JPS62225511A - Modification of polymer - Google Patents

Abstract

PURPOSE:To obtain a modified polymer having excellent color tone and melt characteristics and containing little gelatinous substance, in high stability, by reacting a block copolymer (mixture) with a modifying agent under heating in the presence of specific amounts of specific phenolic compound and phosphorus-based stabilizer. CONSTITUTION:A block copolymer containing a polymer segment composed mainly of one or more vinyl aromatic hydrocarbon and a polymer segment composed mainly of one ore more conjugated dienes and having a vinyl aromatic hydrocarbon content of 5-95(wt)%, preferably 15-85% or its mixture with a thermoplastic resin or rubbery polymer is modified by reacting 100pts.(wt.) of said copolymer (mixture) with at least one kind of modifying agent consisting of an unsaturated carboxylic acid (derivative) in the presence of (A) 0.05-2pts., preferably 0.1-1pt. of a phenolic compound of formula I-IV (R1 is 1-4C alkyl R2 is 2-20C alkyl; R3 is group of formula V) and (B) 0.05-2pts., preferably 0.1-1.5pts.of a phosphorus-based stabilizer at 180-320 deg.C, preferably 200-280 deg.C.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a block copolymer comprising a vinyl aromatic compound and a conjugated diene, or a mixture of the block copolymer and a thermoplastic resin, which is treated with an unsaturated carboxylic acid and a thermoplastic resin. The present invention relates to a method for modifying a polymer using at least one modifier selected from its derivatives.

[Conventional technology]

Conventionally, many attempts have been made to modify resins or rubbers with highly functional unsaturated carboxylic acid compounds, such as maleic acid compounds, to improve adhesive properties, green strength, and the like. For example, JP-A No. 64-27 suggests a method of maleating a block copolymer of butadiene and styrene by generating radicals using a radical initiator or heating. . Father, JP-A Sho Kit-737, 2θ, JP-A Shojj-
, 263/o. discloses a method of maleating a block copolymer consisting of butadiene and styrene in a molar solvent in the presence of a radical polymerization catalyst. Furthermore, JP-A-62-2341413 suggests a method of maleating a block copolymer consisting of polyethylene/butadiene and styrene in a screw extruder in the presence of a radical initiator.

[Problem that the invention seeks to solve]

However, in both of these methods, 7
Because of the rain formation, gelation of the resulting modified block copolymer is unavoidable. The modified block copolymer results in a marked deterioration of properties as a thermoplastic rubber, such as melt flow characteristics and appearance characteristics.

Under these circumstances, the inventor of the present invention conducted extensive research to solve the above problems, and as a result, using a screw extruder,
It was discovered that when the modification reaction is carried out under specific reaction conditions in the absence of a radical initiator, a modified polymer with excellent melting properties and a small amount of toluene insoluble matter can be obtained, and has already been published in JP-A-5! −
It was disclosed in No. 3♂♂θ3 and JP-A No. 0577 in 1983. However, the modified block copolymers obtained by the methods disclosed in these publications did not necessarily have good color tone and needed to be improved.

[Means and effects for solving the problem] Under the present circumstances, the present inventors have developed a method for obtaining a modified polymer that has excellent color tone and melting properties and contains less gel-like substances (two methods have been investigated, and a specific phenol-based Using specific amounts of compounds 1:
As a result, it was discovered that conventional oxidation inhibitors exhibit effects that could not be predicted, leading to the present invention.

That is, the present invention has at least 7 polymer segments mainly composed of vinyl aromatic hydrocarbons and at least 7 polymer segments mainly composed of conjugated dienes, and the vinyl aromatic hydrocarbon content is 5 to 5. De! Blood volume-related block copolymer or a mixture of the block copolymer and a thermoplastic resin or rubbery polymer (containing at least one modifier selected from di-unsaturated 441 carboxylic acids and derivatives thereof) ♂θ
When reacting at a temperature of ~320°C, the block copolymer or mixture/θθ heavy housing part θ, OJ″ ~2
General formula [1], (1), [Seal] and (If) in parts by weight
Provided is a method for modifying a polymer, characterized in that the modification reaction is carried out in the presence of a phosphorus stabilizer of at least 71M, θ, Oj to 2 orthogonals selected from the phenolic compounds represented by

(In each of the above formulas, R represents an alkyl group having a carbon number of 2 to λθ.) The present invention will be described in detail below.

The block copolymer used in the present invention comprises at least one
, preferably 2 or more polymer segments mainly composed of vinyl aromatic hydrocarbons and at least 7 polymer segments mainly composed of conjugated dienes, and the content of vinyl aromatic hydrocarbons is 5 to 95%. The block copolymer has a vinyl aromatic hydrocarbon content of 60 to 90% by weight, preferably 10 to 90% by weight, and preferably 10 to 90% by weight. If the content is 331t% or less, it exhibits properties as a thermoplastic elastic body, and if the content of vinyl aromatic hydrocarbon exceeds 6θ, preferably 2% or more, it exhibits properties as a thermoplastic resin. shows.

Any known method may be used as the method for producing the block copolymer used in the present invention, for example,
? Ko♂ No. 6 Publication, Special Publication No. 4T3-77979, Publication No. 57 of Special Publication No. 4T3-77979, Publication No. 57 of Special Publication No. 4T4-324T
Examples include the method described in Publication No. lj. These are methods in which a conjugated diene and a vinyl aromatic hydrocarbon are block copolymerized using a polymerization initiator such as an organolithium compound in a hydrocarbon solvent. , B+ person-
B) Represented by n (In the above formula, H is a polymer segment mainly composed of vinyl aromatic hydrocarbons, B does not need to be a conjugated diene, and n is an integer of 7 or more.) Linear block copolymer or general formula, [(B-A)n
+, rX, C (A-8), →1■XC (B-person +-yB
-tKTΣX, ((A -B iAd

m and n are integers of 7 or more. ) It is obtained as a radial block copolymer represented by:

In addition, in the above formula C:, the polymer segment mainly composed of vinyl aromatic hydrocarbons means vinyl aromatic hydrocarbons! A copolymer block of a vinyl aromatic hydrocarbon and a conjugated diene containing more than θ superposition and/or a vinyl aromatic hydrocarbon alone .

represents a copolymer block of a conjugated diene and a vinyl aromatic hydrocarbon and/or a conjugated diene homopolymer block containing a conjugated diene.

The vinyl aromatic hydrocarbons in the copolymer block may be uniformly distributed or tapered. Uniform: A plurality of bidistributed portions and/or tapered distributed portions may coexist in each block.

The block copolymer used in the present invention may be any mixture of block copolymers represented by the above general formula.

The conjugated diene used in the present invention is a diolefin having /pair of conjugated double bonds, such as /3-butadiene, comethyl-7.3-butadiene (isoprene)1.
Examples include 2,3-dimethyl-7,3-butadiene, 7,3-pentadiene, /, 3-hexadiene, and particularly common ones include /, 3-butadiene, and isoprene. These may be used not only alone, but also as a mixture of two or more.

The vinyl aromatic hydrocarbons used in the present invention include styrene% O-methylstyrene, p-methylstyrene% p-1
ert-butylstyrene, 7,3-dimethylstyrene,
Examples include α-methylstyrene, vinylnaphthalene, vinylanthracene, etc., and styrene is particularly common. These may be used not only alone, but also as a mixture of two or more.

The number average molecular weight of the block copolymer used in the present invention is /
θ, 0θO~♂θθ, Oθθ, preferably 3θ, θθθ
~r o o, oθθ. Note that the block copolymer used in the present invention may be hydrogenated.

In the present invention, a mixture of the block copolymer and a thermoplastic resin or rubbery polymer can be modified. Examples of thermoplastic resins include polystyrene, impact-resistant rubber-modified styrene polymer, acrylonitrile-styrene copolymer, styrene-maleic anhydride copolymer, acrylonitrile-butadiene-styrene copolymer, and methacrylic acid ester-butadiene-styrene copolymer. Polystyrene-based resins such as polymers, polyethylene, copolymers of ethylene containing 0% or more of ethylene and other copolymers that can co-electrify, such as ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, etc. Polymers and hydrolysates of 7, polyethylene resins such as ethylene-acrylic acid ionomers and chlorinated polyethylene, -polypropylene, copolymers of propylene containing 50% or more of propylene and 7 polymers copolymerizable with it , for example, polypropylene resins such as propylene-ethylene copolymer, propylene-ethyl acrylate copolymer and chlorinated polypropylene, copolymers of polybutene-/, butene-/ and other monomers copolymerizable with it. Certain polybutene resins, polyvinyl chloride, polyvinylidene chloride, vinyl chloride and/or vinylidene chloride! Polyvinyl chloride resin which is a copolymer of vinyl chloride and/or vinylidene chloride containing θ or more and other hexamers copolymerizable with it, vinyl acetate whose vinyl acetate content is jO or more and other copolymerizable monomers, and their hydrolysates, acrylic acid and its esters and amides, methacrylic acid and its esters and amides, and these acrylic acid monomers. Polyacrylate resins, acrylonitrile and/or methacrylonitrile polymers which are copolymers with other copolymerizable monomers containing 0 or more of these acrylonitrile monomers; Nitrile resins that are copolymers with polymerizable heptamers; linear polymers in which the constituent units of the polymer are bonded by repeating amide group bonds, such as ε-
Ring-opening polymer of aminocaprolactam and ω-aminolaurolactam.

Polyamide resins such as condensation polymers of ε-aminoundecanoic acid, condensation polymers of hexamethylene diamine and dibasic acids such as adipic acid and sepanoic acid, and polymer constituent units are bonded by repeated ester bonds. Linear polymers, such as polyester resins and polyphenysine ether resins, which are condensates of dibasic acids such as phthalic acid and isophthalic acid, or their =S forms, and glycol components such as ethylene glycol, propylene glycol, butylene glycol, etc. or a grafted polyphenylene ether resin in which a vinyl-substituted aromatic hydrocarbon is graft-polymerized to the resin;
Polyphenylene sulfide 14 fat.

Polyacetal resins such as polyquinemethylene, triochitin and alkylene oquinide copolymers, linear polymers in which the constituent units of the polymer are bonded by repeating carbonate-type bonds, such as da, dihydroxydiphenyl Polycarbonate resins such as polymers obtained by reaction of dihydroquine compounds such as alkanes, g, 4t'-dihydroxydiphenylsulfirad and phosgene, or polymers obtained by transesterification of the dihydroxy compounds and diphenyl carbonate;
Polysulfone resins such as polyether sulfone and polyallylsulfone, thermoplastic polyurethane resins obtained by polyaddition reaction of diisocyanate components and glycol components, polybutadiene resins such as transpolybutadiene and /1.2-polybutadiene, bisphenol. Polyarylate resin, which is a polycondensation polymer consisting of human and phthalic acid components; fluororesin, which has a structure in which part or all of the hydrogen in a chain hydrocarbon polymer compound is replaced with fluorine; polyoxybenzoyl resin; 9 imide resin, etc.

Further, as the rubbery polymer, polybutadiene, polyisoprene, styrene-butadiene copolymer, butadiene-
Acrylonitrile copolymer and ethylene-propylene copolymer!
Examples include rubber, ethylene-propylene-diene copolymer, silicone rubber, epichlorohydrin rubber, acrylic rubber, and ethylene-vinyl acetate copolymer.

In the present invention, the mixing ratio (charging ratio) of the block copolymer and the thermoplastic resin or rubbery polymer is generally 1/2 to 3/97, preferably 97/3 to 3/97! /9! It is. These may be mixed in advance or may be mixed in the modification reaction apparatus during the modification reaction. The modified mixture of the block copolymer and the thermoplastic resin or the rubbery elastic material has excellent compatibility with the unmodified thermoplastic resin or the rubbery elastic material, and at the same time, it is possible to obtain a mixture of the block copolymer and the thermoplastic resin or rubbery elastic material. higher temperature compared to the case alone, e.g. 200-3
The modification reaction can be carried out more smoothly at 20°C, preferably between θ and 3θO°C.

Examples of unsaturated carboxylic acids and derivatives of 7 that are modifiers used in the present invention include maleic acid, malhydric maleic acid, maleic ester, maleic acid amide, maleic acid imide, fumaric acid, fumaric acid ester, and fumaric acid. Amide, fumaric acid imide, itaconic acid, itaconic anhydride, itaconic ester, itaconic acid amide, itaconic acid imide, halogenated maleic acid, m-water halogenated maleic acid, halogenated maleic ester, halogenated maleic acid amide, halogen maleic acid imide, cis-q-cyclohexene-7,2-dicarboxylic acid, cis-q-cyclohexene anhydride/2-dicarboxylic acid, cis-cyclohexene-codicarboxylic acid ester, cis-glucohexene-2-dicarboxylic acid Acid amide, cis-gucyclohexene-7,2-dicarboxylic imide, endo-
cis-bicyclo(2,2,/)-j-hepteneco, 3-dicarboxylic acid, anhydrous endo-cis-bicyclo(2
,2,/ ) −! -heptene-, 3-dicarboxylic acid, endone-subcyclo(,2,co,/)-J--heptene-, 3-dicarboxylic acid ester, endo-cis-binculo(2,2,/)-J-- Hebutenko,
3-Dicarboxylic acid amide, endo-cis-vinclo(λ
,,2. /)-j-heptene, 3-dicarboxylic imide, acrylic acid, acrylic ester, acrylic amide, methacrylic acid, methacrylic ester, and methacrylic amide. These can be used not only as camphor tree but also as a mixture of λ or more types. Among these, unsaturated dicarboxylic acids or derivatives thereof are preferred, and maleic anhydride is particularly preferred.

In the present invention, the modifier selected from unsaturated carboxylic acids and derivatives thereof is generally 0.7 to 700 parts by weight, preferably 0.7 to 700 parts by weight per part by weight of the block copolymer or Ir1J mixture/θθ. θ, J″~!θ weight is in parts. If the amount of modifier is too small, the modification effect will be small, and conversely, if the amount of modifier is too much (the second is to remove unreacted modifier from the modified product). This is not preferable because it becomes complicated and the homopolymer of the modifier itself is mixed.

In the present invention, the temperature at which the block copolymer or the mixture is reacted with the modifier is /♂θ to 3.2θ°C, preferably KθO to 2♂0°C.

If the reaction temperature is less than /♂0°C, the reaction rate of the modifier will be low and the modification effect will be small, which is not preferred.

On the other hand, if the reaction temperature exceeds 32[theta]C, the color tone and melting properties will deteriorate, and a large amount of gel-like substances insoluble in solvents such as toluene will be formed, which is not preferable. In the present invention, in order to suppress the formation of gel-like substances during the modification reaction, it is preferable to carry out the modification reaction in the absence of a radical initiator such as a peroxide or an azo compound. Operations such as increasing the reaction rate of the modifier using a small amount of radical initiator may be performed within a range that does not result in formation.

The greatest feature of the present invention is that the general formula n+1 [1] is 2 parts by weight, preferably 0.7 to 7 parts by weight, per 700 parts of the block copolymer or mixture. , [1
13. [Table] and at least one kind selected from the phenolic compounds shown in (IV), θ, θ! ~, 2 subvk
The modification reaction is carried out in the presence of a phosphorus stabilizer in an amount of .theta., preferably 7 to/j parts by weight.

The amount of phenolic compounds used is θ, θ! If the amount is less than 1 part by weight, no effect of improving color tone or melting properties or suppressing the formation of gel-like substances will be observed, and on the other hand, if it exceeds 2 parts by weight, no effect beyond the scope of the present invention will be exhibited. In the compound represented by the general formula [1], the substituent (1 represents an alkyl group having 7 to 2 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an isobutyl group, and a tert-butyl group. ,
Particularly preferred is a methyl group. In addition, the compound represented by the general formula (fi) (in 2, the substituent R is a carbon number of 2 to .20,
Preferably, it represents an alkyl group of q to /♂, and examples thereof include a nclohexyl group, an octyl group, and a dodecyl group, with an octyl group being particularly preferred. The phenolic compound is particularly preferably represented by the general formula [1] and/or (It).

Further, specific examples of the phosphorus stabilizer used in the present invention include:
Tris(nonylphenyl)phosphite (hereinafter AO-
7), cyclic neopentanetetryrubis(octadecylphosphite) (hereinafter referred to as AO-,2), tris(2,gu,,>-1crt-butylphenyl)phosphite (hereinafter referred to as 0-3), ), X, 4
t-Butylidene-bis(3-methyl-4-1ert-butylphenyl-di-tridecyl)phosphite (hereinafter referred to as AO-g), 4t'-biphenylene diphosphinic acid tetrakis (,2-di-tert-butyl) At least one phosphorus-based stabilizer selected from cyclic neopentanetetrayl bis(,2,4t-di-tert-butylphenyl)phosphite (hereinafter referred to as AO-6); Medications can be given.

In the present invention, at least one selected from other phenolic and sulfur stabilizers may be used in combination in order to obtain a hydrophobic polymer with even better color tone and melting properties and with less gel-like substances. . Suitable stabilizers include (A) octadecyl-, ? -(3, Yo-Geeter
Tortoise-buteruderhydroquinphenyl) propionate (hereinafter referred to as AOA-/), triethylene glycol-
BisC3-(3-tert-butyl-j-methyl-9
-hydroquinphenyl)propionate] (hereinafter AOA
-2) , /, 3. j -tris-(guter)
t-Butyl-3-hydroxy-but-dimethylpencil)incyanur I! ! 1F (hereinafter referred to as AOA-3)
,J,,2'-methylene-bis-(gumethyl-6-t
At least one phenol thread stabilizer selected from iB+ (hereinafter referred to as 0A-9) dilauryl-3,3'-thiodipropionic acid ester (hereinafter referred to as AOB-/), cimilistyl-3 (hereinafter referred to as AOB-/)
, 3'-thiodipropionic acid ester (hereinafter referred to as AOB-2
), distearyl-3,3'-thiodipropionic acid ester (hereinafter referred to as AOB-3), laurylstearyl-3,3'-thiodipropionic acid ester (hereinafter referred to as AOB-3), distearyl-3,3'-thiodipropionic acid ester (hereinafter referred to as AOB-3),
At least one sulfur-based stabilizer selected from OH-Q) is mentioned. These are generally (: +iiJ block co-bundle coalescence or θ, respectively per ioo parts by weight of the mixture)
It can be used in combination with at least one phenolic compound selected from the following general formulas - (IV) in an amount of 0 to 2 parts by weight, preferably from 0.7 to 7 parts by weight. A particularly preferred combination system is at least one phenolic compound selected from the above general formulas (1) to (IV).
05 to 2 parts by weight, preferably 0.7 to 7 parts by weight, and θ, OS-λ parts by weight of a phosphorus stabilizer, preferably 0.7 to 7 parts by weight.
Parts by weight, the above stabilizers are θ, θj-2 parts by weight, preferably θ, 7~/Tookibe, nil (Bl stabilizers are 0~2 parts by weight)
2 parts by weight, preferably 0.7 parts by weight. Amine-based compounds such as phenothiazine change color tone,
Especially Nikko Trace A! It is not recommended to use them together because the color tone of the bell is inferior.

The method of the present invention is preferably carried out substantially in the absence of an organic solvent and under melt mixing, but if necessary, it may be carried out in a state dissolved in an organic solvent. Examples of melt-kneading methods include methods using general mixers such as internal mixers, coney goo, twin-screw continuous kneaders, single-screw, twin-screw, or multi-screw extruders, especially extrusion. A method using a machine is preferable for continuous production. In the melt mixing method using an extruder, the average residence time in the extruder is generally 70 to 700
0 seconds, preferably 3θ to 5θθ seconds.

If the average residence time is too short, problems such as a low reaction rate or non-uniform reaction may occur.On the other hand, if the average residence time is too long, the formation of gel-like substances will be noticeable (-, which is preferable). do not have.

In addition, in the method of the present invention, the amount of unreacted modifier remaining in the modified polymer after the modification reaction is less than or equal to 700 parts by weight of the modified polymer, preferably less than or equal to O0j or less than C.
: It is preferable to have color tone C: in order to obtain an excellent modified polymer. For this purpose, a method is recommended in which the modification reaction is carried out using an extruder equipped with a device capable of venting, and unreacted modifying agent is removed from the pent part by means such as reduced pressure.

In the method of the present invention, the modification reaction is carried out in the presence of a basic inorganic compound to obtain an ionic crosslinked modified polymer. Basic compounds are generally heptavalent, divalent and trivalent metal compounds, such as sodium compounds,
Potassium compounds, magnesium compounds, calcium compounds, lead compounds, aluminum compounds, etc.
Suitable examples of these metal compounds include hydroxides, alcoholades, carboxylates and oxides.

Among these, magnesium hydroxide, magnesium oxide, calcium hydroxide, aluminum hydroxide, compounds mainly composed of these, and mixtures thereof can be preferably used. These additives may be added in an amount of 0.000 parts per 10 parts of the block copolymer or said mixture. θ/~j heavy parts, preferably θ, Q evening~3 coulometric parts.

In addition to the above-mentioned thermoplastic polymers and rubbery polymers, the modified polymers obtained by the present invention include yuzu strengtheners, fillers, antioxidants, ultraviolet absorbers, colorants, pigments, lubricants, and flame retardants. ,
It is possible to add blowing agents and other additives. More specific examples of the above-mentioned additives that can be added to the modified polymer obtained by the present invention are described in [Handbook of Rubber and Plastic Compounded Chemicals, / published by Verdigest, Inc., published in 2004 by Def 4]. .

〔Effect of the invention〕

The present invention not only provides an industrial production method for stably obtaining a polymer modified with an unsaturated carboxylic acid or its derivative, but also provides a modified polymer with excellent color tone and melt viscosity properties, and with less contamination of gel-like substances. A polymer is obtained.The modified polymer obtained from the present invention (-) is modified with an unsaturated carboxylic acid or its derivative. It can be used as a material for footwear, as a base for pressure-sensitive adhesives and adhesives, as a modifying material for asphalt, as a material for electrical wire gaples, as a modifying material for vulcanized rubber, etc.

〔Example〕

Examples are shown below to explain the present invention in more detail, but these examples are intended to demonstrate the excellent effects obtained by the present invention, and are not intended to limit the scope of the present invention. do not have. On the other hand, the block copolymers used in the examples of the present invention were produced as follows.

[Inside the block copolymer]

7.3-butadiene/j under nitrogen gas atmosphere at C2
Lobetillithium was added to a 0-hexane solution containing 20 parts of 3-butadienda and 20 parts of methyl ref, and polymerized at 70°C for 2 hours.
An n-~chitin solution containing 1 L@ part was added and polymerized at 70°C for 2 hours. The obtained polymer had a styrene content of 4tO, a B-A-B of M I (G) / Of//θ-
It was a block copolymer with -A structure.

[Block copolymer (B)]

In a nitrogen gas atmosphere at C2, a solution of n-butyl lithium containing styrene 3θ heavy moieties was added, and after polymerization at 70°C for 7 hours, /, 3-butadiene 70
A cyclohexane solution containing hydrogen was added, and polymerization was carried out at 70°C for 2 hours. Then tetrachlorosilane was used
-Addition of mol of butyl lithium to reduce styrene content to zero
Heavy weight, MI (0) 20t/10m (A -B -h
An s i structure nofloc co-benefits was obtained.

[Block copolymer (C)]

In a nitrogen gas atmosphere, a nclohexane solution containing 3 parts of styrene and 0 parts of tetrahydrofuran, 3 MV parts: di-n-butyllithium was added, and after polymerization at 70°C for 7 hours, 20 parts by weight of 3-butadiene was added. Part and mechi 2fu 50
A cyclohexynane solution containing a heavy compound was added, and the mixture was incubated at 2θ°C for 2 hours. The obtained polymer has a styrene content of ♂0w
It was a block copolymer with an ABA structure of L, MI(0)♂t/10Iw.

Examples/~9 and Comparative Examples/~ After blending 100 parts by weight of block copolymer (A), 2 parts by weight of maleic anhydride, and the stabilizers shown in Table 7, the mixture was fed to a 3θNme extruder and The maleation reaction was carried out at ℃. The average residence time in the extruder was about 90 seconds. Unreacted maleic anhydride was removed from the tip of the extruder (= a part near the attached vent) under reduced pressure C:, and the amount of residual frenic anhydride in the modified bundle coalescing was below θ, in terms of weight. (I did two.

The amount of maleic anhydride added to the obtained modified block copolymer was θ, q ~ 0.6 M%.

Furthermore, the melt viscosity retention, toluene insoluble content, and color IM'? of the obtained modified block copolymer were evaluated. :Table/Table (=shown. The modified block copolymer subjected to the modification reaction in the presence of the phenolic compound specified in the present invention has excellent color tone and melt viscosity characteristics, and has little inclusion of toluene-insoluble gel-like substances. I understand that.

In Example 1, when the operation of removing unreacted maleic anhydride from the pent portion was not performed, the b value of the obtained modified polymer pellet was 32 and the color tone was slightly inferior.

(Left below) (Note/) The amount of each stabilizer is the blending ratio (]!it part of the block copolymer or a mixture of the block copolymer and the thermoplastic resin or rubbery polymer, based on 10θ weight.) ) is shown.

(Sho 2) A phenolic compound in which R1 is a methyl group in the general formula (1).

(Note 3) A phenolic compound in which R2 in the general formula [n] (= is an octyl group).

(Note) 2. ≦-di-tert-butyl-q-methylphenol (Shoj) The melt viscosity characteristics were determined by the melt viscosity retention rate.

Melt flow was measured under G conditions (<200°C, higher load), and judgment was made according to the following criteria.

◎; Retention rate is 0 or more.

○; Retention rate 60% or more and less than 1.5'O △; Retention rate gu O
% or more, less than 60% ×; Retention rate less than 11 (Sho) After dissolving the modified polymer 39 in toluene at θ02, filter it through 100 meshes of gold copper, and remove the toluene insoluble matter remaining in the gold copper at ?θ℃ After vacuum drying for 2 hours, the heavy equipment was measured to determine the proportion of toluene-insoluble content.The toluene-insoluble content was determined according to the following criteria.

d: 0.03; less than t% Q: 0. Oj subacid % -hi, 0. /Less than heavy weight△1
0. /wt% or more, 0.5 tons full x; 0. txm%
Above (Note 7) The color tone of the pellet-shaped modified polymer was examined using a comprehensive visual measuring instrument ND-4613 manufactured by Nippon A-Shoku Kogyo Co., Ltd.

The quality of the color tone was determined by the b value according to the following criteria. The larger the b value, the greater the apparent yellowness.

◎; b value less than 3θ ○; b value 3θ or more, less than 3 △; b value 3j or more, less than 4to The modification reaction was carried out in the same manner as in Examples/Using Example 1. It was at the level of

When the above modified block copolymer was exposed to sunlight for a week, the color changed to reddish brown and the color tone was poor (rank ×
). In addition, almost no discoloration was observed in the modified block copolymers of Examples/--9 under similar sunlight exposure conditions.

Comparative Example 7 When the modification reaction of Example// was carried out at 330° C., gelation occurred during the modification reaction and a smooth modification reaction could not be carried out.

Example 10-27 According to the compounding method shown in Table 2, maleic anhydride! After mixing Ekibe and stabilizers, the cylinder temperature was supplied to a 3θ18 extruder whose temperature was set as shown in Table 2, and the maleation reaction was carried out. Average residence time in the extruder was adjusted to a range of 60 to /2θ seconds.In addition, unreacted maleic anhydride was removed by reduced pressure from the attached vent part C near the tip of the extruder, and the amount of residual maleic anhydride in the modified polymer was was made to be less than 0.3 weight factor.

The signs of maleic anhydride added to the obtained modified block copolymer are O6λ~/,! It was deeply regrettable.

The melt viscosity of the obtained modified block copolymer was significantly superior to that of the modified block copolymer obtained using stabilizers outside the scope of the present invention, and the color tone was also good and it was gel-like. The presence of insoluble matter was also small.

In addition, Example /θ1, /! and 22, when the stabilizer applicant was used instead of stabilizers C, the difference between the melt flow of the modified polymer and the melt flow of the comparative polymer was 22//
At θ- or higher, excellent melt viscosity characteristics were exhibited.

(Note♂) MMA: Methyl methacrylate polymer PA
; Nylon-6,6 AO8: Acrylonitrile-butadiene-styrene copolymer PC; Polycarbonate'rPgT: Thermoplastic polyester elastomer NBR: Acrylonitrile-butadiene copolymer λS; Acrylonitrile-styrene copolymer ppg; Polyphenylene ether PP3T: Polyethylene terephthalate PBT : Polybutylene terephthalate PS : Polystyrene MS ; Methyl methacrylate/styrene copolymer PP ; Polypropylene pB :/,, 2-polybutadiene (Note 5') A : C1)...θ,! Heavy groin, A
O-7...0.2 parts by weight, AO-2...0.3 parts by weight, AOA-7...θ,! Overlapping part B S [n)-0.3 overlapping part, AU-/・0.7 part by weight, AO-5...0.3 overlapping part, AOA-co...
0.5 part by weight c: C1)...0.5 part by weight, CIY)...θ
6! Part by weight, AO-/...0.3 part by weight, AOB-/
...095 parts by weight (note/θ) As a comparative example corresponding to each example, the stabilizers were AOC-/.../, 0 parts by weight, AO-/...0. j
In the case of Oniwabe, AOB-/...θ, Yushige Keibe: Two modifications were carried out, and the melt flow of the example modified polymer and the comparative example modified polymer (measurement conditions were A8TM D-/2
3♂), and the melt viscosity measurement was determined according to the following & criteria.

(Melt flow of modified polymer of Example) - (Melt flow of modified polymer of Comparative Example) ◎; /70 layers or more

Claims (1)

[Scope of Claims] 1. A polymer having at least one polymer segment mainly composed of a vinyl aromatic hydrocarbon and at least one polymer segment mainly composed of a conjugated diene, and having a vinyl aromatic hydrocarbon content of 5 At least one modifier selected from unsaturated carboxylic acids and derivatives thereof is added to a block copolymer or a mixture of the block copolymer and a thermoplastic resin or rubbery polymer in an amount of 180 to 95% by weight. When reacting at a temperature of 320°C, 0.05 to 2 parts by weight of the general formula [I] per 100 parts by weight of the block copolymer or the mixture
], [II], [III] and [IV], characterized in that the modification reaction is carried out in the presence of 0.05 to 2 parts by weight of a phosphorus stabilizer selected from the phenolic compounds represented by [II], [III] and [IV]. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] , R_2 represents an alkyl group having 2 to 20 carbon atoms.) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] (In the above formula, R_3 is ▲ mathematical formula, Chemical formulas, tables, etc. are shown.)