U.S. patent number 10,385,245 [Application Number 15/325,699] was granted by the patent office on 2019-08-20 for one-component moisture-curable urethane composition and method for producing same.
This patent grant is currently assigned to The Yokohama Rubber Co., Ltd.. The grantee listed for this patent is The Yokohama Rubber Co., LTD.. Invention is credited to Kiminori Araki.
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United States Patent |
10,385,245 |
Araki |
August 20, 2019 |
One-component moisture-curable urethane composition and method for
producing same
Abstract
The present technology is to provide a one-part moisture-curable
polyurethane composition having excellent adhesion to an adherend
(coated plate), and a method for producing such a composition. The
present technology is a one-part moisture-curable urethane
composition including a preliminary composition obtained by mixing
a urethane prepolymer, an aliphatic isocyanate A, and an
aminosilane compound B, and a catalyst; and a method for producing
such a composition.
Inventors: |
Araki; Kiminori (Hiratsuka,
JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
The Yokohama Rubber Co., LTD. |
Minato-ku, Tokyo |
N/A |
JP |
|
|
Assignee: |
The Yokohama Rubber Co., Ltd.
(JP)
|
Family
ID: |
55064138 |
Appl.
No.: |
15/325,699 |
Filed: |
June 30, 2015 |
PCT
Filed: |
June 30, 2015 |
PCT No.: |
PCT/JP2015/068865 |
371(c)(1),(2),(4) Date: |
January 11, 2017 |
PCT
Pub. No.: |
WO2016/006501 |
PCT
Pub. Date: |
January 14, 2016 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20170158927 A1 |
Jun 8, 2017 |
|
Foreign Application Priority Data
|
|
|
|
|
Jul 11, 2014 [JP] |
|
|
2014-143313 |
|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08G
18/165 (20130101); C08G 18/7837 (20130101); C08G
18/792 (20130101); C08L 83/00 (20130101); C08G
18/7831 (20130101); C08G 18/4812 (20130101); C08G
18/4825 (20130101); C08G 18/4829 (20130101); C09J
175/04 (20130101); C08G 18/7671 (20130101); C08G
18/8025 (20130101); C08G 18/2018 (20130101); C08G
18/246 (20130101); C09J 175/08 (20130101); C08G
18/2081 (20130101); C08G 18/12 (20130101); C08G
18/12 (20130101); C08G 18/289 (20130101) |
Current International
Class: |
C09J
175/04 (20060101); C09J 175/08 (20060101); C08G
18/24 (20060101); C08G 18/20 (20060101); C08G
18/16 (20060101); C08G 18/12 (20060101); C08G
18/80 (20060101); C08G 18/79 (20060101); C08G
18/78 (20060101); C08G 18/76 (20060101); C08L
83/00 (20060101); C08G 18/48 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
2000-128949 |
|
May 2000 |
|
JP |
|
2004-168957 |
|
Jun 2004 |
|
JP |
|
2005-239753 |
|
Sep 2005 |
|
JP |
|
2006-131802 |
|
May 2006 |
|
JP |
|
2006131802 |
|
May 2006 |
|
JP |
|
2008-038019 |
|
Feb 2008 |
|
JP |
|
2010-235652 |
|
Oct 2010 |
|
JP |
|
WO 2001/53423 |
|
Jul 2001 |
|
WO |
|
WO 2014/136800 |
|
Sep 2014 |
|
WO |
|
Other References
English machine translation of JP2006131802, created Aug. 2, 2018
(Year: 2018). cited by examiner .
International Search Report for International Application No.
PCT/JP2015/068865 dated Oct. 6, 2015, 4 pages, Japan. cited by
applicant.
|
Primary Examiner: Rodd; Christopher M
Attorney, Agent or Firm: Thorpe North & Western
Claims
The invention claimed is:
1. A one-part moisture-curable urethane composition including: a
preliminary composition obtained by mixing a urethane prepolymer,
an aliphatic isocyanate A, and an aminosilane compound B, and a
catalyst, wherein the catalyst contains N,
N-dimethylaminoethylmorpholine and products formed by reacting
1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl silicate
in a molar ratio of 1:0.8 to 1.2.
2. The one-part moisture-curable urethane composition according to
claim 1, wherein the urethane prepolymer is obtained by reacting
polypropylene glycol with diphenylmethane diisocyanate.
3. The one-part moisture-curable urethane composition according to
claim 1, wherein the aliphatic isocyanate A is at least one type of
aliphatic isocyanate-modified product a selected from the group
consisting of reaction products of a polyol having tri- or higher
functionality and an aliphatic polyisocyanate, allophanates of
aliphatic polyisocyanate, isocyanurates of aliphatic
polyisocyanate, and biurets of aliphatic polyisocyanate.
4. The one-part moisture-curable urethane composition according to
claim 1, wherein the aminosilane compound B contains, in each
molecule, an alkoxysilyl group and a nitrogen atom to which an
aromatic ring and a hydrogen atom are bonded.
5. The one-part moisture-curable urethane composition according to
claim 4, wherein the alkoxysilyl group is a methoxysilyl group or
an ethoxysilyl group.
6. The one-part moisture-curable urethane composition according to
claim 1, wherein, per 100 parts by weight of the urethane
prepolymer, an amount of the aliphatic isocyanate A is from 0.8 to
10 parts by mass, and an amount of the aminosilane compound B is
from 0.1 to 4 parts by mass.
7. The one-part moisture-curable urethane composition according to
claim 1, wherein the catalyst further contains at least one type
selected from the group consisting of dibutyltin acetylacetate, and
dimorpholinodiethyl ether.
8. The one-part moisture-curable urethane composition according to
claim 7, wherein the catalyst contains products formed by reacting
1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl silicate
in a molar ratio of 1:0.8 to 1.2, dibutyltin acetylacetate,
dimorpholinodiethyl ether, and N,
N-dimethylaminoethylmorpholine.
9. The one-part moisture-curable urethane composition according to
claim 8, wherein an amount of the organotin catalyst is from 0.0005
to 0.3 parts by mass per 100 parts by mass of the urethane
prepolymer.
10. The one-part moisture-curable urethane composition according to
claim 8, wherein an amount of the dimorpholinodiethyl ether is from
0.004 to 1.2 parts by mass per 100 parts by mass of the urethane
prepolymer.
11. The one-part moisture-curable urethane composition according to
claim 8, wherein an amount of the N, N-dimethylaminoethylmorpholine
is 1 part by mass or less per 100 parts by mass of the urethane
prepolymer.
12. The one-part moisture-curable urethane composition according to
claim 1, wherein the preliminary composition further contains a
filler.
13. The one-part moisture-curable urethane composition according to
claim 12, wherein the filler is at least one selected from the
group consisting of carbon blacks and white fillers.
14. The one-part moisture-curable urethane composition according to
claim 1, wherein the preliminary composition further contains a
plasticizer.
15. A method for producing a one-part moisture-curable urethane
composition, the method comprising: a mixing step 1 of obtaining a
preliminary composition by mixing a urethane prepolymer, an
aliphatic isocyanate A, and an aminosilane compound B; and a mixing
step 2 of producing the one-part moisture-curable urethane
composition described in claim 1 by mixing the preliminary
composition and a catalyst.
16. The method for producing a one-part moisture-curable urethane
composition according to claim 15, wherein at least one selected
from the group consisting of fillers and plasticizers is further
used in the mixing step 1.
17. The one-part moisture-curable urethane composition according to
claim 4, wherein the alkoxysilyl group is an ethoxysilyl group.
Description
TECHNICAL FIELD
The present technology relates to a one-part moisture-curable
urethane composition and a method for producing such a
composition.
BACKGROUND ART
Various urethane resin compositions have been widely used as
sealing agents, adhesive agents, and the like.
As such urethane resin compositions, use of one-part
moisture-curable polyurethane composition, which cures by moisture
in the air or the like, has been increasing recently from the
perspective of ease in handling that does not require mixing and/or
adjusting the composition on site when the composition is used, or
the like.
For example, Japanese Unexamined Patent Application Publication No.
2000-128949A describes "a one-part moisture-curable polyurethane
composition including: (A) a urethane prepolymer, and (B) a silane
compound containing an average of at least 1.5 NCO groups and an
average of at least 1.5 hydrolyzable alkoxy groups in each
molecule, the silane compound containing at least one type selected
from the group consisting of (B-1) a silane compound obtained by an
addition reaction of a polyisocyanate compound having at least 3
NCO groups in each molecule and a secondary aminoalkoxysilane,
wherein the polyisocyanate compound is a reaction product obtained
by reacting a polyol that is a triol or higher polyol and that has
a molecular weight of 500 or less with diisocyanate and (B-2) a
silane compound that has a lysine backbone and that is obtained by
an addition reaction of a lysine isocyanate having 2 or 3
isocyanate groups with a secondary aminoalkoxysilane" (Japanese
Unexamined Patent Application Publication No. 2000-128949A).
However, it was found that, depending on the type of an adherend
(coated plate), conventionally known one-part moisture-curable
polyurethane compositions described in Japanese Unexamined Patent
Application Publication No. 2000-128949A or the like may exhibit
poor adhesion.
SUMMARY
The present technology provides a one-part moisture-curable
polyurethane composition which exhibits excellent adhesion to an
adherend (coated plate).
The inventor of the present technology has found that excellent
adhesion to an adherend (coated plate) is achieved by allowing a
preliminary composition obtained by mixing a urethane prepolymer,
an aliphatic isocyanate A, and an aminosilane compound B, and a
catalyst to be contained, and thus completed the present
technology.
Specifically, the inventor discovered a one-part moisture-curable
urethane composition having the following features.
1. A one-part moisture-curable urethane composition including:
a preliminary composition obtained by mixing a urethane prepolymer,
an aliphatic isocyanate A, and an aminosilane compound B, and
a catalyst.
2. The one-part moisture-curable urethane composition according to
1 above, where the urethane prepolymer is obtained by reacting
polypropylene glycol with diphenylmethane diisocyanate.
3. The one-part moisture-curable urethane composition according to
1 or 2 above, where the aliphatic isocyanate A is at least one type
of aliphatic isocyanate-modified product a selected from the group
consisting of reaction products of a polyol having tri- or higher
functionality and an aliphatic polyisocyanate, allophanates of
aliphatic polyisocyanate, nurates of aliphatic polyisocyanate, and
biurets of aliphatic polyisocyanate.
4. The one-part moisture-curable urethane composition according to
any one of 1 to 3 above, where the aminosilane compound B contains,
in each molecule, an alkoxysilyl group and a nitrogen atom to which
an aromatic ring and a hydrogen atom are bonded.
5. The one-part moisture-curable urethane composition according to
4 above, where the alkoxysilyl group is a methoxysilyl group or an
ethoxysilyl group.
6. The one-part moisture-curable urethane composition according to
any one of 1 to 5 above, where, per 100 parts by weight of the
urethane prepolymer,
an amount of the aliphatic isocyanate A is from 0.8 to 10 parts by
mass, and
an amount of the aminosilane compound B is from 0.1 to 4 parts by
mass.
7. The one-part moisture-curable urethane composition according to
any one of 1 to 6 above, where the catalyst contains at least one
type selected from the group consisting of products formed by
reacting 1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl
silicate in a molar ratio of 1:0.8 to 1.2, dibutyltin
acetylacetate, dimorpholinodiethyl ether, and diamino
ethylmorpholine.
8. The one-part moisture-curable urethane composition according to
any one of 1 to 7 above, where the catalyst contains, as an
organotin catalyst, at least one selected from the group consisting
of products formed by reacting
1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl silicate
in a molar ratio of 1:0.8 to 1.2 and dibutyltin acetylacetate,
dimorpholinodiethyl ether, and
diamino ethylmorpholine.
9. The one-part moisture-curable urethane composition according to
8 above, where an amount of the organotin catalyst is from 0.0005
to 0.3 parts by mass per 100 parts by mass of the urethane
prepolymer.
10. The one-part moisture-curable urethane composition according to
8 or 9 above, where an amount of the dimorpholinodiethyl ether is
from 0.004 to 1.2 parts by mass per 100 parts by mass of the
urethane prepolymer.
11. The one-part moisture-curable urethane composition according to
any one of 8 to 10 above, where an amount of the diamino
ethylmorpholine is 1 part by mass or less per 100 parts by mass of
the urethane prepolymer.
12. The one-part moisture-curable urethane composition according to
any one of 1 to 11 above, where the preliminary composition further
contains a filler.
13. The one-part moisture-curable urethane composition according to
12 above, where the filler is at least one selected from the group
consisting of carbon blacks and white fillers.
14. The one-part moisture-curable urethane composition according to
any one of 1 to 13 above, where the preliminary composition further
contains a plasticizer.
15. A method for producing a one-part moisture-curable urethane
composition, the method comprising:
a mixing step 1 of obtaining a preliminary composition by mixing a
urethane prepolymer, an aliphatic isocyanate A, and an aminosilane
compound B; and
a mixing step 2 of producing the one-part moisture-curable urethane
composition described in any one of 1 to 14 above by mixing the
preliminary composition and a catalyst.
16. The method for producing a one-part moisture-curable urethane
composition according to 15 above, where at least one selected from
the group consisting of fillers and plasticizers is further used in
the mixing step 1.
Advantageous Effects of Technology
The one-part moisture-curable urethane composition of the present
technology exhibits excellent adhesion to an adherend (coated
plate).
According to the production method of the present technology, a
one-part moisture-curable urethane composition exhibiting excellent
adhesion to an adherend (coated plate) can be produced.
DETAILED DESCRIPTION
The present technology is described in detail below.
The one-part moisture-curable urethane composition of the present
technology (composition of the present technology) is
a one-part moisture-curable urethane composition including:
a preliminary composition obtained by mixing a urethane prepolymer,
an aliphatic isocyanate A, and an aminosilane compound B, and
a catalyst.
The composition of the present technology exhibits excellent
adhesion to an adherend (coated plate) by allowing a preliminary
composition obtained by mixing a urethane prepolymer, an aliphatic
isocyanate A, and an aminosilane compound B to be contained. Note
that, in the present specification, the condition where adhesion to
an adherend (coated plate) is excellent may be simply referred to
as "excellent adhesion".
In the present technology, the preliminary composition is produced
by mixing a urethane prepolymer, an aliphatic isocyanate A, and an
aminosilane compound B. In the preliminary composition, the
urethane prepolymer and the aminosilane compound B may be reacted.
Furthermore, the aliphatic isocyanate A and the aminosilane
compound B may be reacted. Therefore, the preliminary composition
may further contain a reaction product formed by reacting the
aminosilane compound B with the aliphatic isocyanate A, and/or a
reaction product formed by reacting the aminosilane compound B with
the urethane prepolymer, after the mixing.
The urethane prepolymer will be described below. The urethane
prepolymer used in the composition of the present technology is not
particularly limited as long as the urethane prepolymer is a
urethane prepolymer having an isocyanate group at a terminal. For
example, a substance obtained by reacting polyisocyanate with a
compound having two or more active hydrogen-containing groups in
each molecule (active hydrogen compounds) in a manner that the
amount of the isocyanate groups contained in the polyisocyanate is
in excess relative to the amount of the active hydrogen-containing
groups contained in the active hydrogen compound can be used. The
urethane prepolymer may contain from 0.5 to 5 mass % of isocyanate
group at molecular terminals.
The polyisocyanate used during production of the urethane
prepolymer is not particularly limited as long as the
polyisocyanate has two or more isocyanate groups in each
molecule.
Examples of the polyisocyanate include aromatic polyisocyanates,
such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate
(MDI; e.g. 4,4'-diphenylmethane diisocyanate and
2,4'-diphenylmethane diisocyanate), 1,4-phenylene diisocyanate,
polymethylene polyphenylene polyisocyanate, xylylene diisocyanate
(XDI), tetramethylxylylene diisocyanate (TMXDI), tolidine
diisocyanate (TODI), 1,5-naphthalene diisocyanate (NDI), and
triphenylmethane triisocyanate; aliphatic and/or alicyclic
polyisocyanates, such as hexamethylene diisocyanate (HDI),
trimethylhexamethylene diisocyanate (TMHDI), lysine diisocyanate,
and norbornane diisocyanate (NBDI),
transcyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI),
bis(isocyanate methyl)cyclohexane (H.sub.6XDI), and
dicyclohexylmethane diisocyanate (H.sub.12MDI);
carbodiimide-modified polyisocyanates of these; and
isocyanurate-modified polyisocyanates of these.
A single polyisocyanate can be used or a combination of two or more
polyisocyanates can be used.
Among these, an aromatic polyisocyanate is preferable, and MDI is
more preferable, from the perspective of excellent curability.
The compound having two or more active hydrogen-containing groups
in each molecule (active hydrogen compound) that is used during
production of the urethane prepolymer is not particularly limited.
Examples of the active hydrogen-containing group include a hydroxy
(OH) group, amino group, and imino group.
Preferred examples of the active hydrogen compound include polyol
compounds having two or more hydroxy (OH) groups in each molecule,
and the like. Among these, a polyol compound is preferable.
The polyol compound is not particularly limited as long as the
polyol compound is a compound having two or more hydroxy groups.
Examples thereof include polyether polyols; polyester polyols;
polymer polyols having a carbon-carbon bond in a main chain
backbone, such as acrylic polyols, polybutadiene diols, and
hydrogenated polybutadiene polyols; low molecular weight polyhydric
alcohols; and mixed polyols of these. Among these, a polyether
polyol is exemplified as an example of preferable aspects.
The polyether polyol is not particularly limited as long as the
polyether polyol is a compound having a polyether as a main chain
and having two or more hydroxy groups. The term "polyether" is a
group having two or more ether bonds, and specific examples thereof
include a group having a total of two or more of structural units:
--R.sup.a--O--R.sup.b--. Note that, in the structural unit, R.sup.a
and R.sup.b each independently represent a hydrocarbon group. The
hydrocarbon group is not particularly limited. Examples thereof
include a straight-chain alkylene group having from 1 to 10
carbons.
Examples of the polyether polyol include a polyoxyethylene diol
(polyethylene glycol), polyoxypropylene diol (polypropylene glycol;
PPG), polyoxypropylene triol, ethylene oxide/propylene oxide
copolymer, polytetramethylene ether glycol (PTMEG),
polytetraethylene glycol, sorbitol polyol, and the like.
The polyether polyol is preferably polypropylene glycol or
polyoxypropylene triol from the perspective of excellent
miscibility with polyisocyanate.
The weight average molecular weight of the polyether polyol is
preferably from 500 to 20,000 because the viscosity of the urethane
prepolymer, which is obtained by a reaction with isocyanate,
exhibits an appropriate fluidity at the ambient temperature. In the
present technology, the weight average molecular weight is a value
obtained by GPC analysis (solvent: tetrahydrofuran (THF)) based on
calibration with polystyrene.
The active hydrogen compound may be used alone, or a combination of
two or more types of the active hydrogen compounds may be used.
The urethane prepolymer is preferably a urethane prepolymer formed
by reacting a polyether polyol and an aromatic polyisocyanate, from
the perspective of achieving even better adhesion and excellent
curability. The urethane prepolymer is more preferably a urethane
prepolymer obtained by reacting polypropylene glycol and/or
polyoxypropylene triol and diphenylmethane diisocyanate.
The urethane prepolymer may be used alone, or a combination of two
or more types of the urethane prepolymers may be used.
The method of producing the urethane prepolymer is not particularly
limited. For example, the urethane prepolymer can be produced by
using polyisocyanate in a manner that from 1.5 to 2.5 mol of
isocyanate group is reacted per 1 mol of the active
hydrogen-containing group (e.g. hydroxy group) contained in the
active hydrogen compound, and mixing these to perform a
reaction.
Note that the urethane prepolymer may contain at least one type
selected from the group consisting of unreacted polyisocyanates and
unreacted active hydrogen compounds.
The aliphatic isocyanate A will be described below. The aliphatic
isocyanate A used in the composition of the present technology is
not particularly limited as long as the aliphatic isocyanate A is
an aliphatic hydrocarbon compound having at least one isocyanate
group in each molecule.
The aliphatic hydrocarbon group contained in the aliphatic
isocyanate A is not particularly limited. The aliphatic hydrocarbon
group may be a straight-chain, branched-chain, or cyclic aliphatic
hydrocarbon group, and a straight-chain aliphatic hydrocarbon group
is preferable. The aliphatic hydrocarbon group may be a saturated
or unsaturated aliphatic hydrocarbon group, and a saturated
aliphatic hydrocarbon group is preferable.
The number of the isocyanate group contained in each molecule of
the aliphatic isocyanate A is preferably 2 or more, and more
preferably 2 or 3, from the perspective of even better
adhesion.
Examples of the aliphatic isocyanate A include aliphatic
polyisocyanates (including alicyclic polyisocyanate but not
including modified products), such as hexamethylene diisocyanate
(HDI), trimethyl hexamethylene diisocyanate (TMHDI), lysine
diisocyanate, norbornane diisocyanate (NBDI),
trans-cyclohexane-1,4-diisocyanate, isophorone diisocyanate (IPDI),
bis(isocyanatemethyl)cyclohexane (H.sub.6XDI), and
dicyclohexylmethane diisocyanate (H.sub.12MDI) (hereinafter, the
aliphatic polyisocyanate described above may be referred to as
"aliphatic polyisocyanate b"); and modified products of aliphatic
polyisocyanates.
The aliphatic isocyanate A is preferably a modified product of
aliphatic polyisocyanate from the perspective of even better
adhesion and a wider range of adhesion depending on the environment
at the time of curing.
The modified product of the aliphatic polyisocyanate is preferably
at least one type of aliphatic isocyanate-modified product a
selected from the group consisting of reaction products of a polyol
having tri- or higher functionality and an aliphatic
polyisocyanate, allophanates of aliphatic polyisocyanate, nurates
of aliphatic polyisocyanate, and biurets of aliphatic
polyisocyanate, from the perspective of excellent balance between
adhesion and physical properties of the adhesive agent after the
curing.
The aliphatic polyisocyanate used in the aliphatic
isocyanate-modified product a is not particularly limited as long
as the aliphatic polyisocyanate is an aliphatic hydrocarbon
compound having at least two isocyanate groups in each molecule.
Examples include the same as those exemplified for the aliphatic
polyisocyanate b. Among these, a straight-chain aliphatic
polyisocyanate is preferable, and HDI is more preferable, from the
perspectives of achieving even better adhesion and being less
likely to cause foaming due to the added amount.
Examples of the reaction product of a polyol having tri- or higher
functionality and an aliphatic polyisocyanate include
trimethylolpropane (TMP), and reaction products of trifunctional
polyol, such as glycerin, and an aliphatic polyisocyanate b.
Specific examples of reaction products of TMP and HDI (e.g.
compound represented by Formula (5) below) and reaction products of
glycerin and HDI (e.g. compound represented by Formula (6)
below).
##STR00001##
Examples of the allophanate of aliphatic polyisocyanate include an
allophanate of HDI. The compound having one hydroxy group in each
molecule used to form the allophanate is not particularly limited.
An example thereof is pentamethylene diisocyanate.
Examples of the biuret of aliphatic polyisocyanate include a biuret
of HDI. Specifically, preferred examples include a compound
represented by Formula (7) below.
##STR00002##
Examples of the nurate (isocyanurate) of aliphatic polyisocyanate
include a nurate (isocyanurate) of HDI. Specific examples include a
compound represented by Formula (8) below.
##STR00003##
The production of the aliphatic isocyanate A is not particularly
limited. Examples thereof include conventionally known aliphatic
isocyanates. The aliphatic isocyanate A may be used alone, or a
combination of two or more types of the aliphatic isocyanates A may
be used.
The amount of the aliphatic isocyanate A is preferably from 0.8 to
15 parts by mass, more preferably from 0.8 to 10 parts by mass, and
even more preferably from 1 to 5 parts by mass, per 100 parts by
weight of the urethane prepolymer from the perspectives of even
better adhesion, and excellent high-temperature/high-humidity
adhesion and excellent breaking elongation.
The aminosilane compound B will be described below. The aminosilane
compound B used in the composition of the present technology is not
particularly limited as long as the aminosilane compound B is a
compound having an amino group (--NH.sub.2) and/or an imino group
(--NH--) and a hydrolyzable silyl group. The amino group, the imino
group, and the hydrolyzable silyl group can be bonded to each other
through organic group(s).
When the aminosilane compound B contains an imino group, an example
of a preferable aspect is one in which the group bonded to the
imino group is an aromatic hydrocarbon group.
The aromatic hydrocarbon group is not particularly limited as long
as the aromatic hydrocarbon group is a hydrocarbon group having at
least one aromatic ring.
Examples of the aromatic ring include a benzene ring and a
naphthalene ring.
The aromatic ring may have a substituent. Examples of the
substituent include alkyl groups.
Examples of the hydrolyzable silyl group include substances in
which at least one hydrolyzable group is bonded to one silicon
atom. When one or two hydrolyzable groups are bonded to one silicon
atom, other groups that can bond to the same silicon atom are not
particularly limited. Examples thereof include hydrocarbon
groups.
Examples of the hydrolyzable silyl group include alkoxysilyl
groups. Specific examples thereof include methoxysilyl groups
(monomethoxysilyl group, dimethoxysilyl group, and trimethoxysilyl
group) and ethoxysilyl groups (monoethoxysilyl group, diethoxysilyl
group, and triethoxysilyl group).
The organic group is not particularly limited. Examples thereof
include hydrocarbon groups that may have a hetero atom such as an
oxygen atom, nitrogen atom, and sulfur atom. Examples of the
hydrocarbon group include aliphatic hydrocarbon groups (which may
be in a form of straight-chain or branched-chain, and may have an
unsaturated bond), alicyclic hydrocarbon groups (which may have an
unsaturated bond), aromatic hydrocarbon groups, and a combination
of these. At least one of the carbon atom or the hydrogen atom
contained in the hydrocarbon group may be substituted with a
substituent. Among these, an example of a preferable aspect is an
aliphatic hydrocarbon group.
The aminosilane compound B is preferably a compound having an
alkoxysilyl group and an imide group in each molecule, and more
preferably a compound having an alkoxysilyl group and a nitrogen
atom, to which an aromatic ring and a hydrogen atom are bonded, in
each molecule from the perspectives of even better adhesion and
excellent storage stability of adhesive agent.
Examples of the aminosilane compound B include compounds
represented by Formula (I) below.
R.sup.1.sub.n--NH.sub.2-n--R.sup.2--Si--R.sup.3.sub.3 (I)
In Formula (I), R.sup.1 represents an aromatic hydrocarbon group, n
is 0 or 1, R.sup.2 represents a divalent aliphatic hydrocarbon
group, at least one of the three R.sup.3 moieties is an alkoxy
group and the three R.sup.3 moieties may be the same or different.
When one or two of the three R.sup.3 moieties are alkoxy group(s),
the other R.sup.3 is preferably alkyl group(s).
Examples of the aromatic hydrocarbon group include a phenyl
group.
Examples of the divalent aliphatic hydrocarbon group include a
methylene group, an ethylene group, and a propylene group.
Examples of the alkoxy group include a methoxy group and an ethoxy
group.
Examples of the alkyl group include a methyl group and an ethyl
group.
Specific examples of the aminosilane compound B include
N-phenyl-3-aminopropyltrimethoxysilane and
N-phenyl-3-aminopropyltriethoxysilane.
The production of the aminosilane compound B is not particularly
limited. Examples thereof include conventionally known methods. The
aminosilane compound B may be used alone, or a combination of two
or more types of the aminosilane compounds B may be used.
The amount of the aminosilane compound B is preferably from 0.1 to
10 parts by mass, more preferably from 0.1 to 4 parts by mass, and
even more preferably from 0.5 to 2 parts by mass, per 100 parts by
weight of the urethane prepolymer from the perspectives of even
better adhesion, and excellent flow resistance and excellent
breaking elongation.
In the present technology, the preliminary composition may further
contain a filler. In this case, excellent deep curability after the
adhesive agent is applied is achieved.
The filler is not particularly limited. An example of a preferable
aspect is one in which the filler is a carbon black and/or a white
filler. The filler may be, for example, a filler which has
undergone surface treatment by a surface treating agent, such as
fatty acids, resin acids, urethane compounds, and fatty acid
esters.
The carbon black is not particularly limited. Examples thereof
include conventionally known carbon blacks.
The amount of the carbon black is preferably from 30 to 150 parts
by mass, and more preferably from 50 to 120 parts by mass, per 100
parts by mass of the urethane prepolymer from the perspectives of
excellent flow resistance, discharging properties, and physical
properties after the adhesive agent is cured.
Examples of the white filler include calcium carbonate, such as
heavy calcium carbonate, precipitated calcium carbonate (light
calcium carbonate), and colloidal calcium carbonate; magnesium
carbonate and zinc carbonate; silica, such as fumed silica,
calcined silica, precipitated silica, pulverized silica, and molten
silica; diatomaceous earth; iron oxide, zinc oxide, titanium oxide,
barium oxide, magnesium oxide; pyrophyllite clay, kaolin clay, and
calcined clay.
The amount of the white filler is preferably from 10 to 80 parts by
mass, and more preferably from 20 to 50 parts by mass, per 100
parts by mass of the urethane prepolymer from the perspectives of
excellent deep curability and excellent adjustability in specific
gravity.
In the present technology, the preliminary composition may further
contain a plasticizer. In this case, excellent control in viscosity
and physical properties and excellent coatability can be
achieved.
Examples of the plasticizer include diisononyl phthalate (DINP);
dioctyl adipate and isodecyl succinate; diethylene glycol
dibenzoate and pentaerythritol esters; butyl oleate and methyl
acetyl ricinoleate; tricresyl phosphate and trioctyl phosphate;
propylene glycol adipate polyesters and butylene glycol adipate
polyesters; and the like.
The plasticizer may be used alone, or a combination of two or more
types of the plasticizers may be used.
The amount of the plasticizer is preferably from 10 to 100 parts by
mass, and more preferably from 30 to 80 parts by mass, per 100
parts by mass of the urethane prepolymer from the perspectives of
excellent control in viscosity and physical properties, and
excellent coatability.
The catalyst will be described below. The catalyst used in the
composition of the present technology is not particularly limited
as long as the catalyst is a catalyst contributing to curing of the
composition. Furthermore, from the perspectives of achieving even
better adhesion to an adherend (coated plate) and being capable of
adhering to an adherend without using a primer especially at low
temperatures, an example of a preferable aspect is one in which the
catalyst having a function that can contribute to adhesion is
used.
Examples of the catalyst that can contribute to curing of the
composition include amine catalysts and organotin catalysts.
An example of a preferable aspect is one in which the amine
catalyst is a tertiary amine catalyst, from the perspective of
adjusting the curing rate of the composition to an appropriate
range.
Examples of the tertiary amine catalyst include trimethylamine,
triethylamine, tripropylamine, tributylamine, triamylamine,
trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine,
dimethylpropylamine, dimethylbutylamine, dimethylamylamine,
dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine,
dimethyllaurylamine, triallylamine, tetramethylethylenediamine,
triethylenediamine, N-methylmorpholine,
4,4'-(oxydi-2,1-ethanediyl)bis-morpholine,
N,N-dimethylaminoethylmorpholine, N,N-dimethylbenzylamine,
pyridine, picoline, dimethylaminomethylphenol,
trisdimethylaminomethylphenol, 1,8-diazabicyclo[5.4.0]undecene-1,
1,4-diazabicyclo[2.2.2]octane, triethanolamine,
N,N'-dimethylpiperazine, tetramethyl butanediamine,
dimorpholinodiethyl ether, bis(2,2-morpholinoethyl)ether,
bis(dimethylaminoethyl)ether, and the like. One type of these can
be used alone, or two or more types can be used in combination.
Furthermore, the tertiary amine catalyst is preferably a compound
having a dimorpholinodiethyl ether structure from the perspective
of exhibiting superior effect of the present technology, excellent
curability, and excellent storage stability.
The dimorpholinodiethyl ether structure is a structure having a
dimorpholinodiethyl ether as a basic structure.
In the dimorpholinodiethyl ether structure, the hydrogen atom
contained in the morpholine ring may be substituted with a
substituent. The substituent is not particularly limited. Examples
thereof include alkyl groups. Examples of the alkyl group include a
methyl group and an ethyl group.
Examples of the amine catalyst having the dimorpholinodiethyl ether
structure include compounds represented by Formula (9) below.
##STR00004##
In Formula (9) above, R.sup.1 and R.sup.2 are each independently an
alkyl group, and m and n are each independently 0, 1, or 2.
Specific examples of the amine catalyst having a
dimorpholinodiethyl ether structure include dimorpholinodiethyl
ether (DMDEE), di(methylmorpholino)diethyl ether, and
di(dimethylmorpholino)diethyl ether.
Among these amine catalysts, from the perspectives of achieving
excellent coating formability of the adhesive agent (composition of
the present technology) during coating and achieving excellent
balance between storage stability and curing rate,
N,N-dimethylaminoethylmorpholine and compounds having a
dimorpholinodiethyl ether structure are preferable,
N,N-dimethylaminoethylmorpholine and dimorpholinodiethyl ether are
more preferable, and a combination of these is even more preferably
used.
As the catalyst having a function that can contribute to adhesion,
an organotin catalyst can be used.
Examples of the organotin catalyst include dioctyltin dilaurate,
dibutyltin dilaurate, dibutyltin maleate, tin(I) octate, dibutyltin
diacetylacetonate, dioctyltin maleate, and the like. One type of
these compounds can be used alone, or two or more types can be used
in combination.
Other specific examples of the organotin compound described above
include a reaction product of
1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane and ethyl silicate at
a molar ratio of 1:0.8 to 1:1.2 (abbreviated simply as
"distannoxane reaction product" in this paragraph hereafter).
The organotin compound is preferably a dibutyltin diacetylacetonate
or a distannoxane reaction product and more preferably a
distannoxane reaction product, because the compound can improve
adhesion to an adherend (coated plate) at low temperatures and also
can improve water resistant adhesion.
For example, the distannoxane reaction product can be obtained by
mixing 1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane and ethyl
silicate in a molar ratio in a range of 1:0.8 to 1:1.2 and reacting
for 1 to 3 hours at a temperature of 100.degree. C. to 130.degree.
C.
The catalyst is preferably a catalyst containing the organotin
catalyst and/or the amine catalyst, more preferably a catalyst
containing the organotin catalyst and/or the tertiary amine
catalyst, and even more preferably a catalyst containing at least
one type selected from the group consisting of products formed by
reacting 1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl
silicate in a molar ratio of 1:0.8 to 1.2, dibutyltin
acetylacetate, dimorpholinodiethyl ether, and diamino
ethylmorpholine.
Also from the perspectives of even better adhesion, excellent
storage stability of the adhesive agent, and excellent curability
of the adhesive agent, as an organotin catalyst, the catalyst
containing a product formed by reacting
1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane with ethyl silicate
in a molar ratio of 1:0.8 to 1.2 and/or dibutyltin acetylacetate,
dimorpholinodiethyl ether, and diamino ethylmorpholine is
preferable.
The amount of the catalyst is preferably 0.5 parts by mass or less
per 100 parts by mass of the urethane prepolymer.
The amount of the organotin catalyst is preferably from 0.0005 to
0.4 parts by mass, more preferably from 0.0005 to 0.3 parts by
mass, and even more preferably from 0.005 to 0.05 parts by mass,
per 100 parts by mass of the urethane prepolymer from the
perspectives of even better adhesion, excellent storage stability,
and excellent heat-resistant adhesion.
The amount of the amine catalyst is preferably from 0.004 to 2.2
parts by mass per 100 parts by mass of the urethane prepolymer from
the perspectives of even better adhesion, excellent storage
stability of the adhesive agent, and excellent curability.
The amount of the dimorpholinodiethyl ether is preferably from
0.002 to 1.2 parts by mass, more preferably from 0.004 to 1.2 parts
by mass, and even more preferably from 0.05 to 0.3 parts by mass,
per 100 parts by mass of the urethane prepolymer from the
perspectives of even better adhesion, excellent curability, and
excellent heat-resistant adhesion.
The amount of the diamino ethylmorpholine is preferably 1 part by
mass or less, and more preferably from 0.03 to 0.15 parts by mass,
per 100 parts by mass of the urethane prepolymer from the
perspectives of even better adhesion, excellent adhesion, excellent
foaming resistance, and excellent heat-resistant adhesion.
The composition of the present technology may contain, as
necessary, additives, such as isocyanate compounds except the
aliphatic isocyanate A, silane coupling agents except the
aminosilane compound B, adhesion promoters, anti-sagging agents,
anti-aging agents, antioxidants, pigments (dyes), thixotropic
agents, ultraviolet absorbers, flame retardants, surfactants
(including leveling agents), dispersing agents, dehydrating agents,
and antistatic agents, in a range that does not inhibit the object
of the present technology. The amount of the additive can be
adjusted as desired.
Examples of the method for producing the composition of the present
technology include the method for producing a one-part
moisture-curable urethane composition of the present technology
described below.
The composition of the present technology is one-part type.
The composition of the present technology can be cured by water
such as moisture. For example, the composition can be cured by
moisture in the air under conditions of -20 to +50.degree. C.
Examples of the use of the composition of the present technology
include an adhesive agent.
The adherend to which the composition of the present technology can
be applied is not particularly limited. Examples thereof include
metal (including coated plates), plastic, rubber, and glass.
The composition of the present technology can be applied to the
adherend without using a primer on the adherend.
The coated plate is not particularly limited. Examples thereof
include conventionally known coated plates. Examples of coating
used in the coated plate include acid/epoxy-based coating,
acryl/melamine-based coating, and acryl/silicon-based coating.
The method for producing the one-part moisture-curable urethane
composition of the present technology will be described below.
The method for producing the one-part moisture-curable urethane
composition of the present technology (production method of the
present technology) is a method for producing a one-part
moisture-curable urethane composition, the method comprising:
a mixing step 1 of obtaining a preliminary composition by mixing a
urethane prepolymer, an aliphatic isocyanate A, and an aminosilane
compound B; and
a mixing step 2 of producing the one-part moisture-curable urethane
composition of the present technology (composition of the present
technology) by mixing the preliminary composition and a
catalyst.
In the mixing step 1, a preliminary composition is obtained by
mixing a urethane prepolymer, an aliphatic isocyanate A, and an
aminosilane compound B.
The urethane prepolymer, the aliphatic isocyanate A, and the
aminosilane compound B that are used in the mixing step 1 are the
same as those described above.
In the mixing step 1, a filler and/or a plasticizer may be further
used.
When the filler and/or the plasticizer is further used in the
mixing step 1, the preliminary composition may be produced by first
mixing the urethane prepolymer, the aliphatic isocyanate A, and the
aminosilane compound B, and then adding the filler and/or the
plasticizer to the mixture.
Furthermore, the preliminary composition may be produced by mixing
the urethane prepolymer, the aliphatic isocyanate A, the
aminosilane compound B, and the filler and/or the plasticizer at
one time.
Furthermore, for example, the preliminary composition may be
produced by mixing the urethane prepolymer, the plasticizer, and
the aliphatic isocyanate A, then adding and mixing the aminosilane
compound B, and then adding and mixing the filler to the
mixture.
In the mixing step 1, for example, a vertical mixer or a horizontal
mixer can be used.
The mixing temperature in the mixing step 1 is preferably from 40
to 90.degree. C.
The mixing step 1 is preferably performed under reduced
pressure.
Thereafter, in the mixing step 2, the composition of the present
technology is produced by mixing the preliminary composition and a
catalyst.
The catalyst used in the mixing step 2 is the same as that
described above.
In the mixing step 2, for example, a vertical mixer or a horizontal
mixer can be used.
The mixing temperature in the mixing step 2 is preferably from 40
to 70.degree. C.
The mixing step 2 is preferably performed under reduced
pressure.
When the composition of the present technology further contains an
additive, the additive can be appropriately added in the mixing
step 1 and/or 2.
EXAMPLES
The present technology will be described below in detail using
examples. However, the present technology is not limited to these
examples.
Production of Composition
In the mixing step 1, components shown in the "mixing step 1" row
in Table 1 below in compositions (part by mass) shown in Table 1
were used and mixed by a horizontal mixer at 40 to 70.degree. C.
for 1 hour to produce a preliminary composition.
Thereafter, in the mixing step 2, components shown in the "mixing
step 2" row in Table 1 below in compositions (part by mass) shown
in Table 1 were added to the preliminary composition produced as
described above, and mixed by a horizontal mixer to produce a
composition.
Evaluation
The following evaluations were performed using the composition
produced as described below. The results are shown in Table 1.
Adhesion to Coated Plates 1 and 2
To coated plates 1 and 2 obtained by respectively applying the
coating materials 1 and 2 described below to steel plates, the
compositions produced as described above were applied directly
without using a primer. Thereafter, the coated plates were left in
the condition at 20.degree. C. and 60% relative humidity for 7
days, then immersed in warm water at 40.degree. C. for 7 days, and
dried in the condition at 20.degree. C. after the coated plate was
removed from the water. The thickness of the cured product of the
composition after the composition was left in the condition at
20.degree. C. and 60% relative humidity for 7 days was 3 mm
(hereinafter the same).
One end of the cured product of the composition was then held and
peeled back by 180 degrees in the condition at 20.degree. C. to
observe the failure state. Cases where the cohesive failure was
observed on the cured product was evaluated as "CF", and cases
where the interfacial failure was observed on the cured product was
evaluated as "AF".
Coating material 1: Acid/epoxy-based coating material
Coating material 2: Acryl/silicon-based coating material
Time Required for CF to Occur
Each of the compositions produced as described above was directly
applied on the coated plate 2 without using a primer and cured in
the condition at 20.degree. C. or 5.degree. C. and 60% relative
humidity.
Thereafter, one end of the cured product of the composition was
then held and peeled back by 180 degrees in the condition at
20.degree. C. to evaluate the time required for cohesive failure
(CF) to occur on the cured product of the composition.
For the test in which the curing was performed in the condition at
20.degree. C., the 180.degree. peel test was performed after 3 days
from the start of the curing, and if the failure state at this time
was CF, the result was described as "within 3 days".
The 180.degree. peel test was performed on the fourth day, and if
the failure state on the third day was AF but the failure state on
the fourth day was CF, the result was described as "4 days".
The 180.degree. peel test was performed on the tenth day, and if
the failure state at this time was AF, the result was described as
"10 days or longer".
For the test in which the curing was performed in the condition at
5.degree. C., the 180.degree. peel test was performed after seven
days from the start of the curing, and if the failure state at this
time was CF, the result was described as "7 days".
The 180.degree. peel test was performed on the eighth day, and if
the failure state on the seventh day was AF but the failure state
on the eighth day was CF, the result was described as "8 days".
The 180.degree. peel test was performed on the ninth day, and if
the failure state on the eighth day was AF but the failure state on
the ninth day was CF, the result was described as "9 days".
The 180.degree. peel test was performed on the tenth day, and if
the failure state on the ninth day was AF but the failure state on
the tenth day was CF, the result was described as "10 days".
The 180.degree. peel test was performed on the 15th day, and if the
failure state on the tenth day was AF but the failure state on the
15th day was CF, the result was described as "15 days".
The 180.degree. peel test was performed on the 21st day, and if the
failure state at this time was AF, the result was described as "3 W
or longer".
Curability (Curing Rate)
The tack-free time in the case where each of the compositions
produced as described above was cured in the condition at
20.degree. C. and 65% relative humidity was measured.
The composition having a tack-free time of 20 to 120 minutes was
evaluated as having excellent curability and written as
".largecircle.", and the composition having a tack-free time of
longer than 120 minutes was evaluated as having poor curability and
written as ".times.".
Storage Stability
Each of the compositions produced as described above was placed in
a container, sealed, and stored for 7 days at 50.degree. C.
Thereafter, SOD viscosity (Pas) was measured, and the rate of the
viscosity increase was calculated using the SOD viscosity prior to
the storage.
Note that the SOD viscosity was measured using a pressure
viscometer (ASTM D 1092) in accordance with JASO (Japanese
Automotive Standards Organization) M338-89.
Cases where the rate of the viscosity increase was within 30%, the
storage stability was evaluated as being excellent and written as
".largecircle.", and the other cases were evaluated and written as
".times.".
Breaking Elongation (Elongation at Break)
A cured product of each of the compositions produced as described
above was cut out into a dumbbell-shaped test piece with a
thickness of 2 mm (No. 3 dumbbell shape), and the breaking
elongation (%) was measured in accordance with JIS (Japanese
Industrial Standard) K 6251:2010 at a tensile test speed of 500
mm/min at 23.degree. C.
The breaking elongation is preferably 250% or greater.
TABLE-US-00001 TABLE 1 Comparative Examples 1 2 3 4 5 6 7 Mixing
step 1 Urethane prepolymer 1 100 100 100 100 100 100 100 Aliphatic
isocyanate a1 4 (HDI biuret) Aliphatic isocyanate a2 4 (TMP/HDI)
Aliphatic isocyanate a3 (HDI allophanate) Aliphatic isocyanate a4
(HDI nurate) Aminosilane compound 3 B1 (KBM573) Aminosilane
compound 3 B2 (A-1170) Adduct 1 (a1 + B1) 5 Adduct 2 (a1 + B2) 3 4
Carbon black 45 45 45 45 45 45 45 Plasticizer 30 30 30 30 30 30 30
Filler 25 25 25 25 25 25 25 Mixing step 2 Organotin catalyst C1
0.001 0.001 0.001 0.001 0.001 0.001 0.001 Organotin catalyst C2
Tertiary amine catalyst 0.01 0.01 0.01 0.01 0.01 0.01 0.01 D1
Tertiary amine catalyst 0.01 0.01 0.01 0.01 0.01 0.01 0.01 D2
Adhesive Adhesion: coated plate 1 CF CF AF AF CF CF CF
characteristics at 20.degree. C. (after water resistance test at
40.degree. C. for 1 week) Adhesion: coated plate 2 AF AF CF CF CF
CF CF at 20.degree. C. (after water resistance test at 40.degree.
C. for 1 week) Time required for CF to Within 3 Within 3 10 days 10
days 10 days 10 days 10 days occur when cured at days days or or or
or or 20.degree. C. on coated plate 2 longer longer longer longer
longer Time required for CF to 15 days 15 days 3 W or 3 W or 3 W or
3 W or 3 W or occur when cured at longer longer longer longer
longer 5.degree. C. on coated plate 2 Curability (curing rate)
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircl- e. .largecircle. .largecircle. Storage stability
.largecircle. .largecircle. .largecircle. .largecircle.-
.largecircle. X X Breaking elongation 320 340 400 400 320 380 350
Working Examples 1 2 3 4 5 6 Mixing step 1 Urethane prepolymer 1
100 100 100 100 100 100 Aliphatic isocyanate a1 1 1 1 4 4 4 (HDI
biuret) Aliphatic isocyanate a2 (TMP/HDI) Aliphatic isocyanate a3
(HDI allophanate) Aliphatic isocyanate a4 (HDI nurate) Aminosilane
compound 0.1 0.1 0.5 0.1 0.1 0.1 B1 (KBM573) Aminosilane compound
B2 (A-1170) Adduct 1 (a1 + B1) Adduct 2 (a1 + B2) Carbon black 45
45 45 45 45 45 Plasticizer 30 30 30 30 30 30 Filler 25 25 25 25 25
25 Mixing step 2 Organotin catalyst C1 0.001 0.001 0.02 0.01 0.3
0.4 Organotin catalyst C2 Tertiary amine catalyst 0.01 0.01 0.02
0.002 0.01 0.01 D1 Tertiary amine catalyst 0.005 0.01 0.01 0.01
0.01 D2 Adhesive Adhesion: coated plate 1 CF CF CF CF CF CF
characteristics at 20.degree. C. (after water resistance test at
40.degree. C. for 1 week) Adhesion: coated plate 2 CF CF CF CF CF
CF at 20.degree. C. (after water resistance test at 40.degree. C.
for 1 week) Time required for CF to 4 days 4 days 4 days 4 days
Within 3 Within 3 occur when cured at days days 20.degree. C. on
coated plate 2 Time required for CF to 10 days 10 days 9 days 10
days 7 days 7 days occur when cured at 5.degree. C. on coated plate
2 Curability (curing rate) .largecircle. .largecircle.
.largecircle. X .largecircle. .largecir- cle. Storage stability
.largecircle. .largecircle. .largecircle. .largecircle.-
.largecircle. X Breaking elongation 350 350 350 310 300 300 Working
Examples 7 8 9 10 11 12 Mixing step 1 Urethane prepolymer 1 100 100
100 100 100 100 Aliphatic isocyanate a1 4 4 4 10 10 10 (HDI biuret)
Aliphatic isocyanate a2 (TMP/HDI) Aliphatic isocyanate a3 (HDI
allophanate) Aliphatic isocyanate a4 (HDI nurate) Aminosilane
compound 1 1 2 0.1 3 4 B1 (KBM573) Aminosilane compound B2 (A-1170)
Adduct 1 (a1 + B1) Adduct 2 (a1 + B2) Carbon black 45 45 45 45 45
45 Plasticizer 30 30 30 30 30 30 Filler 25 25 25 25 25 25 Mixing
step 2 Organotin catalyst C1 0.001 0.02 0.02 0.02 0.02 Organotin
catalyst C2 0.01 Tertiary amine catalyst 0.01 0.01 0.02 0.02 0.02
0.02 D1 Tertiary amine catalyst 0.005 0.01 0.01 0.01 0.01 0.01 D2
Adhesive Adhesion: coated plate 1 CF CF CF CF CF CF characteristics
at 20.degree. C. (after water resistance test at 40.degree. C. for
1 week) Adhesion: coated plate 2 CF CF CF CF CF CF at 20.degree. C.
(after water resistance test at 40.degree. C. for 1 week) Time
required for CF to Within 3 Within 3 Within 3 Within 3 Within 3
Within 3 occur when cured at days days days days days days
20.degree. C. on coated plate 2 Time required for CF to 8 days 8
days 8 days 9 days 8 days 8 days occur when cured at 5.degree. C.
on coated plate 2 Curability (curing rate) .largecircle.
.largecircle. .largecircle. .largecircle. .largecircl- e.
.largecircle. Storage stability .largecircle. .largecircle.
.largecircle. .largecircle.- .largecircle. .largecircle. Breaking
elongation 300 320 320 350 280 270 Working Examples 13 14 15 16 17
Mixing step 1 Urethane prepolymer 1 100 100 100 100 100 Aliphatic
isocyanate a1 10 12 (HDI biuret) Aliphatic isocyanate a2 4
(TMP/HDI) Aliphatic isocyanate a3 4 (HDI allophanate) Aliphatic
isocyanate a4 4 (HDI nurate) Aminosilane compound 4.5 3 1 1 1 B1
(KBM573) Aminosilane compound B2 (A-1170) Adduct 1 (a1 + B1) Adduct
2 (a1 + B2) Carbon black 45 45 45 45 45 Plasticizer 30 30 30 30 30
Filler 25 25 25 25 25 Mixing step 2 Organotin catalyst C1 0.001
0.001 0.01 0.01 0.01 Organotin catalyst C2 Tertiary amine catalyst
0.01 0.01 0.01 0.01 0.01 Dl Tertiary amine catalyst 0.01 0.01 0.01
0.01 0.01 D2 Adhesive Adhesion: coated plate 1 CF CF CF CF CF
characteristics at 20.degree. C. (after water resistance test at
40.degree. C. for 1 week) Adhesion: coated plate 2 CF CF CF CF CF
at 20.degree. C. (after water resistance test at 40.degree. C. for
1 week) Time required for CF to Within 3 Within 3 Within 3 Within 3
Within 3 occur when cured at days days days days days 20.degree. C.
on coated plate 2 Time required for CF to 8 days 8 days 7 days 7
days 7 days occur when cured at 5.degree. C. on coated plate 2
Curability (curing rate) .largecircle. .largecircle. .largecircle.
.largecircle. .largecircl- e. Storage stability .largecircle.
.largecircle. .largecircle. .largecircle.- .largecircle. Breaking
elongation 170 150 330 330 330
Details of the components listed in Table 1 are as follows.
Urethane prepolymer 1: Urethane prepolymer 1, in which the content
of isocyanate group was 1.45%, was synthesized by mixing 500 g of
polyoxypropylene diol (average molecular weight: 2000), 1150 g of
polyoxypropylene triol (average molecular weight: 5000), and 264 g
of 4,4'-diisocyanate phenylmethane (molecular weight: 250)
(NCO/OH=1.8 in this case), further adding 800 g of diisononyl
phthalate, and stirring in a nitrogen gas stream at 80.degree. C.
for 24 hours to allow reaction to proceed.
Note that, in Table 1, 100 parts by mass of the urethane prepolymer
1 contains no diisononyl phthalate. Aliphatic isocyanate a1: Biuret
of HDI represented by Formula (7) above (D165N, manufactured by
Mitsui Chemicals, Inc.) Aliphatic isocyanate a2: Adduct of
trimethylolpropane and hexamethylene diisocyanate represented by
Formula (5) above (TMP/HDI), Duranate P301-75E, manufactured by
Asahi Kasei Chemicals Corporation Aliphatic isocyanate a3:
Allophanate of hexamethylene diisocyanate (HDI), Takenate D178N,
manufactured by Mitsui Chemicals, Inc. Aliphatic isocyanate a4:
Nurate of hexamethylene diisocyanate (HDI) represented by Formula
(8) above, Takenate D170N, manufactured by Mitsui Chemicals, Inc.
Aminosilane compound B1: N-phenyl-3-aminopropyltriethoxysilane,
KBM-573, manufactured by Shin-Etsu Chemical Co., Ltd. Aminosilane
compound B2: N,N-bis[(3-trimethoxysilyl)propyl]amine, Dynasylan
1124 (manufactured by Evonik) Adduct 1: A compound produced by
mixing the aliphatic isocyanate a1 and the aminosilane compound B1
described above in amounts that made the molar ratio of NCO:NH=1:1,
and reacting for 10 hours at 50.degree. C. Adduct 2: A compound
produced by mixing the aliphatic isocyanate a1 and the aminosilane
compound B2 described above in amounts that made the molar ratio of
NCO:NH=1:1, and reacting for 10 hours at 50.degree. C. Carbon
black: N220, manufactured by NSCC Carbon Co., Ltd. Plasticizer:
Diisononyl phthalate (DINP, manufactured by J-PLUS Co., Ltd.)
Filler: Heavy calcium carbonate (Super S, manufactured by Maruo
Calcium Co., Ltd.) Organotin catalyst C1: A reaction product formed
by reacting 1,3-diacetoxy-1,1,3,3-tetrabutyl-distannoxane and ethyl
silicate at a molar ratio of 1:1 at 100 to 130.degree. C. Organotin
catalyst C2: Dibutyltin diacetylacetonate (manufactured by Nihon
Kagaku Sangyo Co., Ltd.) Tertiary amine catalyst D1:
Dimorpholinodiethyl ether (manufactured by San-Apro Ltd.) Tertiary
amine catalyst D2: N,N-dimethylaminoethylmorpholine (manufactured
by Air Products and Chemicals, Inc.)
As is clear from the results shown in Table 1, Comparative Examples
1 and 2, which contained no aminosilane compound, exhibited low
adhesion.
Comparative Examples 3 and 4, which contained no aliphatic
isocyanate A, exhibited low adhesion.
Comparative Examples 5 to 7, which contained no aliphatic
isocyanate A and no aminosilane compound but instead contained the
adduct 1 or the adduct 2, required a long period of time for
cohesive failure to occur and exhibited low adhesion.
On the other hand, Working Examples 1 to 17 achieved excellent
adhesion.
Furthermore, when Working Examples 1, 2, and 7 and Working Example
14 are compared, Working Examples 1, 2, and 7, in which the amount
of the aliphatic isocyanate A was 10 parts by mass or less per 100
parts by mass of the urethane prepolymer, achieved even better
breaking elongation than that of Working Example 14.
When Working Examples 10 to 12 and Working Example 13 are compared,
Working Examples 10 to 12, in which the amount of the aminosilane
compound B was 4 parts by mass or less per 100 parts by mass of the
urethane prepolymer, achieved even better breaking elongation than
that of Working Example 13.
When Working Example 4 and the other working examples are compared,
working examples having a greater amount of the tertiary amine
catalyst D1 than that of Working Example 4 achieved even better
curability.
When Working Example 5 and Working Example 6 are compared, a
smaller amount of the organotin catalyst C1 resulted in even better
storage stability.
When Working Examples 15 to 17 and Working Example 7 are compared,
Working Examples 15 to 17, in which the aliphatic isocyanate A was
in the form of adduct, allophanate, or nurate, required a short
period of time for CF to occur at 5.degree. C. (low temperature
condition) and achieved even better adhesion than those of Working
Example 7, in which the aliphatic isocyanate A was in the form of
biuret.
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