Electrophotographic dry toner

A dry toner for use in electrophotography including a coloring agent and a polyol resin serving as a binder resin, which has a main chain portion containing an epoxy resin moiety and an alkylene oxide moiety, and protected terminal portions bonded to the main chain portion.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a dry toner for use in electrophotography. 
2. Discussion of Background 
In accordance with a dry-type electrophotographic method, latent 
electrostatic images are formed on a photoconductor by a conventional 
method, and the latent electrostatic images are developed into visible 
toner images with a dry toner. Then, the toner images are transferred to a 
sheet of copy paper and fixed thereon, for instance, by the application of 
heat using heat-application means such as a heated roller. 
The dry toner for use with the above-mentioned electrophotographic method 
comprises a binder resin and a coloring agent as the main components, and 
when necessary, may further comprise other additives such as a charge 
controlling agent and an offset-preventing agent. When various 
characteristics required for the dry toner, namely, transparency, 
electrical insulating properties, water resistance, fluidity of particles, 
mechanical strength, glossiness, thermoplasticity, and grindability are 
taken into consideration, polystyrene, styrene-acrylic copolymer, 
polyester resin and epoxy resin are generally used as the binder agents 
for the dry toner. In particular, styrene-based resins are widely employed 
because the grindability, water resistance and fluidity are superior to 
others. However, in the case where toner images are formed on a sheet of 
copy paper using a toner comprising the styrene-based resin as the binder 
resin, and thereafter the toner-image-bearing sheet is held between a 
document folder made from a vinyl chloride resin for a long period of 
time, the vinyl chloride folder is stained with the toner images when the 
toner-image-bearing sheet is taken out of the folder. The reason for this 
problem is that a plasticizer contained in the vinyl chloride resin is 
transferred to the toner images and plasticizes the same while the toner 
images are brought into contact with the vinyl chloride folder. 
Consequently, the toner images are partially or entirely peeled from the 
copy paper and attached to the vinyl chloride folder. The same problem as 
mentioned above is produced when the toner comprising the polyester resin 
as the binder resin is employed. 
To solve the above-mentioned problem, it is proposed to mix the 
styrene-based resin or polyester resin with an epoxy resin which is not 
plasticized by the plasticizer for use in the vinyl chloride resin, as 
disclosed in Japanese Laid-Open Patent Applications 60-263951 and 
61-24025. 
However, when different kinds of resins are contained in a toner 
composition, especially for a color toner, the offset properties, 
pigmentation, light transmission properties and coloring characteristics 
considerably deteriorate because of incompatibility between the different 
kinds of resins. Furthermore, a toner-image-bearing sheet readily curls 
after image-fixing process, and the glossiness of the obtained toner image 
decreases. The color toner images which are not provided with appropriate 
gloss appear to be poor in quality. 
All the aforementioned problems cannot be solved by using not only any 
conventionally known epoxy resin, but also an acetyl-modified epoxy resin 
as disclosed in Japanese Laid-Open Patent Application 61-235852. 
In the case where the epoxy resin is used alone as the binder resin in the 
dry toner, the reactivity of the epoxy resin and amine causes some 
problems. 
More specifically, the epoxy resin is commonly used as a cured resin in 
such a manner that epoxy group in the epoxy resin is allowed to react with 
a curing agent to form a crosslinking structure, so that excellent 
mechanical strength and chemical resistance can be imparted to the cured 
epoxy resin. The above-mentioned curing agent is roughly classified into 
two groups, that is, an amine-containing compound and an organic acid 
anhydride. 
When the epoxy resin serving as the thermoplastic resin is kneaded with an 
amine-containing dye, pigment or charge controlling agent for the 
preparation of a toner composition, there is the problem that the epoxy 
resin may cause the crosslinking reaction with such an amine-containing 
component in the kneading process. The toner thus obtained is not 
available for use in practice. Further, the epoxy resin irritates the skin 
because of the biochemical activity of epoxy group, so that it is 
necessary to handle the epoxy resin with the utmost care. 
Furthermore, water absorption of the epoxy resin becomes striking under the 
circumstances of high temperature and humidity because of the hydrophilic 
nature of epoxy group. Under such circumstances, therefore, the charging 
characteristics of the toner are decreased, the toner deposition on the 
background of the photoconductor takes place, and the cleaning of the 
photoconductor cannot be successfully carried out. In addition, the 
charging stability of the toner is poor when the epoxy resin is used as 
the binder resin in the toner. 
To prepare a toner composition, a mixture of a coloring agent such as a dye 
or pigment, a charge controlling agent and a binder resin is generally 
kneaded in a heated roll mill to uniformly disperse the coloring agent and 
the charge controlling agent in the binder resin. Some dyes and pigments 
have the charge controlling characteristics, and such dyes and pigments 
function both as the coloring agent and the charge controlling agent. When 
the epoxy resin is used as the binder resin, it is difficult to thoroughly 
disperse the coloring agent and the charge controlling agent in the epoxy 
resin. Poor dispersion of the coloring agent decreases the pigmentation 
and impairs the coloring characteristics of the toner. In addition, when 
the charge controlling agent is not sufficiently dispersed in the binder 
resin, the toner cannot uniformly be charged. Consequently, the charging 
failure occurs, the toner deposition on the background and scattering of 
toner particles in the copying machine easily take place, the obtained 
toner images are lacking in image density and evenness, and the cleaning 
of the photoconductor cannot be successfully carried out. 
There is proposed a toner comprising as a binder resin an ester-modified 
epoxy resin which is prepared by reacting an epoxy resin and 
.epsilon.-caprolactone, as disclosed in Japanese Laid-Open Patent 
Application 61-219051. In this case, the transfer of the toner image 
formed on the copy paper toward a vinyl chloride material can be 
prevented, and the fluidity of toner particles can be increased. However, 
the amount of the ester-modified epoxy resin is as high as 15 to 90 wt. % 
of the entire weight of the epoxy resin, so that the softening point of 
the obtained toner is extremely decreased, and the obtained images become 
too glossy. 
A positively-chargeable resin for use in the toner is proposed, as 
disclosed in Japanese Laid-Open Patent Application 52-86334, which resin 
is obtained by allowing aliphatic primary or secondary amine to react with 
terminal epoxy group of a conventional epoxy resin. However, the epoxy 
group and the amine cause the crosslinking reaction, as previously 
described, so that the toner thus prepared may not be suitable for use in 
practice. 
As disclosed in Japanese Laid-Open Patent Application 52-156632, it is 
proposed that at least one terminal epoxy group of the epoxy resin is 
allowed to react with an alcohol, a phenol, a Grignard reagent, an organic 
acid, a sodium acetylide, and an alkyl chloride. In this case, when one of 
the terminal epoxy groups is not capped, the problems of the reactivity of 
the epoxy group with amine, the toxicity, and the hydrophilic nature 
remain unsolved. In addition, all of the above-mentioned reaction products 
of the epoxy resin are not effective as the binder resin for use in the 
dry toner because some of them are hydrophilic, or have an adverse effect 
on the charging characteristics and the grindability of the toner. 
As disclosed in Japanese Laid-Open Patent Application 1-267560, a resin for 
use in the toner is prepared by allowing both terminal epoxy groups of an 
epoxy resin to react with an active-hydrogen-containing monovalent 
compound, and esterifying the reaction product thus obtained by use of a 
monocarboxylic acid or ester derivatives thereof, and a lactone. Although 
the problems of the reactivity with amine, the toxicity, and the 
hydrophilic nature, of the epoxy resin can be solved, the curling problem 
of the toner image after image-fixing remains unsolved. 
SUMMARY OF THE INVENTION 
Accordingly, a first object of the present invention is to provide an 
electrophotographic dry toner capable of producing images with excellent 
color reproducibility and uniform glossiness. 
A second object of the present invention is to provide a dry toner which is 
unsusceptible to an amine compound and biochemically stable. 
A third object of the present invention is to provide a dry toner with 
excellent environmental stability. 
A fourth object of the present invention is to provide a dry toner capable 
of producing toner images which are not transferred to a vinyl chloride 
sheet even when the toner images are brought into contact with the vinyl 
chloride sheet. 
A fifth object of the present invention is to provide a dry toner capable 
of forming toner images on an image-receiving sheet through the 
image-fixing process without the curling problem. 
The above-mentioned objects of the present invention can be achieved by a 
dry toner for use in electrophotography comprising a coloring agent, and a 
polyol resin serving as a binder resin, which comprises a main chain 
portion comprising an epoxy resin moiety and an alkylene oxide moiety, and 
protected terminal portions bonded to the main chain portion. 
In the first mentioned electrophotographic dry toner, the polyol resin may 
be a reaction product of an epoxy resin, an alkylene oxide adduct of a 
dihydric phenol or a glycidyl ether of the alkylene oxide adduct, a 
compound including in the molecule thereof one active hydrogen atom which 
is capable of reacting with epoxy group, and a compound including in the 
molecule thereof at least two active hydrogen atoms which are capable of 
reacting with epoxy group. 
In the second mentioned electrophotographic dry toner, the epoxy resin for 
use in the polyol resin may comprise at least two kinds of bisphenol A 
type epoxy resin components with different number-average molecular 
weights, which are obtained by polymerizing bisphenol A as a polymerizable 
monomer. 
In the above-mentioned electrophotographic dry toner, the lowest of the 
number-average molecular weights of the bisphenol A type epoxy resin 
components may be in the range from 360 to 2,000, and the highest of the 
number-average molecular weights of the bisphenol A type epoxy resin 
components may be in the range from 3,000 to 10,000. In addition, the 
amount of the bisphenol A type epoxy resin component with the lowest 
number-average molecular weight may be in the range from 20 to 50 wt. % of 
the amount of the polyol resin, and the amount of the bisphenol A type 
epoxy resin component with the highest number-average molecular weight may 
be in the range from 5 to 40 wt. % of the amount of the polyol resin. 
In the second mentioned dry toner, the alkylene oxide adduct of the 
dihydric phenol or glycidyl ether thereof may be a compound of formula 
(1): 
##STR1## 
wherein R is 
##STR2## 
and n and m are integers of 1 or more, provided that (n+m) is 2 to 6. 
In the second mentioned dry toner, the amount of the alkylene oxide adduct 
of the dihydric phenol or glycidyl ether thereof may be in the range of 10 
to 40 wt. % of the amount of the polyol resin. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
The polyol resin for use in the dry toner of the present invention 
comprises a main chain portion comprising an alkylene oxide moiety and an 
epoxy resin moiety, and protected terminal portions bonded to the main 
chain portion. Therefore, the environmental stability and image-fixing 
properties of the dry toner are improved. In addition, the toner image is 
not transferred to a vinyl chloride sheet although the toner image is 
brought into contact with the vinyl chloride sheet. Furthermore, when the 
binder resin for use in the present invention is used for a color toner 
composition, the color images with excellent color reproducibility and 
uniform glossiness can be obtained, and these color images are fixed on an 
image-receiving medium without curling problem. 
The aforementioned polyol resin may be a reaction product of (1) an epoxy 
resin, (2) an alkylene oxide adduct of a dihydric phenol or a glycidyl 
ether of the alkylene oxide adduct, (3) a compound including in the 
molecule thereof one active hydrogen atom which is capable of reacting 
with epoxy group, and (4) a compound including in the molecule thereof at 
least two active hydrogen atoms which are capable of reacting with epoxy 
group. 
An epoxy resin prepared by allowing a bisphenol, for example, bisphenol A 
or bisphenol F, to react with epichlorohydrin is preferably employed for 
the preparation of the polyol resin for use in the present invention. 
To obtain stable image-fixing properties and uniform glossiness of the 
obtained images, it is preferable that the epoxy resin for use in the 
polyol resin comprise at least two kinds of epoxy resin components with 
different number-average molecular weights, which are obtained by 
polymerizing bisphenol A as a polymerizable monomer. This kind of epoxy 
resins will be referred to as bisphenol A type epoxy resins. 
In the case where a plurality of bisphenol A type epoxy resin components 
are employed for the preparation of the polyol resin, the lowest of the 
number-average molecular weights of the bisphenol A type epoxy resin 
components is preferably in the range from 360 to 2,000, and the highest 
of the number-average molecular weights of the bisphenol A type epoxy 
resin components is preferably in the range from 3,000 to 10,000. In 
addition, the amount of the bisphenol A type epoxy resin component with 
the lowest number-average molecular weight is preferably in the range from 
20 to 50 wt. % of the amount of the polyol resin, and the amount of the 
bisphenol A type epoxy resin component with the highest number-average 
molecular weight is preferably in the range from 5 to 40 wt. % of the 
amount of the polyol resin. 
When the number-average molecular weight and the amount ratio of the 
bisphenol A type epoxy resin component with the lowest molecular weight 
are controlled within the above range, the glossiness of the obtained 
toner image is proper for use in practice, and the preservability of the 
toner is not decreased. When the number-average molecular weight and the 
amount ratio of the bisphenol A type epoxy resin component with the 
highest molecular weight are controlled within the above range, the proper 
glossiness of the toner image can be obtained and the image-fixing 
properties of the toner image are not decreased. 
As the alkylene oxide adduct of the dihydric phenol used to prepare the 
polyol resin, a reaction product of an alkylene oxide such as ethylene 
oxide, propylene oxide, butylene oxide or a mixture thereof, and a 
bisphenol such as bisphenol A or bisphenol F is available. The alkylene 
oxide adduct of the dihydric phenol thus obtained may be allowed to react 
with epichlorohydrin or .beta.-methylepichlorohydrin. In particular, a 
diglycidyl ether of the alkylene oxide adduct of bisphenol A having the 
following formula (1) is preferable: 
##STR3## 
wherein R is 
##STR4## 
and n and m are integers of 1 or more, provided that (n+m) is 2 to 6. 
It is preferable that the amount of the alkylene oxide adduct of the 
dihydric phenol or the glycidyl ether of the alkylene oxide adduct be in 
the range of 10 to 40 wt. % of the amount of the polyol resin. In the case 
where the amount ratio of the alkylene oxide adduct of the dihydric phenol 
or the glycidyl ether thereof is within the above range, the curling 
problem can efficiently be prevented. In addition, when the sum of n and m 
in formula (1) is within the range from 2 to 6, the toner image can be 
provided with a proper glossiness, and the decrease of preservability of 
the toner can be avoided. 
As the compound including in the molecule thereof one active hydrogen atom 
which is capable of reacting with epoxy group, which is used to prepare 
the polyol resin, a monohydric phenol, a secondary amine and a carboxylic 
acid can be employed. 
Examples of the monohydric phenol are phenol, cresol, isopropylphenol, 
aminophenol, nonylphenol, dodecylphenol, xylenol, and p-cumylphenol. 
Examples of the secondary amine are diethylamine, dipropylamine, 
dibutylamine, N-methyl(ethyl)-piperazine and piperidine. 
Examples of the carboxylic acid are propionic acid and caproic acid. 
The combination of various kinds of materials is possible to obtain the 
polyol resin for use in the present invention which has an epoxy resin 
moiety and an alkylene oxide moiety in the main chain thereof. For 
instance, an epoxy resin having at both ends glycidyl group and an 
alkylene oxide adduct of a dihydric phenol having at both ends glycidyl 
group may be allowed to react with a dihalide, diisocyanate, diamine, 
dithiol, polyhydric phenol, or dicarboxylic acid. Particularly, the 
reaction with a dihydric phenol is most preferable from the viewpoint of 
reaction stability. In this case, it is also preferable that the dihydric 
phenol may be used in combination with a polyhydric phenol and a 
polyvalent carboxylic acid as long as the obtained reaction product does 
not set to gel. The amount of the polyhydric phenol and polyvalent 
carboxylic acid is preferably 15 wt. % or less, more preferably 10 wt. % 
or less, of the entire weight of the dihydric phenol, the polyhydric 
phenol and the polyvalent carboxylic acid. 
For the compound including in the molecule thereof at least two active 
hydrogen atoms which are capable of reacting with epoxy group, a dihydric 
phenol, a polyhydric phenol and a polyvalent carboxylic acid can be 
employed. 
Specific examples of the dihydric phenol are bisphenol A and bisphenol F. 
Specific examples of the polyhydric phenol are o-cresol novolak, phenol 
novolak, tris(4-hydroxyphenyl)methane, and 
1-[.alpha.-methyl-.alpha.-(4-hydroxyphenyl)ethyl]benzene. 
Specific examples of the polyvalent carboxylic acid are malonic acid, 
succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, 
phthalic acid, terephthalic acid, trimellitic acid, and anhydrotrimellitic 
acid. 
Any conventionally known dyes and pigments can be used as the coloring 
agents for use in the dry toner of the present invention. Examples of the 
dyes and pigments are carbon black, nigrosine dyes, black iron oxide, 
Naphthol Yellow S, Hansa Yellow (10G, 5G, G), cadmium yellow, yellow iron 
oxide, yellow ochre, chrome yellow pigment, Titan Yellow, Oil Yellow, 
Hansa Yellow (GR, A, RN, R), Pigment Yellow L, Benzidine Yellow (G, GR), 
Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, 
Quinoline Yellow Lake, Anthragen Yellow BGL, isoindolinone yellow, red 
oxide, red lead oxide, red lead, cadmium red, cadmium mercury red, 
antimony red, Permanent Red 4R, Para Red, Fire Red, 
p-chloro-o-nitroaniline red, Lithol Fast Scarlet G, Brilliant Fast 
Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), 
Fast Scarlet VD, Vulcan Fast Rubine B, Brilliant Scarlet G, Lithol Rubine 
GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 
5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 
10B, BON Maroon Light, BON Maroon Medium, eosine lake, Rhodamine Lake B, 
Rhodamine Lake Y, Alizarine Lake, Thioindigo Red B, Thioindigo Maroon, Oil 
Red, quinacridone red, Pyrazolone Red, Chrome Vermilion, Benzidine Orange, 
Perynone Orange, Oil Orange, cobalt blue, cerulean blue, Alkali Blue Lake, 
Peacock Blue Lake, Victoria Blue Lake, metal-free phthalocyanine blue, 
Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), indigo, 
ultramarine, Prussian blue, Anthraquinone Blue, Fast Violet B, Methyl 
Violet Lake, cobalt violet, manganese violet, dioxazine violet, 
Anthraquinone Violet, chrome green, zinc green, chrome oxide green, 
Persian, emerald green, Pigment Green B, Naphthol Green B, Green Gold, 
Acid Green Lake, Malachite Green Lake, Phthalocyanine Green, Anthraquinone 
Green, titanium oxide, zinc white, and lithopone. These dyes and pigments 
can be used in combination. 
It is preferable that the amount of the coloring agent be in the range of 
0.1 to 50 parts by weight to 100 parts by weight of the binder resin. 
The dry toner according to the present invention may further comprise a 
charge controlling agent. Any conventional charge controlling agents can 
be used in the present invention. For instance, a nigrosine dye, a 
triphenylmethane dye, a chromium-containing metal complex dye, a molybdic 
acid chelate pigment, a rhodamine dye, an alkoxyamine, a quaternary 
ammonium salt including a fluorine-modified quaternary ammonium salt, 
alkylamide, phosphorus and a phosphorus-containing compound, tungsten and 
a tungsten-containing compound, a fluorine-containing active material, and 
a metallic salt of salicylic acid and a metallic salt of a salicylic acid 
derivative are usable. 
In addition, the toner of the present invention may further comprise 
additives, for example, colloidal silica, hydrophobic silica, fatty acid 
metallic salts such as zinc stearate and aluminum stearate, metallic 
oxides such as titanium oxide, aluminum oxide, tin oxide and antimony 
oxide, and fluoropolymers. 
The dry toner of the present invention can be used for a one-component 
developer, or a two-component developer in combination with a carrier 
component. For the carrier component, the conventionally known materials 
such as iron powders, ferrite particles and glass beads can be employed. 
These carrier particles may be coated with a resin, such as 
polyfluorocarbon, polyvinyl chloride, polyvinylidene chloride, phenolic 
resin, polyvinyl acetal or silicone resin. In this case, it is proper that 
the amount of the toner be in the range of 0.5 to 6.0 parts by weight to 
100 parts by weight of the carrier. 
Other features of this invention will become apparent in the course of the 
following description of exemplary embodiments which are given for 
illustration of the invention and are not intended to be limiting thereof. 
Synthesis Example 1 
Synthesis of polyol resin No. 1 
A mixture of the following components was placed in a separable flask 
equipped with a stirrer, a thermometer, a nitrogen-introducing inlet and a 
condenser: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
378.4 g 
(with a number-average 
molecular weight of about 360) 
Bisphenol A type epoxy resin 
86.0 g 
(with a number-average molecular 
weight of about 2700) 
Diglycidyl ether of bisphenol A 
191.0 g 
type propylene oxide addition 
product having formula (1) 
in which the sum of n and m 
is about 2.1 
Bisphenol F 274.5 g 
p-cumylphenol 70.1 g 
Xylene 200 g 
______________________________________ 
The above mixture was heated to 70.degree. to 100.degree. C. in a stream of 
nitrogen, and 0.183 g of lithium chloride was added thereto. After the 
mixture was further heated to 160.degree. C., xylene was distilled away 
from the reaction mixture under reduced pressure. Then, the polymerization 
was carried out at a reaction temperature of 180.degree. C. for 6 to 9 
hours. Thus, 1000 g of a polyol resin No. 1 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 1 
were respectively 109.degree. C. and 58.degree. C. 
Synthesis Example 2 
Synthesis of polyol resin No. 2 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
205.3 g 
(with a number-average 
molecular weight of about 360) 
Bisphenol A type epoxy resin 
54.0 g 
(with a number-average molecular 
weight of about 3000) 
Diglycidyl ether of bisphenol A type 
432.0 g 
propylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.2 
Bisphenol F 282.7 g 
p-cumylphenol 26.0 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 2 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 2 
were respectively 109.degree. C. and 58.degree. C. 
Synthesis Example 3 
Synthesis of polyol resin No. 3 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
252.6 g 
(with a number-average 
molecular weight of about 360) 
Bisphenol A type epoxy resin 
112.0 g 
(with a number-average molecular 
weight of about 10000) 
Diglycidyl ether of bisphenol A type 
336.0 g 
ethylene oxide addition product 
having formula (1) in which 
the sum of n and m is about 5.9 
Bisphenol AD 255.3 g 
p-cumylphenol 44.1 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 3 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 3 
were respectively 109.degree. C. and 58.degree. C. 
Synthesis Example 4 
Synthesis of polyol resin No. 4 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
289.9 g 
(with a number-average 
molecular weight of about 2400) 
Bisphenol A type epoxy resin 
232.0 g 
(with a number-average molecular 
weight of about 10000) 
Diglycidyl ether of bisphenol A type 
309.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 6.0 
Bisphenol AD 117.5 g 
p-cumylphenol 51.6 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 4 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 4 
were respectively 116.degree. C. and 61.degree. C. 
Synthesis Example 5 
Synthesis of polyol resin No. 5 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
421.5 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
107.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
214.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.0 
Bisphenol F 210.0 g 
p-cumylphenol 47.5 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 5 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 5 
were respectively 114.degree. C. and 60.degree. C. 
Synthesis Example 6 
Synthesis of polyol resin No. 6 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
203.0 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
58.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
462.0 g 
ethylene oxide addition product 
having formula (1) in which 
the sum of n and m is about 2.2 
Bisphenol F 254.6 g 
p-cumylphenol 22.4 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 6 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 6 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 7 
Synthesis of polyol resin No. 7 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
370.6 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
306.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
102.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 5.8 
Bisphenol AD 110.2 g 
p-cumylphenol 111.2 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 7 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 7 
were respectively 118.degree. C. and 62.degree. C. 
Synthesis Example 8 
Synthesis of polyol resin No. 8 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
238.4 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
231.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
308.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 6.0 
Bisphenol AD 168.9 g 
p-cumylphenol 53.7 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 8 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 8 
were respectively 118.degree. C. and 62.degree. C. 
Synthesis Example 9 
Synthesis of polyol resin No. 9 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
401.9 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
242.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
134.0 g 
ethylene oxide addition product 
having formula (1) in which 
the sum of n and m is about 2.0 
Bisphenol F 166.0 g 
p-cumylphenol 56.1 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 9 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 9 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 10 
Synthesis of polyol resin No. 10 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
200.7 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
158.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
351.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.1 
Bisphenol F 182.4 g 
p-cumylphenol 107.9 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 10 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 10 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 11 
Synthesis of polyol resin No. 11 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
430.0 g 
(with a number-average 
molecular weight of about 460) 
Bisphenol A type epoxy resin 
188.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
116.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 5.9 
Bisphenol F 209.2 g 
p-cumylphenol 56.8 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 11 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 11 
were respectively 107.degree. C. and 57.degree. C. 
Synthesis Example 12 
Synthesis of polyol resin No. 12 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
218.8 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
172.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
382.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 6.0 
Bisphenol F 176.8 g 
p-cumylphenol 50.4 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 12 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 12 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 13 
Synthesis of polyol resin No. 13 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
275.4 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
194.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
269.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.3 
Bisphenol AD 203.5 g 
p-cumylphenol 58.1 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 13 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 13 
were respectively 114.degree. C. and 60.degree. C. 
Synthesis Example 14 
Synthesis of polyol resin No. 14 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
244.5 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
188.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
348.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 7.9 
Bisphenol AD 169.9 g 
p-cumylphenol 49.6 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 14 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 14 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 15 
Synthesis of polyol resin No. 15 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
258.3 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
199.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
276.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 4.2 
Bisphenol A 198.3 g 
p-cumylphenol 68.3 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 15 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 15 
were respectively 114.degree. C. and 60.degree. C. 
Synthesis Example 16 
Synthesis of polyol resin No. 16 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
156.1 g 
(with a number-average 
molecular weight of about 400) 
Bisphenol A type epoxy resin 
350.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
230.0 g 
propylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 4.0 
Bisphenol A 119.7 g 
p-cumylphenol 144.1 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 16 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 16 
were respectively 114.degree. C. and 60.degree. C. 
Synthesis Example 17 
Synthesis of polyol resin No. 17 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
17.6 g 
(with a number-average 
molecular weight of about 2000) 
Bisphenol A type epoxy resin 
423.0 g 
(with a number-average molecular 
weight of about 11000) 
Diglycidyl ether of bisphenol A type 
385.0 g 
propylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 6.2 
Bisphenol F 109.6 g 
p-cumylphenol 64.7 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 17 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 17 
were respectively 118.degree. C. and 62.degree. C. 
Synthesis Example 18 
Synthesis of polyol resin No. 18 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
438.1 g 
(with a number-average 
molecular weight of about 340) 
Bisphenol A type epoxy resin 
54.0 g 
(with a number-average molecular 
weight of about 3000) 
Diglycidyl ether of bisphenol A type 
108.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 1.9 
Bisphenol AD 347.9 g 
p-cumylphenol 51.9 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 18 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 18 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 19 
Synthesis of polyol resin No. 19 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
251.2 g 
(with a number-average 
molecular weight of about 400) 
Bisphenol A type epoxy resin 
50.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
400.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.0 
Bisphenol F 276.0 g 
p-cumylphenol 22.7 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 19 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 19 
were respectively 112.degree. C. and 59.degree. C. 
Synthesis Example 20 
Synthesis of polyol resin No. 20 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
82.3 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
683.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
125.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 4.0 
Bisphenol A 9.3 g 
p-cumylphenol 180.0 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 20 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 20 
were respectively 118.degree. C. and 63.degree. C. 
Synthesis Example 21 
Synthesis of polyol resin No. 21 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
428.7 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
318.0 g 
(with a number-average molecular 
weight of about 6500) 
Diglycidyl ether of bisphenol A type 
21.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 3.8 
Bisphenol A 92.3 g 
p-cumylphenol 140.0 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 21 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 21 
were respectively 114.degree. C. and 60.degree. C. 
Synthesis Example 22 
Synthesis of polyol resin No. 22 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
411.9 g 
(with a number-average 
molecular weight of about 680) 
Diglycidyl ether of bisphenol A type 
350.0 g 
ethylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 3.8 
Bisphenol A 199.2 g 
p-cumylphenol 38.9 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 22 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 22 
were respectively 113.degree. C. and 58.degree. C. 
Synthesis Example 23 
Synthesis of polyol resin No. 23 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
480.2 g 
(with a number-average 
molecular weight of about 680) 
Bisphenol A type epoxy resin 
287.0 g 
(with a number-average molecular 
weight of about 6500) 
Bisphenol A 106.8 g 
p-cumylphenol 126.0 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 23 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 23 
were respectively 111.degree. C. and 59.degree. C. 
Synthesis Example 24 
Synthesis of polyol resin No. 24 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
303 g 
(with a number-average 
molecular weight of about 400) 
Bisphenol A type epoxy resin 
135 g 
(with a number-average molecular 
weight of about 5300) 
Diglycidyl ether of bisphenol A type 
230 g 
propylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.1 
Bisphenol A 172 g 
p-cumylphenol 144 g 
o-cresol novolak "OCN80" 
20 g 
(Trademark) made by Nippon 
Kayaku Co., Ltd. with a softening 
point of 80.4.degree. C., and 
OH equivalent of 139 g/eq. 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 24 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 24 
were respectively 113.degree. C. and 61.degree. C. 
Synthesis Example 25 
Synthesis of polyol resin No. 25 
The procedure for preparation of the polyol resin No. 1 in Synthesis 
Example 1 was repeated except that the materials for use in the reaction 
system used in Synthesis Example 1 were changed as follows: 
______________________________________ 
Weight 
______________________________________ 
Bisphenol A type epoxy resin 
324 g 
(with a number-average 
molecular weight of about 400) 
Bisphenol A type epoxy resin 
135 g 
(with a number-average molecular 
weight of about 5300) 
Diglycidyl ether of bisphenol A type 
230 g 
propylene oxide addition product 
having formula (1) in which the sum 
of n and m is about 2.2 
Bisphenol A 216 g 
p-cumylphenol 73 g 
Adipic acid 30 g 
Xylene 200 g 
______________________________________ 
Thus, 1000 g of a polyol resin No. 25 were obtained. The softening 
temperature and glass transition temperature of the polyol resin No. 25 
were respectively 111.degree. C. and 60.degree. C.