WO1997004024A1 - Rubber modifier, rubber composition containing the same, coated rubber molding, and process for production thereof - Google Patents

Abstract

A rubber modifier containing as the active ingredient a polyester having a weight-average molecular weight of 1,000 to 1,000,000 and bearing at least three hydrogen-containing polar groups; a rubber composition containing the modifier; and vulcanized coated rubber moldings produced therefrom and excellent in coatability, adhesiveness and printability.

Description

 Specification

 Rubber Modifier, Rubber Composition Containing It, Painted Rubber Molded Article, and Method for Producing the Same

 The present invention relates to a rubber modifier containing a polyester as an active ingredient, a rubber composition containing the modifier, a vulcanized product of the composition, and a method for producing the coated product. Films and other molded products obtained from the rubber composition containing the rubber modifier of the present invention have excellent coatability, adhesiveness and printability. Background technology

 Highly saturated hydrocarbon rubbers such as α-olefin copolymer rubbers such as ethylene-propylene copolymer rubber and butyl rubber are widely used due to their excellent cold resistance, weather resistance, ozone resistance, etc., and low cost. However, since the molecule has few carbon-carbon double bonds and polar groups, the adhesion of the coating film and the adhesive layer is low, so that a practical adhesive strength cannot be obtained.

 Conventionally, in order to improve the paintability and adhesion of these highly saturated hydrocarbon rubber molded articles, for example, a method of adding polyhydroxy polybutadiene in which 98% or more of its double bonds have been hydrogenated (Japanese Patent Publication No. No. 7-6462) and a method of adding a hydrocarbon polymer having a hydroxyl group at the molecular terminal such as polyhydroxy polyolefin (Japanese Patent Application Laid-Open No. 11-199534). A method of adding a low-molecular-weight polyisoprene in which 50% or more of the bonds are hydrogenated (Japanese Patent Application Laid-Open No. 2-69545) has been proposed. However, these methods have a disadvantage that the adhesion to the paint is not sufficient. Disclosure of the invention

An object of the present invention is to use a new polyester as an active ingredient, which is suitable for improving properties such as paintability, adhesiveness, and printability of a highly saturated and non-polar polymer rubber such as ethylene-propylene copolymer rubber. Rubber modifier, and the addition of it It is to provide a rubber composition. Another object is to provide a coated product of a vulcanized molded article of such a rubber composition and a method for producing the same.

 According to one aspect of the present invention, there is provided, as an active ingredient, a polyester having a weight-average molecular weight of 1,000 to 1.00, 000 and having at least three polar groups containing hydrogen atoms in the molecule. Is provided.

 According to the present invention, in another aspect, there is provided a rubber composition comprising a rubber component and a rubber modifier containing the polyester as an active ingredient.

 According to the present invention, in still another aspect, there is provided a coated rubber molded product obtained by coating the surface of a vulcanized molded product obtained by vulcanizing the above rubber composition.

 According to the present invention, in still another aspect, (1) vulcanization-molding the rubber composition and applying and curing a coating material on the surface of the obtained vulcanized molded article; A method for producing a coated rubber molded article is provided, which comprises molding a rubber composition, and then vulcanizing and coating and curing the obtained unvulcanized molded article. BEST MODE FOR CARRYING OUT THE INVENTION

Polyester

 The polyester used in the present invention is characterized by having at least three polar groups containing a hydrogen atom in the molecule. The polar group containing a hydrogen atom is not particularly limited as long as it has at least one hydrogen atom and at least one hetero atom. Examples of the hetero atom include an oxygen atom, a nitrogen atom, a sulfur atom and the like, and an oxygen atom is preferable. Examples of such a polar group having a hydrogen atom and a hetero atom include a hydroxyl group, a carboxyl group, an amino group, and a thiol group. Among these, a hydroxyl group and a carboxyl group are preferable, and a hydroxyl group is particularly preferable.

At least three such hydrogen atom-containing polar groups are required in the molecule, and if the number is two or less, the adhesiveness to a paint or the like is reduced, which is not preferable. The maximum value of the polar group content is not particularly limited, but is generally selected appropriately within a range in which the polyester retains oil solubility. When the polar group containing a hydrogen atom is, for example, a hydroxyl group or a carboxyl group, the content in the polyester can be represented by a hydroxyl value or an acid value. The sum of the hydroxyl value and the acid value can be appropriately selected depending on the molecular weight of the polyester, but is usually from 10 to 200 mgKOH ^/ g, preferably from 20 to! S OmgKOHZg More preferably from 30 to: LS OmgKOHZg, most preferably from 30 to: LO OmgKOHZg.

 The polyester used in the present invention is usually oil-soluble. Non-oil-soluble polyesters are not preferred because they generally have poor compatibility with rubber. 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.

Put 5 g of polyester in 95 g of toluene and put it under a nitrogen atmosphere. Dissolve with stirring at C for 1 hour, then cool to room temperature (20 ° C). The toluene dilution was allowed to stand for 24 hours at 20 ^e C thermostatic chamber, and then, measuring the transmittance in turbidimeter was stirred again (Tokyo photoelectric Co. "ANA- 14 S"). A tungsten light bulb (6 V, 6 A) is used as the light source, and a 20 mm square glass cell is used as the cell. The transmittance is 0% when the shutter is closed, and the transmittance of toluene used for dilution is 100%.

 The molecular weight of the polyester is from 1,000 to 1,000,000, preferably from 3,000 to 500,000, more preferably from 1,000 to 1,000,000 in terms of polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC). Is in the range of 5,000 to 100,000. If the molecular weight is too small, all of the polyester migrates to the surface of the rubber molded product and the coating film strength is not sufficient.On the other hand, if the molecular weight is too large, the polyester molecules hardly migrate to the surface of the rubber molded product. However, sufficient improvement effects such as improved adhesiveness cannot be obtained, and both are not preferred.

The method for producing the polyester of the present invention is not particularly limited. For example, (A) a divalent higher carboxylic acid component and (B) a dihydric alcohol component, and (C) a trivalent or higher carboxylic acid, At least one polyvalent component selected from the group consisting of alcohols and epoxy compounds having two or more epoxy groups (A) and (B) It can be obtained by condensation polymerization of the three components (A), (B) and (C) at a ratio of 1 to 80 mol% based on the total amount of both components.

 As the divalent higher carboxylic acid (A), those having usually 8 or more carbon atoms, preferably 10 to 200, more preferably 20 to 80 are used. If the number of carbon atoms in the carboxylic acid is too small, the oil solubility decreases, and the compatibility with rubber is poor, which is not preferred. Such divalent higher carboxylic acids may be, for example, any of linear, branched and cyclic, and specifically, suberic acid, azelaic acid, sebacic acid, brassic acid, polyalkylene Examples include succinic acid and dimeric acid of polymerized fatty acid, and among these, at least one selected from polyalkylene succinic acid and dimeric acid of polymerized fatty acid is preferable, and dimeric acid of polymerized fatty acid is particularly preferable. Acids are preferred.

The polymerized fatty acid is obtained by polymerizing a higher fatty acid, and is usually an aliphatic having 8 to 24, preferably 16 to 20 saturated or at least one unsaturated bond or an aliphatic ester thereof. It is a generic term for polymerized acids obtained by polymerizing derivatives. Commercially available polymerized fatty acids are those obtained by polymerizing oleic acid, linoleic acid, ricinoleic acid, eleostearic acid, and the like. It is contained as. Structural analysis of polymerized fatty acids has been reported by D.H.M cmah0n et al. (J.Am.0i1.Chem.Soc., 5_, 52 2 (1974)) ₀ ) 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, hydrogenated polymerized fatty acids having good thermal oxidation stability can be obtained. 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 or a hydride thereof containing 60% by weight or more of a dimer acid component is used. used. The polyalkylene succinic acid has the general formula (1) Ri- CH CO OH (1)

 I

CH2COOH

 (Ri in the formula is a polymer chain of lower alkylene.) Ri is a lower alkylene polymer chain, and preferably the lower alkylene is at least one selected from ethylene, propylene and butylene, and has a degree of polymerization in the range of 10 to 300.

 The dihydric alcohol (B) is not particularly limited as long as it is generally used in a polyester synthesis reaction. Examples thereof include alkanediols, cycloalkanediols, polyoxyalkylene glycols, and polyesterdiol. And hindered glycols. Particularly preferred are alkanediols and hindered glycols. These can be used alone or in combination of two or more.

 Alkanediols include, for example, ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1, 9-nonanjol.

 Cycloalkanediols include cyclopentane-1,2-diol, cyclohexane-1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cyclohexane-1 Examples include 1,4-dimethanol and cyclooctane-1,4-diol.

 Examples of the polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, and polybutylene glycol obtained by polymerizing alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide alone or in a mixture by a known method. These are generally represented by the general formula (2)

HO-((CH ₂ ) m-CHR20) ", — H (2)

Is represented by Here, R ² is a hydrogen atom or a low atom such as a methyl group or an ethyl group. Represents a lower alkyl group, and is preferably a hydrogen atom. m represents an integer of 1 to 6, and is preferably an integer of 1 to 4. n represents an integer of 2 to 1,000, preferably 5 to 500, and more preferably 10 to: an integer of LOO.

 Examples of polyester diols include, for example, those disclosed in JP-A-6-116372: lactones such as proviolactone, ^ -butyrolactone, abutyrolactone, δ-valerolactone and ethylene glycol, diethylene glycol, triethylene lactone. Ring-opening products of (poly) alkylene glycols such as ethylene glycol and tetraethylene glycol can be mentioned.

 HO- (R3-C00-G) ρ -Η (3)

It is represented by Here, R ³ represents an alkylene group having 2 to 6 carbon atoms. ρ represents an integer of 2 to 1,000, preferably an integer of 5 to 500, and more preferably an integer of 10 to 100. G represents one (CH ₂ CHR40) _q — group, where q is an integer of 1 to 4, and R 4 represents a hydrogen atom or a lower alkyl group such as a methyl group.

 As the hindered glycol, for example, the general formula (4)

HO CH ₂ -C (R5R6)-CH ₂ OH (4). Here, R ⁵ and Rs each independently represent an alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to 20, and more preferably 2 to 10. Specific examples of such hindered glycols include, for example, 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 And 2-propyl-1-pentyl-1,3-propanediol.

In the present invention, in addition to the above-mentioned divalent higher carboxylic acid component (A) and the above-mentioned divalent alcohol component (B), it has a trivalent or more carboxylic acid, a trivalent or more alcohol, and two or more epoxy groups. At least one selected from epoxy compounds Use (C).

 The trivalent or higher carboxylic acid is not particularly limited as long as it has three or more carboxyl groups. Usually, a trivalent carboxylic acid is used. Specific examples of the trivalent or higher carboxylic acid include trimellitic acid, trimethylvalivalic acid, camphoronic acid, trimesic acid, and trimeric acid of a polymerized fatty acid. Among them, trimesic acid, trimer acid of polymerized fatty acid and the like are preferable, and trimer acid of polymerized fatty acid is particularly preferable.

 The trihydric or higher alcohol is not particularly limited as long as it has three or more hydroxyl groups. Specific examples of trihydric or higher alcohols include glycerol, sorbitol, glucose, mannitol, sucrose, glucose and the like.

 In addition, as a trihydric or higher alcohol, the general formula

HO CH ₂ -C (R? Ri-a hindered alcohol having 3 or more valences represented by CH ₂ OH (5) can be used. In the formula, R and RS are each independently an alkyl group or An alkyl group having a hydroxyl group, wherein at least one of R? Is an alkyl group having a hydroxyl group, wherein the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 50. The number is preferably 1 to 20, more preferably 2 to 10. Specific examples of such trivalent or higher-valent hindered alcohols include trimethylolethane, trimethylol-propane, trimethylolbutane, and pentaerythritol. And preferred are trimethylolethane, trimethylol pulp bread, pentaerythritol and the like.

 These trihydric or higher alcohols can be used alone or as a mixture of two or more thereof. The trihydric or higher alcohol component contains at least 10 mol% of trihydric or higher hindered alcohol. Preferably, the content is preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

The epoxy compound having two or more epoxy groups is not particularly limited as long as it is a compound having at least two epoxy groups in a molecule. Examples include glycidyl dimer acid ester of fatty acid, glycidyl ether of bisphenol A, glycidyl ether of bisphenol F, and glycidyl ether of aliphatic dibasic acid.

 These components (C) can be used alone or in admixture of two or more. The amount used is the sum of the dihydric carboxylic acid component (A) and the dihydric alcohol component (B). It is 1 to 80 mol%, preferably 5 to 60 mol%, more preferably 10 to 40 mol% based on the amount. If the amount of the component (C) is excessively small, the hydroxyl value or the acid value is not sufficient. On the other hand, if the amount is excessively large, it becomes difficult to control the polycondensation reaction.

 In addition, as long as the object of the present invention is not impaired, the carboxylic acid component may contain, in addition to the divalent higher carboxylic acid (A) and the trivalent or higher carboxylic acid component (C), other carboxylic acids, for example, Divalent lower carboxylic acids such as succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, bimalic acid, methylmalonic acid and dimethylmalonic acid; acetic acid, 2-methylpropanoic acid, isooctylic acid, isononanoic acid, Peric acid, myristic acid, and Monohydric carboxylic acids such as lumitic acid, stearic acid, isostearic acid, arachinic acid, linoleic acid, oleic acid, and elaidic acid; and, in the alcohol component, a dihydric alcohol component (B) and a trihydric or higher alcohol component. In addition to the coal component (C), other alcohols such as methanol, ethanol, isopropanol, neopentyl alcohol, 3-methyl-3-pentanol, 2,3,3-trimethyl-1-butanol, and 1-decanol A monohydric alcohol such as nonyl alcohol may be used in combination. Generally, the tolerable amount is not more than 20 mol% of the total carboxylic acid component or total alcohol component.

 The ratio between the carboxylic acid component and the alcohol component may be appropriately selected according to the desired molecular weight or hydroxyl value (or acid value) of the polyester, and is usually 0.5 to 2.5, depending on the OHZCO OH (equivalent) ratio. Preferably in the range of 0.6 to 2.0 0

The polyester used in the present invention is obtained by condensation polymerization of the above component (A), component (B), component (C), and other optional components such as carboxylic acid and alcohol. It can be obtained by reaction. The polycondensation reaction may be carried out according to a conventional method, for example, at a reaction temperature of 100 to 300 ° C, preferably 150 to 280 ° C, particularly in the presence of inert gas. It is preferable to carry out. 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. During the esterification condensation polymerization reaction, para-toluenesulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate, zinc, titanium, tin and butyltin are usually used as esterification catalysts. Although various metal oxides such as oxides and titanium oxide are used, it is preferable to use metal oxides in view of the oxidation resistance of the obtained polyester.

Rubber component

 The rubber component to which the modifier of the present invention is blended is not particularly limited, and those generally used in the rubber industry can be used. Specifically, for example, natural rubber, polyisoprene rubber, polybutadiene rubber, styrene-butadiene copolymer rubber, styrene-isoprene copolymer rubber, styrene-isoprene butagene copolymer rubber, butadiene-isoprene copolymer rubber, Conjugated-gen-based polymer rubbers such as styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, acrylonitrile-butadiene rubber, and chloroprene rubber; Olefin copolymer rubber; silicone rubber and the like. Among them, rubber components having a small amount of carbon-carbon double bonds in the main chain, for example, having an iodine value of 100 or less, preferably 50 or less, more preferably 35 or less are suitable. Of these, modified polyethylene rubber, α-olefin copolymer rubber, silicone rubber, and the like, particularly α-olefin copolymer rubber, are preferred because the modifying effect of the present invention is remarkably exhibited. These rubbers can be used alone or in combination of two or more.

One-dimensional olefins are olefins having a carbon-carbon double bond at the terminal, such as ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, and 3-methyl-1-olefin. 1—pentene, 4—methyl 1—pentene, etc. But not limited to these.

 The olefin-based copolymer rubber is not particularly limited as long as it is a rubber-like polymer containing the above-mentioned α-year-old fin. Examples include copolymer rubbers of olefin resin and other polymerizable monomers. The amount of α-olefin fin in the copolymer rubber is not particularly limited, but is usually 50% by weight or more, preferably 60 to 100% by weight, more preferably 80 to: L00% by weight. Range. The other polymerizable monomer is not particularly limited, and examples thereof include a common gen and a non-conjugated gen. The conjugated gen is, for example, 1,

Examples thereof include 3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene, and among these, 1,3-butadiene and isoprene are preferable. Examples of the non-conjugated gen include ethylidene norbornene, dicyclopentadiene, 1,4-hexadiene, and the like. Of these, ethylidene norbornene, dicyclopentene gen and the like are preferable. The content of these polymerizable monomers in the copolymer is usually 50% by weight or less, preferably 40% by weight or less, more preferably 20% by weight or less.

 Specific examples of α-olefin copolymer rubber include, for example, ethylene-carbon number.

Two or more kinds of mono-olefin copolymer rubbers such as α-olefin copolymer rubbers of 3 or more; two or more types of non-conjugated copolymer rubbers such as ethylene-non-conjugated rubber having three or more carbon atoms α-olefin and non-conjugated copolymer rubber; α-olefin-monofunctional copolymer rubber; and modified rubbers thereof such as chlorinated products and chlorosulfonated products.

 Examples of the α-olefin copolymer rubber include an ethylene-propylene copolymer rubber and an ethylene butene-11 copolymer rubber. Particularly preferred is an ethylene-propylene copolymer rubber having a weight ratio of ethylene to propylene in the range of 90:10 to 20:80.

Examples of the non-co-gen of the α-bran refine-non-conjugated gen copolymer rubber having 3 ethylene or more carbon atoms include those exemplified above for the α-bran-refin copolymer rubber. Used.

 Examples of the α-refined conjugated conjugated copolymer rubber include butyl rubber obtained by copolymerizing 90 to 99.5% by weight of isobutene and 0.5 to 10% by weight of isoprene.

These rubber components can be used alone or in combination of two or more. The proportion of the rubber component and the polyester modifier used can be appropriately selected according to the use and purpose, but is usually 99: 1 to 50:50, preferably 98: 2 to 60 by weight. : 4 0, more preferably 9 5: 5 to 8 0: 2 _c optional ingredient in the range of 0

 If necessary, additives usually used in the rubber industry can be added to the rubber modifier and the rubber composition of the present invention. Examples of additives include inorganic fillers, vulcanizing agents, vulcanization accelerators, vulcanization aids, plasticizers, antioxidants, antioxidants, lubricants, ultraviolet inhibitors, ultraviolet stabilizers, heat stabilizers , Antistatic agents, nucleating agents, flame retardants, organic and Z or inorganic pigments, oils and the like. These additives can be added alone or in combination of two or more. The amounts of these additives are appropriately determined within a range that does not impair the effects of the present invention.

 Examples of inorganic fillers include calcium carbonate, calcium oxide, magnesium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium carbonate, calcium gayate, magnesium gayate, calcium sulfate, barium sulfate, and sulfurous acid. Examples thereof include calcium, myricite, dolomite, silica, clay, silver, black, black oxide, zinc oxide, glass fiber, and carbon fiber. C Among these, silica and carbon black are particularly preferred. Each of these inorganic fillers is used alone or in combination of two or more. The amount used is usually 100 to 200 parts by weight, based on 100 parts by weight of the rubber component. Preferably it is 20 to 150 parts by weight, more preferably 30 to 100 parts by weight.

Examples of the vulcanizing agent include sulfur-based vulcanizing agents such as zeolite and disulfide; and baroxide-based vulcanizing agents such as dicumyl peroxide and di-tert-butyl peroxydiisopropylbenzene. Each of these vulcanizing agents, alone, Alternatively, two or more kinds can be used in combination. The amount used is generally 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber component.

 Examples of the vulcanization accelerator include, for example, vulcanization accelerators such as mercaptobenzothiazole, dimethyldithi talented zinc rubamate, and tetramethylthiuram sulfide. These rubbers are used in an amount of usually 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight, per 100 parts by weight of the rubber component. Rubber vulcanized molding

The rubber composition of the present invention, _c for example be prepared according to conventional method performed in the rubber industry, it can be produced by kneading the above components in a mixer. Examples of the kneading machine include extruders such as a single-screw extruder and a twin-screw extruder, Banbury, brabender, brass tominole, calender, kneader, roll, extruder, multi-screw kneader, double-helical ribbon. A stirrer or the like can be used.

 The vulcanized rubber molded article of the present invention can be produced by a method usually performed in the rubber industry. For example, (1) The above components other than the vulcanizing agent are added to Banbury, Brabender, etc., kneaded at 60 ° C. to 300 ° C. for 0.5 to 60 minutes, and (2) It can be obtained by transferring the mixture to a roll, adding a vulcanizing agent at 100, and then kneading the mixture, followed by (3) heat molding with a molding machine such as an extruder.

Surface coating Rubber molded body

By applying a coating material on the surface of the vulcanized molded article of the rubber composition as described above and curing it, a coating film having excellent adhesiveness is formed. Alternatively, the vulcanizable rubber composition may be molded into an unvulcanized rubber molded body, a coating may be applied to the surface, and then the vulcanization of the rubber molded body and the curing of the coating film may be simultaneously performed. The paint used for surface coating is not particularly limited, but examples thereof include a solvent-type thermoplastic (meth) acrylic resin paint, a solvent-type thermosetting (meth) acrylic resin paint, an acrylic-modified alkyd-based paint, and an epoxy resin. Paints, acrylic urethane resin paints, silicone-modified urethane resin paints, polyurethane resin paints, melamine resin paints, and the like. these Can be used alone or in combination of two or more.

 As a method of applying the paint to the molded body, for example, a method such as electrostatic painting, spraying (air spray) painting, or brush painting is used. These paints may be applied by a method of applying an undercoat and then an overcoat. The method of curing the coating film after application of the coating material is appropriately selected depending on the material and shape of the molded article, the properties of the coating material, and the like.For example, the coating is dried by a method such as natural drying or forced drying using a nichrome wire, infrared rays, high-frequency heating, or the like. A cured coating is formed.

 Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples. Parts and percentages in these examples are on a weight basis unless otherwise specified.

 The physical property measurement method is as follows.

 (1) Weight average molecular weight

 The weight average molecular weight of the polyester was measured as a standard polystyrene equivalent according to the GPC method.

 (2) hydroxyl value and acid value

 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 Chemists' Society).

Hydroxyl value 2, 4, 9, 2-83

Acid value 2, 4, 1-83

 (3) Adhesion test

(1) Cross-cut test adhesion rate: Conducted according to JIS K5400. After making one cut at right angles at 1 mm intervals with a load of 350 kg on the surface of the coating film and making 100 grids per 1 cm ² , use an adhesive tape with a width of 18 mm using a pressure roller. (Ciban Co., Ltd.) with a load of 1300 kg and a peeling test of peeling at a peeling angle of 180 °. Of the 100 squares, the number of grids that were not peeled was the adhesion rate (%). Displayed as.

(2) Peeling strength test: A 1 cm wide cut is made on the coating surface with a power cutter blade until the blade reaches the base material, the edges are separated, and the edge of the peeled coating film is 50 cm / Minute The maximum peel strength (kgZcm) was determined by pulling in the 180 ° direction at a speed <Manufacturing Example 1

 In a 100 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid Haridima-1 200 (acid value 193 mg KOHZg, monomeric acid 8.0%, dimer 75.0% monoacid, 17.0% trimer monoacid; Harima Kasei Co., Ltd.) 420.0 g, 2-ethyl-2,3-butyl-1,3-butane 15.0 g of pandiol, trimethylolpropane 94. 6 g and 0.26 g of monobutyltin oxide were charged as a catalyst. (OHZCOOH equivalent ratio = 1.10)

Stirring was performed while introducing nitrogen gas, and the temperature was increased to 100 ^eC . Subsequently, the temperature was raised from 100 ^e C to 260 ° 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 260 ° C. The obtained polyester A had a weight average molecular weight of 11,700, an acid value of 0.2 mgKOHZg, and a hydroxyl value of 82 mgKOHZg. The light transmittance of the toluene solution was 99%.

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 300 (acid value 195 mg KOHZg, monomeric acid 0.5%, 97.0% of acid, 2.5% of trimer acid; Harima Kasei Co., Ltd.) 440.0 g, 3-methyl 1,5-heptanediol 28.lg, trimethylolpropane 85.0 g and monobutyltin oxide 0 as a catalyst 26 g was charged. (OHZCOOH equivalent ratio = 1.05) The mixture was stirred while introducing nitrogen gas, and the temperature was increased to 100 ° C. Subsequently, the temperature was raised from 100 ° C to 260 ° 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 260 ° C. The obtained polyester B had a weight average molecular weight of 17,800, an acid value of 0.2 mgK0H, g, and a hydroxyl value of 58 mgK0HZg. The light transmittance of the toluene solution was 97%. Production Example 3

In a 1000 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, add hydrogenated polymerized fatty acid halidimemer 300 (acid value 195 mg KOHZg, monomeric acid 0.3% 97.0% of dimer monoacid, 2.7% of trimer monoacid; 460.0 _g , manufactured by Harima Chemicals, Inc. 871 (polymerized fatty acid glycidyl ester; manufactured by Shell) 63.4 g, 2, 2 —Dimethyl-1,3-propanediol (79.2 g) and monobutyltin oxide (0.26 g) were charged as a catalyst. [(0H + epoxy) / C00H equivalent ratio = 1.09]

 Stirring was performed while introducing nitrogen gas, and the temperature was raised to 100 ° C. Subsequently, 100, while removing water and unreacted diol formed during the reaction. The temperature was raised from C to 260 C in 6 hours. Thereafter, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester C had a weight average molecular weight of 6,500, an acid value of 0.1 mgKOH / g, and a hydroxyl value of 5 SmgKOH / g. The light transmittance of the toluene solution was 94%.

Production Example 4

 In a 100 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid Haridima-1 250 (acid value 193 mg KOHZg, monomeric acid 3.0%, dimer 79.0% of monoacid, 18.0% of trimeric acid; Harima Chemicals) 420, 0 g, 113.4 g of 2,2-getyl-1,3-propanediol 113.4 g, 41.4 g of pentaerythritol and molybdenum as catalyst 0.26 g of nobutyltin oxide was charged. (0HZC00H 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 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 OmgHg. The obtained polyester D had a weight average molecular weight of 21,500, an acid value of 0.2 mgKOHZg and a hydroxyl value of 82 mgKOHZg. The light transmittance of the toluene solution is 97%. I got it.

Production Example 5

 In a 100 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube, polymerized fatty acid haridimer 250 (acid value: 193 mg KOH g, monomeric acid: 3.0% , 79.0% of dimer acid, 18.0% of trimeric acid; manufactured by Harima Chemicals, Inc.) 420.0 g, 2-ethyl-2-propyl-1,3-propylpandiol 109.0 g, trimethylolpropane 39.3 g and 0.26 g of monobutyltin oxide were charged as a catalyst. (OHZC O OH equivalent ratio = 1.35)

 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 OmgHg. The obtained polyester E had a weight average molecular weight of 30,500, an acid value of 0.1 mg KOHZg, and a hydroxyl value of 91.3 mg KOHZg. The light transmittance of the toluene solution was 98% .o

Production Example 6

 A 100 cc four-necked flask equipped with a stirrer, thermometer, reflux condenser, water separator, and nitrogen gas inlet tube was charged with hydrogenated polymerized fatty acid halide dimer 250 (acid value 1993 mg KOH / g, monomer Monoacid 3.0%, dimer acid 79.0%, trimer monoacid 18.0%; manufactured by Harima Chemicals) 420.0 g, 2-ethyl-2-butyl-1,3 monopropanediol 16.5 g, 69.6 g of diethylene glycol, 44.3 g of pentaerythritol tonole, and 0.17 g of tetra n-butyl orthotitanate as a catalyst. (0H / C 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 ° C 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 ° C, and finally, the reaction was performed for 3 hours under a reduced pressure of 10 OmgHg. Obtained Polyester F had a weight average molecular weight of 13,700, an acid value of 0.1 mg KOH / g, and a hydroxyl value of 96.1 mg KOHZg. The light transmittance of the toluene solution was 93%.

 m ι. 2 and ratio! ^ eg ι, 2

Using the polyesters A and c produced above, a rubber composition was prepared according to the formulation shown in Table 1. For comparison, samples without the addition of polyester were also prepared (Comparative Examples 1 and 2). Components other than sulfur and the vulcanization accelerator were analyzed using a Brabender-type Banbury mixer. After kneading with C for 5 minutes, sulfur and a vulcanization accelerator were added on a 6-inch roll and kneaded at 60 ^eC . Next, the kneaded material was extruded using an extruder (LZD = 70, 75 mm) in a cross-sectional shape having a width of 30 mm and a thickness of 5 mm, and then vulcanized at 200 ° C. for 5 minutes.

 Next, a urethane paint (SOFLEX 2500; manufactured by Kansai Paint Co., Ltd.) was applied to the surface of the vulcanized molded product by spraying, baked in a hot air oven of 100 for 15 minutes, and a cross-cut test and a peel strength test were performed. . Table 1 shows the results.

Example Example Comparative Example

 1 2 1 2

 Rubber

 E P * 1 90 90 100 100

 Surface modifier Polyester A 10 C 10

 Power Bon Black * 2 67.5 67.5

 Silver force * 3 50 50 oil * 4 35.0 20 35.0 20 Zinc white 55 5 5 5 Stearic acid 1 1 1 1 1.5 2 1.5 2 Accelerator

 Merkafu to N ン so 'Chia, Factory 2.0 1.5 2.0 1.5

 Tetramethylthiurammo / sulfur τ-id 2 2

 Adhesion rate (¾) 100% 100¾ 0% 5¾ Release strength (kg / cm) 0.95 0.74 0.1 0.1

Less than ¾1 * 1 Esplen 505A manufactured by Sumitomo Chemical Co., Ltd.

 * 2 FEF grade 40—50 m

* 3 Nip seal VN ₃ Nippon Silica Industry Co., Ltd.

 * 4 Process oil (PW-380) manufactured by Idemitsu Kosan

Example 3

 EP-103 A (ethylene-propylene-non-gen-based rubber; Nippon Synthetic Rubber Co., Ltd.) 100 parts by weight, carbon black (Asahi F-200; Asahi Carbon Co., Ltd.) 67.5 parts by weight, mineral oil 35 parts by weight, zinc 5 parts by weight of Hana and 1 part by weight of stearic acid are kneaded with a Brabender type 1 Banbury mixer, followed by 1.5 parts by weight of sulfur, 2 parts by weight of 2-mercaptobenzothiazole and the polyester produced in Production Example 2. 10 parts by weight of B was added by a roll, further kneaded, and taken out into a sheet. Then, it was vulcanized with a breath at 160 ° C. for 30 minutes.

 The above vulcanized molded product was coated with OFLEX No. 500 having a terminal isocyanate (NCO) group (urethane polymer; manufactured by Ohashi Chemical Industry Co., Ltd.), cured at room temperature, and subjected to a grid test and a peel test. . The adhesion rate was 100%, and the peel strength was 3.5 kgZcm, an excellent value.

Comparative Example 3

 An isolation test was performed in the same manner as in Example 3 except that 10 parts by weight of polyester B was used instead of 10 parts by weight of polyester B, and 10 parts by weight of polyhydroxy polyolefin (Polytail; manufactured by Mitsubishi Chemical Corporation) was used. The separation strength was 0.9 kcm.

Examples 4, 5, 6 and Comparative Example 4

 Using the polyesters D, E and F produced above, a rubber composition was prepared according to the formulation shown in Table 2. For comparison, a polyester without addition of polyester was also prepared (Comparative Example 4). Each component other than sulfur and the vulcanization accelerator was kneaded with a Banbury mixer at 50 at 5 minutes, then sulfur and the vulcanization accelerator were added with 6-inch roll and kneaded at 60 ° C. Next, the kneaded material was extruded using an extruder (LZD = 70, 2 Omm ^) into a flat shape with a width of 25 mm and a thickness of 3 mm.

Next, the surface of the extruded product is coated with a polyurethane paint (see Japanese Patent Application Laid-Open No. 7-150074). The above Comparative Example 2) was applied to a thickness of about 100 m with a spatula, and 180. Vulcanization of the rubber and curing of the paint were simultaneously performed in a hot air oven of C for 12 minutes, and a peel strength test was performed. Table 2 shows the results. ·

 & 2

 Example Example Comparative Example

 4 5 6 4 Rubber E P M * 5 100 100 100 100

 Surface modifier '' Reester D 10 E 10 F 10

 Carbon black * 6 130 130 130 130

 Paraffin Oy 70 70 70 80

 Stearic acid 1 1 1 1

 Zinc flower 5 5 5 5

 Sulfur 1.5 1.5 1.5 1.5

 Vulcanization accelerator ('Pashi / -L TRA) * 7 2.2 2.2 2.2 2.2

 Separation strength (kg / cm) 0.67 0.85 0.91 0.12

* 5 Keltane 5 1 2 (made by Idemitsu DSM)

 * 6 Asahi Carbon # 60 (F E F)

 * 7 Soxinol TRA: Sumitomo Chemical Dipentamethylene Lumetura Sulfide As is clear from the comparison between the above Examples and Comparative Examples, the addition of a rubber composition containing the modifier of the present invention was carried out. The coated product of the sulfur molded product (Examples 1 and 2) has a remarkably higher adhesion rate and peel strength by a cross-cut test than those without a modifier (Comparative Examples 1 and 2). In addition, the product of the present invention (Example 3) has considerably higher peel strength of the coating film as compared with a product containing a conventionally known polyhydroxy polyolefin modifier (Comparative Example 3). When the rubber composition containing the modifier of the present invention is coated after molding, and then vulcanization and curing of the coating film are performed (Examples 5, 5 and 6), the case where no modifier is added (Comparative Example) Peel strength is significantly higher than 4). Industrial applicability

 The molded article of the rubber composition containing the rubber modifier of the present invention is excellent in properties such as paintability, adhesiveness and printability.

Examples of uses of the vulcanized molded article of such a rubber composition include the following. <(A) Medical devices (ice sac, drain bag, catheter balloon, urine catheter) One tell)

 (Mouth) Tube, gloves, packing rubber

 (C) Exterior materials for automobiles such as weather strips, mat cards, side protect panels, etc.

 (2) Automotive interior materials such as airbags and interior skin materials

 (E) Rubber ports and other rubber materials used for VTR, audio equipment, OA equipment, camera parts, etc.

 (To ") Synthetic leather, sports shoes, pet shoes, etc.

Claims

The scope of the claims 1. A rubber modifying agent containing, as an active ingredient, a polyester having a weight average molecular weight of 1,000 to 1,000,000 and having at least three polar groups containing a hydrogen atom in the molecule.  2. The rubber modifier according to claim 1, wherein the sum of the acid value and the hydroxyl value of the polyester is 10 to 200 mgKOHZg.  3. Polyester containing (A) a divalent higher carboxylic acid component and (B) a divalent alcohol component, and (C) a trivalent or more carboxylic acid, a trivalent or more alcohol, and an epoxy having two or more epoxy groups. At least one compound selected from the compounds is used in an amount of 1 to 80 mol% with respect to the total amount of both components (A) and (B); 3. The rubber modifier according to claim 1, which is obtained by condensation polymerization of (A), (B) and (C) three components.  4. The rubber modifier according to any one of claims 1 to 3, wherein the polyester is oil-soluble.  5. A rubber composition comprising a rubber component and the rubber modifier according to any one of claims 1 to 4.  6. The rubber composition according to claim 5, wherein the ratio (weight ratio) between the rubber component and the rubber modifier is 99 :, 1 to 50:50.  7. The rubber composition according to claim 5, wherein the rubber component is at least one selected from the group consisting of a modified polyethylene rubber, an α-olefin-based copolymer rubber, and a silicone rubber.  8. The rubber composition according to any one of claims 5 to 7, wherein the iodine value of the rubber component is 100 or less.  9. For 100 parts by weight of rubber component, 0.1 to 20 parts by weight of vulcanizing agent, 0.5 to 5 parts by weight of vulcanization accelerator, and 10 to 200 parts by weight of inorganic filler The rubber composition according to any one of claims 5 to 8. 10. Vulcanization molding of the rubber composition according to any one of claims 5 to 9 A rubber molded body whose surface is painted.  11. A method for producing a coated rubber molded article, comprising vulcanizing and molding the rubber composition according to any one of claims 5 to 9, and applying a coating material on the surface thereof and curing the composition. .  12. Molding the rubber composition according to any one of claims 5 to 9, applying a paint to the surface of the obtained molded article, and then curing the formed coating film and forming the molded article. Vulcanization of a coated rubber molded article.  1 3. Paint is solvent-type thermoplastic (meth) acrylic resin paint, solvent-type thermosetting (meth) acrylic resin paint, acrylic-modified alkyd paint, epoxy resin paint, acrylic urethane resin paint, silicon-modified urethane resin paint, polyurethane The production method according to claim 11 or 12, wherein the production method is at least one selected from a resin paint and a melamine resin paint.