JP5089031B2 - Process for producing modified polyolefin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a modified polyolefin constituting a coatability modifier for improving coatability (adhesion of coated film, etc.) of a resin without reducing the mechanical properties of a resin by the addition of a small amount because the coatability modifier having a coatability-improving effects of the resin without reducing the resin properties of the resin by the addition of the small amount is not known, although a method for kneading a large amount of a modified polyolefin having a polar functional group grafted on the polyolefin with a polypropylene for improving the coatability (adhesion of the coated film, etc.) of the polypropylene has been known; and to provide a thermoplastic resin composition containing the coatability improver in the thermoplastic resin. <P>SOLUTION: The method for producing the modified polyolefin comprises reacting (a) a 6-30C olefin polymer with (b) a hydroxy group-containing unsaturated monomer in the presence or absence of (c) a radical initiator. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

The present invention relates to a method for producing a modified polyolefin. More specifically, the present invention relates to a method for producing a hydroxyl group-containing modified polyolefin having excellent properties for improving the adhesion of a coating film to a resin such as polyolefin.

Polypropylene is widely used as an injection molding material in the industrial parts field represented by automobile interior and exterior parts and home appliance parts. However, since polypropylene is nonpolar, it is usually inferior in paintability (here, paintability includes printability; the same shall apply hereinafter) and a paint film (here, the paint film includes a print film). (The same shall apply hereinafter.) For this reason, the primer is apply | coated to the surface of a polypropylene and the device which makes a coating film contact | adhere is made | formed. However, since the primer is expensive and the number of painting steps increases, there is a drawback that the painting cost is increased. For this reason, attempts have been made to reduce the coating cost by providing the coating film adhesion to polypropylene, omitting the primer coating step. For example, a method is known in which a modified polyolefin obtained by grafting a polar functional group to a polyolefin is kneaded into polypropylene as a coating property improving agent, and a coating film is adhered without applying a primer (for example, Patent Documents 1 to 3). reference).
Japanese Patent Laid-Open No. 62-257946 Japanese Patent Laid-Open No. 5-039383 Japanese Patent Laid-Open No. 9-048885

However, in these methods, a large amount of modified polyolefin has to be added in order to adhere the coating film, and this has the disadvantage that mechanical properties such as impact strength are greatly reduced.
The object of the present invention is to produce a modified polyolefin constituting a coating property improver that improves the coating properties (coating adhesion, etc.) of a resin without reducing the mechanical properties of the resin with a small amount of addition, and the coating properties An object of the present invention is to provide a thermoplastic resin composition in which an improving agent is contained in a thermoplastic resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention is characterized in that the olefin polymer having 6 to 30 carbon atoms (a) and the hydroxyl group-containing unsaturated monomer (b) are reacted in the presence or absence of the radical initiator (c). A method for producing a modified polyolefin, wherein a reaction product or copolymer comprising an olefin multimer (a) having 6 to 30 carbon atoms and an unsaturated polycarboxylic acid (d) is reacted with a functional group derived from (d). A method for producing a modified polyolefin, comprising reacting the reactant or the copolymer with a compound (e) for introducing a hydroxyl group; a coating property improver (A) comprising the modified polyolefin; A thermoplastic resin composition contained in the plastic resin (B); and a molded article formed by molding the composition.

The production method of the first embodiment (first invention) of the modified polyolefin production method of the present invention will be described.
The production method of the first embodiment of the production method of the modified polyolefin of the present invention comprises an olefin multimer (a) having 6 to 30 carbon atoms (hereinafter abbreviated as C) and a hydroxyl group-containing unsaturated monomer (b). Is reacted in the presence or absence of the radical initiator (c).
If (a) C is less than 6, the mechanical properties of the molded product described later deteriorate, and if it exceeds 30, the paintability of the molded product deteriorates. C in the “C6-30 olefin multimer (a)” refers to the carbon number of the multimer, not the carbon number of the monomer constituting (a).
(A) includes a multimer (a1) composed of propylene, a multimer (a2) composed of an olefin other than propylene, and a mixture thereof. Among these, preferred from the viewpoint of mechanical properties of the molded product are (a1) and a mixture of (a1) and (a2).

(A1) includes propylene multimers and mixed multimers of propylene and other olefins.
Examples of the propylene multimer include propylene dimer to 10-mer. Among these, 3 to 7-mer is preferable from the viewpoint of mechanical properties and paintability of the molded product. These propylene multimers include all isomers having different double bond positions.

Other olefins constituting the mixed multimer of propylene and other olefins include C2 or C4 to 27 (preferably C2 or C4 to 25, particularly C2 or C4 to 20) olefins such as ethylene, 1-2, -And isobutene, 1-hexene, 1-decene, 1-dodecene, 1-pentadecene.
Specific examples of mixed multimers of propylene and other olefins include multimers of propylene and ethylene (2-ethyl-4-methyl-1-pentene, 2,4-dimethyl-1-hexene, 2-methyl- 1-heptene, etc.), multimers of propylene and 1-butene (4-ethyl-2-methyl-1-heptene, 4-ethyl-6-methyl-2-heptene, 2-ethyl-4-methyl-1- Octene, 5,7-dimethyl-3-nonene, etc.), multimers of propylene and 1-pentene (2-methyl-4-propyl-1-heptene, 6-methyl-4-ethyl-2-heptene, 4- Methyl-2-propyl-1-nonene, 6,8-dimethyl-4-nonene, etc.).

Examples of the olefin constituting the multimer (a2) composed of olefins other than propylene include the same as the other olefins described above, and (a2) includes ethylene multimers (hexene-1, hexene-2, octene-1, Decene-1, dodecene-1), multimers of ethylene and butene-1 (eg, 3-ethyl-5-methyl-1-heptene, 3-ethyl-5-methyl-2-heptene, 2-ethyl-1- Octene, 3-methyl-2-nonene) and the like. Of these, ethylene multimers are preferred.

The hydroxyl group-containing unsaturated monomer (b) includes a hydroxyl group-containing unsaturated poly (divalent to tetravalent or higher) carboxylic acid derivative (ester, amide, imide, etc.) (b1), a hydroxyl group-containing unsaturated ether (b2). ), A hydroxyl group-containing unsaturated monocarboxylic acid ester (b3), and an unsaturated alcohol (b4). The number of hydroxyl groups per molecule of (b) is preferably from 1 to 12, more preferably from 1 to 6, particularly preferably 1 from the viewpoint of the paintability of the molded product described later and the compatibility with the polyolefin resin described later. ~ 4.

(B1) is C2 or more and a number average molecular weight [hereinafter abbreviated as Mn. Examples of the measurement include those having a gel permeation chromatography (GPC) method of 2,000 or less, such as a hydroxyl group-containing dicarboxylic acid derivative [for example, aliphatic [C4-30, for example, a dicarboxylic acid ester (hydroxyethyl maleate, maleate). Acid glycerin mono- and diesters, trimethylolpropane maleate mono- and diesters, pentaerythritol maleate monoester, sorbitol monoester maleate, sucrose monoester maleate, hydroxyethyl fumarate, hydroxyethyl itaconate, hydroxy mesaconate Ethyl, hydroxyethyl citraconic acid, etc.), dicarboxylic acid amides (N-hydroxy- and N, N′-dihydroxyethylmaleamide, N-hydroxy- and N, N′-dihi Roxyethyl fumaramide, N-hydroxy- and N, N′-dihydroxyethyl itaconamide, N-hydroxy- and N, N′-dihydroxyethyl mesaconamide, N-hydroxy- and N, N′-dihydroxyethyl citraconic amide ), Dicarboxylic acid imides (N-hydroxyethylmaleimide, N-hydroxypropylmaleimide, N-hydroxyethylitaconimide, etc.)] and alicyclic [C8-30, such as dicarboxylic acid esters (hydroxyethyl cyclohexenedicarboxylate, cycloheptidyl). Dicarboxylic acid amides), dicarboxylic acid amides (N-hydroxy- and N, N′-dihydroxyethylcyclohexene dicarboxylic acid amides, N-hydroxy- and N, N′-dihydroxyethylcyclohexanes). Dicarboxylic acid amides), dicarboxylic acid imides (N-hydroxyethyl and N-hydroxypropylcyclohexene dicarboxylic acid imides, N-hydroxyethyl and N-hydroxypropylcycloheptene dicarboxylic acid imides, etc.)]]; hydroxyl group-containing poly (3 Valent to tetravalent or higher) carboxylic acid derivatives [eg aliphatic (C5-24, eg hydroxyethyl aconitate, N-hydroxy-, N, N′-dihydroxy- and N, N ′, N ″ -trihydroxy Ethyl aconitic acid amide, N-hydroxyethyl- and N-hydroxypropyl aconitic acid imide)] and ethylene oxide (hereinafter abbreviated as EO) and / or propylene oxide (hereinafter abbreviated as PO) adducts and the like. Of these, a hydroxyl group-containing dicarboxylic acid derivative is preferred.

Examples of the hydroxyl group-containing unsaturated ether (b2) include C2 or more and Mn2,000 or less, such as hydroxyalkyl (C1-6) vinyl ether [eg aliphatic (C3-30, eg hydroxymethyl vinyl ether, hydroxy Ethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether), and cycloaliphatic (C5-30, eg hydroxycyclohexyl vinyl ether)], hydroxyalkyl (C1-6) allyl ether [eg aliphatic (C4-30, eg hydroxymethylallyl) Ethers, hydroxyethyl allyl ether, hydroxypropyl allyl ether, hydroxybutyl allyl ether, ethylene glycol monoallyl ether), and alicyclic (C7-30, for example Mud carboxymethyl cyclohexyl allyl ether) and their EO and / or PO adducts.

Examples of the hydroxyl group-containing unsaturated monocarboxylic acid ester (b3) include C3 or more and Mn 2,000 or less, such as hydroxycarbyl (C2-30) acrylate [eg aliphatic (C5-30, eg hydroxy Ethyl acrylate, hydroxybutyl acrylate, glycerin monoacrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, dipentaerythritol monoacrylate, sorbitol monoacrylate, sucrose monoacrylate), and alicyclic (C7-30, for example hydroxycyclohexyl) Acrylate)], hydroxycarbyl (C2-30) methacrylate [eg aliphatic (C6-30, eg hydroxyethyl methacrylate, hydroxybuty Methacrylate), and alicyclic (C8-30, e.g. hydroxycyclohexyl methacrylate)] and their EO and / or PO adducts.
As unsaturated alcohol (b4), C2 or more and Mn2,000 or less are mentioned, For example, vinyl alcohol, allyl alcohol, these EO and / or PO adducts, etc. are mentioned.

Of these, (b1) and (b4) are preferred from the viewpoint of paintability, and (b1) is more preferred.

In the production method of the modified polyolefin of the present invention, the ratio of (a) based on the total weight of (a) and (b) is preferably 20%, more preferably 25%, particularly preferably from the viewpoint of the mechanical properties of the molded product. The upper limit is preferably 80%, more preferably 75%, particularly preferably 70% from the viewpoint of paintability.

Examples of the radical initiator (c) include azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, 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, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxyhexahydroterephthalate, diallylperoxydicarbonate, t-butylperoxy Allyl carbonate etc.]] and the like.
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 lower limit of the amount of (c) used is preferably 0.001% based on the total weight of (a) and (b), from the viewpoints of the reaction rates of (a) and (b) and the coating properties described later. Is 0.01%, particularly preferably 0.1%, and the upper limit is preferably 30%, more preferably 20%, particularly preferably 15% from the viewpoint of paintability.

The modified polyolefin in the first embodiment of the present invention is obtained by reacting an olefin multimer (a) with a hydroxyl group-containing unsaturated monomer (b) in the presence or absence of a radical initiator (c). Can be manufactured.
As a specific method for producing the modified polyolefin, (a) and (b) are heated and melted, or an appropriate organic solvent [C3-18, such as hydrocarbon (hexane, heptane, octane, decane, dodecane, benzene, toluene). , Xylene, etc.), halogenated hydrocarbons (di-, 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.)] or the like, and if necessary, (c) a chain transfer agent and / or a polymerization inhibitor described later [or A solution prepared by dissolving these in a suitable organic solvent] Ri method of the modified polyolefin [or the modified polyolefin in a suitable organic solvent solution obtained by dissolving (as defined above)] was stirred and heated adding reaction. Hereinafter, cases where (a) and (b) are heated and melted, suspended in an organic solvent, and dissolved in an organic solvent are abbreviated as a melting method, a suspension method, and a solution method, respectively.

Among these methods, the melting method and the solution method are preferable from the viewpoints of the reactivity between (a) and (b) and the coating properties described later.

The reaction temperature in the melting method may be a temperature at which (a) and (b) melt, and is preferably 60 to 60 from the viewpoint of the reactivity between (a) and (b) and the decomposition temperature of the modified polyolefin produced. It is 260 degreeC, More preferably, it is 100-240 degreeC.

The reaction temperature in the solution method may be a temperature at which (a) and (b) are dissolved in a solvent, and is preferable from the viewpoint of the reactivity between (a) and (b) and the decomposition temperature of the modified polyolefin to be produced. Is 50 to 220 ° C, more preferably 60 to 210 ° C, particularly preferably 80 to 180 ° C.

Examples of the chain transfer agent include hydrocarbons [C6-24, such as aromatic hydrocarbons (eg, toluene, xylene, ethylbenzene, isopropylbenzene, etc.)]; halogenated hydrocarbons (C1-24, eg, dichloromethane, chloroform, tetrachloride). Carbon, dichloroethane, tetrachloroethane, dibromomethane, tribromomethane, carbon tetrabromide, benzyl chloride, benzyl bromide, etc.); alcohol (C1-24, such as methanol, ethanol, 1-propanol, 2-methyl-2-propanol) Thiol (C1-24, such as ethylthiol, propylthiol, 1- and 2-butylthiol, 1- and 2-pentylthiol, 1-octylthiol, 1-butanol, 2-butanol, allyl alcohol, etc.) Dodecyl thiol etc.); Tons (C3-24, such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, ethyl butyl ketone, etc.); aldehydes (C 2-18, such as 2-methyl-2-propyl aldehyde, 1- and 2-butyl) Aldehyde, 1-pentylaldehyde, 1-hexylaldehyde, 1-octylaldehyde, etc.); phenol (C6-36, such as phenol, m-cresol, p-cresol, o-cresol, etc.); quinone (C6-24, such as hydroquinone) Amines (C3-24, such as diethylmethylamine, triethylamine, tri-1-butylamine, diphenylamine, etc.); disulfides (C2-24, such as diethyl disulfide, di-1-propyl disulfide, di-2-methyl-2) Propyl disulfide, di-1-butyl disulfide, ethyl-1-propyl disulfide, di-1-octyl disulfide, etc.).
The amount of the chain transfer agent used is usually 20% or less based on the total weight of (a) and (b), preferably from the viewpoint of the reactivity between (a) and (b) and the paintability of the molded product described later. 0 to 10%.

Examples of the polymerization inhibitor include inorganic [for example, oxygen, sulfur, metal salts (for example, ferric chloride) and the like] and organic [catechol (C6-36, for example, 2-methyl-2-propylcatechol), quinone (C6). -24, such as p-benzoquinone, duroquinone, etc.), hydrazine (C2-36, such as 1,1-diphenyl-2-picrylhydrazine, etc.), ferdazine (C5-36, such as 1,3,5-triphenyl ferrazine) ), Nitro compounds (C3-24, such as nitrobenzene), stable radicals [C5-36, such as 1,1-diphenyl-2-picrylhydrazyl (DPPH), 2,2,6,6-tetramethyl- 1-piperidinyloxy (TEMPO), 1,3,5-triphenylferdazyl etc.]].
The amount of the polymerization inhibitor used is usually 2% or less based on the total weight of (a) and (b), preferably from the viewpoint of the reactivity between (a) and (b) and the paintability of the molded product described later. 0 to 0.5%.

The Mn of the modified polyolefin obtained by the production method of the first embodiment of the present invention is 200 to 50,000, preferably 250 to 30,000, from the viewpoints of mechanical properties and paintability of the molded product described later.
In addition, Mn of the modified polyolefin of the present invention is a value measured by a GPC method using high temperature GPC [manufactured by Waters Co., Ltd., column: PLgel MIX ED-B, manufactured by Polymer Laboratories Co., Ltd.].

The hydroxyl value of the modified polyolefin is 20 to 600, preferably 50 to 550, from the viewpoints of paintability and mechanical properties of the molded product. In the present specification, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of a sample, and is measured by acetylating the sample with acetic anhydride and titrating with an indicator (phenolphthalein). Is done.

The heat softening point of the modified polyolefin is 40 to 170 ° C., preferably 50 to 160 ° C., from the viewpoint of mechanical properties and paintability of the molded product. In the present specification, the thermal softening point is a value measured by an automatic softening point tester [manufactured by Meitec Co., Ltd.].

The modified polyolefin has different bonding modes as follows depending on conditions such as the type of the hydroxyl group-containing unsaturated monomer (b) in the absence or presence of the radical initiator (c) in the above production method.
(I-1) In the absence of the reaction initiator (c) in the absence of the radical initiator (c), a modified polyolefin having the following bonding mode [1] and / or [2] is obtained.
[1] Regardless of the type of the modified polyolefin (b) of the (a)-(b) type, for example, the (a)-(b) modified polyolefin is obtained according to the following general formula (1).

[2] [(a)-(b)] When the m-type alternating copolymerization modified polyolefin (b) is the above (b2) to (b3), for example, according to the following general formula (2) [(a)-( b)] m-type alternating copolymerization modified polyolefin is obtained.

(I-2) In the presence of the reaction (c) in the presence of the radical initiator (c), regardless of the type of (b), for example, according to the following general formula (3) [(a)-(b)] _{An n-} type alternating copolymerization modified polyolefin is obtained.

[In the formulas (1) to (3), R ^{1 to} R ⁴ are olefin multimer residues, R ⁵ is H or a methyl group, Z ¹ is H, an organic group containing an ester group or an amide group, Z ² is Represents an organic group including an ether group, an ester group or an amide group, and when Z ¹ and Z ² have a carbonyl group, they may be bonded to each other via an N atom to form an imide group having an OH group; I is a radical initiator residue or H; p and q are integers of 0 to 12 that are not 0 simultaneously, and m and n are integers of 1 to 300. ]

The production method of the second embodiment (second invention) among the production methods of the modified polyolefin of the present invention will be described.
The production method of the second embodiment of the production method of the modified polyolefin of the present invention is a reaction product or copolymer comprising an olefin multimer (a) having 6 to 30 carbon atoms and an unsaturated polycarboxylic acid (d), The compound (e) which reacts with the functional group derived from (d) and introduces a hydroxyl group into the reaction product or the copolymer is reacted.

As (a), the same thing as 1st this invention can be used.
(D) includes unsaturated poly (divalent to tetravalent or higher) carboxylic acids and anhydrides such as dicarboxylic acids [aliphatic (C4-24, such as maleic acid, fumaric acid, itaconic acid, Citraconic acid, mesaconic acid, etc.), alicyclic (C8-24, such as cyclohexene dicarboxylic acid, cycloheptene dicarboxylic acid, etc.)]; trivalent to tetravalent or higher polycarboxylic acids [aliphatic polycarboxylic acids (C5 To 24, such as aconitic acid)] and their anhydrides. Of these (d), from the viewpoint of paintability, unsaturated dicarboxylic acid and its anhydride are preferred, and maleic anhydride is more preferred.

The molar ratio (a) / (d) [(a) / (d)] is preferably 80/20 to 20/80, more preferably 75/25, from the viewpoints of paintability and mechanical properties of the molded product. 25/75, particularly preferably 70/30 to 30/70.

(E) includes a functional group that reacts with the functional group derived from (d) (carboxyl group and / or acid anhydride group), such as a hydroxyl group, an amino group or an epoxy group, and the functional group of (d) The compound which introduce | transduces a hydroxyl group in a reaction material or a copolymer by reacting is mentioned.
(E) includes the following (e1) polyhydric alcohol, (e2) hydroxylamine and (e3) epoxide. Of these, (e2) is preferred from the viewpoint of the reactivity between the functional group (d) and (e) and the absence of by-products.

(E1) Polyhydric alcohol diol (C2-50, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, neopentyl Glycols, etc.); triols (C3-75, such as glycerin, trimethylolpropane, etc.); tetrahydric to octahydric or higher polyhydric alcohols (C5-100, such as pentaerythritol, sorbitan, diglycerin, α-methylglucoside, Sorbitol, xylit, mannitol, dipentaerythritol, glucose, fructose, sucrose, etc.); and their alkylene oxides (hereinafter abbreviated as AO, C2-4) (molecular weight 106 or more and Mn 1,000 or less).

(E2) Hydroxylamine Hydroxylamine represented by the following general formula is included.
HO—R ⁷ —NHR ⁶
In the general formula, R ⁶ is H or a C 1-20 hydrocarbon group (preferably H or a C 1-15 hydrocarbon group, more preferably H or a C 1-5 hydrocarbon group), and R ⁷ is a C 2-20 group. It represents a divalent hydrocarbon group, and R ⁶ and R ⁷ may be substituted with a hydroxyl group and / or an amino group.
Specific examples of (e2) include primary amino alcohols (C2-20, such as monoethanolamine, monopropanolamine, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3 -Propanediol, 2-amino-2-ethyl-1,3-propanediol, cyclohexanolamine, etc.), secondary amino alcohol (C3-20, such as 2-methylaminoethanol, 2-ethylaminoethanol, diethanolamine, 3-methylamino-1,2-propanediol, N-methylcyclohexanolamine, etc.). Of these, primary amino alcohols are preferred.

(E3) Epoxides The following aliphatic, alicyclic, heterocyclic ring-containing and aromatic ring-containing epoxides can be mentioned.
(E3-1) Aliphatic Epoxides As aliphatic monoepoxides, monovalent aliphatic alcohols (C1-20, such as methanol, ethanol, 2-ethylhexyl alcohol, etc.) or polyvalent (divalent to octavalent or higher) fats Monoglycidyl ethers of aliphatic alcohols, monoglycidyl esters of monovalent fatty acids, and the like.
Examples of aliphatic polyepoxides include polyglycidyl ethers of polyvalent (divalent to octavalent or higher) aliphatic alcohols, polyglycidyl esters of polyvalent (divalent to trivalent or higher) fatty acids, and glycidyl (meth) acrylates. Examples include (co) polymers.
Examples of the polyhydric aliphatic alcohol include the same as the above (e1), and examples of the polyhydric fatty acid include dicarboxylic acids (C2-15, such as oxalic acid, malonic acid, maleic acid, succinic acid, itaconic acid, and adipic acid. , Suberic acid, dodecanedioic acid, etc.), trivalent or higher polyvalent fatty acids (C6-20, such as tricarballylic acid) and the like.

(E3-2) Alicyclic epoxides Examples of alicyclic epoxides include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, and ethylene glycol bisepoxy dicyclopentyl ether. 3,4-epoxy-6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, containing an aromatic ring described later Examples thereof include a nuclear hydrogenated product of polyepoxide.

(E3-3) Heterocycle-containing epoxide Examples of the heterocycle-containing epoxide include trisglycidylmelamine.

(E3-4) Aromatic ring-containing epoxides As aromatic ring-containing epoxides, glycidyl ethers of polyvalent (divalent to tetravalent or higher) phenols, such as glycidyl ethers of divalent phenols (for example, bisphenol F, -A, -B, -AD and -S diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, bisphenol A 2 mol and epichlorohydrin 3 mol A diglycidyl ether obtained by the above reaction); a glycidyl ether of a trihydric phenol (eg, pyrogallol triglycidyl ether); a glycidyl ether of a tetrahydric or higher polyphenol (For example, glycidyl ether of phenol- or cresol novolac resin, polyglycidyl ether of polyphenol obtained by condensation reaction of phenol and glycoxal, glutaraldehyde or formaldehyde, polyglycidyl ether of polyphenol obtained by condensation reaction of resorcin and acetone, etc. ) And the like.

The equivalent ratio [(d) / (e)] of the carboxyl group derived from (d) in the copolymer and (e) is preferably 0.8 / 1 to from the viewpoint of paintability and mechanical properties of the molded product. 1 / 0.8, more preferably 0.9 / 1 to 1 / 0.9, the equivalent ratio of the acid anhydride group derived from (d) in the copolymer and (e) is preferably from the same viewpoint. 0.4 / 1 to 1 / 0.8, more preferably 0.45 / 1 to 1 / 0.9.

The modified polyolefin in the second embodiment of the present invention comprises a reactant or copolymer comprising an olefin multimer (a) having 6 to 30 carbon atoms and an unsaturated polycarboxylic acid (d), and a function derived from (d). It is produced by reacting a compound (e) that reacts with a group to introduce a hydroxyl group into the copolymer. As a specific method for producing the modified polyolefin, (a) and (d) are heated and melted as in the first embodiment, or suspended in an appropriate organic solvent (the same as described above). If necessary, add (c) the chain transfer agent and / or polymerization inhibitor [or a solution obtained by dissolving these in an appropriate organic solvent] and heat and stir to obtain a reaction product or copolymer. Thereafter, (e) is melted or suspended or dissolved in an appropriate organic solvent, added to the copolymer, and heated and stirred (melting method, suspension method and solution method). The same chain transfer agent and polymerization inhibitor as described above can be used.

Of these methods, the melting method is preferred from the viewpoints of the reactivity between (a) and (d), the reactivity between the copolymer comprising (a) and (d) and (e), and the coating properties described below. And solution method. The reaction temperature in the melting method may be a temperature at which (a), (d), and (e) are melted, and the reactivity of (a) and (d), and the combination of (a) and (d). From the viewpoint of the reactivity between the polymer and (e) and the decomposition temperature of the modified polyolefin produced, the temperature is preferably 60 to 260 ° C, more preferably 100 to 240 ° C.
The reaction temperature in the solution method may be any temperature at which (a), (d), and (e) are dissolved in the solvent, and the reactivity between (a) and (d), from (a) and (d) From the viewpoint of the reactivity between the copolymer obtained and (e) and the decomposition temperature of the resulting modified polyolefin, it is preferably 50 to 220 ° C, more preferably 60 to 210 ° C, and particularly preferably 80 to 180 ° C.

The Mn, hydroxyl value and thermal softening point of the modified polyolefin obtained by the production method of the second embodiment of the present invention are the same as those of the modified polyolefin obtained by the production method of the first embodiment. It is the same.

As in the first embodiment, the modified polyolefin has different bonding modes as follows depending on the conditions in the absence or presence of the radical initiator (c).
(II-1) Reaction in the absence of radical initiator (c) [1] In the absence of modified polyolefin (c) of type (a)-(b) (a)- After (d) type-modified polyolefin is obtained, for example, when hydroxylamine (e2) is used as (e), (a)-(b) type modified polyolefin is obtained according to the following general formula (5).

(II-2) In the presence of the reaction (c) in the presence of the radical initiator (c), an [(a)-(d)] n-type alternating copolymerization modified polyolefin is obtained according to the following general formula (6). Then, for example, when hydroxylamine (e2) is used as (e), an [(a)-(b)] n-type alternating copolymerized modified polyolefin is obtained according to the following general formula (7).

[In the formulas (4) to (7), R ^{1 to} R ⁷ , I and n are the same as above. The two carboxyl groups in the (d), (a)-(d) type and [(a)-(d)] n type may combine to form an anhydride group, in which case (e2) and An imide group may be formed by this reaction. ]

Next, the modified polyolefin according to the third aspect of the present invention will be described.
The modified polyolefin comprises a C6-30 olefin multimer (a) and a hydroxyl group-containing unsaturated monomer (b) as structural units, a hydroxyl value of 20 to 600, Mn of 200 to 50,000, and 40 to 170. It has a thermal softening point of ° C. Here, (a) and (b) are the same as described above.
The modified polyolefin can be produced, for example, according to the method for producing a modified polyolefin according to the first embodiment of the present invention and the method for producing a modified polyolefin according to the second embodiment of the present invention.

The modified polyolefin includes those having the bonding mode represented by (I-1), (I-2) and (II-1), (II-2).

The characteristic values (for example, hydroxyl value, Mn and thermal softening point) of the modified polyolefin of the present invention and preferred ranges thereof, and the form when used as a coating property improving agent are the production methods according to the first and second embodiments. In the following, the modified polyolefin refers to both the modified polyolefin obtained by the production method according to the first and second embodiments and the modified polyolefin according to the third aspect of the present invention. .

The coating property improving agent (A) of the fourth aspect of the present invention is composed of the modified polyolefin obtained by the production method of the present invention or the modified polyolefin of the third aspect of the present invention. When the modified polyolefin is used as the coating property improving agent (A), the modified polyolefin itself, an aqueous dispersion in which the modified polyolefin is dispersed in water, and the modified polyolefin are dissolved in an organic solvent. A solution is included.
In the method for producing the aqueous dispersion, [1] a modified polyolefin is dissolved in a solvent such as toluene, and this is dropped into water with stirring or added at a constant speed, while a high speed (usually a rotational speed of 50 to (2) A method in which the solvent is distilled off under reduced pressure by heating, and [2] after heating to above the melting point of the modified polyolefin, the solution is added dropwise to water with stirring or at a constant speed. A method of stirring and dispersing with a parser or the like at high speed (same as above) is included. As the method of dispersing, for example, an emulsifier such as a surfactant and / or a dispersant [the amount used is usually 0.1 to 80% based on the weight of the modified polyolefin, preferably from the viewpoint of the functional expression of the modified polyolefin. 0.2 to 40%] is used.

Examples of the surfactant include nonionic, cationic, anionic and amphoteric surfactants.
As the nonionic surfactant, for example, AO [C2-4, for example, EO, PO, butylene oxide, and a combination of two or more thereof. ] Addition type nonionic surfactant [higher alcohol (C8-18), higher fatty acid (C12-24), higher alkylamine (C8-24), etc.] [for example, dodecyl, stearyl, oleyl alcohol and amine, and laurin, stearin, Oleic acid, etc.] directly added with AO [molecular weight 174 or more and Mn 20,000 or less], polyalkylene glycol [eg polyethylene glycol (molecular weight 106 or more and Mn 80,000 or less) and higher fatty acid etc. AO is obtained by reacting a higher fatty acid with a polyhydric alcohol (C2-24 divalent to octavalent or higher, such as ethylene glycol, propylene glycol, glycerin, pentaerythritol, sorbitan, etc.). (Molecular weight 286) And Mn 20,000 or less), higher fatty acid amide added with AO (molecular weight 241 or more and Mn 35,000 or less), polyhydric alcohol (same as above) alkyl (C3-60) ether with AO (Mn 1,000 to 50,000), EO added to polypropylene glycol (Mn 500 to 5,000) (Mn 1,000 to 50,000, for example, pluronic-type nonionic surface activity) Polyhydric alcohol type nonionic surfactants [for example, polyhydric alcohol fatty acid ester (C3-60), polyhydric alcohol alkyl ether (C3-60), fatty acid alkanolamide (C3-60), etc.], etc. Is mentioned.

As the cationic surfactant, quaternary ammonium salt type [tetraalkyl (C4-100) ammonium salt such as lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide, stearyltrimethylammonium bromide, etc .; trialkyl (C3-80) benzylammonium salts such as lauryldimethylbenzylammonium chloride (benzalkonium chloride) and the like; alkyl (C2-60) pyridinium salts such as cetylpyridinium chloride and the like; (poly) (n = 1 to 100 or more) ) Oxyalkylene (C2-4) trialkyl (C3-80) ammonium salt, such as polyoxyethylenetrimethylammonium chloride; Sapamine type quaternary Ammonium salts such as stearamide ethyl diethyl methylammonium methosulfate], amine salt type [aliphatic higher amine (C8-24, such as laurylamine, stearylamine, cetylamine, hardened tallow amine, rosinamine, etc.) , Sulfuric acid, nitric acid, phosphoric acid, etc.) salts or organic acids [C2-22, such as acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid, azelaic acid, etc.] salts; aliphatic amines (C1 To 30) inorganic acid (above) salt or organic acid (above) salt such as EO adduct; inorganic acid of tertiary amine (triethanolamine monostearate, stearamide ethyl diethylmethylethanolamine, etc.) (Above-mentioned) salt or organic acid (above-mentioned) salt, etc.].

Anionic surfactants include carboxylic acids (C8-22 saturated or unsaturated fatty acids) or salts thereof, carboxymethylated salts [eg C8-18 aliphatic alcohols and / or EO (1-10 mol) thereof. Salt of carboxymethylated product such as adduct], sulfate ester salt [for example, higher alcohol (C8-18) sulfate ester salt], higher alkyl ether sulfate ester salt [for example, higher alcohol (C8-18) EO (1 to 10 mol) ) Sulphate salts of adducts], sulfated oils (salts neutralized by sulphating natural unsaturated fats or unsaturated waxes), sulfated fatty acid esters (sulfated lower alcohol esters of unsaturated fatty acids) Neutralized salts), sulfated olefins (salts neutralized by sulfating C12-18 olefins), sulfonates [e.g. Alkylbenzene sulfonate, alkylnaphthalene sulfonate, sulfosuccinic acid diester type, α-olefin (C12-18) sulfonate, Igepon T type, etc.] and phosphoric acid ester salts [eg higher alcohol (C8-60) phosphoric acid Ester salt, higher alcohol (C8-60) EO adduct phosphate ester salt, alkyl (C4-60) phenol EO adduct phosphate ester salt, etc.].

Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, propionic acid (salts) of higher alkylamines (C12-18)], betaine type amphoteric surfactants [for example, alkyl (C12-18) dimethylbetaine, alkyl ( C12-18) dihydroxyethyl betaine and the like], sulfate (salt) type amphoteric surfactants [for example, higher alkyl (C8-18) amine sulfate (salt) and hydroxyethyl imidazoline sulfate (salt)], sulfonic acid ( Salt) type amphoteric surfactants [for example, pentadecyl sulfotaurine, imidazoline sulfonic acid (salt), etc.], phosphate ester (salt) type amphoteric surfactants [for example, glycerin higher fatty acid (C8-22) esterified phosphate ester (Salt) etc.] etc. are mentioned.

Examples of the salt in the amphoteric surfactant and the anionic surfactant include alkali metal (for example, sodium and potassium) salts, alkaline earth metal (for example, calcium and magnesium) salts, ammonium salts, and alkylamines (C1-20). Salts, alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts and the like.

The concentration of the modified polyolefin in the aqueous dispersion is usually 5% by weight or more, preferably 10 to 90% by weight.

When the modified polyolefin is used as a paint improver (A) in the form of a solution, examples of the organic solvent to be used include hydrocarbons, cellosolves, ketones, alcohols, esters, amides and the like.
As hydrocarbons, aromatic (C6-24, such as benzene, toluene, xylene, ethylbenzene, triethylbenzene, amylbenzene, diamylbenzene, amyltoluene, diphenylethane, tetralin, etc.), aliphatic (C6-24, such as hexane) , Heptane octane, decane, etc.) and alicyclic (C6-24, such as cyclohexane, cyclohexene, methylcyclohexane, decalin, etc.) hydrocarbons.
As cellosolve, C3-18, such as methyl cellosolve, ethyl cellosolve, n- and i-propyl cellosolve, n-, sec-, i- and t-butyl cellosolve, etc .;
Examples of the ketone include C3-17, such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, and the like;
Examples of the alcohol include C1-18, such as methanol, ethanol, n- and i-propanol;
Esters include C3-18, such as ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, and the like;
Examples of the amide include C1-18, such as dimethylformamide.
Of these, hydrocarbons, cellosolves, ketones and alcohols are preferred from the viewpoint of the storage stability of the solution, and hydrocarbons, cellosolves and alcohols are more preferred.
The concentration of the modified polyolefin in the solution is usually 1% by weight or more, preferably 3 to 95% by weight.

When the modified polyolefin is used as the paintability improving agent (A), other resin additives (C) that are usually used may be used in combination.
(C) includes plasticizer (C1), lubricant (C2), adhesion, dispersibility and / or compatibility imparting agent (C3), antioxidant (C4), ultraviolet absorber (C5), colorant ( Examples thereof include one or more additives selected from the group consisting of C6), filler (C7), flame retardant (C8) and antistatic agent (C9).

The following are mentioned as a plasticizer (C1).
(C11) Monocarboxylic acid ester aliphatic carboxylic acid ester [C10-96, such as butyl stearate (BS), methoxyethyl oleate (MEO), methyl acetylricinoleate (MAR), ethyl acetylricinoleate (EAR), acetyl Methoxyethyl ricinoleate (MEAR), glycerin triheptanoate, etc.], aromatic (aliphatic) carboxylic acid ester [C7-96, such as butyl benzoate, octyl benzoate, butyl phenylacetate, phenylacetate hexyl plasticizer], fat Cyclic carboxylic acid esters [C5-96, such as methyl cyclopropanecarboxylate, butyl cyclopropanecarboxylate, methoxyethyl cyclobutanecarboxylate, ethyl cyclopentanecarboxylate, butyl cyclopentanecarboxylate, cyclohexane Methyl Bonn acid, cyclohexanecarboxylic acid methoxyethyl, cyclohexanecarboxylic acid octyl]

(C12) Dicarboxylic acid ester aliphatic dicarboxylic acid ester [C10-96, such as adipic acid ester [eg, di-2-ethylhexyl adipate (DOA), diisodecyl adipate (DIDA), di (methylcyclohexyl) adipate, etc.], Azelaic acid esters [eg azelaic acid di-n-hexyl (DNHZ), azelaic acid di-2-ethylhexyl (DOZ) etc.], sebacic acid esters [eg dibutyl sebacate (DBS), di-2-ethylhexyl sebacate (DOS) And the like]], aromatic (aliphatic) dicarboxylic acid esters [C10-96, such as phthalic acid esters [eg, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), heptylnonyl phthalate (HNP]). ), Di-2-phthalate Tylhexyl (DOP), di-n-octyl phthalate (DNOP), di-i-octyl phthalate (DIOP), di-s-octyl phthalate (DCapP), di (79 alkyl) phthalate (D79P), phthalate Acid-i-decyl (DIDP), ditridecyl phthalate (DTDP), dicyclohexyl phthalate (DCHP), butyl benzyl phthalate (BBP), ethyl phthalyl ethyl glycolate (EPEG), butyl phthalyl butyl glycolate (BPBG) And so on

(C13) Tricarboxylic acid ester aliphatic tricarboxylic acid ester [C5-96, for example, citrate ester [for example, triethyl citrate (TEC), tributyl citrate (TBC), acetyl triethyl citrate (ATEC), acetyl citrate tributyl (ATBC) ), Acetyl citrate tricyclohexyl, trioctyl citrate, tri (octyldecyl) citrate]], aromatic (aliphatic) tricarboxylic esters [C10-96, such as ethyl benzenetricarboxylate, octyl benzenetricarboxylate, etc.] C14) Epoxy C10-96, for example, epoxidized soybean oil (ESO), 4,5-epoxycyclohexane-1,2-dicarboxylic acid di-2-ethylhexyl (E-PS), etc.

(C15) Phosphate esters C3 to 96, such as tributyl phosphate (TBP), triphenyl phosphate (TPP), tricresyl phosphate (TCP), diphenyl monocresyl phosphate, 2-ethylhexyldiphenyl phosphate, phosphoric acid Tripropylene glycol, tributoxyethyl phosphate, trichloroethyl phosphate, triethyl phosphate, trixyl phosphate, etc. (C16) chlorine-containing hydrocarbons C10-96, such as chlorinated paraffins, chlorinated aromatic hydrocarbons (for example, chlorinated) Naphthalene, chlorinated biphenyl, etc.).

Of these, (C11) to (C13) are preferable from the viewpoint of the functional expression of (A) and (C1), and aliphatic di- and tricarboxylic acid esters and aromatic dicarboxylic acid esters are particularly preferable. Di-2-ethylhexyl adipate (DOA), citrate ester and phthalate ester.

Examples of the lubricant (C2) include hydrocarbons [eg liquid paraffin, natural paraffin, microwax, polyethylene wax (Mn100 to 10,000), etc.]; higher fatty acids [C8 to 48, eg lauric acid, palmitic acid, stearic acid, olein Acid, linoleic acid, linolenic acid, esyl acid, etc.]; higher fatty acid amides [C8-48, such as palmitic acid amide, stearic acid amide, oleic acid amide, esylic acid amide, erucic acid amide, methylene bisstearamide, etc.]; Higher fatty acid esters [C8-48 such as butyl stearate, octyl stearate, ethylene glycol monooctylate, ethylene glycol monostearate, etc.]; higher alcohols [C8-48 such as cetyl alcohol, stearyl alcohol, oleyl alcohol Metal soap [C8-48, for example, a metal salt of a higher fatty acid (as described above) [for example, alkali metal (for example, sodium, potassium, etc.), alkaline earth metal (for example, calcium, magnesium, etc.), lead, aluminum Etc.]]. Of these, higher fatty acids, higher fatty acid amides and higher fatty acid esters are preferred from the viewpoints of compatibility with (A), functional expression of (A) and functional expression of (C2) as a lubricant.

Examples of the adhesion, dispersibility and / or compatibility imparting agent (C3) include polymers having Mn of 1,000 to 100,000, such as vinyl resins {for example, polyolefins [for example, polyethylene, polypropylene, ethylene / butene copolymers [copolymerization ratio] (Weight ratio) 1-99 / 99-1], propylene / butene copolymer [copolymerization ratio (weight ratio) 1-99 / 99-1], ethylene / propylene / butene copolymer [copolymerization ratio (weight Ratio) 1 to 98/1 to 98/1 to 98], modified polyolefin [for example, polyethylene oxide (polyethylene oxidized with ozone or the like to introduce carboxyl group, carbonyl group and / or hydroxyl group, etc.), polypropylene oxide (above (Oxidized polyethylene can be obtained in the same way by replacing polyethylene with polypropylene), epoxy-modified polyester Ren (epoxy equivalent 100 to 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), hydroxyl-modified propylene / butene copolymer (hydroxyl value 0.1-60, copolymer weight) Ratio 1 to 99 / 99-1)], vinyl resins other than the above polyolefins [for example, polyhalogenated vinyl [for example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinyl iodide, etc.], polyvinyl acetate, polyvinyl alcohol , Polymethyl vinyl ether, poly (meth) acrylic acid, poly (meth) acrylic Acid esters [eg poly (meth) acrylic acid-methyl, -ethyl, -n- and i-propyl, -n- and t-butyl etc.], styrene resins [eg polystyrene, acrylonitrile / styrene (AS) resin, acrylonitrile / Butadiene / styrene (ABS) resin, etc.]]};

Polyester [eg polyalkylene (C2-24) terephthalate [eg polyethylene terephthalate (PET), polybutylene terephthalate (PBT) etc.], polyalkylene (C2-24) isophthalate [eg polyethylene isophthalate, polybutylene isophthalate etc.], Poly-p-phenylene ester [for example, poly-p-phenylene malonate, poly-p-phenylene adipate, poly-p-phenylene terephthalate, etc.]];
Polyamide [for example, polycoupleramide (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon), poly-ω -Aminoheptanoic acid (7-nylon), poly-ω-aminononanoic acid (9-nylon), etc.]; polyether [eg polyoxymethylene, polyoxyethylene, polyoxyphenylene, poly-1,3-dioxolane, etc.];
Polycarbonate; polyphenylene resin (PPO); and block copolymers thereof.
Of these, modified polyolefins and (A) and (C3) are preferred from the viewpoints of compatibility, (A) function expression, and (C3) adhesion, dispersibility, and / or function expression as a compatibility imparting agent. Polyester.

Examples of the antioxidant (C4) include hindered phenols [for example, pt-amylphenol-formaldehyde resin, 2,6-bis (1-methylheptadecyl) -p-cresol, butylated cresol, styrenated cresol. 4,4′-butylidenebis (6-t-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-methylphenol (BHA), 6-t-butyl-2,4-dimethylphenol (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-t-butylphenyl) propionate, 4,4′-butylidenebis (6-t-butyl) -3-methylphenol), 4,4'-methylenebis (6-t-butylphenol), 4,4'-bis (2,6-di-t-butylphenol), 2,2'-methylenebis (4-methyl-) 6-tert-butylphenol), 2,2′-thiobis (6-tert-butyl-4-hydroxy-2-methylphenol), 1,6-bis (3,5-di-tert-butyl-4-hydro Cis-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-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [β- (3,5-di-t-butyl- 4-hydroxyphenyl) propionyloxymethyl] methane etc.];

Sulfur-containing systems (for example, N, N′-diphenylthiourea, dimyristylthiodipropionate, dilaurylthiodipropionate, 4,4′-thiobis (6-t-butyl-m-cresol), distearylthiodipropio 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 systems [for example, 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.].

Examples of the ultraviolet absorber (C5) include salicylates (for example, phenyl salicylate, 4-t-butylphenyl salicylate, p-octylphenyl salicylate, etc.); benzophenones [for example, 2,4-dihydroxybenzophenone, 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 Hydroxybenzophenone, etc.]; benzotriazole [such as 2- (2'-hydroxy-5'-methylphenyl) - benzotriazole, etc.] and the like.

Examples of the colorant (C6) include white pigments (eg, titanium oxide, zinc white, barium sulfate, calcium carbonate, etc.), black pigments (eg, carbon black, iron black, aniline black, etc.), yellow pigments (eg, yellow lead, cadmium yellow). , Iron oxide yellow, benzidine yellow, Hansa yellow, oil yellow 2G, etc.), orange pigment (eg red lead yellow lead, chrome vermilion, cadmium orange, pyrazolone orange, etc.), red pigment (eg Bengala, cadmium red, permanent red, lake red) C, Carmine 6B, Pigment Scarlet 3B, Permanent Red F5R, Quinacridone Red, Thioindigo Maroon, etc., Purple Pigment (eg, Cobalt Violet, Mineral Violet, etc.), Blue Dyeing Pigment (eg, Ultramarine Blue, Bituminous Blue, Cobalt Blue, Phthalose) Nburu etc.), a green pigment (e.g. phthalocyanine green, chrome green, etc.), metal powder pigments (e.g. aluminum powder, bronze powder, pearl essence and the like) and the like.

Examples of the filler (C7) include metal powder (eg, aluminum powder), metal oxide (eg, alumina, wollastonite, silica, talc, mica, kaolin clay, calcined kaolin, etc.), metal hydroxide (eg, water). Aluminum oxide, etc.), metal salts (eg, calcium carbonate, calcium silicate, etc.), fibers [eg, inorganic fibers (carbon fiber, fiber, α-fiber, glass fiber, asbestos, etc.), organic fibers (eg, cotton fiber, jute) Fiber, nylon fiber, acrylic fiber, rayon fiber, etc.)], microballoon (eg, glass, shirasu, phenol resin, etc.), carbon (eg, carbon black, graphite, etc.), metal sulfide (eg, molybdenum disulfide, etc.), organic powder (For example, wood powder etc.), inorganic powder (for example, coal powder etc.), etc. are mentioned.

Examples of the flame retardant (C8) include organic [eg, phosphorus-containing [eg, phosphate esters (eg, tricresyl phosphate)], bromine-containing (eg, tetrabromobisphenol A, decabromobiphenyl ether, etc.), Chlorine-containing (for example, chlorinated paraffin, anhydrous heptic acid)] and inorganic (for example, antimony trioxide, magnesium hydroxide, borate, zinc borate, barium metaborate, aluminum hydroxide, red phosphorus, magnesium hydroxide) , Ammonium polyphosphate, etc.].
As the antistatic agent (C9), nonionic, cationic, anionic and amphoteric surfactants described in the above, US Pat. Nos. 3,929,678 and 4,331,447 are used. Agents and the like.

The thermoplastic resin composition of the fifth aspect of the present invention comprises a thermoplastic resin (B) containing a paintability improver (A), if necessary, in combination with the above other resin additives (C). Is. When (A) and (C) are used in combination, a mixture of (A) and (C) may be added, or may be added separately.

Examples of (B) include polyolefin resin (B1), polyester resin (B2), polyamide resin (B3), vinyl resin (B4) [excluding (B1)], polyether resin (B5), and the like. The Mn of (B) is usually 10,000 to 1,000,000, preferably 50,000 to 500,000.

Examples of the polyolefin resin (B1) include polyolefin resins obtained by (co) polymerizing at least one olefin selected from the group consisting of ethylene, propylene, and C4-12 α-olefins. Examples of the C4-12 α-olefin include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and the like.

Examples of the polyester resin (B2) include polyalkylene (C2-24) terephthalate [polyethylene terephthalate (PET), polybutylene terephthalate (PBT), etc.], polyalkylene (C2-48) isophthalate [polyethylene isophthalate, polybutylene isophthalate. Etc.], poly-p-phenylene ester [poly-p-phenylene malonate, poly-p-phenylene adipate, poly-p-phenylene terephthalate, etc.] and the like.

As the polyamide resin (B3), polycapramide (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene sebacamide (6,10-nylon), polyundecanamide (11-nylon) ), Poly-ω-aminoheptanoic acid (7-nylon), poly-ω-aminononanoic acid (9-nylon), and the like.

Examples of the vinyl resin (B4) excluding (B1) include polyvinyl halide [eg, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyiodide, etc.], polyvinyl acetate, polystyrene, polyvinyl alcohol, polymethyl vinyl ether. , Poly (meth) acrylic acid, poly (meth) acrylic acid ester [eg poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylic acid-n- and i-propyl, poly (meth ) Acrylic acid-n- and t-butyl etc.] and the like.

Examples of the polyether resin (B5) include polyoxymethylene, polyoxyethylene, polyoxyphenylene, and poly-1,3-dioxolane.

Among these (B), from the viewpoint of compatibility with (A) and the functional expression of (A), (B1), (B2), (B3) and (B4) are more preferable, B1), (B2) and (B3).

The amount of (A) used in the thermoplastic resin composition of the present invention is preferably 0 based on the weight of the thermoplastic resin (B), from the viewpoint of the functional expression of (A) and the mechanical properties of the molded product described later. 0.01 to 15%, more preferably 0.1 to 10%. The total amount of (C) used is usually 30% or less based on the weight of (B), preferably from 0.01 to 15%, more preferably from 0.1 to 10% from the viewpoint of the effect of (C) and economy. %.
The amounts of (C1) to (C8) based on the weight of (B) are usually 15% or less for (C1), (C2) and (C3), and (C4), (C5) and (C8) are 10% or less, (C6) and (C7) are 30% or less, and (C1), (C2) and (C3) are preferably 0.01 to 10% from the viewpoint of the effect of (C) and economy. Preferably 0.1 to 5%, (C4), (C5) and (C8) are preferably 0.01 to 10%, more preferably 0.1 to 3%, (C6) and (C7) are preferably 0.01 to 25%, more preferably 0.1 to 20%.

In the method for producing the thermoplastic resin composition of the present invention, (1) (A) and (B) and, if necessary, (C) are all melt-mixed, (2) (A) and a small amount of (B ) And, if necessary, melt-mixing (C) to prepare a masterbatch resin composition, then adding the remaining (B) and melt-mixing, and (3) a part of (A) and a small amount of (B) ) And, if necessary, (C) are melt-mixed to prepare a masterbatch resin composition, and then the remaining (B) and the remaining (A) are added and melt-mixed [(2) and (3) Includes a master batch method. The melting temperature is preferably 40 to 300 ° C, more preferably 90 to 280 ° C, from the viewpoint of the melting temperature and decomposition temperature of (A) and (B).
Among the above methods, the method (2) is preferable from the viewpoint of the functional expression (A).
Examples of the melt mixing apparatus include a batch kneader [for example, Banbury [trade name, manufactured by Farrel Co., Ltd.] and a kneader], a continuous kneader [for example, FCM [trade name, manufactured by Farrel Co., Ltd.], LCM [trade name, ( Co., Ltd., Kobe Steel, Ltd.] and CIM [trade name, manufactured by Nippon Steel, Ltd.]], single screw extruder, twin screw extruder, and the like.

The masterbatch resin composition is also one aspect of the present invention.
The ratio of (A) based on the total weight of (A) and (B) in the masterbatch resin composition of the present invention is 10 from the viewpoint of the functional expression of (A) and the mechanical properties and workability of the molded product described later. -95%, preferably 20-80%.

The molded product of the sixth aspect of the present invention is formed by molding the thermoplastic resin composition. Examples of the molding method include extrusion molding, injection molding, compression molding, slush molding, rotational molding, transfer molding, stampable molding, blow molding, stretched film molding, laminate molding, calendar molding, and foam molding. Examples of the foaming agent used in foam molding include inorganic foaming agents (for example, nitrogen, carbon dioxide, air, argon, water, ammonia carbonate, calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium nitrite, ammonium chloride, nitrourea) and Organic foaming agents [nitroso foaming agents (eg, dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide), sulfohydrazide foaming agents (eg, benzenesulfonylhydrazide, p-toluene) Sulfonyl hydrazide, pp′-oxybisbenzenesulfonyl hydrazide, 3-3 ′ disulfone hydrazide diphenyl sulfone, toluene disulfonyl hydrazide, etc.), sulfohydrazone foaming agents (eg, p-toluenesulfonyl hydrazone etc.), azide foams (E.g., p-toluenesulfonyl azide), azo foaming agents (e.g., azobisisobutyronitrile, azodicarbonamide, barium azodicarboxylate, diethyl azodicarboxylate, etc.) It is usually 20% or less, preferably 1 to 15%, based on the total weight of the plastic resin composition.

The molded article of the present invention has excellent mechanical properties and good paintability, and can be formed into a molded article by painting and / or printing. Examples of the method for coating the molded product include spray coating (air spray, airless spray, electrostatic spray coating, etc.), dip coating, roller coating, brush coating, and the like.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint. The coating film thickness (film thickness after drying) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.
In addition, as a method for printing on the molded article, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing, screen printing, pad printing, dry offset printing, Examples include offset printing.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexo ink, screen ink, pad ink, dry offset ink, offset ink and the like can be used.

The coating property improver comprising the modified polyolefin obtained by the production method of the present invention is excellent in the effect of improving the coating properties (coating film adhesion, etc.) of the polyolefin resin, etc., so that the mechanical properties of the polyolefin resin are impaired by adding a small amount. The effect that paintability can be improved is produced.

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”, “retention ratio in impact strength” and “%” other than mol% represent “% by weight”.
Example 1
30 parts of maleic anhydride and 50 parts of monoethanolamine were placed in a three-necked flask equipped with a cooling tube, purged with nitrogen, heated to 160 ° C. under nitrogen flow, and stirred at 160 ° C. for 1 hour. Thereafter, 50 parts of propylene tetramer [trade name: Light Tetramer, manufactured by Shin Nippon Petrochemical Co., Ltd., the same below] was added, mixed uniformly, and then di-tert-butyl peroxide 2 dissolved in 10 parts of xylene. A portion was added dropwise and stirring was continued at 180 ° C. for 4 hours. Under reduced pressure, xylene, unreacted propylene tetramer and unreacted monoethanolamine were distilled off to obtain a modified polyolefin having a hydroxyl value of 250, Mn 600, and a thermal softening point of 80 ° C. The modified polyolefin was used as a coating property improving agent (A1) in Example 4 described later.

Example 2
After putting 50 parts of propylene tetramer into a three-necked flask with a cooling tube and purging with nitrogen, the temperature was raised to 180 ° C. under nitrogen flow, 30 parts of maleic anhydride was added, mixed uniformly, and dissolved in 10 parts of xylene. 2 parts of the prepared di-t-butyl peroxide was added dropwise and stirring was continued at 180 ° C. for 4 hours. Thereafter, xylene, unreacted propylene tetramer and unreacted maleic anhydride were distilled off under reduced pressure. 50 parts of monoethanolamine was added to the obtained product, and stirring was continued at 180 ° C. for 2 hours. Thereafter, unreacted monoethanolamine was distilled off under reduced pressure to obtain a modified polyolefin having a hydroxyl value of 260, Mn 700, and a heat softening point of 80 ° C. The modified polyolefin was used as a coating property improving agent (A2) in Example 5 described later.

Example 3
Example 2 except that instead of 50 parts of propylene tetramer, a mixture of 40 parts of propylene tetramer and 10 parts of ethylene hexamer [trade name: Dialene 12, manufactured by Mitsubishi Chemical Corporation] was used. In the same manner, a modified polyolefin having a hydroxyl value of 260, Mn 1,000 and a heat softening point of 80 ° C. was obtained. The modified polyolefin was used as a coating property improving agent (A3) in Example 6 described later.

Comparative Example 1
The hydroxyl value was changed in the same manner as in Example 2 except that 50 parts of polypropylene (trade name: Biscol 660-P, manufactured by Sanyo Chemical Industries) was used instead of 50 parts of propylene tetramer. A modified polyolefin having 60, Mn 2,300 and a thermal softening point of 145 ° C. was obtained. The modified polyolefin was used as a coating property improving agent (ratio A1) in Comparative Example 3 described later.

Comparative Example 2
After putting 50 parts of propylene tetramer into a three-necked flask with a cooling tube and purging with nitrogen, the temperature was raised to 180 ° C. under nitrogen flow, 30 parts of maleic anhydride was added, mixed uniformly, and dissolved in 10 parts of xylene. 2 parts of the prepared di-t-butyl peroxide was added dropwise and stirring was continued at 180 ° C. for 4 hours. Thereafter, xylene, unreacted propylene tetramer and unreacted maleic anhydride were distilled off under reduced pressure to obtain a modified polyolefin having a hydroxyl value of 0, Mn 600 and a thermal softening point of 70 ° C. The modified polyolefin was used as a coating property improving agent (ratio A2) in Comparative Example 4 described later.

Examples 4, 5, 6 and Comparative Examples 3, 4
100 parts of commercially available polypropylene [trade name: Chisso Polypro K1011, manufactured by Chisso Corporation], 3 parts of each of the modified polyolefins obtained in Examples 1, 2, 3 and Comparative Examples 1 and 2, respectively, are paintability improvers (A1 ), (A2), (A3) and (Ratio A1) and (Ratio A2) after blending for 3 minutes with a Henschel mixer, respectively, using a vented twin screw extruder at 240 ° C., 100 rpm, residence time 20 minutes And kneaded to obtain a polyolefin resin composition. Using these, an injection molding machine [trade name: PS40E5ASE, manufactured by Nissei Plastic Industry Co., Ltd.] is used to form a predetermined test piece by molding at a cylinder temperature of 230 ° C. and a mold temperature of 40 ° C., and then according to the following test method. The mechanical properties and paintability of the molded products were evaluated. The results are shown in Table 1.

<Test method>
(1) Impact strength A molded article test piece (thickness: 3.2 mm) was measured by Method A based on ASTM D256 (notched, thickness: 3.2 mm) (unit: kgf · cm / cm ² ).
(2) The flexural modulus molded product test piece (100 × 10 × 4 mm) was measured based on ASTM D790 at a fulcrum distance of 60 mm (unit: kgf / cm ² ).
(3) Paintability test Molded product test piece (150 × 70 × 2 mm) with a commercially available melamine alkyd top coat [trade name: Flexen # 101, manufactured by Nippon B Chemical Co., Ltd.] as a thinner [trade name: # 101 -10, manufactured by Nippon Bee Chemical Co., Ltd.] (paint / thinner weight ratio = 2/1) was spray-coated using a spray machine, and then allowed to stand at room temperature for 15 minutes and circulated and dried. The film was baked at 120 ° C. for 20 minutes (film thickness after drying was about 40 μm). The obtained coated surface was subjected to an adhesion test by a cross-cut tape method based on JIS K5400. The number of the part which the coating film did not peel among the grids 100 was represented by 0-100.

The modified polyolefin obtained by the production method of the present invention or the coating property improver (A) comprising the modified polyolefin of the present invention reduces the mechanical properties of the thermoplastic resin by adding a small amount to the thermoplastic resin (B). The paintability (coating film adhesion, etc.) of the resin can be improved without any problems. Further, a molded article formed by molding a thermoplastic resin composition containing (A) in (B), and a molded article obtained by coating and / or printing the molded article, In particular, it is widely used in interior and exterior materials and home appliances in the automotive field.

Claims (10)

Propylene 3- to 7-mer (a1) or a mixture of (a1) and a polymer (a2) composed of an olefin other than propylene, an olefin polymer (a) having 9 to 21 carbon atoms, and a hydroxyl group-containing unsaturated dicarboxylic acid A modified polyolefin comprising an acid imide monomer (b) as a structural unit and having a hydroxyl value of 20 to 600, a number average molecular weight of 200 to 1,000 , and a heat softening point of 40 to 170 ° C. A paint improver (A) comprising the modified polyolefin according to claim 1 . A thermoplastic resin composition comprising the thermoplastic resin (B) containing the paint improver (A) according to claim 2 . The composition according to claim 3 , wherein the proportion of (A) based on the weight of (B) is 0.01 to 15%. Further, one or two selected from the group consisting of plasticizers, lubricants, adhesion, dispersibility and / or compatibility imparting agents, antioxidants, ultraviolet absorbers, colorants, fillers, flame retardants and antistatic agents. The composition according to claim 3 or 4, comprising at least one kind of additive. A master batch resin composition comprising the paintability improving agent (A) according to claim 2 and a thermoplastic resin (B), wherein the ratio of (A) based on the total weight of (A) and (B) is 10 to 95%. object. A molded article formed by molding the composition according to any one of claims 3 to 5 . A molded article obtained by coating and / or printing the molded article according to claim 7 . Propylene 3- to 7-mer (a1) or a mixture of (a1) and a polymer (a2) composed of an olefin other than propylene, an olefin polymer (a) having 9 to 21 carbon atoms, and a hydroxyl group-containing unsaturated dicarboxylic acid The method for producing a modified polyolefin according to claim 1 , wherein the acid imide monomer (b) is reacted in the presence or absence of the radical initiator (c). Anhydrous of unsaturated dicarboxylic acid and olefin multimer (a) having 9 to 21 carbon atoms consisting of propylene 3- to 7-mer (a1) or a mixture of (a1) and multimer (a2) composed of olefins other than propylene Reacting a reaction product or copolymer comprising the product (d) with a compound (e) that reacts with the acid anhydride group derived from (d) to introduce a hydroxyl group-containing dicarboxylic imide into the reaction product or the copolymer. The method for producing a modified polyolefin according to claim 1 , wherein: