the rosins or the rosins
modified with an unsaturated carboxylic acid is subjected to
reduction treatment.
[0067] The rosin esters can be obtained by, for example, allowing
the above-mentioned rosins and polyhydric alcohol (described later)
to react by a known esterification method.
[0068] In the mixing ratio of the rosins to the polyhydric alcohol
(described later), the molar ratio (OH/COOH) of the hydroxyl group
of the polyhydric alcohol (described later) to the carboxyl group
of the rosins is, for example, 0.2 to 1.2. In the reaction of the
rosins with the polyhydric alcohol (described later), the reaction
temperature is, for example, 150 to 300.degree. C. and the reaction
time is, for example, 2 to 30 hours. In the reaction, a known
catalyst can be blended at an appropriate proportion as needed.
[0069] The unsaturated carboxylic acid-modified rosins can be
obtained by, for example, allowing .alpha.,.beta.-unsaturated
carboxylic acids to react with the above-mentioned rosins by a
known method.
[0070] Examples of the .alpha.,.beta.-unsaturated carboxylic acids
include an .alpha.,.beta.-unsaturated carboxylic acid and an
anhydride thereof. Specific examples thereof include fumaric acid,
maleic acid, maleic anhydride, itaconic acid, citraconic acid,
citraconic anhydride, maleic anhydride, acrylic acid, and
methacrylic acid. These .alpha.,.beta.-unsaturated carboxylic acids
may be used either singly or in combination of two or more.
[0071] The mixing ratio of the .alpha.,.beta.-unsaturated
carboxylic acids with respect to 1 mol of the rosins is, for
example, 1 mol or less. In the reaction of the rosins with the
.alpha.,.beta.-unsaturated carboxylic acids, the reaction
temperature is, for example, 150 to 300.degree. C. and the reaction
time is, for example, 1 to 24 hours. In the reaction, a known
catalyst can be blended at an appropriate proportion as needed.
[0072] The unsaturated carboxylic acid-modified rosin esters can be
obtained by allowing the above-mentioned polyhydric alcohol
(described later) and the above-mentioned
.alpha.,.beta.-unsaturated carboxylic acids to successively or
simultaneously react with the above-mentioned rosins.
[0073] When the above-mentioned components are allowed to
successively react, the rosins first react with the polyhydric
alcohol (described later) and thereafter, the
.alpha.,.beta.-unsaturated carboxylic acids react, or the rosins
first react with the .alpha.,.beta.-unsaturated carboxylic acids
and thereafter, the polyhydric alcohol (described later) reacts.
The reaction conditions in esterification reaction of the rosins
with the polyhydric alcohol (described later) and those in
modification reaction of the rosins with the
.alpha.,.beta.-unsaturated carboxylic acids are the same as those
described above.
[0074] Examples of the rosin derivatives further include an amide
compound of rosin and an amine salt of rosin.
[0075] The amide compound of rosin can be obtained by allowing the
above-mentioned rosins to react with an amidating agent.
[0076] Examples of the amidating agent include a primary and/or
secondary polyamine compound, a polyoxazoline compound, and a
polyisocyanate compound.
[0077] The primary and/or secondary polyamine compound are/is a
compound having, in a molecule, two or more primary and/or
secondary amino groups and can amidate the rosins by a condensation
reaction with a carboxyl group contained in the rosins. Specific
examples of the polyamine compound include chain diamines such as
ethylenediamine, N-ethylaminoethylamine, 1,2-propanediamine,
1,3-propanediamine, N-methyl-1,3-propanediamine,
bis(3-aminopropyl)ether, 1,2-bis(3-aminopropoxy)ethane,
1,3-bis(3-aminopropoxy)-2,2-dimethylpropane, 1,4-diaminobutane, and
laurylaminopropylamine; cyclic diamines such as
2-aminomethylpiperidine, 4-aminomethylpiperidine,
1,3-di(4-piperidyl)-propane, and homopiperazine; polyamines such as
diethylenetriamine, triethylenetetramine, iminobispropylamine, and
methyliminobispropylamine; and furthermore, a hydrohalogenic acid
salt thereof.
[0078] These primary and/or secondary polyamine compounds may be
used either singly or in combination of two or more.
[0079] The polyoxazoline compound is a compound having, in a
molecule, two or more polyoxazoline rings and can amidate the
rosins by an addition reaction with a carboxyl group contained in
the rosins. An example of the polyoxazoline compound includes
2,2'-(1,3-phenylene)-bis(2-oxazoline).
[0080] These polyoxazoline compounds may be used either singly or
in combination of two or more.
[0081] The polyisocyanate compound is a compound having, in a
molecule, two or more isocyanate groups and can amidate the rosins
by an addition condensation decarboxylation reaction with a
carboxyl group contained in the rosins. Examples of the
polyisocyanate compound include aromatic diisocyanates (for
example, tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate
or mixture thereof), phenylene diisocyanate (m- or p-phenylene
diisocyanate or mixture thereof), 1,5-naphthalene diisocyanate,
diphenylmethane diisocyanate (4,4'-, 2,4'-, or 2,2'-diphenylmethane
diisocyanate or mixture thereof), 4,4'-toluidine diisocyanate, or
the like); araliphatic diisocyanates (for example, xylylene
diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixture
thereof), tetramethylxylylene diisocyanate (1,3- or
1,4-tetramethylxylylene diisocyanate or mixture thereof), or the
like); aliphatic diisocyanates (for example, 1,3-trimethylene
diisocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene
diisocyanate, 1,6-hexamethylene diisocyanate, or the like);
alicyclic diisocyanates (for example, cyclohexane diisocyanate,
3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone
diisocyanate), methylenebis(cyclohexyl isocyanate), norbornane
diisocyanate, bis(isocyanatomethyl)cyclohexane, or the like); and
furthermore, a derivative (for example, multimer, polyol adduct, or
the like) thereof.
[0082] These polyisocyanate compounds may be used either singly or
in combination of two or more.
[0083] These amidating agents may be used either singly or in
combination of two or more.
[0084] In the mixing ratio of the rosins to the amidating agent,
the molar ratio (active group/COOH) of the active group (primary
and/or secondary amino group, polyoxazoline ring, isocyanate group)
of the amidating agent to the carboxyl group of the rosins is, for
example, 0.2 to 1.2. In the reaction of the rosins with the
amidating agent, the reaction temperature is, for example, 120 to
300.degree. C. and the reaction time is, for example, 2 to 30
hours. In the reaction, a known catalyst can be blended at an
appropriate proportion as needed.
[0085] The amine salt of rosin can be obtained by neutralizing a
carboxyl group contained in the rosins by a tertiary amine
compound.
[0086] Examples of the tertiary amine compound include tri-C1 to C4
alkylamines such as trimethylamine and triethylamine and
heterocyclic amines such as morpholine.
[0087] These tertiary amine compounds may be used either singly or
in combination of two or more.
[0088] These rosin-based resins may be used either singly or in
combination of two or more.
[0089] In this method, the rosin-based resin can be used as it is
and can be also used as, for example, rosin emulsion, saponified
rosin, or the like as needed.
[0090] The rosin emulsion is produced by, for example, a known
emulsification method such as solvent-type emulsification method,
solventless-type emulsification method, phase-transfer
emulsification method, or another method.
[0091] The emulsification method is not particularly limited and
can be, for example, based on the method described in paragraph
numbers [0024] to [0025] in Japanese Unexamined Patent Publication
No. 2008-303269.
[0092] To be specific, for example, in the solvent-type
emulsification method, first, the rosin-based resin is dissolved in
an organic solvent to obtain a rosin-based resin solution. Examples
of the organic solvent include a chlorine-based hydrocarbon solvent
such as methylenechloride; an aromatic solvent such as toluene and
xylene; a ketone solvent such as methyl ketone and methyl isobutyl
ketone; and another solvent capable of dissolving the rosin-based
resin. Next, emulsified water obtained by mixing and dissolving an
emulsifier and water is separately prepared. The emulsified water
and the above-mentioned rosin-based resin solution were
preliminarily mixed, so that an aqueous emulsion (preliminarily
emulsified product) containing coarse particles is prepared.
Thereafter, the obtained aqueous emulsion is minutely emulsified by
using various mixers, a colloid mill, a high-pressure
emulsification device, a high-pressure discharge-type
emulsification device, a high-shear emulsification disperser, or
the like to be then heated under a normal pressure or a reduced
pressure, so that the organic solvent is removed.
[0093] In the solventless-type emulsification method, for example,
the melted rosin-based resin and the emulsified water are
preliminarily mixed under a normal pressure or under
pressurization, so that an aqueous emulsion containing coarse
particles is prepared. Thereafter, the obtained aqueous emulsion is
minutely emulsified in the same manner as that described above by
using various emulsification dispersers.
[0094] In the phase-transfer emulsification method, after the
rosin-based resin is heated and melted under a normal pressure or
under pressurization, emulsified water is, while being stirred,
gradually added thereto, so that an oil-in-water emulsion is first
obtained to be then phase-inverted to the water-in-oil emulsion.
This method can be applied to either the solvent-type method or the
solventless-type method.
[0095] Examples of the emulsifier used in the above-mentioned
emulsification method include a nonionic emulsifier, an amphoteric
emulsifier, and a synthesized polymeric emulsifier.
[0096] Examples of the nonionic emulsifier include polyoxyethylene
alkyl (or alkenyl) ethers such as polyoxyethylene lauryl ether and
polyoxyethylene oleyl ether; polyoxyethylene alkyl phenyl ethers
such as polyoxyethylene nonyl phenyl ether and polyoxyethylene
styryl phenyl ether; sorbitan higher fatty acid esters such as
sorbitan monolaurate and sorbitan trioleate; polyoxyethylene
sorbitan higher fatty acid esters such as polyoxyethylene sorbitan
monolaurate; polyoxyethylene higher fatty acid esters such as
polyoxyethylene monolaurate and polyoxyethylene monooleate;
glycerin higher fatty acid esters such as monoglyceride oleate and
monoglyceride stearate; and polyoxyethylene-polyoxypropylene-block
copolymers.
[0097] Examples of the amphoteric emulsifier include
carboxybetaine, imidazoline betaine, sulfobetaine, aminocarboxylic
acid, sulfation of condensation product of ethyleneoxide and/or
propyleneoxide and alkylamine or diamine, and a sulfonated
adduct.
[0098] An example of the synthesized polymeric emulsifier includes
an aqueous dispersion polymer obtained by allowing a polymer
obtained by polymerizing two or more polymerizable monomers to form
salt with, for example, alkalis such as sodium hydroxide, potassium
hydroxide, and ammonia to be dispersed or solubilized in water.
Examples of the polymerizable monomer include styrene,
.alpha.-methylstyrene, vinyltoluene, (meth)acrylic acid, maleic
acid, (meth)acrylate, acrylamide, vinyl acetate, styrenesulfonic
acid, isoprenesulfonic acid, vinyl sulfonic acid, allyl sulfonic
acid, and 2-(meth)acrylamide-2-methylpropane sulfonic acid. These
emulsifiers may be used either singly or in combination of two or
more.
[0099] These rosin emulsions may be used either singly or in
combination of two or more.
[0100] In the rosin emulsion, the rosin-based resin has a solid
content concentration of, for example, 0.1 mass % or more,
preferably 1 mass % or more and for example, 99 mass % or less,
preferably 80 mass % or less.
[0101] The saponified rosin can be obtained by saponifying a
rosin-based resin with a saponification agent.
[0102] The saponification agent is not particularly limited and a
known saponification agent can be used. Specific examples thereof
include alkali metals such as potassium hydroxide and sodium
hydroxide and ammonia. These saponification agents may be used
either singly or in combination of two or more.
[0103] The saponified rosin has a saponification rate of, for
example, 1% or more, preferably 10% or more and usually 100% or
less.
[0104] The mixing ratio of the rosin-based resin to the
saponification agent is determined as needed in accordance with the
kind or the like of the rosin-based resin and the saponification
agent so that the saponification rate falls within the
above-mentioned range.
[0105] In the saponification reaction, the reaction temperature is,
for example, 0.degree. C. or more, preferably 10.degree. C. or more
and for example, 150.degree. C. or less, preferably 120.degree. C.
or less. The reaction time is, for example, 1 minute or more,
preferably 5 minutes or more and for example, 24 hours or less,
preferably 18 hours or less.
[0106] By the reaction, a saponified rosin can be obtained.
[0107] These saponified rosins may be used either singly or in
combination of two or more.
[0108] The saponified rosin can be used without using a solvent or
can be used as a saponified rosin solution by being dissolved in a
solvent.
[0109] The solvent is not particularly limited and examples thereof
include water, alcohols, ethers, ketones, esters, aliphatic
hydrocarbons, and aromatic hydrocarbons. Water, alcohols, and
ethers are preferred, with water being more preferred.
[0110] These solvents may be used either singly or in combination
of two or more.
[0111] In the saponified rosin solution, the saponified rosin has a
solid content concentration of, for example, 1 mass % or more,
preferably 5 mass % or more and for example, 99 mass % or less,
preferably 80 mass % or less.
[0112] The polyhydric alcohol is an organic compound having, in a
molecule, two or more hydroxyl groups and examples thereof include
dihydric alcohols such as ethylene glycol, propylene glycol,
neopentyl glycol, trimethylene glycol, tetramethylene glycol,
1,3-butanediol, and 1,6-hexanediol; trihydric alcohols such as
glycerin, trimethylol propane, trimethylol ethane, and triethylol
ethane; tetrahydric alcohols such as pentaerythritol and
dipentaerythritol; and amino alcohols such as triethanolamine,
tripropanolamine, triisopropanolamine, N-isobutyl diethanolamine,
and N-normalbutyl diethanolamine. These polyhydric alcohols may be
used either singly or in combination of two or more.
[0113] As the polyhydric alcohol, trihydric alcohols and
tetrahydric alcohols are preferred, with glycerin and
pentaerythritol being more preferred and glycerin being further
more preferred.
[0114] By allowing the lignin, the phenols, the aldehydes, the
rosin-based resin, and the polyhydric alcohol to react, a resin for
ink can be obtained.
[0115] In the preparation of the resin for ink, for example, the
above-mentioned components (lignin, phenols, aldehydes, rosin-based
resin, and polyhydric alcohol) are collectively formulated to be
heated and pressurized, so that they can react. Or, the
above-mentioned components are successively formulated to be heated
and pressurized, so that they can also react.
[0116] From the standpoint of equipment cost and production cost,
preferably, the above-mentioned components are successively
formulated to react.
[0117] In such a case, to be specific, first, by allowing the
lignin, the phenols, and the aldehydes to react, a
lignin-containing resol-type phenolic resin is prepared and next,
the obtained lignin-containing resol-type phenolic resin, the
rosin-based resin, and the polyhydric alcohol are allowed to
react.
[0118] In the preparation of the lignin-containing resol-type
phenolic resin, preferably, first, the lignin reacts with the
phenols under the presence of an acid catalyst.
[0119] Examples of the acid catalyst include an organic acid and an
inorganic acid.
[0120] Examples of the organic acid include sulfonic acid compounds
such as methanesulfonic acid, p-toluenesulfonic acid,
dodecylbenzenesulfonic acid, cumenesulfonic acid, dinonyl
naphthalenemonosulfonic acid, and dinonyl naphthalenedisulfonic
acid; phosphate esters having a C1 to C18 alkyl group such as
trimethyl phosphate, triethyl phosphate, monobutyl phosphate,
dibutyl phosphate, tributyl phosphate, and trioctyl phosphate; and
carboxylic acids such as formic acid, acetic acid, oxalic acid,
maleic acid, and succinic acid.
[0121] Examples of the inorganic acid include phosphoric acid,
hydrochloric acid, sulfuric acid, and nitric acid.
[0122] These acid catalysts may be used either singly or in
combination of two or more.
[0123] As the acid catalyst, an inorganic acid is preferred, with
sulfuric acid being more preferred.
[0124] The mixing ratio of the phenols with respect to 100 parts by
mass of the lignin is, for example, 50 parts by mass or more,
preferably 150 parts by mass or more, more preferably 200 parts by
mass or more, further more preferably 400 parts by mass or more and
for example, 1500 parts by mass or less, preferably 800 parts by
mass or less.
[0125] In other words, the mass ratio (phenols/lignin) of the
phenols to the lignin is, for example, 0.5 or more, preferably 1.5
or more, more preferably 2.0 or more, further more preferably 4.0
or more and for example, 15 or less, preferably 8 or less.
[0126] When the mass ratio of the phenols to the lignin falls
within the above-mentioned range, improvement of solubility of the
resin for ink in a solvent or vegetable oil (described later) can
be achieved.
[0127] The mixing ratio of the acid catalyst with respect to 100
parts by mass of the lignin is, for example, 0.1 part by mass or
more, preferably 1 part by mass or more and for example, 10 parts
by mass or less, preferably 5 parts by mass or less.
[0128] With regard to reaction conditions, the reaction temperature
is, for example, 70.degree. C. or more, preferably 110.degree. C.
or more and for example, 180.degree. C. or less, preferably
150.degree. C. or less under the atmospheric pressure.
[0129] The reaction time is, for example, 0.5 hour or more,
preferably 1 hour or more and for example, 10 hours or less,
preferably 5 hours or less.
[0130] In this manner, the lignin is modified with the phenols, so
that a phenol-modified lignin is obtained.
[0131] Next, in this method, the obtained reaction product (that
is, phenol-modified lignin) reacts with the aldehydes under the
presence of an alkali catalyst.
[0132] An example of the alkali catalyst includes hydroxides such
as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium
hydroxide, and magnesium hydroxide. Examples thereof further
include aliphatic amines such as dimethylamine, triethylamine,
butylamine, dibutylamine, tributylamine, diethylenetriamine, and
dicyandiamide; araliphatic amines such as N,N-dimethylbenzylamine;
aromatic amines such as aniline and 1,5-naphthalenediamine;
ammonia; in addition, naphthenic acids of divalent metal; and
hydroxides of divalent metal. These alkali catalysts may be used
either singly or in combination of two or more.
[0133] As the alkali catalyst, sodium hydroxide is preferred.
[0134] The mixing ratio of the aldehydes with respect to 100 parts
by mass of the phenols is, for example, 15 parts by mass or more,
preferably 20 parts by mass or more and for example, 100 parts by
mass or less, preferably 40 parts by mass or less.
[0135] The mixing ratio of the alkali catalyst with respect to 100
parts by mass of the phenols is, for example, 0.01 part by mass or
more, preferably 0.05 part by mass or more and for example, 5.0
parts by mass or less, preferably 2.0 parts by mass or less.
[0136] With regard to reaction conditions, the reaction temperature
is, for example, 30.degree. C. or more, preferably 50.degree. C. or
more and for example, 200.degree. C. or less, preferably
100.degree. C. or less under the atmospheric pressure.
[0137] The reaction time is, for example, 1 hour or more,
preferably 3 hours or more and for example, 15 hours or less,
preferably 10 hours or less.
[0138] In this manner, a lignin-containing resol-type phenolic
resin is obtained.
[0139] The method of obtaining the lignin-containing resol-type
phenolic resin is not limited to the above-mentioned method. The
lignin, the phenols, and the aldehydes can be also collectively
formulated to allow them to collectively react under the presence
of the above-mentioned alkali catalyst.
[0140] In such a case, the mixing ratio of the phenols with respect
to 100 parts by mass of the lignin is, for example, 50 parts by
mass or more, preferably 190 parts by mass or more and for example,
1500 parts by mass or less, preferably 770 parts by mass or
less.
[0141] The mixing ratio of the aldehydes with respect to 100 parts
by mass of the phenols is, for example, 15 parts by mass or more,
preferably 20 parts by mass or more and for example, 100 parts by
mass or less, preferably 40 parts by mass or less.
[0142] The mixing ratio of the alkali catalyst with respect to 100
parts by mass of the phenols is, for example, 0.01 part by mass or
more, preferably 0.05 part by mass or more and for example, 5.0
parts by mass or less, preferably 2.0 parts by mass or less.
[0143] With regard to reaction conditions, the reaction temperature
is, for example, 30.degree. C. or more, preferably 50.degree. C. or
more and for example, 200.degree. C. or less, preferably
100.degree. C. or less under the atmospheric pressure.
[0144] The reaction time is, for example, 1 hour or more,
preferably 3 hours or more and for example, 15 hours or less,
preferably 10 hours or less.
[0145] In this manner, a lignin-containing resol-type phenolic
resin is obtained.
[0146] In the preparation of the lignin-containing resol-type
phenolic resin, preferably, first, the lignin reacts with the
phenols under the presence of an acid catalyst. Thereafter, the
obtained reaction product (the phenol-modified lignin) reacts with
the aldehydes under the presence of an alkali catalyst.
[0147] According to this method, first, the lignin is modified with
the phenols, so that the reactivity of the lignin can be improved
and improvement of production efficiency of the lignin-containing
resol-type phenolic resin can be achieved.
[0148] Next, in this method, the obtained lignin-containing
resol-type phenolic resin, the rosin-based resin, and the
polyhydric alcohol are allowed to react, so that a resin for ink is
obtained.
[0149] In the preparation of the resin for ink, preferably, first,
the lignin-containing resol-type phenolic resin obtained in the
above-mentioned manner reacts with the rosin-based resin.
[0150] The mixing ratio of the rosin-based resin with respect to
100 parts by mass of the lignin-containing resol-type phenolic
resin is, for example, 20 parts by mass or more, preferably 100
parts by mass or more and for example, 1000 parts by mass or less,
preferably 300 parts by mass or less.
[0151] With regard to reaction conditions, the reaction temperature
is, for example, 150.degree. C. or more, preferably 200.degree. C.
or more and for example, 280.degree. C. or less, preferably
230.degree. C. or less under the atmospheric pressure.
[0152] The reaction time is, for example, 0.5 hour or more,
preferably 1 hour or more and for example, 5 hours or less,
preferably 3 hours or less.
[0153] Next, in this method, polyhydric alcohol is further added to
the obtained mixture to allow them to react.
[0154] The mixing ratio of the polyhydric alcohol with respect to
100 parts by mass of the lignin-containing resol-type phenolic
resin is, for example, 7 parts by mass or more, preferably 10 parts
by mass or more and for example, 25 parts by mass or less,
preferably 22 parts by mass or less.
[0155] With regard to reaction conditions, the reaction temperature
is, for example, 150.degree. C. or more, preferably 200.degree. C.
or more and for example, 350.degree. C. or less, preferably
300.degree. C. or less under the atmospheric pressure.
[0156] The reaction time is, for example, 1 hour or more,
preferably 3 hours or more and for example, 30 hours or less,
preferably 20 hours or less.
[0157] In this manner, a resin for ink is obtained.
[0158] The method of obtaining the resin for ink is not limited to
the above-mentioned method. The lignin-containing resol-type
phenolic resin, the rosin-based resin, and the polyhydric alcohol
can be also collectively formulated to allow them to react.
[0159] In such a case, the mixing ratio of the rosin-based resin
with respect to 100 parts by mass of the lignin-containing
resol-type phenolic resin is, for example, 20 parts by mass or
more, preferably 100 parts by mass or more and for example, 1000
parts by mass or less, preferably 300 parts by mass or less.
[0160] The mixing ratio of the polyhydric alcohol with respect to
100 parts by mass of the lignin-containing resol-type phenolic
resin is, for example, 7 parts by mass or more, preferably 10 parts
by mass or more and for example, 25 parts by mass or less,
preferably 22 parts by mass or less.
[0161] With regard to reaction conditions, the reaction temperature
is, for example, 150.degree. C. or more, preferably 200.degree. C.
or more and for example, 350.degree. C. or less, preferably
300.degree. C. or less under the atmospheric pressure.
[0162] The reaction time is, for example, 1 hour or more,
preferably 3 hours or more and for example, 30 hours or less,
preferably 20 hours or less.
[0163] In this manner, a resin for ink is obtained.
[0164] In the preparation of the resin for ink, a catalyst may be
added as needed.
[0165] An example of the catalyst includes a known esterification
catalyst. Specific examples thereof include metal oxides such as
zinc oxide, magnesium oxide, and calcium oxide and known acid
catalysts such as Broensted acid and Lewis acid.
[0166] As the catalyst, metal oxides are preferred, with zinc oxide
being more preferred.
[0167] The mixing ratio of the catalyst with respect to 100 parts
by mass of the rosin-based resin is, for example, 0.05 part by mass
or more, preferably 0.2 part by mass or more and for example, 2.5
parts by mass or less, preferably 1.0 part by mass or less.
[0168] According to the resin for ink, excellent printing
properties are ensured and improvement of misting resistance can be
achieved. Furthermore, according to the above-mentioned resin for
ink, excellent glossiness can be obtained.
[0169] Thus, the resin for ink can be preferably used in ink such
as printing ink.
[0170] The ink contains the above-mentioned resin for ink. To be
more specific, the ink contains, a varnish containing the
above-mentioned resin for ink, vegetable oil, and a solvent and
colorant.
[0171] Examples of the vegetable oil include drying oils such as
linseed oil, tung oil, and safflower oil; semi-drying oils such as
soybean oil, rapeseed oil, and corn oil; non-drying oils such as
castor oil and olive oil; synthetic drying oils such as dehydrated
castor oil and thermal polymerization oil; mixtures thereof; and
reclaimed oils.
[0172] These vegetable oils may be used either singly or in
combination of two or more.
[0173] As the vegetable oil, semi-drying oils are preferred, with
soybean oil being more preferred.
[0174] Examples of the solvent include aliphatic hydrocarbon
solvents such as hexane, heptane, octane, nonane, and decane;
aromatic hydrocarbon solvents such as benzene, toluene, and xylene;
and petroleum solvents such as paraffin-based solvent,
naphthene-based solvent, and aroma-based solvent.
[0175] A commercially available solvent can be also used. Specific
examples thereof include AF Solvent No. 4, AF Solvent No. 5, AF
Solvent No. 6, AF Solvent No. 7, No. 6 Solvent, and Ink Oil 35
(hereinbefore, products of JX Nippon Oil & Energy
Corporation).
[0176] These solvents may be used either singly or in combination
of two or more.
[0177] In the varnish, with respect to 100 parts by mass of the
total amount of the resin for ink, the vegetable oil, and the
solvent, the mixing ratio of the resin for ink is, for example, 20
to 60 parts by mass; the mixing ratio of the vegetable oil is, for
example, 20 to 40 parts by mass; and the mixing ratio of the
solvent is, for example, 20 to 40 parts by mass.
[0178] The varnish can contain a known resin for ink (petroleum
resin, alkyd resin, gilsonite resin, and the like) without
impairing the excellent advantages of the invention.
[0179] In such a case, the content ratio of the known resin for ink
with respect to 100 parts by mass of the above-mentioned resin for
ink is, for example, 20 parts by mass or less, preferably 10 parts
by mass or less.
[0180] The varnish can contain a gelling agent as needed. The
varnish is prepared as a gel varnish by containing the gelling
agent.
[0181] Examples of the gelling agent include aluminum
ethylacetoacetate diisopropylate, aluminum tris(ethylacetoacetate),
aluminum isopropylate, aluminum stearate, and aluminum
octylate.
[0182] These gelling agents may be used either singly or in
combination of two or more.
[0183] Examples of the colorant include an organic pigment and an
inorganic pigment.
[0184] Examples of the organic pigment include soluble azo pigments
such as Lake Red C and brilliant carmine 6B; insoluble azo pigments
such as allylide pigment, acetoacetic acid allylide disazo pigment,
and pyrazolone pigment; and polycyclic and heterocyclic pigments
such as copper phthalocyanine blue, sulfonated copper
phthalocyanine blue, quinacridon pigment, dioxazine pigment,
pyranthrone pitment, industron pigment, thioindigo pigment,
anthraquinone pigment, perinone pigment, metal complex pigment, and
quinophthalone pigment.
[0185] Examples of the inorganic pigment include carbon black,
titanium oxide, calcium carbonate, zinc white, Prussian blue,
ultramarine blue, and red oxide.
[0186] These colorants may be used either singly or in combination
of two or more.
[0187] The colorant is appropriately selected, depending on the
using purpose and intended use. When the above-mentioned resin for
ink is black, black pigment is preferably selected. An example of
the black pigment includes carbon black.
[0188] In the ink, with respect to 100 parts by mass of the total
amount of the varnish and the colorant, the mixing ratio of the
varnish is, for example, 70 to 90 parts by mass and the mixing
ratio of the colorant is, for example, 10 to 30 parts by mass.
[0189] The ink can contain an additive as needed.
[0190] Examples of the additive include antiskinning agents, wax
compounds, flame retardants, fillers, and stabilizers.
[0191] These additives may be used either singly or in combination
of two or more. The content of the additive is appropriately set,
depending on the using purpose and intended use, without impairing
the excellent advantages of the invention.
[0192] The additive may be, for example, added to the
above-mentioned varnish; it may be mixed with the pigment; it may
be simultaneously added at the time of mixing of the varnish and
the pigment; or furthermore, it may be separately added to the
mixture of the varnish and the pigment.
[0193] The ink thus obtained contains the above-mentioned resin for
ink, so that it is excellent in printing properties and misting
resistance.
[0194] In other words, the concentration of the above-mentioned ink
is adjusted by the above-mentioned vegetable oil and solvent so as
to satisfy the printing properties. In a case where the viscosity
and the tackiness (stickiness) are adjusted, the above-mentioned
ink has excellent misting resistance.
[0195] From the standpoint of printing properties, the ink has a
viscosity at 25.degree. C. of, for example, 4 Pas or more,
preferably 10 Pas or more and for example, 200 Pas or less,
preferably 150 Pas or less.
[0196] The viscosity can be measured in accordance with JIS K-5701
(2000 edition).
[0197] The ink has a tack value (400 rpm) of, for example, 4 or
more, preferably 4.5 or more and for example, 9.5 or less,
preferably 8 or less.
[0198] The tack value can be measured in accordance with JIS K-5701
(2000 edition).
[0199] When the viscosity and the tackiness (stickiness) are
adjusted within the above-mentioned range, the above-mentioned ink
is excellent in misting resistance and furthermore, excellent in
quick drying properties, abrasion resistance, and glossiness.
[0200] Thus, the above-mentioned ink is preferably used as printing
ink in offset printing or the like.
EXAMPLES
[0201] The invention will hereinafter be described based on
Examples and Comparative Examples. The invention is however not
limited by the following Examples. All designations of "part" or
"parts" and "%" mean part or parts by mass and % by mass,
respectively, unless otherwise particularly specified. The specific
numerical values in mixing ratio (content ratio), property value,
and parameter used in the following description will be replaced
with upper limits (numerical values defined as "or less" or
"below") or lower limits (numerical values defined as "or more" or
"above") of corresponding numerical values in mixing ratio (content
ratio), property value, and parameter described in the
above-mentioned "Embodiment of the Invention".
Production of Acetic Acid-Modified Lignin
Production Example 1
[0202] Corn stover (100 parts by mass) was mixed with 1000 parts by
mass of 95 mass % acetic acid and 3 parts by mass of sulfuric acid.
The resulting mixture was allowed to react for 4 hours under
reflux. After the reaction, the reaction mixture thus obtained was
filtered to remove pulp and collect a pulp waste liquor. Then,
acetic acid was removed from the pulp waste liquor by using a
rotary evaporator. After concentration to reduce its volume to
1/10, water was added to the concentrate in an amount 10 times the
concentrate (on a mass basis), followed by filtration to obtain an
acetic acid-modified lignin as a solid component.
[0203] The phenolic hydroxyl group equivalent of the obtained
acetic acid-modified lignin was 435.9 g/eq.
[0204] The phenolic hydroxyl group equivalent was obtained in the
following manner.
[0205] That is, first, 10 mg of an acetic acid-modified lignin
sample was dissolved in 10 mL of 2-methoxyethanol/water (1/1, w/w)
to obtain a reference sample.
[0206] Next, 1 mL of the reference sample was diluted with
2-methoxyethanol/water (1/1, w/w) to obtain 10 mL thereof and the
obtained sample was defined as Sample 1.
[0207] Furthermore, 1 mL of the reference sample was diluted with
2-methoxyethanol/2N sodium hydroxide aqueous solution (1/1, w/w) to
obtain 10 mL thereof and the obtained sample was defined as Sample
2.
[0208] The two samples (Sample 1 and Sample 2) thus obtained were
subjected to the spectrometry shown in the following.
[0209] To be more specific, first, 2-methoxyethanol/water (1/1,
w/w) was put into the front and back cells to obtain the base line.
Next, Sample 1 was set at the reference side and Sample 2 was set
at the sample side to measure the absorption (absorbance) at 296 nm
and 366 nm.
[0210] The absorption (absorbance) at 296 nm was caused by a
structure of the following formula (1) and the molar absorptivity
as for the phenolic hydroxyl group concentration was 4100
L/(molcm).
[0211] The absorption (absorbance) at 366 nm was caused by a
structure of the following formula (2) and the molar absorptivity
as for the phenolic hydroxyl group concentration was 37250
L/(molcm).
[0212] Then, the phenolic hydroxyl group concentration in the
sample was obtained from the absorption (absorbance) and the molar
absorptivity at the above-mentioned two wavelengths and the
obtained values were converted to the phenolic hydroxyl group
equivalent.
##STR00001##
Production of Unmodified Lignin
Production Example 2
[0213] A pulp waste liquor (black liquor) obtained by alkali
digestion of wheat straws was neutralized, followed by filtration
to obtain an unmodified lignin as a solid component.
Preparation of Resin for Ink
Example 1
[0214] Synthesis of Lignin-Containing Resol-Type Phenolic Resin
(Presence of Phenol Modification of Lignin)
[0215] Nonylphenol (616 g (2.8 mol)) was put into a 1 L-flask under
a room temperature to be stirred at 250 rpm. Next, 60 g (0.4 mol)
of the acetic acid-modified lignin obtained in Production Example 1
was added and then, 2.4 g of concentrated sulfuric acid (98%
solution) was added thereto. Then, the temperature of the resulting
mixture was increased until 130.degree. C., a drain pipe was
attached, and the obtained mixture was allowed to react under a
nitrogen atmosphere for 2.5 hours. In this manner, a
phenol-modified lignin was obtained.
[0216] Thereafter, the temperature of the phenol-modified lignin
was decreased until 50.degree. C., 182.6 g of paraformaldehyde (92%
solution) was added, and then, 4.4 g of sodium hydroxide was added
thereto. After the temperature was increased until 95.degree. C. at
a temperature increasing rate of 1.0.degree. C./min, the resulting
mixture was allowed to react at 95.degree. C. at 250 rpm for 5
hours.
[0217] In this manner, a lignin-containing resol-type phenolic
resin was obtained.
[0218] Preparation of Resin for Ink
[0219] Chinese gum rosin (515 g) was put into a 1 L-reaction flask
to be then heated and gradually melted, while the stirring rate was
gradually increased until 250 rpm. After the temperature of the
Chinese gum rosin was increased until 210.degree. C., 10.3 g of
maleic anhydride was added thereto to allow them to react for 30
minutes. In this manner, an unsaturated carboxylic acid-modified
rosin was obtained.
[0220] Next, 2.6 g of zinc oxide was added and next, 360 g of the
above-mentioned lignin-containing resol-type phenolic resin was
added dropwise thereto at a dropping rate of 3 ml/min over 2 hours
with a dropping funnel.
[0221] Thereafter, 57 g of glycerin was added thereto and the
temperature of the resulting mixture was increased until
250.degree. C. at a temperature increasing rate of 0.3.degree.
C./min. Furthermore, the mixture was allowed to react at
250.degree. C. for 5 hours.
[0222] In this manner, a resin for ink was obtained.
Examples 2 to 3
[0223] A lignin-containing resol-type phenolic resin was
synthesized in the same manner as in Example 1 except that the
mixing formulation of the components was changed to that shown in
Table 1. Thereafter, a resin for ink was prepared in the same
manner as in Example 1.
Example 4
[0224] Synthesis of Lignin-Containing Resol-Type Phenolic Resin
(Absence of Phenol Modification of Lignin)
[0225] Nonylphenol (616 g (2.8 mol)) was put into a 1 L-flask under
a room temperature to be stirred at 250 rpm. Next, 60 g (0.4 mol)
of the acetic acid-modified lignin obtained in Production Example 1
was added thereto and the temperature of the resulting mixture was
increased until 50.degree. C.
[0226] Thereafter, 182.6 g of paraformaldehyde was added and then,
2.5 g of sodium hydroxide was added thereto. After the temperature
was increased until 95.degree. C. at a temperature increasing rate
of 1.0.degree. C./min, the resulting mixture was allowed to react
at 95.degree. C. for 5 hours.
[0227] In this manner, a lignin-containing resol-type phenolic
resin was obtained.
[0228] Preparation of Resin for Ink
[0229] A resin for ink was obtained in the same manner as in
Example 1 except that the mixing formulation of the components was
changed to that shown in Table 1 by using the above-mentioned
lignin-containing resol-type phenolic resin.
Example 5
[0230] A lignin-containing resol-type phenolic resin was
synthesized in the same manner as in Example 1 except that the
mixing formulation of the components was changed to that shown in
Table 1 by using the unmodified lignin obtained in Production
Example 2 instead of the acetic acid-modified lignin. Thereafter, a
resin for ink was prepared in the same manner as in Example 1.
Example 6
[0231] A lignin-containing resol-type phenolic resin was
synthesized in the same manner as in Example 4 except that the
mixing formulation of the components was changed to that shown in
Table 1 by using the unmodified lignin obtained in Production
Example 2 instead of the acetic acid-modified lignin. Thereafter, a
resin for ink was prepared in the same manner as in Example 4.
Example 7
[0232] A lignin-containing resol-type phenolic resin was
synthesized in the same manner as in Example 1 except that 308 g
(1.4 mol) of nonylphenol and 308 g of p-tert-octylphenol (1:1 in
mass ratio) were used instead of 616 g (2.8 mol) of nonylphenol.
Thereafter, a resin for ink was prepared in the same manner as in
Example 1.
Example 8
[0233] A lignin-containing resol-type phenolic resin was
synthesized in the same manner as in Example 1 except that 308 g of
nonylphenol and 308 g of p-tert-butylphenol (1:1 in mass ratio)
were used instead of 616 g of nonylphenol. Thereafter, a resin for
ink was prepared in the same manner as in Example 1.
Comparative Example 1
[0234] Synthesis of Non-Lignin Resol-Type Phenolic Resin
[0235] Nonylphenol (700 g (2.8 mol)) was put into a 1 L-flask under
a room temperature to be stirred at 250 rpm. Next, after the
temperature of the nonylphenol was increased until 50.degree. C.,
207.5 g of paraformaldehyde was added and then, 2.8 g of sodium
hydroxide was added thereto. After the temperature was increased
until 95.degree. C. at a temperature increasing rate of 1.0.degree.
C./min, the resulting mixture was allowed to react at 95.degree. C.
for 5 hours.
[0236] Preparation of Resin for Ink
[0237] Chinese gum rosin (540 g) was put into a 1 L-reaction flask
to be then heated and gradually melted, while the stirring rate was
gradually increased until 250 rpm. After the temperature of the
Chinese gum rosin was increased until 210.degree. C., 10.8 g of
maleic anhydride was added thereto to allow them to react for 30
minutes. In this manner, an unsaturated carboxylic acid-modified
rosin was obtained.
[0238] Next, 2.7 g of zinc oxide was added and next, 360 g of the
above-mentioned non-lignin resol-type phenolic resin was added
dropwise thereto at a dropping rate of 3 ml/min over 2 hours with a
dropping funnel.
[0239] Thereafter, 59.8 g of glycerin was added thereto and the
temperature of the resulting mixture was increased until
250.degree. C. at a temperature increasing rate of 0.3.degree.
C./min. Furthermore, the mixture was allowed to react at
250.degree. C. for 5 hours.
[0240] In this manner, a resin for ink was obtained.
TABLE-US-00001 TABLE 1 No. Comp. Ex. 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex.
5 Ex. 6 Ex. 7 Ex. 8 Lignin Kind -- Production Ex. 1 Production Ex.
2 Production Ex. 1 Phenol Modification -- Presence Absence Presence
Absence Presence Resol Resin Mixing Nonylphenol 700 616 577.5 481.3
616 616 616 308 308 Formulation p-octylphenol -- -- -- -- -- -- --
308 -- (g) p-tert-butylphenol -- -- -- -- -- -- -- -- 308 Lignin --
80 150 250 80 80 80 80 80 98% Concentrated -- 2.4 4.5 7.5 -- 2.4 --
2.4 2.4 Sulfuric Acid 92% Paraformaldehyde 207.5 182.6 171.2 142.7
182.6 182.6 182.6 182.6 182.6 Sodium Hydroxide 2.5 4.4 6 8.1 2.5
4.4 2.5 4.4 4.4 Ink Resin Mixing Resol Resin 360 360 360 360 360
360 360 360 360 Formulation Chinese Gum Rosin 540 515 515 515 515
515 515 515 515 (g) Maleic Anhydride 10.8 10.3 10.3 10.3 10.3 10.3
10.3 10.3 10.3 Glycerin 59.8 57 57 57 57 57 57 57 57 Zinc Oxide 2.7
2.6 2.6 2.6 2.6 2.6 2.6 2.6 2.6 Phenols/Lignin (Mass Ratio) -- 7.7
3.9 1.9 7.7 7.7 7.7 7.7 7.7
[0241] In Table, "Lignin" represents an acetic acid-modified lignin
or an unmodified lignin. "Resol Resin" represents a
lignin-containing resol-type phenolic resin or a non-lignin
resol-type phenolic resin.
Examples 9 to 16 and Comparative Example 2
[0242] A varnish and ink were prepared by using each of the resins
for ink obtained in Examples 1 to 8 and Comparative Example 1 in
the following method.
[0243] Preparation of Varnish
[0244] Soybean oil (soybean refined oil) (54 g) and 45 g of resin
for ink were added, while being stirred, to a 250 ml-reaction flask
under a room temperature. The stirring rate was 200 rpm.
[0245] Next, the temperature of the resulting mixture was increased
until 100.degree. C. and immediately after heating, 1 g of gelling
agent (Kelope EP-2, ethyl acetoacetate aluminum diisopropylate,
product of Hope Chemical Co., LTD.) was added thereto.
[0246] Thereafter, the temperature of the obtained mixture was
increased until 180.degree. C. over 30 minutes to be further heated
at 180.degree. C. for 1 hour.
[0247] Then, the temperature thereof was decreased until
120.degree. C. to take a sample and the viscosity thereof was
measured with a TV-20 EHD-type viscometer (product of TOKI SANGYO
CO., LTD.).
[0248] Soybean oil (soybean refined oil) was added thereto so that
the viscosity of the sample was about 100.+-.20 Pas.
[0249] Preparation of Ink
[0250] With respect to 70 g of the above-mentioned varnish, 18 g of
neutral carbon (carbon black) and 2 g of AF Solvent No. 6 (solvent,
product of JX Nippon Oil & Energy Corporation) were added to be
dispersed with a three-roll.
[0251] Furthermore, a varnish or AF Solvent No. 6 was added thereto
so that the tack value thereof at 400 rpm was 4 to 5 with an
incometer (product of TOYO SEIKI SEISAKU-SHO, LTD.).
[0252] In this manner, ink was prepared.
[0253] <Evaluation>
[0254] The properties of each of the ink obtained in Examples and
Comparative Examples were evaluated using the following methods.
The results are shown in Table 2.
[0255] (1) Misting Resistance
[0256] Ink (2.8 ml) was applied to a roll of a misting tester
(product of TOYO SEIKI SEISAKU-SHO, LTD.) and the roll was rotated
at 1000 rpm for 1 minute. The scattered state of the ink on the
lower surface of the roll and on the white paper placed near the
roll was observed and visually evaluated by 10 steps (1: Bad to 10:
Good).
[0257] (2) Quick Drying Properties
[0258] Ink (0.1 ml) was spread on a coating paper with a three-part
roll of RI-II type printing tester (product of IHI Machinery and
Furnace Co., Ltd.). After the spreading, the spread object was cut
into a piece having a width of about 1 cm and the printed surface
thereof was attached to another coating paper.
[0259] As for the sample, the time (minute) until the ink was not
attached to the coating paper was measured.
[0260] (3) Gloss Value and Abrasion Resistance
[0261] Ink (0.2 ml) was spread on a coating paper with a two-part
roll of RI-II type printing tester (product of IHI Machinery and
Furnace Co., Ltd.). After the spreading, the sample was allowed to
stand still at 25.degree. C. for 24 hours.
[0262] Thereafter, the gloss value thereof was measured at a
measurement angle of 60.degree. with a micro-TRI-gloss glossmeter
(product of BYK-Gardner GmbH).
[0263] Next, a friction test was performed in accordance with the
method in JIS K 5701-1 (2000)-P16 with an S-type friction tester to
measure the abrasion resistance.
[0264] The number of friction was set to 20 times and the obtained
results were visually evaluated by 10 steps (1: Bad to 10:
Good).
TABLE-US-00002 TABLE 2 No. Comp. Ex 2 Ex. 9 Ex. 10 Ex. 11 Ex. 12
Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ink Resin Comp. Ex 1 Ex. 1 Ex. 2 Ex. 3
Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Lignin Kind -- Producction Ex. 1
Production Ex. 2 Production Ex. 1 Phenol Modification -- Presence
Absence Presence Absence Presence Kind of Phenols NP NP NP NP NP NP
NP NP/POP NP/POP (Mass (Mass Ratio: Ratio: 1/1) 1/1) Phenols/Lignin
(Mass Ratio) -- 7.7 3.9 1.9 7.7 7.7 7.7 7.7 7.7 Tack Value (400
rpm) 5.1 6 5.5 4.7 5.5 4.8 4.8 4.6 5 Evaluation Misting Resistance
(1: Bad to 10: Good) 4 8 8 9 7 5 5 9 10 Quick Drying Properties
(min) 15 7 15 22 11 30 >60 5 4 Abrasion Resistance (1: Bad to
10: Good) 6 7 4 2 5 3 4 7 7 Gloss Value 78 77 71 72 71 58 56 70
63
[0265] The details of abbreviations are shown below.
[0266] NP: nonylphenol
[0267] POP: p-tert-octylphenol
[0268] PTBP: p-tert-butylphenol
[0269] While the illustrative embodiments of the present invention
are provided in the above description, such are for illustrative
purpose only and are not to be construed as limiting in any manner.
Modification and variation of the present invention that will be
obvious to those skilled in the art are to be covered by the
following claims.
INDUSTRIAL APPLICABILITY
[0270] The resin for ink and ink of the present invention are
preferably used, for example, in printing ink in various printing
fields such as offset printing.
* * * * *