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BACKGROUND OF THE INVENTION
This invention relates generally to hardening resin compositions of
solventless type. More specifically, the invention relates to oil-modified
alkyd resin compositions which can be applied as coatings to form coating
films of excellent hardness, resistance to bending, resistance to impacts,
property of being applicable as thick layers (thereinafter referred to as
thickly applicable property), and resistance to water. The term "paint" is
herein used to designate collectively coating materials such as paints,
varnishes, enamels, coating compounds, and the like.
Still more specifically, the invention relates to improvements in the water
resistance and hardness of the paint ingredients in the ingredient system
of my prior invention disclosed in my previous Japanese Patent Application
No. 44317/1976
In general, oil-modified alkyd resins are prepared from polybasic acids,
polyhydric alcohols, and saturated or unsaturated fatty acids or oils.
These oil-modified alkyd resins are being used for various paints such as
paints for drying at room temperature, the characteristic of these resins
to harden as a result of participation of the double bond of the
unsaturated fatty acid in the composition in a bridging or cross-linking
reaction because of the oxygen in air being utilized.
Under the assumption that the fatty acid or oil in the resin in an
oil-modified alkyd resin has reacted with glycerine to form a
triglyceride, the weight percentage of the triglyceride in the resin is
called the oil length. This oil length is closely related to the physical
properties such as solubility, hardness, luster or gloss, color
retentivitiy, weather resistance, hardening time, and preservability of
the paint. For example, while an increase in the oil length results in an
increase in the flexibility of the paint film and its solubility in
organic solvents, it tends to decrease the hardness of the paint film. On
the other hand, a decrease in the oil length is useful in improving the
luster and color retentivity of the paint film but tends to decrease the
spreadability of the paint. Of course, the oil length is not the only
factor influencing the above mentioned physical properties of the paint,
these properties being influenced also by the properties of the other
ingredients of the oil-modified alkyd resin.
Heretofore, oil-modified alkyd resins of oil lengths of the order of 30 to
80 percent have been generally dissolved in solvents such as turpentine
oil and toluene and used in room temperature drying paints and baking
paints. However, oil-modified alkyd resin paints diluted by such solvents
are accompanied by problems such as long drying times and pollution of the
working environment by the evaporation of the solvents at the time of
drying.
Oil-modified alkyd resin paints in which solvents are not used, that is,
paints of the solventless type (which may be called pollutionless type) in
which all paint ingredients react, are now being studied. However, those
that have been developed to date have been accompanied by problems such as
poor adhesion to metals, inadequate mechanical properties such as impact
resistance and bending resistance, and inadequate coating property and
have not been reduced to practical use, as far as I am aware.
In order to solve these problems, I have previously proposed oil-modified
alkyd resins comprising the following ingredients as disclosed in the
patent applications cited hereinbefore.
1. An oil-modified alkyd resin composition comprising:
(A) 50 to 80% by weight of an oil-modified alkyd resin which is modified
with a fatty acid containing at least 65% by weight of linoleic acid
and/or linolenic acid and has an oil length of 40 to 70%; and
(B) 50 to 20% by weight of an acrylate and/or methacrylate which is a
monoester of an alcohol having from 2 to 20 carbon atoms and acrylic acid
or methacrylic acid.
This paint composition has the advantages of excellent adhesion to metals
and short hardening time, thereby possessing great practicability.
However, it requires approximately one day to produce a water resistant
film therefrom. For this reason, there has been a great demand for
improvement of these compositions for obtaining water resistant films in a
short time particularly in the fields of structures exposed to the
atmosphere such as bridges, production plants, and ships.
SUMMARY OF THE INVENTION
It is an object of this invention to solve the above described problems by
providing a composition formed by dissolving an oil-modified alkyd resin,
which has been modified with an .alpha.,.beta.-unsaturated monocarboxylic
acid, in a polymerizable monomer.
According to this invention, briefly summarized, there are provided
oil-modified alkyd resin compositions each comprising: from 30 to 70
percent by weight of an ingredient (A) comprising an oil-modified alkyd
resin of an oil length of from 30 to 70 percent which has been modified
with an .alpha.,.beta.-unsaturated monocarboxylic acid selected from the
group consisting of sorbic acid, crotonic acid, and 2-(.beta.-furyl)
acrylic acid, the content of the .alpha.,.beta.-unsaturated monocarboxylic
acid being from 0.5 to 30 percent by weight; and from 70 to 30 percent by
weight of an ingredient (B) comprising a polymerizable monomer in which
the ingredient (A) is dissolved.
I have found that the oil-modified alkyd resin compositions of solventless
type can be dried at room temperature of hardened by baking to have
excellent properties such as surface smoothness, hardness, adhesiveness,
bending resistance, impact resistance, thickly applicable property, and
water resistance as described in detail hereinafter.
The nature, utility, and further features of this invention will be
apparent from the following detailed description beginning with a
consideration of general aspects of the invention and concluding with
specific examples of experiments in production illustrating preferred
embodiments thereof.
DETAILED DESCRIPTION OF THE INVENTION
Ingredient (A): oil-modified alkyd resin modified with an unsaturated
carboxylic acid
The ingredient (A) as set forth above is substantially the same as
oil-modified alkyd resins which are known heretofore or may be provided in
the future except that it has been modified with a specific
.alpha.,.beta.-unsaturated monocarboxylic acid. The method by which this
modification with the .alpha.,.beta.-unsaturated monocarboxylic acid is
carried out is also the same as the ordinary method of modifying an alkyd
resin with a fatty acid.
Accordingly, examples of the polybasic acid of the alkyd resins are
aromatic, aliphatic or alicyclic saturated or unsaturated polybasic acids
such as phthalic anhydride, isophthalic acid, tetrahydrophthalic
anhydride, adipic acid, sebacic acid, azelaic acid, branched
1,2,3,6-tetrahydrophthalic anhydride derivatives which are Diels-Adler
adducts of an isoprene dimer having conjugated double bonds and maleic
anhydride such as maleinated myrcene, maleinated alloocimene, maleinated
ocimene, 3-(.beta.-methyl-2-butenyl)-5-methyl-1,2,3,6-tetrahydrophthalic
acid or anhydride thereof, hexahydrophthalic anhydride,
4-methyl-tetrahydrophthalic anhydride, trimellitic acid, and mixtures of
two or more of these acids.
Within limits wherein gelation will not occur, a part of given saturated
polybasic acid such as the one mentioned above may be substituted by an
unsaturated polybasic acid such as, for example, maleic acid, maleic
anhydride, fumaric acid, and itaconic acid. Of these, a particularly
preferable polybasic acid is a combination of phthalic acid and
3-(.beta.-methyl-2-butenyl)-5-methyl-1,2,3,6-tetrahydrophthalic anydride
(hereinafter referred to by the abbreviation MBTHP). When MBTHP is used in
a quantity of 2 to 100 mole percent, preferably 30 to 50 mole percent of
the polybasic acid, it has a remarkable effect in lowering the viscosity
of the alkyd resin.
Examples of polyhydric alcohols which can be used for the polyhydric
alcohol ingredient are ethyleneglycol, diethyleneglycol, propyleneglycol,
dipropyleneglycol, 1,4-butanediol, neopentylglycol, glycerine,
pentaerythritol, trimethylol propane, trimethylolethane,
tris(2-hydroxylethyl) isocyanurate, and mixtures of two or more of these
alcohols. In general, dihydric-, trihydric- and tetrahydric alcohols of
from 2 to 12 carbon atoms are usually preferable. Particularly preferable
polyhydric alcohol is a combination of glycerine and pentaerythritol.
For the fat, oil, or fatty acid for forming the oil-modified alkyd resin,
those which can be dried in air are used, examples being oils and fats
such as linseed oil, soybean oil, tall oil, and safflower oil, dehydrated
castor oil or fatty acids separated from these oils. Particularly
desirable fatty acids are dehydrated castor oil fatty acid and safflower
oil fatty acid contining more than 60 mole percent in the fatty acid
moiety of linoleic acid and linolenic acid independently or as a mixture
system.
According to this invention, the oil-modified alkyd resin comprising the
above described three indispensable ingredients is further modified with
an .alpha.,.beta.-unsaturated monocarboxylic acid.
.alpha.,.beta.-unsaturated monocarboxylic acids which are suitable for use
in this invention are crotonic acid, sorbic acid, and 2-(.beta.-furyl)
acrylic acid, as mentioned hereinbefore, sorbic acid being particularly
preferable. This .alpha.,.beta.-unsaturated carboxylic acid introduced
into the oil-modified alkyd resin may be considered to react similarly as
the fatty acid for oil modification and to be present as a side chain in
the alkyd resin. Since this acid undergoes radical copolymerization with
the ingredient (B) in the composition of this invention and thereby
contributes to hardening of the formed film, it is highly effective
particularly for improving the hardness and the water resistance of the
formed paint film.
Of these four indispensable ingredients, the oil-modified alkyd resin is
prepared by an ordinary process. Specific examples are the process wherein
the .alpha.,.beta.-unsaturated monocarboxylic acid, the fatty acid, the
polybasic acid, and the polyhydric alcohol are simultaneously charged into
the reaction system and caused to react and the process in which the fatty
acid, the polybasic acid, and the polyhydric alcohol are first caused to
react, and then the .alpha.,.beta.-unsaturated monocarboxylic acid is
caused to react with these reactants. The latter process is desirable on
the point of preventing gelation during this preparation process.
These four indispensable ingredients can be supplied to the reaction in the
form of their functional derivatives, for example, in the form of esters
resembling fats and oils. In the case where an oil or fat is used, the
polyhydric alcohol and ester only are ordinarily caused to react
beforehand thereby to carry out ester exchange. Furthermore, whatever
method is used, it is desirable that an agent for preventing gelation such
as hydroquinone, for example, be added in order to prevent gelation during
reaction.
An oil-modified alkyd resin suitable for use in this invention has an oil
length of 30 to 70 percent, preferably 55 to 65 percent. I have found that
if the oil length is less than 30 percent, it will give rise to a lowering
of resistance such as water resistance of the formed paint film. On the
other hand, if this oil length is higher than 70 percent, it gives rise to
undesirable results such as a lowering the hardness of the formed film at
the initial stage of drying and a deterioration of the surface smoothness.
As mentioned hereinbefore, the oil length of this invention is the
percentage by weight of the monobasic acid triglyceride the monobasic acid
of which has originated from the fat or oil or the fatty acid separated
therefrom in the oil-modified alkyd resin after its modification with the
.alpha.,.beta.-unsaturated monocarboxylic acid.
The content of the .alpha.,.beta.-unsaturated monocarboxylic acid in the
oil-modified alkyd resin which has been modified with the
.alpha.,.beta.-unsaturated monocarboxylic acid is 0.5 to 30 percent by
weight, preferably 2 to 15 percent by weight. I have found that if this
content is less than 0.5 percent, there will be no appreciable effect in
improving the water resistance and hardness of the formed paint film. On
the other hand, if this content exceeds 30 percent, gelation will very
readily occur during the alkyd preparation, which will thereby become
difficult.
The acid value of the oil-modified alkyd resin modified with the
.alpha.,.beta.-unsaturated monocarboxylic acid which is used in this
invention is ordinarily of the order of 5 to 40, and the number of
hydroxyl groups is ordinarily from 20 to 150.
Ingredient (B): polymerizable monomer
For this monomer, it is possible to use any monomer which is capable of
undergoing radical polymerization, has at least one ethylenically
unsaturated bond, and is capable of dissolving the above described
ingredient (A) to a desired concentration as described in detail
hereinafter. However, since it is an object of this invention to provide a
resin composition which can be hardened at room temperature or hardened
upon being heated, a polymerizable monomer of high boiling point of an
order exceeding 200.degree. C., for example, an acrylate or a methacrylate
of a boiling point above 200.degree. C. is especially preferable. A
polymerizable monomer of such a high boiling point is advantageous on the
point of odor.
Specific examples of polymerizable monomers suitable for use as the
ingredient (B) in this invention are as set forth below. These monomers
can be used in combinations thereof.
Mono(meth)acrylates of high boiling points:
Monoacrylates and monomethacrylates of monohydric or polyhydric alcohols
having 2 to 20, preferably 2 to 18 carbon atoms, preferably monoacrylates
and monomethacrylates of monohydric and dihydric alcohols. In each of
these alcohols, the group to which the hydroxyl group is to be bonded is
not necessarily a hydrocarbon, but the alcohol may be one having, for
example, an ether linkage.
Specific examples of these monoacrylates and monomethacrylates are as set
forth below. In the following list, the term "(meth)acrylate" means
acrylate and methacrylate: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl
(meth)acrylate, 2-hydroxyethoxyethyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl
(meth)acrylate, neopentylglycol mono(meth)acrylate,
3-butoxy-2-hydroxypropyl (meth)acrylate, 2-hydroxy-1- or -2-phenylethyl
(meth)acrylate, polypropylene glycol mono(meth)acrylate, glycerine
mono(meth)acrylate monohalfmaleate, diethyleneglycol mono(meth)acrylate,
cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl
(meth)acrylate, 2-butoxyethyl (meth)acrylate, and tetrahydrofuryl
(meth)acrylate.
(3) Di-tetra (meth)acrylate of high boiling points:
Examples are di-, tri-, and tetraesters of alcohols each having at least
two hydroxyl groups and having 2 to 20 carbon atoms, preferably 2 to 6
carbon atoms, preferably dihydric, trihydric, and tetrahydric alcohols and
acrylic acid and methacrylic acid. The alcohol is not necessarily one in
which the group to which each hydroxyl group is to be bonded is a
hydrocarbon but may be one which has ether bonds. Furthermore, in the case
of a trihydric or higher polyhydric alcohol, it is suitable as long as its
at least two hydroxyl groups have been esterified with acrylic acid or
methacrylic acid.
Specific examples of these di-, tri-, and tetraacrylates and methacrylates
are: ethyleneglycol di(meth)acrylate, diethyleneglycol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,
neopentylglycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate,
pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
and glycerine monoacrylate monomethacrylate.
Examples of particularly suitable polymerizable monomers for the ingredient
(B) of this invention are: tetrahydrofurfuryl acrylate, 2-hydroxyethyl
methacrylate, 2-hydroxypropyl acrylate, 3-butoxy-2-hydroxypropyl acrylate,
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and
trimethylolpropane tri(meth)acrylate.
Composition
Each oil-modified alkyd resin composition according to this invention
contains the above described indispensable two ingredients (A) and (B) in
a specific ratio.
The quantity of the ingredient (A) is from 30 to 70 percent by weight,
preferably 40 to 60 pecent by weight, of the total weight of these two
ingredients (A) and (B). If this quantity exceeds 70 percent, the resin
composition will acquire a remarkably high viscosity, and its preparation
and utilization, for example, as a paint, will become difficult. On the
other hand if this quantity is less than 30 percent, the water resistance,
impact resistance, and bending resistance of the formed paint film will
deteriorate.
The quantity of the ingredient (B) is from 70 to 30 percent by weight,
preferably 60 to 40 percent by weight, of the total weight of the two
ingredients (A) and (B). A large quantity of the di-, tri-, or
tetra(meth)acrylate in the ingredient (B) is desirable for obtaining a
paint film of excellent water resistance and alkali resistance and high
hardness. In this case, however, a tendency of the bending resistance and
impact resistance of the paint film to decrease is observable.
Accordingly, the content of the di-, tri-, or tetra(meth)acrylate is
selected in accordance with the purpose of use.
Modifications
Various modifications or variations can be made in the oil-modified alkyd
resin composition according to this invention provided that it comprises
the above prescribed quantities of the two indispensable ingredients (A)
and (B).
Accordingly, various additives can be added to the resin composition of
this invention similarly as in the case of resin compositions in general.
Examples of such additives are fillers, coloring agents, stabilizers,
thixotropic agents, agents for improving the surface characteristics of
the paint film, and pigment dispersants. These additives are appropriately
added according to the use. Hardening agents and drying agents will be
discussed hereinafter.
An important feature of the oil-modified alkyd resin composition according
to this invention is that it is solventless, but this does not mean that
it cannot be used by converting it into a solvent type. Accordingly, if so
desired, this resin composition can be dissolved in a solvent such as
toluene, xylene or mineral spirit and utilized in a solution state.
Utilization
The paint composition of this invention can be hardened by using a
hardening agent, that is, a redox catalyst comprising an organic peroxide
and a reducing agent and used, according to the necessity, in conjunction
with a metal drying agent such as manganese naphthenate or cobalt
naphthenate. Examples of hardening agents are:
(a) A combination of methylethylketone peroxide and cobalt naphthenate;
(b) A combination of a redox catalyst comprising benzoyl peroxide and
dimethylaniline and cobalt naphthenate or manganese naphthenate; and
(c) A combination of cyclohexanone peroxide and cobalt naphthenate.
Of these hardening agents, cobalt naphthenate is particularly suitable
because it not only participates as a reducing agent in radical generation
but functions also as a metal drying agent participating also in the
oxidation hardening of the oil-modified alkyd resin.
The above described catalyst is used in proportions of 0.5 to 5 parts by
weight of the organic peroxide and of 0.01 to 5 parts by weight of the
reducing agent relative to 100 parts by weight of the paint composition.
Pigments such as titanium oxide, zinc white, ultramarine, and chromium
oxide, agents for improving surface characteristics such as a stabilizing
agent and polyethylene glycol, and a pigment dispersant may be added to
the paint composition of this invention provided that they do not give
rise to adverse results such as impairment of paint film properties and of
the preservability of the paint.
The paint composition of this invention can be dried by drying and
hardening at room temperature and also by baking and hardening by heating
to a temperature above 100.degree. C. Particularly when it is used as a
room temperature drying paint, its hardening time is short, and, moreover,
it is thickly applicable to thickness which is approximately 1.5 times
that of an oil-modified alkyd resin paint of known solvent type (solvent,
toluene 40 percent by weight). Therefore, the paint composition of this
invention is highly suitable for use in painting structures exposed to
outdoor air such as ships, production plants, steel frames of buildings,
and bridges.
In order to indicate more fully the nature and utility of this invention,
the following specific examples of experiments relating to production of
resin compositions of the invention and comparison examples are set forth,
it being understood that these examples are presented as illustrative only
and that they are not intended to limit the scope of the invention.
Throughout the following examples of experiments and comparison examples,
all quantities expressed in "parts" are parts by weight.
(1) PREPARATION OF ALKYD RESIN
PREPARATION EXAMPLE 1
A reaction vessel equipped with an agitator, a temperature gage, a cooler,
a water separator, and a nitrogen introducing pipe was charged with 62.0
parts of dehydrated castor oil fatty acid, 12.6 parts of phthalic
anhydride, 9.9 parts of MBTHP, 1.5 parts of glycerine, and 17.8 parts of
pentaerythritol, and 0.1 part of hydroquinone and 4.0 parts of xylene
where further added thereto. Reaction of these materials was then carried
out in a stream of nitrogen gas at 220.degree. C.
When the acid value of the formed alkyd became 40, 3.0 parts of sorbic acid
and 0.2 part of hydroquinone were added to the reaction system, and the
reaction was continued further until the acid value became 10, whereupon
an oil-modified alkyd resin (herein referred to as resin A) of a sorbic
acid constituent concentration of 3.0 percent and an oil length of 64.8
percent was obtained.
PREPARATION EXAMPLE 2
The reaction of Preparation Example 1 was carried out as described therein
except for the use of 53.5 parts of dehydrated castor oil fatty acid, 14.9
parts of phthalic anhydride,, 11.8 parts of MBTHP, 5.9 parts of glycerine,
14.6 parts of pentaerythritol, and 6.5 parts of sorbic acid. As a result,
an oil-modified alkyd resin (herein referred to as resin B) of a sorbic
acid constituent concentration of 6.5 percent and an oil length of 55.9
percent was obtained.
PREPARATION EXAMPLE 3
The reaction of Preparation Example 1 was carried out as described therein
except for the use of 53.4 parts of dehydrated castor oil fatty acid, 13.5
parts of phthalic anhydride, 10.7 parts of MBTHP, 21.7 parts of
pentaerythritol, and 10.7 parts of sorbic acid and except for the setting
of the final acid value at 25. As a result, an oil-modified alkyd resin
(herein referred to as resin C) of a sorbic acid constituent concentration
of 10.7 percent and an oil length of 55.8 percent was obtained.
PREPARATION EXAMPLE 4
The reaction of Preparation Example 1 was carried out as set forth therein
except for the use of 30.0 parts of dehydrated castor oil fatty acid, 22.1
parts of phthalic anhydride, 17.5 parts of MBTHP, 20.4 parts of glycerine,
3.3 parts of pentaerythritol, and 15.0 parts of sorbic acid and except for
the setting of the final acid value at 35. As a result, an oil-modified
alkyd resin (herein referred to as resin D) of a sorbic acid constituent
concentration of 15.0 percent and an oil length of 31.4 percent was
obtained.
PREPARATION EXAMPLE 5
The reaction of Preparation Example 1 was carried out as set forth therein
except for the use of 55.6 parts of safflower oil fatty acid, 15.1 parts
of phthalic anhydride, 11.9 parts of MBTHP, 7.3 parts of glycerine, 12.8
parts of pentaerythritol, and 4.4 parts of sorbic acid. As a result, an
oil-modified alkyd resin (herein referred to as resin E) of a sorbic acid
constituent concentration of 4.4 percent and an oil length of 58.1 percent
was obtained.
PREPARATION EXAMPLE 6
The reaction of Preparation Example 1 was carried out as specified therein
except for the use of 52.9 parts of soybean oil fatty acid, 14.9 parts of
phthalic anhydride, 11.7 parts of MBTHP, 5.5 parts of glycerine, 15.1
parts of pentaerythritol, and 7.1 parts of sorbic acid. As a result, an
oil-modified alkyd resin (herein referred to as resin F) of a sorbic acid
constituent concentration of 7.1 percent and an oil length of 55.3 percent
was obtained.
PREPARATION EXAMPLE 7
The reaction of Preparation Example 1 was carried out as specified therein
except for the use of 65.0 parts of dehydrate castor oil fatty acid, 18.6
parts of phthalic anhydride, 20.0 parts of pentaerythritol, and 3.4 parts
of sorbic acid. As a result, an oil-modified alkyd resin (herein referred
to as resin G) of a sorbic acid constituent concentration of 3.4 percent
and an oil length of 67.9 percent was obtained.
PREPARATION EXAMPLE 8
The reaction of Preparation Example 1 was carried out as set forth therein
except for the use of 56.5 parts of dehydrated castor oil fatty acid, 15.0
parts of phthalic anhydride, 11.9 parts of MBTHP, 6.7 parts of glycerine,
13.5 parts of pentaerythritol, and 3.5 parts of crotonic acid. As a
result, an oil-modified alkyd resin (herein referred to as resin H) of a
crotonic acid constituent concentration of 3.5 percent and an oil length
of 59.0 percent was obtained.
PREPARATION EXAMPLE 9
The reaction of Preparation Example 1 was carried out as set forth therein
except for the use of 54.6 parts of dehydrated castor oil fatty acid, 15.1
parts of phthalic anhydride, 12.0 parts of MBTHP, 7.7 parts of glycerine,
12.1 parts of pentaerythritol, and 5.4 parts of 2-(.beta.-furyl) acrylic
acid. As a result, an oil modified alkyd resin (herein referred to as
resin I) of a 2-(.beta.-furyl) acrylic acid constituent concentration of
5.4 percent and an oil length of 57.1 percent was obtained.
PREPARATION EXAMPLE 10
A reaction vessel similar to that of Preparation Example 1 was charged with
60.0 parts of dehydrated castor oil fatty acid, 15.5 parts of phthalic
anhydride, 12.2 parts of MBTHP, 10.1 parts of glycerine, and 8.9 parts of
pentaerythritol, and 0.05 part of hydroquinone and 4 parts of xylene were
further added thereto. The above enumerated materials were then caused to
react in a stream of nitrogen gas at 220.degree. C. until the acid value
of the alkyd became 10. As a result, an oil-modified alkyd resin (herein
referred to as resin J) of an oil length of 62.8 percent was obtained.
PREPARATION EXAMPLE 11
The reaction of Preparation Example 1 was carried out as set forth therein
except for the necessary modification to produce an oil-modified alkyd
resin (herein referred to as resin K).
(2) PRODUCTION OF RESIN COMPOSITION AND EVALUTION THEREOF AS PAINTS
The oil-modified alkyd resins prepared in the above described manner were
respectively dissolved in the polymerizable monomers shown in the
following Tables to the respectively indicated concentrations.
To 100 parts by weight of each of the solutions thus obtained, 1.0 part of
cobalt naphthenate (cobalt content 6 percent), 0.2 part of manganese
naphthenate (manganese content 4 percent), and 1.0 part of cyclohexanone
peroxide were added. The paint thus obtained was applied so as to produce
a dried film coating of a film thickness of 30 microns in Run I and Run
III wherein the coating was air-dried or 40 microns in Run II wherein the
coating was baked on a mild steel plate of 150-mm length, 50-mm width, and
0.3-mm thickness abraded with a No. 320 emery cloth, and was thereafter
dried in an air bath at 30.degree. C. in Run I and Run III or baked in an
air bath at 100.degree. C. for 5 minutes in Run II. The physical
properties of the paint films thus obtained were measured under the
conditions set forth below. Whereupon the results shown in Table were
obtained.
MEASURING METHODS
Viscosity: EMILA rotating viscometer (manufactured by Reciprotor Company,
Denmark).
Set to touch time: in accordance with Japanese Industrial Standards, JIS
K-5400.
Pencil hardness: carried out by the procedure of JIS K-5652. Judged by the
occurrence or nonoccurrence of scratches.
Bending resistance: in accordance with JIS K-5400 (2 mm.) (sample dried
more than 7 days)
Impact resistance: Dupont impact strength (1/2 inch .times. 500 g. .times.
50 cm.) (sample dried more than 7 days).
Water resistance: observation of change due to 24 hours of immersion in
water at room temperature. ( no change whatsoever; o slight loss of
luster; x rusting)
Acid resistance: observation of change due to 5 hours of immersion in 5%
aqueous solution of sulfuric acid at room temperature. (sampled dried more
than 7 days) ( no change whatsoever)
Alkali resistance: observation of change due to 5 hours of immersion in 5%
aqueous solution of sodium carbonate at room temperature. (sample dried
more than 7 days) ( no change whatsoever; o slight loss of luster; x
dissolved)
Table (No. 1)
__________________________________________________________________________
Oil-modified alkyd resin
Unsaturated monocar-
boxylic acid Paint composition
Constitu- Polymerizable monomer
Vis-
Oil ent con- B T coci-
Fatty acid,
len- centra-
Alkyd
H D M M ty at
indicated
gth tion in
resin
P D P S M 25.degree. C.
Run*.sup.1
Resin
by oil name
(%) Name alkyd (%)
(%) A A A T A (poise)
__________________________________________________________________________
I-1 A Dehydrated
64.8
Sorbic acid
3.0 55 10 35 -- -- -- 1.7
castor oil
I-2 B " 55.9
" 6.5 50 20 30 -- -- -- 3.1
I-3 C " 55.8
" 10.7 " " " -- -- -- 4.5
I-4 D " 31.4
" 15.0 33.4 33.3 33.3 -- -- -- 4.6
I-5 E Safflower
58.1
" 4.4 55 10 35 -- -- -- 1.6
oil
I-6 F Soybean oil
62.7
" 5.0 " " " -- -- -- 1.9
I-7 G Dehydrated
67.9
" 3.4 50 20 30 -- -- -- 4.0
castor oil
I-8 H " 59.0
Crotonic
3.5 55 10 35 -- -- -- 2.3
acid
I-9 C " 55.8
Sorbic acid
10.7 50 10 30 10 -- -- 5.0
I-10 I " 57.1
2-(.beta.-furyl)
5.4 55 10 35 -- -- -- 2.5
acrylic acid
I-11**
C " 55.8
Sorbic acid
10.7 60 -- 10 -- 30 -- 3.0
I-12 K " 58.1
" 4.4 55 15 30 -- -- -- 3.5
I-13**
K " " " " 60 -- -- 10 -- 30 1.8
__________________________________________________________________________
HPA : 2-hydroxypropylacrylte, BDDA: 1, 4-butandioldiacrylate,
TMPA : trimethylrolpropanetriacrylate, ST : styrene, MMA : methyl
methacrylate
*1 Run I : Present invention, air-dried.
**Runs I-11 and I-13 are reference runs wherein ingredient B is a low
boiling monomer, viz styrene or methyl methacrylate.
Table (No. 2)
__________________________________________________________________________
Water resistance
Surface Pencil hardness Dried 1 day
Bending
Impact
Acid
Alkali
Set to
smooth- Dried
Dried
Dried
Dried
immersed
resis-
resis-
resis-
resis-
touch
Run*.sup.1
ness 1 day
3 days
7 days
5 hrs
1 day
3 days
tance
tance
tance
tance
time
__________________________________________________________________________
I-1 O H-2H
2H 2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 1.3
I-2 O H-2H
2H 2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 0.7
I-3 O 2H 2H 2H-3H
O .circleincircle.
.circleincircle.
O O .circleincircle.
O 3.0
I-4 O H 2H 2H-3H
O .circleincircle.
.circleincircle.
O O .circleincircle.
O 1.3
I-5 O H H-2H H-2H O .circleincircle.
.circleincircle.
O O .circleincircle.
O 2.5
I-6 O H H-2H H-2H O .circleincircle.
.circleincircle.
O O .circleincircle.
O 2.5
I-7 O F-H H-2H H-2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 1.5
I-8 O H H-2H 2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 2.5
I-9 O 2H 2H 2H-3H
.circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 2.0
I-10 O H-2H
2H 2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 1.5
I-11 O 2H 2H-3H
2H-3H
O .circleincircle.
.circleincircle.
O O .circleincircle.
O 0.6
I-12 O H-2H
2H 2H .circleincircle.
.circleincircle.
.circleincircle.
O O .circleincircle.
O 1.0
I-13 O H-2H
2H 2H-3H
O .circleincircle.
.circleincircle.
O O .circleincircle.
O 0.5
__________________________________________________________________________
*1 Run I: Present invention except for Runs I-11 and I-13 which are
Reference examples, as set forth on page 22, air-dried
Table (No. 3)
__________________________________________________________________________
Oil-modified alkyd resin
Unsaturated monocar-
boxylic acid Paint composition
Constitu- Polymerizable monomer
Vis-
Oil ent con- B T coci-
Fatty acid,
len- centra-
Alkyd
H D M M ty at
indicated
gth tion in
resin
P D P S M 25.degree. C.
Run.sup.*1
Resin
by oil name
(%) Name alkyd (%)
(%) A A A T A (poise)
__________________________________________________________________________
II-1 K Dehydrated
58.1
Sorbic acid
4.4 40 -- -- 60 -- -- 8.0
castor oil
II-2 C " 55.8
" 10.7 " -- 20 40 -- -- 5.0
II-3 D " 31.4
" 15.0 " -- -- 60 -- -- 5.5
III J Dehydrated
62.8
-- -- 55 10 35 -- -- -- 1.6
castor oil
__________________________________________________________________________
HPA : 2-hydroxypropylacrylate, BDDA : 1,4-butanedioldiacrylate,
TMPA : trimethyrolpropanetriacrylate, ST : styrene, MMA : methyl
methacrylate
*1 Run II : Present invention, baked. Run III : Reference
Table (No. 4)
__________________________________________________________________________
Water resistance
Surface Pencil hardness Dried 1 day
Bending
Impact
Acid
Alkali
Set to
smooth- Dried
Dried
Dried
Dried
immersed
resis-
resis-
rsis-
resis-
touch
Run.sup.*1
ness 1 day
3 days
7 days
5 hrs
1 day
3 days
tance
tance
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