WO2006093106A1 - Rubber composition for resin modification, process for production of the same, and a rubber-reinforced resin composition - Google Patents

Abstract

[PROBLEMS] To provide a rubber composition for use in the modification of a resin, which is highly stable during storage and use and can provide a rubber-reinforced resin having excellent gloss, color tone and transparency with little fisheyes; a process for producing the composition; and a rubber-reinforced resin composition produced by using the rubber composition. [MEANS FOR SOLVING PROBLEMS] A rubber composition for use in the modification of a resin, comprising 100 parts by weight of a conjugated diene polymer rubber, 0.01 to 0.20 part by weight of a phosphite compound heat stabilizer having at least two phosphorus atoms in the molecule, and 0.01 to 0.20 part by weight of at least one additional heat stabilizer selected from the group consisting of a thioether compound heat stabilizer and an acrylate compound heat srabilizer. A process for producing the rubber composition, comprising steps of adding a phosphite compound heat stabilizer having at least two phosphorus atoms in the molecule to a conjugated diene polymer rubber, and adding an additional heat stabilizer other than the phosphite compound heat stabilizer to the resulting mixture. A rubber-reinforced resin composition comprising the rubber compound and a resin.

Description

 Rubber composition for resin modification, method for producing the same, and rubber-reinforced resin composition

 [0001] The present invention relates to a rubber composition for refining a resin suitable for modification of a resin, particularly an aromatic bur resin such as styrene resin, a production method thereof, and a rubber composition for modifying this resin. The present invention relates to a rubber reinforced resin composition obtained by use. More specifically, the present invention is excellent in stability at the time of production and storage, and is used to obtain a rubber-reinforced resin composition having excellent gloss and color tone, excellent transparency, and less fishiness. The present invention relates to a rubber composition for modifying a resin, a method for producing the composition, and a rubber-reinforced resin composition obtained using the rubber composition for modifying a resin.

 Background art

 [0002] Aromatic vinyl resin such as styrene resin is used in a wide variety of applications because of its good moldability, high rigidity, and easy availability of its raw monomer. This is important as the thermoplastic resin used. However, on the other hand, it has the drawback of being vulnerable to impact and brittle. For this reason, rubber is reinforced for applications that require impact resistance. Typical aromatic burrs reinforced with rubber include the impact polystyrene (HIPS) reinforced with cross-linked rubber particles of polystyrene and the ABS resin reinforced with cross-linked rubber particles of styrene-acrylonitrile copolymer. And modified polyphenylene ether blended with HIPS and polyphenylene ether. Conjugated polymers are most commonly used as rubbery polymers used to obtain these rubber-reinforced resins. However, since the conjugate polymer has a large amount of double bonds in its molecule, it has a problem that its stability to heat and oxygen during storage and use is low.

[0003] In order to improve the stability of the conjugated diene polymer with respect to heat and oxygen, hydrogenation may be performed on a part of the unsaturated bond remaining in the conjugated diene polymer. However, antioxidants are usually added because hydrogenation is not possible in all applications. [0004] For this reason, many studies have been made on the anti-oxidation agent to be added to the rubber composition for modifying a resin.

 For example, Patent Document 1 discloses a rubber-reinforced styrene system containing 0.002% by weight or more and less than 0.02% by weight of a phenolic antioxidant having a molecular weight of 400 to 700 and having one or more thioether structures in the molecule. A rosin composition is disclosed. However, in the presence of a gen-based polymer containing this antioxidant, there is a problem in polymerization stability when polymerizing a styrene monomer.

 [0005] Patent Document 2 contains an impact modifier for thermoplastic resin, which contains three components: a thioether heat stabilizer, a phosphite heat stabilizer, and a phenol heat stabilizer having a molecular weight of 500 or more. By doing so, it has been reported that a saturated polyester resin having excellent heat-resistant coloring property and heat-resistant deterioration property can be obtained. However, in the study by the present inventors, when this impact modifier is applied to a thermoplastic resin other than a saturated polyester resin, the color tone is poor and the color tone is poor and only the resin is obtained. ,.

 [0006] On the other hand, the invention is not limited to the resin modification, but a device for preventing coloring or deterioration of the rubber itself has been devised.

 In Patent Document 3, when a polymer obtained using an organolithium compound as an initiator is subjected to steam stripping to remove the solvent, the polymerization is stopped with water, alcohol or the like, preferably an organic acid, and then a phenol-based stabilizer. And tris (2,4-dibutylbutyl) phosphite and other tris (disubstituted or trisubstituted filed) phosphite stabilizers to improve transparency and devitrification resistance. Is obtained. However, there is a problem that the transparency of the resin is lowered in some cases.

[0007] As described above, despite a great variety of studies, it has so far been excellent in stability at the time of production and storage, and has excellent gloss and color tone and transparency. The present situation is that a rubber composition for refining a resin capable of obtaining a rubber-reinforced refining resin with excellent fish eyes and little fish eye can be obtained.

Patent Document 1: Japanese Patent Laid-Open No. 11 71489

 Patent Document 2: Japanese Patent Laid-Open No. 1-245044

Patent Document 3: Japanese Patent Laid-Open No. 1-182307 Disclosure of the invention

 Problems to be solved by the invention

 Accordingly, an object of the present invention is to obtain a rubber-reinforced resin having excellent gloss and color tone, excellent transparency, and less fish eyes by using the high stability during storage and use. An object of the present invention is to obtain a rubber composition for modifying a resin.

 Another object of the present invention is to provide a method for producing the rubber composition for modifying a resin.

 Still another object of the present invention is to provide a rubber-reinforced resin composition using this rubber composition for modifying a resin.

 Means for solving the problem

[0010] As a result of intensive studies to achieve the above object, the present inventors add and use a plurality of heat stabilizers having a specific structure in a specific ratio to the conjugated polymer rubber. As a result, it has been found that the above problems can be solved, and the present invention has been completed based on this finding.

 [0011] Forcibly, according to the present invention, 100 parts by weight of a conjugated polymer rubber, 0.01 to 0.20 parts by weight of a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule, and Choe Iterty compound heat stabilizer and attaretoi compound heat stabilizer power Group power of at least one kind of heat stabilizer selected from 0.01 to 0.20 parts by weight A quality rubber composition is provided.

 Further, according to the present invention, 100 parts by weight of the conjugated polymer rubber, 0.01 to 20.20 parts by weight of a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule, and at least one thioether compound There is provided a rubber composition for modifying a resin, comprising 0.01 to 0.20 part by weight of a total of a physical heat stabilizer and at least one kind of an attareitohi compound heat stabilizer.

 In the rubber composition for modifying a resin of the present invention, the amounts of the thioether compound heat stabilizer and the acrylate compound compound heat stabilizer are both preferably 0.01-0.20 parts by weight. Yes.

[0012] In the rubber composition for modifying a resin of the present invention, a photopolymer having two or more phosphorus atoms in the molecule. It is preferred that the sphite compound heat stabilizer is a diphosphite heat stabilizer.

 Further, in the rubber composition for modifying a resin of the present invention, the amount of the phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is 0.02 per 100 parts by weight of the conjugated polymer rubber. -0. 10 parts by weight is preferred 0.03-0.09 parts by weight is even more preferred.

 In the rubber composition for modifying a resin of the present invention, the thioether compound thermal stabilizer preferably has a phenol group in its molecule.

 In the rubber composition for modifying a resin of the present invention, the amount of the thioether compound heat stabilizer is preferably 0.01 to 0.10 parts by weight per 100 parts by weight of the conjugated polymer rubber. More preferably, it is 0.02 to 0.09 parts by weight.

 In the rubber composition for modifying a resin according to the present invention, it is preferable that the talato toy compound thermal stabilizer has a phenol group in its molecule.

 Further, in the rubber composition for modifying a resin of the present invention, it is preferable that the amount of the heat stabilizer of the attalylate compound is 0.01 to 0.10 parts by weight per 100 parts by weight of the conjugated polymer rubber. More preferably, it is 0.02-0.09 parts by weight.

 [0014] Also, according to the present invention, after adding a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule to the conjugated polymer rubber, another thermal stabilizer is added. There is provided a method for producing a rubber composition for modifying a resin according to the present invention.

 In the method for producing a rubber composition for modifying a resin of the present invention, the conjugated polymer rubber obtained by using an organolithium compound as a polymerization initiator is less than 1 equivalent with respect to the lithium of the organolithium compound. After adding at least one selected from the group of organic acid, inorganic acid, and Lewis acid power, the phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is added to the conjugate gene. It is preferable to add to the polymer rubber.

 [0015] Further, in the method for producing a rubber composition for modifying a resin of the present invention, at least a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is added to the conjugated polymer rubber. It is preferable to carry out before adding a compounding agent other than the heat stabilizer to the conjugated polymer rubber.

Furthermore, in the method for producing a rubber composition for modifying a resin of the present invention, all of the heat stabilizers It is preferable to add to the conjugated polymer rubber before adding a compounding agent other than the heat stabilizer to the conjugated polymer rubber.

 [0016] Further, according to the present invention, there is provided a rubber-reinforced resin composition comprising the resin composition for modifying a resin of the present invention and a base resin.

 In the rubber-reinforced resin composition, it is preferable that the base resin contains at least an aromatic vinyl resin! /.

 The invention's effect

 [0017] According to the present invention, it is possible to obtain a rubber composition for modifying a resin having excellent stability during production and storage. In addition, a rubber-reinforced resin composition having excellent gloss and color tone, excellent transparency, and having a small fish eye can be obtained by using this rubber yarn composition for modifying a resin. BEST MODE FOR CARRYING OUT THE INVENTION

[0018] The rubber composition for modifying a resin of the present invention comprises 100 parts by weight of a conjugated polymer rubber, 0.01 to 0.20 part by weight of a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule. In addition, at least one kind of heat stabilizer selected from the group consisting of a thioether compound heat stabilizer and an atherato toy compound heat stabilizer is contained in an amount of 0.01 to 20.20 parts by weight.

[0019] (Conjugated polymer rubber)

 The conjugation polymer rubber used in the present invention is a homopolymer rubber of conjugation or a copolymer rubber of a co-gene and a monomer copolymerizable therewith.

 The ratio of the conjugation monomer unit to the conjugation copolymer rubber is not particularly limited, but is preferably 40% by weight or more, more preferably 50 to 75% by weight. When a conjugated-gen copolymer rubber having the above ratio in this range is used, the resulting rubber-reinforced resin composition has excellent impact resistance.

[0020] The conjugation monomer for obtaining the conjugation polymer rubber is not particularly limited. 1S Specific examples thereof include butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentagen, and the like. Can do. Of these, butadiene and isoprene are preferred, and butadiene is particularly preferred.

These conjugation monomers may be used alone or in combination of two or more. [0021] The monomer copolymerizable with the conjugation is not particularly limited. Specific examples include styrene, a-methylol styrene, 2-methylol styrene, 3-methylol styrene, 4-methyl styrene, 4-tert-butyl styrene, 2,4-dimethyl styrene, 2,4-diisopropylene. Aromatic butyl monomers such as nostyrene, 5-t-butyl-2-methylstyrene, 1,5-hexagen, 1,6-hexabutadiene, 1,7-octadiene, dicyclopentadiene, 5-ethylidene 2 —Non-conjugate monomers such as norbornene; (Meth) acrylic acid ester monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, and butyl acrylate; And _α , β-ethylenically unsaturated-tolyl monomer such as oral acrylonitrile.

 Of these, styrene is particularly preferred, with aromatic bull monomers being preferred.

 [0022] In the case of using a copolymer as the conjugation polymer rubber, the bonding mode of each monomer is selected according to the purpose and application. For example, in the case of using an aromatic butyl monoconjugate copolymer, when the impact strength is most important, a random copolymer is selected, and a block copolymer is selected for an application in which gloss is important.

 [0023] When an aromatic bull-conjugene copolymer is used as the conjugated-gen polymer rubber, the aromatic bur content is usually 3 to 60% by weight, preferably 10 to 50% by weight, more preferably 20 When it is ˜35% by weight, the impact strength and transparency are excellent.

 In the case of a block copolymer, when importance is given to gloss, the aromatic vinyl block ratio is preferably 70% by weight or more, more preferably 80% by weight or more. If the balance between impact strength and gloss is the purpose, the block ratio is preferably 20 to 80% by weight, more preferably 30 to 75% by weight.

The aromatic vinyl block rate is the amount of units that form a chain with a molecular weight of about 1,000 or more, consisting of only aromatic bull monomer units in the total aromatic bull monomer units in the block copolymer rubber. , Measured according to the osmium acid decomposition method described in IM Kolthoff et al., Journal 'Ob' Science (J. Polym. Sci.), Part 1, _P 429 (1948).

 Value.

[0024] The bonding mode in the conjugation monomer unit is not particularly limited, but a vinyl bonding unit. The ratio is usually 1-90 mol ⁰ /. , Preferably 7-50 mol ⁰ /. More preferably, it is 10-40 mol%.

 Bullet unit strength S When in this range, the rubber-reinforced resin composition of the present invention is excellent in impact resistance and gloss, and in molded products, there is little variation in gloss due to surface parts. Can be obtained.

 The amount of the monomer other than the aromatic vinyl monomer that can be copolymerized with the conjugation monomer is usually 40% by weight or less, preferably 30% by weight or less, more preferably 15% in all monomers. Weight% or less.

 [0025] Specific examples of the conjugated-gen polymer rubber include polymer rubbers composed only of conjugated-gen monomer units such as butadiene rubber, isoprene rubber, butadiene-isoprene rubber; styrene butadiene rubber, styrene isoprene rubber, styrene butadiene. Random copolymer rubber of aromatic bur monomer such as isoprene rubber and conjugation monomer; styrene butadiene block copolymer rubber, styrene isoprene block copolymer rubber, styrene-butadiene isoprene block copolymer rubber, etc. And a block copolymer rubber of an aromatic vinyl monomer and a conjugated diene monomer.

 [0026] The molecular weight of the conjugated polymer rubber is not particularly limited, but is a polystyrene-reduced weight average molecular weight by gel permeation chromatography, usually 50,000 to 1,000,000, preferably < When it is 100,000-600,000, more preferably <150,000-500,000, it gives a resin composition with excellent impact strength and gloss.

 [0027] When the conjugated-gen polymer rubber is an aromatic bull-conjugated conjugated copolymer rubber, a 5% styrene solution viscosity force of the aromatic-bule-conjugated conjugated block copolymer rubber is 5 to 200 mPa's, preferably When the viscosity is 10 to 100 mPa's, more preferably 15 to 70 mPa's, the impact strength of the resin composition and the handleability of the solution during production of the resin composition are excellent.

 [0028] The glass transition temperature of the conjugated polymer rubber (in the case of a block copolymer, the glass transition temperature of the block of the conjugated polymer) is not particularly limited, but is preferably 40 ° C or lower. More preferably, it is 90 to 1-50 ° C, more preferably 85 to 1550C.

[0029] The polymerization method of the conjugated polymer rubber is not particularly limited, and a conventionally known method can be employed. For example, an organic alkali metal catalyst, an organic alkaline earth metal catalyst, or an organic acid salt of a transition metal such as cobalt, nickel, neodymium, samarium, or gadolinium in a hydrocarbon solvent as a polymerization initiator, If necessary, the polymer solution is produced by combining other monomers used.

 When solution polymerization is performed using an organic alkali metal catalyst, an organic alkaline earth metal catalyst, or an organic acid salt of a transition metal such as cobalt, nickel, neodymium, samarium, gadolinium, etc., a conjugate gen weight having the above glass transition temperature is obtained. The combined rubber can be easily obtained. Among these, a method using an organic alkali metal catalyst is preferred.

[0030] The organic alkali metal catalyst is preferably an organic lithium compound in which one or more lithium atoms are bonded in the molecule. Examples of organolithium compounds include ethyllithium, n-propynolethium, isopropyllithium, n-butynolethium, sec-butyllithium, tert-butyllithium, hexamethylenedilithium, butagellithium, isoprenyldilithium, etc. Can do. These organolithium compounds may be used alone or as a mixture of two or more.

[0031] The polymerization solvent is not particularly limited as long as it is inert to the polymerization initiator. For example, a chain hydrocarbon solvent, a cyclic hydrocarbon solvent, or a mixed solvent thereof is used.

 Chain hydrocarbon solvents include n-butane, isobutane; 1-butene, isoptylene, trans-2-butene, cis-1-butene, 1-pentene, trans-2-pentene, cis-2-pentene, n- Examples thereof include linear alkanes and alkenes having 4 to 5 carbon atoms such as pentane, isopentane, neo-pentane and the like.

 Specific examples of the cyclic hydrocarbon solvent include aromatic compounds such as benzene, toluene and xylene; and alicyclic hydrocarbons such as cyclohexane.

 These polymerization solvents may be used alone or in combination of two or more.

[0032] Upon polymerization, the polymerization rate is adjusted, the microstructure of the polymerized conjugation monomer unit portion (cis, trans, ratio of vinyl), the reactivity ratio of the conjugation monomer and the bull aromatic compound. A polymerization regulator can be used for the purpose of adjusting the above. As the polymerization regulator, an aromatic or aliphatic ether having a relative dielectric constant of 2.5 to 5.0 or a polar compound such as tertiary amine can be preferably used.

 Specific examples of such polar compounds include aromatic ethers such as diphenyl ether and ether; aliphatic ethers such as jetyl ether, dibutyl ether, and ethylene glycol dibutyl ether; trimethylamine, triethylamine, and tripropyl. Tertiary monoamines such as amines; tertiary polyamines such as N, N, Ν ', Ν, monotetramethylethylenediamine, Ν, Ν, Ν', ，, -tetraethylethylenediamine; etc. One or more of these are preferably used.

 In addition to the above, examples of polar compounds include thioethers; phosphines such as triphenylphosphine; phosphoramides such as hexamethylphosphoramide; alkylbenzene sulfonates; alkoxides of potassium or sodium;

[0033] The polymerization temperature for producing the conjugated polymer rubber is generally -10 ° C to 150 ° C, preferably 40 ° C to 120 ° C. The time required for the polymerization varies depending on the conditions. Usually, it is within 48 hours, particularly preferably 0.5 to 10 hours. When it is difficult to control the reaction temperature, it is preferable to control the temperature by reflux cooling using a reaction vessel equipped with a reflux condenser.

 The polymerization is desirably performed in an atmosphere of an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited as long as it is carried out in a pressure range sufficient to maintain the monomer and solvent in the liquid phase within the above polymerization temperature range.

[0034] The polymerization method of each monomer is not particularly limited, and batch polymerization in which the total amount of the monomer and the total amount of the initiator are collectively charged into the polymerization system and reacted, and these are continuously supplied to the polymerization system. While continuing the polymerization while reacting to a predetermined conversion rate using a part of the monomer and initiator, and then continuing the polymerization by adding the remaining monomer and initiator. You can use a deviation from the commonly used method.

 The polymerization reaction may be stopped using a polymerization stopper such as alcohol as necessary.

In addition, the conjugated polymer rubber may be one obtained by hydrogenating after polymerization to saturate at least a part of the unsaturated bonds in the polymer. [0035] The conjugation polymer rubber solution after polymerization may be acidic or alkaline due to various metal compounds used as a polymerization catalyst. Therefore, before operations such as coagulation and heat stabilizer blending, it is preferable to neutralize with a basic or acidic compound corresponding to the liquidity.

 [0036] The basic compound used for the neutralization includes alkali metal hydroxides; alkali carbonate metal salts; alkali metal hydrogen carbonate salts; ammonia; amine compounds such as ethanolamine. be able to.

 As the acidic compound, a Lewis acid can be used in addition to an inorganic acid and an organic acid.

 Examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, boric acid, phosphoric acid, and carbon dioxide gas.

 Examples of organic acids include the power of carboxylic acids such as benzoic acid and citrate, sulfonic acid, sulfinic acid, phenolic compounds and the like.

 Examples of Lewis acids include aluminum chloride, iron chloride, boron fluoride and the like.

 Among these, carboxylic acid is preferable among organic acids.

[0037] The amount of these neutralizing agents is preferably used less than the amount necessary to completely neutralize the catalyst metal residue. Preferably, with respect to the amount necessary for complete neutralization (for example, when an organolithium compound is used as the polymerization initiator, relative to the lithium of the organolithium compound used), 0.1 ˜0.9 equivalents, more preferably 0.2 to 0.7 equivalents, particularly preferably 0.3 to 0.6 equivalents.

 By setting the use amount of the neutralizing agent within this range, precipitation of the neutralizing agent in the conjugated polymer rubber can be completely prevented, and the rubber-reinforced resin composition obtained by using this can be transparent. The property is good.

 [0038] It should be noted that the resin composition for modifying a resin of the present invention can be combined with a conjugated polymer rubber.

Other rubbers may be blended.

[0039] The rubber composition for modifying a resin of the present invention contains a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule as an essential thermal stabilizer. The phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule is not particularly limited, but is preferably a diphosphite heat stabilizer.

 Specific examples thereof include di (tridecyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, and other dialkylpentaerythritol diphosphites; di (norphenol) pentaerythritol diphosphite, bis (2 , 4 tert-butylphenol) pentaerythritol diphosphite, bis (2,6-dibutylbutyl) pentaerythritol diphosphite, bis (2,6 di-tert-butyl-4-methylphenol) pentaerythritol Diphosphite, bis (2,4 di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl 4-isopropylphenyl) pentaerythritol diphosphite, bis ( 2, 6 Di-t-butyl 4 sec-butylphenol) pentaerythritol diphosphine Iite, bis (2, 4, 6-tree t-butyl phenol) pentaerythritol diphosphite and other dialyl pentaerythritol diphosphites; and others such as pentaerythritol diphosphite, tetra (tridecyl) isopropylidene diphenyl -Rudiphosphite, tetra (tridecyl) -1,1,1,3 tris (2-methyl 5-t-butyl-4-hydroxyphenol) butanediphosphite, tetra (C to C

 12 15 Mixed alkyl) 4, 4, monoisopropylidene diphenyl diphosphite, tetra (tridecyl) -4, 4, 4-butylidenebis (2-tert-butyl-5-methylphenyl) diphosphite, tetra (tridecyl) 4, 4 , -Butylidenebis (3-methyl-6-t-butylphenol) diphosphite, bis (octylphenol) bis [4,4, -butylidenebis (3-methyl-6-tbutylphenol)] 1,6 hexanediol diphosphite, etc. Can be mentioned.

 The phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is tris [2-t-butyl-4- (3-tert-butyl-4-hydroxy-5-methylphenylthio) 5-methylphenyl] phosphite. Thus, it may have two or more thioether structures in the molecule.

Of these phosphite compound heat stabilizers having two or more phosphorus atoms in the molecule, diphosphite heat stabilizers that are liquid at room temperature are also preferable in terms of uniform dispersibility. Further, the molecular weight is preferably 700 or more, more preferably 800 or more. The amount of the phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule in the rubber composition for modifying the resin is 0.01 to 0.20 weight per 100 parts by weight of the conjugated polymer rubber. Preferably it is 0.02 to 0.10 wt., More preferably 0.03 to 0.09 wt.

 When the amount used is within this range, the coloration and degradation of the conjugated polymer rubber is unlikely to occur, the polymerization stability during the production of the rubber-reinforced resin composition, and the color tone of the resulting rubber-reinforced resin composition, Good transparency and gloss.

[0041] When a phosphite compound thermal stabilizer having one phosphorus atom in the molecule is used instead of a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule, the conjugated The amount of gel in the combined rubber increases, the storage stability becomes poor, and the color and transparency of the resulting resin composition and the rubber-reinforced resin composition are inferior.

[0042] The resin composition for rubber modification of the present invention includes a thioether compound heat stabilizer and an attalitoy compound compound in addition to a phosphate compound heat stabilizer having two or more phosphorus atoms in the molecule. It is necessary to further contain at least one heat stabilizer selected from the group power consisting of heat stabilizers.

 The amount of the at least one heat stabilizer needs to be 0.01 to 0.20 parts by weight per 100 parts by weight of the conjugated polymer rubber. When the amount used is within this range, the coloration of the conjugated polymer rubber and the polymerization stability during the production of the rubber-reinforced resin composition that hardly causes deterioration, the color tone of the resulting rubber-reinforced resin composition, and transparency Property and gloss are improved.

[0043] These thioether compound heat stabilizers and attalylate compound heat stabilizers may be used alone or in combination. When both are used in combination, the total amount used must be 0.01 to 0.20 parts by weight per 100 parts by weight of the conjugated polymer rubber. When a thioether compound heat stabilizer and an attalylate compound heat stabilizer are used in combination, a further excellent heat stability effect can be obtained as compared with the case where each is used alone.

[0044] The thioether compound thermal stabilizer is not particularly limited as long as it has a thioether structure in which a sulfur atom is bonded to two hydrocarbon groups. However, the thioether structure has two or more thioether structures in the molecule. What has is preferable. Specific examples thereof include dilauryl 3, 3 ′ thiopropionate, dimyristyl 3, 3, monothiodipropionate, distearyl 3, 3, monothiodipropionate, lauryl stearyl 3, 3 ′ thiopropionate, Pentaerythritol-tetrakis (3-laurylthiopropionate), 3, 9 Bis (2 dodecylthioethyl) 2, 4, 8, 10-Tetraoxaspiro [5,5] undecane; 4, 6-bis (Otachi) 1-cresol, 2, 2 thiodiethylene bis [3- (3,5 di-tert-butyl 4-hydroxyphenol) propionate], 2,4 bis- (n-octylthio) -6- (4 hydroxy-1,3,5-di-t-butyla-lino) -1,3,5 triazine; and the like.

 These thioether compound heat stabilizers may be used alone or in combination of two or more.

 Of these thioether compound thermal stabilizers, phenol compounds, that is, those having a phenol group in the molecule are preferred.

[0045] The amount of the thioether compound heat stabilizer used is from 0.01 to 0.10 wt% per 100 parts by weight of the conjugated polymer rubber, preferably 0.02 to 0.09 wt%. Preferably ί is 0.03 to 0.08 parts by weight.

 When the amount used is within this range, the conjugated polymer rubber is not easily colored or deteriorated, the stability during storage is good, and the stability during the production of the rubber-reinforced resin composition is good. The color tone of the rubber-reinforced resin composition becomes good.

[0046] The talaretoy compound heat stabilizer is a heat stabilizer having an attalyloyl group or a methacryloyl group in the molecule. Any other structure is acceptable as long as it has one or more of these groups in the molecule.

Preferable talate toy compound heat stabilizers are those having the structure of an acrylic acid ester or methacrylic acid ester having a phenol group, which is obtained with an alcohol having a phenol group in the molecule and acrylic acid or methacrylic acid. Can be mentioned. Specific examples include 2-t-butyl 6- (3-t-butyl 2-hydroxy-1-5-methylbenzil) 4-methylphenol acrylate, 2- [1-(2-hydroxy-1,3,5 di-one) tert-amyl tertylate). 4,6-Di-tert-amyl acrylate. This talate toy compound heat stabilizer is preferable because it does not cause coloring of the rubber composition.

 [0047] The amount of the attalylate compound heat stabilizer used is from 0.01 to 0.10 wt% preferably 100% by weight per 100 parts by weight of the conjugated polymer rubber, and more preferably 0.02 to 0.09 wt%. It is 0.03 to 0.08 parts by weight.

 When the amount used is within this range, the conjugated polymer rubber is not easily colored or deteriorated, the stability during storage is good, and the stability during the production of the rubber-reinforced resin composition is good. The color tone of the rubber-reinforced resin composition becomes good.

[0048] The rubber composition for modifying a resin of the present invention is a heat stabilizer other than a phosphite compound heat stabilizer, a thioether compound heat stabilizer and an attalylate compound heat stabilizer having two or more phosphorus atoms in the molecule. Contain, may be.

 Examples of such heat stabilizers include phosphite compound heat stabilizers having one phosphorus atom in the molecule, phosphonite compound heat stabilizers having two or more phosphorus atoms in the molecule, thioether structure and attalyloyl in the molecule. And phenolic compound heat stabilizers having no methacryloyl group or methacryloyl group.

 These heat stabilizers are used in an amount of 0.01 to 0.10 wt.% Per 100 parts by weight of the conjugated polymer rubber, preferably [0.02 to 0.09 wt. ~ 0.08 parts by weight.

[0049] Specific examples of phosphite compound thermal stabilizers having one phosphorus atom in the molecule include tris (norphenyl) phosphite and tris (2,4 di-t-butylphenol). Phosphite, tris (2,5 di-t-butylphenol) phosphite, tris (2,4 bis (1,1-dimethylpropyl) phenol) phosphite, tridecyl phosphite, octyl diphenyl phosphate, Di (decyl) monophenyl phosphite, tris (3,5-di-tert-butyl 4-hydroxyphenyl) phosphite, tris (mono- and di-monophenol) phosphite 2, 2, 1-methylenebis (4,6 di-tert-butylphenol) 2-ethylhexyl phosphite, 2, 2, 1-methylenebis (4,6 di-tert-butylphenol) -2-2-octadecyl phosphite, 2, 2, ェ Tilidenebis (4, 6 t Buchirufue - Le) Full O Russia phosphite and the like can be ani gel. [0050] Specific examples of the phosphonite compound thermal stabilizer having two or more phosphorus atoms in the molecule include tetrakis (2, 4 di-t-butylphenol) biphenol-diphosphophosphonite, tetrakis (2, 4-dione). t-Butyl 5-methylphenol) biphenol dirange phosphonite.

 [0051] Specific examples of thermal stabilizers for phenolic compounds other than phenolic compounds having a thioether structure in which a sulfur atom is bonded to two hydrocarbon groups, or an allyloyl group or a methacryloyl group in the molecule include tetrakis [methylene 3 (3,5, -di-tert-butyl-4-hydroxyphenyl) propionate] methane, 1, 3, 5 trimethyl 2, 4, 6 tris (3,5 di-t-butyl 4-hydroxybenzyl) benzene, 2, 4 Bis (n-octylthio) —6— (4-Hydroxy-1,3,5 Di-t-Butyl-lino) -1,3,5 Triazine, Octadecyl- 3 -— (3,5-Di-t-butyl-4-hydroxyphenol -L) propionate, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenol) pionate], 1, 3, 5 tris- (4-t-butyl-3 Hydroxy — 2, 6-dimethylbenzyl) isocyanuric acid, 2,2'-methylene bis (4-methyl-6-t-butylphenol), 3, 9 bis [2- {3— (3-t-butyl-4 hydroxy) — 5—methylphenol) propio-loxy} -1,1-dimethylethyl] —2, 4, 8, 10—tetraoxaspiro [5 · 5] undecane, 4-hydroxymethyl-2,6 di-t-butylphenol, 2 , 6 di-tert-butyl-4-ethylphenol, butylated hydroxy vinylol, 2, 2, 1-dihydroxy 3, 3'-dicyclohexyl, 5, 5, 1-dimethyl-diphenylmethane, 1, 1, 3-tris ( 2-Methyl-4-hydroxy-5t-butylphenol) butane, 4,4, -butylidenebis (6—t-butyl-m cresol, 4,4, thiobis (3-methyl-6-tert-butylphenol), bis (3cyclo Hexyl 2-hydroxy-1 5-me Rufyl) methane, 2, 2, 1-methylene bis (4 ethyl 6-t-butyl monophenol), 1, 1-bis (2, 1-methyl-4, -hydroxy-5, 1-t-butyl-phenol) butane, etc. Can do.

[0052] The method for preparing the resin composition for modifying a resin of the present invention is not particularly limited as long as various heat stabilizers are added to the conjugated polymer rubber.

There is no limitation in particular in the addition method of each heat stabilizer. After polymerization, it may be added to the coagulated conjugated polymer rubber, but when added to the conjugated polymer rubber solution before coagulation, It is preferable because the heat stabilizer can be easily dispersed uniformly.

 The shape of the heat stabilizer when added to the conjugated polymer rubber may be as it is or in the form of a solvent solution, but is preferably a solvent solution having a concentration of 1 to 50% by weight.

[0053] In the method for producing a rubber composition for modifying a resin of the present invention, the order in which the heat stabilizer is added to the conjugated polymer rubber is not particularly limited, but it has two or more phosphorus atoms in the molecule. After adding the phosphite compound heat stabilizer, it is preferable to add other heat stabilizers in order to prevent coloring of the 1S conjugate polymer rubber.

 [0054] In the present invention, the time when the heat stabilizer is added to the conjugated polymer rubber is not particularly limited, and may be any time after the polymerization.

 When an organolithium compound is used as a polymerization initiator, from the viewpoint of preventing coloring of the resulting resin composition for modifying a resin, the conjugated diene polymer rubber obtained by polymerization is used with respect to the organolithium compound. Phosphite compound having two or more phosphorus atoms in the molecule after addition of at least one acid selected from organic acids, inorganic acids and Lewis acid powers in amounts less than 1 equivalent It is preferred to add a heat stabilizer to the conjugate polymer rubber and then add another heat stabilizer.

 Various compounding agents such as liquid paraffin, calcium carbonate, silica, flame retardant and light stabilizer can be added to the rubber composition for modifying a resin of the present invention, if necessary. In the production method of the present invention, it is preferable to add a phosphite compound thermal stabilizer having at least two phosphorus atoms in the molecule to the conjugated polymer rubber before adding these compounding agents. It is preferred to add all the heat stabilizers that are used immediately.

 [0055] The rubber-reinforced resin composition of the present invention comprises the above-described rubber composition for modifying a resin of the present invention and a base resin.

 The base resin is not particularly limited, and examples thereof include aromatic vinyl resin and olefin fin resin.

Examples of aromatic bur resins include: acrylonitrile / atylate / styrene resin, acrylo-tolyl / ethylene / styrene resin, acrylonitrile / styrene resin, tali / tri-butadiene / styrene resin, polystyrene resin. , High impact polystyrene resin, methyl methacrylate-butadiene styrene resin, methyl methacrylate-styrene resin Etc. can be mentioned.

 Examples of olefin resins include polyethylene and polypropylene.

 Further, the base resin may be an engineering resin such as polyphenylene ether, polyamide, polycarbonate, polyacetal, polyester, etc., in addition to the above-mentioned aromatic bur resin and olefin resin.

 These base resin resins may be used alone or in combination of two or more. The rubber-reinforced resin composition of the present invention preferably contains at least an aromatic beef resin among these base resin resins.

[0056] The amount of the resin composition for modifying the resin in the rubber-reinforced resin composition is a weight ratio of the conjugate polymer rubber Z base resin in the composition for modifying the resin, The range is 2Z98 to 25Z75, preferably 3Z97 to 20Z80, more preferably 5 to 95 to 15 to 85.

 If the amount of the conjugated polymer rubber is too large, the gloss, rigidity, weather resistance, hardness, etc. of the molded product obtained from the rubber-reinforced resin composition are inferior. If the amount of the base resin is too large, Insufficient impact resistance.

 [0057] The method for producing the rubber-reinforced resin composition of the present invention is not particularly limited, and the base resin resin and the rubber-reinforced resin composition may be mixed by any method. In the presence of the modifying rubber composition, a monomer that is a raw material for the base resin may be polymerized (hereinafter sometimes referred to as “resin monomer”). It is preferable because a composition excellent in impact resistance can be obtained.

 [0058] The base resin and the rubber-reinforced resin composition are mixed using various kneading apparatuses such as a single screw extruder or a multi-screw extruder such as a twin screw, a Banbury mixer, a roll, and a kneader. Is possible. The mixing temperature is preferably in the range of 100 to 250 ° C.

 [0059] When polymerizing a resin composition in the presence of a rubber composition for modifying a resin, a polymerization stock solution in which the resin composition for modifying a resin is dissolved or dispersed in the resin composition is used. Polymerize in the reactor. The polymerization method is not particularly limited, and any of a bulk polymerization method, a suspension polymerization method, a solution polymerization method, an emulsion polymerization method and the like may be used.

[0060] In the bulk polymerization method, the rubber composition for modifying the resin is dissolved or dispersed in the resin monomer, If necessary, add a molecular weight regulator, lubricant, etc., add an initiator, and polymerize with stirring in an inert gas atmosphere. When the aromatic vinyl monomer is polymerized by a bulk polymerization method, the polymerization temperature is preferably 60 to 200 ° C.

 In the suspension polymerization method, as in the bulk polymerization method, the rubber composition for modifying the resin is dissolved in the resin, and if necessary, a molecular weight regulator, a lubricant, etc. are added, and an initiator is added. The obtained solution is dispersed in an aqueous solution in which the suspension stabilizer is dissolved, polymerized while maintaining the suspended state, and after completion of the polymerization, the suspension stabilizer is thoroughly washed to remove the resin composition. do it. When the aromatic bulle monomer is polymerized by suspension polymerization, the polymerization is preferably completed at 60 to 150 ° C.

 In the solution polymerization method, as in the bulk polymerization method, the rubber composition for modifying the resin is dissolved in the resin monomer, and a molecular weight regulator, a lubricant, and an organic solvent for adjusting the viscosity are added as necessary. In addition, an initiator may be added, and polymerization may be performed while stirring in an inert gas atmosphere. When the aromatic bulle monomer is polymerized by a solution polymerization method, the polymerization temperature is preferably 60 to 200 ° C.

 Bulk polymerization may be performed until about 10 to 50% by weight of the resin monomer is polymerized, and then polymerization may be performed by a two-stage polymerization method such as suspension polymerization or solution polymerization.

 After completion of the polymerization, the rubber-reinforced resin composition is recovered by performing a process such as coagulation and drying by a conventional method.

 [0061] When the resin is a thermoplastic resin, the rubber-reinforced resin composition of the present invention preferably has a lower limit of the melt flow rate measured at 200 ° C under a load of 5 kg according to JIS K 687 1. Is 0.1, more preferably 0.5, and the upper limit is preferably 20. When the melt flow rate is within the above range, kneading can be facilitated, the dispersion of the rubber composition for modifying the resin is uniform, and the effect of modifying the resin is exhibited well.

[0062] To the rubber-reinforced resin composition of the present invention, various compounding agents that are usually used in the resin industry can be added as necessary within a range that does not impair the effects of the present invention. Such compounding agents include mineral oil, liquid paraffin, organic or inorganic fillers, weathering stabilizers, stabilizers other than heat stabilizers other than light stabilizers, plasticizers, lubricants, ultraviolet absorbers, colorants. And pigments, release agents, antistatic agents, flame retardants, and the like. Example

 [0063] The present invention will be described more specifically with reference to the following reference examples, examples and comparative examples. Unless otherwise specified, parts and% in each example are based on mass.

 Each characteristic was evaluated by the following method.

[0064] (Molecular weight of polymer)

 The molecular weight is calculated in terms of polystyrene by gel permeation chromatography using tetrahydrofuran as a carrier. Specifically, the measurement is performed using a high performance liquid chromatography apparatus HLC8220 and two columns GMH-HR-H (both manufactured by Tosoh Corporation). (Aromatic vinyl compound content in Conjugated Polymer Rubber (Aromatic Vinyl-Conjugated Copolymer))

 Measured by proton NMR.

 (Vinyl bond amount of conjugation monomer unit in conjugation polymer rubber)

 Measured by proton NMR.

 (Aromatic vinyl block rate)

 Measured by osmium acid decomposition method.

[0065] (Polymerization stability of resin in the presence of a rubber composition for resin modification)

 Prepare a 10% solution of styrene in a rubber composition for modifying the resin. This is heated to 125 ° C, and immediately after reaching 125 ° C, 1 part of n-dodecyl mercaptan is added and maintained at 125 ° C. Next, the polymerization conversion rate is measured every 30 minutes, and the measurement is terminated when the polymerization conversion rate exceeds 70%, and the polymerization start time is determined by the following method.

 Repeat this measurement three times. When the difference between the maximum value and the minimum value of the polymerization start time obtained in three measurements is less than 30 minutes, “Polymerization stability is good”. Is not good. "

[0066] (Method for determining polymerization start time)

Plotting the polymerization conversion rate on the time-polymerization conversion rate graph with time on the horizontal axis (time when n-dodecyl mercabtan is applied) is 0 and the vertical axis is the polymerization conversion rate. An approximate straight line is obtained by the least square method using measurement points with a rate of 20% or more. The time at the intersection of this approximate line and the X axis (horizontal axis) is the polymerization start time. Even if this value is negative, The numerical value of is used.

 [0067] (Initial color tone of rubber composition for modifying oil) (APHA)

 5. Measure the 43% toluene solution of the rubber composition for modifying the resin using a color measuring instrument (trade name “OME-2000” manufactured by Nippon Denshoku Industries Co., Ltd.) according to ASTM D125. .

[0068] (Presence or absence of precipitation of neutralizing agent)

 Press the rubber composition rubber modifying composition at 100 ° C to make a 2mm thick sheet. The degree of cloudiness of the resulting transparent sheet is visually determined.

[0069] (Amount of gel in the rubber composition for modifying oil)

 5 g of the sample is put into 95 g of toluene in an Erlenmeyer flask, stirred for 4 hours with a magnetic stirrer, and the gel (toluene insoluble matter) is filtered using filter paper (No. 2). When the entire filter paper is dyed with osmic acid, the gel is dyed. Count the number of gels visually and judge according to the following criteria.

 1: A gel with a diameter of 0.5 mm or more!

 2: Several gels having a diameter of about 0.5 to lmm are observed.

 3: A gel with a diameter of about lmm can be seen on one side of the filter paper.

 4: In addition to gel with a diameter of about lmm, a gel with a diameter of about 2.5mm can be seen.

[0070] (Storage stability of rubber composition for modifying oil)

 Leave the sheets (preparation, size, etc.) in a gear oven at 70 ° C (ventilation 2 times Z1 hour) for 1 week.

 Thereafter, the color tone of the sheet is visually observed. When it is transparent without coloring, it is judged as “good”.

[0071] (Gloss of rubber-reinforced resin composition)

 Using a rubber-reinforced resin composition pellet, injection molding machine SAV-30 / 30 (manufactured by Yamashiro Seiki Co., Ltd .; mold temperature 50 ° C, nozzle tip temperature 240 ° C), length 9cm, width 5cm, thickness 2mm A test piece is manufactured by injecting perpendicularly in the thickness direction from the point of lcm on the center line in the horizontal direction and the force at one end in the vertical direction (at 8cm from the other end).

 Using this specimen, measure at an incident angle of 60 ° in accordance with JIS Z 8741. A gloss of more than 85 is considered “good” and a gloss of 85 or less is “inferior”.

The measurement was performed on the center line in the horizontal direction of the test piece, and the distance of the injection locus was lcm each. In the part (gate part) and 6cm (end part), the line is averaged.

 [0072] (Color tone of rubber-reinforced resin composition)

 The rubber-reinforced resin composition is press-molded at 200 ° C to obtain a 50mm x 50mm x 3mm sheet. The color tone of this sheet is visually determined. When it is milky white, “good” is set.

 [0073] (Fisheye in rubber-reinforced resin composition)

 The rubber reinforced resin composition was extruded at 200 ° C. from a 40 mm short screw extruder equipped with a 30 cm wide T-die. 1. Stretch 5 times to obtain a film with a thickness of about 0.2 mm, and after 30 minutes, count the number of fish eyes with a diameter of 3 mm or more present in 30 cm x 10 cm of the film. If there are 5 or more, “Yes” is given.

 [0074] (Transparency of MBS oil)

 A rubber-reinforced resin composition obtained by polymerizing a resin monomer in the presence of a resin composition for resin modification has the same refractive index as that of the resin thread for resin modification. As described above, the composition of the resin monomer is adjusted and polymerization is performed to obtain a rubber-reinforced resin composition. A sheet of 50 mm × 50 mm × 3 mm is prepared from the obtained rubber-reinforced resin composition in accordance with ASTM D-1003, and its light transmittance is measured. A product with a light transmittance of 85 or more and no yellowing or turbidity is considered “good”.

 [0075] (Reference Example 1)

 (Preparation of Conjugated Polymer Rubber (al))

The autoclave with a cooling condenser, jacket and stirrer with a capacity of 2,000 liters purged with nitrogen was charged with 600 kg of cyclohexane purified by molecular sieve 3A after distillation and 60 kg of butadiene purified in the same manner at 50 ° C. Adjusted. Polymerization was initiated by adding 50 mmol of tetramethylethylenediamine and 1.05 mol of n-butyllithium. Ten minutes later, 60 kg of 1,3-butadiene was added for 30 minutes. 30 minutes after completion of the addition, when the polymerization conversion rate was almost 100%, 80 kg of styrene purified as described above was added over 30 minutes while maintaining the temperature at 80 ° C. Thereafter, the reaction was continued for 50 minutes, and then 2.1 mol of isopropyl alcohol was added and stirring was continued for 5 minutes, whereby a solution of conjugated polymer polymer rubber (al) was obtained. Conjugated polymer rubber (al) had a weight average molecular weight of 340,000 and a molecular weight distribution of 1.2. The styrene content is 39.8%. 1 E emission portion, 2 Bulle structure 10.5 mole _^0/0, styrene block was 95%.

[0076] (Preparation of Conjugated Copolymer Rubber (b))

 A 2,000 liter autoclave equipped with a nitrogen-cooled condenser, jacket and stirrer was charged with 600 kg of cyclohexane, 25 kg of butadiene, and 66 kg of styrene, both purified after distillation and partly molecular 3A. 50 Adjusted to ° C. To this, 290 mmol of tetramethylethylenediamine and 2.67 mol of n-butyllithium were added to initiate polymerization. After 15 minutes, 40 kg of 1,3 butadiene was added over 15 minutes while maintaining the temperature at 65 ° C. Subsequently, 30 kg of 1,3 butadiene was added over 15 minutes, followed by addition of 10 kg of 1,3 butadiene over 15 minutes, and 20 minutes after the addition was completed, the polymerization conversion rate became approximately 100%. By the way, 4 kg of 1,3 butadiene was added for 1 minute. Then, when the reaction was continued for 10 minutes, 670 mmol of tetramethoxysilane was added. Next, the reaction was continued for 30 minutes, and then 5.3 mol of isopropyl alcohol was added, and stirring was continued for 5 minutes to obtain a solution of a conjugated polymer rubber (b). Conjugated polymer rubber (b) had a weight average molecular weight of 320,000 and a molecular weight distribution of 1.3. The styrene content was 25.2%, and the 1,2-bule structure content of the butadiene portion was 17.8 mol%.

 [0077] (Example 1)

 (Preparation of rubber composition for resin modification (R))

 Cyclohexane of tetra (tridecyl) -4,4, -butylidenebis (2-tert-butyl-5-methylphenol) diphosphite (a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule) 10 % Solution is added to a solution of conjugated polymer rubber (al) at 50 ° C so that the amount of heat stabilizer is 0.10 parts with respect to 100 parts of conjugated polymer rubber (a), and for 5 minutes. Stirred. Thereafter, a cyclohexane 10% solution of 4,6-bis (octylthiomethyl) o-taresol [thioether compound thermal stabilizer] was added to 0.09 parts, and the mixture was further stirred for 5 minutes. did.

The coagulated crumb desolvated by the steam stripping method is adjusted to about 10% moisture through a squeezer, dried in an extrusion dryer at about 150 ° C, and then dried in hot air at 70 ° C to modify the fat. A rubber composition (R1) was obtained. Table 1 shows the results of the evaluation of the properties of the rubber composition (Rl) for resin modification.

[0078] (Preparation of rubber-reinforced resin composition (S))

 Ten parts of the resin composition for modifying a resin (R1) was dissolved in 90 parts of a styrene monomer, and a styrene polymerization stock solution containing 300 ppm of n-dodecyl mercaptan (chain transfer agent) was prepared.

 In a 4 liter jacketed reactor, 2,300 g of the styrene polymerization stock solution was placed, and polymerized at 130 ° C. with sufficient stirring until the solid content concentration reached 45%.

 Remove the polymerization reaction liquid from the reactor, cool to 20 ° C, and add 625g of polyalcohol alcohol (GOHSENOL GH-20, manufactured by Nippon Synthetic Chemical Industry) as a dispersant. The mixture was placed in a stainless steel reactor equipped with a stirrer and heated to 70 ° C while stirring.

 Next, as a radical polymerization initiator, 1.25 g of benzoyl peroxide and 0.63 g of dicumyl peroxide were added, 1 hour at 70 ° C, 1 hour at 90 ° C, 1 hour at 110 ° C, and further. Suspension polymerization was carried out while increasing the temperature stepwise at 130 ° C for 4 hours. After completion of the polymerization, the mixture was cooled to 20 ° C., the polymer was separated by filtration, the polymer was recovered, and washed with water. After dehydration, it was dried under reduced pressure at 60 ° C. for 12 hours to obtain a polystyrene resin composition as a rubber-reinforced resin composition (S1).

 The gloss, color tone, and fish eye of the obtained rubber-reinforced resin composition (S1) were evaluated. The results are shown in Table 1.

[0079] (Preparation of MBS rosin (M))

Also, a solution comprising 50 g of the resin composition for modifying the resin (R), 320 g of styrene, 62 g of methyl methacrylate and 10 g of ethylbenzene was prepared in a 10 liter autoclave. To this, 0.1 g of n-dodecyl mercaptan and 0.02 g of t-butyl peroxybenzoate were added, and polymerization was started at 120 ° C. with stirring at 300 rpm. After 2 hours, the temperature was raised to 135 ° C and the reaction was continued for another hour. Thereafter, the temperature was further raised to 150 ° C. and reacted for 1 hour. Finally, the temperature was raised to 200 ° C. and the reaction was continued until the polymerization conversion rate became approximately 100%. While maintaining the reaction solution at 200 ° C, volatile components were removed under reduced pressure of 50 mmHg to obtain MBS resin (Ml). The transparency of the obtained MBS rosin composition (Ml) was evaluated. The results are shown in Table 1.

[0080] (Example 2)

 Tetra (tridecyl) -4,4, -butylidenebis (2-t-butyl-5-methylphenol) diphosphite was changed to 0.09 parts, and 4, 6bis (octylthiomethyl) o-tale The amount of sol was changed to 0.05 parts, and 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) 4 methylphenol talate (heat stabilizer for acrylate compounds). A rubber composition for modifying a resin was obtained in the same manner as in Example 1 except that 04 parts was used in combination.

 Table 1 shows the results of the evaluation of the properties of the rubber composition for oil refining (R2). A rubber-reinforced resin composition (S2) and MBS resin (M2) were obtained in the same manner as in Example 1 by using this resin composition for resin modification (R2).

 Table 1 shows the results of evaluating the properties of this rubber-reinforced resin composition (S2) and MBS resin (M2).

[Example 3]

 Add 0.525 moles of benzoic acid (corresponding to 0.5-fold equivalent of n-butyllithium used for polymerization) as a 5% solution of xylene in a solution of conjugated polymer rubber (al), 70 ° C The solution was stirred for 10 minutes to obtain a solution of the neutralized conjugated polymer rubber (a2).

 A rubber composition for resin modification (R3) in the same manner as in Example 2 except that a solution of the neutralized conjugated polymer rubber (a2) was used instead of the solution of the conjugated polymer polymer (al). )

 Table 1 shows the results of the evaluation of the properties of this resin composition for modifying oil (R3). A rubber-reinforced resin composition (S3) and MBS resin (M3) were obtained in the same manner as in Example 1 by using this resin composition for modifying a resin (R3).

 Table 1 shows the results of evaluating the properties of this rubber-reinforced resin composition (S3) and MBS resin (M3).

[Example 4]

Tetra (tridecyl) -4,4, -butylidenebis (2-t-butyl-5-methylphenol) diphosphite was changed to 0.05 parts and 4,6 bis (octylthiomethyl) one o-tale Example 1 except that instead of 0.09 part of sol, 2-t-butyl 6- (3-t-butyl 2-hydroxy-5-methylbenzyl) -4 methylphenol acrylate is used. In the same manner as described above, a rubber composition (R4) for modifying a resin was obtained.

 Table 1 shows the results of the evaluation of the properties of the rubber composition for oil refining (R4). A rubber-reinforced resin composition (S4) and MBS resin (M4) were obtained in the same manner as in Example 1 by using this resin composition for modifying a resin (R4).

 Table 1 shows the results of evaluating the properties of this rubber-reinforced resin composition (S4) and MBS resin (M4).

[0083] (Example 5)

Instead of the solution of conjugated diene polymer rubber _(a l), using a solution of the conjugated diene polymer rubber (b), tetra (tridecyl) -4, 4, Buchiridenbisu (2-t-butyl-5 Mechirufue two Honoré) In the same manner as in Example 1, except that the amount of diphosphite was changed to 0.08 parts and the amount of 4,6bis (Otatinolethiomethinole) o-Talesol was changed to 0.04 parts. A quality rubber composition (R5) was obtained.

 Table 1 shows the results of the evaluation of the properties of this resin composition for modifying oil (R5). A rubber-reinforced resin composition (S5) and MBS resin (M5) were obtained in the same manner as in Example 1 by using this resin composition for resin modification (R5).

 Table 1 shows the results of evaluating the properties of this rubber-reinforced resin composition (S5) and MBS resin (M5).

[0084] (Comparative Example 1)

 Tetra (tridecyl) -4,4, -butylidenebis (2-t-butyl-5-methylphenol) Instead of diphosphite, the thermal stabilizer Tris (2, 4 —Di-tert-butylphenol) phosphite, 4, 6-bis (octylthiomethyl) —o-Talesol 0.0.09 parts instead of octadecyl 3- (3, 5 A rubber composition for rubber modification (RC1) was obtained in the same manner as in Example 1, except that 0. 10 parts of di-tert-butyl-4-hydroxyphenol) propionate was used.

Table 2 shows the results of evaluation of the properties of this rubber composition for resin modification (RC1). A rubber-reinforced resin composition (SC1) and MBS resin (MC1) were obtained in the same manner as in Example 1 using this resin composition for modifying a resin (RC1).

 Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC1) and MBS resin (MC1).

[0085] (Comparative Example 2)

 To a solution of conjugated polymer rubber (al), 1.05 mol of benzoic acid (corresponding to 1.0 equivalent of n-butyllithium used for polymerization) was added as a 5% solution of xylene, and 70 ° The mixture was stirred at C for 10 minutes to obtain a solution of neutralized conjugated polymer rubber (a3).

 A rubber composition for modifying a resin (RC2) in the same manner as in Comparative Example 1 except that a solution of the neutralized conjugated polymer rubber (a3) was used instead of the solution of the conjugated polymer polymer (al). )

 Table 2 shows the results of the evaluation of the properties of this rubber modifying rubber composition (RC2). Using this rubber modifying rubber composition (RC2), rubber was obtained in the same manner as in Example 1. A reinforced resin composition (SC2) and MBS resin (MC2) were obtained.

 Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC2) and MBS resin (MC2).

[0086] (Comparative Example 3)

 Instead of the solution of conjugated polymer rubber (al), a solution of neutralized conjugated polymer rubber (a3) was used, and the thermal stabilizer was tetra (tridecyl) 4,4'-butylidenebis (2 tert-butyl 5 Methylphenol) diphosphite 0. 10 parts and 4, 6 bis (octylthiomethyl) —o-talesol 0.09 parts, 4, 6 bis (octylthiomethyl) o — talesole only 0.20 parts In the same manner as in Example 1 except that the rubber composition for rubber modification (RC3) was obtained.

Table 2 shows the results of the evaluation of the properties of this rubber modifying rubber composition (RC3). Using this rubber modifying rubber composition (RC3), rubber was obtained in the same manner as in Example 1. Reinforced resin composition (SC3) and MBS resin (MC3) were obtained. Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC3) and MBS resin (MC3).

[0087] (Comparative Example 4)

Instead of the solution of conjugated diene polymer rubber _(a l), using a solution of neutralized conjugated diene polymer rubber (a2), a heat stabilizer tetra (tridecyl) -4, 4'-butylidene bis (2-t —Butyl-5-methylphenol) diphosphite 0.09 parts, 4, 6 Bis (octylthiomethyl) —0.0 parts of o-taresol and 2-t-butyl-6- (3-t-butyl-2 Hydroxy 5 methylbenzyl) -4 methylphenol acrylate A 0.04 part combination of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenol) propionate, a thermal stabilizer for phenolic compounds 0.10 parts And 4,6 bis (octylthiomethyl) o-taresole 0.28 parts in the same manner as in Example 3 except that a rubber composition (RC4) for modifying a resin was obtained.

 Table 2 shows the results of the evaluation of the properties of this rubber modifying rubber composition (RC4). Using this rubber modifying rubber composition (RC4), rubber was obtained in the same manner as in Example 1. A reinforced resin composition (SC4) and MBS resin (MC4) were obtained.

 Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC4) and MBS resin (MC4).

[0088] (Comparative Example 5)

 Tetra (tridecyl) -4,4, -butylidenebis (2-t-butyl-5-methylphenol) Instead of diphosphite, the thermal stabilizer Tris (2, 4 Except that the amount of 4,6-bis (octylthiomethyl) -o-taresole was increased to 0.20 parts using di-tert-butylphenol) phosphite, A rubber composition for fat modification (RC5) was obtained.

Table 2 shows the results of the evaluation of the properties of this rubber modifying rubber composition (RC5). Using this rubber modifying rubber composition (RC5), rubber was obtained in the same manner as in Example 1. A reinforced resin composition (SC5) and MBS resin (MC5) were obtained. Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC5) and MBS resin (MC5).

[0089] (Comparative Example 6)

 Instead of the solution of the conjugated polymer polymer rubber (al), the solution of the conjugated polymer polymer rubber (b) is used, and the thermal stabilizer is octadecyl, a phenolic compound thermal stabilizer— 3— (3, 5— Di-tert-butyl-4-hydroxyphenyl) propionate A rubber composition (RC6) for resin modification was obtained in the same manner as in Example 1 except that only 0.08 part was changed.

 Table 2 shows the results of the evaluation of the properties of this rubber modifying rubber composition (RC6). Using this rubber modifying rubber composition (RC6), rubber was obtained in the same manner as in Example 1. Reinforced resin composition (SC6) and MBS resin (MC6) were obtained.

 Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC6) and MBS resin (MC6).

[0090] (Comparative Example 7)

 Instead of using the conjugated polymer rubber (al) solution instead of the conjugated polymer rubber (al) solution, the heat stabilizer is changed to only 0.50 parts of distearyl pentaerythritol diphosphite. In the same manner as in Example 1, a rubber composition for rubber modification (RC7) was obtained.

 Table 2 shows the results of the evaluation of the properties of this resin composition for modifying a resin (RC7). Using this composition for modifying rubber (RC7), rubber was obtained in the same manner as in Example 1. Reinforced resin composition (SC6) and MBS resin (MC7) were obtained.

 Table 2 shows the results of evaluating the properties of this rubber-reinforced resin composition (SC7) and MBS resin (MC7).

[0091] [Table 1]

Table 2] Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Neutralization Treatment during Polymerization Yes Yes Yes No No No Amount of Neutralizing Agent (* 1) 1.0 1.0 0.5 ― ― ― Conjugation Polymer rubber a3 a3 a2 a1 bb Heat stabilizer usage

 P2 (* 2) ― ― ― ― ― ―

P2P (* 3) ― ― ― ― 0.50

S2P (* 4) ― 0.20 0.20 0.20 ― ―

FA (* 5) ― ― ― ― ― ―

PI (* 6) 0. 10 ― ― 0. 10 ― ―

PH (* 7) 0.10 ― 0.10 ― 0.08 ― Rubber composition for wedge grease modification RC2 RC3 C4 RC5 RC6 RC7 Initial color tone 15 19 12 14 5 25 Neutralizing agent Presence Yes Yes No No No No Gel amount 3 1 1 1 2 1 Storage stability Yellow Light yellow Yellow Light yellow Light yellow Light yellow Polymerization of resin monomer

 Good Bad Bad Bad Good Good Stability

Rubber Reinforced Resin Composition SC2 SC3 SC4 SC5 SC6 SC7 Gloss Inferior Inferior Inferior Inferior Good Good Color Tone Good Yellow Pale Yellow Pale Yellow Pale Yellow Fish Eye Yes No No No Yes No No

BS resin C2 C3 MC4 MC5 MC6 C7 Transparency Turbidity Stagnation_Yellow SpringYellow Pale yellow Pale yellow Pale yellow [0093] Notes to Table 1 and Table 2

 * 1: Equivalent ratio of polymerization catalyst to metal

 * 2: Tetra (tridecyl) 4, 4, -butylidenebis (2 tert-butyl-5-methylphenol) diphosphite

 * 3: Distearyl pentaerythritol diphosphite

 * 4: 4, 6-Bis (octylthiomethyl) o-Talesol

 * 5: 2 t butyl 6— (3 t butyl 2 hydroxy 5 methyl benzyl)-4 methyl phenyl acrylate

 * 6: Tris (2,4 di-t-butylphenol) phosphite

 * 7: Octadecyl 3— (3,5-Di-tert-butyl 4-hydroxyphenol) propionate

 [0094] From the results in Tables 1 and 2, the following can be understood.

 Even if a phosphite compound thermal stabilizer having one phosphorus atom and a phosphite compound thermal stabilizer having one phosphorus atom are used in combination, a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule can be used. The resulting rubber composition for modifying grease is inferior in storage stability due to a large amount of gel, and the rubber-reinforced greave composition capable of obtaining this strength is inferior in various properties (Comparative Example 1). In the production process of the conjugated polymer rubber used for the resin composition for modifying a resin, neutralization treatment of the catalyst residue with an acid hardly improves the above characteristics (Comparative Example 2).

 Even if a thioether compound heat stabilizer is used as a heat stabilizer, or if a phenol compound heat stabilizer is used in combination with this, no improvement is observed, and storage stability, polymerization stability, etc. are poor, and resin modification The color tone of the rubber composition for rubber and the rubber-reinforced resin composition is inferior (Comparative Examples 3 and 4).

 Even if a phosphite compound heat stabilizer having one phosphorus atom and a thioether compound heat stabilizer having a phenol group in the molecule are used in combination, the polymerization stability is not excellent, and it is suitable for resin modification. The color tone of the rubber composition and the rubber-reinforced resin composition is not so good (Comparative Example 5). In addition, the use of only the heat stabilizer of the phenolic compound compound is inferior in storage stability of the rubber composition for modifying the resin, and fish eyes are produced by molding the rubber-reinforced resin composition (Comparative Example 6). .

In addition, when a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is used in a large amount exceeding the range specified in the present invention, each characteristic deteriorates instead (Comparative Example). 7).

 On the other hand, a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule, a thioether compound thermal stabilizer, and a talato toy compound thermal stabilizer, at least one kind selected. The above-mentioned heat stabilizer added in an amount of 0.01 to 0.20 parts by weight with respect to 100 parts by weight of the conjugated polymer rubber exhibits excellent properties (Examples). In particular, a combination of a phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule, a thioether compound heat stabilizer, and an attalitoy compound compound heat stabilizer has excellent characteristics. Shown (Examples 2 and 3). In addition, due to the synergistic effect of the combination of the neutralization treatment of the catalyst residue by the acid and the heat stabilizer of the present invention in the production process of the conjugated polymer rubber (comparison between Example 2 and Example 3), it was particularly excellent. Characteristics are obtained.

Claims

The scope of the claims

 [1] Conjugated polymer rubber 100 parts by weight, phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule 0.01 to 0.20 part by weight, thioether compound heat stabilizer and talate toy Compound heat stabilizer power Group power at least one kind of heat stabilizer selected 0.

A rubber composition for modifying a resin containing 01 to 0.20 part by weight.

[2] Conjugated polymer rubber 100 parts by weight, phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule 0.01 to 0.20 part by weight, and at least one thioether compound heat stabilizer And a total of at least one atallylate compound heat stabilizer from 0.01 to 0.

A rubber composition for modifying a resin containing 20 parts by weight.

[3] The rubber composition for modifying a resin according to claim 1 or 2, wherein the phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule is a diphosphite heat stabilizer.

[4] The amount of the phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule is 0.02-0.10 parts by weight per 100 parts by weight of the conjugated polymer polymer rubber. Item-No.

4. A rubber composition for modifying a resin according to any one of items 3.

[5] The amount of the phosphite compound heat stabilizer having two or more phosphorus atoms in the molecule is 0.03 to 0.09 parts by weight per 100 parts by weight of the conjugated polymer polymer rubber. Item-No.

5. A rubber composition for modifying a resin according to any one of items 4.

6. The rubber composition for modifying a resin according to any one of claims 1 to 5, wherein the thioether compound heat stabilizer has two or more thioether structures in the molecule. object

[7] The resin composition for rubber modification according to any one of claims 1 to 6, wherein the thioether compound thermal stabilizer has a phenol group in its molecule.

 [8] The amount of the thioether compound heat stabilizer is 0.01 to 0.10 parts by weight per 100 parts by weight of the conjugated polymer polymer rubber, according to any one of claims 1 to 7. A rubber composition for refining oil.

[9] The amount of the thioether compound heat stabilizer is 0.02 to 0.09 parts by weight per 100 parts by weight of the conjugated polymer rubber, according to any one of claims 1 to 8. A rubber composition for refining oil.

[10] The rubber composition for modifying a resin according to any one of [1] to [9], wherein the thermal stabilizer for the attareto toy compound has a phenol group in its molecule.

 [11] Any one of claims 1 to 10, wherein the amount of the heat stabilizer of the talate toy compound is 0.01 to 0.10 parts by weight per 100 parts by weight of the conjugated polymer rubber. A rubber composition for modifying fats as described in 1.

 [12] Any one of claims 1 to 11, wherein the amount of the heat stabilizer of the talate toy compound is 0.02 to 0.09 parts by weight per 100 parts by weight of the conjugated polymer rubber A rubber composition for modifying fats as described in 1.

 [13] Claims 1 to 2 comprising adding a thermal stabilizer other than the above after adding a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule to the conjugate polymer rubber. 13. A process for producing a rubber composition for modifying a resin according to any one of items 12.

 [14] Conjugated polymer rubber obtained by using an organolithium compound as a polymerization initiator also has an organic acid, an inorganic acid, and a Lewis acid power in an amount of less than 1 equivalent with respect to lithium of the organolithium compound. After adding at least one kind of acid whose group power is also selected, a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule is added to the conjugated polymer rubber. 14. A process for producing a rubber composition for modifying a resin according to item 13.

[15] At least add a phosphite compound thermal stabilizer having two or more phosphorus atoms in the molecule to the conjugated polymer rubber, before adding a compounding agent other than the thermal stabilizer to the conjugated polymer rubber. 15. The method for producing a rubber composition for modifying a resin according to claim 13 or 14 according to claim 13.

 [16] The resin modification according to claim 15, wherein all of the heat stabilizer is added to the conjugated polymer rubber before adding a compounding agent other than the heat stabilizer to the conjugated polymer rubber. For producing a rubber composition for quality.

[17] A rubber-reinforced resin composition comprising the resin composition for modifying a resin according to any one of claims 1 to 12 and a base resin.

[18] The first aspect of the present invention is that the base resin contains at least an aromatic bur resin.

8. A rubber-reinforced resin composition according to item 7.