JPH07137171A - Roll - Google Patents

Abstract

PURPOSE:To provide a roll which is flexible, elastic and highly heat-resistant. CONSTITUTION:A roll consists of an elastic element layer, formed on the outer periphery of an axial element, which is made mainly of a thermoplastic elastomer consisting of a thermoplastic graft copolymer obtained by allowing an aromatic polyester oligomer having a fluid temperature of at least, 100 deg.C to undergo a chemical reaction with a thermoplastic polymer composed of a monomer with an unsaturated double bond having radical reactivity in an identical molecule and an epoxy group, and ester of acrylate as main constituent units. This thermoplastic polymer has a glass transition temperature of 10 deg.C or lower. The fluid temperature shows an apparent fusion viscosity of 48000 poise when the elastic element is thermally fused at a heating-up rate of 4 deg.C/min. and measured by a method of extruding from a nozzle with an inner diameter of 1mm and a length of 10mm at load at 100kg/cm<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The roll of the present invention relates to a roll in which an elastic layer containing a thermoplastic elastomer composed of a specific thermoplastic graft copolymer as a main component is formed on the outer periphery of a shaft. More specifically, it relates to rolls used in electrophotographic copying machines and the like, for example, paper feed rolls, film transport rolls, fixing rolls, pressure rolls and the like.

[0002]

2. Description of the Related Art Rolls used in electronic copying machines and the like have heretofore been referred to as so-called added rubber such as polynorbornene rubber, natural rubber, ethylene / propylene / diene rubber, silicone rubber, and fluororubber on the outer periphery of a metallic cylindrical mandrel. Sulfur rubber has been used as the outermost elastic layer. Among them, as the elastic layer used for the developing roll that needs conductivity, a conductive material such as carbon black and a plasticizer are polynorbornene in order to obtain desired conductivity and flexibility.
A mixture of natural rubber, ethylene / propylene / diene rubber, etc. is used. Further, for the pressure roll and the fixing roll, those having a single layer structure, a two-layer structure, a three-layer structure or the like using silicone rubber and fluororubber as elastic layers have been proposed. Furthermore, in recent years, various thermoplastic elastomers have been developed as materials having elastic properties similar to vulcanized rubber. This thermoplastic elastomer can be molded by injection molding, blow molding, extrusion molding, etc. in the same way as ordinary thermoplastic materials.
Its uses are expanding.

[0003]

However, in the case of vulcanized rubber, there is a complicated process of vulcanization in the manufacturing process thereof, and it is difficult to reprocess scraps or products generated in the manufacturing process and utilize them. is there. Further, in the vulcanized rubber, it is necessary to add a large amount of a plasticizer when flexibility is particularly required, and in that case, there is a problem that the plasticizer bleeds over time. On the other hand, a thermoplastic elastomer does not require a step of vulcanization unlike vulcanized rubber, and scrap or its product can be reprocessed and reused. However, it cannot be said that the thermoplastic elastomers currently on the market have sufficient flexibility to be used as the elastic layer on the outer circumference of the roll, and the elasticity (compression set characteristic) is not sufficient. An object of the present invention is to solve these problems and provide a roll having both flexibility and elasticity and excellent heat resistance.

[0004]

[Means for Solving the Problems] In view of such circumstances,
As a result of intensive studies, the present inventors have found that a thermoplastic polymer obtained by reacting a thermoplastic polymer having a glass transition temperature of 10 ° C. or lower with a specific monomer as a constituent with an aromatic polyester oligomer having a flow temperature of 100 ° C. or higher. Finding a roll in which an elastic layer mainly composed of a thermoplastic elastomer composed of a graft copolymer is formed on the outer periphery of a shaft, and further finding that the roll is extremely flexible and has excellent elasticity,
The present invention has been completed.

That is, the present invention comprises the following inventions. (1) A glass transition temperature of which a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group and an acrylic acid ester as a main constituent unit is 10
A thermoplastic polymer-based elastic layer comprising a thermoplastic graft copolymer obtained by reacting a thermoplastic polymer having a temperature of 100 ° C. or lower with an aromatic polyester oligomer having a flow temperature of 100 ° C. or higher as defined below Roll formed on the outer circumference of the shaft. Flow temperature: 100 kg by heating and melting at a temperature rising rate of 4 ° C / min
The apparent melt viscosity measured by a method of extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of / cm ² is 4
A temperature of 8000 poise.

(2) To a thermoplastic polymer having a glass transition temperature of 10 ° C. or less, which has a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group, an acrylate ester and ethylene as constitutional units. An elastic body layer containing a thermoplastic elastomer, which is a thermoplastic graft copolymer obtained by reacting an aromatic polyester oligomer having a flow temperature of 100 ° C. or higher according to claim 1, as a main component is formed on an outer periphery of a shaft body. Rolled.

Next, the present invention will be described in detail. Specific examples of the thermoplastic polymer having a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group and an acrylic acid ester as a main constituent unit and having a glass transition temperature of 10 ° C. or lower include: Ethyl acrylate
Glycidyl methacrylate copolymer, propyl acrylate / glycidyl methacrylate copolymer, butyl acrylate / glycidyl methacrylate copolymer, hexyl acrylate / glycidyl methacrylate copolymer,
Dodecyl acrylate / glycidyl methacrylate copolymer, ethyl acrylate / glycidyl styrene copolymer, propyl acrylate / glycidyl styrene copolymer, butyl acrylate / glycidyl styrene copolymer, hexyl acrylate / glycidyl styrene copolymer, dodecyl acrylate / glycidyl styrene Copolymer, ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, propyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, butyl acrylate
N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, hexyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer Examples thereof include polymers and various copolymers such as dodecyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer. Also,
A copolymer containing three or more kinds of constitutional units in the above-mentioned copolymer may also be mentioned if necessary.

Further, as the copolymer containing ethylene as a constitutional unit, an ethylene / methyl acrylate / glycidyl methacrylate copolymer, an ethylene / ethyl acrylate / glycidyl methacrylate copolymer, an ethylene / propyl acrylate / glycidyl methacrylate copolymer, Ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / hexyl acrylate / glycidyl methacrylate copolymer, ethylene /
Dodecyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl styrene copolymer, ethylene / ethyl acrylate / glycidyl styrene copolymer, ethylene / propyl acrylate / glycidyl styrene copolymer, ethylene / butyl acrylate / glycidyl styrene copolymer Polymer, ethylene
Hexyl acrylate / glycidyl styrene copolymer,
Ethylene / dodecyl acrylate / glycidyl styrene copolymer, ethylene / methyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene / ethyl acrylate / N- [4- (2,3-epoxypropoxy)
-3,5 dimethylbenzyl] acrylamide copolymer,
Ethylene propyl acrylate N- [4- (2,3
-Epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene butyl acrylate
N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene.
Hexyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer, ethylene / dodecyl acrylate / N-
Examples thereof include various copolymers such as [4- (2,3-epoxypropoxy) -3,5 dimethylbenzyl] acrylamide copolymer. In addition, a copolymer containing four or more kinds of constitutional units in the above-mentioned copolymer is also included if necessary. Among these, ethylene / methyl acrylate / glycidyl methacrylate copolymer is preferably used. These various copolymers can be usually obtained by a well-known radical polymerization method.

However, the composition of each copolymer must be controlled so that its glass transition temperature is 10 ° C. or lower. When the glass transition temperature (hereinafter sometimes abbreviated as Tg) of the copolymer exceeds 10 ° C., the copolymer and the below-mentioned aromatic polyester oligomer are graft-copolymerized in the operating temperature range near room temperature. It is not preferable because the flexibility of the copolymer is impaired.

The aromatic polyester oligomer constituting the thermoplastic graft copolymer of the present invention has a flow temperature of 100.
It is an aromatic polyester oligomer having a temperature of ℃ or higher, preferably 150 ℃ or higher. This flow temperature was measured using a capillary rheometer with a nozzle having an inner diameter of 1 mm and a length of 10 mm.
This is a temperature at which the melt viscosity measured by a method of extruding a heated melt from a nozzle under a load of 100 kg / cm ^{2 at} a temperature rising rate of ° C / min shows 48,000 poise. When the flow temperature of the aromatic polyester oligomer is lower than 100 ° C., the temperature range showing rubber elasticity in the obtained graft copolymer becomes narrow, that is, the graft copolymer and further the graft copolymer are formed in the outer layer. It is not preferable because the heat resistance and elasticity (compression set characteristic) of the roll become insufficient.

The aromatic polyester oligomer having a flow temperature of 100 ° C. or higher, which constitutes the graft copolymer of the present invention, is an oligomer mainly composed of a polycondensation product of hydroxyarylcarboxylic acid. The oligomer mainly composed of a polycondensation product of hydroxyarylcarboxylic acid is an oligomer containing 50% by weight or more, preferably 60% by weight or more of the structural unit represented by the following general formula.

[Chemical 1]

(Where Ar is

[Chemical 2] Or

[Chemical 3] Or

[Chemical 4] And R is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and n is an integer of 0 to 2. )

The oligomer mainly composed of a polycondensation product of hydroxyarylcarboxylic acid has a number average molecular weight of 300.
It is preferably in the range of to 1500, and more preferably in the range of 400 to 1000. Number average molecular weight is 30
When it is less than 0, the polycondensate is likely to be thermally decomposed, the flow temperature is remarkably lowered, and the heat resistance of the resulting graft copolymer is lowered, which is not preferable, and when the number average molecular weight exceeds 1500, The flow temperature becomes close to the thermal decomposition temperature of the oligomer, and the moldability of the resulting graft copolymer deteriorates, which is not preferable.

In order to control the properties such as the melting point of the oligomer, which is mainly composed of a polycondensation product of hydroxyarylcarboxylic acid, hydroxyalkylcarboxylic acid,
It may include a structure in which monomers such as aminoalkylcarboxylic acid and aminoarylcarboxylic acid are polycondensed and a structure in which a monofunctional carboxylic acid compound, a phenol compound and an amino compound are condensed.

The aromatic polyester oligomer which can be particularly preferably used in the present invention is represented by the following general formula.

[Chemical 5]

(Wherein R ¹ is an alkyl group having 5 or more carbon atoms or an aryl group having 6 or more carbon atoms, and Ar is

[Chemical 6] Or

[Chemical 7] Or

[Chemical 8] R ² is an alkyl group having 1 to 3 carbon atoms or a phenyl group, and p is an integer of 0 to 2. )

It is also possible to copolymerize and use a hydroxycarboxylic acid having 2 to 6 carbon atoms in the above oligomer. The number average molecular weight of the aromatic polyester oligomer having a carboxylic acid group at one end is 300 to 150.
It is preferably in the range of 0, and n is a number in the range of 2 to 12 on average depending on the selected species of R ¹ and Ar. More preferably, n is in the range of 3-8.

The polycondensates of mainly hydroxyarylcarboxylic acids are hydroxyarylcarboxylic acids and optionally small amounts of copolymerizable monomers with them, such as hydroxyalkylcarboxylic acids having 2 to 6 carbon atoms, aminoalkylcarboxylic acids, Aminoarylcarboxylic acid,
Although any method may be used as long as it is a method of producing a polycondensate from a monofunctional phenol compound, a carboxylic acid compound, an amino compound or the like as a raw material, it is preferably produced by the following method.

That is, acetylating agents such as acetic anhydride and acetyl chloride are added to hydroxyarylcarboxylic acid,
Acetoxyarylcarboxylic acid is obtained by heating and stirring. When acetylating a hydroxyarylcarboxylic acid or the like with acetic anhydride in the above reaction, the reaction is
Acetylation is achieved by performing the reaction at 00 ° C. or higher for 15 minutes or more, and in the reaction with acetyl chloride at room temperature or higher for 30 minutes or more. In any reaction, it is preferable to add acetic anhydride and acetyl chloride in excess, preferably about 1.1 times, the number of moles of hydroxyl groups to be reacted. After the acetylation is finished,
The polycondensation reaction proceeds by deacetic acid while heating the system and stirring. The temperature in the system should preferably be 200 ° C. or higher. The number average molecular weight can be controlled by the amount of acetic acid to be distilled off.To control the desired degree of polymerization, calculate the amount of charged monomers such as hydroxyarylcarboxylic acid and the amount of acetic acid to be distilled off. is necessary.

The aromatic polyester oligomer having a carboxylic acid group at one end has 5 or more carbon atoms, preferably 5 to 5 carbon atoms.
20 alkyl groups or 6 or more carbon atoms, preferably 6 to
A mixture of a monocarboxylic acid having 15 aryl groups, a hydroxyarylcarboxylic acid and, if necessary, a hydroxycarboxylic acid having 2 to 6 carbon atoms is used in the same manner as in the above-mentioned method for producing a polycondensate of hydroxyarylcarboxylic acid. Then, a polycondensate can be obtained by acetylating with acetic anhydride or acetyl chloride and then deacetic acid. In this reaction, the number average molecular weight is determined by the molar ratio of monocarboxylic acid and hydroxycarboxylic acid. Further, the obtained oligomer is preferably washed appropriately with a solvent such as methanol or acetone to remove low molecular weight components.

The graft copolymer constituting the present invention is T
Obtained by reacting a polymer having a functional group capable of reacting with a carboxylic acid group with g of 10 ° C. or lower, and an aromatic polyester oligomer having a carboxylic acid group at one end and a flowing temperature of 100 ° C. or higher. You can The reaction method is not particularly limited, but a method of reacting by melt kneading is preferable.

This melt-kneading is carried out by using an ordinary kneading machine for mixing the aromatic polyester oligomer with the polymer having a Tg of 10 ° C. or lower at a temperature not lower than the flowing temperature of the aromatic polyester oligomer.
For example, Banbury mixer, single screw extruder, twin screw extruder,
Any device such as a roll or a kneader that can apply a high shearing force at a high temperature may be used.

The reaction temperature is preferably at least the flow temperature of the aromatic polyester oligomer used, and is preferably less than the thermal decomposition temperature of the polymer having Tg of 10 ° C. or less. If the reaction temperature is lower than the flowing temperature of the aromatic polyester oligomer used, the carboxylic acid of the aromatic polyester oligomer and the polymer having Tg of 10 ° C. or less are difficult to react with each other, and a graft copolymer is difficult to obtain. , Tg of 10 ° C. or less, which is higher than the thermal decomposition temperature of the polymer, is not preferable because the polymer is significantly decomposed during kneading and adversely affects the reduction of the molecular weight. In order to promote the grafting, it is preferable that the temperature is high within the above temperature range, the reaction time is long, and the shearing force is large. Furthermore, it is preferable to add a phosphine compound such as triphenylphosphine or the like, a tertiary amine or the like in order to accelerate grafting.

However, in any case, the polymer having a Tg of 10 ° C. or less which constitutes the graft copolymer is 50% by weight or more and 99% by weight or less, preferably 65% by weight or less of the total polymer.
It is not less than 97% by weight and not more than 100% by weight. When the polymer having Tg of 10 ° C. or lower is less than 50% by weight of the total polymer, the thermoplastic elastomer obtained is not preferable because it is difficult to exhibit rubber elasticity in the temperature range of room temperature or higher and the flexibility is deteriorated. In addition, the number of physical crosslinking points of the graft copolymer is reduced, and the resulting polymer is extremely plastically deformed at room temperature, which is not preferable.

Further, as the thermoplastic elastomer forming the elastic layer forming the outer layer of the roll of the present invention, carbon book, silica, talc, diatomaceous earth, titanium dioxide,
Fillers such as glass beads and glass fibers, plasticizers, antioxidants, colorants, flame retardants, antistatic agents, scorch inhibitors and the like can be arbitrarily blended and used according to the purpose of the roll. Particularly, when used at high temperature, an arylamine compound is preferably blended for the purpose of preventing its thermal deterioration.

The roll of the present invention can be obtained by a method in which a composition containing a thermoplastic elastomer composed of the graft copolymer as a main component is closely formed on the outer periphery of a roll shaft.

The molding method may be any of compression press molding, extrusion molding, and injection molding. Among them, the method of molding the roll of the present invention by compression press molding is preferable from the viewpoint of dimensional stability.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 An ethylene / methyl acrylate / glycidyl methacrylate terpolymer (ethylene / methyl acrylate / glycidyl methacrylate = 38.7) was used according to the method described in Example 5 of JP-A-61-127709. / 59
/2.3 (weight ratio), MI at a temperature of 190 ° C. and a load of 2.16 kg = 8.7 g / 10 minutes). The glass transition temperature of this polymer was measured with a stand-alone type differential scanning calorimeter DSC-50 type manufactured by Shimadzu Corporation in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. From the obtained figure, the endothermic onset temperature was determined by the tangential method according to the conventional method and used as the glass transition temperature.
The glass transition temperature was -31.5 ° C. Also, the heating weight loss curve of this polymer was measured with a stand-alone thermogravimetric analyzer TGA-50 manufactured by Shimadzu Corporation in a nitrogen atmosphere at 10 ° C.
It was measured at a temperature rising rate of / min. From this measurement, it was found that this polymer was thermally stable with no weight loss up to around 350 ° C.

Next, an aromatic oligomer having a carboxyl group at one end was synthesized as follows. A 2 liter separable flask with an Ikari type stirring blade, three-way cock,
A Dimroth condenser was attached, and benzoic acid 1.4 mol (1
70.8 g), para-hydroxybenzoic acid 5.6 mol (7
72.8 g) and acetic anhydride 6.2 mol (633 g) were charged. Teflon sheets cut out were used for the upper and lower packings of the separable flask. Rotate the squid-type stirring blade at 80 rpm, introduce nitrogen from the three-way cock to create a nitrogen atmosphere in the system, put the separable flask in the oil bath with cooling water flowing through the Dimroth condenser, and set the oil bath to 1
The temperature was raised to 60 ° C. The acetylation reaction was carried out for 2 hours while refluxing acetic anhydride while keeping the oil bath at 160 ° C. After the acetylation reaction is complete, the Dimroth condenser tube is
The tube was quickly replaced with one fitted with a Liebig cooling tube and the oil bath was heated to 280 ° C. 160 ° C to 280 ° C
It took about 50 minutes to raise the temperature. After that, the temperature of the oil bath was kept at 280 ° C., and acetic acid and acetic anhydride distilled from the system were recovered from the Liebig condenser. The acetic acid and the like were recovered after the Vigreux tube was replaced with a Liebig cooling tube, and 731 g of acetic acid and the like were recovered and polycondensation was completed in about 3 hours. After the completion of polycondensation, the aromatic oligomer was taken out and pulverized with a pulverizer to a particle size of 1 mm or less.

When the flow temperature of this aromatic polyester oligomer was measured, it was 192 ° C. Next, the heating weight loss of this aromatic polyester oligomer was adjusted to the above TGA-5.
The measurement was performed using a type 0 apparatus in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. From this, it was found that this aromatic polyester oligomer was stable up to around 280 ° C. The aromatic polyester oligomer showed optical anisotropy when melted. Next, the number average degree of polymerization of this aromatic polyester oligomer was analyzed and measured according to the chemical decomposition method described in Example 1 of JP-A-4-11657, and n = 4.9 in the following general formula 9. It was

[0032]

[Chemical 9]

The above-mentioned ethylene / methyl acrylate / glycidyl methacrylate terpolymer, an aromatic polyester oligomer having a number average degree of polymerization of 4.9 represented by the above general formula and having a carboxylic acid at one end, and triparatolylphosphine (Hokuko Kagaku Kogyo Co., Ltd.) and Uniroyal's arylamine compound Naugard 445 are used as ethylene / methyl acrylate / glycidyl methacrylate terpolymer / aromatic polyester oligomer / triparatolylphosphine / Naugard 445 = 80/20 /
0.4 / 2.0 (= 320 g / 80 g / 1.6 g / 8.
Laboplast mill 1 manufactured by Toyo Seiki Seisakusho at a weight ratio of 0 g)
00R-100 type B-600 type mixer and R-50
Roller type blade for 0 type is installed and set temperature is 120
Preblending was carried out at a temperature of 50 ° C. and a blade rotation speed of 50 rpm for 2 minutes, and this was taken out and cut into 10 mm square pieces. Next, this pre-blended product was used in a twin-screw extruder TEX30XSST-42BW-4V manufactured by Japan Steel Works, with a cylinder temperature of 260 ° C. and a screw rotation speed of 200 rp.
It is supplied at a supply rate of 10 to 11 kg / hour under the condition of m 2
The grafting reaction was carried out in the axial extruder. At this time, the residence time in the twin-screw extruder was about 90 seconds. The melt index (260 ° C., 10 kg load) of the obtained graft copolymer was 4.50 g / 10 minutes. The graft efficiency of the obtained graft copolymer (= reactivity of epoxy group)
According to the method described in Example 1 of JP-A-4-11657, the compound was chemically decomposed and analyzed by high performance liquid chromatography to calculate 83%.

Next, the obtained graft copolymer was treated at 280 ° C.
Then, a press sheet having a thickness of 2 mm was molded and the following physical properties were evaluated. Hardness (H _s (JIS
A)), tensile strength and elongation were measured according to JIS K6301. The compression set characteristics are in accordance with JIS K 6301: 25 ° C x 22hr, 50 ° C x 22hr, 70 ° C x
It was measured under the conditions of 22 hours and 100 ° C. × 22 hours. Regarding heat resistance, a JIS No. 3 dumbbell was punched out from the press sheet, left in an air oven at 120 ° C and 150 ° C for 2 weeks, and then cooled to room temperature to obtain hardness (H _s (JIS
A)), tensile strength and elongation were measured. The results are shown in Table 1.

Comparative Example 1 A polyester elastomer, Perprene P-30B manufactured by Toyobo Co., Ltd. was used to prepare a press sheet in the same manner as in Example 1 (however, the molding temperature was 200 ° C.). The same physical properties as in Example 1 were evaluated for this press sheet.
The results are also shown in Table 1.

[0036]

[Table 1]

[0037]

INDUSTRIAL APPLICABILITY The roll of the present invention is one in which an elastic layer containing a thermoplastic elastomer made of a specific graft copolymer as a main component is formed on the outer circumference of a shaft body, and the roll has flexibility and elasticity. It also has excellent heat resistance. Further, unlike ordinary vulcanized rubber, the product can be obtained by melt molding without the need for a vulcanizing step, and therefore it is excellent in terms of productivity and is extremely useful.

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[Procedure amendment]

[Submission date] November 15, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

Next, the present invention will be described in detail. Specific examples of the thermoplastic polymer having a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group and an acrylic acid ester as a main constituent unit and having a glass transition temperature of 10 ° C. or lower include: Ethyl acrylate
Glycidyl methacrylate copolymer, propyl acrylate / glycidyl methacrylate copolymer, butyl acrylate / glycidyl methacrylate copolymer, hexyl acrylate / glycidyl methacrylate copolymer,
Dodecyl acrylate / glycidyl methacrylate copolymer, ethyl acrylate / glycidyl styrene copolymer, propyl acrylate / glycidyl styrene copolymer, butyl acrylate / glycidyl styrene copolymer, hexyl acrylate / glycidyl styrene copolymer, dodecyl acrylate / glycidyl styrene Copolymer, ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, propyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, butyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5
- dimethylbenzyl] acrylamide copolymer, hexyl acrylate · N-[4- (2,3-epoxypropoxy) -3,5 - dimethyl benzyl] acrylamide copolymer, dodecyl acrylate · N-[4- (2,3 −
Examples thereof include various copolymers such as epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer.
Further, a copolymer containing 3 or more kinds of constitutional units in the above-mentioned copolymer may also be mentioned if necessary.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

Further, as the copolymer containing ethylene as a constitutional unit, an ethylene / methyl acrylate / glycidyl methacrylate copolymer, an ethylene / ethyl acrylate / glycidyl methacrylate copolymer, an ethylene / propyl acrylate / glycidyl methacrylate copolymer, Ethylene / butyl acrylate / glycidyl methacrylate copolymer, ethylene / hexyl acrylate / glycidyl methacrylate copolymer, ethylene /
Dodecyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl styrene copolymer, ethylene / ethyl acrylate / glycidyl styrene copolymer, ethylene / propyl acrylate / glycidyl styrene copolymer, ethylene / butyl acrylate / glycidyl styrene copolymer Polymer, ethylene
Hexyl acrylate / glycidyl styrene copolymer,
Ethylene / dodecyl acrylate / glycidyl styrene copolymer, ethylene / methyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / ethyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer Combined, ethylene / propyl acrylate / N- [4-
(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / butyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer Combined, ethylene hexyl acrylate N- [4-
(2,3-Epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer, ethylene / dodecyl acrylate / N- [4- (2,3-epoxypropoxy) -3,5 - dimethylbenzyl] acrylamide copolymer Various copolymers such as coalesced are listed. In addition, a copolymer containing four or more kinds of constitutional units in the above-mentioned copolymer is also included if necessary. Among these, ethylene / methyl acrylate / glycidyl methacrylate copolymer is preferably used. These various copolymers can be usually obtained by a well-known radical polymerization method.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction content]

The polycondensates of mainly hydroxyarylcarboxylic acids are hydroxyarylcarboxylic acids and optionally small amounts of copolymerizable monomers, such as hydroxyalkylcarboxylic acids having 2 to 6 carbon atoms , aminoalkylcarboxylic acids, amino. Although any method may be used as long as it is a method of producing a polycondensate from an arylcarboxylic acid, a monofunctional phenol compound, a carboxylic acid compound, an amino compound or the like as a raw material, it is preferably produced by the following method.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction content]

Furthermore role in the thermoplastic elastomer constituting the elastic layer to form an outer layer suitable carbon <br/> Bed rack of the present invention, silica, talc, diatomaceous earth, titanium dioxide, glass beads, glass fibers A filler, a plasticizer, an antiaging agent, a colorant, a flame retardant, an antistatic agent, an anti-scorch agent, etc., can be arbitrarily blended and used according to the purpose of the roll. Particularly, when used at high temperature, an arylamine compound is preferably blended for the purpose of preventing its thermal deterioration.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0029

[Correction method] Change

[Correction content]

Example 1 An ethylene / methyl acrylate / glycidyl methacrylate terpolymer (ethylene / methyl acrylate / glycidyl methacrylate = 38.7) was used according to the method described in Example 5 of JP-A-61-127709. / 59
/2.3 (weight ratio), MI at a temperature of 190 ° C. and a load of 2.16 kg = 8.7 g / 10 minutes). The glass transition temperature of this polymer was measured with a stand-alone type differential scanning calorimeter DSC-50 type manufactured by Shimadzu Corporation in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. From the obtained figure, the endothermic onset temperature was determined by the tangential method according to the conventional method and used as the glass transition temperature.
The glass transition temperature was -31.5 ° C. Also, the heating weight loss curve of this polymer was measured with a stand-alone thermogravimetric analyzer TGA-50 manufactured by Shimadzu Corporation in a nitrogen atmosphere at 10 ° C.
It was measured at a temperature rising rate of / min. From this measurement, it was found that this polymer was thermally stable with no weight loss up to around 350 ° C.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0030

[Correction method] Change

[Correction content]

Next, an aromatic oligomer having a carboxyl group at one end was synthesized as follows. A 2 liter separable flask with an Ikari type stirring blade, three-way cock,
A Dimroth condenser was attached, and benzoic acid 1.4 mol (1
70.8 g), para-hydroxybenzoic acid 5.6 mol (7
72.8 g) and acetic anhydride 6.2 mol (633 g) were charged. Teflon sheets cut out were used for the upper and lower packings of the separable flask. Rotate the squid-type stirring blade at 80 rpm, introduce nitrogen from the three-way cock to create a nitrogen atmosphere in the system, put the separable flask in the oil bath with cooling water flowing through the Dimroth condenser, and set the oil bath to 1
The temperature was raised to 60 ° C. The acetylation reaction was carried out for 2 hours while refluxing acetic anhydride while keeping the oil bath at 160 ° C. After the acetylation reaction is complete, the Dimroth condenser tube is
The tube was quickly replaced with one fitted with a Liebig cooling tube and the oil bath was heated to 280 ° C. 160 ° C to 280 ° C
It took about 50 minutes to raise the temperature. After that, the temperature of the oil bath was kept at 280 ° C., and acetic acid and acetic anhydride distilled from the system were recovered from the Liebig condenser. Recovery of acetic acid and the like was performed after replacing with a Liebig cooling tube with a Vigreux tube, and 731 g of acetic acid and the like was recovered and polycondensation was completed in about 3 hours. After the completion of polycondensation, the aromatic oligomer was taken out and pulverized with a pulverizer to a particle size of 1 mm or less.

Claims (2)

[Claims] 1. A thermoplastic polymer having a glass transition temperature of 10 ° C. or less, which comprises a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group and an acrylic ester as a main constituent unit, A roll in which an elastic body layer containing a thermoplastic elastomer composed of a thermoplastic graft copolymer obtained by reacting an aromatic polyester oligomer having a flow temperature of 100 ° C. or higher as defined in 1. . Flow temperature: 100 kg by heating and melting at a temperature rising rate of 4 ° C / min
The apparent melt viscosity measured by a method of extruding from a nozzle having an inner diameter of 1 mm and a length of 10 mm under a load of / cm ² is 4
A temperature of 8000 poise. 2. A thermoplastic polymer having a glass transition temperature of 10 ° C. or less, which comprises a monomer having an unsaturated double bond having a radical reactivity in the same molecule and an epoxy group, an acrylic acid ester and ethylene as structural units, An elastic body layer containing a thermoplastic elastomer as a main component, which is composed of a thermoplastic graft copolymer obtained by reacting an aromatic polyester oligomer having a flow temperature of 100 ° C. or more according to claim 1, is formed on the outer periphery of a shaft body. roll.