U.S. patent application number 13/927356 was filed with the patent office on 2013-12-12 for michael acceptor having multiple hydroxyl groups, and michael addition product derived therefrom.
The applicant listed for this patent is Korea Research Institute of Chemical Technology. Invention is credited to Young Chul Kim, Byung Hoon Lee.
Application Number | 20130331600 13/927356 |
Document ID | / |
Family ID | 44761401 |
Filed Date | 2013-12-12 |
United States Patent
Application |
20130331600 |
Kind Code |
A1 |
Kim; Young Chul ; et
al. |
December 12, 2013 |
Michael Acceptor Having Multiple Hydroxyl Groups, and Michael
Addition Product Derived Therefrom
Abstract
Provided is a Michael addition product prepared from a
multifunctional acryl monomer having multiple hydroxyl groups
allowing introduction of acryl functional groups, as a Michael
acceptor, and a Michael donor. The Michael addition product is a
novel multifunctional compound having an oligomer and a
photoinitiator moiety in the molecule. Since it can be cured under
a standard UV curing condition without having to add a
photoinitiator, it is reduced to air pollution or health problem.
Therefore the superior physical properties were obtained by cured
coatings without surface tackiness. In addition, its hydroxyl
groups allow, through isocyanate bonding or introduction of acryl
groups, 3-dimensional crosslinking and molecular and compositional
design for improving expandability, friction, and reactivity and
hydrophilicity for self-adhesion, hardness of cured film, or the
like. Consequently, a very useful, multifunctional or
water-dispersible coating composition may be prepared.
Inventors: |
Kim; Young Chul; (Daejeon,
KR) ; Lee; Byung Hoon; (Gyeongsangbuk-do,
KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Korea Research Institute of Chemical Technology |
Daejeon |
|
KR |
|
|
Family ID: |
44761401 |
Appl. No.: |
13/927356 |
Filed: |
June 26, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
12876935 |
Sep 7, 2010 |
8507625 |
|
|
13927356 |
|
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Current U.S.
Class: |
560/193 ;
560/198 |
Current CPC
Class: |
C08F 222/1006 20130101;
C08G 18/755 20130101; C08F 290/067 20130101; C07C 2601/14 20170501;
C07C 67/347 20130101; C08G 18/3821 20130101; C07C 69/716 20130101;
C07C 69/73 20130101; C09D 175/16 20130101; C08F 222/1006 20130101;
C07C 271/16 20130101; C07C 69/73 20130101; C07C 67/347 20130101;
C07C 69/73 20130101; C08F 220/325 20200201; C08F 222/1006 20130101;
C08F 220/325 20200201; C09D 133/14 20130101; C08G 18/673 20130101;
C07C 67/26 20130101; C07C 67/26 20130101 |
Class at
Publication: |
560/193 ;
560/198 |
International
Class: |
C07C 69/73 20060101
C07C069/73; C07C 67/26 20060101 C07C067/26 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 8, 2010 |
KR |
10-2010-0032257 |
Claims
1. A Michael acceptor represented by Chemical Formula 1:
##STR00014## wherein X is C.sub.1-C.sub.6 alkylene or
C.sub.3-C.sub.10 cycloalkylene; R.sub.1 and R.sub.2, which may be
identical to or different from each other, are hydrogen or
C.sub.1-C.sub.6 alkyl; and n is an integer from 0 to 10.
2. The Michael acceptor according to claim 1, which is represented
by Chemical Formula 8: ##STR00015##
3. The Michael acceptor according to claim 1, which is represented
by Chemical Formula 9: ##STR00016##
4. A method for preparing a Michael acceptor represented by
Chemical Formula 1, comprising reacting an acrylate having a
carboxyl group represented by Chemical Formula 4 or 5 with an epoxy
resin represented by Chemical Formula 6: ##STR00017## wherein X is
C.sub.1-C.sub.6 alkylene or C.sub.3-C.sub.10 cycloalkylene, R.sub.1
and R.sub.2, which may be identical to or different from each
other, are hydrogen or C.sub.1-C.sub.6 alkyl, and n is an integer
from 0 to 10; ##STR00018## wherein X is alkylene, R.sub.1 is
hydrogen or C.sub.1-C.sub.6 alkyl, Y is cycloalkylene, phenyl,
ethylene or caprolactone, and n is an integer 2 or 3; and
##STR00019## wherein X is C.sub.1-C.sub.6 alkylene or
C.sub.3-C.sub.10 cycloalkylene, and n is an integer from 0 to
10.
5. The method for preparing a Michael acceptor according to claim
4, wherein the acrylate having a carboxy group represented by
Chemical Formula 4 or 5 is 2-carboxyethyl acrylate, 2-carboxypropyl
acrylate, 2-acryloyloxyethyl phthalate, 2-acryloyloxyethyl
hexahydrophthalate, .omega.-acryloyloxypropyl phthalate, ethylene
oxide (EO) added succinic acid acrylate,
.omega.-carboxypolycaprolactone acid acrylate or a methacrylate
thereof.
6. The method for preparing a Michael acceptor according to claim
4, wherein the epoxy resin represented by Chemical Formula 6 is one
or more selected from the group consisting of 1,4-butanediol
diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether,
diglycidyl 1,2-cyclohexanedicarboxylate, glycerol diglycidyl ether,
neopentyl glycol diglycidyl ether, pentaerythritol diglycidyl
ether, ethylene glycol diglycidyl ether, propylene glycol
diglycidyl ether, 1,6-hexanediol diglycidyl ether,
trimethylolpropane diglycidyl ether and diethylene glycol
diglycidyl ether.
7. The method for preparing a Michael acceptor according to claim
4, wherein the reaction is promoted by an onium salt or a tertiary
amine.
Description
[0001] This application is a division of U.S. patent application
Ser. No. 12/876,935 filed Sep. 7, 2010 which claims priority under
35 U.S.C. .sctn.119 to Korean Patent Application No.
10-2010-0032257, filed on Apr. 8, 2010, in the Korean Intellectual
Property Office, the disclosures of which are both incorporated
herein by reference in their entirety.
TECHNICAL FIELD
[0002] The following disclosure relates to a Michael acceptor
having multiple hydroxyl groups and a Michael addition product
derived therefrom. More particularly, the following disclosure
relates to a Michael acceptor having multiple hydroxyl groups
allowing introduction of functional groups to provide mechanical
properties such as expandability, friction, etc., as well as
various other properties such as reactivity and hydrophilicity for
self-adhesion as desired, and a Michael addition product derived
therefrom. The Michael acceptor and its addition product may be
used as a UV- and electron beam-curable self-photoinitiator as well
as an oligomer. Accordingly, they may be widely applicable in
information and communications, semiconductors, electric/electronic
fields, micropattern printing, wood coating and others.
BACKGROUND
[0003] UV-curable resin, when exposed to UV, forms oligomers and
monomers having UV-reactive groups. The resulting polymer is an
insoluble material having a highly dense network as well as good
heat resistance and chemical stability and superior optical and
mechanical properties. Since the UV curing is accomplished in a
relatively short time, it consumes less energy and provides good
productivity thus being widely used in various fields. In addition,
it has many other advantages that it is environment friendly, by
not using any solvent, providing convenience by requiring only a
small workplace, etc.
[0004] In general, the UV-reactive (meth)acrylate groups of
monomers and oligomers may be crosslinked by a free radical chain
mechanism by a photoinitiator. When exposed to UV or electron beam
(EB), they turn to free radicals by the photoinitiator at a lower
activation energy.
[0005] The photoinitiator has a disadvantage that it raises a
safety issue. In fact, during or after the preparation of the
photoinitiator, there is produced volatile, low-molecular-weight
decomposition product, which can be easily absorbed through the
respiratory organs or skin of workers, thereby affecting their
health conditions.
[0006] Several solutions to this problem have been introduced. For
example, there was an attempt to solve the problem by using a
(meth)acrylate resin having a self-photoinitiating ability.
[0007] U.S. Pat. No. 5,565,525 (Nippon Paint, Japan, 1994)
discloses a Michael addition product which is a UV-curable resin
having four acryl functional groups prepared from a
.beta.-dicarbonyl Michael donor and a multifunctional acrylate
Michael acceptor. It is prepared via a Michael addition reaction in
the presence of an epoxide residue and a quaternary salt as
catalyst. Although crosslinking is achieved without a
photoinitiator, surface properties may not be good because of
steric hindrance and improper acryl crosslinking density.
[0008] U.S. Pat. Appl. Pub. No. 2005-0261388 (Ashland, 2005)
discloses a liquid, uncrosslinked, UV-curable Michael addition
product having four acryl functional groups prepared from a
multifunctional acrylate Michael acceptor and an optically active
.beta.-dicarbonyl Michael donor substituted with a photoinitiator.
When exposed to UV, the resulting oligomer facilitates addition
polymerization of the acryl groups through self-photoinitiation and
improvement of optical activity by the introduced photoinitiator.
Although viscosity is low and curing reactivity is superior,
surface properties are not greatly improved because of improper
acryl crosslinking density.
[0009] The self-photoinitiating (meth)acrylate oligomer prepared by
Michael addition does not provide a desired effect when considering
the additional preparation processes and cost. It is because the
Michael acceptor has low acrylic functionality. Accordingly, it may
be still required to add a volatile, low-molecular-weight
multifunctional monomer to improve crosslinkability of the
composition, which may negatively affect the reactivity and final
property, as well as a photoinitiator.
[0010] Thus, various technical developments are underway to allow
preparation of a photocurable (meth)acrylate resin in a safe and
environment-friendly way without using an additional
photoinitiator. Especially, techniques of preparing a
(meth)acrylate oligomer having a built-in photoinitiator using no
photoinitiator are presented.
[0011] In 1997, Ashland developed and patented a
self-photoinitiating resin having 8 acryl functional groups from a
multifunctional acrylate Michael acceptor and a .beta.-dicarbonyl
diacetoacetate Michael donor (U.S. Pat. Nos. 5,945,489 and
6,025,410). In 2009, Chokwang Paint developed a photocurable
(meth)acrylate resin having four acryl functional groups through
addition of a hydroxyacrylate Michael acceptor to a
.beta.-dicarbonyl donor followed by urethane bonding, which is
capable of photocuring in the absence of a photoinitiator (Korean
Patent No. 10-0903209).
[0012] U.S. Pat. Appl. Pub. No. 0004815 A1 (Ashland, 2007)
discloses a self-photoinitiating multifunctional urethane acrylate
having four acryl functional groups prepared from a Michael
addition reaction with a .beta.-dicarbonyl Michael donor, wherein
an amine-based synergist is used to provide improved photocuring
reactivity.
[0013] However, in order to improve effective performance, a
Michael addition product having more acryl functional groups is
required.
SUMMARY
[0014] The inventors of the present invention have been making
efforts to develop a Michael addition product having more acryl
functional groups than existing Michael addition products, and, as
a result, completed the present invention.
[0015] An embodiment of the present invention is directed to
providing a Michael acceptor having multiple hydroxyl groups and a
method for preparing the same. Another embodiment of the present
invention is directed to providing a Michael addition product
derived from the Michael acceptor and a method for preparing the
same. Still another embodiment of the present invention is directed
to providing a coating film including a cured, crosslinked residue
of the Michael addition product.
[0016] In one aspect, the present invention provides a Michael
acceptor having multiple hydroxyl groups. The Michael acceptor is
represented by Chemical Formula 1:
##STR00001##
[0017] wherein X is C.sub.1-C.sub.6 alkylene or C.sub.3-C.sub.10
cycloalkylene; R.sub.1 and R.sub.2, which may be identical to or
different from each other, are hydrogen or C.sub.1-C.sub.6 alkyl;
and n is an integer from 0 to 10.
[0018] In another aspect, the present invention provides a Michael
addition product derived from the Michael acceptor, which is
represented by Chemical Formula 2 or Chemical Formula 3:
##STR00002##
[0019] wherein X is C.sub.1-C.sub.6 alkylene or C.sub.3-C.sub.10
cycloalkylene; R.sub.1, R.sub.1', R.sub.2, and R.sub.2', which may
be identical to or different from one another, are hydrogen or
C.sub.1-C.sub.6 alkyl; n is an integer from 0 to 10; R.sub.3 is
C.sub.1-C.sub.12 alkyl, benzyl, benzoyl, acryl or amide; and
R.sub.4 is independently hydrogen or multifunctional
isocyanate.
[0020] In still another aspect, the present invention provides a
coating film including a cured, crosslinked residue of the Michael
addition product.
[0021] The Michael acceptor of the present invention has multiple
hydroxyl groups allowing introduction of functional groups. A
crosslinkage of 3 or higher dimension may be formed by introducing
an adequate binder. Further, mechanical properties such as
expandability, friction, etc., as well as various other properties
such as reactivity for self-adhesion, hydrophilicity, etc., may be
provided. In addition, the Michael acceptor of the present
invention may further have a urethane acrylate moiety, which is
formed through bonding with isocyanate, in addition to the epoxy
acrylate moiety. As such, molecular design is possible by varying
the proportion and the characteristics of the cured resin may be
varied as desired.
[0022] Since the Michael addition product derived from the Michael
acceptor has a high acryl content, it has superior curability and
hardness of the cured film. Further, since it has a photoinitiating
group, it may be cured under a standard UV curing condition without
adhesion, without having to use an additional photoinitiator or
photosensitizer. In addition, energy consumption required for
uniform dispersion of the photoinitiator may be saved. Further,
since no decomposition product is formed after the curing, desired
performance may be attained without air pollution or health
problem.
[0023] Other features and aspects will be apparent from the
following detailed description, the drawings, and the claims.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The above and other objects, features and advantages of the
present invention will become apparent from the following
description of preferred embodiments given in conjunction with the
accompanying drawings, in which:
[0025] FIG. 1 shows an FT-IR spectrum of a Michael acceptor
synthesized according to the present invention in Example 1;
[0026] FIG. 2 shows a .sup.1H-NMR spectrum of a Michael acceptor
synthesized according to the present invention in Example 1;
[0027] FIG. 3 shows a .sup.13C-NMR spectrum of a Michael acceptor
synthesized according to the present invention in Example 1;
[0028] FIG. 4 shows a prep-LC result of a Michael acceptor
synthesized according to the present invention in Example 1;
[0029] FIG. 5 shows an FT-IR spectrum of a Michael acceptor
synthesized according to the present invention in Example 2;
[0030] FIG. 6 shows a .sup.1H-NMR spectrum of a Michael acceptor
synthesized according to the present invention in Example 2;
[0031] FIG. 7 shows a .sup.13C-NMR spectrum of a Michael acceptor
synthesized according to the present invention in Example 2;
and
[0032] FIG. 8 shows a prep-LC result of a Michael acceptor
synthesized according to the present invention in Example 2.
DETAILED DESCRIPTION OF EMBODIMENTS
[0033] The advantages, features and aspects of the present
invention will become apparent from the following description of
the embodiments with reference to the accompanying drawings, which
is set forth hereinafter. The present invention may, however, be
embodied in different forms and should not be construed as limited
to the embodiments set forth herein. Rather, these embodiments are
provided so that this disclosure will be thorough and complete, and
will fully convey the scope of the present invention to those
skilled in the art. The terminology used herein is for the purpose
of describing particular embodiments only and is not intended to be
limiting of example embodiments. As used herein, the singular forms
"a", "an" and "the" are intended to include the plural forms as
well, unless the context clearly indicates otherwise. It will be
further understood that the terms "comprises" and/or "comprising",
when used in this specification, specify the presence of stated
features, integers, steps, operations, elements, and/or components,
but do not preclude the presence or addition of one or more other
features, integers, steps, operations, elements, components, and/or
groups thereof.
[0034] Hereunder is given a more detailed description of the
present invention.
[0035] The present invention provides a Michael acceptor having
multiple hydroxyl groups, which is represented by Chemical Formula
1.
[0036] The Michael acceptor represented by Chemical Formula 1 may
be a Michael acceptor represented by Chemical Formula 8 or 9:
##STR00003##
[0037] Since the Michael acceptor of the present invention has
multiple hydroxyl groups unlike the existing Michael acceptors, it
may be designed to exhibit adequate properties. And, since the
Michael addition product prepared from addition of the Michael
acceptor has an initiating group capable of initiating
photoreaction, it is unnecessary to additionally use a
photoinitiator. As a result, formation of volatile,
low-molecular-weight substances, which are easily absorbed through
skin, due to decomposition by heat or light may be avoided. Hence,
health problem or environmental pollution may be minimized.
[0038] Preferably, the Michael acceptor represented by Chemical
Formula 1 may be synthesized by reacting an acrylate having a
carboxylic acid group represented by Chemical Formula 4 or 5 with
an epoxy resin represented by Chemical Formula 6 in a reactor by
heating:
##STR00004##
[0039] wherein X is alkylene, R.sub.1 is hydrogen or
C.sub.1-C.sub.6 alkyl, Y is cycloalkylene, phenyl, ethylene or
caprolactone, and n is an integer of 2 or 3; and
##STR00005##
[0040] wherein X is C.sub.1-C.sub.6 alkylene or C.sub.3-C.sub.10
cycloalkylene, and n is an integer of from 0 to 10.
[0041] Specifically, the acrylate having a carboxyl group
represented by Chemical Formula 4 or 5 may be 2-carboxyethyl
acrylate, 2-carboxypropyl acrylate, 2-acryloyloxyethyl phthalate,
2-acryloyloxyethyl hexahydrophthalate, 2-acryloyloxypropyl
phthalate, ethylene oxide (EO) added succinic acid acrylate,
.omega.-carboxypolycaprolactone acid acrylate or a methacrylate
thereof.
[0042] And, preferably, the epoxy resin represented by Chemical
Formula 6 may be one or more selected from the group consisting of
1,4-butanediol diglycidyl ether, 1,4-cyclohexanedimethanol
diglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxylate, glycerol
diglycidyl ether, neopentyl glycol diglycidyl ether,
pentaerythritol diglycidyl ether, ethylene glycol diglycidyl ether,
propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
trimethylolpropane diglycidyl ether and diethylene glycol
diglycidyl ether.
[0043] The reaction may be promoted by a base catalyst such as an
onium salt or a tertiary amine. Examples of the catalyst include
triethylamine, benzyldimethylamine, methyltriethylammonium
chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium
iodide, triphenylphosphine, triphenylstibine, chromium octanoate,
zirconium octanoate, etc. Preferably, the catalyst is used in an
amount of 1 to 5 wt % based on the weight of the glycidyl
compound.
[0044] Since the Michael acceptor represented by Chemical Formula
1, 8 or 9 has much more hydroxyl groups than existing Michael
acceptors, it may be designed to exhibit adequate properties.
[0045] The present invention also provides a Michael addition
product derived from the Michael acceptor represented by Chemical
Formula 1.
[0046] The Michael addition product may be represented by Chemical
Formula 2 or 3:
##STR00006##
[0047] wherein X is C.sub.1-C.sub.6 alkylene or C.sub.3-C.sub.10
cycloalkylene; R.sub.1, R.sub.1', R.sub.2, and R.sub.2', which may
be identical to or different from one another, are hydrogen or
C.sub.1-C.sub.6 alkyl; n is an integer from 0 to 10; R.sub.3 is
C.sub.1-C.sub.12 alkyl, benzyl, benzoyl, acryl or amide; and
R.sub.4 is independently hydrogen or multifunctional
isocyanate.
[0048] In Chemical Formula 3, the multifunctional isocyanate is a
structure or a functional group derived from an aliphatic
diisocyanate, an aromatic diisocyanate or a combination
thereof.
[0049] The aliphatic diisocyanate may be one or more selected from
the group consisting of hexamethylene diisocyanate,
4,4-dicyclohexylmethane diisocyanate, 1,4-tetramethylene
diisocyanate, 1,10-decamethylene diisocyanate, isophorone
diisocyanate and 1,4-cyclohexane diisocyanate, and the aromatic
diisocyanate may be one or more selected from the group consisting
of toluene-2,4-diisocyanate, toluene-2,6-diisocyanate,
1,5-naphthalene diisocyanate, 4-methoxy-1,3-phenylene diisocyanate,
4-chloro-1,3-phenylene diisocyanate, 2,4-dimethyl-1,3-phenylene
diisocyanate, 4,4-diisocyanate diphenyl ether, benzidine
diisocyanate, dibenzyl-4,4'-diisocyanate and
methylene-bis(4-phenylisocyanate)-1,3-phenylene diisocyanate.
[0050] All or part of the multifunctional isocyanate may have a
multifunctional acryl group. It may be prepared by reacting the
Michael addition product having an isocyanate group with hydroxyl
acrylate at 50 to 80.degree. C. for 1 to 5 hours. Since the Michael
addition product has a multifunctional acrylate moiety, which is
formed through bonding with isocyanate, in addition to the epoxy
acrylate moiety of existing Michael addition products, it may be
designed to exhibit adequate properties.
[0051] Specifically, the multifunctional isocyanate may be
represented by Chemical Formula 7:
##STR00007##
[0052] The Michael addition product represented by Chemical Formula
2 is a UV-curable, bifunctional acrylate Michael addition product
having hydroxyl groups. It has multiple pendant hydroxyl groups
allowing 3-dimensional crosslinking and molecular and compositional
design for improving expandability, friction, and reactivity and
hydrophilicity for self-adhesion or the like. Further, it may be
modified by substituting the hydroxyl groups with other functional
groups.
[0053] Since the Michael addition product represented by Chemical
Formula 2 or 3 has an initiating group capable of initiating
photoreaction, it is unnecessary to additionally use a
photoinitiator. As a result, formation of volatile,
low-molecular-weight substances, which are easily absorbed through
skin, due to decomposition by heat or light may be avoided. Hence,
health problem or environmental pollution may be minimized.
[0054] The Michael addition product represented by Chemical Formula
2 may be synthesized from a Michael acceptor and a Michael
donor.
[0055] In the present invention, the Michael donor refers to a
compound acting as an electron donor in Michael addition reaction
wherein a compound having activated methylene is added to an
.alpha.,.beta.-unsaturated carbonyl compound or an
.alpha.,.beta.-unsaturated nitrile compound.
[0056] Specifically, the Michael addition product is synthesized by
reacting the Michael acceptor represented by Chemical Formula 1
with a Michael donor in a reactor at 60 to 100.degree. C. for 3 to
5 hours. Preferably, the Michael donor is a .beta.-dicarbonyl
Michael donor.
[0057] The .beta.-dicarbonyl Michael donor may be one or more
selected from the group consisting of a .beta.-keto ester, a
.beta.-diketone, a .beta.-keto amide and a .beta.-keto anilide.
[0058] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of acetoacetate,
2,4-pentanedione, acetoacetanilide and acetoacetamide.
[0059] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of methyl
acetoacetate, ethyl acetoacetate, t-butyl acetoacetate, allyl
acetoacetate, 2-ethylhexyl acetoacetate, lauryl acetoacetate and
2-acetoacetoxyethyl methacrylate (AAEM) having two functional
groups per molecule.
[0060] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of 1,4-butanediol
diacetoacetate, 1,6-hexanediol diacetoacetate, neopentyl glycol
diacetoacetate, cyclohexane dimethanol diacetoacetate and
ethoxylated bisphenol A diacetoacetate having four functional
groups per molecule.
[0061] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of trimethylol
propane triacetoacetate, glycerol triacetoacetate, poly
caprolactone triacetoacetate, ethoxylated or propoxylated
trimethylol propane triacetoacetate and ethoxylated or propoxylated
glycerol triacetoacetate having six functional groups per
molecule.
[0062] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of pentaerythritol
tetraacetoacetate and ethoxylated or propoxylated pentaerythritol
tetraacetoacetate having eight functional groups per molecule.
[0063] Alternatively, the .beta.-dicarbonyl Michael donor may be
one or more selected from the group consisting of malonic acid
ester, o-acetoacetaniside, o-acetoacetatoluidide,
N,N-dimethylacetoacetamide, methyl cyanoacetate, ethyl cyanoacetate
and butyl cyanoacetate.
[0064] That is to say, various Michael donors may be selected
depending on the desired physical property or reactivity.
[0065] The Michael addition reaction between the Michael acceptor
and the .beta.-dicarbonyl Michael donor may be promoted by a strong
base. An example of a base which is sufficiently strong and is
easily solubilized in a monomer mixture is diazabicycloundecene
(DBU). In addition, a cyclic amidine such as diazabicyclononene
(DBN) and guanidine is also suitable to catalyze the reaction.
Typically, also a Group I metal alkoxide base such as potassium
t-butoxide is adequate to promote the reaction. A quaternary
hydroxide and alkoxide, e.g., tetrabutylammonium hydroxide and
benzyltrimethylammonium methoxide, may also be used as a base
catalyst to promote the Michael addition. As a result, an
organophilic alkoxide strong base may be generated in-situ from the
reaction between a halide anion (e.g., quaternary halide) and the
epoxide moiety.
[0066] The Michael addition product represented by Chemical Formula
3 may be prepared from the Michael addition product represented by
Chemical Formula 2 by substituting the hydrogen atoms of the
hydroxyl groups with multifunctional isocyanate. The substitution
may be carried out by adding the Michael addition product
represented by Chemical Formula 2, the multifunctional isocyanate
and a multifunctional acryl monomer to a reactor and then
performing reaction at 30 to 60.degree. C. for 2 to 4 hours.
[0067] The Michael addition product of the present invention may
also be modified to a primary or secondary amine by adding an amine
synergist so as to block oxygen in the air. As a result,
photoreactivity may be enhanced. As an example of such
modification, a primary or secondary amine may be mixed with an
uncured Michael addition product. Specifically, after adding
diethanolamine to the Michael addition product represented by
Chemical Formula 2 or 3, followed by stirring at room temperature,
the resulting product may be exposed to UV. Typical examples of the
primary amine include ethanolamine, methyl-1,6-hexanediamine,
3-aminopropyltrimethoxysilane, diaminopropane, benzylamine,
triethylenetetraamine, isophoronediamine and a mixture thereof.
Typical examples of the secondary amine include dimethylamine,
dibutylamine, diethanolamine, piperidine, morpholine and a mixture
thereof. In case a liquid Michael addition product is modified with
a primary or secondary amine, it may be accomplished simply by
reacting the modified amine with the liquid, uncured Michael
addition product.
[0068] The present invention further provides a coating film
comprising a cured, crosslinked residue of the Michael addition
product. Because the Michael addition product of the present
invention has a built-in photoinitiating group, the coating film
may be prepared by exposing it to UV, without necessitating the use
of an additional photoinitiator or photosensitizer.
Examples
[0069] The examples and experiments will now be described. The
following examples and experiments are for illustrative purposes
only and not intended to limit the scope of this disclosure.
[0070] The Michael addition product of the present invention was
coated on a surface to demonstrate its UV photopolymerization
performance. The resin composition was coated on a glass substrate
by the draw-down technique to a thickness of 10 .mu.m or smaller.
Then, UV was irradiated at 500 mJ/cm.sup.2 for adhesion-free
curing.
Example 1
Synthesis of Michael Acceptor Having Hydroxyl Groups
##STR00008##
[0072] 2-Carboxyethyl acrylate (28.826 g, 0.2 mol), glycerol
diglycidyl ether (20.433 g, 0.1 mol) and triethylamine (2 wt %
based on glycerol diglycidyl ether) were sequentially added to a
4-bulb glass flask reactor equipped with a reflux condenser, a
nitrogen inlet, a stirrer and a heater. After raising temperature
to 60.degree. C., reaction was carried out for 4 hours without
using a polymerization inhibitor. Then, after cooling to room
temperature and transferring to a reparatory funnel, 5% HCl aqueous
solution was added to neutralize the remaining catalyst and the
salt was removed. Then, after washing 2 to 3 times with distilled
water, a Michael acceptor having hydroxyl groups was obtained at
50.degree. C. under reduced pressure as transparent liquid. The
Michael acceptor was separated and purified to obtain a main
product with the byproduct removed.
[0073] FIG. 1 shows an FT-IR spectrum of the Michael acceptor
prepared in Example 1. FIGS. 2, 3 and 4 respectively show a
.sup.1H-NMR spectrum, a .sup.13C-NMR spectrum and a prep-LC
result.
[0074] prep-LC (yield): 83%.
[0075] IR (KBr, cm.sup.-1): 3421 (--OH), 2919 (aliphatic C--H),
1727 (C.dbd.O), 1635 & 1618 (C.dbd.C), 1186 & 1122
(C--O--C), 984 (.dbd.CH.sub.2 twisting vibration).
[0076] .sup.1H-NMR (CDCl.sub.3, 300 MHz), .delta. (ppm): 5.80-6.33
(m, 3H, --CH.dbd.CH.sub.2), 4.13 & 4.31-4.41 (m, 5H,
--CH.sub.2CHOHCH.sub.2OOCCH.sub.2CH.sub.2--), 3.98 (m, 1H,
--CH.sub.2CHOHCH.sub.2--), 3.55 & 3.70 (m, 4H,
--CH.sub.2OCH.sub.2--), 2.61-2.72 (m, 2H, --CH.sub.2COO--).
[0077] .sup.13C-NMR (CDCl.sub.3, 75 MHz), .delta. (ppm): 173.63
(--CH.sub.2COO--), 165.99 (CH.sub.2.dbd.CHCOO--), 131.20
(CH.sub.2.dbd.CH--), 127.97 (CH.sub.2.dbd.CH--), 65.14-73.05
(--COOCH.sub.2CHOHCH.sub.2OCH.sub.2CHOH--), 59.83
(CH.sub.2=CHCOOCH.sub.2--), 33.18
(CH.sub.2.dbd.CHCOOCH.sub.2CH.sub.2--).
Example 2
Synthesis of Michael Acceptor Having Hydroxyl Groups
##STR00009##
[0079] 2-Carboxyethyl acrylate (28.826 g, 0.2 mol),
1,4-cyclohexanedimethanol diglycidyl ether (25.634 g, 0.1 mol) and
triethylamine (2 wt % based on 1,4-cyclohexanedimethanol diglycidyl
ether) were sequentially added to a 4-bulb glass flask reactor
equipped with a reflux condenser, a nitrogen inlet, a stirrer and a
heater. After raising temperature to 60.degree. C., reaction was
carried out for 4 hours without using a polymerization inhibitor.
Then, after cooling to room temperature and transferring to a
separatory funnel, 5% HCl aqueous solution was added to neutralize
the remaining catalyst and the salt was removed. Then, after
washing 2 to 3 times with distilled water, a Michael acceptor
having hydroxyl groups was obtained at 50.degree. C. under reduced
pressure as transparent liquid. The Michael acceptor was separated
and purified to obtain a main product with the byproduct removed.
FIG. 5 shows an FT-IR spectrum of the Michael acceptor prepared in
Example 2. FIGS. 6, 7 and 8 respectively show a .sup.1H-NMR
spectrum, a .sup.13C-NMR spectrum and a prep-LC result.
[0080] prep-LC (yield): 73%.
[0081] IR (KBr, cm.sup.-1): 3421 (--OH), 2919 (aliphatic C--H),
1727 (C.dbd.O), 1635 & 1618 (C.dbd.C), 1186 & 1122
(C--O--C), 984 (.dbd.CH.sub.2 twisting vibration).
[0082] .sup.1H-NMR (CDCl.sub.3, 300 MHz), .delta. (ppm): 5.80-6.33
(m, 3H, --CH.dbd.CH.sub.2), 4.32-4.40 (m, 2H,
--COOCH.sub.2CH.sub.2COO--), 3.91-4.17 (m, 3H,
--COOCH.sub.2CHOHCH.sub.2--), 3.22-3.57 (m, 4H,
--CHOHCH.sub.2OCH.sub.2--), 2.60-2.68 (m, 2H, --CH.sub.2COO--),
0.85-2.60 (m, 5H, --CHCH.sub.2CH.sub.2CH-(cyclohexane)).
[0083] .sup.13C-NMR (CDCl.sub.3, 75 MHz), .delta. (ppm): 173.54
(--CH.sub.2COO--), 165.54 (CH.sub.2.dbd.CHCOO--), 130.93
(CH.sub.2.dbd.CH--), 127.54 (CH.sub.2.dbd.CH--), 68.13-74.42
(--COOCH.sub.2CHOHCH.sub.2OCH.sub.2CH--), 59.41
(CH.sub.2.dbd.CHCOOCH.sub.2--), 37.53 (cyclohexane,
--CHCH.sub.2--), 33.00 (--CH.sub.2COO--), 28.72 (cyclohexane,
--CHCH.sub.2CH.sub.2CH--).
Example 3
Synthesis of Michael Addition Product Having Built-In
Photoinitiating Group
##STR00010##
[0085] The Michael acceptor having hydroxyl groups prepared in
Example 1 (20.19 g, 0.04 mol), ethyl acetoacetate (2.64 g, 0.02
mol), glycidyl methacrylate (0.46 g, 2 wt %) and tetrabutylammonium
bromide (0.12 g, 0.5 wt %) were added to a 4-bulb glass flask
reactor equipped with a reflux condenser, a nitrogen inlet, a
stirrer and a heater. The mixture was mixed while stirring
adequately using a mechanical stirrer. Then, the reactor was heated
to 80.degree. C. at a rate of 1.degree. C./min and then kept at the
temperature for 3 hours. 3 hours later, the resulting resin was
taken out of the reactor and then cooled to obtain a Michael
addition product having a built-in photoinitiating group.
[0086] The Michael addition product was coated on a glass substrate
to a thickness of 10 .mu.m, and then adhesion-freely cured by
exposing to UV at 500 mJ/cm.sup.2. The cured coating was smooth,
glossy and soft.
[0087] IR (KBr, cm.sup.-1): 3421 (--OH), 2919 (aliphatic C--H),
1727 (C.dbd.O), 1635 & 1618 (C.dbd.C), 1186 & 1122
(C--O--C), 984 (.dbd.CH.sub.2 twisting vibration).
[0088] .sup.13C-NMR (CDCl.sub.3, 75 MHz), .delta. (ppm) : 208.7
(CH.sub.3C.dbd.OC--), 173.63 (--CH.sub.2COO--), 172.7
(--CCOOCH.sub.2CH.sub.3), 165.99 (CH.sub.2.dbd.CHCOO--), 131.20
(CH.sub.2.dbd.CH--), 127.97 (CH.sub.2.dbd.CH--), 65.14-73.05
(--COOCH.sub.2CHOHCH.sub.2OCH.sub.2CHOH--), 61.6
(--COOCH.sub.2CH.sub.3), 59.83 (--COOCH.sub.2CH.sub.2COO--), 33.18
(--COOCH.sub.2CH.sub.2COO--), 26.9-28.4
(--OOCCH.sub.2CH.sub.2CCH.sub.2CH.sub.2COO--), 25.9
(CH.sub.3C.dbd.OC--), 14.1 (--COOCH.sub.2CH.sub.3).
Example 4
Synthesis of Michael Addition Product Having Built-In
Photoinitiating Group
##STR00011##
[0090] The Michael acceptor having hydroxyl groups prepared in
Example 2 (21.78 g, 0.04 mol), ethyl acetoacetate (2.64 g, 0.02
mol), glycidyl methacrylate (0.50 g, 2 wt %) and tetrabutylammonium
bromide (0.12 g, 0.5 wt %) were added to a 4-bulb glass flask
reactor equipped with a reflux condenser, a nitrogen inlet, a
stirrer and a heater. The mixture was mixed while stirring
adequately using a mechanical stirrer. Then, the reactor was heated
to 80.degree. C. at a rate of 1.degree. C./min and then kept at the
temperature for 3 hours. 3 hours later, the resulting resin was
taken out of the reactor and then cooled to obtain a Michael
addition product having a built-in photoinitiating group.
[0091] The Michael addition product was coated on a glass substrate
to a thickness of 10 .mu.m, and then adhesion-freely cured by
exposing to UV at 500 mJ/cm.sup.2. The cured coating was smooth,
glossy and soft.
[0092] IR (KBr, cm.sup.-1): 3421 (--OH), 2919 (aliphatic C--H),
1727 (C.dbd.O), 1635 & 1618 (C.dbd.C), 1186 & 1122
(C--O--C), 984 (.dbd.CH.sub.2 twisting vibration).
[0093] .sup.13C-NMR (CDCl.sub.3, 75 MHz), .delta. (ppm) : 208.7
(CH.sub.3C.dbd.OC--), 173.54 (--CH.sub.2COO--), 172.7
(--CCOOCH.sub.2CH.sub.3), 165.54 (CH.sub.2.dbd.CHCOO--), 130.93
(CH.sub.2.dbd.CH--), 127.54 (CH.sub.2.dbd.CH--), 68.13-74.42
(--COOCH.sub.2CHOHCH.sub.2OCH.sub.2CH--), 61.6
(--COOCH.sub.2CH.sub.3), 59.41 (--COOCH.sub.2CH.sub.2COO--), 37.53
(cyclohexane, --CHCH.sub.2--), 33.00 (--CH.sub.2COO--), 28.72
(cyclohexane, --CHCH.sub.2CH.sub.2CH--), 25.9 (CH.sub.3C.dbd.OC--),
14.1 (--COOCH.sub.2CH.sub.3).
Example 5
Synthesis of Michael Addition Product Having Built-In
Photoinitiating Group
##STR00012##
[0095] The Michael addition product prepared in Example 3 (30 g,
0.027 mol), acetone (50 g) and dibutyltin dilaurate (0.1 g) were
added to a 4-bulb glass flask reactor equipped with a reflux
condenser, a nitrogen inlet, a stirrer and a heater. The mixture
was mixed while stirring adequately using a mechanical stirrer.
Then, the reactor was heated to 45.degree. C. over 20 minutes.
While maintaining the temperature at 45.degree. C., isophorone
diisocyanate (35.88 g, 0.161 mol) was added dropwise over 1 hour.
Then, the temperature was raised to 60.degree. C. over 3 hours.
[0096] The reaction was monitored by FT-IR. The temperature of the
reaction mixture was lowered to 45-50.degree. C. when the intensity
at 3400 cm.sup.-1 (--OH band) became a minimum value. Then, after
adding pentaerythritol triacrylate (48.02 g, 0.161 mol), the
reaction mixture was further stirred and heated. To prevent
gelation, phenothiazine (0.01 g) was added.
[0097] The reaction was monitored by FT-IR. Acetone was removed by
vacuum distillation at 60.degree. C. and 100 mmHg when the
intensity at 2300 cm.sup.-1 (--NCO band) became a minimum value. A
urethane acrylate type Michael addition product was obtained.
[0098] The Michael addition product was coated on a glass substrate
to a thickness of 10 .mu.m, and then adhesion-freely cured by
exposing to UV at 500 mJ/cm.sup.2. The cured coating was smooth,
glossy and hard.
Example 6
Synthesis of Michael Addition Product Having Built-In
Photoinitiating Group
##STR00013##
[0100] The Michael addition product prepared in Example 4 (30 g,
0.025 mol), acetone (50 g) and dibutyltin dilaurate (0.1 g) were
added to a 4-bulb glass flask reactor equipped with a reflux
condenser, a nitrogen inlet, a stirrer and a heater. The mixture
was mixed while stirring adequately using a mechanical stirrer.
Then, the reactor was heated to 45.degree. C. over 20 minutes.
While maintaining the temperature at 45.degree. C., isophorone
diisocyanate (32.81 g, 0.148 mol) was added dropwise over 1 hour.
Then, the temperature was raised to 60.degree. C. over 3 hours.
[0101] The reaction was monitored by FT-IR. The temperature of the
reaction mixture was lowered to 45-50.degree. C. when the intensity
at 3400 cm.sup.-1 (--OH band) became a minimum value. Then, after
adding pentaerythritol triacrylate (44.15 g, 0.148 mol), the
reaction mixture was further stirred and heated. To prevent
gelation, phenothiazine (0.01 g) was added.
[0102] The reaction was monitored by FT-IR. Acetone was removed by
vacuum distillation at 60.degree. C. and 100 mmHg when the
intensity at 2300 cm.sup.-1 (--NCO band) became a minimum value. A
urethane acrylate type Michael addition product was obtained.
[0103] The Michael addition product was coated on a glass substrate
to a thickness of 10 .mu.m, and then adhesion-freely cured by
exposing to UV at 500 mJ/cm.sup.2. The cured coating was smooth,
glossy and hard.
[0104] While the present invention has been described with respect
to the specific embodiments, it will be apparent to those skilled
in the art that various changes and modifications may be made
without departing from the spirit and scope of the invention as
defined in the following claims.
* * * * *