WO1996025462A1

WO1996025462A1 - Resin modifier, resin composition containing the same, and resin molding

Info

Publication number: WO1996025462A1
Application number: PCT/JP1996/000340
Authority: WO
Inventors: Shizuo Kitahara
Original assignee: Nippon Zeon Co., Ltd.
Priority date: 1995-02-16
Filing date: 1996-02-16
Publication date: 1996-08-22

Abstract

A resin modifier containing an active ingredient comprising a polyester having a hydroxyl value of 30 mgKOH/g or above and a weight-average molecular weight of 1,000 to 500,000 and prepared by the polycondensation of a polybasic higher carboxylic acid and a polyhydric alcohol component containing an at least trihydric alcohol and/or a polyvalent epoxy compound; and a resin composition containing the modifier. Moldings produced from the composition are excellent in coatability, adhesives and printability.

Description

Description Resin modifier for resin, resin composition containing the same, and resin molded article

The present invention relates to a resin modifier containing a polyester as an active ingredient, a resin composition containing the modifier, and a molded article of the resin composition.

Films and other molded articles obtained from the resin composition containing the resin modifier of the present invention are excellent in coatability, adhesiveness and printability. Background technology

Hydrocarbon resins such as polyolefins are widely used because of their excellent physical properties and comparatively low cost.However, since there is no polar group in the molecule, the adhesion of the coating film is low, making it practical. There was a drawback that adhesive strength could not be obtained.

Conventionally, there has been proposed a technique for modifying the surface of a resin molded body for the purpose of improving the paintability and adhesiveness of the molded body of a resin such as polyolefin. For example, there is known a technique of performing a fire treatment on the surface of a resin molded product (J. M at. Sci., 1Α, 1344 (1979)), but it is difficult to perform uniform treatment depending on the shape of the molded product. There were problems such as impairing the surface appearance. In addition, the surface modification method by ultraviolet irradiation disclosed in Japanese Patent Application Laid-Open No. 3-217433 has a problem when a molded article is large and has a complicated shape. A typical surface treatment technique using low-pressure plasma is a glow discharge method (J. Adhesion, 11.57 (1980)), or a plasma treatment with alcohol vapor, followed by a steam plasma treatment technique (Japanese Patent Laid-Open No. Japanese Patent Application Laid-Open No. 2-123210 and Japanese Patent Application Laid-Open No. Hei 6-248103) are known, but these technologies require an extra step related to surface treatment and require a long processing time. If it is long, there remains a problem that the introduced polar group changes with time. The method of surface treatment with a halogen-containing compound such as trichlene, which has been put into practical use, has environmental and sanitary problems since it uses a halogen-containing compound. Instead of the above surface treatment, it has also been proposed to incorporate a modifier into the resin molded body to improve the paintability and adhesion. For example, a technology in which a random copolymer of a hydrophilic monomer such as dimethylaminoethyl methacrylate or 2-hydroxyxethyl methacrylate and a lipophilic monomer such as stearyl methacrylate is blended into a resin as a coating modifier. (Journal of the Adhesion Society of Japan, ___a, 487 (1992)) is known. In this technology, it is necessary to increase the amount of the hydrophilic monomer introduced in order to increase the adhesiveness, which causes a problem that the compatibility with the resin is reduced. Further, according to the technique of adding a modified acid anhydride of polyolefin as disclosed in Japanese Patent Application Laid-Open Nos. Although the adhesiveness of the film is improved, there is a problem that the color of the coating film may deteriorate.

On the other hand, as polyester-based modifiers, for example, Japanese Patent Application Laid-Open No. Hei 6-136068 discloses that poly (butylene adipate) polyol and 2-ethylhexamethacrylate are used in the presence of benzoyl peroxide. The modified polyester obtained by the reaction below is disclosed. However, the modified polyester obtained by this method has excellent compatibility with the polyolefin resin with the polypropylene to be modified and the like, but does not have sufficient adhesiveness and adhesiveness with the paint. Disclosure of the invention

An object of the present invention is to provide a novel resin modifying agent containing a polyester as an active ingredient and a resin obtained by adding the same, which is used to improve the paintability, adhesiveness, and printability of resins such as polyolefin. It is to provide a composition.

Furthermore, an object of the present invention is to provide a molded article capable of forming a coating film having excellent adhesion on a surface thereof by coating.

According to the present invention, in one aspect, the hydroxyl value obtained by polycondensation of a polyvalent higher carboxylic acid and a polyhydric alcohol component containing a tri- or higher-valent alcohol is 30 mg KOHZ g or more. There is provided a resin modifier containing a polyester having an average molecular weight of 1,000 to 500,000 as an active ingredient. According to the present invention, in another aspect, a hydroxyl value obtained by polycondensation of a polyvalent higher carboxylic acid and a polyhydric alcohol component containing a polyvalent epoxy compound having two or more epoxy groups in a molecule is obtained. The present invention provides a resin modifier containing a polyester having an active ingredient of not less than 30 mgK0HZg and a weight average molecular weight of 1,000 to 500,000.

According to the present invention, in another aspect, there is provided a resin composition containing the above-described resin modifier.

According to the present invention, in another aspect, there is provided a resin molded article obtained by molding the above resin composition and coating the surface. BEST MODE FOR CARRYING OUT THE INVENTION

The polyester used in the present invention is usually oil-soluble. Here, “oil-soluble” means that the light transmittance of the polyester solution measured as described below is 80% or more. The preferred light transmittance is 90% or more.

5 g of polyester is put into 95 g of toluene, dissolved under stirring at 80 ° C for 1 hour under a nitrogen atmosphere, and then cooled to room temperature (20 ° C). The toluene diluted solution is allowed to stand in a constant temperature room at 20 ° C. for 24 hours, and then stirred again, and the transmittance is measured with a turbidity meter (“ANA-14S” manufactured by Tokyo Koden Co., Ltd.). A 20-mm square glass cell is used as the light source, using an incandescent incandescent light bulb (6 V, 6 A) as the light source. The transmittance is 0% when the shutter is closed, and the transmittance of toluene used for dilution is 100%.

The polyvalent higher carboxylic acid used in the synthesis of the oil-soluble polyester preferably used in the present invention may be any of linear, branched, cyclic or aromatic, and usually has 10 or more carbon atoms. Preferably 15 or more, more preferably 20 or more carboxylic acids, containing at least 50% by weight, preferably 60% by weight, more preferably 70% by weight or more of divalent higher carboxylic acids Is used. If the carbon number of the carboxylic acid is too small, the oil solubility is poor and the compatibility with the resin to be modified is poor. The polyvalent higher carboxylic acid may be a single acid or a mixture. More specifically, the divalent higher carboxylic acid accounts for 50 to 100% by weight, preferably 60 to: L00% by weight, more preferably 70 to 100% by weight, and the trivalent or higher carboxylic acid accounts for 50 to 100% by weight. Those which occupy 0% by weight, preferably 40 to 0% by weight, more preferably 30 to 0% by weight are used.

Specific examples of polyvalent higher carboxylic acids include: divalent higher carboxylic acids include sebacic acid, brassic acid, polyalkenyl succinic acid, polymerized fatty acid dimeric acid (hereinafter abbreviated as dimer acid) and the like. Examples thereof include hydrides, and among these, at least one selected from polyalkenyl succinic acid, dimer acid and hydrides thereof is preferable. Examples of the trivalent or higher carboxylic acid include, for example, trivalent or higher polymerized fatty acids obtained by polymerizing higher fatty acids, and particularly preferred is a trimer acid of a polymer fatty acid (hereinafter, abbreviated as trimer acid).

The polymerized fatty acid is obtained by polymerizing a higher fatty acid, and is generally a fatty acid having 8 to 24 carbon atoms, preferably 16 to 20 carbon atoms, or a fatty acid having at least one unsaturated bond or a fatty acid ester derivative thereof. It is a generic term for the polymeric acids obtained by the above method. Commercially available polymerized fatty acids are those obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, etc., and contain dimer acid as the main component, and a polymer acid and monomeric acid higher than trimer acid as secondary components. It is doing. A method for analyzing the structure of polymerized fatty acids has been reported by D.H. Mcm a hon et al. (J. Am. Oil. Chem. Soc., 51, 522 (1974)). The polymerization product can be separated into polymerized fatty acids having different contents of each component by a distillation method or a solvent extraction method. By hydrogenating the unsaturated carbon-carbon bonds remaining in these polymerized fatty acids, a hydrogenated polymerized fatty acid having good thermal oxidation stability can be obtained, and this hydride polymerized fatty acid is preferably used in the present invention. it can. In the present invention, an unpurified polymerized fatty acid, a purified polymerized fatty acid or a hydrogenated polymerized fatty acid can also be used. Preferably, a purified polymerized fatty acid containing 60% by weight or more of a dimer or a hydride thereof is used. .

Polyalkenyl succinic acid has the general formula R-CHCOOHC H- C 0 0 H

(Wherein R is a polymer chain of lower argen.) R is a polymer chain of a lower alkene, and preferably, the lower argen is at least one selected from ethylene, propylene and butylene, and the degree of polymerization is in the range of 10 to 300.

If necessary, a small amount of other carboxylic acid (usually 30% by weight or less, preferably 20% by weight or less, based on the total weight of carboxylic acids) is used in combination as long as the object of the present invention is not impaired. be able to. Specific examples of the carboxylic acids that can be used in combination with the above polyvalent higher carboxylic acids include succinic acid, glutaric acid, adibic acid, suberic acid, maleic acid, itaconic acid, bimeric acid, azelaic acid, Divalent lower carboxylic acids such as methylmalonic acid, dimethylmalonic acid and alkenyl succinic acid; trimellitic acid, trivallic acid (1,2,3-propane tricarboxylic acid), camphoronic acid (2,3) —Lower carboxylic acids having a valence of 3 or more, such as —dimethylmethane-1,2,3-tricarboxylic acid) and trimesic acid (1,3,5-benzenetricarboxylic acid); and 2-methylpropanoic acid and isooctyl Saturated fatty acids or linoleic acids such as acids, isononanoic acids, lauric acids, myristic acids, panolemitic acids, stearyl acids, isostearic acids, and araquinic acids And monovalent lower and higher carboxylic acids such as unsaturated fatty acids such as oleic acid, oleic acid and elaidic acid.

The polyhydric alcohol component used for the synthesis of the polyester used in the present invention includes a trihydric or higher alcohol and a polyhydric epoxy compound having Z or two or more epoxy groups in a molecule. By using a trivalent or higher alcohol and a Z or polyepoxy compound, a desired hydroxyl value can be imparted to the polyester.

Specific examples of the trihydric or higher alcohol used in the present invention include trimethylol luethane, trimethylol propane, glycerol, pentaerythritol, Dibene erythritol, sorbitol, glucose, mannitol, sucrose. Glucose and the like. Among them, trimethylolethane, trimethylolpropane, glycerol, bentaerythritol, dibene erythritol, sorbitol and the like are preferable. .

As the polyepoxy compound used in the present invention, a compound having two or more epoxy groups in one molecule is used, and specific examples thereof include polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether and bisphenol. Diglycidyl ether of A, diglycidyl ether of bisphenol F, diglycidyl ether of alkylene oxide adduct of bisphenol A —tel, diglycidyl ether of alkylene oxide adduct of bisphenol F, resorcin diglycidyl ester Ter, neopentylglycol diglycidyl ether, 1,6-hexanedioldiglycidyl ether, polytetramethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, bisphenol Examples thereof include diglycidyl ester of S, diglycidyl ester of adivic acid, diglycidyl ester of 0-phthalic acid, diglycidyl ester of terephthalic acid, and diglycidyl ester of dimer monoacid. Among these, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, resorcinol diglycidyl ether, neobentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl adivic acid ester , 0-phthalic acid diglycidyl ester and terephthalic acid diglycidyl ester are preferred.

The proportion of the trihydric or higher alcohol in the alcohol component used in the present invention is usually in the range of 10 to 90 mol%, preferably 15 to 70 mol%, and more preferably 20 to 50 mol%. The proportion of the polyepoxy compound is usually in the range of 5 to 50 mol%, preferably 5 to 45 mol%, and more preferably 5 to 40 mol%. The balance of the alcohol component is dihydric alcohol.

Specific examples of dihydric alcohols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, and 1,6-hexane. Alkane diols such as diols, 3-methyl-1,5-pentane diol, and 1,9-nonanediol; oligogoxyalkylene glycols such as diethylene glycol, dibrovirene glycol, and triethylene glycol; polyethylene glycol; Polyoxyalkylene glycols having an alkylene group of 2 to 5 carbon atoms and a degree of polymerization of 2 to 100, such as polypropylene glycol and polyoxyethylene monopolyvinylene glycol; 2,2-dimethyl-1,3-butane Mouth pandiol, 2,2—Jetyl-1,3-propanediol, 2,2—Dibromo-1,3,3-Propanediol, 2,2, -Diisobrobyl-1,3,3-Mouthpandiol, 2,2— Diisobutylyl-1,3-propanediol, 2-methyl-2-dodecyl-1,3-propanediol, 2 Hindered glycols such as —ethyl-12-butyl-1,1,3-propanediol, 2-propyl-12-pentyl-11,3-bromophenol; and polycaprolactonediol. Of these, alkendiols and hindered glycols are preferred.

If necessary, other alcohols may be used in a small amount (30% by weight or less, preferably 20% by weight or less based on the total weight of alcohols) as long as the object of the present invention is not impaired. . Other alcohols include monohydric alcohols such as neobenzyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol and nonyl alcohol Is mentioned.

The polycondensation reaction for synthesizing the oil-soluble polyester may be performed according to a conventional method. The polycondensation reaction is usually preferably carried out at a reaction temperature of 150 to 280 in the presence of an inert gas. If necessary, a water-insoluble organic solvent azeotropic with water, such as toluene or xylene, may be used, or the reaction may be performed under reduced pressure. The esterification polycondensation reaction is usually performed using an esterification catalyst. Examples of the esterification catalyst include brenstead acid, such as paratoluenesulfonic acid, sulfuric acid, and phosphoric acid; inorganic Lewis acid, such as boron trifluoride complex, titanium tetrachloride, and tin tetrachloride; zinc stearate, and alkyl. Organometallic compounds such as tin oxide, titanium alkoxide, dibutyltin dilaurate, and iron acetyl acetonate.Organic metal compounds from the viewpoint of the oxidative stability of polyesters, especially organometallic compounds of Group IV of the periodic table (The hydroxyl value in the polyester is determined by the ratio of the dihydric alcohol to the trihydric or higher alcohol in the polyhydric alcohol, or the ratio of the dihydric alcohol to the polyhydric epoxy compound. The molecular weight of the polyester is Determined by the ratio of carboxylic acid component and alcohol component charged Ratio of carboxylic acid component to alcohol component (including epoxy compound) (equivalent ratio) OH (+ epoxy group) ZCOOH is 1.02 to 3 0, preferably 1.05 to 2.5, and more preferably 1.10 to 2.0. However, if the hydroxyl value of the polyester does not become sufficiently high, the acid value becomes high and corrosiveness becomes a problem, and if the equivalent ratio becomes too large, the molecular weight of the polyester does not become high. .

Polyester used as a resin modifier of the present invention, obtained by polycondensation of a polyhydric higher carboxylic acid and a polyhydric alcohol component containing a polyhydric alcohol or a polyhydric epoxy compound as described above. Has the following characteristics:

(A) The weight average molecular weight in terms of polystyrene measured by GPC is from 1,000 to 500,000, preferably from 2,000 to: L 00,000, and more preferably from 3,000 to 20,000. Range. If the molecular weight is excessively small, all of the polyester migrates to the surface of the resin molded product, resulting in insufficient coating film strength.If the molecular weight is excessively large, the polyester molecules hardly migrate to the resin molded product surface layer, The effect of improving the adhesiveness cannot be sufficiently obtained.

(Mouth) The hydroxyl value is 3 Om K OHZg or more, usually 30 to 200 mg K OHZ g, preferably 35 to: L 50 mg K0 H / g, more preferably 40 to 120 mg KOH / g Range. If the hydroxyl value is too small, the amount of hydroxyl groups on the surface is so small that sufficient coating strength cannot be obtained.

(C) It is usually oil-soluble. That is, the light transmittance of the polyester toluene solution measured as described above is usually at least 80%, preferably at least 90%. (2) The acid value is preferably 2 O mg KOHZ g or less, more preferably 1 O mg KOHZ g or less. If the acid value is excessively large, corrosion during resin kneading becomes a problem. <Inorganic powder may be added to the resin modifier of the present invention, if necessary. The inorganic powder generally refers to a filler added to a resin, and specific examples thereof include calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, and gay acid. Examples include calcium, magnesium gayate, calcium sulfate, barium sulfate, calcium sulfite, myriki, dolomite, silica, clay, talc, zinc oxide, glass fiber, and carbon fiber.

The resin to be modified by the polyester modifier of the present invention is not particularly limited as long as it has a proper compatibility with the polyester modifier. However, the effect of the modifier of the present invention is remarkable in thermoplastic resins. Examples of the thermoplastic resin include hydrocarbon resins such as polyolefin resins and styrene resins, ionomer resins, copolymers of ibutylene-maleic anhydride, polyethylene methacrylate, polyvinyl chloride, polyvinylidene chloride, and the like. Examples include vinyl polyacetate, fluororesin, polyamide, and polyolefin. Among these, hydrocarbon-based thermoplastic resins are preferred, and among them, polyolefin-based resins are particularly preferred.

Examples of polyolefin resins include homopolymers of α-olefins such as polyethylene, polypropylene, poly-1-butene, and poly-1-methyl-1-pentene; ethylene-butarene copolymer, ethylene / 1-butene copolymer Copolymer, Ethylene-4-methyl-1 pentene copolymer, Ethylene / butadiene copolymer, Ethylene / Propylene / Gen copolymer, Propylene 1-butene copolymer, Provylene 4-methyl-1 1-pentene copolymer A polymer containing an α-refined olefin component as a main component, such as a copolymer, and a graft copolymer obtained by graft copolymerizing an α, yS-unsaturated polar compound component such as acrylic acid / maleic acid and anhydride with the polymer. Polymerized modified olefin copolymer; acrylic acid is added to the polymer containing the above-mentioned α-olefin component as a main component. α such as maleic acid and anhydride, beta - unsaturated polar Block copolymerized modified olefin copolymer obtained by block copolymerization of compound components; ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-crotonic acid copolymer, ethylene-maleic acid copolymer Examples include a polymer, a random copolymer having an α-olefin component as a main component, such as an ethylene / methyl acrylate copolymer and an ethylene'vinyl acetate copolymer.

As long as the properties of the resin are not impaired, a small amount of a thermoplastic elastomer such as ethylene-propylene copolymer rubber or ethylene-propylene-gen terpolymer rubber is used for these polyolefin resins. May be blended. Styrene resins include polystyrene, high-impact polystyrene, AS resin, ABS resin, AAS resin, ACS resin, MBS resin, styrene-modified polyphenylene ether, resin block polymers such as styrene-butadiene and styrene-isobrene, and the like. And their partially hydrides. Among them, polystyrene, high impact polystyrene and ABS resin are preferred.

The amount of the modifying agent comprising the polyester of the present invention added to the resin is 0.1 to 50% by weight, preferably 0.5 to 10% by weight, and more preferably 0.1 to 50% by weight, based on the total resin weight including the modifying agent. Preferably it is in the range of 1.0 to 5% by weight. If the amount of the modifier is not too small, the desired effect cannot be obtained. If the amount is too large, the inherent properties of the modified resin are significantly reduced.

Various additives can be added to the resin composition containing the modifier of the present invention containing polyester as an active ingredient. Examples of additives include various stabilizers such as antioxidants, weather stabilizers, heat stabilizers, UV stabilizers, UV inhibitors: titanium oxide, zinc oxide, lead white, lead white, lead oxide, cuprous oxide, iron Colorants such as inorganic pigments, organic pigments, etc., such as black, power yellow, molybdenum red, silver vermilion, graphite, chromium oxide, navy blue, carbon black, barium sulfate, alumina white, white carbon; Conductivity-imparting agents: calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium gayate, magnesium gayate, calcium sulfate, barium sulfate, calcium sulfite , My strength, dolomite, silica, Inorganic fillers such as ray, talc, carbon black, zinc oxide, and glass fiber; organic active halogen compounds such as succinimide, succinyl acid, and halogenated hydantoin; reinforcing agents, plasticizers And various additives such as an antistatic agent, a nucleating agent, a flame retardant, and an oil. These can be added alone or in combination. The amounts of these additives can be determined appropriately within a range that does not impair the effects of the present invention.

In order to prepare a resin composition containing a polyester modifier, a resin, a polyester modifier and necessary additives may be kneaded. As the melt kneading method, a kneading method using a known kneading machine generally used for thermoplastic resins can be applied. Examples of the kneading machine used include extruders such as a single screw extruder and a twin screw extruder; a kneading mixer, a brabender-blast graph, a blast mill, a multi-screw kneader, a double helical ribbon mixer and the like. It is exemplified as one that can be used. Among them, extruders are preferred from an industrial point of view.

Above the melting point or钦化point of the resin temperature is used in the melt-kneading, and the temperature below the decomposition temperature is generally in the range of 1 3 0~2 7 0 ^e C is not preferable. Further, the melt-kneading time varies depending on the mixing ratio of each component, the melt-kneading temperature, and the like, and is not necessarily limited, but is preferably 0.5 to 15 minutes.

The resin composition containing the modifier of the present invention can be made into an arbitrary molded product, and by coating the surface thereof, a resin molded product having a coating film with good adhesion can be obtained. Usable molding methods include extrusion, injection molding, hollow molding, compression molding, and rotational molding.

Examples of molded articles include films and sheets, and various industrial parts such as automobile bumpers, corner bumpers, knocker air damscarts, mad guard side moldings, wheel caps, spoilers, side steps, and door mirrors. -Automotive exterior parts such as bases, automotive interior parts such as instrument panels, levers, knobs, dashboards, door liners, etc., and electrical products such as connectors, cap plugs, bots, refrigerators, lighting equipment, audio equipment, and OA equipment _c to the housing, color box, etc. daily commodities and the like, such as storage case The paint applied to the surface of the molded body is not particularly limited as long as it is a paint generally used in the industry.For example, acrylic resin paint, polyurethane resin paint, melamine resin paint, epoxy resin paint, acrylic modified alkyl resin Paints, amine alkyd resin paints and the like are suitable.

The paint can be applied to the surface of the molded body according to a conventional method, and examples thereof include a method such as electrostatic coating, spray coating, brush coating, and coating with a roll coater. The application of the paint may be performed by a method of applying an undercoat and then applying an overcoat. After the paint is applied, it may be cured by heating with nichrome wire, infrared rays, high frequency (UHF), or the like. The thickness of the coating film can be changed according to the purpose of use of the molded article, and is not particularly limited, but is usually in the range of 1 micron to 50,000 microns after drying.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The parts and percentages in the examples are on a weight basis unless otherwise specified. The weight average molecular weight was measured by GPC and converted with standard polystyrene.

The hydroxyl value and the acid value of the polyester were measured according to the following described in "Standard Fat and Oil Analysis Test Method" (Japan Oil Chemical Association).

Hydroxyl value 2, 4, 9, 2 -83

Acid value 2, 4, 1-83

Production Example 1

100 equipped with stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet

In a four-neck flask for 0 c c, polymerized fatty acid Haridimer 200 (manufactured by Harima Chemicals, Inc .; 75.0% of dimer monoacid, 17.0% of trimeric acid, 8.0% of monomeric acid, acid value

193) 420 g, 79.8 g of 2-butyl-2-ethyl-1,3-propanediol, 42.7 g of trimethylolpropane, and 0.26 g of monobutyltin oxide as a catalyst were charged. (OHZCOOH equivalent ratio = 1.35).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, removing water and unreacted diol formed during the reaction, It took 6 hours to raise the temperature. Thereafter, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester 1 had a weight average molecular weight of 7,300, an acid value of 0.2 mgK0HZg and a hydroxyl value of 53 mgK0HZg. The light transmittance of the toluene solution was 98%.

Production Example 2

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid haridimer 270S (manufactured by Harima Chemicals, Inc .; 80.5% dimer monoacid) 17.5% trimeric acid, 0.5% monomeric acid, acid value 192) 454 g, 73.3 g 3-methyl-1,5-pentanediol, 35.7 g trimethylolpropane and monobutyl catalyst 0.26 g of tin oxide was charged. (OHZC 00H equivalent ratio = 1.31).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, the temperature was raised from 100 to 150 ° C over 1 hour while removing water and unreacted diol generated during the reaction. After that, the reaction was continued for 10 hours while dehydrating at 260. The obtained polyester 2 had a weight average molecular weight of 6,800, an acid value of 0.2 mg K0HZg and a hydroxyl value of 4 lmg KOH / g. The light transmittance of the toluene solution was 99%.

Production Example 3

In a 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator, and a nitrogen gas inlet tube, polymerized fatty acid Haridimer 300 (manufactured by Harima Chemicals, Inc .; 97.0% dimer monoacid, 5%, trimeric acid 2.5%, acid value 195) 460 g, 2,2-dimethyl-1,3-propanediol 49.8 g, trimethylolpropane 64.1 g and monobutyltin oxide as catalyst 0.26 g of C was charged. (OHZCOOH equivalent ratio = 1.49).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, the temperature was raised from 100 to 150 for 1 hour while removing water and unreacted diol generated during the reaction. After that, the reaction was continued for 10 hours while dehydrating at 260. The obtained polyester 3 had a weight average molecular weight of 5,700 and an acid value of 0. 1 mg KOH / g The hydroxyl value was 65 mg KOH / g. The light transmittance of the toluene solution was 98%.

Production Example 4

In a 100 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, 460 g of polymerized fatty acid (Haridaima-1 300) and glycidyl dimethyl ester (Shell Epoxy equivalent: 400, Ebicoat 871) 63.4 g, 2,2-dimethyl-1,3-propanediol 95.5 g and monobutyltin oxide 0.26 g as a catalyst were charged. (OH + epoxy group ZCOOH equivalent ratio = 1.25)

Stirring was performed while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 ° C to 150 ° C over 1 hour while removing water and unreacted diol generated during the reaction. After that, the reaction was continued for 10 hours while dehydrating at 260. The obtained polyester 4 had a weight average molecular weight of 6,500, an acid value of 0.1 mg KOHZg and a hydroxyl value of 52 mg KOHZg. The light transmittance of the toluene solution was 96%.

Production Example 5

100 equipped with a bottle stirrer, thermometer, reflux cooling pipe, water separation pipe and nitrogen gas inlet pipe

In a four-neck flask for 0 c c, polymerized fatty acid Haridima-1 250 (manufactured by Harima Chemicals, Inc .; 79.0% of dimeric acid, 18.0% of trimeric acid, 3.0% of monomeric acid, acid value

193) 420 g, 2,2-—ethyl-1,3,3-propanediol 13.4 g, pentaerythritol 41.4 g, and 0.26 g of monobutyltin oxide as a catalyst were charged. (0HZC 00H equivalent ratio = 1.40).

Stirring was performed while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 ° C to 240 ° C over 6 hours while removing water and unreacted diol generated during the reaction. Thereafter, the reaction was continued for 10 hours while dehydrating at 240, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmmHg. The obtained polyester 5 had a weight average molecular weight of 21,500, an acid value of 0.2 mg KOHZg, and a hydroxyl value of 89.5 mg KOHZg. 94% light transmittance of toluene solution Met.

Production Example 6

100 equipped with a stirrer, thermometer, reflux cooling pipe, water separation pipe and nitrogen gas inlet pipe

In a four-neck flask for 0 c c, polymerized fatty acid Haridimer 250 (manufactured by Harima Chemicals, Inc .; 79.0% of dimeric acid, 18.0% of trimeric acid, 3.0% of monomeric acid, acid value

193) 420 g, 1,6.7-hexanediol 80.7 g, Penyu erythritol 39.9 g, and 0.26 g of monobutyltin oxide as a catalyst were charged. (OHZC OOH equivalent ratio = 1.35).

The mixture was stirred while introducing nitrogen gas, and the temperature was increased to 100C. Subsequently, the temperature was raised from 100 to 240 over 6 hours while removing water and unreacted diol generated during the reaction. Thereafter, the reaction was continued for 10 hours while dehydrating at 240, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmmHg. The obtained polyester 6 had a weight average molecular weight of 30,500, an acid value of 0.1 mg KOHZg, and a hydroxyl value of 91. SmgKOHZg. The light transmittance of the toluene solution was 93%.

Production Example 7

In a four-neck flask for 0 c c, polymerized fatty acid Haridimer 250 (manufactured by Harima Chemicals, Inc .; 79.0% of dimer acid, 18.0% of trimeric acid, 3.0% of monomeric acid, acid value

193) 420 g, diethylene glycol 80.5 g, Benyu erythritol 44.3 g, and 0.17 g of tetra-n-butyl-orthothiinate as a catalyst were charged. (OHZC 00H equivalent ratio = 1.50).

Stirring was performed while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 to 240 over 6 hours while removing water and unreacted diol formed during the reaction. Thereafter, the reaction was continued for 10 hours while dehydrating at 240 ° C, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmmHg. The obtained polyester 7 had a weight average molecular weight of 13,700, an acid value of 0.1 mg KOHZg, and a hydroxyl value of 96.1 mg KOHZg. 94% light transmittance of toluene solution Met.

Production Example 8

Hydrogenated polymerized fatty acids (hydride of Hariddimer 300, iodine value 6, acid value 195, monomeric acid 0.5%, dimeric acid 97.0%, trimeric acid 2. 5%) 300 g, epoxy resin (bisphenol type, Evicoat 828; epoxy equivalent: 188, manufactured by Yuka Seal Co., Ltd.) 38.0 g, epoxy resin (bisphenol type, ebicoat, 1001; epoxy equivalent: 478, oil) 88.6 g, and 38.9 g of 1,6-hexanediol were charged. (0H + epoxy group ZCOOH equivalent ratio = 2.00).

Stirring was performed while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, the temperature was raised from 100 ° C to 240 ° C over 6 hours while removing water and unreacted diol generated during the reaction. Thereafter, the reaction was continued for 10 hours while dehydrating at 240, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmmHg. The obtained polyester 8 had a weight average molecular weight of 10,500, an acid value of 0.1 mg KOHZg and a hydroxyl value of 99.mg KOHZg. The light transmittance of the toluene solution was 92%.

Production Example 9

In a 100 Occ four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid Haridima 250 (manufactured by Harima Chemicals, Inc .; 79.0% dimer monoacid) , Trimer acid 18.0%, monomeric acid 3.0%, acid value

1 9 3) 420 g, adibic acid 73 g, 2-butyl-2-ethyl-1,3-butanepandiol 222.5 g, pentaerythritol 81.2 g and tetra-n- as catalyst 0.17 g of butyl-ortho-chinate was charged. (OH / COOH equivalent ratio = 1.60).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, the temperature was raised from 100 ° C to 240 over 6 hours while removing water and unreacted diol generated during the reaction. After that, while dehydrating at 240 ° C, The reaction was continued for a period of time, and finally, the reaction was performed under a reduced pressure of 10 OmmHg for 3 hours. The obtained polyester 9 had a weight average molecular weight of 9,800 and an acid value of 0.1 mg KOHZg and a hydroxyl value of 91.OmgKOH / g. The light transmittance of the toluene solution was 96% .o

Production Example 10

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid Haridima-1 300 (manufactured by Harima Kasei Co .; dimer acid 97.0%, trimer 2.5% of monoacid, 0.5% of monomeric monoacid, acid value of 195) 420 g, 2-butyl-2-ethyl-1,3,14-propanediol 146.3 g and monobutyltin oxide as catalyst 0.26 g was charged. (OH C OOH equivalent ratio = 1.25).

The mixture was stirred while introducing nitrogen gas, and the temperature was raised to 100. Subsequently, the temperature was raised from 100 C to 240 over 6 hours while removing water and unreacted diol formed during the reaction. Thereafter, the reaction was continued for 10 hours while dehydrating at 240, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmmHg. The obtained polyester 10 had a weight average molecular weight of 11,500, an acid value of 0.3 mg K0HZ g, and a hydroxyl value of 20.5 mg KOH / g. The light transmittance of the toluene solution was 99%.

Examples 1 to 5, Comparative Examples 1 and 2

Using 98 parts by weight of polypropylene MS 670 (manufactured by Tokuyama Soda; MF R23) and 2 parts by weight of the polyester modifier shown in Table 1 using a lab blast mill (Toyo Seiki Co., Ltd., model 20C 200, content 60 cc) Kneaded at a temperature above the melting point. The kneaded product was compression-molded between an aluminum plate baked with a silicone release agent at a molding temperature of 220 ° C and a molding time of 5 minutes to produce a film (0.5 mm thick).

The contact angles of the prepared films were measured using a Kyowa Interface Science contact angle measuring device (CA-D type) and are shown in Table 1. In addition, a urethane paint (Kansai Vint; Urethane PG-80) was applied to the resin surface using a sprayer and baked at 60 ° C for 15 minutes. The peeling test of the coating film was performed using a cross cut tester (JI S (1990), paint, K-1 5400, 8.5.1. The cuts were made at a load of 350 kg, and 1 cut was made perpendicular to the cuts at intervals of 1 mm to make 100 bases per cm '.

Adhesive tape with a width of 18 mm manufactured by Nichiban Co., Ltd. was pressed with a pressure roller at a load of 1300 kg, and a 180 ° peel test was performed. The adhesion rate (%) of the coating film was calculated from the amount of the remaining coating film after peeling. The results are shown in Table 1.

In Comparative Example 2, a film was formed in the same manner as in Example 1 from only the same polybrovirene used in Example 1 without using a polyester modifier, and the contact angle was measured. Further, the same coating was performed, and a separation test was performed. <Results are shown in Table 1.

Example Example Comparative Example

1 2 3 4 5 1 2

Transformation Hotel 1 Hotel 1 Hotel 2 Hotel 5 Hotel 8 Hotel 9 Hotel I 10 I Angle (deg.) 70 66 71 58 60 93 93

Adhesion rate (¾) 100 100 100 100 100 18 13

Examples 6 to 9, Comparative Examples 3 and 4

97 parts by weight of high-density polyethylene 2200 J (manufactured by Mitsui Petrochemical Industries) and 3 parts by weight of the polyester modifier shown in Table 2 were mixed using a lab blast mill (Toyo Seiki model 20C200, content 60 cc). Kneaded at a temperature above the melting point. The kneaded material is between aluminum plates baked with a silicone release agent at a molding temperature of 200. C. Compression molding was performed in a molding time of 5 minutes to produce a film (0.5 mm thick).

The contact angles of the prepared films were measured using a Kyowa Interface Science contact angle measuring device (C A-D type) and are shown in Table 2. In addition, an epoxy-based coating (Nippon Bee Chemical; RB 298 HP4) was applied to the resin surface with a doctor blade. C, cured for 2 days. The peeling test of the film was carried out by a cross-cut tester in accordance with the matrix method (JIS (1990), paint, K-5400, 8.5.1.). The cuts were made at a load of 350 kg, and 11 cuts were made perpendicular to each other at intervals of 1 mm to make 100 base lines per lcm2.

Adhesive tape with a width of 18 mm manufactured by Nichiban Co., Ltd. is crimped with a load of 1300 kg using a crimping hole and 180. Was subjected to a peel test.付着 The adhesion rate (%) of the coating film was calculated from the amount of the remaining coating film after separation. The results are shown in Table 2.

In Comparative Example 4, a film was formed from the same high-density polyethylene used in Example 6 by the same method as in Example 6 without using a polyester modifier, and the contact angle was measured. Further, the same coating was performed, and a peeling test was performed. The results are shown in Table 2.

Table 2 Comparative examples

6 7 8 9 3 4 Transformation Hotel List 3 Hotel List 4 Hotel List 6 Hotel List 1 Hotel List 10

ideg.) 77 81 68 73 96 97 Adhesion rate (¾) 100 95 100 100 10 0 Industrial applications

When the resin modifier of the present invention is incorporated into a hydrocarbon-based thermoplastic resin such as an olefin-based resin or other molding resins, the performance of the resin to be modified is hardly reduced, and the coating film, especially It can greatly improve the adhesiveness of paint films such as acrylate or methacrylate, urethane, acrylic urea, polyester and epoxy. In addition, the resin modifier of the present invention also has the effect of improving the adhesive properties of epoxy-based and cyanoacrylate-based (instant adhesives) and the printability of aqueous inks. Can be.

Therefore, the resin composition containing the modifier of the present invention can be widely used in the field of molded articles requiring painting, printing, adhesion and the like. The type of the molded product itself is not particularly limited, and is widely used for, for example, an extruded product such as a film and a sheet, and an injection molded product such as a vehicle exterior component such as a bicycle bumper.

Claims

The scope of the claims

1. The hydroxyl value obtained by polycondensation of a polyvalent higher carboxylic acid and a polyhydric alcohol component containing a tri- or higher valent alcohol is 3 Omg KOHZg or more, and the weight average molecular weight is 1,000 to 500. Modifier for resins containing polyester as active ingredient.

2. The resin modifier according to claim 1, wherein the polyhydric alcohol component is a mixture of a trihydric or higher alcohol and a dihydric alcohol.

3. The resin modifier according to claim 1, wherein the trihydric or higher alcohol accounts for 10 to 90 mol% of the polyhydric alcohol component.

4. The resin modifier according to any one of claims 1 to 3, wherein the OH / COOH equivalent ratio is 1.02 to 3.

5. The hydroxyl value obtained by polycondensation of a polyvalent higher carboxylic acid and a polyhydric alcohol component containing a polyhydric ethoxy compound having two or more epoxy groups in the molecule is 3 Omg KOHZg or more, A resin modifier containing a polyester having a weight average molecular weight of 1,000 to 500,000 as an active ingredient.

6. The resin modifier according to claim 5, wherein the polyhydric alcohol component is a mixture of a polyhydric epoxy compound and a dihydric alcohol.

7. The resin modifier according to claim 5, wherein the polyepoxy compound accounts for 5 to 50 mol% of the polyhydric alcohol component.

8. The resin modifier according to any one of claims 5 to 6, wherein the (OH + epoxy group) ZCO OH equivalent ratio is 1.02 to 3.

9. The resin modifier according to any one of claims 1 to 8, wherein the acid value is 2 OmgKOHZg or less.

10. The resin modifier according to any one of claims 1 to 9, wherein the hydroxyl value is 30 to 20 Omg K0HZg.

11. The resin modifier according to any one of claims 1 to 10, wherein the polyvalent higher carboxylic acid contains at least a divalent higher carboxylic acid.

12. The resin modifier according to claim 11, wherein the polyvalent higher carboxylic acid comprises only a divalent higher carboxylic acid.

13. The resin modifier according to claim 11, wherein the polyvalent higher carboxylic acid is a mixture of a divalent higher carboxylic acid and a trivalent or higher carboxylic acid.

14. The resin modifier according to claim 13, wherein the trivalent or higher carboxylic acid is a trimeric acid of a polymerized fatty acid.

15. The method according to any one of claims 11 to 14, wherein the divalent higher carboxylic acid is selected from polyalkenyl succinic acid, dimer acids of polymerized fatty acids and hydrides thereof. Modifier for resin.

16. The resin modifier according to any one of claims 1 to 15, wherein the polyester is an oil-soluble polyester.

1 7. A resin composition comprising the resin to be modified and the resin modifier according to any one of claims 1 to 16.

18. The resin composition according to claim 17, wherein the content of the resin modifier is 0.1 to 50% by weight based on the resin composition.

19. The resin composition according to claim 17, wherein the resin to be modified is a thermoplastic resin.

20. The resin composition according to claim 19, wherein the thermoplastic resin is a hydrocarbon-based thermoplastic resin.

21. The resin composition according to claim 20, wherein the hydrocarbon-based thermoplastic resin is a styrene-based resin or a polyolefin-based resin.

22. A resin molded article obtained by molding the resin composition according to any one of claims 17 to 21 and coating the surface thereof.