JP6635780B2 - Compatibilizer for resin - Google Patents

Description

  The present invention relates to a compatibilizer for resins. More specifically, the present invention relates to a compatibilizing agent for a resin which makes a polyolefin resin and a polycarbonate resin and / or a polyester resin compatible well.

Polyolefin resins have excellent moldability, rigidity, electrical insulation properties, and are inexpensive, and are therefore widely and widely used as films, fibers, and other molded articles of various shapes. On the other hand, a polyolefin resin is a so-called non-polar and extremely inert polymer substance having no polar group in the molecule.
Further, in order to improve the mechanical strength (impact resistance, etc.) of the polyolefin resin, attempts have been made to blend a polymer with a resin having a polarity such as a polycarbonate resin or a polyester resin, but it is difficult to compatibilize due to a difference in polarity. You cannot simply blend.
In order to overcome these problems, alloys of a polyolefin resin and a polycarbonate resin and / or a polyester resin have been studied (for example, Patent Documents 1 and 2).

JP-A-5-098020 JP 2000-017120 A

However, in the techniques of Patent Documents 1 and 2, the compatibility of the resin composition is insufficient, and the mechanical strength of a molded article of the resin composition is not satisfactory.
An object of the present invention is to provide a compatibilizing agent for a resin, which is capable of satisfactorily compatibilizing a polyolefin resin with a polycarbonate resin and / or a polyester resin and imparting excellent mechanical strength to a molded article of the resin composition. Is to do.

  Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides a modified polyolefin (X) comprising a polyolefin (A) and an unsaturated dicarboxylic acid (anhydride) (B) as constituent units, and a polyoxy resin having one functional group reactive with the (X). A resin compatibilizer (K) containing a polyoxyalkylene-modified polyolefin (Z) formed from an alkylene chain-containing compound (Y); (K), a polyolefin resin (D), and a polycarbonate resin ( E) and / or a polyester resin (F).

The compatibilizer (K) for resins of the present invention has the following effects.
(1) The polyolefin resin (D) and the polycarbonate resin (E) and / or the polyester resin (F) can be compatibilized in a wide weight ratio.
(2) A molded article obtained by molding the resin composition containing the compatibilizer, (D), (E) and / or (F) has a flexural modulus, impact resistance, and the like. Has excellent mechanical strength.

[Polyolefin (A)]
The polyolefin (A) in the present invention includes one or more (co) polymers of an olefin, and a copolymer of one or more olefins with one or more other monomers. Polymers are included.
The olefin includes an alkene having 2 to 30 carbon atoms (hereinafter, may be abbreviated as C), such as ethylene, propylene, 1- and 2-butene, and isobutene, and a C5-30 α-olefin (1- Hexene, 1-decene, 1-dodecene, etc.); Other monomers include C4-30 unsaturated monomers copolymerizable with olefins, such as vinyl acetate.

Specific examples of (A) include (co) polymers containing ethylene units (no propylene units), such as high, medium and low density polyethylene, and ethylene and C4-30 unsaturated monomers [butene (1- (Butene or the like), a C5-30 α-olefin (1-hexene, 1-dodecene or the like), vinyl acetate or the like] (weight ratio is the moldability of the polyolefin resin composition and the molecular terminal of (A)). From the viewpoint of the amount of double bonds in the molecular chain, preferably 30/70 to 99/1, more preferably 50/50 to 95/5); propylene unit-containing (ethylene-free) (co) polymer For example, polypropylene, a copolymer of propylene and a C4-30 unsaturated monomer (same as above) (weight ratio is the same as above); an ethylene / propylene copolymer (weight ratio is polyolefin resin group) From the viewpoint of the moldability of (A) and the amount of double bonds in the molecular terminal and / or the molecular chain of (A), preferably 0.5 / 99.5 to 30/70, more preferably 2/98 to 20/80) C4 and higher olefin (co) polymers, such as polybutene.
Of these, polyethylene, polypropylene, ethylene / propylene copolymer, and propylene / C4-30 unsaturated monomer copolymer are preferable from the viewpoint of reactivity with the unsaturated dicarboxylic acid (anhydride) (B) described later. Polymers, more preferably ethylene / propylene copolymers, and propylene / C4-30 unsaturated monomer copolymers.

  Number average molecular weight of (A) [hereinafter abbreviated as Mn. The measurement is performed by the gel permeation chromatography (GPC) method described later. same as below. ] Is preferably 800 to 50,000, more preferably 1 to 50,000 from the viewpoint of the mechanical strength of the molded article of the composition containing the compatibilizer for resin (K) of the present invention and the productivity of (K). 5,000 to 45,000.

The conditions for measuring Mn by GPC in the present invention are as follows.
Equipment: High temperature gel permeation chromatograph
["Alliance GPC V2000", manufactured by Waters Corporation]
Detector: Refractive index detector Solvent: Orthodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml
Column stationary phase: PLgel 10 μm, MIXED-B 2 in series
[Polymer Laboratories Co., Ltd.]
Column temperature: 135 ° C

(A) preferably has a double bond at the molecular terminal and / or in the molecular chain from the viewpoint of reactivity with the unsaturated dicarboxylic acid (anhydride) (B) described below.
The number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbon atoms (also referred to as 1,000 carbon atoms) of (A) is determined by the reactivity between (A) and (B) and ( From the viewpoint of productivity of K), the number is preferably 0.1 to 20, more preferably 0.3 to 18, particularly preferably 0.5 to 15. Here, the number of double bonds can be determined from the spectrum of ¹ H-NMR (nuclear magnetic resonance) spectroscopy of (A). That is, the peaks in the spectrum are assigned, and the number of double bonds of (A) and the number of double bonds of (A) are determined from the integrated value derived from the double bond at 4.5 to 6 ppm of (A) and the integrated value derived from (A). Is calculated, and the number of double bonds in the molecular terminal and / or the molecular chain per 1,000 carbon atoms in (A) is calculated. The number of double bonds in Examples described later followed the method.

  The production method of (A) includes a polymerization method (for example, the method described in JP-A-59-206409) and a degradation method [thermal, chemical and mechanical degradation methods and the like. Examples of the synthesis method (hereinafter sometimes referred to as thermal degradation method) include those described in JP-B-43-9368, JP-B-44-29742, and JP-B-6-70094.

  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. It is.

  In the degradation method, a polyolefin (A0) having a high molecular weight [preferably Mn of 30,000 to 400,000, more preferably 50,000 to 200,000] obtained by the polymerization method is thermally, chemically or mechanically. The method of degeneration is included. That is, among the above (A), preferred is a thermally degraded product of the polyolefin (A0).

Among the degradation methods, in the thermal degradation method, the polyolefin (A0) is continuously passed for 0.5 to 10 hours at 300 to 450 ° C., usually in the absence of an organic peroxide, under nitrogen aeration. Or a method of discontinuously thermal degradation, and a method of (2) continuous or discontinuous thermal degradation in the presence of an organic peroxide, usually at 180 to 300 ° C for 0.5 to 10 hours. It is.
Among them, preferred from the viewpoint of copolymerizability of (A) and (B) obtained is the method of (1) wherein a compound having a larger number of double bonds in a molecular terminal and / or in a molecular chain is easily obtained. is there.

  Among these production methods of (A), those having a larger number of double bonds in the molecular terminal and / or in the molecular chain are easily obtained, and the copolymerization of (A) and (B) is easy. The preferred is the degradation method, and more preferred is the thermal degradation method.

  Mn of (A) is preferably 800 to 50,000, more preferably 1,500 to 30,000, from the viewpoint of the compatibility of the resin composition described below and the productivity of the compatibilizing agent for resin (K). is there.

[Unsaturated dicarboxylic acid (anhydride) (B)]
The unsaturated dicarboxylic acid (anhydride) (B) in the present invention is a dicarboxylic acid (anhydride) having one polymerizable unsaturated group. In the present invention, the unsaturated dicarboxylic acid (anhydride) represents an unsaturated dicarboxylic acid or an unsaturated dicarboxylic anhydride.
Examples of (B) include C4-30, for example, aliphatic ones (C4-24, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid and anhydrides thereof), and alicyclic ones ( C8-24, for example, cyclohexanedicarboxylic acid, cycloheptenedicarboxylic acid). (B) may be used alone or in combination of two or more.
Of these, unsaturated dicarboxylic anhydrides are preferred from the viewpoint of reactivity with (A), and maleic anhydride is more preferred.

  The weight ratio of (A) / (B) [(A) / (B)] is preferably 99/1 to 1 from the viewpoint of the compatibility of the compatibilizer for resin (K) and the mechanical strength of the molded article. 70/30, more preferably 98/2 to 80/20, particularly preferably 95/5 to 90/10.

[Radical initiator (C)]
The modified polyolefin (X) in the present invention is obtained by copolymerizing (A) and (B) in the presence or absence of a radical generator [radical initiator (C), heat, light, etc.]. Can be
Examples of the radical initiator (C) include azo compounds [azobisisobutyronitrile, azobisisovaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), etc.], peroxides [monofunctional ( Having one peroxide group in the molecule) (benzoyl peroxide, di-t-butyl peroxide, lauroyl peroxide, dicumyl peroxide, etc.) and polyfunctional (having two or more peroxide groups in the molecule) [2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate, etc.]] and the like.
Of these, from the viewpoint of the reactivity between (A) and (B), peroxide is preferable, monofunctional peroxide is more preferable, di-t-butyl peroxide, lauroyl peroxide, Dicumyl peroxide.

  The amount of (C) used is preferably 0.05 to 10%, more preferably 0.2 to 5%, based on the total weight of (A) and (B), from the viewpoint of reactivity and suppression of side reactions. Especially preferably, it is 0.5 to 3%.

[Modified polyolefin (X)]
The modified polyolefin (X) in the present invention comprises the polyolefin (A) and the unsaturated dicarboxylic acid (anhydride) (B) as constituent units.
The modified polyolefin (X) can be produced, for example, by copolymerizing a polyolefin (A) and an unsaturated dicarboxylic acid (anhydride) (B) in the presence or absence of a radical initiator (C). .

Specific manufacturing methods (X) include the following methods [1] and [2].
[1] (A) and (B) are converted to a suitable organic solvent [C3-18, for example, hydrocarbons (hexane, heptane, octane, dodecane, benzene, toluene, xylene, etc.), halogenated hydrocarbons (di-, tri- , And tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-n-butyl ether, di-t-butyl ether, dioxane, etc.)] Suspended or dissolved, and if necessary, (C) [or a solution of (C) dissolved in an appropriate organic solvent (same as above)], a chain transfer agent (t) described below, and a polymerization inhibitor (f) ) And heating and stirring (solution method);
[2] A method in which (A), (B) and, if necessary, (C), (t) and (f) are preliminarily mixed and melt-kneaded using an extruder, a Banbury mixer, a kneader or the like (melting method).

  The reaction temperature in the solution method may be a temperature at which (A) dissolves in an organic solvent, and is preferably from 50 to 220 ° C., and more preferably 110 from the viewpoint of the reactivity and productivity of (A) and (B). -210 ° C, particularly preferably 120-180 ° C.

  The reaction temperature in the melting method may be a temperature at which (A) is melted, and is preferably from 120 to 260 ° C. from the viewpoints of the copolymerizability of (A) and (B) and the decomposition temperature of the reaction product. The temperature is more preferably 130 to 240 ° C.

Examples of the chain transfer agent (t) include alcohols (C1-24, for example, methanol, ethanol, 1-propanol, 2-butanol, allyl alcohol); thiols (C1-24, for example, ethylthiol, propiothiol, 1- And aldehydes (C2-18, such as 2-methyl-2-propylaldehyde, 1- and 2-butylaldehyde, 1-pentylaldehyde); phenols (C6-36, such as phenol) , O-, m- and p-cresol); amines (C3-24, such as diethylmethylamine, triethylamine, diphenylamine); disulfides (C2-24, such as diethyldisulfide, di-1-propyldisulfide).
The amount of (t) used is usually 30% or less based on the total weight of (A) and (B), and preferably 0.1 to 20 from the viewpoint of copolymerizability and productivity of (A) and (B). %.

Examples of the polymerization inhibitor (f) include catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone (C6-24, for example, p-benzoquinone), and hydrazine (C2-36, for example, 1,3,3). 5-triphenylhydrazine), a nitro compound (C3-24, for example, nitrobenzene), a stabilizing radical [C5-36, for example, 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6 -Tetramethyl-1-piperidinyl oxide (TEMPO)].
The amount of (f) used is usually 5% or less based on the total weight of (A) and (B), and the productivity, stability of (A) and (B) and reactivity of (A) and (B) From the viewpoint of, it is preferably 0.01 to 0.5%.

  Mn of (X) is preferably 1,500 to 70,000, more preferably 2,000 to 60,000, particularly preferably 2,500 to 50,000 from the viewpoint of mechanical strength and moldability of a molded product. It is.

The acid value of (X) is preferably from 1 to 250 mg KOH / g (hereinafter, referred to as the acid value) from the viewpoint of the compatibility of the compatibilizing agent for resin (K) with (D) and the compatibility with (E) and (F). Only numerical values are shown.), More preferably 5 to 200, particularly preferably 10 to 100. The acid value here is a value obtained by measuring in accordance with the following procedures (i) to (iii) according to JIS K0070.
(I) 1 g of (X) is dissolved in 100 g of xylene whose temperature has been adjusted to 100 ° C.
(Ii) Titration is performed with a 0.1 mol / L potassium hydroxide ethanol solution [trade name “0.1 mol / L ethanolic potassium hydroxide solution” manufactured by Wako Pure Chemical Industries, Ltd.] using phenolphthalein as an indicator.
(Iii) The amount of potassium hydroxide required for the titration is converted to mg to calculate an acid value (unit: mgKOH / g).
In the above measurement, the carboxyl group and the acid anhydride group were measured equivalently, and the acid value in Examples described later followed the method.

Examples of the method for adjusting the acid value of (X) to the above range include a method of suspending or dissolving in an appropriate organic solvent and copolymerizing the structural units of (A) and (B) under heating and stirring conditions. Can be
Specifically, (A) and (B) are converted to a suitable organic solvent [C3-18, for example, a hydrocarbon (hexane, heptane, octane, decane, dodecane, benzene, toluene, xylene, etc.), a halogenated hydrocarbon (diene). -, Tri- and tetrachloroethane, dichlorobutane, etc.), ketones (acetone, methyl ethyl ketone, diethyl ketone, di-t-butyl ketone, etc.), ethers (ethyl-n-propyl ether, di-i-propyl ether, di-n- Butyl ether, di-t-butyl ether, dioxane, etc.), and if necessary, (C) [or a solution in which (C) is dissolved in a suitable organic solvent (same as above)], The above-mentioned chain transfer agent (t) and polymerization inhibitor (f) can be added and heated and stirred.

[Polyoxyalkylene chain-containing compound (Y)]
The polyoxyalkylene chain-containing compound (Y) in the present invention is a compound having one functional group reactive with (X).
Examples of the functional group include a hydroxyl group, an amino group and an epoxy group.
Specific examples include an alkylene oxide adduct (Y1) of a compound having one active hydrogen, an aminopolyoxyalkylene monoalkyl ether (Y2), and a modified product thereof (Y3).

Examples of the alkylene oxide adduct (Y1) of a compound having one active hydrogen include those obtained by subjecting a compound having one active hydrogen to an addition reaction with an alkylene oxide (hereinafter abbreviated as AO). Include those represented by the general formula (1).

^{R 1 O- (R 2 O)} m -H (1)

R ¹ in the general formula (1) represents a residue obtained by removing one active hydrogen from the compound (Y0) having one active hydrogen.
(Y0) includes a saturated aliphatic monohydric alcohol having 1 to 50 carbon atoms (Y01), an unsaturated aliphatic monohydric alcohol having 1 to 50 carbon atoms (Y02), and a monohydric phenol having 7 to 50 carbon atoms (Y03). ), And a secondary amine having 2 to 50 carbon atoms (Y04).

(Y01) includes methanol, ethanol, n-propanol, isopropanol n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, pentyl alcohol, hexyl alcohol, cyclohexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, Examples include decyl alcohol, tetradecyl alcohol, hexadecyl alcohol, icosa alcohol, triaconta alcohol, pentaconta alcohol, benzyl alcohol, diphenylmethyl alcohol, and the like.
(Y02) includes ethenyl alcohol, propenyl alcohol, isopropenyl alcohol, 3-butenyl alcohol, 3-butynyl alcohol, 4-hexenyl alcohol, 7-octenyl alcohol, 9-decenyl alcohol, oleyl alcohol and the like Is mentioned.
(Y03) includes phenol, nonylphenol and the like.
(Y04) includes dimethylamine, diethylamine, dioctylamine, diphenylamine, ethylmethylamine and the like.

Of the above (Y0), (Y01), (Y03), and (Y04) are preferred from the viewpoints of the compatibility of the compatibilizing agent for resin (K) described below and the industrial viewpoint, and more preferred are those having 25 or less carbon atoms. (Y01) to (Y04), particularly preferably (Y01) having 1 to 20 carbon atoms.
(Y0) may be used alone or in combination of two or more.

R ² in the general formula (1) is an alkylene group having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a 1,2- or 1,3-propylene group, a 1,2-, 1,3-, 1,4- or 2,3-butylene group, and the like, and A mixture of two or more of these may be mentioned.
M in the general formula (1) is a number of 2 to 20, preferably 3 to 18, and more preferably 5 to 18.

The alkylene oxide adduct (Y1) of a compound having one active hydrogen can be produced by subjecting (Y0) to an AO addition reaction.
As AO, AO having 2 to 4 carbon atoms [ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 1, 3-, 1,4- or 2,3-butylene oxide (hereinafter abbreviated as BO), and a combination of two or more of these] is used, and if necessary, other AO [α having 5 to 12 carbon atoms] is used. -Olefin oxide, styrene oxide, epihalohydrin (epichlorohydrin, etc.)] in a small proportion (30% by weight or less based on the total weight of AO).
When two or more types of AO are used in combination, either a random connection or a block connection may be used. From the viewpoint of the compatibility of the compatibilizing agent for resin (K) described later, EO alone or a combination of EO and another AO is preferable, and EO alone is more preferable.

The addition reaction of AO can be performed by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of (R ² O) m based on the weight of (Y1) represented by the general formula (1) is determined from the viewpoint of the compatibility of the resin compatibilizer (K) described later and the mechanical strength of the molded product. It is preferably from 5 to 99.8%, more preferably from 10 to 98%, particularly preferably from 20 to 90%.

Examples of the aminopolyoxyalkylene alkyl ether (Y2) include those represented by the general formula (2).

^{R 1 O- (R 2 O)} n -R 3 -NH 2 (2)

R ¹ in the general formula (2) is the same as R ¹ in the general formula (1), R ² and R ³ is an alkylene group having 2 to 4 carbon atoms, R ¹ and R in the general formula (1) ^{The same} as those exemplified as ² are mentioned, and the preferable range is also the same.
N in the general formula (2) is a number of 2 to 20, preferably 3 to 18, and more preferably 5 to 15.

  The aminopolyoxyalkylene alkyl ether (Y2) is obtained by converting all the hydroxyl groups of the above (Y1) into amino groups. For example, it can be produced by reacting (Y1) with acrylonitrile and hydrogenating the obtained cyanoethylated product.

Examples of the modified product (Y3) include aminocarboxylic acid-modified products (terminal amino groups), isocyanate-modified products (terminal isocyanate groups), and epoxy-modified products (terminal epoxy groups) of (Y1) and (Y2).
The aminocarboxylic acid-modified product can be obtained by reacting (Y1) or (Y2) with an aminocarboxylic acid or a lactam.
The isocyanate-modified product can be obtained by reacting (Y1) or (Y2) with polyisocyanate, or reacting (Y2) with phosgene.
The epoxy-modified product is obtained by reacting (Y1) or (Y2) with a diepoxide (epoxy resin such as glycidyl ether, glycidyl ester and alicyclic diepoxide: epoxy equivalent of 85 to 600), or (Y1) and epihalohydrin (epihalohydrin). Chlorohydrin).

The Mn of the polyoxyalkylene chain-containing compound (Y) is from 150 to 20,000, more preferably from 300 to 20,000, from the viewpoint of the compatibility of the resin modifier (K) and the reactivity with the modified polyolefin (X). It is 10,000, particularly preferably 500 to 5,000.
Of the above (Y1) to (Y3), (Y1) is preferable from an industrial viewpoint.

[Polyoxyalkylene-modified polyolefin (Z)]
The polyoxyalkylene-modified polyolefin (Z) in the present invention is formed from the modified polyolefin (X) and the polyoxyalkylene group-containing compound (Y).
That is, (Z) is a compound in which (X) and (Y) are bonded via an ester bond, an imide bond, an amide bond, an epoxy ring-opening bond, and more preferably an ester bond.

The weight ratio of (X) / (Y) [(X) / (Y)] in (Z) is preferably 30/30 from the viewpoint of the mechanical strength of the molded article and the compatibility of the compatibilizer (K). 70-99 / 1, more preferably 50 / 50-95 / 5, particularly preferably 70 / 30-90 / 10.
Further, the equivalent ratio [(X) / (Y)] of (X) and (Y) is preferably 0.5 to 0.5 from the viewpoint of the compatibility of the compatibilizer (K) and the mechanical strength of the molded article. 1.0, and more preferably 0.8 to 1.0.
The content of the polyoxyalkylene unit in (Z) is preferably from 0.1 to 60% by weight, more preferably from 1 to 55%, from the viewpoint of the compatibility of the compatibilizer (K) and the mechanical strength of the molded article. %, Particularly preferably 5 to 50% by weight.
Further, Mn (number average molecular weight) of (Z) is preferably 3,000 to 100,000, more preferably 5,000 to 70,000, particularly preferably 5,000 to 70,000, from the viewpoint of mechanical strength and moldability of a molded article. Is 10,000 to 50,000.

The polyoxyalkylene-modified polyolefin (Z) can be produced by reacting the modified polyolefin (X) with the polyoxyalkylene chain-containing compound (Y).
As a specific production method of (Z), for example, a method of reacting a dicarboxylic acid (anhydride) of a modified polyolefin (X) with a hydroxyl group, an amino group, and an epoxy group of a polyoxyalkylene group-containing compound (Y) And (X) and (Y) are charged into a reaction vessel, and agitated at a reaction temperature of 100 to 250 ° C. and a pressure of 0.003 to 0.1 MPa by an amidation reaction, an esterification reaction, and an imidation reaction. A method in which the reaction is carried out for 1 to 50 hours while removing water (hereinafter abbreviated as generated water) generated outside the reaction system as needed.

In the case of the esterification reaction, it is preferable to use 0.05 to 0.5% by weight of a catalyst based on the total weight of (X) and (Y) in order to accelerate the reaction. Examples of the catalyst include inorganic acids (such as sulfuric acid and hydrochloric acid), organic sulfonic acids (such as methanesulfonic acid, paratoluenesulfonic acid, xylenesulfonic acid, and naphthalenesulfonic acid) and organic metal compounds (such as dibutyltin oxide, tetraisopropoxytitanate, and bistrisulfonic acid). Ethanolamine titanate and potassium oxalate titanate). When a catalyst is used, the catalyst can be neutralized after the esterification reaction, if necessary, and treated with an adsorbent to remove and purify the catalyst. As a method for removing the generated water out of the reaction system, the following method may be mentioned.
(I) A method in which an organic solvent incompatible with water (for example, toluene, xylene, cyclohexane, or the like) is used, and the organic solvent and produced water are azeotropically refluxed to remove only produced water from the reaction system. .
(Ii) A method in which a carrier gas (for example, air, nitrogen, helium, argon, carbon dioxide, or the like) is blown into the reaction system to remove generated water together with the carrier gas outside the reaction system.
(Iii) A method in which the pressure inside the reaction system is reduced to remove generated water outside the reaction system.

[Compatibilizer for resin (K)]
The compatibilizer (K) for a resin of the present invention is a polyoxyalkylene group-containing compound (Y) having one functional group reactive with the modified polyolefin (X). It comprises an alkylene-modified polyolefin (Z).
The resin compatibilizer (K) of the present invention is used as a compatibilizer for compatibilizing a polyolefin resin (D) described later with a polycarbonate resin (E) and / or a polyester resin (F).

[Resin composition]
The resin composition of the present invention contains the resin compatibilizer (K), a polyolefin resin (D), and a polycarbonate resin (E) and / or a polyester resin (F).

  For the polyolefin resin (D), the polymerization method exemplified as the production method of the above (A), or the degradation (thermal, chemical and mechanical degradation) of a high molecular weight polyolefin (preferably Mn 80,000 to 400,000) ), Which include, for example, the above-mentioned exemplified ethylene unit-containing (propylene unit-free) (co) polymer, propylene unit-containing (ethylene-free) (co) polymer, ethylene / propylene copolymer And (co) polymers of C4 or higher olefins.

As the combination of (D) and (K), the case where the structural unit of (D) and the structural unit of polyolefin (A) constituting (K) are the same or similar is the combination of (D) and (K). It is preferable from the viewpoint of compatibility.
For example, when (D) is a propylene unit-containing (ethylene-free) (co) polymer, (K) constituting (K) is also a propylene unit-containing (ethylene-free) (co) polymer. Certain cases are preferred.

  Mn of (D) is preferably 10,000 to 500,000, and more preferably 20,000 to 400,000, from the viewpoint of the mechanical strength of the molded article and compatibility with (K).

[Polycarbonate resin (E)]
Examples of the polycarbonate resin (E) include an aromatic polycarbonate (E1), an aliphatic polycarbonate (E2), and a mixture of two or more thereof. Examples of (E1) include bisphenols (C12 to C20, for example, bisphenol A, bisphenol F, bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane) based polycarbonate, for example, the above bisphenol and phosgene or carbonate diester And a condensate of Examples of (E2) include polyethylene carbonate, polypropylene carbonate, polycyclohexene carbonate, derivatives thereof, and copolymers thereof.

  The melt flow rate (hereinafter abbreviated as MFR) of (E) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of compatibility with the polyolefin resin (D) and mechanical strength. The MFR of (F2) is measured according to JIS K7210 (280 ° C., load 2.16 kgf for polycarbonate resin).

[Polyester resin (F)]
Examples of the polyester resin (F) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.), alicyclic containing Polyester (eg, polycyclohexane dimethylene terephthalate) and the like.

  The intrinsic viscosity [η] of (F) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from the viewpoint of the mechanical strength of the molded article and the compatibility with (D). Is 0.3 to 3. Here, [η] is a value (unit: dl / g) measured using an Ubbelohde 1A viscometer at 25 ° C. for an orthochlorophenol solution of the polymer.

The resin composition of the present invention can further contain various additives (G) as needed as long as the effects of the present invention are not impaired.
(G) includes a colorant (G1), a flame retardant (G2), a filler (G3), a lubricant (G4), an antistatic agent (G5), a dispersant (G6), an antioxidant (G7), and ultraviolet light. One or more kinds selected from the group consisting of the absorbent (G8) are exemplified.

Examples of the coloring agent (G1) include pigments and dyes.
Examples of the pigment include an inorganic pigment (alumina white, graphite, etc.); and an organic pigment (azo lake type, etc.).
Examples of the dye include an azo type and an anthraquinone type.

  Examples of the flame retardant (G2) include organic flame retardants [nitrogen-containing compounds [salts of urea compounds, guanidine compounds, etc.], sulfur-containing compounds [sulfate esters, sulfamic acids, and salts, esters, amides, etc. thereof], silicon-containing compounds Compounds [polyorganosiloxane etc.], phosphorus-containing [phosphate ester etc.]]; inorganic flame retardants [antimony trioxide, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate etc.] and the like.

  Examples of the filler (G3) include carbonates (eg, magnesium carbonate and calcium carbonate), sulfates (eg, aluminum sulfate), sulfites (eg, calcium sulfite), metal sulfides (eg, molybdenum disulfide), and silicates (eg, aluminum silicate). Etc.), diatomaceous earth, silica stone powder, talc, silica, zeolite, woody materials (wood powder and the like), and mixtures thereof.

  Examples of the lubricant (G4) include wax (such as carnauba wax), higher fatty acid (such as stearic acid), higher alcohol (such as stearyl alcohol), and higher fatty acid amide (such as stearic acid amide).

Antistatic agents (G5) 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, an active hydrogen atom-containing compound having a hydrophobic group (C8-24 or more) [saturated and unsaturated, higher alcohols (C8-18), higher aliphatic amines (C8-24) and higher fatty acids (C8-24), etc.] (higher fatty acid mono- and di-esters of AO adducts and polyalkylene glycols) A (poly) oxyalkylene derivative of a higher fatty acid (C8-24) ester of a polyhydric alcohol (C3-60) (tween type nonionics, etc.); a (poly) oxyalkylene derivative of a (alkanol) amide of a higher fatty acid (described above) A (poly) oxyalkylene of a polyhydric alcohol (above) alkyl (C3-60) ether Derivatives; and polyoxypropylene polyols [polyoxypropylene derivatives of polyhydric alcohols and polyamines (C2-10) (pluronic and tetronic nonionics)]; polyhydric alcohol (above) type nonionics (eg, polyhydric alcohols) Fatty acid esters, polyhydric alcohol alkyl (C3-60) ethers, and fatty acid alkanolamides); and amine oxide type nonionics [for example, (hydroxy) alkyl (C10-18) di (hydroxy) alkyl (C1-3) amine oxide ].

(2) Cationic surfactant Quaternary ammonium salt type cationics [tetraalkylammonium salt (C11-100) alkyl (C8-18) trimethylammonium salt and dialkyl (C8-18) dimethylammonium salt]; trialkyl Benzylammonium salts (C17-80) (lauryl dimethylbenzylammonium salts, etc.); alkyl (C8-60) pyridinium salts (cetylpyridinium salts, etc.); (poly) oxyalkylene (C2-4) trialkylammonium salts (C12-100) ) (Polyoxyethylene lauryl dimethyl ammonium salt and the like); and acyl (C8-18) aminoalkyl (C2-4) or acyl (C8-18) oxyalkyl (C2-4) tri [(hydroxy) alkyl (C1-4) )] Ammoni Salts (sapamine-type quaternary ammonium salts) [These salts include, for example, salts of halides (chloride, bromide, etc.), alkyl sulfates (methosulfate, etc.) and organic acids (described below)]; and amine salt types Cationics: Primary to tertiary amines [for example, higher aliphatic amines (C12 to 60), polyoxyalkylene derivatives of aliphatic amines (methylamine, diethylamine, etc.) [ethylene oxide (hereinafter abbreviated as EO) adducts, etc.], and acyls Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt and organic acid of aminoalkyl or acyloxyalkyl (above) di (hydroxy) alkyl (above) amine (e.g., stearyloxyethyl dihydroxyethylamine, stearamidoethyldiethylamine) Acid (C2-22) salts.

(3) Anionic surfactant Higher fatty acid (above) salt (such as sodium laurate), ether carboxylic acid [carboxymethylated product of EO (1 to 10 mol) adduct and the like], and salts thereof; sulfate salt ( Alkyl and alkyl ether sulfates), sulfated oil, sulfated fatty acid ester and sulfated olefin; sulfonate [alkylbenzene sulfonate, alkylnaphthalene sulfonate, dialkyl sulfosuccinate, α-olefin (C12-18) Sulfonate, N-acyl-N-methyltaurine (Igepon T type and the like) and the like; and phosphate ester salts and the like (alkyl, alkyl ether and alkylphenyl ether phosphate and the like).

(4) Amphoteric surfactant:
Carboxylic acid (salt) type amphoterix [amino acid type amphoterix (laurylaminopropionic acid (salt), etc.) and betaine type amphoterix (alkyl dimethyl betaine, alkyl dihydroxyethyl betaine, etc.)]; sulfuric acid Ester (salt) type amphoterix [laurylamine sulfate (salt), hydroxyethylimidazoline sulfate (salt), etc.]; sulfonic acid (salt) type amphoterix [pentadecyl sulfotaurine, imidazoline sulfonic acid ( Salt) etc.]; and phosphate ester (salt) type amphoterix etc. [phosphate ester (salt) of glycerin laurate ester etc.].

  Salts of the above anionic and amphoteric surfactants include metal salts such as salts of alkali metals (such as lithium, sodium, potassium), alkaline earth metals (such as calcium, magnesium) and Group IIB metals (such as zinc); Ammonium salts; and amine salts and quaternary ammonium salts.

  Examples of the dispersant (G6) include polymers having Mn of 1,000 to 20,000, for example, vinyl resin ｛polyolefin (polyethylene, polypropylene, etc.), modified polyolefin [polyethylene oxide (polyethylene is oxidized by ozone or the like, and carboxyl group, carbonyl group, And / or a hydroxyl group etc.), and a vinyl resin other than the above polyolefin [polyvinyl halide [polyvinyl chloride, polyvinyl bromide, etc.], polyvinyl acetate, polyvinyl alcohol, polymethyl vinyl ether, poly (meta ) Acrylic acid, poly (meth) acrylate [poly (methyl) acrylate, etc.] and styrene resin [polystyrene, acrylonitrile / styrene (AS) resin, etc.] etc .; polyester resin [polyethylene terephthalate, etc.], polyamide Resins [6,6-nylon, 12-nylon, etc.], polyether resins [polyethersulfone, etc.], polycarbonate resins [polycondensates of bisphenol A and phosgene, etc.], and block copolymers thereof. .

  Examples of the antioxidant (G7) include a hindered phenol compound [pt-amylphenol / formaldehyde resin, nordihydroguaiaretic acid (NDGA), 2,6-di-t-butyl-4-methylphenol (BHT) ), 2-t-butyl-4-methylphenol (BHA), 6-t-butyl-2,4, -methylphenol (24M6B), 2,6-di-t-butylphenol (26B), etc.];

Sulfur-containing compounds [N, N'-diphenylthiourea, dimyristylthiodipropionate, etc.];
Phosphorus-containing compound [2-t-butyl-α- (3-t-butyl-4-hydroxyphenyl) -p-cumenylbis (p-nonylphenyl) phosphite, dioctadecyl-4-hydroxy-3,5-di- t-butylbenzylphosphonate and the like].

  Examples of the ultraviolet absorber (G8) include salicylate compounds [phenyl salicylate etc.]; benzophenone compounds [2,4-dihydroxyzenzophenone etc.]; benzotriazole compounds [2- (2′-hydroxy-5′-methylphenyl) ) -Benzotriazole, etc.].

The total content of (G) in the resin composition is usually 20% or less based on the total weight of the resin composition, and is preferably 0.05 to 10% from the viewpoint of the function of each (G) and the industrial viewpoint. , More preferably 0.1 to 5%.
(G1) is usually 5% or less, preferably 0.1 to 3%; (G2) is usually 8% or less, preferably 1 to 3% based on the total weight of the composition; (G3) is usually 5% or less, preferably 0.1 to 1%; (G4) is usually 8% or less, preferably 1 to 5%; (G5) is usually 8% or less, preferably 1 to 3%; (G6) is usually 1% or less, preferably 0.1 to 0.5%; (G7) is usually 2% or less, preferably 0.05 to 0.5%; (G8) is usually 2% or less, preferably Is 0.05 to 0.5%.

  When the additives are the same and overlap between (G1) to (G8), the amount of each additive exerting the corresponding additive effect is not used as it is, but the effect as another additive is simultaneously used. Considering that it can be obtained, the usage amount is adjusted according to the purpose of use.

The method for producing the resin composition is as follows: (1) The above (K), (D), (E) and / or (F), and if necessary, (G) are mixed at once to obtain a resin composition. Method (collective method);
(2) The whole amount of (K), a part of (D), a part of (E) and / or (F), and if necessary, a part or all of (G) are mixed to obtain a high concentration A master batch resin composition containing (K) is once prepared, and then the remaining (D), (E) and / or (F), and if necessary, the rest of (G) are added and mixed. A method for preparing a composition (master batch method) is included.
The method (2) is preferred from the viewpoint of the mixing efficiency of (K).

The weight ratio [(K) / {(D) + (E) + (F)}] of (K) and [the sum of (D), (E), and (F)] is the weight ratio of the resin composition. From the viewpoints of compatibility and mechanical strength of the molded product, the ratio is preferably 1/99 to 20/80, more preferably 2/98 to 15/85, and particularly preferably 3/97 to 10/90.
The weight ratio [(D) / {(E) + (F)}] of (D) and [the sum of (E) and (F)] is determined from the viewpoint of the balance of mechanical strength of the molded product. From 10/90 to 90/10, more preferably from 15/85 to 85/15, and particularly preferably from 20/80 to 80/20.
When (E) and (F) are used in combination, the weight ratio of (E) to (F) [(E) / (F)] is preferably from the viewpoint of the mechanical strength of the molded product. 40/60 to 60/40.

As a specific mixing method in the method for producing the resin composition, (i) each component to be mixed is, for example, a powder mixer [“Henschel mixer” [trade name “Henschel mixer FM150L / B”, Mitsui Mining ( Co., Ltd.), “Nauter Mixer” [trade name “Nauter Mixer DBX3000RX”, manufactured by Hosokawa Micron Corp.], “Banbury Mixer” [trade name “MIXTRON BB-16MIXER”, manufactured by Kobe Steel Ltd.], etc.] And then kneading the mixture at 120 to 220 ° C. for 2 to 30 minutes using a melt kneading apparatus [batch kneader, continuous kneader (single-axis kneader, biaxial kneader, etc.) or the like].
(Ii) A method in which the components to be mixed are directly kneaded under the same conditions using the same melt-kneading apparatus as described above without previously mixing the powder.
Among these methods, the method (i) is preferable from the viewpoint of mixing efficiency.

[Molded articles and articles]
The molded article of the present invention is a molded article of the resin composition. That is, the resin composition is formed.
Examples of the molding method include injection molding, compression molding, calendar molding, slash molding, rotational molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.) and the like. It can be molded by any method incorporating means such as molding, multilayer molding or foam molding. Examples of the form of the molded product include a plate, a sheet, a film, and a fiber (including a nonwoven fabric).

  Since the compatibilizer (K) of the present invention is formed from the modified polyolefin (X) and the polyoxyalkylene chain-containing compound (Y), a polyolefin resin, a polycarbonate resin and / or a polyester resin And both have excellent affinity. Therefore, a molded article of the resin composition containing the compatibilizer (K) is excellent in compatibility and mechanical strength.

The molded article of the present invention has excellent mechanical strength, good coatability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating the molded article include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, brush coating, and the like.
As the paint, for example, a polyester melamine resin paint, an epoxy melamine resin paint, an acrylic melamine resin paint, paints commonly used for coating plastics such as acrylic urethane resin paints, and even these so-called relatively high-polarity paints, In addition, a low-polarity paint (olefin or the like) can be used.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

Further, as a method of applying the coating on the molded article or the molded article and further printing, any printing method generally used for printing of plastics can be used, for example, gravure printing, flexographic printing, and the like. Examples include printing, screen printing, pad printing, dry offset printing, offset printing, and the like.
As the printing ink, those usually used for printing on plastics, for example, gravure ink, flexo ink, screen ink, pad ink, dry offset ink and offset ink can be used.

Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. Parts in the examples are parts by weight and percentages other than mol% are percentages by weight. In the following, Examples 4 to 6, 10 to 13, 16, and 18 to 19 are Reference Examples 1 to 10, respectively.

[Polyolefin (A)]
Production Example 1
In a reaction vessel, a polyolefin (A0-1) having 98 mol% of propylene and 2 mol% of ethylene as constituent units [trade name “Sun Allomer PZA20A”, manufactured by Sun Allomer Co., Ltd., Mn 100,000, molecules per 1,000 carbon atoms] The number of double bonds at the terminal and / or in the molecular chain is 0, and so on. ] 100 parts were charged under a nitrogen atmosphere, heated and melted by a mantle heater while passing nitrogen through the gas phase, and thermally degraded at 360 ° C for 70 minutes with stirring to obtain a polyolefin (A-1). . In (A-1), the number of double bonds in the molecular terminal and / or in the molecular chain per 1,000 carbon atoms was 6.8, and Mn was 4,000.

Production Examples 2 to 6
Polyolefins (A-2) to (A-6) were obtained in Production Example 1 in the same manner as in Production Example 1, except that thermal degradation was performed according to Table 1. Table 1 shows the results.

[Modified polyolefin (X)]
Production Example 7
A reaction vessel was charged with 100 parts of (A-1), 11 parts of maleic anhydride (B-1), and 100 parts of xylene. After purging with nitrogen, the mixture was heated and heated to 140 ° C. under aeration with nitrogen to uniformly dissolve. . A solution of 2.0 parts of dicumyl peroxide [trade name "Park Mill D", manufactured by NOF Corporation] (C-1) in 10 parts of xylene was added dropwise over 10 minutes, and then refluxed under xylene. Stirring was continued for 3 hours. Thereafter, xylene and unreacted maleic anhydride were distilled off under reduced pressure (1.5 kPa, the same applies hereinafter) to obtain a modified polyolefin (X-1). (X-1) had an acid value of 52 and Mn of 7,000.

Production Examples 8 to 12
Production Example 7 was carried out in the same manner as in Production Example 7 except that the raw materials used were used according to Table 2, to obtain modified polyolefins (X-2) to (X-6). Table 2 shows the results.

[Polyoxyalkylene chain-containing compound (Y)]
Production Example 13
A glass autoclave was charged with 268 parts of oleyl alcohol and 1 part of lithium hydroxide monohydrate, and after purging with nitrogen, the temperature was raised to 110 ° C. Thereafter, 440 parts of EO was dropped at 70 to 90 ° C. and a reaction pressure of 0.2 MPa or less for 24 hours to obtain a polyoxyalkylene chain-containing compound (Y-1). In (Y-1), Mn was 600.

Production Example 14
Production Example 13 was repeated, except that 880 parts of EO was used instead of 440 parts of EO, to obtain a polyoxyalkylene chain-containing compound (Y-2). In (Y-2), Mn was 1,000.

Production Example 15
A polyoxyalkylene chain-containing compound (Y-3) was obtained in the same manner as in Production Example 13 except that 32 parts of methanol was used instead of 268 parts of oleyl alcohol. In (Y-3), Mn was 450.

Production Example 16
In Preparation Example 13, a polyoxyalkylene chain-containing compound (Y-4) was obtained in the same manner as in Preparation Example 13 except that 358 parts of pentacontanol and 580 parts of PO were used instead of 268 parts of oleyl alcohol and 440 parts of EO. . In (Y-4), Mn was 900.

Production Example 17
In Preparation Example 13, a polyoxyalkylene chain-containing compound (Y-5) was obtained in the same manner as in Preparation Example 13, except that 220 parts of EO and 290 parts of PO were used instead of 440 parts of EO. In (Y-5), Mn was 750.

Production Example 18
In Preparation Example 13, a polyoxyalkylene chain compound (Y-6) was obtained in the same manner as in Preparation Example 13, except that EO2200 parts were used instead of EO440 parts. In (Y-6), Mn was 2,400.

Production Example 19
A reaction vessel was charged with 100 parts of (Y-1), 100 parts of toluene, 0.5 part of potassium hydroxide, and 2 parts of water. After dropwise addition for 2 minutes, stirring was continued for 2 hours. Then, after distilling off toluene and unreacted acrylonitrile under reduced pressure (1.5 kPa, the same applies hereinafter), 100 parts of methanol, 2 parts of ammonia and 0.01 part of Raney nickel were charged, and the mixture was heated at 20 ° C. and 1.5 MPa. Hydrogen gas was charged and hydrogenation reaction was performed for 24 hours to obtain a polyoxyalkylene chain-containing compound (Y-7). In (Y-7), Mn was 650.

Production Example 21
Production Example 19 was repeated except that 100 parts of (Y-1) and 10 parts of acrylonitrile were replaced with 100 parts of (Y-3) and 10 parts of acrylonitrile. Compound (Y-8) was obtained. In (Y-8), Mn was 500.

Production Example 22
Production Example 19 was repeated except that 100 parts of (Y-1) and 6 parts of acrylonitrile were used instead of 100 parts of (Y-1) and 8 parts of acrylonitrile. Compound (Y-9) was obtained. In (Y-9), Mn was 950.

Production Example 23
Production Example 19 was repeated, except that 100 parts of (Y-5) and 7 parts of acrylonitrile were used instead of 100 parts of (Y-1) and 8 parts of acrylonitrile. Compound (Y-10) was obtained. In (Y-10), Mn was 800.

Production Example 24
Production Example 19 was repeated, except that 100 parts of (Y-6) and 2 parts of acrylonitrile were used instead of 100 parts of (Y-1) and 8 parts of acrylonitrile. Compound (Y-11) was obtained. In (Y-11), Mn was 2,450.

Production Example 25
In Preparation Example 13, a polyoxyalkylene chain-containing compound (Y-12) was obtained in the same manner as in Preparation Example 13, except that 220 parts of nonylphenol was used instead of 268 parts of oleyl alcohol. In (Y-12), Mn was 550.

Production Example 26
A polyoxyalkylene chain-containing compound (Y-13) was obtained in the same manner as in Production Example 13 except that 268 parts of oleyl alcohol was replaced with 58 parts of isopropenyl alcohol. In (Y-13), Mn was 400.

Production Example 27
In Preparation Example 13, a polyoxyalkylene chain-containing compound (Y-14) was obtained in the same manner as in Preparation Example 13, except that 45 parts of dimethylamine was used instead of 268 parts of oleyl alcohol. In (Y-14), Mn was 400.

Production Example 28
A reaction vessel was charged with 100 parts of (Y-1) and 35 parts of 12-aminododecanoic acid, and after a nitrogen substitution, subjected to a dehydration condensation reaction at 200 ° C. for 3 hours under reduced pressure to give a polyoxyalkylene chain-containing compound (Y-15). I got In (Y-15), Mn was 850.

Production Example 29
A reaction vessel was charged with 100 parts of (Y-1) and 28 parts of hexamethylene diisocyanate. After the replacement with nitrogen, the mixture was heated to 70 ° C. under nitrogen aeration and reacted with stirring for 6 hours to give a polyoxyalkylene chain-containing compound (Y- 16) was obtained. In (Y-16), Mn was 800.

Production Example 30
100 parts of (Y-1) and 50 parts of a 50 wt% aqueous sodium hydroxide solution were charged into a reaction vessel, and after purging with nitrogen, the temperature was adjusted to 25 ° C. under nitrogen aeration, and 17 parts of epichlorohydrin was added dropwise for 3 hours. Stirring was performed for hours. Thereafter, extraction was performed using 1,000 parts of toluene, and toluene was distilled off under reduced pressure to obtain a polyoxyalkylene chain-containing compound (Y-17). In (Y-17), Mn was 660.

Production Example 31
In Preparation Example 13, a polyoxyalkylene chain-containing compound (Y-18) was obtained in the same manner as in Preparation Example 13, except that EO6600 parts were used instead of EO440 parts. In (Y-18), Mn was 6,500.

[Compatibilizer for resin (K)]
Example 1
A reaction vessel was charged with 100 parts of (X-1) and 90 parts of (Y-1), and after purging with nitrogen, heated and heated to 180 ° C. under nitrogen aeration to dissolve uniformly, and then reduced pressure (1.5 kPa). The reaction was carried out for 5 hours while distilling off the generated water to obtain a compatibilizing agent for resin (K-1) containing the polyoxyalkylene-modified polyolefin (Z-1). In (Z-1), Mn was 17,000.

Examples 2 to 20
Example 1 was repeated in the same manner as in Example 1 except that the raw materials used were used according to Table 3, to obtain compatibilizing agents for resins (K-2) to (K-20). Table 3 shows the results.

Comparative Example 1
Using the modified polyolefin (X-1) as it was, a resin modifier (ratio K-1) was obtained.

Comparative Example 2
Using the polyoxyalkylene chain-containing compound (Y-1) as it was, a resin modifier (ratio K-2) was obtained. Table 3 shows the results of Comparative Examples 1 and 2.

[Resin composition, molded article]
Examples 21 to 55, Comparative examples 3 to 17
Resin compatibilizers (K-1) to (K-19), (comparison K-1) to (comparison K-2), commercially available polypropylene (D-1) [trade name "Sun Allomer PL500A", Sun Allomer Co., Ltd. ), A commercially available polyethylene (D-2) [trade name “Novatech HJ490”, manufactured by Nippon Polyethylene Co., Ltd., Mn 300,000] and a commercially available ethylene / propylene copolymer (D-3) [trade name “Sun Allomer” PB222A ", manufactured by Sun Allomer Co., Ltd., Mn350,000], commercially available polycarbonate (E-1) [trade name" Panlite L-1250Y ", manufactured by Teijin Chemicals Ltd.], (E-2) [trade name" Iupilon S2000 ", manufactured by Mitsubishi Engineering-Plastics Co., Ltd.], a commercially available polyester resin (F-1) [trade name" Viropet EMC405A ", manufactured by Toyobo Co., Ltd.], (F-2) After blending [trade name “Duranex 2002”, manufactured by Polyplastics Co., Ltd.] with a Henschel mixer for 3 minutes according to the composition (parts) in Tables 4 and 5, respectively, and then biaxially extruding with a vent. The mixture was melt-kneaded at 280 ° C., 100 rpm and a residence time of 5 minutes to obtain a resin composition.
Each resin composition was molded at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. using an injection molding machine [trade name “PS40E5ASE”, Nissei Plastic Industry Co., Ltd.] to prepare a predetermined test piece, and then evaluated as described below. It was evaluated according to the method. The results are shown in Tables 4 and 5.

<Evaluation method>
1. Mechanical strength 1-1. Impact strength (unit: J / m)
Izod impact values were measured according to ASTM D256.
1-2. Flexural modulus (unit: MPa)
The measurement was performed according to ASTM D790.
2. Compatibility The test piece after the impact strength evaluation was cut under a condition of −100 ° C. using an ultramicrotome [model number “EMFC6”, manufactured by LEICA Co., Ltd.] with a glass cutter and a diamond cutter to form a mirror surface, and then a scanning type Observation was performed with an electron microscope [model number “S4800”, manufactured by Hitachi, Ltd.] in a range of 20 μm × 25 μm, and the number average dispersed particle size (unit: μm) of the dispersed resin particles in the matrix resin was measured to determine the compatibility. evaluated. The number average dispersed particle size is a number average value in a range of 20 μm × 25 μm. The smaller the number average dispersed particle size, the better the compatibility of the resin composition.

  From the results in Tables 4 and 5, the compatibilizer (K) for resin of the present invention has a wide weight ratio of the polyolefin resin and the polycarbonate resin (E) and / or the polyester resin (F) as compared with the comparative one. It can be seen that compatibilization is possible. Further, it is clear that the molded article obtained by molding the resin composition of the present invention has better mechanical strength than the comparative one.

  The resin compatibilizer (K) of the present invention can compatibilize the polyolefin resin (D) with the polycarbonate resin (E) and / or the polyester resin (F) in a wide weight ratio. In addition, molded articles obtained by molding the resin composition of the present invention have excellent mechanical strength, so they can be used in a wide range of fields such as electric / electronic devices, packaging materials, transport materials, living materials, and building materials. It can be suitably applied.

Claims (11)

A polyolefin (A) having 0.1 to 20 double bonds per 1,000 carbon atoms and being an ethylene / propylene copolymer [weight ratio: 0.5 / 99.5 to 30/70]; Reactivity with a modified polyolefin (X) having an unsaturated dicarboxylic acid (anhydride) (B) as a constituent unit and at least one kind selected from the group consisting of a hydroxyl group, an amino group and an epoxy group A compatibilizer (K) for a resin comprising a polyoxyalkylene-modified polyolefin (Z) formed from a polyoxyalkylene chain-containing compound (Y) having one functional group. The resin compatibilizer according to claim 1 , wherein (A) is a thermally degraded polyolefin (A0) having a number average molecular weight of 30,000 to 400,000. The polyolefin resin modifier according to claim 1 or 2, wherein Mn (number average molecular weight) of (Z) is 3,000 to 100,000. 4. The method according to claim 1, wherein (X) and (Y) are bonded via at least one bond selected from the group consisting of an ester bond, an imide bond, an amide bond, and an epoxy ring-opening bond . The compatibilizer for a resin according to the above . The compatibilizing agent for a resin according to any one of claims 1 to 4, wherein a weight ratio [(X) / (Y)] between (X) and (Y) is 30/70 to 99/1. The compatibilizer for resins according to any one of claims 1 to 5, wherein the polyoxyalkylene unit content in (Z) is 0.1 to 60% by weight. The resin compatibilizer according to any one of claims 1 to 6, wherein (Y) is an alkylene oxide adduct of a compound having one active hydrogen. The compatibilizer for resins according to claim 7 , wherein the number of moles of the alkylene oxide added to (Y) is 3 to 18. A resin composition comprising the resin compatibilizer (K) according to any one of claims 1 to 8 , a polyolefin resin (D), and a polycarbonate resin (E) and / or a polyester resin (F). The weight ratio of (K) and [the sum of (D), (E), and (F)] [(K) / {(D) + (E) + (F)}] is 1/99 to The resin composition according to claim 9, which is 20/80. A molded article which is a molded article of the resin composition according to claim 9 .