JP5148229B2 - Compatibilizer for thermoplastic resin - Google Patents

Description

  The present invention relates to a compatibilizer for thermoplastic resins. More specifically, the present invention relates to a compatibilizing agent that satisfactorily compatibilizes thermoplastic resins having different polarities.

  In recent years, resin modification by blending polymers having different polarities (polymer blend) has been actively studied. For example, a method of using a styrene-based thermoplastic elastomer as a compatibilizing agent has been proposed (see, for example, Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 56-100900 JP-A-6-256417

  However, a molded article using a polymer blend using a conventional compatibilizing agent has a problem that the compatibility between resins is still insufficient and the impact resistance is insufficient. An object of the present invention is to provide a compatibilizing agent that can satisfactorily mix thermoplastic resins having different polarities.

  The inventor of the present invention has arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises propylene 75 to 99.9 mol% and at least one olefin (a) 0.1 to 25 mol% selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms. Compatibilizing agent for thermoplastic resin, characterized by comprising an esterified product (C) of an acid-modified product of polyolefin (A) as a unit and an aromatic ring-containing alcohol (B) having 7 to 24 carbon atoms; A resin composition comprising an agent in at least one nonpolar thermoplastic resin and at least one polar thermoplastic resin; a molded article formed by molding the composition; and the molded article It is a molded article formed by painting and / or printing.

The compatibilizer for thermoplastic resins of the present invention has the following effects.
(1) It is possible to satisfactorily dissolve thermoplastic resins having different polarities.
(2) A molded product obtained by molding a resin composition containing the compatibilizer is excellent in impact resistance.

The polyolefin (A) in the present invention is selected from the group consisting of 75 to 99.9 (preferably 78 to 99) mol% of propylene, ethylene and an α-olefin having 4 to 12 carbon atoms (preferably 4 to 8). At least one olefin (a) 0.1 to 25 (preferably 1 to 22) mol% is used as a structural unit.
When the proportion of propylene constituting (A) is less than 75 mol%, the compatibility between the compatibilizing agent of the present invention and a nonpolar thermoplastic resin (for example, a polyolefin resin, the same shall apply hereinafter) is deteriorated. If it exceeds .9 mol%, the impact resistance of the molded product described later is lowered.

When the carbon number of the α-olefin (hereinafter abbreviated as C) exceeds 12, the compatibility between the compatibilizing agent of the present invention and the nonpolar thermoplastic resin is deteriorated.
When C of the aromatic ring-containing alcohol (B) exceeds 24, the compatibility between the compatibilizer of the present invention and the nonpolar thermoplastic resin is deteriorated.

  Examples of the α-olefin in (a) include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene and 1-dodecene. Among these, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable from the viewpoint of the compatibility between the compatibilizing agent of the present invention and the nonpolar thermoplastic resin. Further preferred are 1-butene, 1-pentene and 4-methyl-1-pentene, and particularly preferred is 1-butene.

  The molar ratio of ethylene and α-olefin in (a) is usually 0/100 to 100/0, the compatibility between the compatibilizing agent of the present invention and a nonpolar thermoplastic resin, and the impact resistance of the molded product. To preferably 5/95 to 95/5, and more preferably 10/90 to 90/10.

Number average molecular weight of (A) [hereinafter abbreviated as Mn. Measurement by gel permeation chromatography (GPC) method] is preferably from 500 to 40,000, more preferably from 1,000 to 35,000, particularly preferably from the viewpoint of impact resistance of the molded article and industrial viewpoint. 1,500 to 30,000. The GPC conditions are as follows.
<GPC conditions>
[1] Apparatus: Waters 150-CV [manufactured by Waters Co., Ltd.]
[2] Column: PLgel 10. MIXED-B [Polymer Laboratories Co., Ltd.
Made]
[3] Eluent: o-dichlorobenzene [4] Reference material: polystyrene [5] Injection conditions: sample concentration 3 mg / ml, column temperature 135 ° C.

The number of double bonds per 1,000 carbon atoms in the molecular end and / or in the molecule (A) is preferably 0.2 to 10 from the acid modification and industrial viewpoint of (A) described later, Preferably it is 0.3-6, Especially preferably, it is 0.5-5. The number of double bonds is ¹ H-N
It can be calculated from the double bond-derived peak at 4.5 to 6.0 ppm in the spectrum obtained from MR (nuclear magnetic resonance) spectroscopy.

  The production method (A) includes a polymerization method (for example, those described in JP-A-59-206409 and JP-A-55-135102) and a degradation method (thermal, chemical and mechanical degradation). Among them, examples of the thermal degradation method include those described in JP-B 43-9368, JP-B 44-29742, and JP-B 6-70094). Of these, the degradation method is preferred from the viewpoint of acid modification (A) described later.

The polymerization method includes a method of (co) polymerizing one or more olefins and a method of copolymerizing one or more olefins and one or more other monomers.
The olefins include C2-30 (preferably 2-12, more preferably 2-4) alkenes such as ethylene, propylene, 1-, 2- and iso-butene, and C5-30 alpha-olefins (1 -Hexene, 4-methylpentene-1,1-decene, 1-dodecene, etc.); other monomers include unsaturated monomers copolymerizable with olefins such as styrene, vinyl acetate, (meth) acrylic Acids and their alkyl (C1-30) esters are included.

Specific examples of polyolefins by the polymerization method include ethylene polymers such as high density, medium density and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1-butene, etc.), C5 30 [alpha] -olefin (1-hexene, 1-dodecene, etc.), vinyl acetate, (meth) acrylic acid, etc.] (copolymerization ratio 30/70 to 99/1, preferably 50/50 to 95) / 5) etc .; propylene-based polymers such as polypropylene, copolymers of propylene and C4-30 unsaturated monomers (same as above) (copolymerization ratio, same as above); ethylene / propylene copolymers (copolymerization ratio) 0.5 / 99.5-30 / 70, preferably 2 / 98-20 /
80); polymers of C4 or higher olefins such as polybutene, poly-4-methylpentene-1.

In the polyolefin by the degradation method, the lower limit is preferably 8,000, more preferably 10,000, particularly preferably 10,000 from the viewpoint of ease of acid modification with a high molecular weight [(A) polymer similar to the above polymerization method. 15,000, a preferable upper limit from the industrial viewpoint is 500,000, more preferably 300,000, particularly preferably 150,000] polyolefin (A0) which is thermally, chemically or mechanically degraded. In view of the acid modification of (A) described later, those obtained by a thermal degradation method are preferable.
In the thermal degradation method, (A0) is continuously subjected to thermal degradation for 0.5 to 10 hours at 300 to 450 ° C. in the absence of organic peroxide (1) in the presence of nitrogen. And (2) A method of continuously thermally degrading at 180 to 300 ° C. for 0.5 to 10 hours in the presence of an organic peroxide. Among these, the method (1) is preferable from the viewpoint of acid modification (A) described later.

The acid-modified product in the present invention is obtained by modifying (A) with an unsaturated polycarboxylic acid and / or its anhydride (b).
The unsaturated polycarboxylic acid (b1) in (b) includes dicarboxylic acids [for example, aliphatic (C4-24, such as maleic acid, fumaric acid, itaconic acid, citraconic acid and mesaconic acid), and alicyclic (C8 To 24, such as cyclohexene dicarboxylic acid and cycloheptene dicarboxylic acid)]; trivalent to tetravalent or higher polycarboxylic acids [such as aliphatic polycarboxylic acids (C5-24, such as aconitic acid)].

Examples of the unsaturated polycarboxylic acid anhydride (b2) include the above unsaturated polycarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, cyclohexenedicarboxylic anhydride, and aconitic acid.
(B) may be used alone or in combination of two.
Of these, non-polar thermoplastic resins and polar thermoplastic resins (for example, polyester resins, the same shall apply hereinafter) are preferable from the viewpoint of compatibility and industrial viewpoint, and more preferably unsaturated dicarboxylic acid anhydrides. Is maleic anhydride.

The reaction molar ratio between (A) and (b) when (A) is modified with (b) is preferably 99/1 to 2/98, more preferably from the viewpoint of compatibility between thermoplastic resins having different polarities. Is 95 / 5-3 / 97, particularly preferably 80 / 20-4 / 96.
The unreacted (b) in the acid-modified product is preferably 10% by weight or less, more preferably 0 to 1% by weight, particularly preferably 0 to 0.1% by weight, from the viewpoint of impact resistance of the molded product described later. is there.

(A) and (b) can be reacted in the presence or absence of the radical initiator (c). From the viewpoint of the reactivity of (A) and (b), The reaction is preferably carried out in the presence.
Examples of (c) include azo compounds (for example, azobisisobutyronitrile and azobisisovaleronitrile) and peroxides [monofunctional (having one peroxide group in the molecule)] [for example, benzoyl peroxide, di- -T-butyl peroxide, lauroyl peroxide and dicumyl peroxide] and polyfunctional (having two or more peroxide groups in the molecule) [for example, 2,2-bis (4,4-di-t-butyl peroxide) Oxycyclohexyl) propane, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate and t-butylperoxyallylcarbonate ]].
Of these, from the viewpoint of the reactivity of (A) and (b), preferred are peroxides, more preferred are monofunctional peroxides, particularly preferred are di-t-butyl peroxide, lauroyl peroxide and Dicumyl peroxide.

  The amount of (c) used is preferably 0.001%, more preferably 0.01%, particularly preferably 0 based on the weight of (b) from the viewpoint of the reactivity of (A) and (b). The upper limit is preferably 100%, more preferably 50%, and particularly preferably 30% from the industrial viewpoint.

Specific production methods of the acid-modified product include [1] (A) and (b) heated and melted, or a suitable organic solvent [C3-18, such as hydrocarbon (eg, hexane, heptane, octane, decane, Dodecane, benzene, toluene and xylene), halogenated hydrocarbons (eg di-, tri- and tetrachloroethane and dichlorobutane), ketones (eg acetone, methyl ethyl ketone, diethyl ketone and di-t-butyl ketone) and ethers (eg ethyl- n-propyl ether, di-i-propyl ether, di-n-butyl ether, di-t-butyl ether, and dioxane)], and if necessary, (c) [or (c) is suitably used. Solution dissolved in organic solvent (same as above)], chain transfer agent (t) described later, A method of adding the inhibitor (f) and heating and stirring (melting method, suspension method and solution method), and [2] (A), (b) and, if necessary, (c), (t), (f) Are previously mixed and melt kneaded using an extruder, a Banbury mixer or a kneader (melt kneading method).
Among these, the method [1] is preferable from the viewpoint of the reactivity between (A) and (b), and the melting method and the solution method are more preferable.

  The reaction temperature in the melting method may be a temperature at which (A) melts, and is preferably 120 to 260 ° C., more preferably from the viewpoint of the reactivity between (A) and (b) and the decomposition temperature of the acid-modified product. Is 130-240 ° C.

  The reaction temperature in the solution method may be a temperature at which (A) is dissolved in a solvent, and is preferably 50 from the reactivity between (A) and (b), the decomposition temperature of the acid-modified product, and an industrial viewpoint. It is -220 degreeC, More preferably, it is 110-210 degreeC, Most preferably, it is 120-180 degreeC.

Examples of the chain transfer agent (t) include hydrocarbons [C6-24, such as aromatic hydrocarbons (for example, toluene, xylene, ethylbenzene and isopropylbenzene) and unsaturated aliphatic hydrocarbons (for example, 1-butene, 2-butene). 1-pentene, 2-pentene, 1-hexene, 2-hexene, 1-heptene, 2-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene and 1-tetradecene)] Halogenated hydrocarbons (C1-24, such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, tetrachloroethane, dibromomethane, tribromomethane, carbon tetrabromide, benzyl chloride and benzyl bromide); alcohols (C1-24, For example, methanol, ethanol, 1-propanol, 2-methyl-2 Propanol 1-butanol, 2-butanol and allyl alcohol); thiols (C1-24, eg ethylthiol, propylthiol, 1- and 2-butylthiol, 1- and 2-pentylthiol, 1-octylthiol and 1-dodecyl) Thiols); ketones (C3-24, such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone and ethyl butyl ketone); aldehydes (C 2-18, such as 2-methyl-2-propyl aldehyde, 1- and 2). -Butyraldehyde, 1-pentylaldehyde, 1-hexylaldehyde and 1-octylaldehyde); phenols (C6-36 such as phenol, m-cresol, p-cresol and o-cresol); quino (C6-24, eg hydroquinone); amines (C3-24, eg diethylmethylamine, triethylamine, tri-1-butylamine and diphenylamine); and disulfides (C2-24, eg diethyl disulfide, di-1-propyl disulfide, di -2-methyl-2-propyl disulfide, di-1-butyl disulfide, ethyl-1-propyl disulfide and di-1-octyl disulfide).
Of these, hydrocarbons and halogenated hydrocarbons are preferred from the viewpoint of compatibility between the compatibilizer of the present invention and the nonpolar thermoplastic resin, more preferred are hydrocarbons, and particularly preferred are unsaturated aliphatic carbonizations. Hydrogen.
The amount of (t) used is usually 40% or less based on the weight of (A), the reactivity between (A) and (b) and the compatibility between the compatibilizing agent of the present invention and a nonpolar thermoplastic resin. From the viewpoint, it is preferably 0 to 20%.

Examples of the polymerization inhibitor (f) include inorganic compounds [for example, oxygen, sulfur and metal salts (for example, ferric chloride)] and organic compounds [catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone (C6-24, such as p-benzoquinone and duroquinone), hydrazine (C2-36, such as 1,1-diphenyl-2-picrylhydrazine), ferrazine (C5-36, such as 1,3,5-triphenyl ferrazine) ), Nitro compounds (C3-24, such as nitrobenzene) and stable radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl-1- Piperidinyloxy (TEMPO) and 1,3,5-triphenylfeldazyl]].
The amount of (f) used is usually 5% or less based on the weight of (A), the reactivity between (A) and (b) and the compatibility between the compatibilizing agent of the present invention and a nonpolar thermoplastic resin. From the viewpoint, it is preferably 0 to 0.5%.

The compatibilizing agent of the present invention comprises an esterified product (C) formed from the acid-modified product and an aromatic ring-containing alcohol (B) of C7 to 24 (preferably C7 to C17).
(B) is a monoalcohol [C7-24, such as benzyl alcohol, phenylethyl alcohol, 3-phenylpropan-1-ol, 2-phenylpropan-2-ol, salicyl alcohol, 3,4-dihydroxyphenylmethanol, Anisyl alcohol, vanillyl alcohol, veratryl alcohol, 4-isopropylphenylmethanol, 2- (4-hydroxy-3-methoxyphenyl) ethane-1-ol, 2- (3,4-dimethoxyphenyl) ethane-1- All, cinnamyl alcohol, 3- (4-hydroxy-3-methoxyphenyl) prop-2-en-1-ol, benzhydryl alcohol, diphenylmethanol, triphenylmethanol, 1-naphthalenemethanol, 2-naphthaleneethanol, 1-A Tracenemethanol, 1-pyrenemethanol] and polyhydric alcohols [C8-24, such as 1,2-diphenylethane-1,2-diol, 1,1,2,2, -tetraphenylethane-1,2- Diol, benzene-1,2-, -1,3- and -1,4-dimethanol], and their alkylene oxides (hereinafter abbreviated as AO) [C2-12, such as ethylene oxide, propylene oxide, tetrahydrofuran, 1, 2-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, THF, BO), epoxides of C5-12 α-olefin, styrene oxide and epihalohydrin (epichlorohydrin, epibromohydrin) Etc.)] adducts.
Of these, monoalcohols and their AO (particularly EO) adducts are preferred from the viewpoint of compatibilization of thermoplastic resins having different polarities.

In the production method of the esterified product (C), [1] the acid-modified product and (B) are heated and melted or suspended in an appropriate organic solvent (same as exemplified in the method for producing the acid-modified product). Alternatively, a method of dissolving and heating and stirring (melting method, suspension method and solution method), and [2] the acid-modified product and (B) are mixed in advance and melt kneaded using an extruder, a Banbury mixer or a kneader. Method (melt kneading method).
Among these, the method [1] is preferable from the viewpoint of the reactivity between the acid-modified product and (B), and the melting method and the solution method are more preferable.

The reaction temperature in the melting method may be a temperature at which the acid-modified product melts, and is preferably 120 to 260 ° C. from the viewpoint of the reactivity between the acid-modified product and (B) and the decomposition temperature of (C). More preferably, it is 130-240 degreeC.

  The reaction temperature in the solution method may be a temperature at which the acid-modified product is dissolved in a solvent, and is preferable from the reactivity of the acid-modified product with (B), the decomposition temperature of (C), and an industrial viewpoint. Is 50 to 220 ° C, more preferably 110 to 210 ° C, and particularly preferably 120 to 180 ° C.

  Mn of (C) is preferably 500 to 50,000, more preferably 1,000 to 40,000, particularly preferably 1,500 to 30,000, from the viewpoint of impact resistance of the molded article and industrial viewpoint. .

  The acid value of (C) is preferably 40 or less, more preferably 0 to 20 from the viewpoint of compatibility between thermoplastic resins having different polarities. The acid value here is a value measured according to JIS K 0070.

  The saponification value of (C) is preferably 0.1 to 140, more preferably 3 to 120, from the viewpoint of compatibility between thermoplastic resins having different polarities. The saponification value here is a value measured according to JIS K 0070.

  The melting point of (C) is preferably 60 to 165 ° C., more preferably 70 to 160 ° C., from the viewpoint of compatibility between thermoplastic resins having different polarities and an industrial viewpoint. The melting point and the melting point below are melting peak temperatures obtained by a differential scanning calorimetry (DSC) method.

The compatibilizer of the present invention comprising the above (C) is applied to compatibilization of at least one nonpolar thermoplastic resin (D1) and at least one thermoplastic resin (D2).
(D1) includes a polyolefin resin.
(D2) includes polyesters, polyamides, polyethers and polycarbonate resins, and block copolymers thereof.

  For the polyolefin resin of (D1), the polymerization method exemplified as the production method of (A) above, or degradation (thermal, chemical and mechanical reduction) of a high molecular weight polyolefin (preferably Mn 50,000 to 400,000). Examples thereof include those obtained by the above method, for example, the ethylene polymers, propylene polymers, ethylene / propylene copolymers, and polymers of C4 or higher olefins exemplified above.

  Mn of (D1) is usually 30,000 to 400,000, and preferably 50,000 to 300,000 from the impact resistance of the molded product and an industrial viewpoint.

  Among (D2), examples of the polyester resin include aromatic ring-containing polyesters and aliphatic polyesters. Examples of the aromatic ring-containing polyester include polyalkylene (C2-24) terephthalate [for example, polyethylene terephthalate (PET) and polybutylene terephthalate (PBT)], polyalkylene (C2-24) isophthalate [for example, polyethylene isophthalate and polybutylene isophthalate. ] And poly-p-phenylene esters [e.g. poly-p-phenylene malonate, poly-p-phenylene adipate and poly-p-phenylene terephthalate] and the like, the aliphatic polyester includes polybutylene adipate, polyethylene adipate, poly-ε -Caprolactone, polylactic acid, etc .; examples of polyamide resins include polycapramide (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene Camide (6,10-nylon), polyundecanamide (11-nylon), poly-ω-aminoheptanoic acid (7-nylon), poly-ω-aminononanoic acid (9-nylon), etc .; Polyoxymethylene, polyoxyethylene, polyoxyphenylene (PPO), poly-1,3-dioxolane, etc .; polycarbonate resins include bisphenol A, -F and -S polycarbonate resins (of the bisphenol and phosgene or diphenyl carbonate Condensates and the like).

  The Mn of (D2) is usually 30,000 to 400,000, and preferably 50,000 to 300,000 from the impact resistance of the molded product and an industrial viewpoint.

  The weight ratio [(D1) / (D2)] of (D1) and (D2) is not particularly limited and can be variously changed according to the purpose, but is preferably from the viewpoint of impact resistance and moldability of the molded product. 99/1 to 1/99, more preferably 90/10 to 10/90.

  In the method for producing a resin composition containing a compatibilizing agent, (1) the compatibilizing agent, (D1), (D2) and, if necessary, the additive (E) described later are the same as the ratio in the molded product described later. And (2) the total amount of the compatibilizing agent, a part of (D1), a part of (D2) and, if necessary, a part or all of (E). A master batch resin composition containing a high-concentration compatibilizer is once prepared by mixing, and then the remaining (D1), (D2) and, if necessary, the remaining (E) are added and mixed to form a resin composition for molding Includes methods to make things. The method (2) is preferable from the viewpoint of the kneading efficiency of the compatibilizer.

The content of the compatibilizing agent in the resin composition in the method (1) is preferably 1 to 2 from the compatibility and industrial viewpoints of (D1) and (D2) based on the total weight of the composition. 50%, more preferably 5 to 40%, particularly preferably 10 to 30%.
Further, the content of the compatibilizing agent in the masterbatch resin composition in the method (2) is preferably based on the compatibility of (D1) and (D2) and from an industrial viewpoint, based on the weight of the composition. Is 5 to 95%, more preferably 10 to 90%, particularly preferably 20 to 80%. Also in the method (2), a molding resin composition obtained by adding the remaining (D1), (D2) and, if necessary, the remaining (E) to the master batch resin composition once prepared and mixing The content of the compatibilizing agent is the same as in the above method (1).

As a specific manufacturing method of the resin composition (masterbatch resin composition and molding resin composition) containing the above compatibilizer, for example, <1> compatibilizer, (D1), (D2) and, if necessary, An additive (E) described later is mixed at, for example, 0 to 80 ° C. with a powder mixer [Henschel mixer, Nauter mixer, Banbury mixer [trade name, manufactured by Farrel Co., Ltd.], etc.] {Batch kneader (reaction tank, etc.), continuous kneader [FCM [trade name, manufactured by Farrel Co., Ltd.], LCM [trade name, manufactured by Kobe Steel, Ltd.], CIM [trade name, Nippon Steel Co., Ltd.] Etc.], a single screw extruder, a twin screw extruder, etc.} and a method of kneading at 120 to 220 ° C. for 2 to 30 minutes;
<2> Compatibilizer, (D1), (D2) and, if necessary, a method of directly kneading (E) under the same conditions using the same melt-kneader without mixing the powder, Is mentioned.
Among these methods, the method <1> is preferable from the viewpoint of kneading efficiency.

  The additive (E) can be further contained in a resin composition (a masterbatch resin composition and a molding resin composition) as necessary as long as the effects of the present invention are not impaired. The colorant (E1) ), A flame retardant (E2), a filler (E3), an antistatic agent (E4), a dispersant (E5), an antioxidant (E6) and an ultraviolet absorber (E7). More than species.

Examples of the colorant (E1) include pigments such as white pigments (titanium oxide, zinc white, barium sulfate, calcium carbonate, etc.), black pigments (carbon black, iron black, aniline black, etc.), yellow pigments (yellow lead, cadmium yellow). , Iron oxide yellow, benzidine yellow, Hansa yellow, oil yellow 2G, etc.), orange pigment (red lead yellow lead, chrome vermilion, cadmium orange, pyrazolone orange, etc.), red pigment (bengala, cadmium red, permanent red, lake red C, Carmine 6B, pigment scarlet 3B, permanent red F5R, quinacridone red, thioindigo maroon, etc.), purple pigment (cobalt violet, mineral violet, etc.), blue dyed pigment (ultraviolet, bitumen, cobalt blue, phthalocyanine blue, etc.), green pigment ( lid Cyanine green, chrome green, etc.), metal powder pigments (aluminum powder, bronze powder, pearl essence, etc.); dyes such as azo, anthraquinone, indigoid, sulfide, triphenylmethane, pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, Acridine, quinoneimine, thiazole, methine, nitro, nitroso and aniline dyes.

  Examples of the flame retardant (E2) include organic flame retardants [phosphorus-containing [phosphate esters (tricresyl phosphate, etc.)], bromine-containing (tetrabromobisphenol A, decabromobiphenyl ether, etc.), Chlorine (chlorinated paraffin, het acid anhydride, etc.)]; inorganic flame retardant (antimony trioxide, magnesium hydroxide, borate, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, magnesium hydroxide) , Ammonium polyphosphate, etc.].

  As filler (E3), metal powder (aluminum powder, copper powder, etc.), metal oxide (alumina, wollastonite, silica, talc, mica, clay, calcined kaolin, etc.), metal hydroxide (aluminum hydroxide) Etc.), metal salt (calcium carbonate, calcium silicate, etc.), fiber [inorganic fiber (carbon fiber, fiber element, α-fiber element, glass fiber, asbestos, etc.), organic fiber (cotton, jute, nylon, acrylic and rayon) Fiber etc.), microballoons (glass, shirasu, phenol resin, etc.), carbons (carbon black, graphite, coal powder, etc.), metal sulfides (molybdenum disulfide, etc.), organic powders (wood powder, etc.), etc. Can be mentioned.

Antistatic agents (E4) include nonionic, cationic, anionic and amphoteric surfactants described below and in US Pat. Nos. 3,929,678 and 4,331,447. .
(1) Nonionic surfactant Alkylene oxide (hereinafter abbreviated as AO) addition type nonionics, for example, active hydrogen atom-containing compound having a hydrophobic group (C8-24 or more) [saturated and unsaturated, higher alcohol (C8-18), higher aliphatic amines (C8-24) and higher fatty acids (C8-24) and the like: alkyl or alkenyl (dodecyl, stearyl, oleyl, etc.) alcohols and amines, and alkanes or alkenoic acids (laurin, stearin) And oleic acid and the like)] [poly) oxyalkylene derivatives [AO [C2-4, such as EO, PO, THF, BO, and combinations of two or more thereof, particularly preferably EO] (1 to 500 mol or more Above) adduct (molecular weight 174 or more and Mn 30,000 or less), and Realkylene glycol [for example, polyethylene glycol (hereinafter abbreviated as PEG), higher fatty acid mono- and di-ester having a molecular weight of 150 or more and Mn 6,000 or less]; polyhydric alcohol [the above, for example, glycerin, pentaerythritol and sorbitan] (Poly) oxyalkylene derivative of higher fatty acid (above) ester (same as above, molecular weight of 320 or more and Mn 30,000 or less: for example, Tween-type nonionics); (poly) oxyalkylene derivative of (alkanol) amide of higher fatty acid (above) (Same as above, molecular weight 330 or more and Mn 30,000 or less); (Poly) oxyalkylene derivative of polyhydric alcohol (above) alkyl (C3-60) ether (same as above, molecular weight 180 or more and Mn 30,000 or less); and polyoxypropylene Polyol [polyhydric alcohol (above) and polyoxypropylene derivative of polyamine (C2-10, such as ethylenediamine, diethylenetriamine) [for example, polypropylene glycol (hereinafter abbreviated as PPG) and ethylenediamine PO adduct; Mn500 to 5,000)] Polyoxyethylene derivatives (Mn 1,000 to 30,000) [pluronic and tetronic nonionics]; polyhydric alcohol (C3-60) nonionics, such as fatty acid (above) esters of polyhydric alcohol (above), Polyhydric alcohols (above) alkyl (C3-60) ethers and fatty acids (above) alkanolamides; and amine oxide type nonionics such as (hydroxy) alkyl (C10-18: dodecyl, stearyl, Rail, 2-hydroxy-dodecyl) di (hydroxy) alkyl (C1 -3: methyl, ethyl, 2-hydroxyethyl, etc.) amine oxides.

(2) Cationic surfactants Quaternary ammonium salt type cationics, for example, tetraalkylammonium salts (C11-100), such as alkyl (C8-18: lauryl, stearyl, etc.) trimethylammonium salts and dialkyl (C8-18: Decyl, octyl, etc.) dimethylammonium salt; trialkylbenzylammonium salt (C17-80), such as lauryldimethylbenzylammonium salt; alkyl (C8-60) pyridinium salt, such as cetylpyridinium salt; (poly) oxyalkylene (C2-4) , Degree of polymerization 1-100 or more) trialkylammonium salts (C12-100) such as polyoxyethylene lauryldimethylammonium salts; and acyl (C8-18) aminoalkyl (C2-4) or acyl Ru (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4)] ammonium salts, such as stearamide ethyl diethylmethylammonium salt (sapamine-type quaternary ammonium salts) [for these salts For example, halides (chloride, bromide, etc.), alkyl sulfates (methosulphate, etc.) and salts of organic acids (described below); and amine salt type cationics: primary to tertiary amines [eg higher aliphatic amines (C12 -60: Lauryl, stearyl and cetylamine, hardened beef tallow amine, rosinamine, etc.), polyoxyalkylene derivatives of aliphatic amines (methylamine, diethylamine, etc.) (above; EO adducts, etc.), and acylaminoalkyl or acyloxyalkyl (above mentioned) ) Di (hydroxy) al (Above) amines (stearoyloxyethyl dihydroxyethylamine, stearamide ethyldiethylamine, etc.)], inorganic acids (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salts and organic acids (C2-22: acetic acid, propion, laurin, Olein, succinic acid, adipine and azelaic acid, benzoic acid, etc.) salts.

(3) Anionic surfactant Carboxylic acid (salt) such as higher fatty acid (above), ether carboxylic acid [higher alcohol (above) or AO adduct thereof, such as EO (1 to 10 mol) adduct carboxymethylated product And sulfate salts thereof, eg, sulfate esters of the above higher alcohols or AO adducts thereof (alkyl and alkyl ether sulfates, sulfated oils (sulfates of natural unsaturated oils or unsaturated waxes as they are) Neutralized salts), sulfated fatty acid esters (salts neutralized by lower alcohol ester of unsaturated fatty acids) and sulfated olefins (salts neutralized by sulfating olefins of C12-18); sulfonic acids Salts, such as alkyl benzene sulfonates, alkyl naphthalene sulfonates, disulfosuccinic acid Alkyl ester type, α-olefin (C12-18) sulfonate and N-acyl-N-methyl taurine (such as Igepon T type); and phosphate ester salts, such as the above higher alcohols or their AO adducts or alkyl ( C4-60) Phosphate ester salts (alkyl, alkyl ethers and alkylphenyl ether phosphates) of AO adducts of phenol (same as above).

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterics such as amino acid type amphoterics such as alkyl (C8-18) aminopropionic acid (salt), and betaine type amphoterics such as alkyl (same as above) di (hydroxy) Alkyl (above) betaine (alkyldimethylbetaine, alkyldihydroxyethylbetaine, etc.); sulfate ester (salt) type amphoterics, for example, alkyl (same as above) amine sulfate ester (salt), and hydroxyalkyl (C2-4: hydroxy) Ethyl etc.) Imidazoline sulfate ester (salt); Sulfonic acid (salt) type amphoterics, such as alkyl (same as above: pentadecyl etc.) sulfotaurine, and imidazoline sulfonic acid (salt); Foterix, for example glycerin Phosphoric acid esters of grade fatty acids (above) ester (salt).

Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); Ammonium salts; and amine salts and quaternary ammonium salts.
The amine constituting the salt includes C1-20 amines such as hydroxylamine, tertiary amino group-containing diols and primary monoamines, secondary monoamines, and their alkylation (C1-4) and / or hydroxyalkylation ( C2-4) products (AO adducts): for example mono-, di- and tri- (hydroxy) alkyl (amines) (mono-, di- and tri-ethanolamine and ethylamine, diethylethanolamine, morpholine, N-methyl Morpholine, N-hydroxyethylmorpholine and the like). The quaternary ammonium salt includes a quaternized product of these amines [a quaternized product of a quaternizing agent or a dialkyl carbonate (described above) described in US Pat. No. 4,271,217].

  As the dispersant (E5), a polymer having Mn of 1,000 to 20,000, for example, a vinyl resin {for example, polyolefin [for example, polyethylene, polypropylene, ethylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99], Propylene / butene copolymer [copolymerization weight ratio 1 to 99/1 to 99] and ethylene / propylene / butene copolymer [copolymerization weight ratio 1 to 98/1 to 98/1 to 98], modified polyolefin [for example Oxidized polyethylene (polyethylene is oxidized with ozone, etc., and carboxyl groups, carbonyl groups and / or hydroxyl groups are introduced), polypropylene oxide (obtained in the same manner as the above oxidized polyethylene by replacing polyethylene with polypropylene), epoxy-modified polyethylene (Epoxy equivalent 100-20,000), Epoxy Modified polypropylene (epoxy equivalent 100 to 20,000), hydroxyl modified polyethylene (hydroxyl value 0.1 to 60), hydroxyl modified polypropylene (hydroxyl value 0.1 to 60), hydroxyl modified ethylene / butene copolymer (hydroxyl value 0) 1-60, copolymer weight ratio 1-99 / 99-1) and hydroxyl-modified propylene / butene copolymer (hydroxyl value 0.1-60, copolymer weight ratio 1-99 / 99-1)]]] and Vinyl resins other than the above polyolefins [for example, polyhalogenated vinyl [for example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride and polyiodide], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meth) acrylic acid, Poly (meth) acrylic ester [eg poly (meth) acrylic ester Acid-methyl, -ethyl, -n- and i-propyl and -n- and t-butyl] and styrene resins [eg polystyrene, acrylonitrile / styrene (AS) resin and acrylonitrile / butadiene / styrene (ABS) resin]]} And polyester resins, polyamide resins, polyether resins, polycarbonate resins, block copolymers thereof and the like exemplified as the above (D2).

Antioxidants (E6) include hindered phenols [pt-amylphenol / formaldehyde resin, 2,6-bis (1-methylheptadecyl) -p-cresol, butylated cresol, styrenated cresol, 4 , 4'-butylidenebis (6-tert-butyl-m-cresol), 4,4'-cyclohexylidenebis (2-cyclohexylphenol), 2 (2'-hydroxy-5'-methylphenyl) benzotriazole, octadecyl -3,5-di-t-butyl-4-hydroxycinnamate, butylated hydroxyanisole, propyl gallate, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid (NDGA), 2,6-di -T-butyl-4-methylphenol (BHT), 2-t-butyl-4-methylpheno (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B), 2-t-butyl-4-ethylphenol, 2,6 -Di-t-butyl-4-ethylphenol, n-
Octadecyl-3- (4′-hydroxy-3,5-di-tert-butylphenyl) propionate, 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-methylenebis (6 -T-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-thiobis (6 -T-butyl-4-hydroxy-2-methylphenol, 1,6-bis (3,5-di-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1,3-tris (5 -T-butyl-4-hydroxy-2-methylphenyl) butane, 2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) mesitylene, 1,3,5-tris (3 , 5-Di-t-bu Le-4-hydroxybenzyl) isocyanurate, and tetrakis [beta-(3,5-di -t- butyl-4-hydroxyphenyl) propionyloxy methyl] methane];

  Sulfur-containing system [N, N′-diphenylthiourea, dimyristylthiodipropionate, dilaurylthiodipropionate, 4,4′-thiobis (6-tert-butyl-m-cresol), distearylthiodipropionate , 6- (4-oxy-3,5-di-t-butylanilino) 2,4-bis (n-octylthio) -1,3,5-triazine, 4,4′-thiobis (6-t-butyl- 3-methylphenol), 4,4′-thiobis (6-t-butyl-o-cresol) and the like];

  Phosphorus-containing [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, phosphite ester resin, tris (nonylphenyl) phosphite, Dioctadecyl-4-hydroxy-3,5-di-t-butylbenzylphosphonate etc.] and the like.

  Examples of the ultraviolet absorber (E7) include salicylates [phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.]; benzophenones [2,4-dihydroxyzenzophenone, 2 -Hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone (trihydrate), 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 5-chloro-2- Hydroxybenzo Enon etc.]; benzotriazole [2- (2'-hydroxy-5'-methylphenyl) - benzotriazole, etc.] and the like.

The total content of (E) in the masterbatch resin composition is usually 30% or less based on the weight of the composition, preferably from 0.1 to 10 in terms of the functional expression of (E) and an industrial viewpoint. %.
The amount of each additive used based on the weight of the composition is as follows: (E1) is usually 10% or less, preferably 1 to 5%; (E2) is usually 15% or less, preferably 3 to 10%; (E3) Is usually 15% or less, preferably 3 to 10%; (E4) is usually 10% or less, preferably 1 to 5%; (E5) is usually 2% or less, preferably 0 to 0.5%, particularly preferably 0%; (E6) is usually 3% or less, preferably 0.01 to 1%, and (E7) is usually 3% or less, preferably 0.01 to 1%.

The content of the whole (E) in the molding resin composition is usually 20% or less based on the weight of the composition, preferably 0.05 to 5 from the functional expression of (E) and an industrial viewpoint. %.
The amount of each additive used based on the weight of the composition is such that (E1) is usually 5% or less, preferably 1.5 to 5%; (E2) is usually 8% or less, preferably 1.5 to 5%. (E3) is usually 8% or less, preferably 1.5 to 5%; (E4) is usually 8% or less, preferably 1.5 to 5%;
5) is usually 1% or less, preferably 0 to 0.03%, particularly preferably 0%; (E6) is usually 2% or less, preferably 0.005 to 0.5%, and (E7) is usually 2%. Hereinafter, it is preferably 0.005 to 0.5%.

  When the additive is the same and overlaps between (E1) to (E7) above, the amount of each additive having the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” means “part by weight” and “%” other than mol% means “% by weight”.
<Manufacture of compatibilizer>
Example 1
Propylene 98 obtained by thermally degrading a high-molecular-weight polyolefin (Mn 100,000) as a copolymer (performed under normal pressure, 360 ° C. × 80 minutes under nitrogen aeration, in the absence of organic peroxide). 90 parts of a polyolefin having a mole unit of 2 mol% and ethylene of 2 mol%, Mn 4,500, and 2.7 double bonds per 1,000 C were charged into a three-necked flask with a cooling tube, and the nitrogen was replaced. The mixture was heated to 180 ° C. and melted under aeration.
Next, 10 parts of maleic anhydride was added and mixed uniformly, then 0.5 part of dicumyl peroxide dissolved in 10 parts of xylene was added dropwise, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, 22 parts of benzyl alcohol was added and stirred at 180 ° C. for 1 hour to obtain a compatibilizer (X1) comprising an esterified product having an acid value of 0, a saponification value of 88, a melting point of 151 ° C., and Mn of 5,900.

Example 2
Propylene obtained by thermally degrading polyolefin (Mn 8,000) which is an ethylene / propylene copolymer (performed at 320 ° C. for 30 minutes under normal pressure and in the absence of organic peroxide under nitrogen flow) Ninety-five parts of polyolefin with 10 double bonds per 1,000 Mn 2,800 and C, with 99 mol% and 1 mol% of ethylene as structural units, were charged into a three-necked flask equipped with a cooling tube and purged with nitrogen. The temperature was raised to 180 ° C. and melted.
Next, 6 parts of maleic anhydride was added and mixed uniformly, then 0.7 part of dicumyl peroxide dissolved in 10 parts of xylene was added dropwise, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, 23 parts of 2-naphthaleneethanol EO 6 mol adduct was added and stirred at 190 ° C. for 3 hours, and then the produced water was distilled off under reduced pressure to give an acid value of 0, a saponification value of 51, a melting point of 142 ° C., and Mn 3,900. A compatibilizing agent (X2) comprising the esterified product was obtained.

Example 3
Propylene obtained by thermally degrading an ethylene / propylene copolymer polyolefin (Mn500,000) (performed under normal pressure at 360 ° C. for 30 minutes in the presence of nitrogen peroxide and in the absence of organic peroxide) In a three-necked flask equipped with a cooling tube, 99 parts of a polyolefin having 0.29 double bonds per 1,000,000 Mn and 35,000 Mn, each having 99.9 mol% and 0.1 mol% of ethylene as a structural unit, were charged with nitrogen. After the replacement, the mixture was heated to 180 ° C. and melted under a nitrogen stream.
Next, 1 part of maleic anhydride was added and mixed uniformly. Then, 0.2 part of lauroyl peroxide dissolved in 10 parts of xylene was dropped, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, 5 parts of phenylethyl alcohol EO 4 mol adduct was added, and the mixture was stirred at 190 ° C. for 3 hours, and then the generated water was distilled off under reduced pressure to give an acid value of 0, a saponification value of 8, a melting point of 155 ° C., and a Mn of 36,000 A compatibilizing agent (X3) comprising an esterified product was obtained.

Example 4
Obtained by thermally degrading polyolefin (Mn 15,000) which is an ethylene / 1-dodecene / propylene copolymer (implemented at 350 ° C. for 60 minutes under normal pressure and in the absence of organic peroxide under nitrogen flow). 96 parts of a polyolefin having 10.0 double bonds per 1,000 Mn and 1,000 C, comprising 75 mol% of propylene, 20 mol% of ethylene and 5 mol% of 1-dodecene as structural units The flask was charged in a three-necked flask and purged with nitrogen, and then heated to 180 ° C. and melted under nitrogen flow.
Next, after adding 2 parts of maleic anhydride and mixing uniformly, 0.5 part of di-t-butyl peroxide dissolved in 10 parts of xylene was dropped, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, after adding 2 parts of benzyl alcohol and stirring at 190 ° C. for 3 hours, the generated water was distilled off under reduced pressure, and a phase comprising an esterified product having an acid value of 0, a saponification value of 46, a melting point of 114 ° C., and Mn of 1,500. A solubilizer (X4) was obtained.

Example 5
Propylene obtained by thermal degradation of polyolefin (Mn 150,000), an ethylene / propylene copolymer (performed under normal pressure at 360 ° C. for 30 minutes under nitrogen flow, in the absence of organic peroxide) After charging 98 parts of polyolefin with 0.5 double bonds per 29,000 Mn, C1,000, having 78 mol% and 22 mol% of ethylene as a structural unit in a three-necked flask with a condenser tube, and replacing with nitrogen, The mixture was heated to 180 ° C. and melted under nitrogen flow.
Next, 2 parts of maleic anhydride was added and mixed uniformly. Then, 0.3 part of di-t-butyl peroxide dissolved in 10 parts of xylene was dropped, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, 2 parts of benzyl alcohol EO 3 mol adduct was added and the mixture was stirred at 190 ° C. for 3 hours, and then the produced water was distilled off under reduced pressure to give an ester having an acid value of 0, a saponification value of 4, melting point of 125 ° C., and Mn of 30,000. A compatibilizing agent (X5) comprising a chemical compound was obtained.

Example 6
4-methyl-1-pentene / propylene copolymer polyolefin (Mn 100,000) is thermally degraded (under nitrogen flow, in the absence of organic peroxide, at normal pressure, 360 ° C. for 30 minutes). 97 parts of polyolefin having 0.3 double bonds per 30,000 Mn and 3,000 C units containing 95 mol% of propylene and 5 mol% of 4-methyl-1-pentene as cooling units were cooled. After charging into a three-necked flask with a tube and replacing with nitrogen, the mixture was heated to 180 ° C. and melted under a nitrogen stream.
Next, 3 parts of maleic anhydride was added and mixed uniformly, then 0.4 part of di-t-butyl peroxide dissolved in 10 parts of xylene was added dropwise, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, after adding 6 parts of benzyl alcohol and stirring at 190 ° C. for 3 hours, the generated water was distilled off under reduced pressure, and a phase comprising an esterified product having an acid value of 0, a saponification value of 4, a melting point of 158 ° C., and Mn of 31,000. A solubilizer (X6) was obtained.

Example 7
Obtained by thermally degrading a polyolefin (Mn 100,000) which is a 1-octene / propylene copolymer (performed under normal pressure, 360 ° C. × 70 minutes under nitrogen aeration, in the absence of organic peroxide). 97 parts of polyolefin having 0.3 Mn5,600 and 0.3 double bonds per 1,000 C, having 95 mol% of propylene and 5 mol% of 1-octene as structural units are charged into a three-necked flask equipped with a cooling tube, and nitrogen is added. After the replacement, the mixture was heated to 180 ° C. and melted under a nitrogen stream.
Next, 3 parts of maleic anhydride was added and mixed uniformly, then 0.4 part of di-t-butyl peroxide dissolved in 10 parts of xylene was added dropwise, and stirring was continued at 180 ° C. for 3 hours. Thereafter, xylene was distilled off under reduced pressure to obtain an acid-modified product. Next, 3 parts of benzyl alcohol EO 3 mol adduct was added, and the mixture was stirred at 190 ° C. for 3 hours, and then the produced water was distilled off under reduced pressure to give an acid value of 0, a saponification value of 40, a melting point of 148 ° C. A compatibilizing agent (X7) comprising a chemical compound was obtained.

Example 8
In Example 1, the polyolefin obtained by thermal degradation is composed of 80 mol% of propylene and 20 mol% of 1-butene as structural units, and the number of double bonds per 1,000 C is 2.7. In the same manner as in Example 1, a compatibilizing agent (X8) comprising an esterified product having an acid value of 0, a saponification value of 87, a melting point of 90 ° C., and Mn of 5,900 was obtained.

Example 9
The same procedure as in Example 1 was conducted except that 66 parts of benzyl alcohol EO 5 mol adduct was used instead of 22 parts of benzyl alcohol in Example 1, acid value 0, saponification value 65, melting point 148 ° C., Mn 7,900 A compatibilizing agent (X9) comprising the esterified product of was obtained.

Example 10
In Example 1, the polyolefin obtained by thermal degradation was composed of 80 mol% of propylene, 5 mol% of ethylene and 15 mol% of 1-butene, and the number of double bonds per 1,000 C was 2.7. Except that, it carried out similarly to Example 1, and obtained the compatibilizer (X10) which consists of an esterified product of the acid value 0, the saponification value 88, melting | fusing point 85 degreeC, and Mn5,900.

Comparative Example 1
In Example 1, it was carried out in the same manner as in Example 1 except that it was not reacted with benzyl alcohol, and a compatibilizing agent comprising an acid-modified product having an acid value of 57, a saponification value of 0, a melting point of 153 ° C., and Mn of 5,000 (ratio X1). Got.

Comparative Example 2
In Example 1, except that 22 parts of octyl alcohol was used instead of 22 parts of benzyl alcohol, it was carried out in the same manner as in Example 1, and from an esterified product of acid value 7, saponification value 78, melting point 151 ° C., Mn 5,500 A compatibilizer (ratio X2) was obtained.

Comparative Example 3
In Example 1, the polyolefin obtained by thermal degradation was composed of 25 mol% of propylene, 5 mol% of ethylene, and 70 mol% of 1-butene, and the number of double bonds per 1,000 C was 2.7. Except that, a compatibilizer (ratio X3) comprising an esterified product having an acid value of 0, a saponification value of 88, a melting point of 78 ° C., and Mn of 5,900 was obtained.

<Performance evaluation>
Examples 11-20, Comparative Examples 4-6
30 parts of commercially available polypropylene (hereinafter abbreviated as PP) [trade name “Cisso Polypro K1011”, manufactured by Chisso Corporation], polybutylene terephthalate (hereinafter abbreviated as PBT) [trade name “1401-X06”, Toray ( Co., Ltd.] 70 parts and 5 parts of each of the obtained compatibilizers were blended for 3 minutes with a Henschel mixer, and then melted in a twin-screw extruder with a vent at 250 ° C., 100 rpm, and a residence time of 3 minutes. Each resin composition was obtained by kneading. Each composition was molded at a cylinder temperature of 240 ° C. and a mold temperature of 40 ° C. using an injection molding machine [trade name “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd.], and a predetermined test piece was prepared. The impact resistance and compatibility were evaluated according to the method. The results are shown in Table 1.

Example 21, Comparative Example 7
In the performance evaluation, impact resistance and compatibility were evaluated in the same manner as above except that 1 part of the compatibilizer (X1) or (ratio X1) was used instead of 5 parts of the compatibilizer. The results are shown in Table 1.

Example 22, Comparative Example 8
In the above performance evaluation, impact resistance and compatibility were evaluated in the same manner as above except that 100 parts of the compatibilizer (X2) or (ratio X2) were used instead of 5 parts of the compatibilizer. The results are shown in Table 1.

Example 23, Comparative Example 9
In the above performance evaluation, impact resistance and compatibility were evaluated in the same manner as above except that 67 parts of the compatibilizer (X3) or (ratio X3) were used instead of 5 parts of the compatibilizer. The results are shown in Table 1.

<Test method>
[1] Impact Resistance According to ASTM D256 Method A, a notched test piece having a thickness of 3.2 mm was measured. The unit is kgf · cm / cm ² .
[2] Compatibility The test piece for impact resistance evaluation was allowed to stand in liquid nitrogen for 10 seconds, and the notch portion of the test piece was broken by hand immediately after removal. Thereafter, the fracture surface was observed with an electron microscope, and the number average particle diameter of PP dispersed in PBT was measured to evaluate the compatibility. The unit is μm. The smaller the number average particle size, the better the compatibility.

  From the results of Table 1, the thermoplastic resin compatibilizing agent of the present invention can be made to better compatibilize thermoplastic resins having different polarities compared to comparative ones, and a resin composition containing the compatibilizing agent can be obtained. It can be seen that the molded product formed is superior in impact resistance compared to the comparative product.

The compatibilizer for thermoplastic resins of the present invention can satisfactorily dissolve thermoplastic resins having different polarities, and a molded product obtained by molding a resin composition containing the compatibilizer is impact resistant. Therefore, it is widely used in the fields of containers, packaging materials, and casings for foods, medical products, industrial products, and home appliance parts, and is extremely useful.

Claims (7)

Polyolefin (A) comprising 75 to 99.9 mol% of propylene and 0.1 to 25 mol% of at least one olefin (a) selected from the group consisting of ethylene and an α-olefin having 4 to 12 carbon atoms (A A compatibilizer for a thermoplastic resin, which is an esterified product (C) of an acid-modified product of (7) and an aromatic ring-containing alcohol (B) having 7 to 24 carbon atoms. The compatibilizing agent according to claim 1, wherein (A) has 0.2 to 10 double bonds per 1,000 carbon atoms in the molecular end and / or in the molecule. The compatibilizer according to claim 1 or 2, wherein (A) is a polyolefin obtained by thermally degrading a polyolefin having a number average molecular weight of 8,000 to 500,000. A resin composition comprising the compatibilizing agent according to claim 1 in at least one nonpolar thermoplastic resin and at least one thermoplastic resin. The composition according to claim 4, wherein the proportion of the compatibilizer based on the weight of the composition is 1 to 50%. A molded article formed by molding the composition according to claim 4 or 5. A molded article obtained by coating and / or printing the molded article according to claim 6.