JP3528314B2 - Oil-soluble polyester, modifier for resin, and resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin modifier containing an oil-soluble polyester as an active ingredient, and a polyolefin resin composition containing the resin modifier. The resin modifier of the present invention comprising an oil-soluble polyester as an active ingredient is useful as a modifier added to a thermoplastic resin such as a polyolefin resin for the purpose of improving paintability and adhesiveness. A film or other molded article obtained from the resin composition containing the composition has excellent coatability, adhesiveness and printability.

[0002]

2. Description of the Related Art Hydrocarbon resins such as polyolefins are widely used because of their excellent physical properties and relatively low price. However, there is a drawback in that the desired adhesive strength cannot be obtained.

Conventionally, a technique for modifying the surface of a resin molded product has been proposed for the purpose of improving the paintability and adhesiveness of a molded product of a resin such as polyolefin. For example, a technique for flame-treating the surface of a resin molded product (J. Mat. Sci., 14 ,
1344 (1979)) is known, but there are problems that uniform treatment is difficult depending on the shape of the molded product, and the appearance of the surface is impaired. Also, Japanese Patent Laid-Open No. 3-21743
Japanese Unexamined Patent Publication No. 3 discloses a surface modification technique by ultraviolet irradiation, but this technique has a problem when the molded product is large and the shape is complicated. Further, as a typical surface treatment technique using low pressure plasma, a glow discharge method (J. Adhesio) is used.
n, 11 , 57 (1980)) or plasma treatment with alcohol vapor and then steam plasma treatment (JP-A-2-123140 and JP-A-6-24).
No. 8103) is known, but these techniques require an extra step for surface treatment,
When the treatment time is long, there remains a problem that the introduced polar group is changed over time. The method of surface treatment with a halogen-containing compound such as trichlene that has been put into practical use is
The use of halogen-containing compounds presents environmental and hygiene problems.

In place of the above surface treatment, it has also been proposed to incorporate a modifier for improving paintability and adhesiveness into the resin molded product. For example, a technique of blending a random copolymer of a hydrophilic monomer such as dimethylaminoethyl methacrylate and 2-hydroxyethyl methacrylate and a lipophilic monomer such as stearyl methacrylate into a resin as a coating modifier (Japan Adhesive Co., Ltd. Journal, 28,
487 (1992)) is known. In this technique, it is necessary to increase the introduction amount of the hydrophilic monomer in order to improve the adhesiveness, which causes a problem that the compatibility with the resin decreases. Further, according to the technique of adding an acid anhydride-modified product of polyolefin disclosed in JP-A-60-177070 and JP-A-4-63817, the adhesiveness of the coating film is improved, but the amount added However, there is a problem that the strength characteristics of the resin are deteriorated.

On the other hand, as a polyester type modifier, for example, in JP-A-6-136068, it is obtained by reacting poly (butylene adipate) polyol and 2-ethylhexamethacrylate in the presence of benzoyl peroxide. Polyester modifications are disclosed. However, the modified polyester obtained by this method is
Although it has excellent compatibility with polyolefin resins such as polypropylene to be modified, it does not have sufficient adhesion and adhesion with paints.

[0006]

An object of the present invention is to provide a modifier for a resin containing, as an active ingredient, an oil-soluble polyester capable of imparting good paintability, adhesiveness and printability to a resin such as a polyolefin resin. And a polyolefin-based resin composition containing the resin modifier .

[0007]

Means for Solving the Problems The above object of the present invention is to:
The polyhydric carboxylic acid component containing a trivalent or higher carboxylic acid and the polyhydric alcohol component are 1.02 in COOH / OH equivalent ratio.
The weight average molecular weight obtained by polycondensation at a ratio of
000-500,000, acid value 20-200mgK
Tree as an active ingredient an oil soluble polyester is OH / g
Achieved by a fat modifier .

The carboxylic acid used for the synthesis of the oil-soluble polyester of the present invention contains a trivalent or higher carboxylic acid as an essential component. Examples of trivalent or higher carboxylic acids include:
Trimellitic acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), camphoronic acid (2,3-dimethylmethane-1,2,3-tricarboxylic acid), trimesic acid (1,3,5-benzenetricarboxylic acid) Acid), polymerized fatty acid trimer acid, and the like.

These trivalent or higher carboxylic acids are used alone or in combination of two or more, and the proportion of the carboxylic acid component used is usually 10 to 90 mol%, preferably 15 to 70 mol. %, More preferably 20
˜50 mol%. The balance of the carboxylic acid component is 2
It is a carboxylic acid.

The divalent carboxylic acid is not particularly limited and may be any of linear, branched, cyclic and aromatic divalent carboxylic acids. When the divalent carboxylic acid contains 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more of the higher divalent carboxylic acid, the compatibility with the polyolefin resin is suitable. A higher carboxylic acid usually has 10 or more carbon atoms,
The number is preferably 15 or more, more preferably 20 or more.

Specific examples of the divalent carboxylic acid include aliphatic lower dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, suberic acid, maleic acid, itaconic acid, pimelic acid, azelaic acid, methylmalonic acid and dimethylmalonic acid. Acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, methyl isophthalic acid; sebacic acid, brassic acid,
Examples include higher dicarboxylic acids such as polyalkylene succinic acid and dimer acid of polymerized fatty acid. Among these, polyalkylene succinic acid and dimer acid are preferable, and dimer acid is particularly preferable. These can be used alone or in combination of two or more.

The polymerized fatty acid is obtained by polymerizing a higher fatty acid.
And usually has 8 to 24 carbon atoms, preferably 16 to 2 carbon atoms.
Fats having 0 saturated or at least one unsaturated bond
Obtained by polymerizing fatty acids or their fatty acid ester derivatives
Is a general term for polymerized acids. Commercially available polymerized fatty acid
Is oleic acid, linoleic acid, ricinoleic acid, eleo
Polymerized from stearic acid, dimer acid
As a main component, polymer acid and monomer acid above trimer acid
Is contained as an accessory component. Of polymerized fatty acids
Structural analysis is described in D. H. Reported by McMahon et al.
(J. Am. Oil. Chem. Soc.,5
1, 522 (1974)). The polymerized product is
Or polymerized fats with different content of each component depending on the solvent extraction method
It can be separated into acid. In addition, these polymerized fatty acids
Hydrogenating the unsaturated carbon-carbon bonds remaining in
To obtain a hydrogenated polymerized fatty acid with good thermal oxidation stability.
I can do it. In the present invention, unpurified polymerized fatty acid, refined
Use either polymerized fatty acid or hydrogenated polymerized fatty acid
The dimer content is preferably 60% by weight or more.
Purified polymerized fatty acid containing acid component or its hydride is used.
Used.

Polyalkylene succinic acid has the general formula It is represented by. R in the formula is a polymer chain of lower alkylene, and the lower alkylene is preferably at least one selected from ethylene, propylene and butylene, and the degree of polymerization thereof is in the range of 10 to 300.

If necessary, other carboxylic acids may be used in a small amount (usually 30% by weight or less, preferably 20% by weight or less, based on the total weight of the carboxylic acids) within a range not impairing the object of the present invention. You can Specific examples of the carboxylic acid that can be used in combination include saturated fatty acids such as 2-methylpropanoic acid, isooctylic acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, and arachidic acid. ,
Alternatively, monocarboxylic acids such as unsaturated fatty acids such as linoleic acid, oleic acid and elaidic acid may be mentioned.

The alcohol component used in the synthesis of the oil-soluble polyester of the present invention is not particularly limited, and examples thereof include those used in ordinary polyester reactions, and generally those containing a dihydric alcohol as a main component. Is used.

Examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol and neopentyl glycol. , Alkanediols such as 1,9-nonanediol; oligooxyalkylene glycols such as diethylene glycol, dipropylene glycol and triethylene glycol; carbon number of alkylene groups such as polyethylene glycol, polypropylene glycol and polyoxyethylene-polypropylene glycol 2 to
5, polyoxyalkylene glycols having a degree of polymerization of 4 to 100; 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
2,2-dipropyl-1,3-propanediol, 2,
2-diisopropyl-1,3-propanediol, 2,
2-diisobutyl-1,3-propanediol, 2-methyl-2-dodecyl-1,3-propanediol, 2-
Ethyl-2-butyl-1,3-propanediol, 2-
Hindered glycols such as propyl-2-pentyl-1,3-propanediol; polycaprolactanediol and the like. Among these, hindered glycols are preferable.

These dihydric alcohols may be used alone or in combination of two or more kinds,
The proportion in the alcohol component is usually 50 to 100% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight. The balance is trihydric or higher alcohol.

Examples of trihydric or higher alcohols include:
Examples include trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, sorbitol, glucose, mannitol, sucrose, glucose, and the like. Among these, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, Dipentaerythritol, sorbitol and the like are preferable.

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

The polycondensation reaction for synthesizing the oil-soluble polyester may be carried out by a conventional method. The polycondensation reaction is usually 100 to 300 ° C., preferably 150 to 28.
It is carried out at a reaction temperature of 0 ° C., preferably in the presence of an inert gas. If necessary, a water-insoluble organic solvent that is azeotropic with water such as toluene or xylene may be used, or the reaction may be performed under reduced pressure. In the esterification polycondensation reaction, usually, as an esterification catalyst, paratoluenesulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate, zinc,
Various metal oxides such as titanium, tin and butyltin oxide, and titanium oxide are used, but it is preferable to use the metal oxide from the viewpoint of the oxidation resistance stability of the obtained polyester.

The acid value of the polyester is determined by the ratio of the divalent carboxylic acid to the trivalent or higher carboxylic acid in the polyvalent carboxylic acid and the ratio of the charged carboxylic acid component and the alcohol component. The ratio (equivalent ratio) COOH / OH of the carboxylic acid component and the alcohol component is 1.02 to 3.0, preferably 1.05 to 2.5, and more preferably 1.10 to 2.
The range is 0. If this equivalent ratio is too small, the acid value of the polyester produced will not be sufficiently high, and conversely, if the equivalent ratio is too large, the molecular weight of the polyester will not increase.

The polyester of the present invention obtained by polycondensing the polyvalent carboxylic acid component containing a trivalent or higher carboxylic acid and the polyhydric alcohol component as described above has the following characteristics. (A) It is oil-soluble (does not dissolve in water). (B) The polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) is 1,
000 to 500,000, preferably 2,000 to 10
30,000, more preferably 3,000 to 20,000
Is the range. If the weight average molecular weight is too small, the polyester modifier migrates entirely to the surface of the resin molded product and the coating strength is insufficient, and if the molecular weight is too large, the molecules of the polyester modifier become the resin molded product surface layer. It is difficult to obtain the effect of improving the adhesiveness.

(C) Acid value of 20 to 200 mg KOH /
g, preferably 25 to 150 mgKOH / g, more preferably 30 to 100 mgKOH / g. If the acid value is too small, the surface acid value is too small to obtain sufficient coating strength. (D) The hydroxyl value is not particularly limited, but is usually 0.1.
~ 100 mg KOH / g, preferably 0.1-50 mg
It is in the range of KOH / g.

If desired, inorganic powder may be added to the resin modifier of the present invention. The inorganic powder usually 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, calcium silicate. ,
Magnesium silicate, calcium sulfate, barium sulfate,
Examples thereof include calcium sulfite, mica, dolomite, silica, clay, talc, zinc oxide, glass fiber and carbon fiber.

The resin to be modified with the polyester modifier of the present invention is not particularly limited as long as it is a resin having an appropriate compatibility with the polyester modifier. However,
The modifying effect of the present invention is remarkable in a thermoplastic resin, particularly a hydrocarbon-based thermoplastic resin, and among them, an olefin-based resin is particularly preferable.

Examples of the olefin resin include homopolymers of α-olefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene; ethylene / propylene copolymers and ethylene / 1-butene. Copolymer, ethylene / propylene / diene copolymer, propylene / 1-butene copolymer, propylene / 4
-Methyl-1-pentene copolymers and other polymers containing an α-olefin component as a main component; and the polymers containing α, β-, such as acrylic acid, maleic acid and anhydrides.
Graft copolymerization modified olefin-based copolymer obtained by graft-copolymerizing unsaturated polar compound component; α, β-, such as acrylic acid, maleic acid and their anhydrides in the polymer containing the α-olefin component as a main component. Block copolymer modified olefin copolymer obtained by block copolymerizing an unsaturated polar compound component; further, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / crotonic acid copolymer, ethylene / maleic acid Examples thereof include random copolymers containing an α-olefin component as a main component, such as copolymers, ethylene / methyl acrylate copolymers, and ethylene / vinyl acetate copolymers. Other resins include polystyrene, impact-resistant polystyrene, styrene-acrylonitrile copolymer, ABS resin, MB
Examples include S resin and petroleum resin.

The amount of the modifying agent comprising the polyester of the present invention added to the resin is usually 0.1 to 50% by weight, preferably 0.5 to 1 based on the total resin weight including the modifying agent.
It is 0% by weight, more preferably 1.0 to 5% by weight. If the amount of the modifier added is too small, the desired effect cannot be obtained, and if it is too large, the properties originally possessed by the resin to be modified may be significantly impaired. The addition amount of the modifier composition containing the inorganic powder is the same as the above in terms of polyester modifier.

The resin composition containing the modifier of the present invention containing polyester as a main component contains an antioxidant, a lubricant, an anti-UV agent, an ultraviolet stabilizer, a heat stabilizer, an antistatic agent, a nucleating agent, an organic compound. And / or various additives such as an inorganic pigment may be added alone or in combination. Examples of these various additives include those usually added to polyolefin resins, and the addition amount thereof is appropriately determined within a range that does not impair the effects of the present invention.

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 kneader that is generally used for thermoplastic resins can be applied. Examples of the kneader used include an extruder such as a single-screw extruder and a twin-screw extruder; a Banbury mixer, a Brabender plastograph, a plastomill, a multi-screw kneader, and a double helical ribbon agitator. Of these, an extruder is preferable from an industrial viewpoint.

The temperature in the above melt-kneading is generally higher than the melting point or softening point of the resin used and lower than the decomposition temperature, and is usually 100 to 300 ° C, preferably 130 to 270 ° C. The melt-kneading time varies depending on the blending ratio of each component, the melt-kneading temperature, and the like, and is not particularly limited, but 0.5 to 15 minutes is suitable.

The resin composition containing the modifier can be formed into an arbitrary molded article such as a film and other exterior parts for vehicles such as automobile bumpers, and many molding methods such as extrusion molding and injection molding are adopted. To be

[0032]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. The parts and% in the examples are based on weight unless otherwise specified. The weight average molecular weight was measured by GPC and converted into standard polystyrene. The acid value and the hydroxyl value of the polyester were measured in accordance with the following described in "Standard oil and fat analysis test method" (Japan Oil Chemistry Association). Acid value 2,4,1-83 Hydroxyl value 2,4,9,2-83

Example 1 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas introduction tube was charged with polymerized fatty acid halidermer 300 (acid value 195 mgKOH / g,
Monomer acid 0.3%, dimer acid 97.0%, trimer acid 2.7%; manufactured by Harima Kasei Co., Ltd. 182.0 g, polymerized fatty acid halidimer 500 (acid value 186 mg KOH / g, dimer acid 27.1%, trimer acid) 72.9%; manufactured by Harima Chemicals Co., Ltd.) 410.0 g, 2-ethyl-2-butyl-1,
156.0 g of 3-propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. (CO
OH / OH = 1.40)

Stirring is performed while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
It took 6 hours to raise the temperature to ° C. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester 1 has a weight average molecular weight of 8,900 and an acid value of 41.4 m.
It was gKOH / g and the hydroxyl value was 0.8 mgKOH / g.

Example 2 A 1,000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas inlet tube was charged with polymerized fatty acid halider 270S (acid value 192 mgKOH /
g, monomer acid 0.5%, dimer acid 80.5%, trimer acid 17.5%; Harima Chemicals Co., Ltd.) 406.0 g, trimesic acid 63.0 g, 3-methyl-1,3-propanediol 73. 3 g and 0.26 g of monobutyltin oxide as a catalyst were charged. (COOH / OH = 1.3
5)

Stirring is performed while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
It took 6 hours to raise the temperature to ° C. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester 2 has a weight average molecular weight of 5,500 and an acid value of 65.3 m.
It had a gKOH / g and a hydroxyl value of 1.3 mgKOH / g.

Example 3 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing tube and a nitrogen gas introducing tube was charged with polymerized fatty acid halider 200 (acid value 193 mgKOH / g,
Monomer acid 0.7%, dimer acid 76.0%, trimer acid 17.0%; manufactured by Harima Kasei Co., Ltd.) 180.2 g, polymerized fatty acid halidimer 500 (acid value 186 mgKOH / g,
Dimer acid 27.1%, trimer acid 72.9%; manufactured by Harima Chemicals Co., Ltd.) 172.0 g, 2,2-dimethyl-1,3-
93.6 g of propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. (COOH / O
H = 1.20)

Stirring is performed while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Subsequently, while removing water and unreacted diol generated during the reaction, the temperature is changed from 100 ° C. to 260 ° C.
It took 6 hours to raise the temperature to ° C. After that, the reaction was continued for 10 hours while dehydrating at 260 ° C. The resulting polyester 2 has a weight average molecular weight of 7,100 and an acid value of 43.0 m.
It had a gKOH / g and a hydroxyl value of 1.0 mgKOH / g.

Examples 4 and 5 Polypropylene MS670 (MFR23 manufactured by Tokuyama Soda)
98 parts by weight and 2 parts by weight of the polyester modifier shown in Table 1 were used for Labo Plastmill (Model 20C20 manufactured by Toyo Seiki Co., Ltd.
Kneading was performed at a temperature equal to or higher than the melting point by using 0, the internal volume was 60 cc. The kneaded product was compression-molded between aluminum plates baked with a silicone release agent at a molding temperature of 220 ° C. for a molding time of 5 minutes to prepare a film (0.5 mm thick).

The contact angle of the produced film was measured using a contact angle measuring device (CA-D type) manufactured by Kyowa Interface Science Co., Ltd. and shown in Table 1. Further, a urethane coating (Kansai Paint Co., Ltd .; RETAN PG-80) was applied to the resin surface by spraying,
Baking was performed at 60 ° C. for 15 minutes. The peeling test of the coating film is
A cross-cutting method (JIS (199
0), paint, K = 5400, 8.5.1). The cuts have a load of 350 kg and are spaced at 1 mm intervals for 11
The cuts of the book were made orthogonal to each other to make 100 squares per cm ² . An adhesive tape having a width of 18 mm manufactured by Nichiban Co., Ltd. was used, compressed by a pressure roller with 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.

Comparative Example 1 A film was formed in the same manner as in Example 4 from the same polypropylene as used in Example 4 without using a polyester modifier, and the contact angle was measured. Furthermore, the same coating was performed and a peeling test was performed. The results are shown in Table 1.

[0042]

[Table 1]

Examples 6 and 7 High-density polyethylene 2200J (manufactured by Mitsui Petroleum Science Co., Ltd.)
97 parts by weight and 3 parts by weight of the polyester modifier shown in Table 2 were used for Labo Plastomill (Model 20C20 manufactured by Toyo Seiki Co., Ltd.).
Kneading was performed at a temperature equal to or higher than the melting point by using 0, the internal volume was 60 cc). The kneaded product was compression-molded between aluminum plates baked with a silicone release agent at a molding temperature of 200 ° C. for a molding time of 5 minutes to prepare a film (0.5 mm thick).

The contact angle of the prepared film was measured by using a contact angle measuring device (CA-D type) manufactured by Kyowa Interface Science, and shown in Table 1. Further, a urethane coating (Kansai Paint Co., Ltd .; RETAN PG-80) was applied to the resin surface by spraying,
Baking was performed at 60 ° C. for 15 minutes. The peeling test of the coating film is
A cross-cutting method (JIS (199
0), paint, K = 5400, 8.5.1). The cuts have a load of 350 kg and are spaced at 1 mm intervals for 11
The cuts of the book were made orthogonal to each other to make 100 squares per cm ² . An adhesive tape having a width of 18 mm manufactured by Nichiban Co., Ltd. was used, compressed by a pressure roller with 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 2.

Comparative Example 2 A film was formed in the same manner as in Example 6 from the same polypropylene as used in Example 6 without using a polyester modifier, and the contact angle was measured. Furthermore, the same coating was performed and a peeling test was performed. The results are shown in Table 2.

[0046]

[Table 2]

[0047]

Embodiment A resin modifier of the present invention, that is, a polyhydric carboxylic acid component containing a trivalent or higher carboxylic acid and a polyhydric alcohol component in a COOH / OH equivalent ratio of 1.02 to 3 is used.
The weight average molecular weight obtained by polycondensation at a ratio of
0 ~ 500,000, acid value 20 ~ 200mgKOH
The following is a summary of preferred embodiments of the polyolefin resin composition of the present invention containing the resin modifier having an oil-soluble polyester of 0.1 g / g as an active ingredient; and the resin modifier. .

(1) The polyvalent carboxylic acid component containing a trivalent or higher carboxylic acid is 10 to 90 mol% of the trivalent or higher carboxylic acid, more preferably 15 to 70 mol%, and further preferably 20 to 50 mol%. And a divalent carboxylic acid. (2) Trivalent or higher carboxylic acid is trimellitic acid, tricarballylic acid (1,2,3-propanetricarboxylic acid), camphoronic acid (2,3-dimethylmethane-1,
2,3-tricarboxylic acid), trimesic acid (1,3,5
-Benzenetricarboxylic acid) and at least one polymerized fatty acid trimer acid.

(3) The divalent carboxylic acid is 50 wt% or more, preferably 60 wt% or more, of the divalent higher carboxylic acid.
More preferably, it contains 70% by weight or more. (4) The divalent higher carboxylic acid is at least one selected from sebacic acid, brassic acid, polyalkylene succinic acid, and dimer acid of polymerized fatty acid.

(5) The polyhydric alcohol component is mainly composed of dihydric alcohol. (6) The dihydric alcohol is at least one selected from alkanediols, oligooxyalkylene recalls, polyoxyalkylene glycols and hindered glycols.

(7) The COOH / OH (equivalent) ratio of the carboxylic acid component and the alcohol component used in the polycondensation reaction is more preferably 1.05 to 2.5, further preferably 1.1.
0 to 2.0. (8) The polystyrene-equivalent weight average molecular weight of the oil-soluble polyester measured by GPC is more preferably 2,0.
00-100,000, more preferably 3,000-
It is 20,000. (9) The acid value of the oil-soluble polyester is more preferably 2
5 to 150 mg KOH / g, more preferably 30 to 1
It is 00 mgKOH / g.

(10) The resin to be modified with a resin modifier containing an oil-soluble polyester as an active ingredient is a thermoplastic resin, preferably an aliphatic hydrocarbon thermoplastic resin,
More preferably, it is polyolefin. (11) a polyolefin resin composition containing a resin modifier for which the oil-soluble polyester of the active ingredient, based on the resin composition by weight, 0.1 to 50 wt%, more preferably from 0.5 to 10 weight %, More preferably 1.0 to 5% by weight of the modifier.

[0053]

When the modifier of the polyester of the present invention is blended with an olefin resin or other molding resin, a coating film, particularly an acrylate or methacrylate type resin, can be obtained without substantially deteriorating the performance of the resin to be modified. It can greatly improve the adhesiveness of coating films of urethane, acrylic / urethane, polyester, epoxy and other paints. Further, this polyester modifier also has the effect of improving the adhesiveness of epoxy type, cyanoacrylate type (instantaneous adhesive) and the like and the printability of water-based ink, and can widely improve the surface characteristics of non-polar resins. Furthermore, it is also suitable as a compatibilizing agent between different molecules.

Claims (3)

(57) [Claims] 1. A weight average molecular weight obtained by polycondensation of a polyhydric carboxylic acid component containing a trivalent or higher carboxylic acid and a polyhydric alcohol component at a COOH / OH equivalent ratio of 1.02 to 3 1,000 to 500,000 and an acid value of 20
Have the oil-soluble polyester is ~200mgKOH / g
Resin modifier used as an active ingredient . 2. A resin modifier according to claim 1.
Polyolefin resin composition . 3. The content of the resin modifier is the weight of the resin composition.
The amount is 0.1 to 50% by weight based on the amount.
Polyolefin resin composition of.