Coating composition for the prevention of scattering of glass fragments

A coating composition useful for shatter-proofing glass, capable of forming a film which allows an elongation of at least 400%. The coating composition includes (A) a polyurethane compound obtained by reaction of (a) a polycarbonate diol and/or (b) an aliphatic polyester diol, (c) an organic diisocyanate and (d) a chain extender possessing an active hydrogen-containing group in amounts to give an isocyanate group/active hydrogen-containing group equivalent ratio not exceeding 1.0, (B) an organic polyisocyanate compound and (C) a reactive silicone oil.

This invention relates to a coating composition. More particularly, this 
invention relates to a coating composition for shatterproofing glass, 
which exhibits an excellent effect in shatterproofing the glass such as of 
a fluorescent lamp in case of breakage of the glass and, at the same time, 
excels in light-fastness, heat-resisting property, and anti-blocking 
property. 
At present, most fluorescent lamps are not furnished with a scatterproofing 
film, although some of the fluorescent lamps which are intended for 
business use do have such a film. These unprotected fluorescent lamps, 
therefore, have the possibility of being broken by various external causes 
or, on exposure to impacts of the shocks given thereto by family members 
removing or discarding them, sustaining breakage and consequently 
inflicting injuries to the family members. Now that safety is sought 
earnestly in every aspect of society, the prevention of accidents caused 
by scattered fragments of glass from broken fluorescent lamps constitutes 
itself an important task on the part of consumers and manufacturers as 
well. 
With this background, part of the business-grade fluorescent lamps are 
furnished with a shatterproofing film. This fact infers a method for 
protecting a fluorescent lamp with a shrinkable polyester film. This 
method, however, have the disadvantages of (1) expensive raw material for 
the film, (2) inevitable change of the film with the tube diameter of the 
fluorescent lamp, and (3) exclusive applicability to the fluorescent lamps 
of straight-tube type and inapplicability to those of circular type. Thus, 
this method finds extensive utility only with difficulty. 
For the solution of these disadvantages, the feasibility of a concept of 
forming a shatterproofing film on the surface of the glass of a 
fluorescent lamp by the coating technique has been being studied. None of 
the coating compositions developed to date proves suitable for the 
formation of a shatterproofing film by the coating technique. 
This is because the characteristic properties required of the 
shatterproofing coating composition particularly suitable for use on 
fluorescent lamps pose a very steep technical barrier. To be specific, (1) 
the applied film of the coating composition is required to allow 
elongation of at least 400% to manifest the desired shatterproofing 
effect, (2) the film is required to avoid yellowing and suffering from 
serious impairment of tensile strength and elongation in spite of the 
ultraviolet light generated within the fluorescent lamp during its 
illumination, (3) the film is required to suffer from neither coloration 
nor impairment of tensile strength and elongation in spite of the heat 
from the electrodes of the lamp which are heated during the illumination 
of the lamp to an elevated temperature of from 100.degree. to 120.degree. 
C, and (4) the film is required to retain the inherent physical properties 
intact and avoid attracting dust and dirt. Because of the wellknown long 
service life of the fluorescent lamp ranging from 5,000 to 10,000 hours, 
the film is expected to offer durability commensurate to this service life 
of the lamp. Thus, the shatterproofing coating composition for use with 
the glass of the fluorescent lamp has unusually harsh physical properties 
to fulfil. None of the coating compositions developed to date is found to 
satisfy these characteristic properties. 
In view of the problems mentioned above, the present inventors have found 
that a composition which combines a polyurethane compound obtained from a 
polycarbonate diol and/or an aliphatic polyester diol, an organic 
diisocyanate, and a chain extender possessing an active 
hydrogen-containing group with an organic polyisocyanate compound is most 
suitable and further that this composition, on further incorporation of a 
reactive silicone oil therein, enjoys a notable improvement in the 
blocking property to be manifested at elevated temperatures. The present 
invention has been perfected on the basis of this finding. 
To be specific, this invention is directed to a shatter-proofing coating 
composition for use on glass, essentially comprising 100 parts by weight 
of (A) a polyurethane compound obtained by the reaction of (a) a 
polycarbonate diol and/or (b) an aliphatic polyester diol, (c) an organic 
diisocyanate, and (d) a chain extender possessing an active 
hydrogen-containing group in amounts to give an isocyanate group/active 
hydrogen-containing group equivalent ratio not exceeding 1.0 and 0.5 to 40 
parts by weight of (B) an organic polyisocyanate compound and optionally 
further comprising 0.1 to 10 parts by weight of (C) at least one reactive 
silicone oil selected from the group consisting of compounds represented 
by the following general formulas (I) to (VI). 
##STR1## 
(wherein X and X' independently stand for OH group, --RNH.sub.2 group, 
--RCOOH group, or --ROH group, R for an alkylene group of 1 to 20 carbon 
atoms, and .gtoreq.2). 
##STR2## 
The shatterproofing coating composition of this invention for use on glass 
comprises (A) a polyurethane compound, (B) an organic polyisocyanate 
compound, and optionally (C) a reactive silicone oil. 
The (A) polyurethane compound to be used in this invention is obtained by 
the reaction of (a) a polycarbonate diol and/or (b) an aliphatic polyester 
diol, (c) an organic diisocyanate, and (d) a chain extender possessing an 
active hydrogen-containing group in amounts to give an isocyanate 
group/active hydrogen-containing group equivalent ratio not exceeding 1.0. 
The polycarbonate diols which are effectively usable as the component (a) 
herein include ethylene polycarbonate diol, propylene polycarbonate diol, 
1,4-butylene polycarbonate diol, 1,5-pentylene polycarbonate diol, 
1,6-hexylene polycarbonate diol, 3-methyl-1,5-pentylene polycarbonate 
diol, and 1,9-nonylene polycarbonate diol, for example. Suitably, the 
number average molecular weight of such a polycarbonate diol is 
approximately from about 500 to about 3,000. These polycarbonate diols may 
be used either singly or jointly. 
As (b) the aliphatic polyester diol, polyester diols obtained from 
aliphatic and/or alicyclic dicarboxylic acids and aliphatic glycols are 
usable. As aliphatic and alicyclic dicarboxylic acids, succinic acid, 
adipic acid, sebacic acid, azelaic acid, dodecadionic acid, 
hexahydrophthalic anhydride, and hexahydroterephthalic acid are cited, for 
example. As aliphatic glycols, ethylene glycol, propylene glycol, 
neopentyl glycol, butane diol, 1,6-hexane diol, 3-methyl-1,5-pentane diol, 
1,9-nonane diol, cyclohexane dimethanol, hydrogenated bisphenol A or 
ethylene oxide thereof, and propylene oxide adducts are cited, for 
example. Such an aliphatic polyester diol may be copolymerized as with 
glycerin or trimethylol propane and consequently endowed with a branched 
configuration. Suitably, the number average molecular weight of (b) the 
aliphatic polyester diol to be used in this invention is approximately 
from about 500 to about 3,000. 
For this invention, the use of (a) the polycarbonate diol and/or (b) the 
aliphatic polyester diol is an essential requirement. This invention is 
not accomplished by using the other diol component such as, for example, a 
polyether polyol like polyethylene glycol, polypropylene glycol, or 
polytetramethylene glycol or an aromatic polyester diol obtained from an 
aromatic dicarboxylic acid and a glycol. 
In this invention, (a) the polycarbonate diol and (b) the aliphatic 
polyester diol are used either singly or jointly. In the joint use, the 
weight ratio of (a) the polycarbonate diol to (b) the aliphatic polyester 
diol is in the range of from 100 : 0 to 0 : 100, preferably from 100 : 0 
to 30 : 70. 
The organic diisocyanates which are effectively usable as the component (c) 
include aromatic diisocyanates such as tolylene diisocyanate, p-phenylene 
diisocyanate, m-phenylene diisocyanate, 4,4'-diphenyl methane 
diisocyanate, naphthalene diisocyanate and aliphatic or alicyclic 
diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, 
hydrogenated xylylene diisocyanate, 4,4'-dicyclohexyl methane 
diisocyanate, and isophorone diisocyanate, for example. To accomplish the 
object of this invention which resides in shatterproofing the glass of a 
fluorescent lamp, the shatterproofing coating composition should exhibit 
high degrees of lightfastness and heat-resistance As the (c) organic 
diisocyanate compound, therefore, it is desirable to use an aliphatic or 
alicyclic diisocyanate. 
The chain extenders possessing an active hydrogen-containing group which 
are effectively usable herein as the component (d) include glycols such as 
ethylene glycol, propylene glycol, 1,4-butane diol, 1,6-hexane diol, 
cyclohexane dimethanol, diethylene glycol, neopentyl glycol, and 
3-methyl-1,5-pentane diol, amino alcohols such as monoethanol amine and 
N-methylol ethanol amine, diamines such as hexamethylene diamine, 
isophorone diamine, 4,4'-diaminodiphenyl methane, and diaminodiphenyl 
ether, and carboxyl group-containing glycols such as dimethylol propionic 
acid and tartaric acid, for example. 
For the purpose of endowing (A) the polyurethane compound with a branched 
configuration, a polyhydric alcohol such as glycerin, trimethylol propane, 
or dipentaerythritol may be additionally used as a chain extender. The 
polyhydric alcohol is further effective in improving the anti-blocking 
property. 
The (A) polyurethane compound to be used in this invention is synthesized 
by any of the known methods such as a method which comprises placing (a) a 
polycarbonate diol and/or (b) an aliphatic polyester diol, and (d) a chain 
extender possessing an active hydrogen-containing group in a suitable 
solvent inactive to an isocyanate group and then adding (c) an organic 
isocyanate thereto and allowing it to react with the diol at a temperature 
in the range of from 60.degree. C. to 100.degree. C. or a method which 
comprises allowing (a) a polycarbonate diol and/or (b) an aliphatic 
polyester diol to react in advance with (c) an organic diisocyanate in an 
excess of the equivalent weight and causing (d) a chain extender 
possessing an active hydrogen-group to react on the resultant reaction 
product. For the purpose of promoting the reaction of urethanization, a 
known reaction catalyst such as an amine or an organic tin compound may be 
used. In any event, it is essential that the equivalent ratio of [the 
isocyanate group of the component (c)]to [the active hydrogen-containing 
groups of the components (a)+(b)+(c)] should not exceed 1.0. If the 
proportion of the isocyanate group is excessive, the residual isocyanate 
group has the adverse effect of lowering the shelf life of the produced 
shatterproofing coating composition and lowering the reactivity of (A) the 
polyurethane compound with (B) the organic polyisocyanate compound which 
will be described specifically hereinbelow. 
Suitably, (A) the polyurethane compound to be used in this invention 
possesses a reduced viscosity, .eta.sp/c (dl/g), in the range of 0.2 to 
1.0, preferably 0.3 to 0.8. If the reduced viscosity is less than 0.2, the 
produced shatterproofing film fails to acquire sufficient elongation and 
exhibits a poor effect in shatterproofing glass. Conversely, if the 
reduced viscosity exceeds 1.0, the produced coating composition acquires 
an unduly high viscosity, fails to assume a high solids concentration, and 
exhibits poor adaptability for coating. 
The shatterproofing coating composition of this invention for use on glass 
incorporates (B) an organic polyisocyanate compound as a cross-linking 
agent. 
The organic polyisocyanate compounds which are effectively usable herein as 
the component (B) include biuret or isocyanurate trimers of known 
diisocyanates represented by aliphatic diisocyanates such as 
tetramethylene diisocyanate and hexamethylene diisocyanate and alicyclic 
diisocyanates such as isophorone diisocyanate, hydrogenated tolylene 
diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated 
diphenyl methane diisocyanate, adducts between 3 mols of diisocyanate 
compounds and 1 mol of trifunctional polyols, and blocked isocyanate 
compound having an isocyanate group blocked therein, for example. As the 
blocking agent for the isocyanate group, such known blocking agents as 
phenol, .epsilon.-caprolactam, ethyl acetacetate, and methylethyl ketoxime 
may be used. The amount of (c) the organic polyisocyanate compound to be 
incorporated is in the range of from 0.5 to 40 parts by weight, based on 
100 parts by weight of (A) the polyurethane compound. If this amount is 
less than 0.5 part by weight, the incorporated compound manifests no 
sufficient cross-linking effect. If the amount exceeds 40 parts by weight, 
the excess of the incorporated compound only adds to the cost of raw 
material and brings about no increase in the effect. 
The shatterproofing coating composition of this invention for use on glass 
practically wholly attains what it aims to accomplish virtually 
exclusively with (A) the aforementioned polyurethane compound and (B) the 
organic polyisocyanate compound. It has been ascertained to the inventors 
that this composition, on further incorporation of (C) the reactive 
silicone oil therein, enjoys a prominent improvement in the tackiness of 
surface and the anti-blocking property of the film at elevated 
temperatures. The shatterproofing coating composition of this invention 
for use on glass further incorporates therein, when necessary, (C) at 
least one silicone oil selected from the group consisting of the compounds 
represented by the following general formulas (I) to (VI). 
##STR3## 
(wherein X and X' independently stand for OH group, --RNH.sub.2 group, 
--RCOOH group, or --ROH group, R for an alkylene group of 1 to 20 carbon 
atoms, and .gtoreq.2). 
##STR4## 
The incorporation of (C) the reactive silicone oil in the coating 
composition is effective in improving the tackiness of surface of the film 
and, therefore, is desirable for the purpose of preventing the film from 
attracting dust and dirt. 
The reactive silicone oil which are usable for this incorporation include a 
silanol-modified silicone oils (the products of Nippon Unicar Co., Ltd. 
marketed under product codes of "L-9000" and Y-7005", for example), 
amino-modified silicone oils (the products of Nippon Unicar Co., Ltd. 
marketed under product codes of "AFL-40," "FZ-3705," and "FZ-3710," for 
example), carboxylmodified silicone oils (the product of Nippon Unicar 
Co., Ltd. marketed under product code of "FZ-3703," for example), and 
alcohol-modified silicone oils (the products of Nippon-Unicar Co., Ltd. 
marketed under product codes of "F-99-199" and "F-99-258," for example). 
The amount of (C) the reactive silicone oil to be incorporated is in the 
range of from 0.1 to 10 parts by weight, based on 100 parts by weight of 
(A) the polyurethane compound. If this amount is less than 0.1 part by 
weight, it has no notable effect in improving the tackiness of surface. 
Conversely, if the amount exceeds 10 parts by weight, the applied film of 
the composition suffers from poor transparency because of opacification. 
The shatterproofing coating composition of this invention for use on glass 
is generally put to use as dissolved in a solvent. The solvents which are 
effectively usable herein include ketone type solvents such as acetone, 
methylethyl ketone, methylisobutyl ketone, and cyclohexanone, aromatic 
hydrocarbons such as toluene, xylene, Solvesso #100, and solvesso #150, 
alcohol type solvents such as ethyl cellosolve, butyl cellosolve, ethyl 
carbitol, propanol, and butanol, and ester type solvents such as ethyl 
acetate, butyl acetate, ethyl cellosolve acetate, and butyl cellosolve 
acetate, for example. 
The shatterproofing coating composition of this invention for use on glass 
may incorporate therein additives and modifiers such as, for example, 
antioxidant, ultraviolet absorbent, surface-smoothing agent, defoaming 
agent, thixotropic agent, and coloring agent. 
The method to be employed for coating glass with the shatter-proofing 
coating composition of this invention is not particularly limited. Any of 
the known methods such as roll coating, spray coating, and dip coating may 
be used. The layer of the composition applied to the glass is generally 
dried and hardened at a temperature in the range of from 80.degree. C. to 
150.degree. C. for a period in of from 5 minutes to 180 minutes. 
The shatterproofing coating composition of this invention for use on glass 
excels not only in the shatterproofing effect manifested on glass butalso 
in lightfastness, heat-resistance, and anti-blocking property. It can be 
used as a coating agent and an adhesive agent not merely on the 
fluorescent lamp but also on substrates of glass, metals, and plastics.

Examples 
For more specific illustration of the present invention, the following 
examples are presented which are intended to be merely illustrative or and 
not in any sense limitative of the invention. 
Synthesis 1: 
In a reaction vessel provided with a stirrer and a cooling tube, 65 parts 
by weight of butyl acetate, 100 parts by weight of 1,6-hexane 
polycarbonate diol (molecular weight 2,000), 52 parts by weight of 
isophorone diisocyanate, and 0.1 part by weight of dibutyl tin dilaurate 
were placed and stirred at 100.degree. C. for one hour to effect reaction. 
Then, the resultant reaction mixture and 50 parts by weight of butyl 
acetate and 20 parts by weight of neopentyl glycol added thereto were left 
to react at 100.degree. C. for three hours. After this reaction, the 
reaction product was diluted with 204 parts by weight of butyl acetate to 
a solids concentration of 35% by weight. The polyurethane solution (a) 
thus obtained possessed a viscosity of 22 poises and the polyurethane 
compound possessed a reduced viscosity, .eta. sp/c, of 0.69 (dl/g). For 
determination of the reduced viscosity, .eta. sp/c, a solution of 0.1 g of 
this polyurethane compound in 25 cc of a mixed solvent of 
phenol/tetrachloroethane (volume ratio of 6/4) was subjected to the 
measurement at 30.degree. C. In the reaction mentioned above, the 
isocyanate group/active hydrogen-containing group (OH group) equivalent 
ratio was 1.0/1.03. 
Synthesis 2: 
In the same reaction vessel as used in Synthesis 1, 65 parts by weight of 
butyl acetate, 100 parts by weight of hexylene polycarbonate diol 
(molecular weight 2,000), 49 parts by weight of isophorone diisocyanate, 
and 0.1 part by weight of dibutyl tin dilaurate were placed and stirred at 
100.degree. C. for one hour to effect reaction. The resultant reaction 
mixture and 50 parts by weight of butyl acetate, 20 parts by weight of 
neopentyl glycol, and 1 part by weight of trimethylol propane added 
thereto were left react at 100.degree. C. for three hours. After the 
reaction, the reaction product was diluted with 140 parts of butyl acetate 
to a solids concentration of 40% by weight. The polyurethane solution (b) 
thus obtained possessed a viscosity of 7 poises (25.degree. C.) and the 
polyurethane compound possessed a reduced viscosity of 0.39. In the 
reaction mentioned above, the isocyanate group/active hydrogencontaining 
group (OH group) equivalent ratio was 1.0/1.13. 
Synthesis 3: 
In the same reaction vessel in synthesis 1, 65 parts by weight of butyl 
acetate, 50 parts by weight of hexylene polycarboante diol (molecular 
weight 2,000), 50 parts by weight of neopentyl adipate (molecular weight 
2,000) as a polyester diol, 49 parts by weight of isophorone diisocyanate, 
and 0.1 part by weight of dibutyl tin dilaurate were placed and stirred at 
100.degree. C. for one hour to effect reaction. The resultant reaction 
mixture and 50 parts by weight of butyl acetate and 20 parts by weight of 
neopentyl glycol added thereto were left reacting at 100.degree. C. for 
three hours. After the reaction, the reaction product was diluted with 139 
parts by butyl acetate to a solids concentration of 40% by weight. The 
polyurethane solution (c) consequently obtained possessed a viscosity of 6 
poises (25.degree. C.) and the polyurethane compound possessed a reduced 
viscosity, .eta.sp/c, of 0.40. In the reaction mentioned above, the 
isocyanate group/active hydrogen-containing group (OH group) equivalent 
ratio was 1.0/1.1. 
Synthesis 4: 
In the same reaction vessel as used in Synthesis 1, 55 parts by weight of 
butyl acetate, 50 parts by weight of an aromatic polyester diol 
[terephthalic acid/isophthalic acid//ethylene glycol/neopentyl glycol 
=50/50//50/50 (molar ratio), molecular weight 2,000], 50 parts by weight 
of neopentylene adipate (molecular weight 2,000) as an aliphatic polyester 
diol, 29 parts by weight of isophorone diisocyanate, and 0.1 part by 
weight of dibutyl tin dilaurate were placed and stirred at 100.degree. C. 
for one hour to effect reaction. Then, the resultant reaction mixture and 
40 parts by weight of butyl acetate and 10 parts by weight of neopentyl 
glycol added thereto were left reacting at 100.degree. C. for three hours. 
After the reaction, the reaction product was diluted with 114 parts by 
weight of butyl acetate to a solids concentration of 40% by weight. The 
polyurethane solution (d) consequently obtained possessed a viscosity of 2 
poises (25.degree. C.) and the polyurethane compound possessed a reduced 
viscosity, .eta.sp/c, of In the reaction mentioned above, the isocyanate 
group/active hydrogen-containing group (OH group) equivalent ratio was 
1.0/1.12. 
Synthesis 5: 
In a reaction vessel provided with a stirrer and a cooling tube, 65 parts 
by weight of butyl acetate, 100 parts by weight of 1,6-hexylene 
polycarbonate diol (molecular weight 2,000), 15 parts by weight of 
neopentyl glycol, and 5 parts by weight of trimethylol propane, were mixed 
and dissolved. The resultant reaction mixture and 40 parts by weight of 
isophorone diisocyanate and 0.1 part by weight of dibutyl tin dilaurate 
added thereto were left to react at 100.degree. C for four hours. The 
reaction product thus obtained was diluted with 175 parts by weight of 
butyl acetate to a solids concentration of 40% by weight. The polyurethane 
solution (c) consequently obtained possessed a viscosity of 1.6 poises 
(25.degree. C) and the polyurethane compound possessed a reduced 
viscosity, .eta. sp/c, of 0.30 (dl/g). In the reaction mentioned above, 
the isocyanate group/active hydrogen-containing group (OH group) 
equivalent ratio was 1.0/1.1. 
Example 1 
A coating composition (i) of this invention was obtained by combining 100 
parts by weight of (a) the polyurethane solution obtained in Synthesis 1 
and 0.83 part by weight of a timer of isophorone diisocyanate (produced by 
Daicel Huls K.K. and marketed under trademark designation of "Isocyanate 
T-1890") as an organic polyisocyanate. A hard film produced from this 
coating composition (i) was tested for physical properties. The film of 
the same composition applied to a fluorescent lamp was evaluated as to its 
effect manifested in shatterproofing the glass of the lamp. 
Method of evaluation 
(1) Preparation of coating film 
A hard coating film was produced by applying the produced composition (i) 
with a bar coater on a polypropylene film in an amount calculated to give 
a dry layer about 50 .mu.m in thickness and drying and hardening the 
applied layer first at 80.degree. C. for five minutes and then at 
120.degree. C. for 30 minutes. 
(2) Determination of tensile elongation 
By the use of a Tensilon tensile tester, the coating film was tested for 
tensile properties under the conditions of 20.degree. C. in temperature 
and 50 mm/min in stretching speed. (3) Evaluation of heat-resistance 
This property was determined by heating the coating film in the open air at 
120.degree. C. for 240 hours and measuring the color assumed consequently 
by the film with the aid of a color difference meter. 
(4) Evaluation 
This property was determined by irradiating the coating film with an 
ultraviolet light (290 m.mu. Max) by the use of a Q-UV accelerated weather 
tester and measuring the color assumed consequently by the film with a 
color difference meter. 
(5) Evaluation of anti-blocking property of film 
This property was determined by superposing two sheets of the coating film, 
heating the superposed sheets under a load of 200 g/cm.sup.2 at 40.degree. 
C. and 120.degree. C. for two hours, and evaluating the superposed sheets 
as to the blocking property. 
(6) Shatterproofing effect manifested on glass 
This property was determined by applying the coating composition of this 
invention by the dipping method on the glass tube part of a circular type 
30-w fluorescent lamp in an amount calculated to give a dry layer about 60 
to 70 .mu.m in hardening the applied layer of the composition at 
120.degree. C. for three hours, dropping a steel ball 200 g in weight from 
a height of 30 cm onto the fluorescent lamp coated with the film, and 
visually examining the scattering condition of fragments of glass from the 
broken lamp. The results are shown in Table 1. 
Examples 2 and 3 and Comparative Examples 
Varying coating compositions were prepared from polyurethane solutions (b) 
and (c) obtained by following the procedure of Example 1 and these coating 
compositions were evaluated similarly. The results are shown in Table 1. 
For comparison, a polyurethane solution (d) was similarly processed and 
tested. The results are also shown in Table 1. 
It is clearly noted from Table 1 that the coating compositions conforming 
to this invention excelled not only in the shatterproofing effect 
manifested on glass but also in lightfastness and heat-resisting property. 
TABLE 1 
__________________________________________________________________________ 
Composition 
Comparative 
Example 1 
Example 2 
Example 3 
Example 
(i) (ii) (iii) (iv) 
__________________________________________________________________________ 
Kind of polyurethane solution 
a b c d 
Amount incorporated (parts by weight) 
100 100 100 100 
(Solids content, parts by weight) 
(35) (40) (40) (40) 
Organic polyisocyanate compound 
T-1890 
T-1890 
T-1890 
T-1890 
Amount incorporated (parts by weight) 
0.83 3.5 2.4 2.4 
Tensile elongation 620 450 580 380 
Initial coloration (b value) 
0.81 0.89 0.83 0.92 
Heat-resistance after 300 hrs' 
0.83 0.89 0.86 2.01 
standing at 120.degree. C. (b value) 
Lightfastness after 96 hrs' exposure 
0.84 0.91 0.87 2.51 
to Q.UV (b value) 
Anti-blocking property 
40.degree. C. .times. 2 hrs 
o o o o 
120.degree. C. .times. 2 hrs 
x x x x 
Shatterproofing effect 
Initial 5 5 5 4 
(Note) After 500 hrs' 
5 5 4 2 
illumination 
__________________________________________________________________________ 
(Note) 
Shatterproofing effect: Evaluated on the 5point scale (5 for best effect) 
by observation of degree of scattering caused. 
Examples 4 to 11 
A coating composition (v) of this invention was obtained by combining 100 
parts by weight of the polyurethane solution (a) obtained in synthesis 1, 
0.5 part by weight of a reactive silicone oil (produced by Nippon Unicar 
Co., Ltd. and marketed under product code of "F-99.199"), and 4.4 parts by 
weight of a timer of isophorone diisocyanate (produced by Daicel Huls K.K. 
and marketed under trademark designation of "Isocyanate T-1890") as an 
organic polyisocyanate. Similarly, various coating compositions (vi) to 
(xii) were prepared. The hard films produced from the coating composition 
were tested for physical properties and coating films applied to 
fluorescent lamps were evaluated as to shatterproofing effect manifested 
on glass. The results are shown in Table 2. 
It is clearly noted from Table 2 that the incorporation of a reactive 
silicone oil was very effective in improving the antiblocking property at 
elevated temperatures. 
TABLE 2 
__________________________________________________________________________ 
Example 
4 5 6 7 8 9 10 11 
Composition 
v vi vii 
viii 
ix x xi xii 
__________________________________________________________________________ 
Kind of polyurethane solution 
a a a b b b c c 
Amount incorporated (parts by weight) 
100 
100 
100 
100 
100 
100 
100 
100 
(Solids content, parts by weight) 
(35) 
(35) 
(35) 
(40) 
(40) 
(40) 
(40) 
(40) 
Kind of reactive silicone oil* 
Amount incorporated (parts by weight) 
0.3 
0.5 
0.5 
0.4 
0.6 
0.4 
0.4 
0.6 
Organic polyisocyanate compound 
Amount incorporated (parts by weight) 
4.4 
0.83 
0.83 
3.5 
3.5 
2.4 
2.4 
1.6 
Tensile elongation (%) 
620 
600 
610 
450 
430 
450 
580 
590 
Initial coloration (b value) 
0.18 
0.85 
0.85 
0.89 
0.90 
0.92 
0.83 
0.83 
Heat-resistance after 300 
0.83 
0.87 
0.86 
0.89 
0.92 
0.93 
0.86 
0.85 
hrs' standing at 120.degree. C. (b value) 
Lightfastness after 96 hrs' exposure 
0.84 
0.87 
0.86 
0.91 
0.94 
0.94 
0.87 
0.89 
to Q.UV (b value) 
Anti-blocking property 
40.degree. C. 
o o o o o o o o 
120.degree. C. 
o o o o o o o o 
Shatterproofing effect 
Initial 5 5 5 5 5 5 5 5 
(Note) After 500 hrs' 
5 5 5 5 5 5 5 4 
illumination 
__________________________________________________________________________ 
*Reactive silicone produced by Nippon Unicar Co., Ltd. 
(Note): 
The evaluation was done in the same manner as for Table 1. 
EXAMPLE 12 
A coating composition (xiii) of this invention was obtained by combining 
100 parts by weight of the polyurethane solution (e) obtained in Example 
4, 0.2 part by weight of a reactive silicon oil (produced by Nippon Unicar 
Co., Ltd. and marketed under product code of "F-99-199"), 10.6 parts by 
weight of a block of isophorone diisocyanate compound (marketed under 
product code of LPDI-1358) as an organic polyisocyanate compound 0.7 part 
by weight of a defoaming agent, and 0.05 part by weight of dibutyl tin 
dilaurate. A hard film produced from the coating composition (xiii) was 
tested for physical properties and a coating film applied to a fluorescent 
lamp was evaluated as to shatterproofing effect manifested on glass in the 
same manner as in Example 1. The results are shown in Table 3 below. 
TABLE 3 
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Physical 
Item constant 
______________________________________ 
Tensile elongation (%) 420 
Initial coloration (b value) 
0.90 
Heat-resistance after 300 hrs' standing 
0.91 
at 120.degree. C. (b value) 
Lightfastness after 96 hrs' exposure to Q.UV 
0.93 
(b value) 
Anti-blocking property 
40.degree. C. 
0 
120.degree. C. 
0 
Shatterproofing effect 
Initial 5 
After 500 hrs' 
5 
illumination 
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The shatterproofing coating composition of this invention for use on glass 
uses a polyurethane compound obtained from a polycarbonate diol and/or an 
aliphatic diol and an organic isocyanate compound and further incorporates 
therein a reactive silicone oil. It, therefore, enjoys the following 
advantages: 
1) It possesses ample elongation for the manifestation of the 
shatterproofing effect on glass and, at the same time, enjoys stability to 
resist the ultraviolet light and the heat generated inside the fluorescent 
lamp and avoids yielding to impairment of physical properties or 
yellowing. 
2) It excels in transparency and in freedom from the phenomenon of blocking 
and, therefore, avoids attracting dust. 
3) It allows a notable drop in cost as compared with the coating produced 
from the conventional thermally shrinkable film. 
It can be used extensively as a coating composition for substrates of 
plastic and metallic materials besides as a shatter-proofing composition 
on the glass of a fluorescent lamp.