Thermo and active energy ray curable resin composition used for protecting layer of transfer material transfer material surface protecting material and process for producing molded article excellent in abrasion resistance and chemical resistance

The sheet material of the present invention has a protecting layer which comprises a heat reactant of a heat and active energy ray curable resin composition comprising as an active ingredient a polyfunctional isocyanate and a polymer having a (meth)acryl equivalent weight from 100 to 300 g/eq, a hydroxyl value from 20 to 500 and a weight-average molecular weight from 5000 to 50000. And, this protecting layer applied to the surface of a molded article is cured by active energy ray irradiation. Therefore, a molded article excellent in abrasion resistance and chemical resistance can be obtained, and cracking is not caused in the curved part of the molded article. Further, since the protecting layer is cured in part by heat in sheet material production, a large scale active energy ray irradiation apparatus is not required in active energy ray irradiation to realize low cost.

TECHNICAL FIELD 
The present invention relates to a heat and active energy ray curable resin 
composition used for the protecting layer of a transfer material, which 
can provide at a low cost a molded article excellent in abrasion 
resistance and chemical resistance, and which does not cause crack in the 
curved part of the molded article, a transfer material, a surface 
protecting material, and a process for producing a molded article 
excellent in abrasion resistance and chemical resistance. 
PRIOR ART 
As a method for producing a molded article excellent in abrasion resistance 
and chemical resistance, there are a method in which the protecting layer 
of a transfer material produced by forming a protecting layer on a 
substrate sheet having releasing property, is adhered on the surface of a 
molded article, and the substrate sheet is released, a method in which the 
substrate sheet of a surface protecting material produced by forming a 
protecting layer on a substrate sheet having no releasing property, is 
adhered on the surface of a molded article, and the like. 
As a protecting layer used for a sheet material such as the above-described 
transfer material and surface protecting material, a heat curable resin 
and an active energy ray curable resin are generally used. 
However, when a heat curable resin is used as a protecting layer, the 
surface of a molded article is inferior in chemical resistance and 
abrasion resistance in general. 
On the other hand, when an active energy ray curable resin is used as a 
protecting layer, the crosslinking density of a resin which forms the 
protecting layer increases, and chemical resistance and abrasion 
resistance are improved. However, the resultant protecting layer becomes 
fragile. As a result, cracking occurs on the protecting layer at the part 
which curves along a molded article in adhering. 
Therefore, there has been suggested a method in which, an active energy ray 
curable resin formed as a protecting layer, is irradiated with an active 
energy ray first for semi-curing the resin to form a sheet material. The 
protecting layer is applied on the surface of a molded article, and the 
active energy ray curable resin is again irradiated with an active energy 
ray for completely curing. 
However, in this method, if the irradiation amount of the active energy ray 
is deficient in the first irradiation step, flowability and stickiness 
remain on the surface of the protecting layer of the sheet material. As a 
result, handling of the sheet material becomes inconvenient. 
On the other hand, when the irradiation amount is excess, cracking is 
liable to occur in the protecting layer at the curved part of the molded 
article in adhering. 
To prevent such a problem, it is necessary to control the irradiation 
amount in the first irradiation step. However, a radical polymerization 
proceeds quickly and a dark reaction progresses even after irradiation of 
an active energy ray, therefore, it is not easy to control the irradiation 
amount. There is also a problem that the irradiation condition is liable 
to be unstable due to degradation of the light source of the active energy 
ray. 
Further, the sheet material has wide and large surface area, and a large 
scale and costly irradiation apparatus is required for irradiating it. 
The object of the present invention is to provide a resin composition used 
for the protecting layer of a sheet material which solves the 
above-mentioned problems, which can give a molded article excellent in 
abrasion resistance and chemical resistance at a low cost, and which does 
not cause cracking at the curved part of the molded article in adhering 
the sheet material. 
SUMMARY OF THE INVENTION 
The present inventors have intensively studied to solve the above-mentioned 
problems. As a result, we have found that the above-mentioned problems can 
be solved, on condition that a heat and active energy ray curable 
composition comprising a specific polymer and polyfunctional isocyanate is 
used as an active ingredient, in producing the protecting layer of a sheet 
material, such as a transfer material and a surface protecting material. 
That is, the heat and active energy ray curable resin composition used for 
the protecting layer of the sheet material of the present invention, 
comprises as an active ingredient a polyfunctional isocyanate and a 
polymer having a (meth)acrylic equivalent weight from 100 to 300 g/eq, a 
hydroxyl value from 20 to 500 and a weight-average molecular weight from 
5000 to 50000.

DETAILED DESCRIPTION OF THE INVENTION 
First, the transfer material 106 of the present invention will be described 
by reference to FIG. 1. 
As the substrate sheet 101 having releasing property, there can be used any 
material which is usually used as a substrate sheet of a transfer 
material, such as a sheet of a polypropylene-based resin, 
polyethylene-based resin, polyamide-based resin, polyester-based resin, 
polyacryl-based resin, polyvinyl chloride-based resin or the like, a metal 
foil such as an aluminium foil, copper foil or the like, a cellulose-based 
sheet such as a glassine paper, coat paper, cellophane or the like, a 
complex of the above-mentioned sheets, or the like. 
If the releasing property of a transfer layer 105 from the substrate sheet 
101 is excellent, the transfer layer 105 may be applied directly on the 
substrate sheet 101. If the releasing property of the transfer layer 105 
from the substrate sheet 101 is poor, a releasing layer (not indicated) 
may be formed on the whole surface before the transfer layer 105 is 
applied on the substrate sheet 101. 
In general, when the substrate sheet 101 is released after the transfer, 
the releasing layer is released from the transfer layer 105 together with 
the substrate sheet 101. As a raw material of the releasing layer, a 
melamine resin-based releasing agent, silicone resin-based releasing 
agent, fluorine resin-based releasing agent, cellulose derivative-based 
releasing agent, urea rein-based releasing agent, polyolefin resin-based 
releasing agent, paraffin-based releasing agent and complex-based 
releasing agent composed of them can be used. As a forming method of the 
releasing layer, there are coating methods such as a gravure coating 
method, roll coating method, spray coating method, lip coating method, 
comma coating method and the like, and printing methods such as a gravure 
printing method, screen printing method and the like. 
The protecting layer 102 is a layer which becomes a most outer layer of the 
transferred material by being released from the substrate sheet 101 or the 
releasing layer when the substrate sheet 101 is released after transfer, 
and protects the molded article and the picture layer 103 from chemicals 
and abrasion. To form this protecting layer 102, there is used a heat and 
active energy ray curable resin composition comprising as an active 
ingredient a polyfunctional isocyanate and a polymer having a 
(meth)acrylic equivalent weight from 100 to 300 g/eq, a hydroxyl value 
from 20 to 500 and a weight-average molecular weight from 5000 to 50000. 
The polymer used for the protecting layer 102 has a (meth)acrylic 
equivalent weight from 100 to 300 g/eq, preferably from 150 to 300 g/eq, 
in view of curing property in an active energy ray irradiation. When the 
(meth)acrylic equivalent weight is more than 300 g/eq, abrasion resistance 
after active energy ray irradiation is insufficient, and the polymer 
having a (meth)acrylic equivalent weight of less than 100 g/eq is 
difficult to be obtained. And, the hydroxyl value of the polymer is from 
20 to 500, preferably from 100 to 300, in view of reactivity with the 
polyfunctional isocyanate used together. When the hydroxyl value is less 
than 20, reactivity with the polyfunctional isocyanate becomes 
insufficient, and the heat crosslinking degree of the protecting layer 102 
of the transfer material 106 becomes low. Therefore, stickiness remains or 
solvent resistance is deficient, and consequently, rolling and 
overprinting of the transfer material 106 become difficult. Further, the 
polymer having a hydroxyl value of over 500 is difficult to be obtained. 
The weight-average molecular weight of the polymer is from 5000 to 50000, 
preferably from 8000 to 40000. When the weight-average molecular weight of 
the polymer is less than 5000, solvent resistance becomes poor or 
stickiness remains on the protecting layer 102 of the transfer material 
106, and consequently, rolling and overprinting of the transfer material 
106 become difficult and a clear picture is not obtained. Further, when 
over 50000, viscosity of the resin becomes too high, and applying 
workability of the ink decreases. 
The production method of the polymer is not particularly restricted, and 
conventionally known methods can be employed. For example, there are a 
method [1] in which a (meth)acryloyl group is introduced into a part of 
side chains of a polymer having a hydroxyl group, a method [2] in which an 
.alpha.,.beta.-unsaturated monomer having a hydroxyl group is subjected to 
a condensation reaction with a copolymer having a carboxylic group, a 
method [3] in which an .alpha.,.beta.-unsaturated monomer having an epoxy 
group is subjected to an addition reaction with a copolymer having a 
carboxylic group, and a method [4] in which an .alpha.,.beta.-unsaturated 
carboxylic acid is reacted with a polymer having an epoxy group. 
The production method of the polymer used in the present invention will be 
specifically described using as an example the method [4]. For example, 
the polymer used in the present invention can be obtained by a method in 
which a polymer having a glycidyl group is reacted with an 
.alpha.,.beta.-unsaturated carboxylic acid such as acrylic acid or the 
like. 
The preferable polymer having a glycidyl group is glycidyl 
(meth)acrylate-based polymer. As the glycidyl (meth)acrylate-based 
polymer, for example, a homopolymer of glycidyl (meth)acrylate and a 
copolymer of glycidyl (meth)acrylate and an .alpha.,.beta.-unsaturated 
monomer having no carboxyl group are exemplified. 
As this .alpha.,.beta.-unsaturated monomer having no carboxyl group, 
various (meth)acrylates, styrene, vinyl acetate, acrylonitrile and the 
like can be exemplified. If an .alpha.,.beta.-unsaturated monomer having a 
carboxyl group is used, crosslinkage is formed in the copolymerization 
reaction with glycidyl (meth)acrylate, and increasing in viscosity and 
gelling are unpreferably caused. 
When the polymer used for the protecting layer 102 is produced, it is 
necessary to appropriately set conditions such as the kind of the monomer 
used, the kind of the polymer and the amounts used thereof, so as to 
suffice the above-described numerical value restriction ranges regarding 
to the polymer. Such procedure is known to those skilled in the art. 
As the polyfunctional isocyanate used together with the polymer in the 
present invention, known various isocyanates can be used. For example, 
isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene 
diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, 
1,6-hexane diisocyanate, a trimer of the above-mentioned isocyanates, a 
prepolymer obtained by the reaction of polyfunctional alcohol and the 
above-mentioned diisocyanate and the like can be used. 
The reason why the polyfunctional isocyanate is used together with the 
polymer in the present invention is that the isocyanate keeps stickiness 
of the protecting layer 102 before active energy ray irradiation low, and 
it provides resistance to the solvent which is contained in the ink of the 
picture layer 103 and the adhesion layer 104, in laminating the picture 
layer 103 and the adhesion layer 104 on the protecting layer 102. That is, 
a hydroxyl group contained in the polymer is reacted with an isocyanate 
group of the polyfunctional isocyanate to form a slightly heat-crosslinked 
compound, which has the above-described characteristics. 
The ratio used of the polymer to the polyfunctional isocyanate is 
determined so that the ratio of the number of a hydroxyl group to the 
number of an isocyanate group in the polymer is from 1/0.01 to 1/1, 
preferably from 1/0.05 to 1/0.8. 
The heat and active energy ray curable resin composition used for the 
protecting layer 102 may optionally contain the following components in 
addition to the polymer and the polyfunctional isocyanate. That is, a 
reactive diluting monomer, solvent, coloring agent and the like. When an 
electron beam is used in active energy ray irradiation, sufficient effect 
can be obtained without using a photopolymerization initiator. On the 
other hand, when ultraviolet ray is used, it is necessary to add known 
various photopolymerization initiators. The protecting layer 102 may be 
either one which has been colored or one without coloring. 
It is preferable for the resin composition used for the protecting layer 
102 to contain a UV absorber. The object thereof is to impart weather 
resistance to the protecting layer which has been transferred to a molded 
article. 
As the UV absorber, conventional compounds may be used. For example, 
salicylic acid-based, benzophenone-based, diphenyl acrylate-based, 
benzotriazole-based, triazine-based, and amine-based UV absorbers can be 
used. 
The preferable UV absorber is one which comprises an aliphatic group having 
from 3 to 30, preferably from 10 to 20 carbon atoms containing a 
2-hydroxypropylene dioxy moiety represented by the formula: 
EQU --O--CH.sub.2 CH(OH)CH.sub.2 --O--. 
The reason for this is that such a UV absorber is excellent in 
compatibility with the resin composition which forms the protecting layer 
102, and can be contained in a large amount with maintaining transparency 
of the protecting layer. 
Specifically, hydroxyphenylbenzotriazol represented by the formula: 
##STR1## 
and hydroxyphenyl-S-triazine represented by the formula 
##STR2## 
can be used. 
The UV absorbers represented by the formulae are contained in an amount 
from 5 to 30% by weight, preferably from 8 to 20% by weight. When the 
amount of the UV absorber is lower than 5% by weight, weather resistance 
of the protecting layer becomes insufficient, and when over 30% by weight, 
(1) transparency of the protecting layer becomes poor, (2) flowability and 
coatability become poor, and (3) surface strength of the coated protecting 
layer becomes poor. 
It is preferable for the resin composition used for the protecting layer 
102 to contain a photostabilizer together with the UV absorber. The reason 
for this is that weather resistance of the protecting layer after 
transferring to a molded article is further improved. As the 
photostabilizer, conventional compounds may be used. The example thereof 
can include benzophenone-based, diphenyl acrylate-based, amine-based 
photostabilizers and the like. 
The photostabilizer is contained in an amount from 0.2 to 5% by weight, 
preferably from 0.5 to 2.0% by weight. When the photostabilizer is lower 
than 0.2% by weight, weather resistance of the protecting layer becomes 
poor, and when over 5% by weight, (1) transparency of the protecting layer 
becomes poor, (2) flowability and coatability become poor, and (3) surface 
strength of the coated protecting layer becomes poor. 
The preferable photostabilizer is a hindered amine-based compound. 
Specifically, "Tinuvin 123", "Tinuvin 144" and "Tinuvin 292" available 
from Ciba Geigy Ltd. can be used. 
The resin composition used for the protecting layer 102 may optionally 
contain a lubricant. The reason for this is that the surface of the 
protecting layer is made rough, therefore, the protecting layer becomes 
easy to be rolled as a sheet, the sheet becomes difficult to be blocked, 
and the sheet has resistance against rubbing or scratching. As the 
lubricant, for example, waxes such as polyethylene wax, paraffine wax, 
synthesized wax, montan wax, and silicone-based, or fluorine-based 
synthetic resin can be used. 
The lubricant is contained in an amount from 0.5 to 15% by weight, 
preferably from 1 to 6% by weight. When the amount of the lubricant is 
lower than 0.5% by weight, rubbing, scratching resistance, on blocking 
resistance of the sheet becomes poor, and when over 5% by weight, 
transparency of the protecting layer becomes poor. 
The resin composition used for the protecting layer 102 contains an 
ethylenically unsaturated group, hydroxyl group and isocyanate group. When 
this resin composition is heated, the hydroxyl group and isocyanate group 
react to crosslink the resin. Further, when this resin composition is 
exposed to an active energy ray, the ethylenically unsaturated group is 
polymerized to crosslink the resin. That is, the resin composition used 
for the protecting layer 102 is a heat and active energy ray curable resin 
composition which is crosslinked by both heat and an active energy ray. 
As methods for forming the protecting layer 102, there are coating methods 
such as a gravure coating method, roll coating method, comma coating 
method, lip coating method and the like, and printing methods such as a 
gravure printing method, screen printing method and the like. In general, 
the protecting layer 102 is formed in a thickness from 0.5 to 30 .mu.m, 
more preferably from 1 to 6 .mu.m. When the thickness of the protecting 
layer is lower than 0.5 .mu.m, abrasion resistance or chemical resistance 
becomes poor, and when over 30 .mu.m, cost of the sheet material becomes 
high, and cutability of the protecting layer becomes poor, and when it is 
used as a transfer material, a flash may occur. 
Then, this protecting layer 102 is heated for crosslinking to make a tack 
free surface. However, in this stage, an ethylenically unsaturated group 
contained in the resin composition is not substantially crosslinked, and 
the resin is not completely cured. Therefore, the protecting layer 102 can 
be applied to the curved surface of a molded article and has such a 
flexibility which does not cause cracking. 
A crosslinking reaction by heating is easier to be controlled by comparison 
with a crosslinking reaction by an active energy ray irradiation. 
Therefore, degree of crosslinking of the protecting layer 102 can 
appropriately be determined according to the kind of a resin composition 
used, curvature of a molded article and the like. 
The picture layer 103 is formed on the protecting layer 102 usually by a 
printing method. Regarding to the raw material of the picture layer 103, 
resins such as a polyvinyl-based resin, polyamide-based resin, 
polyester-based resin, polyacryl-based resin, polyurethane-based resin, 
polyvinyl acetal-based resin, polyesterurethane-based resin, cellulose 
ester-based resin, alkyd resin and the like may be used as a binder, and 
coloring ink containing a dye or pigment having suitable color as a 
coloring agent may be used. As methods for forming the picture layer 103, 
usual printing methods such as an offset printing method, gravure printing 
method, screen printing method and the like may be used. 
Particularly, an offset printing method and gravure printing method are 
suitable for conducting multi-color printing and gradation expression. 
Further, in the case of mono-color printing, coating methods such as a 
gravure coating method, roll coating method, comma coating method and the 
like can also be employed. The picture layer 103 is formed on a part of 
the surface or the whole surface according to a picture to be expressed. 
Further, the picture layer 103 may be composed of a metal film layer or 
composed of a combination of a printing layer and a metal film layer. 
The adhesion layer 104 is one which adhere the above-mentioned respective 
layers on the surface of a molded article (not indicated). The adhesion 
layer 104 is formed on the part to be adhered to the molded article of the 
protecting layer 102 or of the picture layer 103. That is, when whole 
surface is to be adhered, the adhesion layer 104 is formed on the whole 
surface. And, when a part of the surface is to be adhered, the adhesion 
layer 104 is formed partially. As the adhesion layer 104, a heat sensible 
or pressure sensible resin suitable for the raw material of the molded 
article is appropriately used. However, if the protecting layer 102 or the 
picture layer 103 has sufficient adhesiveness to the molded article, the 
adhesion layer 104 may be omitted. 
For example, when the raw material of the molded article is a 
polyacryl-based resin, a polyacryl-base resin may be used. Further, when 
the raw material of the molded article is a polyphenylene 
oxide-polystyrene-based resin, polycarbonate-based resin, styrene 
copolymer-based resin or polystyrene-based blend resin, a polyacryl-based 
resin, polystyrene-based resin, polyamide-based resin and the like which 
has affinity with the resins may be used. Further, the raw material of the 
molded article is a polypropylene resin, a chlorinated polyolefin resin, 
chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber and 
cumarone-indene resin can be used. 
As a method for forming the adhesion layer 104, there are coating methods 
such as a gravure coating method, roll coating method, comma coating 
method and the like, and printing methods such as a gravure printing 
method, screen printing method and the like. 
In the present invention, construction of the transfer layer is not 
restricted to the above-mentioned embodiments. For example, when only 
surface protection is intended for utilizing the background pattern and 
transparency of the molded article, the protecting layer 202 and adhesion 
layer 204 can be formed in order on the substrate sheet 201 as described 
above, and the picture layer can be omitted as shown in FIG. 2. 
Further, an anchor layer may be formed between the protecting layer and the 
adhesion layer which constitute the transfer layer. The anchor layer is a 
resin layer which enhances adhesiveness between the protecting layer and 
the adhesion layer and protects the molded article and the picture layer 
from chemicals. For example, thermoplastic resins such as a two-pack 
setting urethane resin, melamine-based or epoxy-based thermosetting resin, 
vinyl chloride copolymer resin and the like can be used. As a method for 
forming the anchor layer, there are coating methods such as a gravure 
coating method, roll coating method, comma coating method and the like and 
printing methods such as a gravure printing method, screen printing method 
and the like. 
A method for producing a molded article excellent in abrasion resistance 
and chemical resistance using the transfer material of the present 
invention will be described bellow. 
First, as shown in FIG. 3, the transfer material 306 is placed on the 
molded article 307 with the adhesion layer thereof facing to the molded 
article (below). 
Then, by using a transferring machine such as a roll transferring machine 
equipped with the heat resistant rubber-like elastomer 308, for example a 
silicon rubber, up-down transferring machine, and the like, heat and/or 
pressure is applied to the transfer material 306 from the side of the 
substrate sheet 301 through the heat resistant rubber-like elastomer 308 
set at the conditions of a temperature from 80 to 260.degree. C. and a 
pressure from 50 to 200 kg/m.sup.2. According to the procedure, the 
protecting layer is adhered to the surface of the molded article 307 via 
the adhesion layer. Then, the substrate sheet 301 is pulled after cooling, 
peeling occurs in the boundary surface between the substrate sheet 301 and 
the protecting layer. 
If a releasing layer is formed on the substrate sheet 301, when the 
substrate sheet 301 is pulled, peeling occurs in the boundary surface 
between the releasing layer and the protecting layer. Finally, an active 
energy ray is irradiated to the protecting layer transferred to the molded 
article 307 to cure. The step of irradiating the active energy ray may be 
conducted before the step of peeling the substrate sheet 301. 
As the active energy ray, an electron beam, ultraviolet ray, .gamma.-ray 
and the like can be used. The irradiation condition may be determined 
according to the kind of the heat and active energy ray curable resin 
composition. 
Regarding the molded article 307, though the raw material thereof is not 
restricted, there can be exemplified in particular a resin molded article, 
wooden article or complex article thereof. These may be transparent, 
translucent or opaque. The molded article 307 may be colored or not 
colored. The example of the resin includes general-purpose resins such as 
a polystyrene-based resin, polyolefin-based resin, ABS resin, AS resin, AN 
resin and the like. 
Further, there can be used general-purpose engineering resins such as a 
polyphenylene oxide-polystyrene-based resin, polycarbonate-based resin, 
polyacetal-based resin, acryl-based resin, polycarbonate modified 
polyphenylene ether resin, polyetylene terephthalate resin, polybutylene 
terephthalate resin, ultra high molecular weight polyethylene resin and 
the like, and super engineering resins such as a polysulfone resin, 
polyphenylene sulfide-based resin, polyphenylene oxide-based resin, 
polyacrylate resin, polyether imide resin, polyimide resin, liquid crystal 
polyester resin, polyallyl-based heat resistant resin and the like. 
Further, a complex resin obtained by adding a reinforcing material such as 
a glass fiber, inorganic filler or the like can also be used. 
A molded article excellent in abrasion resistance and chemical resistance 
can also be produced, by utilizing a simultaneous molding and transferring 
method in which transferring is conducted simultaneously with molding by 
injection molding, using the transfer material of the present invention. 
First, as shown in FIG. 4, into a mold comprising the movable mold 409 and 
the fixed mold 410 is fed the transfer material 406 with the protecting 
layer 402 facing the inside, that is with the substrate sheet 401 
contacting the fixed mold 410. In this process, separate transfer 
materials 406 may be fed in one by one, or necessary portions of a long 
transfer material 406 may be fed in intermittently. 
When the long transfer material 406 is used, it is preferable to make the 
position of the picture layer of the transfer material 406 correspond to 
the mold by using a feeding apparatus having positioning mechanism. 
Further, if the position of the transfer material 406 is detected by a 
sensor when the transfer material 406 is fed in intermittently and 
thereafter the transfer material 406 is fixed by the movable mold 409 and 
the fixed mold 410, the transfer material 406 can be fixed constantly at 
the same position and deviation of the picture layer does not occur, 
therefore such process is convenient. 
The mold is closed, through a gate formed in the movable mold 409 is 
injected the molten resin 411 into the mold for filling, a molded article 
is formed and simultaneously to its surface is adhered the protecting 
layer 402 of the transfer material 406 or the adhesion layer formed on the 
surface thereof. 
Then, the resin molded article is cooled, the mold is opened and the resin 
molded article is taken out. Finally, the substrate sheet 401 is peeled, 
and the protecting layer 402 is cured by irradiation of an active energy 
ray. Otherwise, the substrate sheet 401 may be peeled after irradiation of 
an active energy ray. 
As an another embodiment of the present invention, there is an another 
method in which a molded article excellent in abrasion resistance and 
chemical resistance is produced, using the above-mentioned resin 
composition. In this method, there is used a surface protecting material 
comprising a substrate sheet having no releasing property and a protecting 
layer formed on it. The surface protecting material is produced using the 
same procedure and material as the transfer material except that a 
material having no releasing property is used as a substrate sheet and the 
adhesion layer is not formed on the protecting layer. 
As a substrate sheet having no releasing property, a sheet of an 
acryl-based resin, polycarbonate-based resin, vinyl chloride-based resin, 
urethane-based resin, polyester-based resin and the like can be used. 
An adhesion layer may optionally be formed on the surface on which the 
protecting layer is not formed, of the substrate sheet. The adhesion layer 
is formed using the same procedure and material as the transfer material 
except that it is formed on the surface of the substrate sheet. 
First, the surface protecting material 501 is placed to cover the molded 
article 502 with the protecting layer thereof facing above as shown in 
FIG. 5. Then, by using a heater 503 and the like, the surface protecting 
material 501 is heated to soften, and vacuum suction 504 is conducted from 
the lower side. By this procedure, the substrate sheet or the adhesion 
layer formed on it is adhered to the surface of the molded article 502. 
Finally, the protecting layer is cured by irradiating an active energy 
ray. 
Otherwise, pressure may be applied from the upper side of the surface 
protecting material 501 in addition to the vacuum suction 504 from the 
lower side. Pressure can be applied using a liquid or the like directly or 
further via a flexible sheet and the like. 
As in the case of the transfer material, a molded article excellent in 
abrasion resistance and chemical resistance can also be produced, by 
utilizing a simultaneous method in which transferring is conducted 
simultaneously with molding by injection molding. 
First, as shown in FIG. 6, into a mold comprising the movable mold 605 and 
the fixed mold 606 is fed the surface protecting material 601 with the 
protecting layer facing outside, that is with the protecting layer 
contacting the fixed mold 606. In this process, the same procedure as in 
the production method using the transfer material may be used. 
The mold is closed, through a gate formed in the movable mold 605 is 
injected the molten resin 607 into the mold for filling, a molded article 
is formed and simultaneously to its surface is adhered the substrate sheet 
of the surface protecting material 601 or the adhesion layer formed on the 
surface thereof. Then, the resin molded article is cooled, the mold is 
opened and the resin molded article is taken out. Finally, the protecting 
layer is cured by irradiating an active energy ray. 
EXAMPLES 
The present invention will be further specifically described by the 
following examples and comparative examples, however, the present 
invention is not restricted to them. In the examples, all "parts" and "%" 
are by weight. 
Example 1 
A polyester resin film having a thickness of 38 .mu.m was used as a 
substrate sheet. A melamine resin-based releasing agent was applied on the 
substrate sheet in a thickness of 1 .mu.m by using the gravure printing 
method to form a releasing layer, and a protecting layer composed of 200 
parts (solid content: 100 parts) of varnish A described below and 5 parts 
of 1,6-hexane diisocyanate trimer (trade name: Coronate HX, manufactured 
by Nippon Polyurethane Industry K.K.), and 5 parts of a 
photopolymerization initiator (trade name: Irgacure 184, manufactured by 
Ciba-Geigy Co., Ltd.), was formed thereon by using the gravure printing 
method. The thickness of the protecting layer was 5 .mu.m. The protecting 
layer was semi-cured by heating at 150.degree. C. for 20 seconds, and a 
picture layer composed of an acryl-based ink and an adhesion layer 
composed of an acrylic resin were formed in order by printing according to 
the gravure printing method to obtain a transfer material. 
The varnish A was obtained in the following method. First, into a reacting 
apparatus equipped with a stirring apparatus, cooling tube, dropping 
funnel and nitrogen introducing tube were charged 175 parts of glycidyl 
methacrylate (hereinafter, referred to as GMA), 75 parts of methyl 
methacrylate (hereinafter, referred to as MMA), 1.3 parts of lauryl 
mercaptan, 1000 parts of butyl acetate and 7.5 parts of 
2,2'-azobisisobutyronitrile(hereinafter, referred to as AIBN), and they 
were heated until the temperature in the content rose to about 90.degree. 
C. under nitrogen flow over 1 hour and kept at this temperature for 1 
hour. Then, from a dropping funnel previously charged with a mixture 
composed of 525 parts of GMA, 225 parts of MMA, 3.7 parts of lauryl 
mercaptan and 22.5 parts of AIBN, the mixture was dropped into the 
reacting apparatus over about 2 hours under nitrogen flow. The resulting 
mixture was kept at the same temperature for 3 hours. To this was added 10 
parts of AIBN and the mixture was kept at the temperature for 1 hour. 
Then, the mixture was heated up to 120.degree. C., and kept at the 
temperature for 2 hours. After cooling to 60.degree. C., the nitrogen 
introducing tube was changed to an air introducing rube, and 355 parts of 
acrylic acid (hereinafter, referred to as AA), 2.0 parts of methoquinone 
and 5.4 parts of triphenylphosphine were charged and mixed, then, the 
mixture was heated to 110.degree. C. under air bubbling. The mixture was 
kept at the same temperature for 8 hours, then, 1.4 parts of methoquinone 
was charged. The mixture was cooled, and to this was added ethyl acetate 
until the nonvolatile content reached to 50% to obtain the varnish A. The 
polymer contained in the varnish A had an acryl equivalent weight of 270 
g/eq, a hydroxyl value of 204 and a weight-average molecular weight (in 
terms of styrene by GPC) of 18000. 
This transfer material was transferred to the surface of a molded article 
by utilizing the simultaneous transferring and molding method, then, the 
substrate sheet was peeled, and ultraviolet ray was irradiated to 
completely cure the protecting layer. The molding conditions included a 
resin temperature of 240.degree. C., a mold temperature of 55.degree. C., 
and a resin pressure of about 300 kg/cm.sup.2. The raw material of the 
molded article was an acrylic resin, and it was molded into a tray-shaped 
article having a longitudinal length of 95 mm, a transverse length of 65 
mm, a rising edge height of 4.5 mm and R at the corner part of 2.5 mm. 
Irradiation conditions included 120 W/cm, six lamps, a lamp height of 10 
cm and a belt speed of 15 m/min. 
Example 2 
A polyester resin film having a thickness of 38 .mu.m was used as a 
substrate sheet. A melamine resin-based releasing agent was applied on the 
substrate sheet in a thickness of 1 .mu.m by using the gravure coating 
method to form a releasing layer, and a protecting layer composed of 200 
parts (solid content: 100 parts) of the varnish A and 10 parts of 
1,6-hexane diisocyanate trimer (trade name: Coronate HX, manufactured by 
Nippon Polyurethane Industry K.K.), and 5 parts of a photopolymerization 
initiator (trade name: Irgacure 184, manufactured by Ciba-Geigy Co., 
Ltd.), was formed thereon by using the lip coating-method. The thickness 
of the protecting layer was 5 .mu.m. The protecting layer was semi-cured 
by heating at 150.degree. C. for 20 seconds, and an anchor layer composed 
of an urethane-based ink, a picture layer composed of an acryl-based ink 
and an adhesion layer composed of an acrylic resin were formed in order by 
printing according to the gravure printing method to obtain a transfer 
material. 
This transfer material was transferred to the surface of a molded article 
according to the same manner as in Example 1, by utilizing the 
simultaneous transferring and molding method, then, the substrate sheet 
was peeled, and ultraviolet ray was irradiated to completely cure the 
protecting layer. Irradiation conditions included 120 W/cm, two lamps, a 
lamp height of 10 cm and a belt speed of 2.5 m/min. 
Example 3 
A molded article was produced in the same manner as in Example 1 except 
that varnish B was used instead of the varnish A of Example 1. The varnish 
B was prepared by changing the amount used of the monomer (GMA) in the 
initial charging to 250 parts, the amount used of the monomer (GMA) in the 
later charging to 750 parts, and the amount used of AA to 507 parts. The 
polymer contained in the varnish B had an acryl equivalent weight of 214 
g/eq, a hydroxyl value of 262 and a weight-average molecular weight of 
20000. 
Comparative Example A1 
A protecting layer composed of a silicon-based resin (TPR 6701.RTM. 
manufactured by Toshiba silicone K.K.) was formed into a layer by the 
gravure printing method on the same polyester film as used in Example 1. 
Then, this resin composition was completely cured by heating. A molded 
article was produced in the same manner as in Example 1 except that the 
resulting transfer material was used and ultraviolet irradiation was not 
conducted after molding. 
Comparative Example A2 
A protecting layer composed of an urethane acrylate having a polymerizable 
double bond, a reactive diluting agent and a photopolymerization initiator 
was formed into a layer by the gravure printing method on the same 
polyester film as used in Example 1. Then, this resin composition was 
completely cured by irradiation with ultraviolet ray. A molded article was 
produced in the same manner as in Example 1 except that the resulting 
transfer material was used and ultraviolet irradiation was not conducted 
after molding. Irradiation conditions in preparing the transfer material 
included 120 W/cm, two lamps, a lamp height of 5 cm, and a belt speed of 
20 m/min. 
Comparative Example A3 
A protecting layer composed of an urethane acrylate having a polymerizable 
double bond, a thermoplastic acrylic resin, and a photopolymerization 
initiator was formed into a layer by the gravure printing method on the 
same polyester film as used in Example 1. Then, this active energy ray 
curable resin composition was semi-cured by the first irradiation with 
ultraviolet ray. 
A molded article was produced in the same manner as in Example 1 except 
that the resulting transfer material was used. Irradiation conditions in 
preparing the transfer material included 120 W/cm, one lamp, a lamp height 
of 10 cm, and a belt speed of 50 m/min. 
Comparative Example B 
A molded article was produced in the same manner as in Example 1 except 
that varnish C was used instead of the varnish A. The varnish C was 
prepared by changing the amounts used of the monomers in the initial 
charging to 125 parts of GMA and 125 parts of MMA respectively, the 
amounts used of the monomers in the later charging to 375 parts of GMA and 
375 parts of MMA respectively, and the amount used of AA to 254 parts. The 
polymer contained in the varnish C had an acryl equivalent weight of 355 
g/eq, a hydroxyl value of 158 and a weight-average molecular weight of 
17000. 
Performance Test 
Crack occurrence, chemical resistance ability and abrasion resistance 
ability were evaluated with respect to the above-mentioned Examples 1 to 
3, Comparative Examples A1 to A3, and Comparative Example B (Table 1). 
Crack occurrence was evaluated by observing the condition of the surface 
of the molded article according to the following evaluation standards 
judged by naked eyes: .largecircle. no occurrence, .DELTA. occurred a 
little, .times. occurred much. 
Chemical resistance was evaluated by impregnating a gauze with methanol, 
observing the condition of the surface after 50 times reciprocating 
abrasion according to the following evaluation standards judged by naked 
eyes: .circleincircle. no occurrence, .largecircle. little occurrence, 
.DELTA. occurred a few, .times. occurred much. 
Abrasion resistance was evaluated by applying a load (100 g, 300 g) to a 
#000 steel wool of 1 cm square, observing the degree to be injured of the 
surface after 200 times reciprocating movements at the condition of 2 
reciprocation/second and a moving distance of 2 cm according to the 
following evaluation standards judged by naked eyes: .largecircle. good, 
.DELTA. relatively bad, .times. bad. 
TABLE 1 
______________________________________ 
Chemical Abrasion resistance 
Crack 
resistance 100 g 300 g 
______________________________________ 
Example 1 .smallcircle. 
.smallcircle. 
.smallcircle. 
.DELTA. 
Example 2 .smallcircle. .smallcircle. .smallcircle. .DELTA. 
Example 3 .smallcircle. .smallcircle. .smallcircle. .smallcircle. 
Comparative .DELTA. .DELTA. .DELTA. 
x 
Example A1 
Comparative x .smallcircle. .smallcircle. .smallcircle. 
Example A2 
Comparative .smallcircle. .DELTA. .DELTA. x 
Example A3 
Comparative .smallcircle. .smallcircle. x x 
Example B 
______________________________________ 
From the evaluation results of Table 1, the followings are evident. That 
is, the molded articles of Examples 1 to 3 having as the most outer layer 
a protecting layer composed of a heat reactant of the heat and active 
energy ray curable resin composition comprising as an active ingredient a 
polyfunctional isocyanate and a polymer having an acryl equivalent weight 
from 100 to 300 g/eq, a hydroxyl value from 20 to 500 and a weight-average 
molecular weight from 5000 to 50000 are excellent in abrasion resistance 
and chemical resistance, and have no cracks in the curved part of the 
molded article. However, the molded article of Comparative Example A1 has 
no sufficient result in any of crack occurrence, abrasion resistance and 
chemical resistance. The molded article of Comparative Example A2 has a 
lot of cracks while it is excellent in abrasion resistance and chemical 
resistance. The molded article of Comparative Example A3 is inferior in 
abrasion resistance and chemical resistance while it has no cracks. 
Further, the molded article of Comparative Example B having a protecting 
layer composed of a heat reactant of the conventional heat and active 
energy ray curable resin composition is also inferior in abrasion 
resistance, since the acryl equivalent weight of the polymer contained in 
the heat and active energy ray curable resin composition is over the 
specific range. 
Example 4 
An acrylic resin film having a thickness of 125 .mu.m was used as a 
substrate sheet. A picture layer composed of an acryl-based ink and an 
adhesion layer composed of an acrylic resin were formed by printing on the 
one surface of the substrate sheet in order according to the gravure 
printing method. A protecting layer obtained by blending 200 parts (solid 
component: 100 parts) of the varnish A obtained in Example 1 and 5 parts 
of 1,6-hexane diisocyanate trimer (trade name: Coronate HX, manufactured 
by Nippon Polyurethane Industry K.K.), and 5 parts of a 
photopolymerization initiator (trade name: Irgacure 184, manufactured by 
Ciba-Geigy Co., Ltd.), were formed by printing on the opposite surface of 
the substrate sheet according to the gravure printing method. The 
thickness of the protecting layer was 5 .mu.m. The protecting layer was 
semi-cured by heating at 80.degree. C. for 30 seconds to obtain a surface 
protecting material. 
This surface protecting material was adhered to the surface of a molded 
article by utilizing the insert molding method, then it was irradiated 
with ultraviolet ray. The molding conditions included a resin temperature 
of 220.degree. C., a mold temperature of 55.degree. C., and a resin 
pressure of about 300 kg/cm.sup.2. The raw material of the molded article 
was an acrylic resin, and it was molded into a tray-shaped article having 
a longitudinal length of 95 mm, a transverse length of 65 mm, a rising 
edge height of 4.5 mm and R at the corner part of 2.5 mm. Irradiation 
conditions included 120 W/cm, six lamps, a lamp height of 10 cm and a belt 
speed of 15 m/min. 
Example 5 
An acrylic resin film having a thickness of 125 .mu.m was used as a 
substrate sheet. A picture layer composed of an acryl-based ink and an 
adhesion layer composed of an acrylic resin were formed by printing on the 
one surface of the substrate sheet in order according to the gravure 
printing method. A protecting layer obtained by blending 200 parts (solid 
component: 100 parts) of the varnish A obtained in Example 1 and 10 parts 
of 1,6-hexane diisocyanate trimer (trade name: Coronate HX, manufactured 
by Nippon Polyurethane Industry K.K.), and 5 parts of a 
photopolymerization initiator (trade name: Irgacure 184, manufactured by 
Ciba-Geigy Co., Ltd.), were formed by printing on the opposite surface of 
the substrate sheet according to the lip coating method. The thickness of 
the protecting layer was 5 .mu.m. The protecting layer was semi-cured by 
heating at 80.degree. C. for 30 seconds to obtain a surface protecting 
material. 
This surface protecting material was adhered to the surface of a molded 
article by utilizing the insert molding method according to the same 
manner as in Example 4, then it was irradiated with ultraviolet ray. 
Irradiation conditions included 120 W/cm, two lamps, a lamp height of 10 
cm and a belt speed of 2.5 m/min. 
Example 6 
A molded article was produced in the same manner as in Example 4 except 
that the varnish B obtained in Example 3 was used instead of the varnish A 
of Example 4. 
Comparative Example C1 
A protecting layer composed of a silicon-based resin (TPR 6701.RTM. 
manufactured by Toshiba silicone K.K.) was formed into a layer by the 
gravure printing method on the same acrylic resin film as used in Example 
4. Then, this resin composition was completely cured by heating. A molded 
article was produced in the same manner as in Example 4 except that the 
resulting surface protecting material was used and ultraviolet irradiation 
was not conducted after molding. 
Comparative Example C2 
A protecting layer composed of an urethane acrylate having a polymerizable 
double bond, a reactive diluting agent and a photopolymerization initiator 
was formed into a layer by the gravure printing method on the same acrylic 
film as used in Example 4. Then, this resin composition was completely 
cured by irradiation with ultraviolet ray. A molded article was produced 
in the same manner as in Example 4 except that the resulting surface 
protecting material was used and ultraviolet irradiation was not conducted 
after molding. Irradiation conditions in preparing the transfer material 
included 120 W/cm, two lamps, a lamp height of 5 cm, and belt speed of 20 
m/min. 
Comparative Example C3 
A protecting layer composed of an urethane acrylate having a polymerizable 
double bond a thermoplastic acrylic resin, and a photopolymerization 
initiator was formed into a layer by the gravure printing method on the 
same acrylic resin film as used in Example 4. Then, this active energy ray 
curable resin composition was semi-cured by the first irradiation with 
ultraviolet ray. 
A molded article was produced in the same manner as in Example 4 except 
that the resulting surface protecting material was used. Irradiation 
conditions in preparing the transfer material included 120 W/cm, one lamp, 
a lamp height of 10 cm, and belt speed of 50 m/min. 
Comparative Example D 
A molded article was produced in the same manner as in Example 4 except 
that the varnish C obtained in Comparative Example B was used instead of 
the varnish A of Example. 
Performance Test 
Crack occurrence, chemical resistance ability and abrasion resistance 
ability were evaluated with respect to the above-mentioned Examples 4 to 
6, Comparative Examples C1 to C3, and Comparative Example D (Table 2). The 
evaluation standards were the same as those of Example 1. 
TABLE 2 
______________________________________ 
Chemical Abrasion resistance 
Crack 
resistance 100 g 300 g 
______________________________________ 
Example 4 .smallcircle. 
.circleincircle. 
.circleincircle. 
.smallcircle. 
Example 5 .smallcircle. .circleincircle. .circleincircle. .smallcircle. 
Example 6 .smallcircle. .circleincircle. .circleincircle. .circleincircl 
e. 
Comparative .DELTA. .DELTA. .DELTA. x 
Example C1 
Comparative x .smallcircle. .smallcircle. .smallcircle. 
Example C2 
Comparative .smallcircle. .DELTA. .DELTA. x 
Example C3 
Comparative .smallcircle. .smallcircle. x x 
Example D 
______________________________________ 
From the evaluation results of Table 2, the followings are evident. That 
is, the molded articles of Examples 4 to 6 having as the most outer layer 
a protecting layer composed of a heat reactant of the heat and active 
energy ray curable resin composition comprising as an active ingredient a 
polyfunctional isocyanate and a polymer having an acryl equivalent weight 
from 100 to 300 g/eq, a hydroxyl value from 20 to 500 and a weight-average 
molecular weight from 5000 to 50000 are excellent in abrasion resistance 
and chemical resistance, and have no cracks in the curved part of the 
molded article. However, the molded article of Comparative Example C1 has 
no sufficient result in any of crack occurrence, abrasion resistance and 
chemical resistance. The molded article of Comparative Example C2 has a 
lot of cracks while it is excellent in abrasion resistance and chemical 
resistance. The molded article of Comparative Example C3 is inferior in 
abrasion resistance and chemical resistance while it has no cracks. 
Further, the molded article of Comparative Example D having a protecting 
layer composed of a heat reactant of the conventional heat and active 
energy ray curable resin composition is also inferior in abrasion 
resistance since the acryl equivalent weight of the polymer contained in 
the heat and active energy ray curable resin composition is over the 
specific range. 
Example 7 
A polyester resin film having a thickness of 38 .mu.m was used as a 
substrate sheet. A melamine resin-based releasing agent was applied on the 
substrate sheet in a thickness of 1 .mu.m by using the gravure printing 
method to form a releasing layer, and a protecting layer composed of 200 
parts (solid content: 100 parts) of the varnish B obtained in Example 3, 
and 10 parts of 1,6-hexane diisocyanate trimer (trade name: Coronate HX, 
manufactured by Nippon Polyurethane Industry K.K.), and 5 parts of a 
photopolymerization initiator (trade name: Irgacure 184, manufactured by 
Ciba-Geigy Co., Ltd.), 8 parts of the following UV absorber A, and 2 parts 
of a photostabilizer was formed thereon by using the lip coating method. 
The thickness of the protecting layer was 5 .mu.m. The protecting layer 
was semi-cured by heating at 150.degree. C. for 20 seconds, and an anchor 
layer composed of an urethane-based ink, a picture layer composed of an 
acryl-based ink and an adhesion layer composed of an acrylic resin were 
formed in order by printing according to the gravure printing method to 
obtain a transfer material. 
UV Absorber A 
Hydroxyphenylbenzotriazol represented by the formula: 
##STR3## 
This transfer material was transferred to the surface of a molded article 
by utilizing the simultaneous transferring and molding method, then, the 
substrate sheet was peeled, and ultraviolet ray was irradiated to 
completely cure the protecting layer. The molding conditions included a 
resin temperature of 240.degree. C., a mold temperature of 55.degree. C., 
and a resin pressure of about 300 kg/cm.sup.2. The raw material of the 
molded article was an acrylic resin, and it was molded into a tray-shaped 
article having a longitudinal length of 95 mm, a transverse length of 65 
mm, a rising edge height of 4.5 mm and R at the corner part of 2.5 mm. 
Irradiation conditions included 120 W/cm, two lamps, a lamp height of 10 
cm and a belt speed of 2.5 m/min. 
Example 8 
A molded article was produced in the same manner as in Example 7, except 
that the following UV absorber B was used instead of the UV absorber A of 
Example 7. 
UV Absorber B 
Hydroxyphenyl-S-triazine represented by the formula: 
##STR4## 
Comparative Example E1 
A molded article was produced in the same manner as in Example 7, except 
that the UV absorber C: 
2-(2'-Hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole was used 
instead of the UV absorber A of Example 7. 
Comparative Example E2 
A molded article was produced in the same manner as in Example 7, except 
that the UV absorber D: 
Ethandiamide-N-(2-ethoxyphenyl)-N'-(4-isododecylphenyl)-(oxalicanilide) 
was used instead of the UV absorber A of Example 7. 
Comparative Example E3 
A molded article was produced in the same manner as in Example 7, except 
that the UV absorber E: 2,2',4,4'-Tetrahydroxybenzophenone was used 
instead of the UV absorber A of Example 7. 
Comparative Example F 
A molded article was produced in the same manner as in Example 7, except 
that no UV absorber was used. 
Performance Test 
Yellow resistance (light resistance, or weather resistance), abrasion 
resistance, and transparency were evaluated with respect to the 
above-mentioned Examples 7 and 8, Comparative Examples E1 to E3, and 
Comparative Example F (Table 3). 
The yellow resistance was evaluated by the colour difference .DELTA.E as 
defined by the formula: 
EQU .DELTA.E=.sqroot. (.DELTA.L.sup.2 +.DELTA.a.sup.2 +.DELTA.b.sup.2) 
The values of .DELTA.L, .DELTA.a, and .DELTA.b are determined by measuring 
the values L, a, and b of the protecting layer before and after the light 
resistance test, by using the spectroscopic colour difference meter 
"SZ-.SIGMA.80" manufactured by Nippon Denshoku Kogyo K.K. 
Condition of Light Resistance Test 
Apparatus: I Super UV Tester (Iwasaki Denki K.K.) 
UV intensity: 100 mw/cm.sup.2 
Temperature: 75.degree. C. 
Period: 80 hours 
Abrasion resistance was evaluated by applying a load (300 g) to a #000 
steel wool of 1 cm square, observing the degree to be injured of the 
surface after 200 times reciprocating movements at the condition of 2 
reciprocation/second and a moving distance of 2 cm, according to the 
following evaluation standards judged by naked eyes: .largecircle. good, 
.DELTA. relatively bad, .times. bad. 
Transparency was evaluated by observing the protecting layers which 
contains the UV absorber in equal amounts, according to the following 
evaluation standards judged by naked eyes: .largecircle. transparent, 
.DELTA. rather translucent, .times. much translucent. 
TABLE 3 
______________________________________ 
Yellow Abrasion 
resistance resistance Transparency 
______________________________________ 
Example 7 20 .smallcircle. 
.smallcircle. 
Example 8 20 .smallcircle. .smallcircle. 
Comparative 39 .DELTA. x 
Example E1 
Comparative 43 .DELTA. .DELTA. 
Example E2 
Comparative 36 x .DELTA. 
Example E3 
Comparative 45 .smallcircle. -- 
Example F 
______________________________________ 
From the evaluation results of Table 3, the followings are evident. That 
is, Example 7 in which the protecting layer contains UV absorber A, and 
Example 8 in which the protecting layer contains UV absorber B are 
excellent in all of the yellow resistance, abrasion resistance, and 
transparency. However, Comparative Examples E1to E3 are poor in all of the 
yellow resistance, abrasion resistance, and transparency. Comparative 
Example F is excellent in abrasion resistance, but poor in yellow 
resistance. 
Example 9 
An acrylic resin film having a thickness of 125 .mu.m was used as a 
substrate sheet. A picture layer composed of an acryl-based ink, and an 
adhesion layer composed of an acrylic resin were formed by printing on the 
one surface of the substrate sheet in order according to the gravure 
printing method. A protecting layer obtained by blending 200 parts (solid 
component: 100 parts) of the varnish B obtained in Example 3, 10 parts of 
1,6-hexane diisocyanate trimer (trade name: Coronate HX, manufactured by 
Nippon Polyurethane Industry K.K.), and 5 parts of a photopolymerization 
initiator (trade name: Irgacure 184, manufactured by Ciba-Geigy Co., 
Ltd.), 8 parts of the UV absorber A as in Example 7, 2 parts of a 
photostabilizer was formed by printing on the opposite surface of the 
substrate sheet according to the lip coating method. The thickness of the 
protecting layer was 5 .mu.m. The protecting layer was semi-cured by 
heating at 80.degree. C. for 30 seconds to obtain a surface protecting 
material. 
This surface protecting material was adhered to the surface of a molded 
article by utilizing the insert molding method, then the protecting layer 
was irradiated with ultraviolet ray to completely cure. The molding 
conditions included a resin temperature of 220.degree. C., a mold 
temperature of 55.degree. C., and a resin pressure of about 300 
kg/cm.sup.2. The raw material of the molded article was an acrylic resin, 
and it was molded into a tray-shaped article having a longitudinal length 
of 95 mm, a transverse length of 65 mm, a rising edge height of 4.5 mm and 
R at the corner part of 2.5 mm. Irradiation conditions included 120 W/cm, 
two lamps, a lamp height of 10 cm, and a belt speed of 2.5 m/min. 
Example 10 
A molded article was produced in the same manner as in Example 9, except 
that the UV absorber B of Example 8 was used instead of the UV absorber A 
of Example 9. 
Comparative Example G1 
A molded article was produced in the same manner as in Example 9, except 
that the UV absorber C of Comparative Example E1 was used instead of the 
UV absorber A of Example 9. 
Comparative Example G2 
A molded article was produced in the same manner as in Example 9, except 
that the UV absorber D of Comparative Example E2 was used instead of the 
UV absorber A of Example 9. 
Comparative Example G3 
A molded article was produced in the same manner as in Example 9, except 
that the UV absorber E of Comparative Example E3 was used instead of the 
UV absorber A of Example 9. 
Comparative Example H 
A molded article was produced in the same manner as in Example 9, except 
that no UV absorber was used. 
Performance Test 
Yellow resistance, abrasion resistance, and transparency were evaluated 
with respect to the above-mentioned Examples 9 and 10, Comparative 
Examples G1 to G3, and Comparative Example H (Table 4). The evaluation 
standards were the same as those of Example 7. 
TABLE 4 
______________________________________ 
Yellow Abrasion 
resistance resistance Transparency 
______________________________________ 
Example 9 20 .circleincircle. 
.smallcircle. 
Example 10 20 .circleincircle. .smallcircle. 
Comparative 39 .DELTA. x 
Example G1 
Comparative 43 .DELTA. .DELTA. 
Example G2 
Comparative 36 x .DELTA. 
Example G3 
Comparative 45 .circleincircle. -- 
Example H 
______________________________________ 
From the evaluation results of Table 4, the followings are evident. That 
is, Example 9 in which the protecting layer contains UV absorber A, and 
Example 10 in which the protecting layer contains UV absorber B are 
excellent in all of the yellow resistance, abrasion resistance, and 
transparency. However, Comparative Examples G1 to G3 are poor in all of 
the yellow resistance, abrasion resistance, and transparency. Comparative 
Example H is excellent in abrasion resistance, but poor in yellow 
resistance. 
TECHNICAL EFFECTS OF THE INVENTION 
The sheet material of the present invention has a protecting layer which is 
composed of a heat reactant of a heat and active energy ray curable resin 
composition comprising as an active ingredient a polyfunctional isocyanate 
and a polymer having a (meth)acryl equivalent weight from 100 to 300 g/eq, 
a hydroxyl value from 20 to 500 and a weight-average molecular weight from 
5000 to 50000. And, this protecting layer transferred to the surface of a 
molded article is cured by active energy ray irradiation. Therefore, a 
molded article excellent in abrasion resistance and chemical resistance 
can be obtained, and cracking is not caused in the curved part of the 
molded article. Further, since the protecting layer is cured in part by 
heat in transfer material production, a large scale active energy ray 
irradiation apparatus is not required in active energy ray irradiation to 
realize low cost.