JPH08217864A - Polyester - Google Patents

Abstract

PURPOSE: To obtain an oil-soluble polyester having a high molecular weight and a high hydroxyl value and useful as a modifier for a resin to improve paintability, adhesivity and printability of a resin molding by carrying out the polycondensation of polyvalent higher carboxylic acids with polyvalent alcohols at a specific ratio. CONSTITUTION: This polyester is produced by carrying out the polycondensation of polyvalent higher carboxylic acids [preferably, >=20C carboxylic acids and the mixture containing >=20wt.% of divalent carboxylic acids and 30-0wt.% of carboxylic acids having higher valence than 2] with polyvalent alcohols containing alcohols having higher valences than 2 (preferably, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol or sorbitol) at the equivalent ratio, OH/COOH, of 1.02-3. The polyester has a weight-average molecular weight of 1000-500,000 and a OH value of >=30%.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an oil-soluble polyester, and more particularly to an oil-soluble polyester useful as a modifier for resins. A film or other molded article obtained from a resin composition containing the oil-soluble polyester of the present invention as a modifier for resin 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, since there are no polar groups in the molecule, the adhesion of the coating film is low, It has a drawback that practical 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. In addition, JP-A-3-2174
The surface modification method by ultraviolet irradiation disclosed in Japanese Patent No. 33 is problematic when the molded product is large and the shape is complicated. The glow discharge method (J. Adhesion, 11 , 57 (198) is a typical surface treatment technique using low-pressure plasma.
0)) or plasma treatment with alcohol vapor, and then steam plasma treatment (JP-A-2-12314).
No. 0 and Japanese Patent Application Laid-Open No. 6-248103) are known, but these techniques require an extra step related to surface treatment, and if the treatment time is long, the introduced polar group may be deteriorated over time. Problems such as changing to. The method of practically treating the surface with a halogen-containing compound such as trichlene is problematic in terms of environment and hygiene since the halogen-containing compound is used.

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 (Adhesion Society of Japan Magazine, 28 , 4
87 (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 coating film is improved. There is a problem that it may worsen the hue.

On the other hand, as a polyester type modifier, for example, in JP-A-6-136068, poly (butylene adipate) polyol and 2-ethylhexamethacrylate are obtained by reacting them in the presence of benzoyl peroxide. Polyester modified products 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]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel polyester useful as a resin modifier for improving the paintability, adhesiveness and printability of resins such as polyolefins. .

[0007]

The object of the present invention is to:
OH / COOH equivalent ratio of polyhydric higher carboxylic acid and polyhydric alcohol containing trihydric or higher alcohol is 1.02
The weight average molecular weight obtained by polycondensation at a ratio of 3 is 1,0
An oil-soluble polyester having a hydroxyl value of 30 or more and a polyhydric higher carboxylic acid and a polyhydric alcohol containing a diepoxy compound of 0.002 to 500,000 at an (OH + epoxy group) / COOH equivalent ratio of 1.02. The weight average molecular weight obtained by polycondensation at a ratio of 3 to 1,000 is from 1,000 to 50.
It is achieved by an oil-soluble polyester having a hydroxyl value of 30,000 and a hydroxyl value of 30 or more.

The polyvalent higher carboxylic acid used in the synthesis of the oil-soluble polyester of the present invention is a carboxylic acid having 10 or more, preferably 15 or more, and more preferably 20 or more carbon atoms. Further, those containing at least 50% by weight or more, preferably 60% by weight or more, more preferably 70% by weight or more of a divalent higher carboxylic acid are used. If the carbon number in 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 carboxylic acid accounts for 50 to 100% by weight, preferably 60 to 100% by weight, more preferably 70 to 100% by weight, and the trivalent or higher carboxylic acid accounts for 50 to 0% by weight, preferably Is used in an amount of 40 to 0% by weight, more preferably 30 to 0% by weight.

Specific examples of the polyvalent higher carboxylic acid include:
Examples of the divalent carboxylic acid include linear, branched, cyclic and aromatic divalent carboxylic acids, which may be used alone or as a mixture. Specific examples include sebacic acid, brassic acid, polyalkylene succinic acid, and dimer acid of polymerized fatty acid. Among these, at least one selected from polyalkylene succinic acid and dimer acid of polymerized fatty acid may be used. preferable. Examples of the trivalent or higher carboxylic acid include a trivalent or higher polymerized fatty acid obtained by polymerizing a higher fatty acid, and particularly a trimer acid of the polymerized fatty acid. The most preferable polycarboxylic acid component is 6
Examples include purified polymerized fatty acid containing 0% by weight or more of a dimer acid component or a hydride thereof.

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.
It is a general term for polymerized acids obtained by polymerizing a fatty acid having 0 saturated or at least one unsaturated bond or a fatty acid ester derivative thereof. Commercially available polymerized fatty acids are those obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, etc., containing dimer acid as the main component, and polymer acid and monomer acid of trimer acid or more as sub-components. Is what you are doing. The structure analysis method of the polymerized fatty acid is described in D. H. McMahon et al. (J. Am. Oil. Chem. Soc., 51,522 (1
974)). 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. Further, hydrogenated polymerized fatty acids having good thermal oxidation stability can be obtained by hydrogenating the unsaturated carbon-carbon bonds remaining in these polymerized fatty acids. In the present invention, unpurified polymerized fatty acid, purified polymerized fatty acid or hydrogenated polymerized fatty acid can also be used, and preferably 6
A purified polymerized fatty acid or hydride thereof containing 0% by weight or more of a dimer component is used.

Polyalkylene succinic acid has the general formula (R in the formula is a polymer chain of lower alkylene). R is a polymer chain of lower alkylene, preferably the lower alkylene is 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, a small amount of other carboxylic acid (usually 30% by weight or less, preferably 20% by weight based on the total weight of the carboxylic acid) is used as long as the desired properties as a resin modifier are not impaired. The following) can be used together. Specific examples of the carboxylic acid that can be used in combination with the polyvalent higher carboxylic acid include succinic acid, glutaric acid,
Aliphatic lower dicarboxylic acids such as adipic acid, suberic acid, maleic acid, itaconic acid, pimelic acid, azelaic acid, methylmalonic acid, dimethylmalonic acid; terephthalic acid,
Aromatic lower dicarboxylic acids such as isophthalic acid and methylisophthalic acid; Other divalent lower carboxylic acids such as alkylene succinic acid; 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 other trivalent or lower carboxylic acids Acid; and 2-
Saturated fatty acids such as methylpropanoic acid, isooctylic acid, isononanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid or lower unsaturated fatty acids such as linoleic acid, oleic acid, and elaidic acid. And higher monocarboxylic acids.

The alcohol component used in the synthesis of the oil-soluble polyester of the present invention contains a trihydric or higher alcohol and / or a diepoxy compound. A desired hydroxyl value can be imparted to the polyester by using a trivalent or higher alcohol and / or diepoxy compound. That is, the hydroxyl group in the polyester is obtained by converting a part of the dialcohol having a hydroxyl value corresponding to the acid value of the dicarboxylic acid used as the carboxylic acid component to an alcohol having a valence of 3 or more, or in addition to such an alcohol, an epoxy resin. It can be introduced by using a compound.

Specific examples of trihydric or higher alcohols used in the synthesis of the oil-soluble polyester of the present invention include trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol,
Examples thereof include sorbitol, glucose, mannitol, sucrose, glucose and the like. Among these, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol,
Sorbitol and the like are preferable.

As the epoxy compound used in the synthesis of the oil-soluble polyester of the present invention, a compound having two or more epoxy groups in one molecule is used. Specific examples thereof include glycidyl ether of bisphenol A and glycidyl of bisphenol F. Examples thereof include ethers, dimer acid glycidyl esters, and aliphatic glycidyl ethers.
The proportion of trihydric or higher alcohol in the alcohol component used in the synthesis of the oil-soluble polyester of the present invention is usually 10
To 90 mol%, preferably 15 to 70 mol%, more preferably 20 to 50 mol%, and the ratio of the diepoxy compound is usually 5 to 50 mol%, preferably 1
It is in the range of 0 to 40 mol%, more preferably 15 to 35 mol%. The balance of the alcohol component is dihydric alcohol.

Specific examples of the dihydric alcohol include ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol and 3-methyl-1,5-pentanediol. ,
Alkanediols such as neopentyl glycol and 1,9-nonanediol; oligooxyalkylene glycols such as diethylene glycol, dipropylene glycol and triethylene glycol; alkylene groups such as polyethylene glycol, polypropylene glycol and polyoxyethylene-polypropylene glycol Polyoxyalkylene glycols having 2 to 5 carbon atoms and a degree of polymerization of 2 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-diisobutyryl-1,3-propanediol,
Hindered glycols such as 2-methyl-2-dodecyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-propyl-2-pentyl-1,3-propanediol A polycaprolactone diol and the like can be mentioned. Among these, hindered glycols are preferable.

If necessary, a small amount of another alcohol (30% by weight or less, preferably 20% by weight or less based on the total weight of the alcohols) is used in combination so long as the desired properties as a resin modifier are not impaired. be able to. Other alcohols include neopentyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3.
And monohydric alcohols such as pentanol, 2,3,3-trimethyl-2-butanol, 1-decanol and nonyl alcohol.

The polycondensation reaction for synthesizing the oil-soluble polyester may be carried out by a conventional method. The polycondensation reaction is usually preferably carried out at a reaction temperature of 150 to 280 ° C. 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. Further, at the time of esterification polycondensation reaction, usually, as an esterification catalyst, paratoluenesulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate,
Various metal oxides such as zinc, 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 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 and the epoxy compound. The molecular weight of polyester is determined by the ratio of the charged carboxylic acid component and alcohol component.
Ratio (equivalent ratio) of carboxylic acid component and alcohol component (including epoxy compound) OH (+ epoxy group) / COO
H is 1.02 to 3.0, preferably 1.05 to 2.5,
More preferably, the range is 1.10 to 2.0. If the equivalent ratio is too small, the hydroxyl value of the polyester produced will not be sufficiently high, and the acid value will be high, which will cause problems such as corrosivity. Conversely, if the equivalent ratio is too large, the molecular weight of the polyester will be There are problems such as not getting higher.

As described above, polyvalent higher carboxylic acid and 3
The polyester of the present invention obtained by polycondensing a polyhydric alcohol containing a polyhydric alcohol and / or a diepoxy compound has the following characteristics. (A) It is oil-soluble. (B) The polystyrene-equivalent weight average molecular weight measured by GPC is 1,000 to 500,000, preferably 2,000 to 100,000, and more preferably 3,0.
The range is from 00 to 20,000. If the molecular weight is too small, the polyester will not migrate sufficiently to the resin molded product surface and the coating strength will not be sufficient, and if the molecular weight is too large, the polyester molecules will not readily migrate to the resin molded product surface layer,
Adhesiveness improvement effect cannot be obtained sufficiently.

(C) Hydroxyl value is 30 or more, usually 30 to 2
00, preferably 35 to 100, more preferably 40
The range is from -80. If the hydroxyl value is too small, the amount of hydroxyl groups on the surface is small and sufficient coating strength cannot be obtained. (D) The acid value is preferably 20 or less, more preferably 10
It is the following. If the acid value is excessively large, corrosion during resin kneading becomes a problem.

When using the resin modifier containing the oil-soluble polyester of the present invention as an active ingredient, an inorganic powder may be added, if necessary. 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, calcium sulfite, mica, dolomite, silica, clay, talc, zinc oxide, glass fiber, carbon fiber and the like.

The resin to be modified with the modifier containing the oil-soluble polyester of the present invention as an active ingredient is not particularly limited as long as it is a resin having a proper compatibility with the polyester modifier. However, the effect of the polyester modifier of the present invention is remarkable in a thermoplastic resin, particularly a hydrocarbon-based thermoplastic resin, and among them, an olefin-based resin is preferable. As the olefin resin, polyethylene, polypropylene, poly-1-butene, poly-4-methyl-
Α-Olefin homopolymers such as 1-pentene; ethylene / propylene copolymers, ethylene / 1-butene copolymers, ethylene-4-methyl-1-pentene copolymers,
A polymer containing an α-olefin component as a main component such as an ethylene / butadiene copolymer, a propylene / 1-butene copolymer and a propylene / 4-methyl-1-pentene copolymer, and acrylic acid or Graft copolymerization modified olefin-based copolymer obtained by graft-copolymerizing α, β-unsaturated polar compound components such as maleic acid and anhydride; acrylic acid or maleic acid in a polymer containing the α-olefin component as a main component. And α, such as anhydrous,
Examples thereof include a block copolymer modified olefin copolymer obtained by block copolymerizing a β-unsaturated polar compound component.

The amount of the modifier 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, based on the total weight of the resin added with the modifier. More preferably, it is in the range of 1.0 to 5% by weight.
If the added amount of the modifier is too small, the desired effect cannot be obtained,
If the amount is too large, the properties originally possessed by the modified resin are significantly reduced. 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 containing the oil-soluble polyester of the present invention as an active ingredient contains an antioxidant, a lubricant, an ultraviolet absorber, an ultraviolet stabilizer, a heat stabilizer, an antistatic agent, a nucleating agent. Various additives such as organic and / or inorganic pigments 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 desired modifying effect.

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 a single-screw extruder, a twin-screw extruder and the like; a Banbury mixer, a Brabender plastograph, a plastomill, a multi-screw kneader, a double helical ribbon stirrer and the like. 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 preferably in the range of 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.

[0028]

The present invention is 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 by weight unless otherwise specified. The weight average molecular weight was measured by GPC and converted by standard polystyrene. The hydroxyl value and the acid value of the polyester were measured according to the following described in "Standard oil and fat analysis test method" (Japan Oil Chemistry Association). Hydroxyl value 2, 4, 9, 2-83 Acid value 2, 4, 1-83

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 inlet tube was charged with polymerized fatty acid Haridimer 200 (manufactured by Harima Chemicals; dimer acid 75.0%, Trimer acid 17.0%, monomer acid 8.0
%, Acid value 193) 420 g, 2-butyl-2-ethyl-
79.8 g of 1,3-propanediol, 42.7 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.35).

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 had a weight average molecular weight of 7,300, an acid value of 0.2 and a hydroxyl value of 53.

Example 2 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water dividing pipe and a nitrogen gas introducing pipe was charged with polymerized fatty acid halider 270S (manufactured by Harima Chemicals; dimer acid 80.5%). Trimer acid 17.5%, monomer acid 0.
5%, acid value 192) 454 g, 3-methyl-1,5-pentanediol 73.3 g, trimethylolpropane 3
5.7 g and monobutyltin oxide 0.26 g as a catalyst were charged. (OH / COOH equivalent ratio = 1.
31).

Stirring is carried out while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Then, 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 ° C. The obtained polyester 2 had a weight average molecular weight of 6,800, an acid value of 0.2 and a hydroxyl value of 41.

Example 3 A 1000 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 Haridimer 300 (manufactured by Harima Chemicals; dimer acid 97.0%, Monomer acid 0.5%, trimer acid 2.5
%, Acid value 195) 460 g, 2,2-dimethyl-1,3
49.8 g of propanediol, 64.1 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio =
1.49).

Stirring is performed while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Then, 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 ° C. The obtained polyester 3 had a weight average molecular weight of 5,700, an acid value of 0.1 and a hydroxyl value of 65.

Example 4 In a 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a water diversion tube and a nitrogen gas inlet tube, 460 g of polymerized fatty acid (Halidimer 300) and glycidyl dimer acid (made by Shell; Epoxy equivalent 400, Epicoat 871) 63.4 g, 2,2-dimethyl-1,
95.5 g of 3-propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH +
Epoxy group / COOH equivalent ratio = 1.25)

Stirring is carried out while introducing nitrogen gas, and 10
The temperature was raised to 0 ° C. Then, 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 ° C. The resulting polyester 4 had a weight average molecular weight of 6,500, an acid value of 0.1 and a hydroxyl value of 52.

Application Example 1 Polypropylene MS670 (Made by Tokuyama Soda; MFR23)
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 by 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. For the peeling test of the coating film, the cross-cut tester is used to measure the substrate (JIS (19
90), paint, K-5400, 8.5.1). The cuts have a load of 350 kg and are spaced by 1 mm.
One cut was made orthogonal to make 100 bases per cm ² .

A pressure-sensitive adhesive tape having a width of 18 mm manufactured by Nichiban Co., Ltd. was used, pressure-bonded with a pressure roller 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.
It was shown to.

Comparative Application Example 1 A film was formed from the same polypropylene as used in Application Example 1 without using a polyester modifier in the same manner as in Application Example 1, 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.

[0041]

[Table 1]

Application Example 2 High Density Polyethylene 2200J (Mitsui Petrochemical Industry)
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 produced film was measured by using a contact angle measuring device (CA-D type) manufactured by Kyowa Interface Science, and shown in Table 2. Further, an epoxy paint (manufactured by Nippon Bee Chemical Co., Ltd .; RB298HP4) was applied to the resin surface with a doctor blade and cured at 25 ° C for 2 days. For the peeling test of the film, the cross-cut tester is used to measure the substrate (JIS (19
90), paint, K-5400, 8.5.1). The cuts have a load of 350 kg and are spaced by 1 mm.
One cut was made orthogonal to make 100 bases per cm ² .

A pressure-sensitive adhesive tape having a width of 18 mm manufactured by Nichiban Co., Ltd. was used, pressure-bonded with a pressure roller of 1300 kg, and a 180 ° peel test was conducted. 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.
It was shown to.

Comparative Application Example 2 A film was formed from the same high-density polyethylene as used in Application Example 2 by the same method as in Application Example 2 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]

When the resin modifier of the present invention is incorporated into an olefin resin containing an oil-soluble polyester as an active ingredient and other molding resins, the performance of the resin to be modified is hardly deteriorated and a coating film, In particular, the adhesiveness of coating films of acrylate or methacrylate-based, urethane-based, acrylic / urethane-based, polyester-based, epoxy-based paints can be greatly improved. In addition, the resin modifier containing the oil-soluble polyester of the present invention as an active ingredient also has an effect of improving the adhesiveness of epoxy-based and cyanoacrylate-based (instant adhesive) and the printability of water-based ink, and is widely nonpolar. The surface properties of the resin can be improved.

[0048]

DETAILED DESCRIPTION OF THE INVENTION The oil-soluble polyester of the present invention, that is,
OH / COOH equivalent ratio of polyhydric higher carboxylic acid and polyhydric alcohol containing trihydric or higher alcohol is 1.02
The weight average molecular weight obtained by polycondensation at a ratio of 3 is 1,0
An oil-soluble polyester having a hydroxyl value of 30 or more, which is from 00 to 500,000; and a polyhydric higher carboxylic acid and a polyhydric alcohol containing a diepoxy compound in an (OH + epoxy group) / COOH equivalent ratio of 1.02 The weight average molecular weight obtained by polycondensation at a ratio of 3 to 1,000 is from 1,000 to 50.
The preferred embodiments of the oil-soluble polyester having a hydroxyl value of 30,000 and a hydroxyl value of 30 or more are summarized as follows.

(1) 10 or more polyvalent higher carboxylic acids, more preferably 15 or more, and even more preferably 20.
It has at least 4 carbon atoms. (2) The polyvalent higher carboxylic acid contains at least 50% by weight or more, more preferably 60% by weight or more, and further preferably 70% by weight or more, of at least divalent higher carboxylic acid. (3) The polyvalent higher carboxylic acid is composed of only divalent carboxylic acid, or is a mixture of divalent carboxylic acid and trivalent or higher carboxylic acid, and the divalent carboxylic acid is 50% by weight or more. More preferably 60% by weight or more, still more preferably 70% by weight or more and trivalent or more carboxylic acid at 50% by weight or less, more preferably 40% by weight or less, further preferably 30% by weight or less.

(4) The polyvalent higher carboxylic acid is a divalent carboxylic acid selected from polyalkylene succinic acid, dimer acid of polymerized fatty acid and anhydride thereof and / or trimer acid of polymerized fatty acid. (5) A purified polymerized fatty acid containing a dimer acid component of 60% by weight or more in a polyvalent higher carboxylic acid or a hydride thereof. (6) 30% by weight or less, and more preferably 20% by weight or less of other carboxylic acids are used together with the polyvalent higher carboxylic acid, based on the total weight of the carboxylic acids.

(7) Trihydric or higher alcohol is trimethylolethane, trimethylolpropane, glycerol,
It is selected from pentaerythritol, dipentaerythritol, sorbitol, glucose, mannitol, sucrose and glucose. (8) The diepoxy compound is glycidyl ether of bisphenol A, glycidyl ether of bisphenol F,
It is selected from dimer acid glycidyl ester and aliphatic glycidyl ether. (9) Polyhydric alcohol containing trihydric or higher alcohol,
It is a mixture of a trihydric or higher alcohol and a dihydric alcohol containing 10 to 90 mol% of a trihydric or higher alcohol, more preferably 15 to 70 mol%, and further preferably 20 to 50 mol%.

(10) The polyhydric alcohol containing a diepoxy compound is 5 to 50 mol%, more preferably 10 to 40 mol%, and further preferably 15 to 3 mol% of the diepoxy compound.
It is a mixture of a diepoxy compound containing 5 mol% and a dihydric alcohol. (11) The ratio OH (+ epoxy group) / COOH (equivalent ratio) of the carboxylic acid component and the alcohol component used in the condensation polymerization reaction is more preferably 1.05 to 2.5, further preferably 1.10 to 2. The range is 0. (12) The polystyrene-equivalent weight average molecular weight of the oil-soluble polyester measured by GPC is more preferably 2,
000-100,000, more preferably 3,000
Is in the range of 20,000.

(13) The hydroxyl value of the oil-soluble polyester is in the range of 30 to 200, preferably 40 to 100, and more preferably 50 to 80. (14) The acid value of the oil-soluble polyester is 20 or less, more preferably 10 or less. (15) The resin modifier containing an oil-soluble polyester as an active ingredient is useful for modifying a thermoplastic resin, preferably a hydrocarbon-based thermoplastic resin, and more preferably a polyolefin. (16) When a resin modifier containing an oil-soluble polyester as an active ingredient is used, it is contained in the resin composition in an amount of 0.1 to 50% by weight, more preferably 0, based on the weight of the resin composition. 0.5 to 10% by weight, more preferably 1.0 to 5% by weight, of the modifier is contained.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shinsuke Hasegawa 67-1 Mizuguchi, Noguchi-cho, Kakogawa-shi, Hyogo 4-4 Harima Kasei Co., Ltd. Central Research Laboratory (72) Inventor Michio Miyamoto 671-Mizufoot, Noguchi-cho, Kakogawa-shi, Hyogo Prefecture No. 4 Harima Kasei Co., Ltd. Central Research Laboratory

Claims (2)

[Claims] 1. A weight average molecular weight obtained by polycondensing a polyhydric higher carboxylic acid and a polyhydric alcohol containing an alcohol having a valence of 3 or more at an OH / COOH equivalent ratio of 1.02 to 3 is 1. 2,000-500,000 and hydroxyl value is 3
Oil-soluble polyester of 0 or more. 2. A polyhydric higher carboxylic acid and a polyhydric alcohol containing a diepoxy compound are added to (OH + epoxy group) /
The weight average molecular weight obtained by polycondensation at a COOH equivalent ratio of 1.02 to 3 is 1,000 to 500,000,
An oil-soluble polyester having a hydroxyl value of 30 or more.