Active energy ray-curable composition

An active energy ray-curable composition substantially comprising at least one of (meth)acrylates and oligomers thereof represented by the following general formula (I) ##STR1## wherein R represents a hydrogen atom or a methyl group, X represents an alkylene group in which at least one hydrogen atom may be replaced by a hydroxyl group, m is 0 or an integer of 1 to 4, Y represents a hydrocarbon group having a cyclic hydrocarbon moiety therein, and n is 1 or 2. The composition is useful as an adhesive, particularly as one in the production of optical discs.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a composition curable by active energy rays such 
as ultraviolet light, electron beams or radioactive rays, and particularly 
to a composition which is suitably used as an adhesive in the production 
of optical discs. 
2. Description of the Prior Art 
Photocurable compositions are known. For example, Japanese Laid-Open Patent 
Publication No. 51035/1973 discloses an ultraviolet light-curable 
composition comprising (a) at least one oligo ester which is selected from 
the group consisting of polyester acrylate, polyester methacrylate, epoxy 
acrylate and epoxy methacrylate having a boiling point at atmospheric 
pressure of at least 200.degree. C. and has an acryloyl group content of 5 
to 100 mole % based on the total amount of the acryloyl and methacryloyl 
groups, (b) a sensitizer and (c) a thermal polymerization inhibitor. The 
patent document describes 
##STR2## 
as the component (a). However, when an ultraviolet light-curable 
composition obtained by using this component is used as an adhesive, it 
has low tensile shear peel strength and tensile adhesion strength. 
U.S. Pat. No. 4,150,170 describes a method of producing an ultraviolet 
light-curable pressure-sensitive adhesive using an ultraviolet 
light-curable pressure-sensitive composition comprising an alpha, 
betaethylenically unsaturated vinyl polymerizable monomer and a benzoin 
C.sub.1 -C.sub.12 hydrocarbon alkyl ether. For example, Example 1 of this 
patent describes a method in which compositions containing butyl acrylate, 
vinyl acetate and acrylic acid as the above monomer is used. 
Japanese Laid-Open Patent Publication No. 142070/1950 discloses a 
photosensitive adhesive consisting predominantly of a mixture of 
(A) 100 parts by weight of a polymeric substance containing acryloxy or 
methacryloxy groups represented by the following formulae (I) to (III) in 
the molecule 
##STR3## 
wherein R represents a hydrogen atom or a methyl group, n represents an 
integer of 2 or 3, m is an integer of 1 to 4, and l is an interger of 1 to 
30, said polymeric substance being obtained by the addition-reaction of a 
polymeric substance having an unsaturated double bond in the molecule with 
an acrylic compound containing a carboxyl or hydroxyl group in the 
presence of an alkyl hypohalite or an N-haloamide compound, and 
(B) at least 50 parts by weight of cyclohexyl methacrylate. This patent 
document describes an example in which methacrylic-modified polybutadiene 
is used as the polymeric substance containing an acryloxy or methacryloxy 
group. 
In the prior art, optical discs are produced by bonding a recording layer 
provided on a substrate and a light-pervious protecting material by means 
of a photocuring agent. A photocurable composition which can be used in 
this application is desirably required to have excellent tensile shear 
peel strength and tensile adhesion strength, effect bonding within a short 
period of time, and be free from components that adversely affects the 
recording layer, and further not to impair the optical properties such as 
transparency of the substrate. 
Photocurable compositions known heretofore do not sufficiently satisfy all 
of these properties. 
SUMMARY OF THE INVENTION 
It is an object of this invention to provide an adhesive having the 
aforesaid desirable properties in combination. 
Another object of this invention is to provide a novel composition curable 
by irradiation of active energy rays such as ultraviolet light, electron 
beams or radioactive rays. 
The above objects are achieved in accordance with this invention by an 
active energy ray-curable composition substantially comprising at least 
one of (meth)acrylates and oligomers thereof represented by the following 
general formula (I) 
##STR4## 
wherein R represents a hydrogen atom or a methyl group, X represents an 
alkylene group in which at least one hydrogen atom may be replaced by a 
hydroxyl group, m is 0 or an integer of 1 to 4, Y represents a hydrocarbon 
group having a cyclic hydrocarbon moiety therein, and n is 1 or 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The present invention provides an active energy ray-curable composition 
substantially comprising at least one of (meth)acrylates and oligomers 
thereof represented by the following general formula (I) 
##STR5## 
wherein R represents a hydrogen atom or a methyl group, X represents an 
alkylene group in which at least one hydrogen atom may be replaced by a 
hydroxyl group, m is 0 or an integer of 1 to 4, Y represents a hydrocarbon 
group having a cyclic hydrocarbon moiety therein, and n is 1 or 2. 
When m is 0 in formula (I), the active energy ray-curable composition of 
this invention has the highest affinity for a substrate and therefore 
excellent adhesion. If m is 5 or more, the composition has poor affinity 
for a substrate and therefore inferior adhesion. When n is 3 or more in 
formula (I), the composition has high shrinkage on curing and is 
excessively hard so that it rather becomes brittle. 
In the (meth)acrylate used in the composition of this invention, the 
organic group constituting the portion derived from the alcohol is a 
hydrocarbon group which without fail has a cyclic hydrocarbon moiety. The 
hydrocarbon group may be bonded to the (meth)acryloyloxy group either 
directly or through an ether linkage represented by X-O. X constituting 
the ether linkage portion is, in principle, an alkylene group of the 
formula CH.sub.2l, but at least one of the hydrogen atoms forming the 
alkylene group may be replaced by a hydroxyl group. The number of carbon 
atoms of the alkylene group should preferably be as small as possible. In 
the present invention, alkylene groups having 1 to 3 carbon atoms are most 
preferably used. If the number of carbon atoms of the alkylene group is 4 
or more, the adhesive property of the resulting composition is reduced. 
It is important that the hydrocarbon group constituting Y should contain a 
cyclic hydrocarbon group such as an alicyclic hydrocarbon group, an 
aromatic hydrocarbon group, a fused polycyclic hydrocarbon group, or a 
crosslinked hydrocarbon group. Of these, the alicyclic hydrocarbon group, 
aromatic hydrocarbon group and crosslinked hydrocarbon group are 
preferred. Table 1 below shows especially preferred species of such 
(meth)acrylates. 
In the compositions of the present invention, at least one of oligomers 
obtained by polymerizing the (meth)acrylates with each other may also be 
used. 
3 TABLE 1 
Chemical formula Nomenclature 
##STR6## 
cyclohexyl acrylate 
##STR7## 
norbonyl acrylate 
##STR8## 
dicyclopentenyl acrylate 
##STR9## 
dicyclopentanyl acrylate 
##STR10## 
isobornyl acrylate 
##STR11## 
cyclohexyl methacrylate 
##STR12## 
hexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-acrylate 
##STR13## 
12-methylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-acrylate 
##STR14## 
11-methylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-acrylate 
##STR15## 
12-ethylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-acrylate 
##STR16## 
11-ethylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-acrylate 
##STR17## 
octacyclo[8,8,1.sup.2,9,1.sup.4,7,1.sup.11,18,1.sup.13,16,0,0.sup.3,8,0. 
sup.12,17 ]-docosyl-5-acrylate 
##STR18## 
15-methyloctacyclo[8,8,1.sup.2,9,1.sup.4,7,1.sup.11,18,1.sup.13,16,0,0.s 
up.3,8,0.sup.12,17 ]docosyl-5-acrylate 
##STR19## 
2,7-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate 
##STR20## 
2,10-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate 
##STR21## 
11,12-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate 
##STR22## 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate 
##STR23## 
9-substituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
] -dodecyl-3-acrylateR = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR24## 
8-substituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 R 
]-dodecyl-3-acrylate = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR25## 
8,9-disubstituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]-dodecyl-3-acrylateR = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR26## 
hexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]heptadecyl-4-methacrylate 
##STR27## 
12-methylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-methacrylate 
##STR28## 
11-methylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-methacrylate 
##STR29## 
12-ethylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-methacrylate 
##STR30## 
11-ethylhexacyclo[6,6,1,1.sup.3,6,1.sup.10,13,0.sup.2,7,0.sup.9,14 
]-heptadecyl-4-methacrylate 
##STR31## 
octacyclo[8,8,1.sup.2,9,1.sup.4,7,1.sup.11,18,1.sup.13,16,0,0.sup.3,8,0. 
sup.12,17 ]-docosyl-5-methacrylate 
##STR32## 
15-methyloctacyclo[8,8,1.sup.2,9,1.sup.4,7,1.sup.11,18,1.sup.13,16,0,0.s 
up.3,8,0.sup.12,17 ]docosyl-5-methacrylate 
##STR33## 
2,7-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]dodecyl-3-methacrylate 
##STR34## 
2,10-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]dodecyl-3-methacrylate 
##STR35## 
11,12-dimethyltetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]dodecyl-3-methacrylate 
##STR36## 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-methacrylate 
##STR37## 
9-substituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]-dodecyl-3-methacrylateR = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR38## 
8-substituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]-dodecyl-3-methacrylateR = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR39## 
8,9-disubstituted tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]-dodecyl-3-methacrylateR = 
methyl, ethyl, propyl, isobutyl, hexyl,cyclohexyl, stearyl, bromo, 
fluoro 
##STR40## 
dicyclopentenyloxyethyl acrylate 
##STR41## 
bisoxyethyl bisphenol A diacrylate 
##STR42## 
.alpha. 
phenoxyl-.beta.-hydroxypropyl acrylate 
The use of a photopolymerization initiator is not essential in this 
invention. However, when an active energy ray of a relatively low energy, 
for example ultraviolet light, is used, it is desirable to incorporate it 
in the composition of this invention. The photopolymerization initiator 
may be any of various known photopolymerization initiators such as those 
of the decomposition type which upon irradiation of UV or the like 
decompose and generate radicals and those of the hydrogen extraction type 
which generate radicals by hydrogen extraction upon irradiation. Specific 
examples of the photopolymerization initiator include benzoin, benzoin 
ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin 
isopropyl ether and benzoin butyl ether, benzophenone compounds such as 
benzophenone, p-chlorobenzophenone and p-methoxybenzophenone, benzil 
compounds such as benzil and benzyl dimethyl ketal, and hydroxyalkylphenyl 
ketone compounds such as 
1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone, 
1-phenyl-2-hydroxy-2-methyl-1-propanone and 
1-(4-tert-butylphenyl)-2-hydroxy-2-methyl-1-propanone. 
The composition of this invention substantially contains the above 
(meth)acrylate and its oligomer as a main component, and preferably 
further contains the photopolymerization initiator. Hence, basically, it 
is of the solventless type. 
The (metha)acrylate oligomer used in the composition of this invention has 
an average degree of polymerization of 2 to 100, preferably 2 to 50, and 
more preferably 2 to 35. 
The amount of the (meth)acrylate oligomer used in this invention is 1 to 
100% by weight, preferably 5 to 95% by weight, more preferably 10 to 90% 
by weight, based on the total weight of the (meth)acrylate oligomer and 
the (meth)acrylate monomer. 
The viscosity of the composition of this invention, which depends upon the 
average molecular weight and the content in % by weight of the 
(meth)acrylate oligomer, is, for example, 10 to 50,000 cps, preferably 100 
to 40,000 cps, more preferably 1,000 to 30,000 cps. 
The composition may contain components usually incorporated in solventless 
adhesives, for example reactive diluents, sensitizers, thickeners, 
antisagging agents, storage stabilizer and plasticizers. 
The amount of the photopolymerization initiator which may be used in the 
composition of this invention is 0.01 to 10 parts by weight, preferably 
0.05 to 7 parts by weight, more preferably 0.1 to 5 parts by weight, per 
100 parts by weight of the (meth)acryate and its oligomer. 
The composition of this invention is prepared, for example, by the 
following procedure. At least one monomer of formula (I) and the 
photopolymerization initiator are fed into a four-necked flask equipped 
with a water-cooled jacket and a stirrer. While the contents were cooled 
with water with stirring, ultraviolet light was irradiated from a 
water-cooled high-pressure mercury lamp with an output of 100 W to effect 
photopolymerization in an air atmosphere. The pressure of the inside of 
the flask was reduced with stirring, and the reaction mixture in purified 
form is obtained. 
The composition of this invention is cured as follows: 
The resulting reaction mixture is used to bond adhesion test pieces. Light 
is irradiated onto the bonded test pieces from a water-cooled high 
pressure mercury lamp with an output of 3 KW to cure the reaction mixture. 
The composition of the present invention is useful, for example, in coating 
and bonding various substrates, particularly transparent substrate 
materials, above all bonding of optical materials, for example the bonding 
of lenses or optical discs. When the substrate used is one which contains 
a component which is likely to react with a chemical substance and undergo 
degeneration, for example a recording layer of an optical disc, it is 
preferred to use a composition in accordance with this invention which 
substantially comprises the above (meth)acrylate oligomer from which 
monomer components have been removed, and as required the 
photopolymerization initiator. 
The composition of this invention exhibit particularly firm adhesiveness to 
such substrates as those made of polycarbonate polymers, (meth)acrylate 
polymers, ethylene/cyclic olefin copolymer or olefin copolymers containing 
4-methyl-1-pentene as a main component. One examples of the 
ethylene/cyclic olefin copolymers is a copolymer of ethylene with a 
monomer component of the following formula (1) which monomer assumes the 
structure of the following formula (2) in the copolymer. In the formulae, 
R.sup.1 to R.sup.12 are identical or different and each represents 
hydrogen, alkyl or halogen, R.sup.9 or R.sup.10 and R.sup.11 or R.sup.12 
may form a ring together, n is 0 or a positive number of at least 1, when 
R.sup.5 to R.sup.8 recur a plurality of times, they may be identical or 
different. 
##STR43## 
According to this invention, there can be provided a novel active energy 
ray-curable composition which cures within a short period of time by 
irradiation of ultraviolet light, electron beams, radioactive rays, etc., 
has high adhesion strength, does not impair the optical properties of 
substrates, and is non-polluting because it is of the solventless type. 
The following examples illustrate the present invention more specifically. 
The adhesion strengths of the compositions in these examples were evaluated 
by the following methods. 
(i) Tensile shear peel strength 
The surface of a test plate, 20.times.120.times.2 mm, cut out from an 
injection-molded plate of a resin was lightly wiped with gauze impregnated 
with isopropanol, and then the composition of the invention was coated on 
it so that the area of adhesion became 4 cm.sup.2. Another test plate was 
superimposed on it, and the assembly was held by quartz glass and fixed. 
Then active energy ray was irradiated to cure the adhesive composition. 
The cross-sectional surface of the test piece is shown in FIG. 1. In FIG. 
1, a=120 mm, b=2 mm, and c=20 mm. 
The resulting test piece assembly was pulled at a rate of 50 mm/min. using 
a tensile tester (Model 1123 made by Instron Co.), and the tensile force 
was measured. The tensile shear peel strength was calculated by dividing 
the tensile force by the area of adhesion. 
(ii) Tensile adhesion strength 
A test piece A (30.times.12.7.times.3 mm) and a test piece B 
(25.times.12.times.6.3 mm) were prepared from a resin by injection 
molding. The surfaces of the test pieces were lightly wiped with gauze 
impregnated with isopropanol. The composition of the invention was then 
coated on the test piece A, and spread uniformly on the adhesion surface 
by using the test piece B (area of adhesion=0.8 cm.sup.2). The test pieces 
were fixed by holding them by quartz glass so that the test piece A was 
situated atop. By irradiating active energy ray onto the assembly, the 
test pieces were cured. The apperance of the test piece assembly after 
bonding is shown in FIG. 2. In FIG. 2, d=30 mm, e=12.7 mm, f=3 mm, g=25 
mm, h=12 mm, and i=6.3 mm. 
The test piece assembly was pulled at a speed of 50 mm/min. by using a 
tensile tester (Model 1123 made by Instron Co.), and the tensile force was 
measured. The tensile adhesion strength was calculated by dividing this 
tensile force by the area of adhesion. 
EXAMPLE 1 
A 1-liter four-necked flask equipped with a water-cooled jacket and a 
stirrer was charged with 500 g of tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]-dodecyl-3-acrylate and 1.5 g of 
1-(4-isopropylphenyl)-2-hydroxy-2-methyl-1-propanone as a 
photopolymerization initiator. While the contents were cooled with water 
with stirring, ultraviolet light was irradiated for 10 minutes onto the 
flask by a 100 W high-pressure mercury lamp placed at a distance of 10 cm 
from the flask to perform photopolymerization in an air atmosphere. Then, 
the flask was evacuated to 1 torr by using a vacuum pump with stirring, 
and the reaction mixture was purified for 3 hours. The resulting reaction 
mixture was a transparent viscous liquid having a viscosity of 1250 cps. 
Gel permeation chromatography showed that the reaction mixture consisted of 
about 70% by weight of the unreacted monomer and about 30% by weight of 
oligomers (dimer to eicosamer). 
Adhesion test pieces of TPX.RTM. (brand TR-18, a product of Mitsui 
Petrochemical Industries, Ltd.) were bonded by using the resulting 
reaction mixture. By irradiating light for 30 minutes from a 3 KW 
high-pressure mercury lamp at a distance of 15 cm, the reaction mixture 
applied to the test pieces was cured. The adhesion strengths of the 
resulting bonded test sample are shown in Table 2. 
EXAMPLE 2 
Adhesion test pieces of polycarbonate were bonded by the same method as in 
Example 1 using the reaction mixture obtained in Example 1. The results 
are shown in Table 2. 
EXAMPLE 3 
Adhesion test pieces of poly(methyl methacrylate) were bonded by the same 
method as in Example 1 using the reaction mixture obtained in Example 1. 
The results are shown in Table 2. 
EXAMPLE 4 
Adhesion test pieces of ethylene/tetracyclododecene copolymer (ethylene 57 
mole %; [.eta.]=0.44 dl/g) were bonded by the same method as in Example 1 
using the reaction mixture obtained in Example 1. The results are shown in 
Table 2. The [.eta.] was measured at 135.degree. C. using decalin as a 
solvent. 
EXAMPLE 5 
The same reaction as in Example 1 was carried out except that 500 g of 
cyclohexyl acrylate was used as the monomer, 1 g of 
1-phenyl-2-hydroxy-2-methyl-1-propanone was used as the 
photopolymerization initiator, and the time of irradiating ultraviolet 
light was changed to 15 minutes. The reaction mixture obtained was a 
transparent viscous liquid having a viscosity of 2610 cps. 
Gel permeation chromatography showed that the reaction mixture consisted of 
about 40% by weight of the unreacted monomer and about 60% by weight of 
oligomers (dimer to hexacosamer). 
Adhesion test pieces of ethylene/tetracyclododecene shown in Example 4 were 
bonded by using this reaction mixture by the same method as in Example 1. 
The results are shown in Table 2. 
EXAMPLE 6 
Example 5 was repeated except that norbornyl acrylate was used as the 
monomer. The results are shown in Table 2. The resulting reaction mixture 
was a transparent viscous liquid having a viscosity of 1860 cps. 
EXAMPLES 7-9 
Example 5 was repeated except that each of the monomers indicated in Table 
3 was used. The results are shown in Table 2. The viscosity and appearance 
of the reaction mixture obtained in each of the examples shown in Table 3. 
EXAMPLES 10-11 
Example 5 was repeated except that each of the adherends shown in Table 2 
was used. The results of the test are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
Example 1 2 3 4 5 
__________________________________________________________________________ 
Monomer tetracyclo[4,4,0,1.sup.2,5 -1.sup.7,10 ]- 
same as left 
same as left 
same as left 
cyclohexyl 
dodecyl-3-acrylate acrylate 
Photopolymerization 
1-(4-isopropylphenyl)-2- 
same as left 
same as left 
same as left 
1-phenyl-2- 
initiator hydroxy-2-methyl-1-propanone hydroxy-2- 
methyl-1- 
propanone 
Adherend TPX (RT-18) polycarbonate 
polymethyl 
ethylene/ 
same as left 
methacrylate 
tetracyclo- 
dodecene 
copolymer 
Tensile shear 
9.7 6.9 7.8 11.2 12.3 -peel strength 
(kg/cm.sup.2) 
Tensile adhesion 
10.4 7.3 8.5 12.1 13.5 
strength 
(kg/cm.sup.2) 
__________________________________________________________________________ 
Example 6 7 8 9 10 11 
__________________________________________________________________________ 
Monomer norbornyl 
dicyclo- 
dicyclo- 
isoboronyl 
cyclohexyl 
same as left 
acrylate 
pentyl pentenyl 
acrylate 
acrylate 
acrylate 
acrylate 
Photopolymerization 
1-phenyl-2- 
same as left 
same as left 
same as left 
same as left 
same as left 
initiator hydroxy-2- 
methyl-1- 
propanone 
Adherend ethylene/ 
same as left 
same as left 
same as left 
TPX(RT-18)/ 
TPX(RT-18)/ 
tetracyclo- PR-PET Polyether 
dodecene sulfone 
copolymer 
Tensile shear 
8.4 6.7 7.8 9.4 6.2 5.0 
peel strength 
(kg/cm.sup.2) 
Tensile adhesion 
7.8 7.9 6.9 8.5 5.3 4.7 
strength 
(kg/cm.sup.2) 
__________________________________________________________________________ 
TABLE 3 
______________________________________ 
Example 7 8 9 
______________________________________ 
Monomer dicyclopentyl 
dicyclopentenyl 
isoboronyl 
acrylate acrylate acrylate 
Viscosity 2960 2780 2640 
(cps) 
Appear- transparent same as left 
same as 
ance viscous left 
liquid 
______________________________________ 
EXAMPLES 12-14 
Example 5 was repeated except that each of the acrylates indicated in Table 
4 was used as the monomer. The results are shown in Table 4. The reaction 
mixtures obtained in these examples were transparent viscous liquids whose 
viscosities are shown in Table 4. 
EXAMPLE 15 
Example 5 was repeated except that 250 g of 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate and 250 g of 
dicyclopentenyloxyethyl acrylate were used as the monomer. The results are 
shown in Table 4. 
The resulting reaction mixture was a transparent viscous liquid whose 
viscosity is shown in Table 4. 
EXAMPLE 16 
A reaction mixture was prepared as in Example 1 except that 400 g of 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]dodecyl-3-acrylate and 100 g of 
bisoxyethyl bisphenol A diacrylate were used as the monomer and the 
ultraviolet light was irradiated for 30 minutes. The resulting reaction 
mixture had a viscosity of 26,500 cps. 
Using the reaction mixture, the same adhesion test as in Example 5 was 
carried out. The results are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
Example 
12 13 14 15 16 
__________________________________________________________________________ 
Monomer 
dicyclo- 
bisoxyethyl 
gamma- 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 ]- 
tetracyclo[4,4,0,1.sup.2,5,1.sup.7,10 
]- 
pentenyloxy- 
bisphenol A 
phenoxy- 
dodecyl-3-acrylate/dicyclo- 
dodecyl-3-acrylate/bisoxy- 
ethylene 
diacrylate 
beta- 
pentenyloxyethyl acrylate 
ethyl bisphenol A diacrylate 
acrylate hydroxy- 
(1:1 by weight) 
(4:1 by weight) 
propyl 
acrylate 
Photo- 
1-phenyl-2- 
same as left 
same as 
same as left 1-(4-isopropylphenyl)-2- 
polymer- 
hydroxy-2- left hydroxy-2-methyl-1-propanone 
ization 
methyl-1- 
initiator 
propanone 
Adherend 
ethylene/ 
same as left 
same as 
same as left same as left 
tetracyclo- left 
dodecene 
copolymer 
Tensile 
10 8.5 10.5 11 11.5 
shear 
peel 
strength 
(kg/cm.sup.2) 
Tensile 
11 10 12 12 10.5 
adhesion 
strength 
(kg/cm.sup.2) 
Viscosity 
2050 2870 2300 2780 26500 
(cps) 
__________________________________________________________________________ 
COMATIVE EXAMPLES 1-17 
Example 5 was repeated except that each of the acrylates indicated in Table 
5 was used as the monomer. The results of the adhesion tests and the 
viscosities of the resulting reaction mixtures are shown in Table 5. 
3 TABLE 5 
Comparative Example 1 Comparative Example 2 Comparative Example 
3 Monomer 
##STR44## 
##STR45## 
##STR46## 
Photopolymerization 1-phenyl-2-hydroxy- same as left same as left 
initiator 2-methyl-1-propanone Adherend ethylene/tetracyclo- same as 
left same as left dodecene copolymer Tensile 1 0 1 shear peel strength 
(kg/cm.sup.2) Tensile 2 0 2 adhesion strength (kg/cm.sup.2) Viscosity 
(cps) 3200 2800 2510 
Comparative Example 4 Comparative Example 5 Comparative Example 
6 Monomer 
##STR47## 
##STR48## 
##STR49## 
Photopolymerization 1-phenyl-2-hydroxy- same as left same as left 
initiator 2-methyl-1-propanone Adherend ethylene/tetracyclo- same as 
left same as left dodecene copolymer Tensile 0 0 0 shear peel strength 
(kg/cm.sup.2) Tensile 0 0 0 adhesion strength (kg/cm.sup.2) Viscosity 
(cps) 2870 2950 2070 
Comparative Example 7 Comparative Example 8 Comparative Example 
9 Monomer 
##STR50## 
##STR51## 
##STR52## 
Photopolymer 1-phenyl-2-hydroxy- same as left same as left ization 
2-methyl-1-propanone initiator Adherend ethylene/tetracyclo- same as 
left same as left dodecene copolymer Tensile 0 0 0 shear peel strength 
(kg/cm.sup.2) Tensile 0 0 0 adhesion strength (kg/cm.sup.2) Viscosity 
(cps) 1910 3250 3510 
Comparative Example 10 Comparative Example 11 Comparative Example 
12 Monomer 
##STR53## 
##STR54## 
##STR55## 
Photopolymerization 1-phenyl-2-hydroxy- same as left same as left 
initiator 2-methyl-1-propanone Adherend ethylene/tetracyclo- same as 
left same as left dodecene copolymer Tensile 0 0 0 shear peel strength 
(kg/cm.sup.2) Tensile 0 0 0 adhesion strength (kg/cm.sup.2) Viscosity 
(cps) 1020 2100 3180 
Comparative Example 13 Comparative Example 14 Comparative Example 
15 Monomer 
##STR56## 
##STR57## 
##STR58## 
Photopolymerization 1-phenyl-2-hydroxy- same as left same as left 
initiator 2-methyl-1-propanone Adherend ethylene/tetracyclo- same as 
left same as left dodecene copolymer Tensile 0 0 0 shear peel strength 
(kg/cm.sup.2) Tensile 0 0 0 adhesion strength (kg/cm.sup.2) Viscosity 
(cps) 2970 1980 2500 
Comparative Example 16 Comparative Example 17 
Monomer 
##STR59## 
##STR60## 
Photopolymerization 1-phenyl-2-hydroxy- same as left initiator 
2-methyl-1-propanone Adherend ethylene/tetracyclo- same as left 
dodecene copolymer Tensile 0 0 shear peel strength (kg/cm.sup.2) Tensile 
0 0 adhesion strength (kg/cm.sup.2) Viscosity (cps) 2090 3520