JPH09328533A - Epoxidized block copolymer, method for producing the same, and composition containing the copolymer - Google Patents

Abstract

(57) 【Abstract】 PROBLEM TO BE SOLVED: A epoxidized block copolymer suitable as a modifier or modification aid for rubber-like polymers or resin-like polymers, adhesives, pressure-sensitive adhesives, sealants, asphalt modifiers, etc. , And a composition using the polymer. SOLUTION: A block copolymer (C) comprising a polymer block (A) mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block (B) mainly composed of a conjugated diene compound.
Alternatively, an epoxidized block copolymer (E) obtained by epoxidizing the hydrogenated product (D) has a molar ratio R of hydroxyl groups to epoxy groups of 0.001 to 0.1. Coalescence, a method for producing the same, and a composition containing the copolymer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxidized block copolymer suitable as a modifier or modification aid for rubber-like polymers or resinous polymers, adhesives, pressure-sensitive adhesives, sealants, asphalt modifiers and the like. The present invention relates to a polymer, a method for producing the polymer, and a composition using the polymer.

[0002]

2. Description of the Related Art A block copolymer comprising a vinyl aromatic hydrocarbon compound and a conjugated diene compound and its hydrogenated product are transparent and have the same properties as vulcanized natural rubber or synthetic rubber without vulcanization. Since it has elasticity at room temperature and has the same processability as a thermoplastic resin at high temperature, it is widely used in the fields of various modifiers and adhesives.

For the purpose of further improving the above performance, use of an epoxidized block copolymer obtained by epoxidizing an unsaturated carbon bond derived from a diene block of the block copolymer or its hydrogenated product. It has been known.
For example, USP3699184 describes that the introduction of an epoxy group increases the polarity of the polymer and improves the adhesion to the adhesive surface. In addition, JP-A-5-125197 and JP-A-6-116321 also propose an epoxidized block copolymer and a method for producing the same.

[0004]

[Problems to be Solved by the Invention]
The epoxidized block copolymer described in Japanese Patent Publication No. 97 has a structure in which, when the epoxidation reaction is carried out in the presence of an acid catalyst, the epoxy group is partially opened to contain both an epoxide and a hydroxyester group. It is stated that it can be. Further, it is described in JP-A-6-116321 that, in some cases, the hydroxyl group thus produced causes a gel in the polymer.

Further, even if an epoxidized block copolymer having a low gelled substance content is obtained, a gelled substance may be formed when it is subsequently heat-melted and molded. The formation of such a gelled substance has a problem that molding processability is significantly adversely affected.

From such a point of view, it is desired to find an epoxidized block copolymer having a low gel content in the polymer and having excellent adhesive properties and resin modification properties.

[0007]

As a result of intensive studies, the inventors of the present invention have found that the ratio of epoxy groups to hydroxyl groups of the epoxidized block copolymer has a great influence on the amount of gelation product. Heading out, the present invention has been completed.

That is, the present invention is a block copolymer (C) comprising a polymer block (A) mainly containing a vinyl aromatic hydrocarbon compound and a polymer block (B) mainly containing a conjugated diene compound. Alternatively, the molar ratio R of the hydroxyl group and the epoxy in the epoxidized block copolymer (E) obtained by epoxidizing the hydrogenated product (D) (represented by the following formula)
Relates to an epoxidized block copolymer, a method for producing the same, and a composition obtained from the copolymer. R = [OH] / [epoxy] (In the formula, [OH] represents the number of moles of the hydroxyl group contained in the epoxidized block copolymer per unit weight, and [epoxy] represents the epoxidized block copolymer per unit weight. Represents the number of moles of epoxy contained in the polymer)

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The block copolymer referred to in the present invention means a polymer block (A) mainly composed of a vinyl aromatic hydrocarbon compound, and a polymer block (B) mainly composed of a conjugated diene compound. A block copolymer (C) consisting of The hydrogenated product (D) of the block copolymer refers to a polymer obtained by partially hydrogenating an unsaturated carbon bond existing in the polymer block (B) of the block copolymer by a hydrogenation reaction. Further, the epoxidized block copolymer (E) referred to in the present invention means that the unsaturated carbon bond present in the polymer block (B) of the block copolymer (C) or its hydrogenated product (D) is epoxidized. Refers to the polymer.

Typical examples of the vinyl aromatic hydrocarbon compound which can form the block copolymer (C) are styrene and α
Examples include various alkyl-substituted styrenes such as styrene, alkoxy-substituted styrenes, vinylnaphthalene, alkyl-substituted vinylnaphthalene, divinylbenzene and vinyltoluene. Of these, styrene is preferred. One of these may be used, or two or more may be used in combination.

Typical examples of the conjugated diene compound which can form the block copolymer (C) include 1,3-butadiene, isoprene, 1,3-pentadiene and 2,3-dimethyl-1,3-
Examples thereof include butadiene, piperylene, 3-butyl-1,3-octadiene, phenyl-1,3-butadiene and the like. Among these, 1,3-butadiene and isoprene are preferable because they are inexpensive and easily available. Among these, one kind or a combination of two or more kinds can be used.

The copolymerization composition ratio (weight ratio) of the vinyl aromatic hydrocarbon compound and the conjugated diene compound which can form the block copolymer (C) is preferably 5/95 to 80/20,
More preferably, it is 10/90 to 60/40. The number average molecular weight of the block copolymer that can be used in the present invention is preferably
5,000 to 500,000, more preferably 10,000 to 10
It is 0,000. When the molecular weight is low, the properties of the rubber-like elastic body are difficult to be exhibited, and when the molecular weight is high, it is difficult to melt, which is not preferable. Here, the number average molecular weight means a standard polystyrene-equivalent molecular weight measured by the GPC method.

The structure of the block copolymer (C) is not particularly limited, but for example, ABA, BAB, ABABA
It may be a block copolymer of a vinyl aromatic hydrocarbon compound and a conjugated diene compound represented by The structure of the molecule itself may be any of linear, branched, radial, and the like, and may be any combination thereof. The vinyl aromatic hydrocarbon compound in the block copolymer may be distributed uniformly or in a taper shape. Further, in the copolymerized portion, a plurality of portions in which the vinyl aromatic hydrocarbon compound is evenly distributed and / or a portion in which the vinyl aromatic hydrocarbon compound is distributed in a tapered shape may coexist.

Block copolymer (C) before epoxidation
The manufacturing method is not particularly limited, and any method may be used. For example, Japanese Patent Publication No. 40-237
As described in Japanese Patent Publication No. 98, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 56-2892, etc.,
A method of producing in an inert solvent using a lithium catalyst or the like can be mentioned.

The method for producing the hydrogenated product (D) of the block copolymer is not particularly limited, and any method may be used. For example, as described in Japanese Patent Publication No. 42-8074 and Japanese Patent Publication No. 43-6636,
Examples thereof include a method of hydrogenating the block copolymer (C) in the presence of a hydrogenation catalyst in an inert solvent. Although the hydrogenation amount is not particularly limited, it is necessary that an unsaturated carbon bond capable of reacting with the epoxidizing agent remains in the molecule of the hydrogenated product (D) during the subsequent epoxidation reaction. This is because the site epoxidized by the epoxidizing agent is the unsaturated bond existing in the polymer block (B).

The method for producing the epoxidized block copolymer (E) of the present invention will be described below.

The production method of the present invention includes the block copolymer (C) produced as described above or its hydrogenated product (D).
To produce an epoxidized block copolymer through the following first to fourth steps.

The first step of the present invention is the block copolymer
In this step, an organic solvent is added to and mixed with (C) or its hydrogenated product (D) to prepare an organic solvent solution having a polymer concentration of 5 to 50% by weight. Typical examples of organic solvents that can be used include linear and branched hydrocarbons such as pentane, hexane, heptane, and octane, and alkyl-substituted derivatives thereof, cyclopentane, cyclohexane, cycloaliphatic hydrocarbons such as cycloheptane, and Those alkyl-substituted derivatives, aromatic and alkyl-substituted aromatic hydrocarbons such as benzene, naphthalene, toluene and xylene, aliphatic carboxylic acid esters such as methyl acetate, ethyl acetate and propyl acetate, halogenated hydrocarbons such as chloroform, etc. Can be mentioned. Among these, from the solubility of the block copolymer (C) or its hydrogenated product (D) and the ease of subsequent solvent recovery, cyclohexane, ethyl acetate, chloroform, toluene, xylene,
Preference is given to using hexane.

Block copolymer (C) or hydrogenated product (D) thereof
If the concentration is less than 5% by weight, substantially too much solvent is used, which is not economical. Further, if it is higher than 50% by weight, the solution viscosity is high, so that the mixing of the epoxidizing agent with the organic solvent solution or the slurry is not sufficiently performed in the second step, and the heat of the reaction is difficult to be removed. It is not preferable for the reason.

The second step of the present invention is a step of using an epoxidizing agent to epoxidize the unsaturated bonds present in the polymer in the organic solvent solution.

Block copolymer (C) or hydrogenated product (D) thereof
The epoxidation of can be performed by reaction with a known epoxidizing agent.

As the epoxidizing agent which can be used in the epoxidation reaction, organic peracids such as peracetic acid, perbenzoic acid, formic acid and trifluoroperacetic acid, hydrogen peroxide, hydrogen peroxide and low molecular weight fatty acids are used. A combination or the like can be exemplified. Of these, peracetic acid, which is industrially produced in large quantities and can be obtained at a low cost and has a relatively high stability, is preferable as the epoxidizing agent. Particularly preferably, peracetic acid is used as a solution prepared by dissolving it in a solvent such as ethyl acetate. Among these, peracetic acid-ethyl acetate solution is particularly preferable.
In addition, a catalyst may be used as necessary during the epoxidation.

The amount of the epoxidizing agent used is not particularly limited, and the reactivity of the epoxidizing agent, the desired degree of epoxidation, the unsaturated carbon in the block copolymer used or its hydrogenated product. The amount of the epoxidizing agent is selected so that the epoxy equivalent of the finally obtained epoxidized block copolymer (E) is 140 to 2700, though any appropriate amount may be used depending on the conditions such as the amount of bonding. Is preferred.

The epoxy equivalent is more preferably 200 to 20.
00. Here, the epoxy equivalent is calculated by the formula: epoxy equivalent = 1600 / {oxirane oxygen concentration in the epoxidized block copolymer (wt%)}, and oxirane oxygen is 1 mol.
The weight of the epoxidized block copolymer per unit is shown.

The oxirane oxygen concentration is determined by titration with an acetic acid solution of hydrogen bromide. When the epoxy equivalent is large, the oxysilane oxygen concentration is low, and conversely, when the epoxy equivalent is small, the oxirane oxygen concentration is high. If the epoxy equivalent is less than 140, the elastic properties of the polymer are hardly developed, which is not preferable. If it is larger than 2,700, the specific physical properties due to epoxidation are hardly developed, which is not preferable.

The epoxidation reaction temperature varies depending on the type and amount of the epoxidizing agent used, the organic solvent used, the block copolymer or the hydrogenated product, and is not particularly limited. For example, the reaction temperature when using peracetic acid as the epoxidizing agent is preferably 0 to 70 ° C. If the temperature is lower than 0 ° C, the reaction rate is slow, and if the temperature is higher than 70 ° C, the formed epoxy group is opened and the decomposition of peracetic acid proceeds. In order to improve the stability of peracetic acid, phosphates may be added to the reaction system during the epoxidation reaction.
Epoxidation reaction time is 0.1 to 72 hours, more preferably
From the viewpoint of productivity, it is preferable to select within the range of 0.2 to 10 hours.

The third step of the present invention is to wash the epoxidation reaction solution with water and / or to neutralize the solution so that the acid value of the solution is 5 m.
This is a step of reducing to gKOH / g or less. Here, the acid value is a value obtained by titration of the weight of potassium hydroxide necessary for neutralizing the acids present in 1 g of the reaction crude liquid after the epoxidation reaction.

The purpose of washing with water and / or neutralization is to remove by-products such as acids by-produced by the epoxidation reaction carried out in the previous step. When the acid value is higher than 5 mgKOH / g, the epoxy groups present in the epoxidized block copolymer are ring-opened and the physical properties are adversely affected, which is not preferable.

The washing with water may be carried out continuously or batchwise. In the case of a batch method, it is preferable to wash several times with 50 to 1000 parts by weight of water with respect to 100 parts by weight of the reaction crude liquid after epoxidation. In particular, when a large amount of epoxidizing agent is used, a corresponding amount of acids is by-produced, so it is preferable to sufficiently remove the acids by increasing the number of times of washing with water. During washing with water, an inorganic salt such as sodium chloride or sodium sulfate may be added in order to improve the separation between the aqueous phase and the organic phase.

Typical examples of the alkaline aqueous solution used for neutralization include lithium hydroxide, sodium hydroxide,
Potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate,
An aqueous solution of sodium acetate, potassium acetate, etc. may be mentioned. The amount of alkali used is preferably a molar amount necessary for neutralizing the acids present in the reaction solution. When the amount of alkali is large, the epoxy ring is opened and a hydroxyl group is generated, which is not preferable. Also, if the amount of alkali is small, the acid remains,
It is not preferable because the physical properties are adversely affected by the deterioration.
In order to prevent ring opening of the epoxy group due to heat generation during neutralization, it is preferable to neutralize the reaction crude liquid while cooling. At this time, the molar ratio R of the hydroxyl group to the epoxy is 0.001 to 0.1, preferably 0.001 to 0.05.

In the fourth step of the present invention, the epoxidation reaction solution containing the epoxidized block copolymer (E) obtained as described above is quantitatively supplied to the evaporator by, for example, a pump, and the reaction is carried out. In this step, the organic solvent is directly evaporated and removed from the solution to recover the epoxidized block copolymer. By this step, the organic solvent content in the epoxy block copolymer (E) is adjusted to 5000 ppm or less.

As the evaporator which can be used in the present invention, a flash tank type evaporator, a stirring tank type evaporator, a thin film evaporator, a wet wall tower type evaporator, a vertical type evaporator capable of multi-stage concentration of one or more stages Examples thereof include an evaporator with a screw and a vent type extruder. From the viewpoint of improving production capacity, two or more kinds of evaporators selected from these may be used in combination. Among these, it is most preferable to use the vent type extruder because the solvent removing ability is high and the amount of resin scorching is small.

The vent type extruder preferably used for carrying out the present invention will be described in detail below. The vent type extruder is an extruder having at least one degassing vent portion, preferably 1 to 10, and more preferably 1 to 5. The extruder has at least one shaft, preferably at least two shafts. Of these, the twin-screw vent type extruder is particularly preferable from the viewpoint of versatility.

The vent type extruder having such a structure is L
/ D = 2 to 50, preferably 4 to 40 (L is the screw length, D is the outer diameter of the screw), and the screw engagement structure may be meshing or non-meshing, and the rotation direction May be in the same direction or different directions.

Among the twin-screw vent type extruders, those having a structure capable of passing a heat medium inside the screw are particularly preferable. An extruder having such a structure is preferable from the viewpoint of being able to sufficiently supply a large amount of heat which is lost when the organic solvent evaporates. Further, the one having a continuous gas phase portion in the upper part of the extruder is preferable from the viewpoint of the removal efficiency of the organic solvent.

The temperature inside the evaporator and the pressure inside the evaporator are selected in consideration of the treatment capacity, the characteristics of the polymer (viscosity, thermal stability, etc.), the type and concentration of the organic solvent, the quality of the product, and the like. The temperature inside the evaporator is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. If the temperature inside the evaporator is less than 80 ° C, the organic solvent is not sufficiently removed and the viscosity becomes low,
On the other hand, if the temperature is higher than 300 ° C, a large amount of gel is generated in the polymer, which is not preferable. In particular, if the epoxidized block copolymer stays at a high temperature in the evaporator used in the fourth step and a large amount of gel is generated, the melt viscosity is increased, and fish eyes are liable to be formed, which causes molding defects, which is not preferable. The gel content is preferably 5 wt% or less,
It is more preferably 3 wt% or less, and particularly preferably 1 wt% or less.

The pressure inside the evaporator is preferably 500 torr.
Below, it is more preferably selected from the range of 400 to 1 torr. The pressure inside the evaporator refers to the pressure at the location showing the lowest pressure in the vapor phase portion in contact with the resin inside the evaporator. In the case of an extruder, it usually means the value read by a pressure gauge attached to the vent part. The pressure inside the evaporator
When it is higher than 500 torr, the organic solvent is not sufficiently removed, which is not preferable. The screw rotation speed when using a vented extruder is 20 to 500 rpm, preferably 30 to 400 rpm.
It is.

The organic solvent is removed from the epoxidation reaction solution by evaporating and removing it directly (hereinafter, also referred to as "direct solvent removal") by the above steps, and the residual organic solvent in the finally obtained epoxidized block copolymer is obtained. The content is preferably 5000 ppm or less, more preferably 2000 ppm or less, particularly preferably 1000 ppm or less. The organic solvent includes those used when producing the block copolymer (C) or its hydrogenated product (D), those used during the epoxidation reaction, or those used in other steps. sell. When the content of the residual organic solvent is more than 5000 ppm, foaming or odor is generated when the epoxidized block copolymer is molded into a product form, which is not preferable. The residual organic solvent content can be easily adjusted by changing conditions such as the temperature of the evaporator, the pressure inside the evaporator, and the processing speed.

The epoxidized block copolymer directly desolvated by an evaporator can be obtained in the form of foam crumb, granules or powder, or in the form of strands or pellets. It is preferably in pellet form.

In carrying out the present invention, a solution of the block copolymer (C) produced as described above or the hydrogenated product (D) thereof in an organic solvent in the fourth step (the product obtained after completion of the third step) is used. , For example, can be quantitatively supplied to the evaporator by a pump, and after adding the phenol stabilizer and / or the phosphorus stabilizer to the epoxidation reaction solution, the organic solvent can be directly evaporated and removed from the reaction solution. . Epoxidized block copolymer (E) obtained by this method
Has a significantly improved thermal stability, does not easily generate a gel even when the epoxidized block copolymer (E) is left at a high temperature, and can significantly suppress a decrease in hue. Also, in general, to add stabilizers to plastics and rubber,
A step of kneading the stabilizer into the copolymer using a device such as a kneading extruder is required. However, according to this method of the present invention, it is only necessary to add a stabilizer to the epoxidation reaction solution of the epoxidized block copolymer (E), a step of kneading the stabilizer is not required, and the operation is economical. Above all preferred.

A typical example of the phenolic stabilizer which can be used in the present invention is tetrakis (methylene-3- (3 ', 5'-
Di-tert-butyl-4'-hydroxyphenyl) propionate) methane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4'-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 2,4-bis- (n-octylthio)-
6- (4-hydroxy-3-5-di-tert-butylanilino) -1,3,5-triazine, octadecyl-3- (3,5
-Di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis (3- (3-
tert-butyl-5-methyl-4-hydroxyphenyl)
Propionate, 1,3,5-Tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid, 2,2′-methylenebis- (4-methyl-6-tert
-Butylphenol, 3,9-bis (2- (3- (3-
tert-butyl-4-hydroxy-5-methylphenyl)
Propionyloxy) -1,1-dimethylethyl) -2,
4,8,10-Tetraoxaspiro [5.5] undecane, 2,6
-Di-tert-butyl-4-ethylphenol, butylated hydroxyanisole, 2,2'-dihydroxy-3,3 '
-Dicyclohexyl-5,5'-dimethyl-diphenylmethane, 1,1,3-tris (2-methyl-4-hydroxy-5)
-Tert-butylphenyl) butane, 4,4'-butylidenebis-6-tert-butyl m-cresol, bis (3-
Cyclohexyl-2-hydroxy-5-methylphenyl)
Methane, 2,2'-methylenebis- (4-ethyl-6-tert
-Butylphenol), 1,1-mebis- (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) butane, and the like. These phenolic stabilizers can be used in combination of two or more kinds.

Typical examples of the phosphorus-based stabilizer that can be used in the present invention are trisnonylphenylphosphite and tris.
(2,5-di-tert-butylphenyl) phosphite, tris (2-di-tert-butylphenyl) phosphite, tris (2,4-bis (1,1-dimethylpropyl) phenyl) phosphite, etc. Can be mentioned. These phosphorus stabilizers are 2
A combination of more than one type can also be used.

In the present invention, the phenol-based stabilizer or the phosphorus-based stabilizer may be used alone, or both may be used in combination. The amount of the phenolic stabilizer and / or phosphorus stabilizer added is 0.005 to 10 parts by weight based on 100 parts by weight of the epoxidized block copolymer finally obtained after removing the solvent. Parts, preferably 0.05 to 3 parts by weight, more preferably 0.1.
~ 2 parts by weight. The amount of stabilizer to be added can be easily calculated from the block copolymer concentration in the solution and the desired concentration. If the amount of stabilizer added is less than 0.005 parts by weight,
It is inferior in thermal stability, and even if it is more than 10 parts by weight, the effect of improving thermal stability further is small, which is not preferable from the economical viewpoint.

In carrying out the present invention, the block copolymer (C) produced as described above in the fourth step is also used.
Alternatively, the organic solvent solution of the hydrogenated product (D) (the product obtained by the third step above) is removed by the first evaporator (one-step concentration), and then the second kneading evaporator is used. Distill off the remaining volatiles (two-stage concentration) and evaporate the organic solvent under conditions with a short residence time to produce a polymer with a residual organic solvent concentration of 500 ppm or less without giving a long-term heat history. be able to.

As the evaporator (first evaporator) used for the one-step concentration in this method, a multi-tube evaporator, a liquid film evaporator, a centrifugal thin film evaporator, a plate evaporator and the like can be exemplified, and particularly preferred. Is a multi-tube evaporator, centrifugal thin film evaporator,
It is a plate-type evaporator. These have many contact surfaces with the epoxidation reaction solution and are suitable for concentration when the solvent content is high. The concentration of organic solvent (concentration of volatile matter) is 5 by one-step concentration.
˜70% by weight, preferably 20 to 30% by weight. By using the first evaporator, the size of the second evaporator can be reduced.

The kneading evaporator (second evaporator) used for the two-stage concentration has a kneading shaft such as a biaxial type surface renewal type self-cleaning type evaporator and a vent type extruder. In order to secure a large heat transfer area, it is preferable to select a kneading type evaporator capable of passing a heat medium inside the screw. The kneading type evaporator having such a structure,
A large amount of heat necessary for the evaporation of the organic solvent can be sufficiently supplied. Further, it is particularly preferable because it has excellent kneading performance due to the piston flow property without backmixing, and the evaporation area can be increased. The structure of the kneading evaporator is L / D = 2
-50, preferably 4-40 (L is the length of the screw, D is the outer diameter of the screw), and the screw engagement structure may be either "meshing" or "non-meshing". May be in the same direction or in different directions. The kneading type evaporator can remove the organic solvent without impairing the stability of the epoxidized product even when the organic solvent concentration becomes low and the viscosity of the epoxidation reaction solution becomes high.

As a heat source for each evaporator, a heat medium such as oil, steam, or an electric heater can be used.

As a specific embodiment of this method, first, the epoxidation reaction solution is continuously fed to a first evaporator by a gear pump, and the solvent is distilled off in a flash tank at a heating temperature higher than the boiling point of the solvent. Here, the epoxidation reaction solution may be washed in advance with water. Washing with water may be carried out continuously or batchwise. In the case of a batch system, it is preferable to wash with 50 to 1,000 parts by weight of water several times to 100 parts by weight of the reaction crude liquid after epoxidation.

By heating and evaporating in the first evaporator, the organic solvent contained in a large amount in the epoxidation reaction solution can be easily removed.

In this method, the volatile matter is distilled off from the concentrate from the first evaporator in the second evaporator, and the organic solvent and the epoxidized block copolymer are separated. By distilling off the volatile components using the second evaporator, the remaining organic solvent contained in the concentrate can be stably evaporated under conditions where the residence time is short, without giving a long-term heat history. Epoxidized block copolymers can be produced.

The epoxidized block copolymer obtained is
It can be extruded by a conventional method to select any form of strands, pellets, foam crumbs, granules and powders, but pellets are preferred.

The temperature and pressure inside the evaporator and the kneading type evaporator are selected in consideration of the treatment capacity, the characteristics of the polymer (viscosity, thermal stability, etc.), the kind and concentration of the solvent, the quality of the product and the like. The temperature inside both evaporators is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. If the temperature inside the evaporator is lower than 80 ° C., the viscosity increases, so that it is difficult to extract the organic solvent unless the degree of vacuum is increased, and if the temperature is higher than 300 ° C., gel is generated in the polymer, which is not preferable. In particular, when the epoxidized block copolymer stays in the evaporator and a large amount of gel is generated, the melt viscosity becomes high, and fish eyes are liable to be generated in the product, resulting in defective molding, which is not preferable. The gel content is preferably 5% by weight or less, more preferably 3% by weight or less, and particularly 1% by weight.
The following is preferred. The gel content is shown by weight% of tetrahydrofuran (THF) insoluble matter.

As another method for carrying out the fourth step of the present invention, the following method can be adopted. That is, the organic solvent solution of the block copolymer (C) or its hydrogenated product (D) produced as described above (the product of the above third step), the solvent is removed by the steam stripping method, A slurry is obtained in which the coalescence is crumb-like and dispersed in water. The specific processing method by the steam stripping method is not particularly limited, and any of well-known methods can be used. A crumbing agent may be used in the steam stripping, and as such a crumbing agent, an anionic surfactant, a cationic surfactant, or a nonionic surfactant is generally used. The amount of these surfactants added is preferably 1 to 20 relative to the water in the tank for steam stripping.
The range is 000 ppm, more preferably 5 to 5000 ppm, and particularly preferably 10 to 500 ppm. If it is less than 1 ppm, the dispersibility of the deposited crumbs will be reduced, and if it exceeds 20,000 ppm, bubbling will be severe and operation will be disturbed, which is not preferable. That is, it is preferably as small as possible within the range where stable crumb dispersibility can be maintained. In addition to these surfactants, Li,
Water-soluble salts of metals such as K, Na, Mg, Ca, Al and Zn can be used as dispersion aids.

The slurry of the epoxidized block copolymer containing water obtained above is dehydrated and dried by a general method. As the dehydrator, a rotary screen, a vibrating screen, a centrifugal dehydrator, a screw extruder type squeezing dehydrator or the like can be used. As the drying device, a screw extruder type or kneader type dryer, an expander type dryer,
A hot air dryer or the like can be used. The water content in the dried polymer is generally less than 1% by weight, preferably 0.5% by weight or less,
More preferably, it is 0.1% by weight or less. A particularly suitable dryer is a multi-screw vent extruder type dryer having one or more than one screw, and L / D = 10 to 40 can be used.

When the water content after drying is 1% by weight or more, it is not preferable because foaming occurs when the polymer is molded and appearance defects such as silver occur. The dried polymer can be obtained in any form such as granular form, powder form, pellet form and strand form. In addition, dehydration and drying can be carried out at the same time with an apparatus having both a dehydrator and a dryer. Such a device has at least one, preferably 2 to 4 slits for dehydration.
A vent extruder having a shaft or more can be used. The vent extruder having such a structure preferably has an L / D of about 15 to 50, and the screw meshing structure may be either meshing or non-meshing, and the rotating direction may be the same direction or different directions. But it's okay.

The screw rotational speed, cylinder temperature, and vent pressure of such a vent extruder are selected in consideration of extrusion capability, polymer characteristics (viscosity, thermal stability, etc.), product quality, etc. However, the screw speed is generally 20 to 500rp
m, preferably 30-400 rpm, cylinder temperature 100-300
C., preferably 120 to 250.degree. C., and the pressure in the vent section is selected from the range of atmospheric pressure to 1 torr, preferably 500 to 5 torr.

Also in this method, in order to obtain an epoxidized block copolymer having excellent thermal stability and hue, the above-mentioned phenol-based stabilizer and / or phosphorus-based stabilizer is blended with the epoxidized block copolymer. You can By blending these stabilizers, thermal deterioration of the epoxidized block copolymer when placed under heating can be significantly suppressed.

In this method, the phenolic stabilizer or the phosphorus stabilizer may be used alone or in combination. The amount of phenolic stabilizer and / or phosphorus stabilizer added is 100% by weight of the epoxidized block copolymer.
The amount is 0.005 to 10 parts by weight, preferably 0.05 to 3 parts by weight, and more preferably 0.1 to 2 parts by weight. If the amount added is less than 0.005 parts by weight, the thermal stability will be poor, and if it is more than 10 parts by weight, the effect of improving the thermal stability will be less, and it is not preferable from the economical aspect. The timing of adding these stabilizers is not particularly limited, and may be any step until the final production of the epoxidized block copolymer. For example, a heat-resistant stabilizer or the like may be added to the organic solution or slurry of the epoxidized block copolymer before steam stripping. Further, when the hydrous crumb after steam stripping is dehydrated and dried by an extruder, it may be added at the same time. Further, the dried polymer may be kneaded again using a kneading extruder.

A feature of the present invention is that the molar ratio R of hydroxyl groups to epoxy groups in the epoxidized block copolymer (E) obtained as described above (represented by the following formula) is 0.001 to 0.1.
It is to be. R = [OH] / [epoxy] (In the formula, [OH] represents the number of moles of the hydroxyl group contained in the epoxidized block copolymer per unit weight, and [epoxy] represents the epoxidized block copolymer per unit weight. The number of moles of epoxy contained in the polymer is shown.) A hydroxyl group is mainly formed by ring opening of an epoxy group with an acid or a base. R is preferably 0.001 to 0.05. R is
When it is larger than 0.1, gel is likely to be generated in the polymer, which is not preferable.

In order to control the ratio R of the hydroxyl groups to the epoxy groups to be low, it was found that the following means should be taken. Peracetic acid is used as an epoxidizing agent for the reaction under mild temperature conditions. By using a peracetic acid-ethyl acetate epoxidizing agent, an epoxy group ring-opening reaction (formation of a hydroxy ester group, etc.) can be performed as compared with an epoxidizing agent system containing a strong acid such as sulfuric acid or p-toluenesulfonic acid and / or water. ) Can be reduced, and as a result, the R value is also reduced. By removing acetic acid by washing with water and neutralization, epoxy ring-opening at high temperature in solvent removal can be reduced, and as a result, the R value also becomes low.

The acid value of the epoxidized block copolymer is preferably 10 mgKOH / g or less. Here, the acid value of the epoxidized block copolymer means that the acids present in 1 g of the epoxidized block copolymer obtained by removing the solvent and drying after the epoxidation reaction are neutralized. The required weight of potassium hydroxide is a value obtained by titration. Acids are mainly by-produced during the epoxidation reaction. For example, when peracetic acid is used as the epoxidizing agent, acetic acid is by-produced during the epoxidation reaction. In addition, the raw material impurities and acids derived from various additives used in the production of the epoxidized block copolymer as described above may also be used in the present invention as long as they can be quantified by titration with potassium hydroxide. It is included in the acid value. Acid value is 10mgKOH /
When it is higher than g, the amount of the gelled product in the finally obtained epoxidized block copolymer increases, and the melt flow processability deteriorates, which is not preferable. In particular, when the epoxidized block copolymer and another resin or rubber are melt-kneaded at a high temperature, a high acid value causes a large amount of a gelled product to be formed during the melt-kneading, which results in molding and processing of the composition. Have a significant adverse effect on sex.

The chloride ion content in the epoxidized block copolymer is preferably 7 ppm or less. In order to reduce the chloride ion content in the epoxidized block copolymer, a method of using a peracetic acid-based epoxidizing agent containing no chloride ion as the epoxidizing agent can be mentioned.

The epoxidized block copolymer of the present invention is
It can be obtained in any form of liquid, foam crumb, strand, pellet, or powder, but is preferably pellet.

In the epoxidized block copolymer of the present invention, various additives such as a heat stabilizer, an antiaging agent, a crosslinking agent, an ultraviolet absorber, or silica, talc, carbon, glass fiber, etc. may be added as required. Inorganic fillers, organic fillers, plasticizers, and softeners such as oil can be blended and used. The timing of addition of these is not particularly limited and may be any step until finally obtaining the epoxidized block copolymer.

In the present invention, in order to prevent the epoxidized block copolymer (E) of the present invention from blocking each other, an antiblocking agent is added per 100 parts by weight of the epoxidized block copolymer (E). 0.001 to 5 parts by weight, preferably 0.01 to 2 parts by weight, and more preferably 0.05 to 1 part by weight. If the compounding amount of the antiblocking agent is less than 0.001 part by weight, a sufficient blocking suppressing effect is not observed, and if it is more than 5 parts by weight, blocking can be avoided, but the inherent properties of the epoxidized block copolymer, especially All of them are not preferable because they have a significant adverse effect on transparency. The epoxidized block copolymer composition thus obtained can significantly prevent the powder itself, the pelletized composition itself, and various products such as films and sheets prepared therefrom from blocking each other. To be done.

As the antiblocking agent which can be used,
Examples thereof include silicon compounds, fatty acid salts, fatty acid esters, fatty acid amides, nonionic surfactants and the like. Typical examples of the silicon-based compound include silicon fluids such as silicon oxide, silicon oil, and silicon emulsion. Silicon fluids include alkyl, aryl having 0 to 12 carbon atoms per unit,
Includes cycloalkyl substituted silicon compounds. Of these, silicon oxide and polydimethylsiloxane are particularly preferable. The silicon oxide preferably has an average particle size of 0.005 to 25 μm.

The fatty acid residue constituting the fatty acid salt and the fatty acid ester as the antiblocking agent is selected from the range of 10 to 20 carbon atoms per molecule, preferably
12 to 18 things. Less than 10 carbon atoms, or
When it is more than 20, it is not preferable because a sufficient blocking inhibiting effect is not recognized. Typical examples of the fatty acid salt include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc.
Examples thereof include salts of metals belonging to Group III and Group IV. Among these, calcium stearate is preferable. Representative examples of the fatty acid ester include glycerin monostearate, glycerin distearate, glycerin tristearate, and the like, and glycerin monostearate is particularly preferable. The fatty acid salt and the fatty acid ester may be used alone or as a mixture of two or more kinds.

Typical examples of the fatty acid amide as the antiblocking agent include stearic acid amide, oleic acid amide, ethylene bisstearamide and the like.
Representative examples of nonionic surfactants as antiblocking agents include sorbitan ester, propylene glycol fatty acid ester, sucrose fatty acid ester, citric acid mono (di or tri) stearate ester, pentaerythritol fatty acid ester, trimethylol fatty acid ester. , Polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester, polypropylene glycol fatty acid ester, polyoxyethylene glycol fatty alcohol ether, polyoxyethylene alkylphenyl ether, N, N -Bis (2-hydroxyethylene)
Examples thereof include a fatty amine, a condensation product of a fatty acid and diethanolamine, a block polymer of forioxyethylene and polyoxypropylene, polyethylene glycol, polypropylene glycol and the like. Particularly preferred nonionic surfactants are those having a polyoxyethylene unit, and polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene Examples thereof include block polymers of ethylene and polyoxypropylene.

It is also possible to use at least one kind from each group of the above-mentioned anti-blocking agents, and optionally to mix two or more kinds from the group. Further, a mixture of at least two kinds selected from different groups such as a silicon compound, a fatty acid salt, a fatty acid ester, a fatty acid amide, an anti-blocking agent made of a nonionic surfactant, and the like is mixed and used. You can also

As a method of incorporating the anti-blocking agent, it is preferable from the economical viewpoint that the epoxidized block copolymer (E) is attached to the surface of the pellet. Specifically, (i) a method in which the pellets are directly sprinkled with an anti-blocking agent or applied, and then dried if necessary,
(ii) A method of attaching the antiblocking agent to the pellet surface by cutting the strand extruded from the die of the extruder in water in which the antiblocking agent is dissolved or suspended in advance and drying the wet pellets. (Iii) A method in which the polymer (E) and the antiblocking agent are dry-blended, and then kneaded and granulated by a general-purpose extruder.

Next, the epoxidized block copolymer of the present invention can also be used as a thermoplastic resin composition with a thermoplastic resin and / or a rubbery polymer. The thermoplastic resin composition of the present invention contains (a) an epoxidized block copolymer of 99 to 1% by weight, and (b) a thermoplastic resin and / or a rubbery polymer of 1 to 99% by weight. .

The thermoplastic resin in the component (b) used in the present invention is a generic term for a thermoplastic resin that can be melted by heating to be molded into an arbitrary shape. Specific examples of this thermoplastic resin include:
Polyolefin resin such as polyethylene and polypropylene, polyamide resin such as nylon 46, nylon 6, nylon 66, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, crystalline thermoplastic polymer such as polyamide elastomer and polyester elastomer, ABS resin, AES resin, AAS resin, M
Rubber modified polymer such as BS resin, acrylonitrile-styrene copolymer, styrene-methyl methacrylate copolymer, polystyrene, polymethylmethacrylate, polycarbonate, non-crystalline thermoplastic polymer such as polyphenylene oxide, or 2 to 8 carbon atoms. Another polymer graft polymerized into a polymerized unit having an α-monoolefin as a main repeating structural unit, for example, an ethylene-propylene copolymer acrylonitrile-styrene copolymer graft polymerized graft polymer, Ethylene
Acrylonitrile-styrene copolymer graft-polymerized with butene copolymer, ethylene-butene copolymer butyl acrylate-methyl methacrylate copolymer-grafted polymer, ethylene-butene copolymer methyl Examples thereof include a graft polymer obtained by graft-polymerizing a methacrylate copolymer, and particularly, polyamide resin, polyester resin, polycarbonate and the like are preferable as a component for improving the heat resistance of the composition.

The rubbery polymer which is the other component constituting the component (b) is a general term for natural rubber and synthetic rubber. Specific examples of the rubbery polymer include styrene-butadiene rubber and hydrogenated products thereof, isoprene rubber, nitrile rubber and hydrogenated products thereof, chloroprene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylenediene rubber, ethylene- Butene rubber, ethylene-butene diene rubber, acrylic rubber, α, β-unsaturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, chlorinated polyethylene rubber, fluororubber, silicone rubber, urethane rubber, epichlorohydrin rubber, polysulfide rubber, Representative examples include styrene-butadiene block polymers and hydrogenated products thereof.

Among these rubbery polymers, preferably a hydrogenated product of styrene-butadiene rubber and ethylene-
Propylene rubber, ethylene-propylene-diene rubber,
Ethylene-butene rubber, ethylene-butene-diene rubber, acrylic rubber, chlorinated polyethylene rubber, fluororubber, silicone rubber, urethane rubber, epichlorohydrin rubber, polysulfide rubber, hydrogenated styrene-butadiene block polymer, α, β-non- A rubber having a substantially low degree of saturation or unsaturation, such as a saturated nitrile-acrylic acid ester-conjugated diene copolymer rubber, and a modified rubber having a functional group added thereto.

The thermoplastic resin composition and elastomer composition of the present invention are (a) an epoxidized block copolymer and
(B) The main component is a thermoplastic resin and / or a rubbery polymer, but the mixing ratio is (a) component 99 to 1% by weight,
The amount is preferably 95 to 5% by weight, more preferably 90 to 10% by weight, the component (B) is 1 to 99% by weight, preferably 5 to 95% by weight, and more preferably 10 to 90% by weight.

Here, if the content of the component (a) exceeds 99% by weight, the effect of improving the physical properties is insufficient, while if it is less than 1% by weight, various physical properties as an elastomer are inferior, which is not preferable. If the amount of the component (b) is less than 1% by weight, the effect of improving the physical properties due to the addition of the component (b) is not recognized,
On the other hand, if it exceeds 99% by weight, the characteristics as a thermoplastic elastomer will be lost, which is not preferable.

The component (b) used in the present invention is in a very wide range, because the epoxidized block copolymer which is the component (a) has a rubbery and extremely flexible form. This is because the resin has a wide variety of forms, including hard ones.

Therefore, whether the thermoplastic resin is used, the rubbery polymer is used, or both are used as the component (b) is mainly determined by the properties of the component (a) and the composition to be obtained. It is due to the purpose of.

More specifically, usually, when the vinyl aromatic compound in the component (a) is 40% by weight or less, the component (a) exhibits a rubber-like flexible property, and therefore, as the component (b), It is desirable to blend a thermoplastic resin and design to obtain a well-balanced thermoplastic polymer composition.

On the other hand, if the vinyl aromatic compound in the component (a) is 60% by weight or more, the component (a) exhibits a relatively resin property, so that a rubbery polymer is blended as the component (b). It is desirable to design as a thermoplastic elastomer. (A) The content of vinyl aromatic compounds in the component is 40
When the content is more than 60% by weight and less than 60% by weight, it is desirable to use a thermoplastic resin and a rubber polymer as the component (B) together to design a thermoplastic elastomer having a comprehensive balance.

Further, in the present invention, the composition is designed by taking advantage of the unique property of the epoxidized block copolymer as the component (a), that is, the property of acting as a compatibilizing agent between different polymers. You can also In general, when a block polymer is used as a compatibilizer, it is known that the addition amount thereof is about several% by weight. The minimum amount of component (A) used in the present invention is about 1% by weight because it is considered to use component (A) as a compatibilizer.

That is, when the component (a) is used as a compatibilizer, a thermoplastic resin and a rubbery polymer are used as the component (b), and a thermosetting resin is used as the component (c).

Here, the component (a) effectively acts as a compatibilizing agent is a combination of a specific thermoplastic resin and a specific rubbery polymer.

In this case, for example, as the thermoplastic resin, a styrene resin (polystyrene, AS resin, ABS
Resin, AAS resin, AES resin, ACS resin, MBS resin, HIPS resin, styrene-butadiene copolymer, etc.), aromatic polyethers (polyphenylene ether, etc.), polycarbonate resin, polyethylene, polypropylene, polyolefin such as polybutene-1 Examples thereof include a system resin, a graft polymer in which another polymer is graft-polymerized to a polymer having a C 2-8 α-monoolefin as a main constituent, and a mixture of two or more thereof.

The rubbery polymer in this case is
Ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-butene-
Examples thereof include monoolefin copolymer rubbers such as diene rubber, chlorinated polyethylene rubbers, styrene-butadiene rubber hydrogenated products, nitrile rubber hydrogenated products, and styrene-butadiene block polymer hydrogenated products.
The combination of the thermoplastic resin and the rubbery polymer described above has a structure similar to the polystyrene structure, which is the basic structure of the epoxidized block polymer of the present invention, or a polyolefin structure,
Alternatively, it is a combination of polymers having a structure having an affinity with the aromatic vinyl polymer. However, since the epoxidized block polymer of the present invention has an epoxy group, it can function as a compatibilizer with a polymer that is usually incompatible through a chemical reaction between functional groups or affinity. is there. The epoxidized block polymer of the present invention is
As a thermoplastic resin having reactivity and affinity with an epoxy group that works effectively as a compatibilizer, (here, having reactivity and affinity with an epoxy group means reacting with an epoxy group in the resin, A residue (for example, a carboxylic acid group, a hydroxyl group amino group, etc.) or a bond (for example, an ester bond, an amide bond, etc.) is meant, for example, 6-nylon, 6,6-nylon, 4,6-nylon, 11-nylon,
Polyamide resin such as 12-nylon, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, polyimide, polyamide imide, carboxylic acid-containing polyolefin (ethylene- (meth) acrylic acid copolymer, maleic acid modified polypropylene, etc.), poly Examples thereof include vinyl acetate, ethylene-vinyl acetate copolymer, and a mixture of two or more thereof.

Further, examples of the rubbery polymer reactive with the epoxy group effectively acting as the compatibilizer include polyamide elastomer, polyester elastomer, epichlorohydrin rubber, urethane rubber and the like.

Even when the component (a) is used as a compatibilizer, a thermoplastic resin and / or a rubber polymer other than the above may be blended.

Further, as the other component (c), a phenol resin, an epoxy resin, a melamine resin, an unsaturated polyester resin, an alkyd resin or the like may be blended.

Regarding the contents of the combination of the component (a) and the component (b), the relationship between the properties of the component (a) and the polymer used as the component (b) is generalized. Thus, the composition of the present invention is not limited to the above contents, and the contents of the component (b) can be selected according to the purpose.

The polymer used as the component (b) is
A plurality of thermoplastic resins and / or a plurality of rubbery polymers may be mixed and used.

Further, when a thermoplastic resin and a rubbery polymer are used in combination as the component (b), each of them can be used in an arbitrary ratio depending on the desired performance of the final composition.

The thermoplastic polymer composition containing the component (a) and the component (b) of the present invention described above can be used in a conventional kneading machine such as a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a twin screw. An extruder or the like can be used, but a sealed type or an open type, which can be replaced by an inert gas, is preferable.

The kneading temperature is a temperature at which all the components to be mixed melt, and is usually 140 to 300 ° C., preferably 1
It is preferably in the range of 60 to 280 ° C. Further, in kneading, each component may be kneaded together, or after kneading any component, the remaining components are added,
A multi-stage divided kneading method of kneading can also be adopted.

In the thermoplastic resin composition of the present invention, various additives such as anti-aging agent, cross-linking agent, heat stabilizer, UV absorber, silica, talc, carbon, glass fiber, etc. may be added as required. Inorganic fillers, plasticizers, and softeners such as oil can be blended and used.

Next, the epoxidized block copolymer of the present invention can be used as a thermosetting resin composition. As the thermosetting resin that can be blended with the epoxidized block copolymer used in the present invention, phenol resin, epoxy resin, melamine resin, unsaturated polyester resin,
Examples thereof include alkyd resins, but phenol resins, epoxy resins, and unsaturated polyester resins are preferable from the viewpoint of easy mixing work.

The mixing ratio of the thermosetting resin and the epoxidized block copolymer varies depending on the purpose, but the content of the epoxidized block copolymer in the composition is 1 to 80% by weight, preferably 1 to 50% by weight, more preferably 2 to 25
% By weight.

The content of epoxidized block copolymer is 1
If it is less than 80% by weight, the impact resistance improving effect is poor.
When it exceeds, it becomes impossible to maintain the high strength which is the original characteristic of the thermosetting resin.

The method of mixing the thermosetting resin composition of the present invention is not particularly limited, but heating and kneading are preferable. A closed mixer such as a Banbury mixer, a roll or an extruder can be used.

Further, in the thermosetting resin composition of the present invention,
If necessary, various additives such as antiaging agents, stabilizers, plasticizers, softeners, various inorganic or organic fillers, reinforcing agents, curing agents and the like can be compounded and used.

As the curing agent used in the present invention, known curing agents used for epoxy resins can be used, and amines, polyamide resins, acid anhydrides, polymercaptan resins, novolac resins, dicyandiamide, boron trifluoride can be used. And the amine complex of Here, the amines include the following. Aliphatic polyamines such as diethylenetriamine, triethylenetetramine, menthenediamine, metaxylylenediamine, bis (4-amino-3-methylcyclohexyl) methane, etc., and adducts of said aliphatic polyamines with known epoxy compounds, and reaction with acrylonitrile Substance, a reaction product with a ketone. Aromatic polyamines such as metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and diaminodiphenyl sulfide, and adducts of the aromatic polyamines with known epoxy compounds. Secondary and tertiary amines such as tris (dimethylaminomethyl) phenol, piperidine, imidazole and its derivatives, and salts thereof. And mixtures of said amines.

The polyamide resin includes a reaction product of a fatty acid such as fatty acid, dimer acid and trimer acid with an aliphatic polyamine.

The acid anhydride includes the following.
Phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic acid anhydride Acid anhydrides such as succinic anhydride, dodecenyl succinic anhydride and succinic anhydride, and mixtures of the acid anhydrides.

Novolak resins include low molecular weight resinous products made by condensation of phenol or a mixture of phenol and cresol, dihydroxybenzene with formaldehyde.

As the amine complex of boron trifluoride, monoethylamine, piperidine, aniline, butylamine,
Included are complexes of boron trifluoride with low molecular weight amine compounds such as dibutylamine, cyclohexylamine, dicyclohexylamine, tributylamine, triethanolamine.

Other curing agents include salts of super strong acids such as boron tetrafluoride, phosphorus hexafluoride and arsenic hexafluoride, such as diazonium salts, iodonium salts, bromonium salts and sulfinium salts.

The epoxidized block copolymer obtained by the method of the present invention can be used as various molded products such as sheets, films, injection molded products of various shapes, hollow molded products, and the like, and can be modified with various thermoplastic resins. It is useful as a material for quality agents, adhesives, adhesives, asphalt modifiers, home appliances, automobile parts, industrial parts, household products, toys, and the like.

Among these applications, the epoxidized block copolymer of the present invention can be used as an adhesive (including a pressure-sensitive adhesive, a pressure-sensitive adhesive, a laminating adhesive and a secondary adhesive), a sealant and a coating. , Asphalt modifier, film,
It is useful as a printing plate. In particular, the epoxidized block copolymer of the present invention can be suitably used as an adhesive composition, a sealant composition, a coating composition, and an asphalt composition.

In addition to the epoxidized block copolymer and the curing aid or curing agent (as described above), the various compositions of the present invention may be formulated so as to meet the required performances of individual applications.
It is compounded with various combinations of components including adhesion promoters or tackifiers, plasticizers, fillers, solvents, stabilizers and other components (eg asphalt).

Typical tackifiers include diene-olefin copolymers of piperidine and 2-methyl-2-butene, and aliphatic hydrocarbon resins composed of 1,3-pentadiene.

Aromatic resins can also be used as tackifiers, provided that they are compatible with the particular polymer used in the formulation. In general, mixtures of aromatic resins having a high softening point and aromatic resins having a low softening point may be used, but these resins should also have a Ring and Ball softening point of 80-118 ° C. A useful resin is coumarone-
Indene resin, polystyrene resin, vinyltoluene-α
Methylstyrene copolymers and polyindene resins are mentioned.

Tackifiers also useful in the compositions of the present invention include hydrogenated rosins, rosin esters, polyterpenes, terpene phenolic resins and polymerized mixed olefins, low softening point resins and liquid resins.
An example of a liquid resin is Adtac LV (Adtac is a trademark) resin from Hercules. To obtain good thermal oxidation and color stability, the tackifier is a saturated resin, hydrogenated dicyclopentadiene resin, hydrogenated polystyrene or poly alpha methyl styrene resin. The amount of tackifier used is 0 to 400 parts by weight, preferably 20 to 350 parts by weight, and optimally 20 to 150 parts by weight, per 100 parts by weight of the epoxidized block copolymer. The choice of a particular tackifier depends mainly on the particular polymer used in each adhesive composition.

The compositions of the present invention may contain plasticizers such as rubber extender plasticizers, compounding oils or organic or inorganic pigments and dyes. Rubber compounding oils are well known to those skilled in the art and include both highly saturated oils and highly aromatic oils. Suitable plasticizers are highly saturated oils (eg Arco Tufflo 6056 (Tufflo
lo is a trademark) and 6204 oil), and process oils (eg She
ll Shellflex 371 (Shellflex is a trademark)). Also,
You may use plasticizers, such as phthalic acid ester, aliphatic dibasic acid ester, and phosphoric acid ester. The amount of the rubber compounding oil used in the composition of the present invention is 0 to 500 parts by weight, preferably 0 to 100 parts by weight per 100 parts by weight of the epoxidized block copolymer.
100 parts by weight, optimally 0 to 60 parts by weight.

Various fillers and pigments can be incorporated into the coating or sealant formulation. Such examples may include in particular external coatings or sealants which add fillers to improve the performance of the coating and sealant such as weathering as well as producing the desired effect. As the filler, various fillers can be used, and suitable fillers include, for example, calcium carbonate, clay, talc, silica, glass fiber, zinc oxide, titanium dioxide and the like. The amount of filler will usually range from 0 to the solvent-free portion of the formulation, depending on the type of filler used and the intended use of the coating or sealant.
65% by weight. A particularly suitable filler is titanium dioxide.

When the coating or sealant is applied from a solvent solution, the organic portion of the formulation is dissolved in the solvent or solvent blend. Aromatic hydrocarbon solvents such as toluene, xylene or Shell Cyclo Sol 53 are suitable. Aliphatic hydrocarbon solvents such as hexane, naphtha or mineral spirits can also be used. You may use the solvent blend which consists of a hydrocarbon solvent and a polar solvent as needed. Suitable polar solvents include esters (eg isopropyl acetate), ketones (eg methyl isobutyl ketone) and alcohols (eg isopropyl alcohol). The amount of polar solvent used depends on the particular polar solvent selected and the structure of the particular polymer used in the formulation. Usually, the amount of polar solvent used is 0 to 50% by weight in the solvent blend.

Antioxidants may be added to the composition to protect the product from oxidative degradation during manufacture and use of the composition. A combination of a primary antioxidant and a secondary antioxidant is suitable. Such combinations include sterically hindered phenolic derivatives and phosphites or thioethers, such as hydroxyphenylpropionate and aryl phosphates or thioethers, or aminophenols and aryl phosphates. Specific examples of useful antioxidant combinations include 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate) methane (Chiba-Geigy Ir.
ganox 1010 (Irganox is a trademark) and tris (nonylphenyl) phosphite (Uniroyal Polygard HR (Polygard
Is a trademark), Irganox 1010 and bis (2,4-di-t-butyl)
Pentaerythritol diphosphite (Ultranox 626 manufactured by Borg-Warner (Ultranox is a trademark)) can be mentioned.

All adhesive, coating and sealant compositions based on the epoxidized block copolymers of the present invention include certain combinations of the various formulation ingredients disclosed herein. There is no limitation as to which component is used. The particular type of component can be selected and its concentration adjusted to provide the exact combination of properties required in the composition for any particular adhesive, coating or sealant application. The content of the epoxidized block copolymer in these compositions was 5% by weight.
The above is preferable.

The two components that are always used in all adhesives, coatings or sealants are the epoxidized block copolymer and the curing agent, but the curing agent can be selected from a number of types as described above. Whether or not various resins, fillers and pigments, plasticizers, reactive oligomers, stabilizers and solvents are used other than these two components can be selected.

The coating is often a thin, non-tacky, pigmented composition which is applied over the support to protect or decorate the support. Therefore, hydrogenated epoxidized block copolymers may be needed to provide sufficient durability. The resin is chosen to ensure maximum durability and minimum dust absorption. Fillers and pigments are carefully selected to give the proper durability and color. The coatings often contain a relatively high concentration of solvent to facilitate application and give a smooth, dry coating.

The sealant is a gap filling agent. Therefore, it is used in a fairly thick layer to fill the space between the two supports. Since the two substrates often move relative to each other, sealants are usually low modulus compositions that allow for this movement. Since sealants are often exposed, hydrogenated epoxidized block copolymers are usually used. Resins and plasticizers are selected to maintain low modulus and minimize dust pickup. Fillers and pigments are selected to provide suitable durability and color. Since the sealant is applied in a fairly thick layer, the solvent concentration should be as low as possible to minimize shrinkage.

The adhesive, coating and sealant compositions of the present invention can be prepared by blending the components at elevated temperature (preferably 50-200 ° C.) until a homogenous blend is obtained (typically less than 3 hours). . Various blending methods are known and any method that produces a homogeneous blend is sufficient. The resulting composition can then be used in various applications. Alternatively, the ingredients may be blended in a solvent.

The adhesive composition of the present invention comprises a wide variety of adhesives such as laminating adhesives, pressure sensitive adhesives, tie layers, hot melt adhesives, solvent based adhesives and water-removed water before curing. It can be used as an adhesive. Although the adhesive may consist solely of the epoxidized block copolymer, it more generally comprises a blended composition containing a significant portion of the epoxidized block copolymer and other known adhesive composition components. 100 ℃
The preferred method of application is hot melt application at temperatures of about 100 ° C. or higher, as hot melt application at these temperatures minimizes the presence of water and other low molecular weight inhibitors of cationic polymerization. Heating the adhesive before and after curing can further facilitate cure or post cure.

The preferred use of the compositions of the invention is in the production of pressure sensitive adhesive tapes and the production of labels. The pressure sensitive adhesive tape is composed of a soft packing sheet and a layer of the adhesive composition of the present invention applied to one main surface of the packing sheet. The packing sheet may be plastic film, paper or any other suitable material, and the tape may include various other layers or coatings used in the manufacture of pressure sensitive adhesive tapes (eg, primers, release coatings, etc.). Alternatively, when no tackifier is added, the composition of the present invention is used for an adhesive that does not damage papers and molded articles.

The coating composition of the present invention can be used in a number of applications depending on the hardness, adhesion, durability and curing conditions selected by the formulator. As the plastic protective coating, a fairly soft coating formulated for low adhesion can be used. A fairly soft coating formulated for high adhesion can be used as a shatterproof coating for carbonated beverage glass bottles. As a metal anticorrosion coating for artificial turf, automobiles, etc., a fairly hard coating formulated for high adhesion and long term durability can be used.

The sealant composition of the present invention can be used in numerous applications. It is particularly suitable for use as a construction gap filler, which is burnt-in after application of the sealant (eg in a paint baking oven). This also includes use in automobile manufacturing and appliance manufacturing. Another preferred application is the use in gasket materials such as lids for food and beverage containers.

Asphalt is another conventional material that is advantageous in combination with the epoxidized block copolymers of this invention. Asphalt refers to bituminous materials such as straight asphalt, cutback asphalt, blown asphalt, natural asphalt, tar pitch and petroleum pitch, and one or more of these are used in combination. Compatible asphalts are preferred for use in the present invention. Compatible asphalt is an asphalt that gives a blend that does not phase separate after standing. The amount of asphalt used in the formulation can vary widely depending on the performance requirements of the particular application. However, asphalt is generally 5% in the formulation.
˜95 wt%, more preferably 5-90 wt%.

[0126]

EXAMPLES The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples.

Example 1 Polystyrene-polybutadiene-polystyrene (SB
S) block copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR-2000) 300 parts by weight is completely dissolved in 1500 parts by weight of ethyl acetate, and 169 parts by weight of a 30% ethyl acetate solution of peracetic acid 169 parts by weight. Parts were continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution is returned to room temperature, washed three times with the same amount of pure water as the reaction solution, and epoxidized polystyrene-polybutadiene-polystyrene polymer (ESBS) with an acid value of 1.5 mgKOH / g.
An ethyl acetate solution of This solution was sent to a deaerator, and ethyl acetate was removed under reduced pressure with heating. The total chlorine concentration in the obtained resin was 4.9 ppm. Table 1 shows the molar ratio of OH groups to epoxy groups (hereinafter referred to as R value), melt viscosity, etc. of the epoxidized block copolymer thus obtained.

Example 2 In the same manner as in Example 1, except that after the completion of the epoxidation reaction, the reaction solution was washed with 0.1N-sodium carbonate aqueous solution instead of being washed with pure water. Acid value
An ESBS solution of 0.9 mg KOH / g was obtained. Table 1 shows the R value, melt viscosity, etc. of the epoxidized block copolymer thus obtained.

Example 3 ESBS was obtained in the same manner as in Example 1 except that the amount of the 30% ethyl acetate solution of peracetic acid used during the epoxidation was changed to 422.5 parts by weight. The R value, melt viscosity, etc. of the epoxidized block copolymer thus obtained are shown in Table 1.
Shown in

Example 4 A block copolymer of polystyrene-polybutadiene-polystyrene was added to a jacketed reactor equipped with a stirrer and a thermometer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR-2000).
Parts by weight are dissolved in 3000 parts by weight of cyclohexane. As hydrogenation catalyst, di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mmol
/ l) 40 ml and n-butyllithium solution (concentration 5 mmol / l)
A mixture of 8 ml and 0 ° C. under a hydrogen pressure of ² kg / cm ² was added to the above polymer solution and reacted at a hydrogen partial pressure of 2.5 kg / cm ^{2 for} 30 minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure to take out the polymer (the hydrogenation rate of double bonds derived from butadiene was 30%). 300 parts by weight of this partially hydrogenated block copolymer was dissolved in 1500 parts by weight of cyclohexane, and 30% of peracetic acid was added to this.
Continuously add 300 parts by weight of ethyl acetate solution and stir 40
The epoxidation reaction was carried out at 3 ° C for 3 hours. The reaction solution is returned to room temperature, washed with the same amount of pure water as the reaction solution three times, and the acid value is 1.2 mgKOH / g.
Epoxidized Partially Hydrogenated Polystyrene-Polybutadiene-
A solution of polystyrene copolymer (ESEBS) was obtained. From this solution, the solvent was removed and the resin was recovered in the same manner as in Example 1. Table 1 shows the R value, melt viscosity, etc. of the epoxidized block copolymer thus obtained.

Example 5 Polystyrene-polyisoprene-polystyrene (SI
S) block copolymer (manufactured by Shell Kagaku Co., Ltd., trade name: Califlex TR1111) is dissolved in 1500 parts by weight of cyclohexane, and 222 parts by weight of a 30% ethyl acetate solution of peracetic acid is continuously added thereto. Was added dropwise to the mixture, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution was returned to room temperature and washed three times with the same amount of pure water as the reaction solution to obtain a solution of epoxidized polystyrene-polyisoprene-polystyrene polymer (ESIS) having an acid value of 1.5 mgKOH / g. From this solution, the solvent was removed and the resin was recovered in the same manner as in Example 1. The R of the epoxidized block copolymer thus obtained
Table 1 shows the values and melt viscosity.

Comparative Example 1 In the method of Example 1, as the epoxidizing agent, a 35% peracetic acid aqueous solution (peracetic acid-acetic acid-hydrogen peroxide solution-sulfuric acid-water) was used instead of the 30% ethyl acetate solution of peracetic acid. A polymer was obtained in the same manner as in Example 1 except that the epoxidation reaction was carried out using 145 parts by weight of. Table 1 shows the R value, melt viscosity, etc. of the epoxidized block copolymer thus obtained.

Comparative Example 2 The procedure of Example 1 was repeated except that the epoxidation reaction was carried out by using 169 parts by weight of a 30% ethyl acetate solution of peracetic acid added with 20 parts by weight of water as the epoxidizing agent. A polymer was obtained in the same manner as in Example 1. Table 1 shows the R value, melt viscosity, etc. of the epoxidized block copolymer thus obtained.

[0134]

[Table 1]

* 1: Value calculated by quantitative ¹³ C-NMR * 2: Value measured with a flow tester at 200 ° C. and a load of 100 kgf (die φ1 mm × 10 mm) Comparative Examples 1 and 2 are compared with Examples 1-5. As a result, the amount of gelation product and the melt viscosity value increase. The formation of this gelled amount adversely affects workability, compatibility and solubility, and is not preferable.

Comparative Example 3 By the same method as in Example 1 except that the epoxidation reaction crude liquid was not washed with water in the method of Example 1.
A polymer was obtained. The acid value of the obtained polymer was 15.2 mgKOH / g.
Met. The epoxy equivalent was 540, and some loss of the epoxy group was recognized. Table 2 shows the results of this test. Tables 2 and 3 also show the above Examples 1, 3, and 4.

Comparative Example 4 In the method of Example 1, a polymer was obtained without washing with water after the epoxidation reaction. The acid value of the obtained polymer was 40.3.
It was mgKOH / g. The epoxy equivalent is 610,
Some loss of epoxy groups was observed. Table 2 shows the results of this test.

Comparative Example 5 In the method of Example 1, a polymer was obtained without completely washing the epoxidation reaction crude liquid with water. The acid value of the obtained polymer was 21.5 mgKOH / g. The epoxy equivalent is 580.
And a slight loss of the epoxy group was recognized. Table 2 shows the results of this test.

Comparative Example 6 In the method of Example 3, a polymer was obtained without washing with water after the epoxidation reaction. The acid value of the obtained polymer is 82.4.
It was mgKOH / g. Also, the epoxy equivalent is 420,
Some loss of epoxy groups was observed. Table 2 shows the results of this test.

Comparative Example 7 By the same method as in Example 4 except that the epoxidation reaction crude liquid was not washed with water in the method of Example 4.
A polymer was obtained. The acid value of the obtained polymer was 15.1 mgKOH / g.
Met. Further, the epoxy equivalent was 350, and a slight loss of the epoxy group was recognized. Table 2 shows the results of this test.

[0141]

[Table 2]

* 1: A value obtained by titration of the weight of potassium hydroxide necessary for neutralizing the acids present in 1 g of the epoxidized block copolymer. Through Comparative Examples 3 to 7, in all examples. Also, as compared with the results of Examples 1, 3, and 4, it can be seen that the amount of the gelled product in the polymer after heating at 180 ° C. for 15 minutes increased. The formation of these gelled substances is not preferable because it has a great adverse effect on molding processability.

Comparative Example 8 An epoxidized polystyrene-polybutadiene-polystyrene polymer (E having an acid value of 1.5 mgKOH / g in the method of Example 1 was used.
Sodium chloride in 100 parts by weight of SBS) in ethyl acetate
Ethyl acetate was removed in the same manner as in Example 1 except that 0.03 part by weight was added to obtain a resin. The total chlorine concentration in the obtained resin is
It was 1100 ppm. The resins obtained in Examples and Comparative Example 8 were formed into a sheet, and the volume resistivity was measured. Example 1 is 8.5
× 10 ¹⁵ Ω · cm, Comparative Example 8 was 8.5 × 10 ¹³ Ω · cm. From this, it became clear that the epoxidized block copolymer of the present invention is a material excellent in electrical insulation.

Example 6 70 parts by weight of polybutylene terephthalate (polyplastic, Duranex 400FP) and 30 parts by weight of the epoxidized block copolymer obtained in Example 1 were blended and melt-kneaded with a twin-screw extruder. Then, a composition pellet was obtained (melt viscosity of the obtained composition was 1950 poise / 250 ° C.). A molding test product was prepared with an injection molding machine, and the notched Izod impact strength was 89 kgcm / cm 2. For evaluation of the composition with the thermoplastic resin composition, the melt viscosity was measured using a Shimadzu flow tester with a die of 1 ^* 10 mm (diameter of die hole:
1mm, length: 10mm), measured with a load of 100kg, Izod impact strength was made into a sample piece with mold notch,
The measurement was performed in an environment of room temperature of 23 ° C and humidity of 50%.

Comparative Example 9 Evaluations were made in the same manner as in Example 6 except that the epoxidized block copolymer obtained in Comparative Example 1 was used as the epoxidized block copolymer. The melt viscosity of the composition was 2010 poise (240 ° C., flow tester), and the notched Izod impact strength was 72 kgcm / cm 2.

From these results, it was confirmed that the thermoplastic resin composition obtained in Example 6 had a lower melt viscosity and an excellent Izod impact strength than the thermoplastic resin composition obtained in Comparative Example 9. . That is, in the present invention, a thermoplastic resin composition having excellent Izod impact strength and excellent processability such as injection molding can be obtained.

Example 7 and Comparative Example 10 The epoxidized block copolymers obtained in Example 1, Example 4, Comparative Example 1 and Comparative Example 7 were melt-kneaded with various thermoplastic resins or elastomers to obtain resins. A composition was obtained.
The compounding ratio and mechanical properties of the resin composition are shown in Table 3 and Table 4.
Shown in

The abbreviations in the table are as follows. PS: Daicel Styrol R53 (manufactured by Daicel Chemical Industries, Ltd.) PBT: Duranex 400FP (manufactured by Polyplastics Co., Ltd.) PET: Tetoron TR4550BHK (manufactured by Teijin Ltd.) PP: Noblen H501 (manufactured by Sumitomo Chemical Co., Ltd.) ) HSBR: Dynaron 1320P (manufactured by Japan Synthetic Rubber Co., Ltd.) TPU: Miractolan P480 (Japan Miractoran Co., Ltd.)
Product: SEPS: Septon 2063 (manufactured by Kuraray Co., Ltd.) TPEE: Hytrel 4047 (manufactured by DuPont Toray Co., Ltd.) Nylon: Nylon 6 Ube (manufactured by Ube Industries, Ltd.) PC: Panlite L1225 (Teijin Kasei Co., Ltd.) Made)

[0149]

[Table 3]

[0150]

[Table 4]

It is apparent that the resin composition and elastomer composition containing the epoxidized block copolymer according to the present invention have excellent mechanical properties and fluidity (the melt viscosity does not increase).

Example 8 10 parts by weight of the epoxidized block copolymer obtained in Example 1 and 90 parts by weight of an alicyclic epoxy compound (Celoxide 2021, manufactured by Daicel Chemical Industries Ltd.) were blended to give a transparent mixture. A liquid composition was obtained. This was stored at 50 ° C. and the change in viscosity with time was measured. Table 5 shows the results.

Comparative Example 11 10 parts by weight of the epoxidized block copolymer obtained in Comparative Example 1 and 90 parts by weight of an alicyclic epoxy compound (Celoxide 2021, manufactured by Daicel Chemical Industries, Ltd.) were mixed to obtain a solution viscosity. Was measured in the same manner as in Example 8. Table 5 shows the results.

Example 9 10 parts by weight of the epoxidized block copolymer obtained in Example 3 and 90 parts by weight of Epicoat 828 (produced by Yuka Shell Co., Ltd.) were mixed and the solution viscosity was measured. Table 5 shows the results.

[0155]

[Table 5]

From the results shown in Table 5, the composition of the epoxy compound with the epoxidized block copolymer of the present invention has good thermal stability and excellent storage stability.

Examples 10 to 11 and Comparative Example 12 Epoxy compositions 1 obtained in Examples 8 and 9 and Comparative Example 11
50 parts by weight of methyltetrahydrophthalic anhydride as a curing agent was added to 00 parts by weight, and the mixture was applied to an iron plate so as to have a thickness of 50 μm, and cured at 90 ° C. × 2 hours and further at 160 ° C. × 2 hours. The appearance of the cured coating film was good and glossy and smooth in Examples 8 and 9, but was slightly inferior in glossiness in Comparative Example 11 because it had lumps. Under the same curing conditions, a sample piece for measuring the fracture toughness value (kic) was further prepared and measured. In Example 8, the pressure was 1.7 MPa · m ^1/2 (glass transition temperature 160 ° C.), and in Comparative Example 11, the pressure was 1.0 MPa · m ^1/2 (glass transition temperature 158 ° C.). From these results, it became clear that the epoxidized block copolymer according to the present invention can impart the toughness of the cured epoxy resin product. Further, when used as a coating composition, the appearance of the coating film is good.

Example 12 50 parts by weight of the epoxidized block copolymer of Example 1 and 50 parts by weight of Ultrasen 541L (manufactured by Tosoh Corp.) were melt-blended at 180 ° C. to prepare a film with a T-die extruder. . The obtained film did not generate fish eyes or gel. Tensile strength of 290 kgf / c at film thickness of 40 μm
The tensile elongation at m ² was 900%.

Comparative Example 13 50 parts by weight of the epoxidized block copolymer of Comparative Example 1 and 50 parts by weight of Ultrasen 541L (manufactured by Tosoh Corp.) were melt-blended at 180 ° C., and a film was produced by a T-die extruder. . The resulting film had many fish eyes and gels. Tensile strength 250kgf / c at film thickness 40μm
The tensile elongation at m ² was 550%.

Example 13 and Comparative Example 14 The films obtained in Example 12 and Comparative Example 13 were treated with aluminum foil.
A T-peel test was carried out by sandwiching (0.5 mm thickness), pressure-bonding at 200 ° C. and 2 kg / cm ² for 1 minute. In Example 12, 3.5 kg / 25
mm, and that of Comparative Example 13 was 2.0 kg / 25 mm. Further, the epoxidized block copolymer obtained in Example 1 was formed into a film in the same manner, and a T peel test was conducted.
It was g / 25 mm.

Examples 14-20 and Comparative Examples 15-16 Polystyrene-polybutadiene-polystyrene (SB
S) block copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR-2000) 300 parts by weight is dissolved in 1500 parts by weight of ethyl acetate, and 169 parts by weight of a 30% ethyl acetate solution of peracetic acid is added thereto. It was continuously added dropwise, and the epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring. The reaction solution is returned to room temperature and washed with pure water, acid value 1.1 mgK
An OH / g epoxidized polystyrene-polybutadiene-polystyrene copolymer (copolymer X) solution in ethyl acetate was obtained. The concentration of the ethyl acetate solution of this polymer was 20 wt%. The stabilizer shown in Table 6 was added to this solution and mixed well. When steam-stripping this polymer solution, the water in the steam-stripping tank was mixed with Asahi Denka Co., Ltd. nonionic surfactant "Bluronic F-10".
8 "was added to water in an amount of 100 ppm, and steam stripping was performed at a water temperature of 95 ° C. The polymer was crumb-like and stably dispersed, and neither mutual adhesion of the polymer nor adhesion to the vessel wall or stirring blade was observed. Then, the water-dispersed slurry of the polymer obtained above was sent to a rotary screen to give a water content of 40% by weight.
To obtain a hydrous crumb. This crumb can be dehydrated and dried at the same time with a two-stage slit with a slit interval of 0.1 mm.
It was sent to a twin-screw extruder type squeezing dewatering dryer with a step vent. The extrusion conditions were a cylinder temperature of 180 ° C., a screw rotation speed of 200 rpm, a first vent at normal pressure, and a second vent at a pressure of 200 torr to dry. The polymer discharged from the tip of the extruder was pelletized by a cutter (R value of the obtained pellet resin was 0.01). Table 6 shows the measurement results of ΔYI indicating the gel content after heating and the coloring degree before and after heating from the obtained pellets by the method described below.

Examples 21 to 23 and Comparative Examples 17 to 18 In a jacketed reactor equipped with a stirrer and a thermometer, a polystyrene-polybutadiene-polystyrene block copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR -2000) 300
Part by weight was dissolved in 3000 parts by weight of cyclohexane. As a hydrogenation catalyst, di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (1 mmol / l)
40 ml and n-butyllithium solution (concentration 5 mmol / l) 8 ml
A mixture of and under 0 ° C. and 2 kg / cm ² hydrogen pressure conditions,
Add to the above polymer solution and add hydrogen at a partial pressure of 2.5 kg / cm ^{2 to} 30
Allowed to react for minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure, and the polymer was taken out (hydrogenation rate of double bond derived from butadiene was 50%). 300 parts by weight of this partially hydrogenated block copolymer is dissolved in 1500 parts by weight of cyclohexane, 180 parts by weight of a 30% ethyl acetate solution of peracetic acid are continuously added dropwise thereto, and epoxidized at 40 ° C. for 3 hours with stirring. The reaction was carried out. The reaction solution is returned to room temperature, washed three times with the same amount of pure water as the reaction solution, and an epoxidized partially hydrogenated polystyrene-polybutadiene-polystyrene copolymer (copolymer Y) solution with an acid value of 1.1 mgKOH / g is added. Obtained. When steam-stripping this polymer solution, the nonionic surfactant "Emulgen PP-290" manufactured by Kao Co., Ltd. was added to the water in the steam-stripping tank at 100 ppm with respect to the water, and the water temperature was 95%. Steam stripping was performed at ℃. The polymer was crumb-like and stably dispersed, and neither mutual adhesion of the polymer nor adhesion to the vessel wall or stirring blade was observed. Then, the water-dispersed slurry of the polymer obtained above was sent to a rotary screen to obtain a water-containing crumb having a water content of 40% by weight. This crumb can be dehydrated and dried at the same time.
It was sent to a twin-screw extruder type squeezing dewatering dryer with a two-stage slit having m 2 and a two-stage vent. Extrusion conditions are cylinder temperature 180 ℃, screw rotation speed 200 rpm,
The first vent was extruded and dried at atmospheric pressure and the second vent was extruded at a pressure of 200 torr. The polymer discharged from the tip of the extruder was pelletized with a cutter (R of the obtained pellet resin
The value was 0.02). The residual water content in the polymer after drying is
It was 200 ppm. Table 6 shows the measurement results for gel content and ΔYI from the resulting pellets, as for polymer X.

In Table 6, the symbol 1 in the type of the phenolic stabilizer is tetrakis (methylene-3- (3 ', 5'-di-te.
rt-butyl-4'-hydroxyphenyl) propionate) methane, symbol 2 is 1,3,5-trimethyl-2,4,6-
Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, symbol 3 is 2,6-di-tert-butyl-4
-Indicates methylphenol. Regarding the type of phosphorus-based stabilizer, the symbol 1 indicates trisnonylphenyl phosphite, and the symbol 2 indicates tris (2,5-di-tert-butylphenyl) phosphite. The addition amount of each of the phenol-based stabilizer and the phosphorus-based stabilizer is shown by the addition amount with respect to 100 parts by weight of the polymer. The gel content after heating is the weight% of THF insoluble matter after the obtained pellets are left in an oven at 180 ° C for 30 minutes.
Indicated by ΔYI made a press sheet with a thickness of 3 mm,
The difference in YI value measured by a color difference meter before and after being left for 30 minutes in an oven at 180 ° C is shown.

[0164]

[Table 6]

Examples 24 to 33, Comparative Examples 19 to 23 In a reactor having a capacity of 5 liter equipped with a stirrer, a thermometer and a jacket, a block copolymer of polystyrene-polybutadiene-polystyrene (SBS) (Japan Synthetic Rubber ( Co., Ltd., trade name: TR-2000) 300 parts by weight, ethyl acetate
1500 parts by weight were charged and SBS was dissolved in ethyl acetate. The internal temperature of the reactor was raised to 40 ° C., and while maintaining the internal temperature at this temperature, 169 parts of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise over 3 hours while stirring, An epoxidation reaction was performed. After finishing the epoxidation reaction, return the internal temperature to room temperature,
It was washed with pure water to obtain an ethyl acetate solution of an epoxidized polystyrene-polybutadiene-polystyrene polymer. This polymer solution was treated with a steam stripping method to remove ethyl acetate, and then an aqueous dispersion slurry of the polymer obtained above was drained by a rotary screen,
Furthermore, it was supplied to a twin-screw extruder with a vent and melted, and the strand extruded from the die was cut. The residual water content in the polymer after solvent removal is 500 ppm, the gel content is 0.2 wt% or less, and the epoxy equivalent of the polymer is 5
20, R value was 0.01. Further, no foaming of the molded product was observed. The resulting pellets (size: diameter about 2
mm, 3 mm long columnar shape, the same shall apply to the following) The surface of each block is coated with the anti-blocking agent, and the amount of each anti-blocking agent listed in Table 7 is applied per 100 parts by weight of the pellet. Then, an epoxidized block copolymer composition was obtained. The degree of blocking and haze of the obtained epoxidized block copolymer composition were evaluated by the methods described below. Table 7 shows the results. (1) Degree of blocking A pellet of the sample was placed in a plastic cylinder having a diameter of 5 cm, a load of 2 kg was applied to the upper part of the sample, the sample was left at 40 ° C for 48 hours, and then the sample was taken out to evaluate the blocking state of the pellet. . The result is ○ = no blocking,
Δ = Slightly blocked, × = Significantly blocked (2) Haze A sheet having a thickness of 2 mm was prepared from the pellet of the sample by the compression molding method, and the sheet was measured according to JIS K 7105.

[0166]

[Table 7]

Examples 34 to 39, Comparative Examples 24 to 27 In a reactor having a capacity of 10 liter equipped with a stirrer, a thermometer and a jacket, a block copolymer of polystyrene-polybutadiene-polystyrene (SBS) (Japan Synthetic Rubber ( Co., Ltd., trade name: TR-2000) 300 g and cyclohexane
3000 g was charged and SBS was dissolved in cyclohexane. To this solution, 40 ml of di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mmol / l) and 8 ml of n-butyllithium solution (concentration 5 mmol / l) were added as hydrogenation catalysts. The mixture was added under hydrogen pressure conditions of ² ° C. and 2 kg / cm ² , and the mixture was reacted for 30 minutes under the condition of hydrogen partial pressure of 2.5 kg / cm ² . The solvent was removed from the resulting partially hydrogenated polymer solution by drying under reduced pressure, and the polymer was taken out (hydrogenation rate of double bond derived from butadiene is 50%).
Met). 300 parts of this partially hydrogenated block copolymer,
It was dissolved in 1500 parts of cyclohexane and the internal temperature was raised to 40 ° C. While maintaining the internal temperature of the reactor at this temperature, 180 parts of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise over 3 hours with stirring to carry out an epoxidation reaction. The reaction solution was returned to room temperature and washed with pure water equivalent to the reaction solution three times to obtain a solution of epoxidized partially hydrogenated polystyrene-polybutadiene-polystyrene polymer. When steam-stripping this polymer solution, 100 ppm of nonionic surfactant "Emulgen PP-290" manufactured by Kao Corporation was added to the water in the steam-stripping tank, and the water temperature was adjusted. Steam stripping was performed at 95 ° C. The polymer was crumb-like and stably dispersed, and neither mutual adhesion of the crumb-like polymer nor adhesion of the polymer to the vessel wall or stirring blade was observed. The solvent was removed by this steam stripping method, and the resulting water-dispersed slurry of the polymer was sent to a rotary screen to drain water, and then sent to a twin-screw extruder with a vent and extruded from a melt-kneaded die. The cut strands. The surface of each of the obtained pellets was coated with an anti-blocking agent, and each of the anti-blocking agents described in Table 8 was added to 100 parts of the pellet.
The amount described in 1 above was applied to obtain an epoxidized block copolymer composition.

[0168]

[Table 8]

Example 40 Polystyrene-Polybutadiene-Polystyrene (SB
S) block copolymer (manufactured by Nippon Synthetic Rubber Co., Ltd., trade name: TR-2000) 300 parts by weight is dissolved in 1500 parts by weight of ethyl acetate, and 169 parts by weight of a 30% ethyl acetate solution of peracetic acid is added thereto. The reaction solution was continuously added dropwise and epoxidized at 40 ° C. for 3 hours under stirring, returned to room temperature and washed with pure water to obtain an ethyl acetate solution of epoxidized polystyrene-polybutadiene-polystyrene polymer (ESBS). Obtained. The concentration of the ethyl acetate solution of this polymer was 30 wt%. This solution was supplied to a twin-screw two-stage vent type extruder having a screw outer diameter of 40 mm and L / D = 38.5, and the solvent was degassed under reduced pressure from the vent section. The vented extruder used had a cylinder temperature of 160 ° C, the pressure of the first vent was 200 torr, and the pressure of the second vent was 50.
The screw rotation speed was 200 rpm at torr. Further, the solution was supplied so that the production rate of the obtained polymer would be 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. The residual solvent content in the polymer after desolvation is 2300 ppm, the epoxy equivalent of the polymer is 520, R
The value was 0.01. No foaming of the molded product was observed. In the molding, the polymer was pressed at 200 ° C. and a 2 mm thick sheet was visually judged.

Example 41 A solution of an epoxidized block copolymer obtained in exactly the same manner as in Example 40 in ethyl acetate (concentration: 30 wt%) can be passed through a heating medium inside the screw, and the upper part in the extruder can be passed through. With a continuous vapor phase part, screw outer diameter 40 mm,
It was supplied to a twin-screw vent type extruder with L / D = 9, and the solvent was degassed under reduced pressure from the vent part. The vent type extruder used had a cylinder temperature of 160 ° C and a vent pressure of 100 torr.
The screw rotation speed was 200 rpm. Further, the solution was supplied so that the production rate of the obtained polymer would be 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. The residual solvent content in the polymer after solvent removal is
It was 420 ppm and the epoxy equivalent of the polymer was 520.
Further, as in Example 40, no foaming of the molded product (press sheet) was observed.

Example 42 In a jacketed reactor equipped with stirrer and thermometer, polystyrene-polybutadiene-polystyrene (S
300 parts by weight of a block copolymer of BS) (trade name: TR-2000, manufactured by Nippon Synthetic Rubber Co., Ltd.) was dissolved in 3000 parts by weight of cyclohexane. As hydrogenation catalysts, 0.40 parts by weight of di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mmol / l) and 0.08 parts by weight of n-butyllithium solution (concentration 5 mmol / l) were used. ℃, 2kg
The mixture obtained under the hydrogen pressure condition of / cm ² was added to the above polymer solution and reacted at a hydrogen partial pressure of 2.5 kg / cm ^{2 for} 30 minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure, and the polymer was taken out (hydrogenation rate of double bond derived from butadiene was 50%). 300 parts by weight of this partially hydrogenated block copolymer is dissolved in 1500 parts by weight of cyclohexane, 180 parts by weight of a 30% ethyl acetate solution of peracetic acid are continuously added dropwise thereto, and epoxidized at 40 ° C. for 3 hours with stirring. The reaction was carried out. The reaction solution is returned to room temperature, washed three times with the same amount of pure water as the reaction solution, and the epoxidized partially hydrogenated polystyrene-polybutadiene-polystyrene copolymer solution (concentration 26 wt
%) Was obtained. This polymer solution is fed to a twin-screw vent type extruder with a screw outer diameter of 40 mm and L / D = 9, which allows a heat medium to pass through the screw and has a continuous gas phase part in the upper part of the extruder. Then, the solvent was degassed under reduced pressure from the vent portion. The vented extruder used had a cylinder temperature of 170 ° C.
The pressure at the vent is 100 torr and the screw speed is
It was operated at 200 rpm. Also, the production rate of the obtained polymer is
The solution was supplied at 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. The residual solvent content in the polymer after removal of the solvent was 380 ppm, the epoxy equivalent of the polymer was 285, and the R value was 0.02. Further, as in Example 40, no foaming of the molded product (press sheet) was observed.

Examples 43 to 45 A solution of the epoxidized block copolymer obtained in exactly the same manner as in Example 40 in ethyl acetate (concentration: 30 wt%) can be passed through a heating medium inside the screw, and inside the extruder. With a continuous gas phase part on the top of the screw, outer diameter of screw 40mm,
It was supplied to a twin-screw vent type extruder with L / D = 9, and the solvent was degassed under reduced pressure from the vent part. The cylinder temperature and the pressure of the vent part of the vent type extruder used were as shown in Table 9, and the screw rotation speed was 200 rpm. Further, the solution was supplied so that the production rate of the obtained polymer would be 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. The properties in the polymer after removing the solvent are also shown in Table 9.

Comparative Example 28 In the method of Example 41, peracetic acid was used as the epoxidizing agent.
A polymer was obtained by the same method except that the epoxidation reaction was carried out using 145 parts by weight of 35% peracetic acid aqueous solution (peracetic acid-acetic acid-hydrogen peroxide solution-sulfuric acid-water) instead of the 30% ethyl acetate solution. It was Table 9 shows the properties of the polymer after removing the solvent.

[0174]

[Table 9]

Example 46 Block copolymer of polystyrene-polybutadiene-polystyrene (SBS, manufactured by Japan Synthetic Rubber Co., Ltd., "TR-2000"
)) Dissolve 300 parts by weight in 1500 parts by weight of ethyl acetate completely (first step), and add 30% ethyl acetate solution of peracetic acid to it.
169 parts by weight was continuously added dropwise, and an epoxidation reaction was carried out at 40 ° C. for 3 hours with stirring (second step). The reaction liquid was returned to room temperature and washed with pure water to obtain an ethyl acetate solution of an epoxidized polystyrene-polybutadiene-polystyrene copolymer (ESBS) (third step). The ethyl acetate solution of this epoxidized block copolymer had a concentration of 30 wt%. The acid value of this solution was 1.0 mg KOH / g. This solution is capable of passing a heat medium inside the screw, and has a screw outer diameter of 40 m, L /
The mixture was supplied to a twin-screw vent type extruder with D = 9, and the solvent was degassed under reduced pressure from the vent section. The vented extruder used was operated at a cylinder temperature of 160 ° C., a vent pressure of 100 torr, and a screw rotation speed of 200 rpm. Further, the solution was supplied so that the production rate of the obtained polymer would be 10 kg / h. Next, the polymer discharged from the tip of the extruder was pelletized with a cutter. After removing the solvent, the residual solvent content in the polymer was 420 rpm, the gel content was 0.2 wt% or less, the epoxy equivalent of the polymer was 520, and the R value was 0.01. Further, no foaming of the molded product was observed. In addition, molding is performed with a polymer
It was pressed at 200 ° C. to obtain a 2 mm thick sheet, which was visually observed. The results are shown in Table 10.

Example 47 Ethyl acetate solution of epoxidized block copolymer obtained by exactly the same method as in Example 46 (concentration 30 wt%), screw outer diameter 40 mm, L / D = 38.5 biaxial two-stage vent type It was supplied to the extruder and the solvent was degassed under reduced pressure from the vent. The vented extruder used had a cylinder temperature of 160 ° C. and the pressure of the vents was 100 torr for both the first and second vents. The screw rotation speed was 200 rpm. Further, the solution was supplied so that the production rate of the obtained polymer would be 10 kg / h. Next, the polymer discharged from the tip of the extruder was pelletized with a cutter. After removing the solvent, the residual solvent content in the polymer was 2300 ppm, the gel content was 0.2 wt% or less, the epoxy equivalent of the polymer was 520, and the R value was 0.01. Further, no foaming of the molded product was observed. The results are shown in Table 10.

Example 48 In a jacketed reactor equipped with a stirrer and a thermometer, 300 parts by weight of a polystyrene-polybutadiene-polystyrene block copolymer (“TR-2000” manufactured by Japan Synthetic Rubber Co., Ltd.) was added to 3000 parts by weight of cyclohexane. Dissolve in. As hydrogenation catalyst, di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mmol / l)
40 g and 8 g of n-butyllithium solution (concentration 5 mmol / l)
A mixture of and under 0 ° C. and 2 kg / cm ² hydrogen pressure conditions,
Add to the above polymer solution and add hydrogen at a partial pressure of 2.5 kg / cm ^{2 to} 30
Allowed to react for minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by vacuum drying to take out the polymer (the hydrogenation rate of the double bond derived from butadiene was 30%).
300 parts by weight of this partially hydrogenated polymer was added to 15 parts of cyclohexane.
It is dissolved in 00 parts by weight (first step), 300 parts by weight of a 30% ethyl acetate solution of peracetic acid is continuously added dropwise thereto, and the mixture is stirred at 40 ° C.
The epoxidation reaction was carried out for 3 hours (second step). The reaction solution was returned to room temperature and washed with pure water to obtain a solution of epoxidized partially hydrogenated polystyrene-polybutadiene-polystyrene copolymer (ESEBS) (third step). The concentration of the block copolymer solution was 22 wt%. The acid value of this solution was 1.3 mg KOH / g. This solution is
It was supplied to the same twin-screw, two-stage vented extruder as in Example 47, and
The solvent was degassed under reduced pressure under exactly the same conditions as in 47 (fourth step). The polymer discharged from the tip of the extruder was pelletized with a cutter. The amount of residual solvent in the polymer after solvent removal is
The content was 1500 ppm, the gel content was 0.2 wt% or less, the epoxy equivalent of the polymer was 285, and the R value was 0.02. The results are shown in Table 10.

Examples 49 to 51 Polystyrene-polybutadiene-polystyrene block copolymer (SBS, manufactured by Nippon Synthetic Rubber Co., Ltd. "TR-2000"
]) Was dissolved in ethyl acetate (first step), and an epoxidation reaction was performed using peracetic acid (second step). The reaction solution was returned to room temperature and washed with pure water to obtain an ethyl acetate solution of an epoxidized polystyrene-polybutadiene-polystyrene polymer (ESBS) having the properties shown in Table 10 (third step). This solution was fed to a twin-screw vent type extruder having a screw outer diameter of 40 mm and L / D = 9, which can pass a heat medium inside the screw and has a continuous gas phase part in the upper part of the extruder, Volatilization was performed under reduced pressure under the conditions shown in. The results are shown in Table 10
Shown in

Comparative Example 29 A block copolymer was obtained in the same manner as in Example 46 except that the epoxidation reaction crude liquid was not washed with water in the third step of Example 46. The residual solvent amount of the obtained resin is 6
It was 20 ppm and the gel content was 5.2 wt%. The epoxy equivalent was 620. The results are shown in Table 10.

Comparative Example 30 A block copolymer was obtained in the same manner as in Example 48 except that the epoxidation reaction crude liquid was not washed with water in the third step of Example 48. The residual solvent amount of the obtained resin is 1700
ppm and gel content was 5.3 wt%. The epoxy equivalent was 340. The results are shown in Table 10.

[0181]

[Table 10]

Examples 52 to 56 and Comparative Examples 31 to 32 Polystyrene-polybutadiene-polystyrene block copolymer (SBS, manufactured by Nippon Synthetic Rubber Co., Ltd. "TR-20"
00 ") 300 parts by weight was dissolved in 1500 parts by weight of ethyl acetate, 169 parts by weight of a 30% ethyl acetate solution of peracetic acid was continuously added dropwise thereto, and the epoxidation reaction was carried out at 40 ° C for 3 hours with stirring. The reaction solution was returned to room temperature and washed with pure water to obtain an ethyl acetate solution of an epoxidized polystyrene-polybutadiene-polystyrene polymer (epoxidized SBS copolymer). The concentration of the ethyl acetate solution of this polymer was 30 wt%. Stabilizers were added to this solution as shown in Table 11 and mixed well. The amount of each addition was made to be the amount shown in Table 11 with respect to the polymer finally obtained. This organic solution
A screw outer diameter of 40 mm, which allows a heat medium to pass through the inside of the screw, and which has a continuous gas phase portion in the upper part of the extruder.
The solvent was supplied to a twin-screw vent extruder with L / D = 9, and the solvent was degassed under reduced pressure from the vent section. The vent extruder used was operated at a cylinder temperature of 160 ° C., a vent pressure of 100 torr, and a screw rotation speed of 200 rpm. The supply rate of the organic solution is
The production rate of the obtained polymer was adjusted to be 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. Residual solvent concentration in the polymer after solvent removal,
Table 11 shows the gel content, R value, and hue change amount. The respective measuring methods are shown below.

(Measurement method) (1) Residual solvent concentration: The polymer was dissolved in toluene and measured by gas chromatography.

(2) Gel content after heating: Tetrahydrofuran (THF) after standing in an oven at 180 ° C for 30 minutes
It is shown in% by weight of insoluble matter.

(3) Yellow index: thickness 3 mm
The press sheet of was prepared and heated in an oven at 180 ° C for 30 minutes. The YI before and after heating is represented by ΔYI.

[0186]

[Table 11]

Examples 57 to 58 and Comparative Examples 33 to 34 Polystyrene-polybutadiene-polystyrene block copolymer (SBS, "TR-2000" manufactured by Nippon Synthetic Rubber Co., Ltd.) was placed in a jacketed reactor equipped with a stirrer and a thermometer. ) 3
00 parts by weight was dissolved in 3000 parts by weight of cyclohexane. As a hydrogenation catalyst, di-p-tolylbis (1-cyclopentadienyl) titanium / cyclohexane solution (concentration 1 mm
ol / l) 40 g and n-butyllithium solution (concentration 5 mmol /
l) 8 g was mixed with 0 g under a hydrogen pressure condition of ² kg / cm ² and added to the above polymer solution to obtain a hydrogen partial pressure of 2.5 kg.
The reaction was performed at / cm ^{2 for} 30 minutes. The solvent was removed from the obtained partially hydrogenated polymer solution by drying under reduced pressure, and the polymer was taken out (hydrogenation rate of double bond derived from butadiene was 50%). 300 parts by weight of this partially hydrogenated block copolymer,
It was dissolved in 1500 parts by weight of cyclohexane and 30 parts of peracetic acid was added to it.
180 parts by weight of ethyl acetate solution was continuously added dropwise with stirring.
The epoxidation reaction was carried out at 40 ° C for 3 hours. The reaction solution was returned to room temperature and washed with the same amount of pure water as the reaction solution three times to obtain a solution of epoxidized partially hydrogenated polystyrene-holibutadiene-polystyrene copolymer (concentration 30 wt%). This organic solution can pass a heat medium inside the screw, and has a screw outer diameter 40 having a continuous gas phase portion in the upper part of the extruder.
mm, L / D = 9, and fed to a twin-screw vent extruder, and the solvent was depressurized and degassed from the vent section. The vent extruder used had a cylinder temperature of 160 ° C and a vent pressure of 100 torr.
The screw rotation speed was 200 rpm. Further, the supply rate of the organic solution was adjusted so that the production rate of the obtained polymer was 10 kg / h. The polymer discharged from the tip of the extruder was pelletized with a cutter. Table 12 shows the residual solvent concentration, gel content, R value, and hue change amount in the polymer after removing the solvent.

[0188]

[Table 12]

Example 59 Polystyrene-polybutadiene-polystyrene block copolymer (SBS, manufactured by Nippon Synthetic Rubber Co., Ltd., "TR-2000"
"Styrene / butadiene weight ratio 40/60) 300 parts by weight is dissolved in 1500 parts by weight ethyl acetate, and 30% of peracetic acid is added to this.
169 parts by weight of an ethyl acetate solution was added dropwise and stirred to carry out an epoxidation reaction at 40 ° C. for 3 hours. The reaction solution was returned to room temperature and washed with pure water to obtain an ethyl acetate solution of epoxidized polystyrene-polybutadiene-polystyrene polymer (ESBS). The concentration of this polymer was 20% by weight (hereinafter referred to as "ethyl acetate dope"). A multi-tube heat exchanger with a heat transfer area of 7.80 m ² (hereinafter referred to as “shell and tube”) was loaded with ethyl acetate dope at 60-80 kg / h (E
SBS: 18.0-22.5 kg / h) was charged. The heat medium supply temperature to the shell and tube is 160 ° C, and the system pressure is 46
It was set to 0 torr. As a result, the volatile component concentration in the epoxidized block copolymer was concentrated to 20% by weight (the epoxidized block copolymer concentration was 80% by weight). This concentrate was placed in a vented twin-screw kneading evaporator (heat transfer area 1 m ² , L / D = 9).
It was charged at a speed of 20 to 25 kg / h (ESBS: 18.0 to 22.5 kg / h). The heating medium supply temperature to the twin-screw kneading type evaporator is 150 to 160
The pressure in the system was 200 torr. The flow is shown in FIG.
As a result, the volatile component concentration in the epoxidized block copolymer was 0.04% by weight (the epoxidized block copolymer concentration was 99.6% by weight).
% By weight). Table 13 shows the operating conditions and the amount of residual organic solvent in the epoxidized block copolymer. In the table, concentration by shell and tube is defined as one-stage concentration,
The concentration by the twin-screw kneading type evaporator was made into two-stage concentration. Table 13 shows the measurement results of the gel content of the obtained epoxidized block copolymer.

[0190]

[Table 13]

[0191]

INDUSTRIAL APPLICABILITY According to the present invention, an epoxidized block copolymer having a low gel content and excellent in moldability can be obtained. Such an epoxidized block copolymer has a small amount of gel formation particularly during heating, melt-kneading, and a composition with a thermoplastic resin or a rubber-like polymer, a coating composition, a sealant composition, a thermosetting composition, and an adhesive. It can be particularly preferably used as an agent, an asphalt modifier, and the like.

[Brief description of drawings]

FIG. 1 shows a flow chart of organic solvent removal from an epoxidation reaction solution of Example 59.

[Explanation of symbols]

 1 Ethyl acetate dope supply tank 2 Charge pump 3 Shell and tube 4 Two-axis kneading evaporator 5 Extraction gear pump 6 Concentrated resin 7 Vacuum pump

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C09J 163/08 JFM C09J 163/08 JFM C09K 3/10 C09K 3/10 L // C08F 8/08 MGD C08F 8/08 MGD

Claims (29)

[Claims] 1. A block copolymer (C) comprising a polymer block (A) mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block (B) mainly composed of a conjugated diene compound.
Or the epoxidized block copolymer (E) obtained by epoxidizing the hydrogenated product (D) has a molar ratio R of hydroxyl groups and epoxy (represented by the following formula) of 0.001 to 0.1. An epoxidized block copolymer characterized by: R = [OH] / [epoxy] (In the formula, [OH] represents the number of moles of the hydroxyl group contained in the epoxidized block copolymer per unit weight, and [epoxy] represents the epoxidized block copolymer per unit weight. Represents the number of moles of epoxy contained in the polymer) 2. The epoxidized block copolymer according to claim 1, wherein R is 0.001 to 0.05. 3. The epoxidized block copolymer according to claim 1, wherein the epoxidized block copolymer (E) has an acid value of 10 mgKOH / g or less. 4. The epoxidized block copolymer according to claim 1, wherein the epoxidized block copolymer (E) has an organic solvent content of 5000 ppm or less. 5. The epoxy equivalent of the epoxidized block copolymer (E) is 140 to 2700.
The epoxidized block copolymer according to any one of items 1 to 4. 6. The epoxidized block copolymer according to claim 1, wherein the content of chlorine ions in the epoxidized block copolymer (E) is 7 ppm or less. 7. A block copolymer (C) comprising a polymer block (A) mainly composed of a vinyl aromatic hydrocarbon compound and a polymer block (B) mainly composed of a conjugated diene compound.
Alternatively, the epoxidized block copolymer obtained by epoxidizing the hydrogenated product (D) thereof has an acid value of 10 mgKOH / g or less. 8. A phenolic stabilizer and / or a phosphorus stabilizer is added in an amount of 0.005 to 10 parts by weight to 100 parts by weight of the epoxidized block copolymer according to any one of claims 1 to 7. An epoxidized block copolymer composition comprising: 9. An epoxidized block copolymer comprising 0.001 to 5 parts by weight of an antiblocking agent based on 100 parts by weight of the epoxidized block copolymer according to claim 1. Composition. 10. A heat resistance stabilizer, an antioxidant, a cross-linking agent, an ultraviolet absorber, an inorganic filler, and an organic filler for the epoxidized block copolymer according to any one of claims 1 to 7. An epoxidized block copolymer composition containing at least one selected from the group consisting of a plasticizer and a softening agent. 11. A thermoplastic resin composition containing the epoxidized block copolymer according to any one of claims 1 to 7. 12. The epoxidized block copolymer is from 1 to 99.
12. The thermoplastic resin composition according to claim 11, wherein the thermoplastic resin composition is contained in a weight percentage. 13. A thermosetting resin composition containing the epoxidized block copolymer according to claim 1. Description: 14. The epoxidized block copolymer is 1 to 80.
14. The thermosetting resin composition according to claim 13, wherein the thermosetting resin composition is contained in a weight percentage. 15. An elastomer composition containing the epoxidized block copolymer according to claim 1. Description: 16. The epoxidized block copolymer is 1 to 99.
16. The elastomer composition according to claim 15, wherein the elastomer composition is contained in a weight percentage. 17. A compatibilizer comprising the epoxidized block copolymer according to any one of claims 1 to 7. 18. An adhesive composition containing the epoxidized block copolymer according to claim 1. Description: 19. The adhesive composition according to claim 18, which contains 5% by weight or more of an epoxidized block copolymer. 20. A sealant composition containing the epoxidized block copolymer according to any one of claims 1 to 7. 21. The sealant composition according to claim 20, which contains 5% by weight or more of an epoxidized block copolymer. 22. A coating composition containing the epoxidized block copolymer according to any one of claims 1 to 7. 23. The coating composition according to claim 22, which contains 5% by weight or more of the epoxidized block copolymer. 24. An asphalt composition containing the epoxidized block copolymer according to any one of claims 1 to 7. 25. The epoxidized block copolymer is contained in an amount of 5 to 95.
25. The asphalt composition according to claim 24, wherein the asphalt composition is contained in a weight percentage. 26. (1) A block copolymer (C) or a hydrogenated product (D) thereof is mixed with an organic solvent to give a polymer having a concentration of 5 to 50.
A step of obtaining an organic solvent solution or an organic solvent slurry having a weight% of (2) a step of using an epoxidizing agent to epoxidize an unsaturated carbon bond present in a polymer in the organic solvent solution or the organic solvent slurry, ( 3) A step of reducing the acid value of the solution or slurry to 5 mgKOH / g or less by washing and / or neutralizing the epoxidation reaction solution or slurry obtained in the above step, (4) Washing and / or neutralizing epoxy The step of supplying the epoxidation reaction solution or slurry to an evaporator, directly removing the organic solvent by evaporation, and recovering the epoxidized block copolymer. A method for producing the epoxidized block copolymer described. 27. (1) The block copolymer (C) or its hydrogenated product (D) is mixed with an organic solvent, and the concentration of the polymer is 5 to 50.
A step of obtaining an organic solvent solution or an organic solvent slurry having a weight% of (2) a step of using an epoxidizing agent to epoxidize an unsaturated carbon bond present in a polymer in the organic solvent solution or the organic solvent slurry, ( 3) A step of reducing the acid value of the solution or slurry to 5 mgKOH / g or less by washing and / or neutralizing the epoxidation reaction solution or slurry obtained in the above step, (4) Washing and / or neutralizing epoxy The reaction solution or slurry is quantitatively supplied to the evaporator, and the addition amount of the phenolic stabilizer and / or phosphorus stabilizer is 0.005 per 100 parts by weight of the epoxidized block copolymer finally obtained. 8. The step of removing an organic solvent from the reaction solution after adding to the epoxidation reaction solution or the slurry so as to be 10 to 10 parts by weight. Method for producing an epoxidized block copolymer according to item 1. 28. The epoxidizing agent is an acetic acid ester solution containing peracetic acid and is water-free.
Or the method for producing the epoxidized block copolymer according to 27. 29. (1) The block copolymer (C) or its hydrogenated product (D) is mixed with an organic solvent, and the concentration of the polymer is 5 to 50.
A step of obtaining an organic solvent solution or an organic solvent slurry having a weight% of (2) a step of using an epoxidizing agent to epoxidize an unsaturated carbon bond present in a polymer in the organic solvent solution or the organic solvent slurry, ( 3) A step of reducing the acid value of the solution or slurry to 5 mgKOH / g or less by washing and / or neutralizing the epoxidation reaction solution or slurry obtained in the above step, (4) Washing and / or neutralizing epoxy The oxidization reaction solution or slurry is supplied to the first evaporator to evaporate the organic solvent to concentrate the epoxidation reaction solution, and then the concentrated solution is removed of the organic solvent by the second kneading evaporator. The method for producing an epoxidized block copolymer according to any one of claims 1 to 7.