JP3242697B2 - Urethane reaction method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a reaction method for obtaining a highly viscous urethane-modified resin by continuously reacting a polyisocyanate compound with one or more polyols having high reactivity. Relates to an improved method for producing a urethane-modified resin suitable as a binder resin for an electrophotographic toner by mixing one or more polyols having a hydroxyl group at a molecular terminal with a polyisocyanate compound and subjecting the mixture to a urethane-forming reaction. .

[0002]

2. Description of the Related Art Conventionally, as a method of reacting a polyol to obtain a modified resin having a higher molecular weight, for example, a) When the polyol is a solid, it is supplied as a fine powder to an extruder and melted. Later, the isocyanate compound is added from the intermediate feed port, the reaction is advanced while stirring and mixing, and a reaction mixture is obtained from the outlet of the extruder. B) A polyol is put in a tank, the isocyanate compound is added, and the mixture is stirred and reacted. There are methods.

In the method using an extruder of the above a), the supply of raw materials is generally limited to powder due to the structure of the apparatus. In addition, if the raw material is a polymer material and has high viscosity, it should be able to be supplied to the extruder.However, the extruder cannot change the fluid temperature too abruptly in order to avoid thermal deterioration in the feed direction. The supply temperature is around the reaction temperature. At this time, the viscosity of the raw material is usually extremely lower than the viscosity of the outlet of the resin after the reaction, and when the raw material is supplied in a low-viscosity state near the reaction temperature, the pressure difference from the outlet side causes a screw feed to be performed. There is a problem that it becomes difficult or the device becomes long in order to solve the problem.

In the early stage of the urethanization reaction,
In order to homogenize the reaction product, high-speed mixing of the reaction raw materials is necessary, and the rotation speed of the extruder inevitably requires high-speed rotation. Will be agitated at a high speed, and the motor for reduction of the extruder, the reduction gear, etc., will become huge,
There are problems such as heat generation due to high-speed rotation of the shaft and deterioration of the resin. In particular, when a long post-reaction is required, the length of the extruder is inevitably increased, resulting in many problems as industrial production equipment.

The method of performing the reaction in the stirring tank described in b) above is frequently used in the polymerization step of converting a monomer into a polymer. However, in order to avoid increasing the viscosity of the product, the reaction is carried out using water as a medium. It is an emulsion polymerization method or a solution polymerization method in which a solvent is added, and requires a complicated apparatus. Since the amount of additives allowed in the product does not always reasonably match the required additives such as the stirring and mixing capacity of the equipment and the heat conduction capacity, the reaction in the tank is performed by increasing the amount of solvent added, for example. After that, post-treatments such as removal of excess additions are required, which deteriorates equipment costs and operation costs.

Further, in the case of a general system in which the viscosity is rapidly increased in the late stage of the reaction even if the viscosity is low in the early stage of the reaction, equipment capable of adapting to each of the extreme cases related to the batch reaction tank is provided. Need to be prepared, driving operation becomes complicated,
There are many problems such as a decrease in control accuracy and a decrease in product quality.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to enable continuous urethanization reaction without being affected by differences in raw material viscosity and product viscosity. It is an object of the present invention to provide a method for producing a highly viscous urethane-modified resin excellent in water resistance.

[0008]

Means for Solving the Problems The present invention provides the following (1)-
The present invention relates to the invention (7). (1) One or more polyols (A) are reacted with an amount of a polyisocyanate compound (B) containing 0.3 to 1.5 mole equivalent of isocyanate groups per mole of hydroxyl groups in the polyol (A). (1) It does not substantially react with the polyisocyanate compound (B), and has a hydroxyl value of 10 in eq · KOH mg / g-resin.
The following third component (C) and the polyol (A) previously mixed, and a polyisocyanate compound (B)
Is continuously injected from the inlet of a non-stirring mixer (I) maintained at 90 ° C. to 200 ° C. where the reaction can substantially proceed,
Or (2) a mixture of the third component (C) and the polyisocyanate compound (B) in advance and the polyol (A) at 90 ° C. to 200 ° C. at which the reaction can substantially proceed.
A urethanization reaction method comprising continuously injecting from the inlet of a non-stirring mixer (I) held in the reactor, causing the urethanization reaction to proceed therein, and discharging continuously. (2) The reaction method according to (1), wherein the isocyanate group of the polyisocyanate compound (B) is added at a ratio of 0.3 to 1.2 mole equivalent per mole of the hydroxyl group of the polyol (A). (3) The third component (C) is a fatty acid ester, a phosphate ester, a polyester having a molecular weight of about 1,000 to about 10,000, and a molecular weight of about 1,000 to about 10,000.
(1) or the reaction method according to (2), which is selected from vinyl polymers. (4) The reaction according to any one of (1) to (3), wherein the amount of the third component (C) added to the polyol (A) is in the range of 95: 5 to 10:90 (weight ratio). Method. (5) The reaction product mixture obtained by the method according to any one of (1) to (4), wherein the flow linear velocity of the mixture is one of the linear flow velocity in the mixer (I). / 5 to 1/1
Lead to a non-stirring mixer (II) designed to be 00
A urethane-forming reaction method comprising performing a post-reaction. (6) The additive of the polyisocyanate group per mol of the hydroxyl group of the polyol (A) is about 0.8 mol equivalent to 1.5 mol equivalent, and the urethane in the reaction product mixture from the mixer (I) is used. The reaction method according to (5), wherein the reaction product mixture is injected into the mixer (II) when the conversion rate is in the range of 50% to 80%. (7) The reaction product mixture obtained by the method according to any one of (1) to (6) is further provided with a self-cleaning type screw device for a high-viscosity fluid, or a spiral blade or a spiral band blade. A urethane-forming reaction method in which the mixture is guided into a stirred tank for post-reaction.

A preferred method of the present invention is to mix a third component (C), which does not substantially react with the polyisocyanate compound (B), with the polyol (A) or the polyisocyanate compound (B). It consists of continuously injecting from the inlet of the non-stirring type mixer (I), and then injecting other corresponding reaction components to advance the urethanization reaction and continuously discharge.

According to another method of the present invention, the reaction mixture obtained from the non-stirring type mixer (I) is further mixed with a mixture having a flow linear velocity of 1/5 of the flow linear velocity in the mixer (I). ~ 1 /
Lead to a non-stirring mixer (II) designed to be 100
Post-reaction. Yet another method of the present invention is:
The reaction mixture obtained from the non-stirring type mixer (I) or (II) is further introduced into a self-cleaning type crawler for high-viscosity fluid or a stirring tank having a built-in spiral blade or spiral band blade. The post-reaction is carried out for 2020 hours.

Hereinafter, the present invention will be described in detail. The one or more polyols (A) in the present invention refers to one kind of the polyol itself selected from the polyols described in detail below or a mixture of the polyol and one or more other polyols selected from the above polyols. Means any of the mixtures. Here, the polyols are dihydric to tetrahydric polyhydric alcohols, polyether polyols, acrylic polyols, polyester polyols and other polyols.

As the dihydric to tetrahydric polyhydric alcohol,
For example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, 1,
4-butylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Decamethylene glycol, 2,4,4-trimethyl-
1,3-pentanediol, cyclohexanediol,
Cyclohexane dimethanol, xylylene diglycol and the like can be mentioned.

As the polyether polyols, low molecular weight polyvalent active hydrogen compounds such as ethylene glycol, propylene glycol, glycerin, pentaerythritol and aniline are used as initiators, and ethylene oxide, propylene oxide, butylene oxide, Examples thereof include those to which an alkylene oxide such as styrene oxide is added, and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

Further, the acrylic polyol has a hydroxyl group such as, for example, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, polycaprolactone (meth) acrylate. It can be easily obtained by reacting the monomer (a) with the monomer (b) having no hydroxyl group in combination with a copolymerization catalyst.

Here, as the monomer (b) having no hydroxyl group, for example, methyl (meth) acrylate,
Ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, tridecyl (meth) acrylate, stearyl ( Esters of acrylic acid and methacrylic acid such as (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate can be used. In the above, for example, methyl (meth) acrylate means methyl methacrylate and methyl acrylate.

The other copolymerizable monomers having no hydroxyl group (b) include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl propionate, acrylamide, Examples include methacrylamide, vinyl chloride, propylene, ethylene, and α-olefins having 4 to 20 carbon atoms.

Representative copolymerization catalysts (initiators) include diazo compounds such as azobisisobutylnitrile, benzoyl peroxide, tert-butylpivalate, te
peroxides such as rt-butyl perbenzoate and tert-butyl parka plate;

Examples of the polyester polyols include dihydric to tribasic acids such as maleic acid, fumaric acid, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, isophthalic acid, terephthalic acid and trimellitic acid. And those obtained by a condensation reaction with the dihydric to tetrahydric polyhydric alcohol.

The dihydric to tetrahydric polyhydric alcohols include, in addition to the above, hydroxynon bis (hydroxyethyl ether), bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct,
Examples include hydrogenated bisphenol, trimethylolpropane, glycerin, 1,2,6-hexanetriol, pentaerythritol, sorbitol, castor oil and the like.

Further, for example, higher fatty acids such as coconut oil fatty acid, linseed oil fatty acid, soybean oil fatty acid, cottonseed oil fatty acid, kiri oil fatty acid, castor oil fatty acid and the like are used in combination with the above-mentioned dibasic acid or tribasic acid and the above-mentioned divalent or tetravalent fatty acid. An oil-modified polyester polyol blended in a polyhydric alcohol component is also used.

As the polyisocyanate compound (B) in the present invention, for example, tolylene diisocyanate,
Isophorone diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, diisocyanate compounds such as diphenylmethane 4,4'-diisocyanate and isocyanurates derived from these diisocyanates, glycol adducts modified with various polyols described above, water adducts and the like. is there.

The non-stirring type mixer used in the method of the present invention is described in, for example, Section 18.4 (Solid Mixing), p. Representative examples are shown. That is, it is a pipe having a structure in which a flow path dividing plate, a mixing plate, and the like are placed in the transport conduit to perform fluid division and coalescence to promote mixing. The cross section of this tube is usually circular and is most suitable for the flow form, but may be a polygon or the like in terms of shape processing of the mixing plate to be filled.

There are various types of non-stirring type mixers mainly depending on the shape of the internal mixing plate and the manufacturers and types of the mixers. For example, Sulzer (Switzerland) (the koch sulz)
ermixer) SMX, SMXL type mixers, etc., and as shown in the above handbook, the rectangular plate was twisted so that the flow rotated 180 ° to the left or right, and then rotated 180 ° in the opposite direction. There is a kenics type mixer (the kenics mixer) that incorporates a rectangular twisted plate called an element. These non-stirring mixers are also called static mixers or static mixers or in-line mixers, and are conventionally used for mixing gas, liquid, and powder systems. It has been used for operations that require mixing, such as absorption, but most have been used only for the purpose of mixing and stirring low-viscosity materials (see, for example, US Pat. No. 3,950,317). In recent years, it has also been used for mixing medium-viscosity substances, and in certain fields such as urethane foam molding, in which a reactive raw material is injected into a mold and molded, with the aim of initial stirring and mixing of a medium-viscosity reactive compound. It has been used (Japanese Patent Application Laid-Open No. 60-105514, Japanese Patent Publication No. 1-34539).

However, use in these fields is
It is not intended for a reaction in a non-stirring mixer at all. It was extremely simple as a result of using it for the purpose of homogenizing the composition, and the possibility that the initial reaction was slightly generated was to some extent.

In the present invention, the ratio of the isocyanate group in the polyisocyanate compound (B) to 1 mole of the hydroxyl group in the polyol (A) is to be determined by the characteristics of the desired urethane-forming resin. However, for example, in the case of an electrophotographic toner binder resin, 0.3 to 1.5 molar equivalent is suitable. When the amount is less than 0.3 molar equivalent, the problem of the reaction operation in the present invention does not occur, but the polymerization as a urethane modified resin becomes insufficient, and the offset resistance is poor when used as a binder resin for a toner. Also, if it exceeds 1.5 molar equivalents,
If the mixture is cooled at the outlet of the non-stirring mixer (I), unreacted isocyanate remains and causes various problems. Further heating of the product at the outlet causes a crosslinking reaction to proceed, resulting in a very high viscosity, It requires a lot of fluid energy. In addition, the pressure of the piping system is also high, which results in excessive equipment. If the temperature is further increased to avoid this, there is a problem that the resin is deteriorated.

The holding temperature of the non-stirring type mixer (I) in the present invention is from 90 ° C. to 200 ° C. at which the reaction can substantially proceed. In the non-stirring type mixing in the conventional method, generally, a high-speed mixing is performed at a reaction temperature or lower, and a method of immediately discharging the mixture is taken in a short time. If the holding temperature is lower than 90 ° C., the reaction slows down and does not substantially proceed, and the required length of the non-stirring type mixer (I) becomes excessively large. This causes a problem that the power is dramatically increased. On the other hand, if the holding temperature is higher than 200 ° C., the deterioration of the resin becomes remarkable, which is not preferable.

As described above, according to the method of the present invention, the non-stirring type mixer (I), which has been conventionally used only for mixing of multiple components, is used as a reactor, and the urethanization reaction is sufficiently advanced. After that, a novel process for continuously and stably producing a urethane-modified resin is provided.

The standard of the size of the non-stirring mixer in the present invention is as follows. First, in addition to the number of mixing elements (elements) sufficient to sufficiently mix the required amounts of the polyol (A) and the polyisocyanate (B), reaction volume product of only securing the reaction time sufficient to obtain a urethane-forming reaction rate is required.

In a preferred method of the present invention, the method further comprises mixing the third component (C) which does not substantially react with the polyisocyanate compound (B) with the polyol (A) or the polyisocyanate compound (B). After doing
A urethanization reaction method characterized by continuously injecting from the inlet of the non-stirring type mixer (I), and then injecting other corresponding reaction components to advance the urethanization reaction and continuously discharge. It is.

The preferred method of the present invention is particularly applicable to the case where the rate of addition of the polyisocyanate compound (B) is high and the molecular weight is less than 400, and the urethanization reaction in the non-stirring mixer (I). Is a particularly preferred method for obtaining products with a significant increase in the molecular weight of the modified resin. It prevents pressure fluctuations that may occur in the non-stirring mixer (I) depending on the reaction conditions in such a case,
This is because the period of stable operation can be prolonged.

In the present invention, the third component (C) which does not substantially react with the polyisocyanate compound is:
For example, phthalic acid esters such as dibutyl phthalate and dioctyl phthalate; fatty acid esters made from fatty acids having 6 to 8 carbon atoms and alcohols such as ethylene glycol and triethylene glycol; phosphate esters such as trioctyl phosphate; The molecular weight of the reaction between dihydric or trihydric alcohols such as diethylene glycol and acids such as succinic acid and adipic acid 1,000-1
It means a plasticizer for resins represented by about 0,000 polyesters.

As the third component (C), a vinyl polymer may be used. These are suitably polymers having a number average molecular weight of 1,000 to 10,000 obtained by polymerizing a vinyl monomer, and are usually bulk polymerization, solution polymerization, suspension polymerization,
It can be obtained by a method such as emulsion polymerization.

Examples of the vinyl monomer include aromatic vinyl compounds such as styrene and α-methylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, and acrylic acid. Isobutyl, cyclohexyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, methacryl Such as 2-ethylhexyl acid, stearyl methacrylate, lauryl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate; ) Acrylic acid esters, acrylonitrile, vinyl chloride, vinyl acetate, vinyl propionate, methacrylonitrile, can be exemplified acrylamide, methacrylic amide, and the like.

In the case of a polymer having a number average molecular weight of more than 10,000, the viscosity is too high even at the reaction temperature, so that homogeneous mixing cannot be sufficiently promoted. If the number is less than 1,000, the urethanization reaction is delayed, especially when the addition amount is low. The effect is low.

Further, a solvent such as xylene or toluene for dissolving or suspending the polyols and / or the third component (C) and subjecting it to a urethanization reaction is also included in the third component (C). . In the third component, a polyvinyl chloride stabilizer generally called a resin molding aid,
An antioxidant, an ultraviolet absorber or the like may be added as an auxiliary.

The amount of the third component (C) to be added to the polyol (A) is suitably 5 wt% or more and 90 wt%.
wt% or more is good. When only a solvent such as xylene or toluene is used, the addition amount is desirably 30% by weight or more.

The mixture of the above components has a number average molecular weight of 10,0
10 wt% of high molecular weight third component (C) around 10 and xylene 10 wt%
% Is mixed with the polyisocyanate (B) and then reacted with the polyol (A).

The fact that the third component (C) does not substantially react with the polyisocyanate compound (B) means that when the component constituting the third component (C) is an ester, Depending on the blending of the raw materials acid and alcohol and the reaction conditions, an acid group or a hydroxyl group remains and can react with the polyisocyanate compound. Therefore, the hydroxyl group value (eq. KOH mg /
g-resin) and less than 10 components. When a large component exceeding 10 is used as the third component (C), the effect of delaying the reaction between the polyisocyanate compound (B) and the polyol (A) is reduced, and the sufficient effect is obtained in the non-stirring mixer (I). Before mixing, a very heterogeneous urethanization reaction proceeds, closing the non-stirring mixer (I), making it impossible to continue the reaction.

An appropriate amount of the third component (C) added to the polyol (A) is 95: 5 to 10:90 by weight.
In particular, it is preferable that the content of (C) is more than 90:10.

Next, in a preferred method of the present invention, the reaction mixture obtained by the above-mentioned method is further mixed with a mixture having a flow velocity of 1/5 to 1 of the linear flow velocity in the non-stirring mixer (I). /
Lead to a non-stirring mixer (II) designed to be 100,
This is a urethanization reaction method wherein a post-reaction is carried out for 5 minutes to 3 hours. Here, as the mixer (II), those exemplified as the non-stirring type mixer (I) described above can be used.

Here, the flow rate of the mixture is a value obtained by dividing the supply volume per unit time of the mixture by the average sectional area of the mixer. From the results of various experiments by the present inventors, the standard for the transition from the mixer (I) to the mixer (II) is based on the urethanization reaction rate (based on the reactive hydroxyl group) defined by the following [Equation 1]. % Or more. The reason for this is that firstly, the viscosity of the reaction mixture is 50% less than the viscosity of the urethane raw material mixture.
This is because the pressure rises rapidly from the above, and the fluid pressure loss increases. If this mixture is introduced into the non-stirring mixer (II) at a reaction rate of less than 50%, gel-like resin may be deposited near the inlet. This is because the long-term stable operation of the equipment may be deteriorated and the product quality may be uneven.

[0042]

(Equation 1) In the formula, (-OH) _o and (-NCO) _o represent the number of moles of reactive hydroxyl groups and isocyanate groups at the time of charging the raw materials,
[-OH] is the number of moles of reacted hydroxyl groups and [-NCO]
Indicates the number of moles of isocyanate groups consumed.

When a product is obtained only by the mixer (I) in the method of the present invention, the equivalent weight of the polyisocyanate group added is
0.3 to 1.2 mol is particularly suitable. When almost all of the hydroxyl groups in the polyol (A) are reacted, and when the addition equivalent of the polyisocyanate group is more than about 0.8 mol and 1.5 mol or less, the mixing machine (I) It is particularly preferable to inject the reaction product mixture into the mixer (II) when the conversion of the polyol (A) in the reaction product mixture from the above is 50% or more and 80% or less based on the hydroxyl group.

In the latter half of the urethanization reaction in the method of the present invention, the fluid viscosity exceeds several tens of times the initial viscosity, and reaches several hundred times or more after a conversion of 90%. When the post-reaction is continued by increasing the amount of the polyisocyanate added, the viscosity becomes higher. However, the linear velocity in the non-stirring mixer (II) is set to 1/5 to 1/100, and the reaction is continued. Can proceed more smoothly.

The holding temperature of the non-stirring mixer (II) is 90 ° C.
At a temperature between 200 ° C., any temperature may be selected as long as it is selected in accordance with the equipment conditions from the relationship between the corresponding reaction time and the flow pressure loss, and may be higher or lower than that of the mixer (I). In addition, it is desirable that the connecting portion between the mixers (I) and (II) has a pipe-expanding structure to gradually increase the cross-sectional area in order to prevent stagnation. Further, a dispersion plate or a relay non-stirring mixer for homogenizing the flow, changing the temperature of the fluid, or the like may be inserted into the connection portion. (I) -1
If it is less than / 100, drift tends to occur and the fluid temperature is also undesirably distributed, which is undesirable because it causes a decrease in product quality.

The residence time of the reaction mixture in the non-stirring type mixer (II) can be selected based on the degree of reaction completion in the mixer (I) and the exit viscosity, depending on the physical properties to be imparted to the product. In the case where the reaction with the isocyanate is intended mainly for the urethane-forming reaction alone, and when the addition amount of the third component (C) is 10 to 20 parts by weight or less, the time is preferably from 5 minutes to 1 hour. In the case where the addition amount of the third component (C) is 20 parts by weight or more, the addition amount of the isocyanate group is 1 mole equivalent or more to the hydroxyl group in the polyol (A), and a high-viscosity product is required, the upper limit is 5 parts. Time is appropriate. As a property required for the target resin, there may be a case where modification by a post-reaction of 5 hours or more is required, but according to extensive studies by the present inventors,
Those requiring a long post-reaction in the non-stirring mixer (II) have a viscosity of the reaction mixture of at least 1,000 poise, which is not industrially advantageous from the viewpoint of flow pressure loss.

The reaction mixture obtained by the method of the present invention or any one of the above-mentioned methods is further subjected to a self-cleaning type kneading apparatus for a high-viscosity fluid.
r) or a urethanization reaction method in which the spiral wing is guided to a stirring tank having a built-in double ribbon and a post-reaction is performed.

In the method of the present invention, the above-mentioned stiffening device is a device for strongly kneading a high-viscosity material.
Regardless of whether it is a continuous type or a batch type, it is typically a multi-screw extruder, a co-kneader, a double-armed screw machine or the like (see, for example, USP 3,642,964, 4,245,081, 4,261,946). In the self-cleaning type, the wall of the container body to which the content adheres is scraped by a screw or an arm or a wing, and the screw, the arm or the wing is scraped off by itself or a wall or a protrusion to be renewed. This is a mold-type device, which is excellent in mixing a high-viscosity material and making the residence time uniform.

Although various modifications have been made to the above-mentioned toweling apparatus by each equipment manufacturer, the present invention may be any apparatus capable of heating or cooling at 90 ° C to 200 ° C. Extruders are suitable.

A stirrer with a built-in spiral blade or spiral band blade has a low self-screening property, but has a simpler structure and a larger tank volume than a screw extruder or the like. As in the case of the reaction, it is possible to secure a heating residence time of 5 minutes to 20 hours. Further, in the case of a stirring tank, a vertically long tank is preferable in order to avoid an extremely large stirring power when the inside diameter of the tank is large.

The viscosity of the reaction mixture using the stirring tank is not more than 400,000 poise at the post-reaction temperature. Particularly preferably, the pressure is 100,000 poise or less, and when it exceeds this, the stirring power is increased and the self-cleaning property is reduced. Also, 40
If it exceeds 10,000 poise, the homogeneity will be poor.

[0052]

The following examples illustrate the method of the present invention, but the present invention is not limited to these examples. Examples 1 to 4 A polyhydric alcohol and a polycarboxylic acid in the composition shown in Table 1,
Dehydration polycondensation was carried out together with 0.05% by weight of dibutyltin oxide as a dehydration catalyst to obtain polyols (A1 to A4).
On the other hand, a polyhydric alcohol and a polycarboxylic acid were subjected to dehydration polycondensation in the manner shown in Table 2 in the same manner as described above, and the third component (C1) having a residual hydroxyl group of 1 or less in OH value (mg KOH / g-resin). ~
C4) was obtained. Polyols (A1 to A4) shown in Table 1
And the third component (C1 to C4) shown in Table 2 from a tank maintained near the reaction temperature shown in Table 3 by a gear pump at a blending amount (parts by weight) shown in Table 3 without stirring for resin mixing. After pouring the mixture into a mold mixer and sufficiently mixing the mixture, a urethanization reaction was performed by a non-stirring mixer (I) capable of injecting the polyisocyanate shown in Table 3 through a thin tube at the center of the inlet-side flow path. About 500 g of the outlet resin was sampled, solidified by cooling, and pulverized to obtain an analysis sample. Details of the manufacturing conditions,
Table 3 shows the physical properties of the urethane-modified resin obtained as a result. The reaction was continued for 8 hours, but the pressure at the gear pump outlet was constant and the fluctuation was extremely small. As a result of infrared analysis of the sample of Example 4, the presence of some unreacted -NCO groups was confirmed, but was not detected in Examples 1 to 3.

[0053]

[Table 1] * 1): KB-300K is bisphenol A- (2,2 ')
-Propylene oxide adduct (Mitsui Toatsu Chemical Co., Ltd.)
* 2): A value determined by gel permeation chromatography using an eluent using monodispersed standard polystyrene as a standard.

[0054]

[Table 2]

[0055]

[Table 3]

Comparative Examples 1 and 2 Comparative experiments shown in Table 3 were carried out in the same manner as in Examples 1 and 4 without adding the third component (C). From about one minute after the start of the experiment, the pressure gauge repeatedly repeated irregular vibration, and the average internal pressure gradually increased.
In Example 2, the experiment was abandoned after 30 minutes because the pressure exceeded 40 kg / cm ² G and the instantaneous value of the pressure vibration exceeded 100 kg / cm ² G. When the element portion of the mixer was washed with a solvent, the resin insoluble matter was fixed, and the element interval was partially closed. In any of Examples 1 to 4, no insolubles were detected on the element surface.

Examples 5 to 7 Non-stirring mixers (II) having the contents shown in Table 4 were connected to the equipments of Examples 3 and 4, and a post-reaction was carried out. In Example 5, a SMXL type manufactured by Through The Company and a nominal diameter of 3 inches were used. By setting the flow rate ratio with the mixer (I) to 1/43, a sufficient post-reaction time was secured, and the outlet resin viscosity was about 800,000 poise, but the pump outlet pressure was 27 / cm ² G. Stayed. Further, the ethyl acetate insoluble content was increased from 3% in Example 3 to 8% by the method of Example 5. Examples 6 and 7 are examples in which the modified resin obtained in Example 4 was subjected to a post-reaction, and used as a non-stirring type mixer (II) of Noritake Co., Ltd. with a nominal diameter of 2 1/2 inches and 1 inch. 1/2 inch was used. The post-reaction time was secured by setting the flow rates in the mixer (II) to 1/27 and 1/11, respectively, as compared with the flow rates in the mixer (I), and high viscosity products could be obtained. Ethyl acetate insoluble content was twice or more as compared with Example 4.

Comparative Example 3 A mixer (II) having the same diameter and a length of 60 cm was connected to the outlet of the mixer (I) using the equipment used in Example 3, and the post-reaction was started under the conditions shown in Table 4. Was. Immediately after the isocyanate was added to the mixer (I), the pressure at the pump outlet gradually increased, and then suddenly exceeded 200 kg / cm ² G, so the reaction was stopped. It became clear that in the mixer (II) having the same diameter as the mixer (I), the post-reaction could not be continued for more than 1 minute.

Comparative Example 4 In the equipment of Example 4, a mixer (II) having a nominal diameter of 1 inch was connected to the outlet of the mixer (I) under the conditions shown in Table 4, and a post-reaction was carried out. The flow rate ratio was 1 / 4.6 and the reaction time was about 3 or 4 minutes. However, the reaction was stopped because the pump outlet pressure exceeded the maximum value of the pressure gauge of 200 kg / cm ² G. In a later survey, resin leaks were found at some of the flange connections. The situation could lead to equipment destruction.

[0060]

[Table 4]

Example 8 The urethanized resin obtained in Example 1 was mixed with a mixer (I)
, And air-cooled to about 150 ° C at the outlet, and then fed in a molten state directly to the powder supply port of a twin-screw extruder (TEX-30 manufactured by Japan Steel Works, Ltd.). Due to the high viscosity resin, the screw exhibited sufficient biting characteristics of the supplied resin, and the supply port did not overflow even at a resin flow rate of 12 L / hr. In a reaction in a twin-screw extruder under the same conditions, when the melted resin and isocyanate are directly supplied at the reaction temperature without using the mixer (I) and reacted, the viscosity of the raw material resin is lower than the viscosity of the product resin. Since it was extremely low, the resin flow rate of 12 L / hr could not be continuously supplied, and overflowed from the supply port. This is because the difference in resin viscosity between the inlet side and the outlet side was too large, and the holding pressure on the supply side could not be sufficiently secured against the rise in the internal pressure on the extruder outlet side. Is considered to have been able to send a quantitative liquid because it has a sufficiently high viscosity. 3.2 wt% of TDI was additionally added to the molten resin supplied to the twin screw extruder by a plunger pump. The injection section is 8 extruders as a whole.
At the position of the second upstream feed screw in the barrel, the total barrel temperature was 135 ° C. The residence time in the extruder is not always clear, but on average was a post-reaction of 6 to 7 minutes. The exit resin reactant was comminuted into chunks of about 3 kg and analyzed. A product having an ethyl acetate insoluble content of 19 wt% was stably obtained.

Example 9 A jacket was formed on the outside of a stainless steel pipe having a nominal diameter of 8 inches and a length of 120 cm, and 0.75 kw mounted on an upper flange portion.
Using a motor with a speed reducer, a reactor with a double helical stirring blade was used. That is, the wing has an outer diameter of 190 mm and a coil pitch of 1
The drive shaft of 20mm, 20mm width, 8-stage helical, 50mm diameter,
It is divided into crosses above the liquid level, penetrates at positions where each helical ribbon is divided into four in the circumferential direction, and forms an integral wing structure. That is, the reactor has no axis at the center of the liquid and has a structure in which the high-viscosity resin does not accumulate and stay. A gear pump was connected to the lower part of the reactor to make a pump for extracting the reaction resin. After completion of the reaction in Example 3, the resin exiting the non-stirring mixer (I) was injected into the reactor with stirring blades, and the jacket temperature was adjusted.
Post-reaction was carried out at 150 ° C. The internal volume was always 30 L, and the blade rotation speed was 1 rpm. The average residence time was 5 hours. After the resin obtained in this example was cooled and solidified to around room temperature by a cooling roll provided at the outlet of the gear pump, the pulverized sample was analyzed for ethyl acetate-insoluble matter, and as a result, it was found to have increased to 12% by weight. It is clear that the post-reaction is remarkably progressing even in comparison with Example 3.

Application Example 6 parts by weight of carbon black MA-100 (manufactured by Mitsubishi Kasei Co., Ltd.), 100 parts by weight of the urethane resin obtained in Example 5, and Spiron Black TRH (Hodogaya Chemical Co., Ltd.) as a charge controlling agent 2 parts by weight) and 2 parts by weight of polypropylene wax biscol 550P (manufactured by Sanyo Kasei Kogyo Co., Ltd.) were dispersed and mixed with a Henschel mixer, and then a twin-screw kneader PCM30 (manufactured by Ikegai Iron Works) At 160 ° C. to obtain a lump toner composition. This is roughly crushed by a hammer mill, finely crushed by a jet crusher (IDS2 type manufactured by Nippon Pneumatics Co., Ltd.), and then subjected to airflow classification to have an average particle diameter of 10μ (5% or less 3% by weight, 20% by weight or more, 2% by weight) of toner particles. This toner
One hundred parts by weight was mixed with 1 part by weight of hydrophobic silica Aerosil R972 (manufactured by Nippon Aerosil Co., Ltd.) to obtain a one-component developer. Using a commercially available non-magnetic one-component laser beam printer (LP3000 manufactured by Seiko Epson Corporation)
A copy test was performed in an environment at 25 ° C. and a relative humidity of 50%. The evaluation was made on development sleep stainability and image density stability during printing. As a result, it was found that by using the resin obtained according to the present invention, a good image having excellent durability image density stability was obtained, and a toner comparable to a commercially available toner was obtained.

[0064]

According to the present invention, it is possible to continuously produce a urethane-modified resin by promoting a urethanization reaction in a high viscosity region where a crosslinked gel is generated.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Takayasu Ikeda 1-6-6 Takasago, Takaishi City, Osaka Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Soichi Kuya 1900 Togo, Togo, Mobara City, Chiba Prefecture Co., Ltd. (72) Inventor Eiji Kuwamoto 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Pref.Mitsui Toatsu Chemical Co., Ltd.Examiner Kenji Sato (56) References JP-A-50-123797 (JP, A) 5-170865 (JP, A) JP 42-25318 (JP, B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/00-18/87 C08L 75/04-75 / 12

Claims (7)

(57) [Claims] 1. One or more polyols (A) and an amount of a polyisocyanate compound (B) containing an isocyanate group in an amount of 0.3 to 1.5 mole equivalent per mole of hydroxyl group in the polyol (A). When the urethane-modified resin is obtained by the reaction, (1) it does not substantially react with the polyisocyanate compound (B), and has a hydroxyl value of 10 in eq · KOH mg / g-resin.
The following third component (C) and the polyol (A) previously mixed, and a polyisocyanate compound (B)
Or (2) a mixture of the third component (C) and the polyisocyanate compound (B) in advance, and the polyol (A) at 90 ° C. to 200 ° C. at which the reaction can substantially proceed.
A urethanization reaction method comprising continuously injecting from the inlet of a non-stirring mixer (I) held in the reactor, causing the urethanization reaction to proceed therein, and discharging continuously. 2. The reaction method according to claim 1, wherein the isocyanate group of the polyisocyanate compound (B) is added at a ratio of 0.3 to 1.2 mole equivalent per 1 mole of the hydroxyl group of the polyol (A). 3. The method according to claim 2, wherein the third component (C) is a fatty acid ester,
Phosphate esters, molecular weight of about 1,000 to about 10,000
0 polyesters and a molecular weight of about 1,000 to about 10,
The reaction method according to claim 1 or 2, wherein the reaction method is selected from 000 vinyl polymers. 4. The reaction according to claim 1, wherein the amount of the third component (C) added to the polyol (A) is in the range of 95: 5 to 10:90 (weight ratio). Method. 5. The reaction product mixture obtained by the method according to any one of claims 1 to 4, wherein the flow linear velocity of the mixture is one of the linear flow velocity in the mixer (I). / 5-1
A urethane-forming reaction method in which the mixture is guided to a non-stirring mixer (II) designed to have a ratio of / 100, and then subjected to a post-reaction. 6. The polyisocyanate group additive per mole of hydroxyl group of the polyol (A) is from about 0.8 mole equivalent to 1.
When it is 5 molar equivalents and the urethanization reaction rate in the reaction product mixture from the mixer (I) is in the range of 50% to 80%, the reaction product mixture is injected into the mixer (II). The reaction method according to claim 5. 7. The reaction product mixture obtained by the method according to claim 1, further comprising a self-cleaning type screw device for a high-viscosity fluid, or a spiral blade or a spiral band blade. A urethane-forming reaction method in which the mixture is guided into a stirred tank for post-reaction.