JP3453386B2 - "Rubber modifier, rubber composition containing the same, painted rubber molded article and method for producing the same" - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber modifier containing polyester as an active ingredient, a rubber composition containing the modifier, a coated product of a vulcanized product of the composition, and Regarding the manufacturing method of painted products. Films and other molded articles obtained from the rubber composition containing the rubber modifier of the present invention are excellent in coatability, adhesiveness and printability.

BACKGROUND ART Highly saturated hydrocarbon rubbers such as α-olefin copolymer rubbers such as ethylene-propylene copolymer rubbers and butyl rubbers are widely used because they are excellent in cold resistance, weather resistance, ozone resistance and the like and are inexpensive. However, since there are few carbon-carbon double bonds and polar groups in the molecule, there is a drawback that the adhesiveness of the coating film or the adhesive layer is low and practical adhesive strength cannot be obtained.

Conventionally, for the purpose of improving the paintability and adhesiveness of these highly saturated hydrocarbon rubber molded products, for example, 98% of its double bond is used.
The above is a method of adding hydrogenated polyhydroxypolybutadiene (Japanese Patent Publication No. 57-6462) and a method of adding a hydrocarbon polymer having a hydroxyl group at the molecular end such as polyhydroxypolyolefin (Japanese Patent Laid-Open No. 1197534). ), And a method of adding low molecular weight polyisoprene in which 50% or more of the double bonds are hydrogenated (Japanese Patent Laid-Open No. 2-69545). However, these methods have the drawback that the adhesion to the paint is not sufficient.

DISCLOSURE OF THE INVENTION An object of the present invention is to provide a novel polyester suitable for improving properties such as coating property, adhesive property and printability of highly saturated and non-polar polymer rubber such as ethylene-propylene copolymer rubber. It is intended to provide a rubber modifier as an active ingredient and a rubber composition to which the modifier is added. Another object is to provide a vulcanized molded article coated with such a rubber composition and a method for producing the same.

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

According to another aspect of the present invention, 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 article obtained by coating the surface of a vulcanized molded article obtained by vulcanizing and molding the above rubber composition.

According to the present invention, in still another aspect, (1) the above-mentioned rubber composition is vulcanized and molded, and the surface of the vulcanized molded body is coated with a coating material and cured, or (2) the above-mentioned rubber. Provided is a method for producing a coated rubber molded article, which comprises molding the composition, and then vulcanizing 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 hydrogen atoms 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 the 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.

The polar group containing a hydrogen atom is at least 3 in the molecule.
It is not preferable that the number of pieces is required, and if the number is two or less, the adhesiveness with a paint or the like is deteriorated. The maximum value of the polar group content is not particularly limited, but generally, it is appropriately selected within the 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, its 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 10 to 200 mgKOH / g, preferably 20 to 150 mgK.
OH / g, more preferably 30-120 mg KOH / g, most preferably
It is in the range of 30 to 100 mgKOH / g.

The polyesters used in this invention are usually oil-soluble. Polyesters that are not oil-soluble are generally not preferred because they have poor compatibility with rubber. Here, "oil-soluble" means that the polyester solution has a light transmittance of 80% or more, which is measured as described below. The preferred light transmittance is 90% or more.

Put 5 g of polyester in 95 g of toluene, dissolve in a nitrogen atmosphere at 80 ° C for 1 hour with stirring, and then dissolve at room temperature (20
(° C). This toluene diluted solution is allowed to stand in a thermostatic chamber at 20 ° C. for 24 hours, then stirred again to measure the transmittance with a turbidimeter (“ANA-14S” manufactured by Tokyo Koden Co., Ltd.). A tungsten incandescent lamp (6V, 6A) 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 itself used for dilution is 100%.

The molecular weight of the polyester is 1,000 to 1,000,000, preferably a polystyrene-converted weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).
The range is 3,000 to 500,000, and more preferably 5,000 to 100,000. If the molecular weight is too small, the polyester will all migrate to the surface of the rubber molded product and the coating strength will be insufficient.
On the contrary, when the molecular weight is excessively large, the polyester molecules are difficult to migrate to the surface of the rubber molded product, and the improvement effect such as the improvement of the adhesiveness is not sufficiently obtained, which is not preferable.

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 divalent alcohol component, and (C) a trivalent or higher carboxylic acid, a trivalent or higher Of the alcohol and at least one polyvalent component selected from epoxy compounds having two or more epoxy groups in a proportion of 1 to 80 mol% based on the total amount of both components (A) and (B), (A), ( It can be obtained by polycondensation of the three components B) and (C).

The divalent higher carboxylic acid (A) has usually 8 or more carbon atoms, preferably 10 to 200 carbon atoms, more preferably 20 to 8 carbon atoms.
0 is used. If the number of carbon atoms in the carboxylic acid is too small, the oil solubility is lowered and the compatibility with the rubber is poor, which is not preferable. Such divalent higher carboxylic acid may be, for example, linear, branched or cyclic, and specifically, suberic acid, azelaic acid, sebacic acid, brassic acid, polyalkylene succinic acid. And dimer acid of polymerized fatty acid. Among them, at least one selected from polyalkylene succinic acid and dimer acid of polymerized fatty acid is preferable, and dimer acid of polymerized fatty acid is particularly preferable.

Polymerized fatty acid is a polymer of higher fatty acid,
Usually, it is a general term for polymerized acids obtained by polymerizing an aliphatic group having 8 to 24, preferably 16 to 20 saturated or at least one unsaturated bond or an aliphatic ester derivative thereof. Commercially available polymerized fatty acids are oleic acid,
It is obtained by polymerizing linoleic acid, ricinoleic acid, eleostearic acid and the like, and contains dimer acid as a main component, and a polymer acid and a monomer acid at least trimer acid as auxiliary components. Structural analysis of polymerized fatty acid
Reported by Mcmahon et al. (J. Am. Oil. Chem. Soc.,
51 , 522 (1974)). The polymerization product can be separated into polymerized fatty acids having different contents of each component by a distillation method or a solvent extraction method. 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 purified polymerized fatty acid containing 60% by weight or more of a dimer acid component or its hydride is used.

The polyalkylene succinic acid has the general formula (1) (R ¹ in the formula is a polymer chain of lower alkylene.). R ¹ 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.

The dihydric alcohol (B) is not particularly limited as long as it is one generally used in polyester synthesis reactions. For example, alkane diols, cycloalkane diols, polyoxyalkylene glycols, polyester diols, hinders. Examples thereof include deglycols, and alkanediols and hindered glycols are particularly preferable. These can be used alone or in combination of two or more.

Examples of the alkanediols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,4-butanediol, 1,6-hexanediol, and 3
-Methyl-1,5-pentanediol, 1,9-nonanediol and the like can be mentioned.

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

Examples of the polyoxyalkylene glycols include polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, polybutylene glycol and the like obtained by polymerizing ethylene oxide, propylene oxide, alkylene oxide such as butylene oxide alone or in a mixture by a known method. And these are generally
Formula (2) HO - is it represented by ^{_{((CH 2) m -CHR 2}} O) n -H (2). Here, R ² represents a hydrogen atom or a lower alkyl group such as a methyl group and an ethyl group, and preferably a hydrogen atom. m represents an integer of 1 to 6, and 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 100.

Examples of polyester diols include, for example, JP-A-6-
-116372, β-propiolactone, β disclosed in
Ring-opening products of lactones such as -butyrolactone, γ-butyrolactone, and δ-valerolactone and (poly) alkylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; and general formula (3) represented by _{^{HO- (R 3 -COO-G)}} p -H (3). Here, R < ³ > shows a C2-C6 alkylene group. p represents an integer of 2 to 1,000, preferably 5 to 5
00, more preferably an integer of 10 to 100. G is-(CH ₂
CHR ⁴ O) _q -group, wherein 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.

Examples of the hindered glycol include those represented by the general formula (4) HOCH ₂ —C (R ⁵ R ⁶ ) —CH ₂ OH (4). Here, R ⁵ and R ⁶ each independently represent an alkyl group. The carbon number of the alkyl group is not particularly limited, but is usually 1 to 50, preferably 1 to
It is 20 pieces, 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 and 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-propyl-2-pentyl -1,3-propanediol etc. are mentioned.

In the present invention, in addition to the divalent higher carboxylic acid component (A) and the dihydric alcohol component (B),
At least one (C) selected from trivalent or higher carboxylic acids, trivalent or higher alcohols and epoxy compounds having two or more epoxy groups is used.

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

It can also be used as a trihydric or higher alcohol, a formula _{(5) HOCH 2 -C (R} 7 R 8) trivalent or more hindered alcohol represented by -CH ₂ OH (5). R ⁷ and R ⁸ in the formula each independently represent an alkyl group or an alkyl group having a hydroxyl group,
At least one of R ⁷ and R ⁸ is an alkyl group having a hydroxyl group. Here, the carbon number of 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 the trihydric or higher hindered alcohol include trimethylolethane, trimethylolpropane, trimethylolbutane,
Pentaerythritol and the like can be mentioned, with preference given to trimethylolethane, trimethylolpropane, pentaerythritol and the like.

Each of these trihydric or higher alcohols is,
Alternatively, two or more kinds may be mixed and used, but at least 10 mol% of a trihydric or higher hindered alcohol in a trihydric or higher alcohol component, preferably 30 to 100 mol%, more preferably 50 to 100 mol. % Is preferable.

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 the molecule, and examples thereof include dimer acid glycidyl ester of polymerized fatty acid, glycidyl ether of bisphenol A, and bisphenol F. And glycidyl ether of aliphatic dibasic acid.

Such component (C) can be used alone or in admixture of two or more, and the amount of the component (C) used is such that the divalent carboxylic acid component (A) and the divalent alcohol component (B) are used.
Is 1 to 80 mol%, preferably 5 to 60 mol%, and more preferably 10 to 40 mol%. If the amount of component (C) used is too small, the hydroxyl value or acid value will be insufficient. On the contrary, if the amount is too large, it becomes difficult to control the polycondensation reaction, which is not preferable.

In addition to the divalent higher carboxylic acid (A) and the trivalent or higher carboxylic acid component (C) in the carboxylic acid component, other carboxylic acids such as amber, as long as the object of the present invention is not impaired. Divalent lower carboxylic acids such as acids, glutaric acid, adipic acid, maleic acid, itaconic acid, pimelic acid, methylmalonic acid, dimethylmalonic acid; acetic acid, 2-methylpropanoic acid, isooctylic acid, isononanoic acid,
Monovalent carboxylic acids such as lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, arachidic acid, linoleic acid, oleic acid, and elaidic acid, and the divalent alcohol component (B) and trihydric alcohol component in the alcohol component. Other than the alcohol component (C) having a valency or higher, other alcohols such as methanol, ethanol, isopropanol, neopentyl alcohol, 3-methyl-3-pentanol, 2,3,3-trimethyl-2-butanol, 1-
You may use together monohydric alcohols, such as decanol and nonyl alcohol. Generally, the permissible amount is 20 mol% or less in the total carboxylic acid component or the total alcohol component.

The ratio of the carboxylic acid component and the alcohol component may be appropriately selected according to the molecular weight or hydroxyl value (or acid value) of the desired polyester, but is usually 0.5 to 2.5, preferably 0.6 in OH / COOH (equivalent) ratio. It is in the range of ~ 2.0.

The polyester used in the present invention is the above component (A),
It can be obtained by subjecting the component (B), the component (C), and other optional components such as carboxylic acid and alcohol components to polycondensation 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, and particularly 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. Also, during the esterification polycondensation reaction,
Usually, as esterification catalysts, various metal oxides such as paratoluene sulfonic acid, sulfuric acid, boron trifluoride complex, phosphoric acid, hydrochloric acid, potassium acetate, zinc stearate, zinc, titanium, tin and butyltin oxide, titanium oxide, etc. Although the thing etc. are used, it is preferable to use a metal oxide from the viewpoint of the oxidation resistance stability of the obtained polyester.

Rubber Component The rubber component to be blended with the modifier of the present invention 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-butadiene copolymer rubber, butadiene-isoprene copolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, acrylonitrile butadiene rubber, chloroprene rubber, etc. conjugated diene polymer rubber; chlorinated polyethylene rubber Modified polyethylene rubber such as chlorosulfonated polyethylene rubber; α-olefin copolymer rubber; silicone rubber. Among these, the main chain has a small amount of carbon-carbon double bonds, for example, an iodine value of 100
The following rubber components are suitable, preferably 50 or less, and more preferably 35 or less. Among these, modified polyethylene rubber, α-olefin-based copolymer rubber, silicone rubber and the like, particularly α-olefin-based copolymer rubber, are preferable because the modifying effect of the present invention is remarkably exhibited. These rubbers can be used alone or in combination of two or more.

The α-olefin is an olefin having a carbon-carbon double bond at the terminal, and examples thereof include ethylene, propylene, 1-butene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, Examples include, but are not limited to, 4-methyl-1-pentene.

The α-olefin copolymer rubber is not particularly limited as long as it is a rubber-like polymer containing the above α-olefin. For example, a copolymer rubber of two or more α-olefins, α-olefin and other Copolymer rubbers with the above-mentioned polymerizable monomers. The amount of α-olefin in the copolymer rubber is not particularly limited, but is usually 50% by weight or more, preferably
It is in the range of 60 to 100% by weight, more preferably 80 to 100% by weight. The other polymerizable monomer is not particularly limited,
Examples include conjugated dienes and non-conjugated dienes. Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and 1,3-hexadiene, and among them, 1,3- Butadiene and isoprene are preferred. Examples of the non-conjugated diene include ethylidene norbornene, dicyclopentadiene, and 1,4-hexadiene. Among these, ethylidene norbornene and dicyclopentadiene 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.
It is the following.

Specific examples of the α-olefin copolymer rubber include, for example, two or more α-olefin copolymer rubbers such as ethylene-α-olefin copolymer rubber having 3 or more carbon atoms; ethylene-α-olefin having 3 or more carbon atoms. Copolymer rubber of two or more kinds of α-olefin and non-conjugated diene such as olefin-non-conjugated diene copolymer rubber; α-olefin-conjugated diene copolymer rubber;
And modified rubbers such as chlorinated products and chlorosulfonated products thereof.

Examples of the α-olefin copolymer rubber include ethylene-propylene copolymer rubber and ethylene-butene-1 copolymer rubber. The weight ratio of ethylene and propylene is 9
An ethylene-propylene copolymer rubber in the range of 0:10 to 20:80 is particularly preferable.

As the non-conjugated diene of the ethylene-C3 or more α-olefin-non-conjugated diene copolymer rubber, those exemplified for the α-olefin copolymer rubber are used.

Examples of the α-olefin-conjugated diene copolymer rubber include, for example, isobutene of 90 to 99.5% by weight and isoprene of 0.5.
Examples thereof include butyl rubber copolymerized with about 10% by weight.

These rubber components may be used alone or in admixture of two or more. The use ratio of the rubber component and the polyester modifier can be appropriately selected depending on the application or purpose, but is usually 99: 1 to 50:50, preferably 98: 2 to 60:40, more preferably by weight ratio. Ranges from 95: 5 to 80:20.

Optional Components To the rubber modifier and the rubber composition of the present invention, additives usually used in the rubber industry can be added as required. Examples of the additives include inorganic fillers, vulcanizing agents, vulcanization accelerators, vulcanization aids, plasticizers, antioxidants, antioxidants, lubricants, UV inhibitors, UV stabilizers, heat stabilizers, Examples include antistatic agents, nucleating agents, flame retardants, organic and / or inorganic pigments, oils and the like. These additives can be added alone or in combination of two or more.
The addition amount of these is appropriately determined within a range that does not impair the effects of the present invention.

Examples of the inorganic filler 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, and mica. ,
Examples thereof include dolomite, silica, clay, talc, carbon black, zinc oxide, glass fiber, carbon fiber and the like. Among these, silica and carbon black are particularly preferable. These inorganic fillers are used alone or in admixture of two or more, and the amount thereof is usually 10 to 200 parts by weight, relative to 100 parts by weight of the rubber component,
It is preferably 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 sulfur and disulfide; peroxide-based vulcanizing agents such as dicumyl peroxide and di-t-butylperoxydiisopropylbenzene. These vulcanizing agents may be used alone or in admixture of two or more. The amount used is usually 100 parts by weight of the rubber component.
The amount is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight.

Examples of the vulcanization accelerator include vulcanization accelerators such as mercaptobenzothiazole, zinc dimethyldithiocarbamate, and tetramethylthiuram sulfide. The amount used of these is usually 100 parts by weight of the rubber component.
The amount is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, more preferably 1 to 3 parts by weight.

Rubber composition and rubber vulcanization molded product The rubber composition of the present invention is prepared according to a usual method performed in the rubber industry. For example, it can be manufactured by kneading each of the above components in a mixer. As the kneading machine, for example, an extruder such as a single-screw extruder or a twin-screw extruder, a Banbury, a Brabender, a plastomill, a calendar, a kneader, a roll, an extruder, a multi-screw kneader, a double helical ribbon stirrer, etc. may be used. it can.

The vulcanized rubber molded product of the present invention can be manufactured by a method generally used in the rubber industry. For example, (1) adding the above components other than the vulcanizing agent to Banbury, Brabender, etc.,
After kneading at 60 ℃ ~ 300 ℃ for 0.5 ~ 60 minutes, (2) transfer the kneaded material to the roll, add the vulcanizing agent at 100 ℃ or less, knead, and then (3) heat mold with a molding machine such as an extruder. Obtainable.

Surface-Coated Rubber Molded Product A coating film having excellent adhesiveness is formed by applying a coating material to the surface of a vulcanized molded product of the above rubber composition and curing it. Alternatively, the vulcanizable rubber composition may be molded into an unvulcanized rubber molded body, a coating material may be applied to the surface thereof, and then the rubber molded body may be vulcanized and the coating film cured. The paint used for the surface coating is not particularly limited, but examples thereof include a melting agent thermoplastic (meth) acrylic resin paint, a solvent-type thermosetting (meth) acrylic resin paint, an acrylic modified alkyd-based paint, and an epoxy resin paint. , Acrylic urethane resin coatings, silicone modified urethane resin coatings, polyurethane resin coatings, melamine resin coatings and the like. These paints can be used alone or in combination of two or more.

As a method for applying the paint to the molded body, for example, a method such as electrostatic coating, spraying (air spray) coating, or brush coating is used. These paints may be applied by a method of overcoating after undercoating. The coating film curing method after coating the coating material is appropriately selected depending on the material of the molded body, the shape, the properties of the coating material, and the like, for example, natural drying, nichrome wire, infrared rays,
It is dried by a method such as heating forced drying such as high frequency heating to form a cured coating film.

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% in these examples are by weight unless otherwise specified.

  The methods for measuring physical properties are as follows.

(1) Weight average molecular weight The weight average molecular weight of polyester is determined according to the GPC method.
It was measured as a standard polystyrene equivalent amount.

(2) Hydroxyl Value and Acid Value The hydroxyl value and 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 (3) Adhesion test Cross-cut test Adhesion rate: It was performed in accordance with JIS K5400. With the load of 350 kg on the coating surface, 11 cuts are made orthogonal at 1 mm intervals,
After making 100 squares per 1 cm ² , use a pressure roller to crimp an 18 mm wide adhesive tape (manufactured by Nichiban Co., Ltd.) with a load of 1300 kg, and perform a peel test to peel at a peel angle of 180 °. Out of 100, the number of grids that were not peeled off was shown as an adhesion rate (%).

Peel strength test: Make a 1 cm wide cut on the surface of the coating film with a cutter blade until the blade reaches the base material, peel off the edge, and peel the edge of the peeled coating film at a speed of 50 cm / min for 180 The maximum peel strength (kg / cm) was obtained by pulling in the ° direction.

Production Example 1 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 halidimer 200 (acid value 193 mgKOH / g, monomer acid 8.0%,
Dimer acid 75.0%, trimer acid 17.0%; manufactured by Harima Chemicals Co., Ltd.) 420.0 g, 2-ethyl-2-butyl-1,3-propanediol 15.0 g, trimethylolpropane 94.6 g and monobutyltin oxide 0.26 g as a catalyst. I prepared it.
(OH / COOH equivalent ratio = 1.10) Stirring was carried out while introducing nitrogen gas, and the temperature was raised to 100 ° C. Then, the temperature was raised from 100 ° C. to 260 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, the reaction was continued for 10 hours while dehydrating at 260 ° C. The resulting polyester A had a weight average molecular weight of 11,700, an acid value of 0.2 mgKOH / g, and a hydroxyl value of 82 mgKOH / g. The light transmittance of the toluene solution was 99%.

Production Example 2 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube was charged with polymerized fatty acid halider 300 (acid value 195 mgKOH / g, monomer acid 0.5%,
Dimer acid 97.0%, trimer acid 2.5%; manufactured by Harima Chemicals Co., Ltd.) 440.0 g, 3-methyl 1,5-heptanediol 28.1 g,
85.0 g of trimethylolpropane and 0.26 g of monobutyltin oxide as a catalyst were charged. (OH / COOH equivalent ratio = 1.05) The temperature was raised to 100 ° C by stirring while introducing nitrogen gas. Then, the temperature was raised from 100 ° C. to 260 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, 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 mgKOH / g and a hydroxyl value of 58 mgKOH / g. The light transmittance of the toluene solution was 97%.

Production Example 3 A 1000 cc four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, a diversion tube and a nitrogen gas inlet tube was charged with hydrogenated polymerized fatty acid halidermer 300 (acid value 195 mgKOH / g, monomer acid 0.3).
%, Dimer acid 97.0%, trimer acid 2.7%; Harima Chemicals Co., Ltd.) 460.0 g, Epicoat 871 (polymerized fatty acid glycidyl ester; Shell Co., Ltd.) 63.4 g, 2,2-dimethyl-1,3-
79.2 g of propanediol and 0.26 g of monobutyltin oxide as a catalyst were charged. [(OH + epoxy) / CO
OH equivalent ratio = 1.09] The temperature was raised to 100 ° C. while stirring while introducing nitrogen gas. Then, the temperature was raised from 100 ° C. to 260 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, the reaction was continued for 10 hours while dehydrating at 260 ° C. The obtained polyester C has a weight average molecular weight.
It had an acid value of 6,500, an acid value of 0.1 mgKOH / g, and a hydroxyl value of 52 mgKOH / g.
The light transmittance of the toluene solution was 94%.

Production Example 4 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 250 (acid value 193 mgKOH / g, monomer acid 3.0%,
Dimer acid 79.0%, trimer acid 18.0%; manufactured by Harima Chemicals Co., Ltd.) 420.0 g, 2,2-diethyl-1,3-propanediol 11
3.4 g, pentaerythritol 41.4 g, and monobutyltin oxide 0.26 g as a catalyst were charged. (OH / COOH equivalent ratio = 1.40) The temperature was raised to 100 ° C. with stirring while introducing nitrogen gas. Then, the temperature was raised from 100 ° C. to 240 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. Then, 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 100 mgHg. Polyester D obtained had a weight average molecular weight of 21,50.
The acid value was 0, the acid value was 0.2 mgKOH / g, and the hydroxyl value was 82 mgKOH / g. The light transmittance of the toluene solution was 97%.

Production Example 5 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 halidimer 250 (acid value 193 mgKOH / g, monomer acid 3.0%,
Dimer acid 79.0%, trimer acid 18.0%; manufactured by Harima Chemicals Co., Ltd.) 420.0 g, 2-ethyl-2-butyl-1,3-propanediol 109.0 g, trimethylolpropane 39.3 g and monobutyltin oxide 0.26 g as a catalyst. I prepared it. (OH / COOH equivalent ratio = 1.35) The temperature was raised to 100 ° C. with stirring while introducing nitrogen gas. Then, the temperature was raised from 100 ° C. to 240 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. After that, 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 100 mgHg. Polyester E obtained had a weight average molecular weight of 30,50.
The acid value was 0, the acid value was 0.1 mgKOH / g, and the hydroxyl value was 91.3 mgKOH / g. The light transmittance of the toluene solution was 98%.

Production Example 6 A hydrogenated polymerized fatty acid halidimer 250 (acid value 193 mgKOH / g, monomer acid 3.0 was added to 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.
%, Dimer acid 79.0%, trimer acid 18.0%; manufactured by Harima Chemicals Co., Ltd.) 420.0 g, 2-ethyl-2-butyl-1,3-propanediol 16.5 g, diethylene glycol 69.6 g, pentaerythritol 44.3 g and tetra n as a catalyst. -0.17 g of butyl orthotitanate was charged. (OH / COOH equivalent ratio = 1.50) The temperature was raised to 100 ° C. with stirring while introducing nitrogen gas. Then, the temperature was raised from 100 ° C. to 240 ° C. over 6 hours while removing water and unreacted diol generated during the reaction. After that, 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 100 mgHg. The obtained polyester F has a weight average molecular weight of 13,70.
The acid value was 0, the acid value was 0.1 mgKOH / g, and the hydroxyl value was 96.1 mgKOH / g. The light transmittance of the toluene solution was 93%.

Examples 1 and 2 and Comparative Examples 1 and 2 Using the polyesters A and C produced above, rubber compositions were prepared according to the compounding recipe shown in Table 1. For comparison, those without addition of polyester were also prepared (Comparative Examples 1 and 2). Each component other than sulfur and the vulcanization accelerator was kneaded with a Brabender type Banbury mixer at 80 ° C. for 5 minutes, and then the sulfur and the vulcanization accelerator were added with a 6 inch roll and kneaded at 60 ° C. Next, the kneaded product is extruded (L / D = 70, 75 mm
Φ) was used to extrude a cross section having a width of 30 mm and a thickness of 5 mm, and then vulcanized at 200 ° C. for 5 minutes.

Next, urethane coating (Soflex
2500; manufactured by Kansai Paint Co., Ltd.) was applied by spraying, baking was performed for 15 minutes in a hot air oven at 100 ° C., and a cross-cut test and a peel strength test were performed. The results are shown in Table 1.

Example 3 EP-103A (ethylene-propylene-non-diene rubber;
Brabender type Banbury mixer: 100 parts by weight of Japan Synthetic Rubber Co., 67.5 parts by weight of carbon black (Asahi F-200; Asahi Carbon Co., Ltd.), 35 parts by weight of mineral oil, 5 parts by weight of zinc white, 1 part by weight of stearic acid. Kneading with, then sulfur 1.5
Parts by weight, 2 parts by weight of 2-mercaptobenzothiazole and 10 parts by weight of the polyester B produced in Production Example 2 were added by a roll, further kneaded, and taken out as a sheet. Then, it was vulcanized by a press at 160 ° C. for 30 minutes.

Overflex No500 (urethane polymer; manufactured by Ohashi Chemical Industry Co., Ltd.) having an isocyanate (NCO) group at the end was applied to the above vulcanized molded product, and after curing at room temperature, a cross-cut test and a peel test were performed. The adhesion rate was 100% and the peel strength was 3.5 kg / cm, which were excellent values.

Comparative Example 3 A peeling test was performed in the same manner as in Example 3 except that 10 parts by weight of polyhydroxypolyolefin (Polytail; manufactured by Mitsubishi Kasei Co.) was used instead of 10 parts by weight of polyester B. The peel strength was 0.9 kg / cm.

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. In addition,
For comparison, a polyester was also added (Comparative Example 4). Each component other than sulfur and the vulcanization accelerator was kneaded at 50 ° C. for 5 minutes with a Banbury mixer, and then the sulfur and the vulcanization accelerator were added with a 6-inch roll and kneaded at 60 ° C. Then, use the extruder (L / D = 70, 20mmφ) for the kneaded product to give a width of 2
Extruded in a flat shape with a thickness of 5 mm and a thickness of 3 mm.

Next, urethane coating was applied to the surface of the extruded product (Japanese Patent Laid-Open No. 7-
Comparative Example 2) described in JP-A No. 150074 was applied with a spatula to a thickness of about 100 μm, and vulcanization of the rubber and curing of the paint were simultaneously performed for 12 minutes in a hot air oven at 180 ° C., and a peel strength test was performed. The results are shown in Table 2.

As is clear from the comparison between the above Examples and Comparative Examples, the vulcanized molded articles of the rubber composition containing the modifier of the present invention (Examples 1 and 2) do not contain the modifier. Compared with the ones (Comparative Examples 1 and 2), the adhesion rate and the peel strength by the cross-cut test are remarkably high. Further, the product of the present invention (Example 3) has considerably higher peel strength of the coating film as compared with the product containing a conventionally known polyhydroxypolyolefin modifier (Comparative Example 3). Even when the rubber composition containing the modifier of the present invention was applied after molding, and then vulcanization and curing of the coating film were carried out (Examples 4, 5, and 6), the case where the modifier was not mixed (comparison) Example 4)
The peel strength is significantly higher than that of

INDUSTRIAL APPLICABILITY A molded article of a rubber composition containing the rubber modifier of the present invention has excellent properties such as paintability, adhesiveness and printability.

As the use of the vulcanized molded article of such a rubber composition,
The following is exemplified.

(A) Medical equipment (ice pack, drapeback, catheter balloon, urethral catheter) (b) Tubes, gloves, packing rubber (c) weather strips, mat cards, side protect panels, and other automotive exterior materials (d) Air Rubber rolls and other rubber materials used in automobile interior materials (e) VTRs such as bags and interior skin materials (e) VTRs, audio equipment, OA equipment, camera parts (f) Synthetic leather, sports shoes, wet suits, etc.

Front page continued (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08C 19/20 C08G 63/00-63/91 C08L ⁷ /00-21/02 C08L 23/00-23/36 C08L 83 / 04-83/10 WPI / L (QUESTEL)

Claims (13)

(57) [Claims] 1. A rubber modifier 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 hydrogen atoms in the molecule. 2. The sum of the acid value and the hydroxyl value of the polyester is 10
The rubber modifier according to claim 1, wherein the modifier is about 200 mgKOH / g. 3. A polyester having (A) a divalent higher carboxylic acid component and (B) a divalent alcohol component, and (C) a trivalent or higher carboxylic acid, a trivalent or higher alcohol and two or more epoxy groups. At least one compound selected from the epoxy compounds having (A), in a proportion of 1 to 80 mol% with respect to the total amount of both components (A),
The rubber modifier according to claim 1 or 2, which is obtained by polycondensing three components (B) and (C). 4. A 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. A ratio (weight ratio) of a rubber component and a rubber modifier.
The rubber composition according to claim 5, wherein the ratio is 99 :, 1 to 50:50. 7. The rubber composition according to claim 5, wherein the rubber component is at least one selected from modified polyethylene rubber, α-olefin copolymer rubber and silicone rubber.
The rubber composition according to the item. 8. The rubber composition according to claim 5, wherein the iodine value of the rubber component is 100 or less. 9. A vulcanizing agent of 0.1 to 20 parts by weight, a vulcanization accelerator of 0.5 to 5 parts by weight, and 10 to 2 with respect to 100 parts by weight of a rubber component.
Claims 5 to 5 comprising 00 parts by weight of inorganic filler.
The rubber composition according to any one of item 8. 10. A vulcanized molded product of the rubber composition according to any one of claims 5 to 9, wherein the surface is coated. 11. A method for producing a coated rubber molded article, characterized in that the rubber composition according to any one of claims 5 to 9 is vulcanized and molded, and a coating material is applied to the surface of the rubber composition to cure the rubber composition. Method. 12. A rubber composition according to any one of claims 5 to 9 is molded, a coating material is applied to the surface of the obtained molded product, and then the resulting coating film is cured and cured. A method for producing a coated rubber molded article, which comprises vulcanizing the molded article. 13. A solvent-type thermoplastic (meth) acrylic resin paint, a solvent-type thermosetting (meth) acrylic resin paint,
The acrylic modified alkyd paint, epoxy resin paint, acrylic urethane resin paint, silicone modified urethane resin paint, polyurethane resin paint and at least one selected from melamine resin paints according to claim 11 or claim 12. Manufacturing method.