WO2012096281A1 - Coating material to be applied to crosslinked rubber, molded article coated with the coating material, and process for producing same - Google Patents

Coating material to be applied to crosslinked rubber, molded article coated with the coating material, and process for producing same Download PDF

Info

Publication number
WO2012096281A1
WO2012096281A1 PCT/JP2012/050330 JP2012050330W WO2012096281A1 WO 2012096281 A1 WO2012096281 A1 WO 2012096281A1 JP 2012050330 W JP2012050330 W JP 2012050330W WO 2012096281 A1 WO2012096281 A1 WO 2012096281A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
unsaturated carboxylic
coating film
carboxylic acid
parts
Prior art date
Application number
PCT/JP2012/050330
Other languages
French (fr)
Japanese (ja)
Inventor
雅照 井上
浩登 竹本
文彦 服部
Original Assignee
丸五ゴム工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 丸五ゴム工業株式会社 filed Critical 丸五ゴム工業株式会社
Priority to JP2012552738A priority Critical patent/JP5825610B2/en
Publication of WO2012096281A1 publication Critical patent/WO2012096281A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D153/02—Vinyl aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a paint for coating crosslinked rubber, a molded article in which a coating film is formed by applying the paint, and a method for producing the same.
  • protective coating materials have been applied to various rubber surfaces to provide functions such as weather resistance and heat dissipation.
  • Patent Document 1 discloses a two-component liquid paint that can be cured at an ambient temperature and includes a functional group that reacts with an active hydrogen-containing curing agent, or the functional group is an active hydrogen-containing group.
  • a paint comprising a coalescence, a curing component that reacts with the functional group, and a carrier liquid is described.
  • Patent Document 2 discloses a two-part liquid coating composition that can be cured at ambient temperature, and contains a reactive functional group in the active hydrogen-containing curing agent, or the functional group is active hydrogen.
  • a coating composition comprising a flexible film-forming polymer as a holding group, a curing component capable of reacting with the functional group, a carrier liquid, and thermally conductive metal particles is described.
  • the coating film to be formed is cross-linked, there is a possibility that the adhesion is insufficient. Furthermore, when a pigment is included, the dispersibility may be poor.
  • Patent Document 3 discloses a muffler hanger interposed between a vehicle body and an exhaust pipe in order to suspend the exhaust pipe from the vehicle body, and the surface of a molded product made of a crosslinked rubber is a styrene-diene block copolymer.
  • a muffler hanger covered with a heat-reflective coating made of a thermoplastic elastomer composition containing a hydrogenated product and metal powder is described. Accordingly, it is said that a muffler hanger that is covered with a heat-reflecting film having good adhesion and stretchability and excellent in heat resistance can be provided.
  • the adhesion to the crosslinked rubber may be insufficient.
  • Patent Document 4 discloses a crosslinked product of rubber partially modified with maleic anhydride, or an SEBS elastomer, polypropylene (PP), polyethylene (PE) or ethylene partially modified with unmodified rubber with the modified rubber or maleic anhydride.
  • PP polypropylene
  • PE polyethylene
  • ethylene partially modified with unmodified rubber with the modified rubber or maleic anhydride Forming a film of one or a mixture of two or more of nylon, polyurethane, polyvinylidene chloride, polyvinyl chloride, or polyvinylidene fluoride on the surface of a crosslinked product obtained by mixing a vinyl acetate copolymer (EVA).
  • EVA vinyl acetate copolymer
  • a rubber resin film forming method is described. According to this, since an adhesive is not used and a surface treatment such as a halogenation treatment is not required, the manufacturing process can be simplified. However, the abrasion resistance of the rubber thus obtained is not always good, and improvement has been
  • Patent Document 5 a hydrogenated isoprene-based resin primer is applied to a rubber substrate, and then a topcoat containing at least one selected from a fluoroolefin resin, an acrylic urethane resin, and an acrylic resin is applied.
  • a coating method characterized in that is described. According to this, it is said that a coating film made of a fluoroolefin resin or the like can be sufficiently adhered and coated on the surface of the rubber substrate.
  • a pigment is contained in the top coat coated on the rubber substrate, the dispersibility of the pigment is not always good, and improvement has been desired.
  • the present invention has been made to solve the above problems, and provides a coating material that has good adhesion to a crosslinked rubber, can follow a large deformation, and can form a coating film excellent in pigment dispersibility. It is intended to do. It is another object of the present invention to provide a method for producing a molded product in which such a paint is applied to the surface of a molded product made of a crosslinked rubber. Furthermore, it aims at providing the molded article in which the coating film obtained by apply
  • the above-mentioned problem is a coating for coating a crosslinked rubber, which is 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, This is solved by providing a paint containing 10,000 parts by weight and 1 to 200 parts by weight of pigment.
  • the content of units derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the modified styrene-diene block copolymer hydrogenated product is preferably 0.2 to 5% by weight.
  • the hydrogenated product of the modified styrene-diene block copolymer is preferably modified with maleic anhydride.
  • the above-mentioned problem is that a coating film containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and a pigment is formed on the surface of the crosslinked rubber. It is also solved by providing goods.
  • a polyurethane film is further formed on the surface of the coating film.
  • the modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is used. It is preferable to contain 1 to 200 parts by weight of pigment with respect to 100 parts by weight of the polymer hydrogenated product.
  • the crosslinked rubber is an olefin rubber or a diene rubber.
  • the above-mentioned problems are that 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment.
  • the present invention can also be solved by providing a method for producing a molded article characterized in that a coating material containing a coating is applied to the surface of a crosslinked rubber and the liquid medium is removed to form a coating film.
  • a polyurethane coating is applied to the surface of the coating film to form a polyurethane film.
  • the coating material of the present invention it is possible to form a coating film having good adhesion to the crosslinked rubber, capable of following a large deformation, and having excellent pigment dispersibility.
  • a coating film can be easily formed.
  • the molded article of the present invention has good adhesion to the surface of the crosslinked rubber, can follow large deformations, and has a coating film excellent in pigment dispersibility. Furthermore, since the dispersibility of the pigment in a coating film is excellent, the designability of a molded article can also be improved.
  • the paint of the present invention is a paint for coating a crosslinked rubber, comprising a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment. contains.
  • the cross-linked rubber used in the present invention is not particularly limited, but olefin rubber and diene rubber are preferably employed from the viewpoint of adhesion to the paint of the present invention.
  • the olefin rubber examples include ethylene-propylene copolymer rubber (EPM), ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), and butyl rubber.
  • EPM and EPDM are preferably used.
  • EPDM is particularly suitable because it is easy to vulcanize and has an excellent balance of strength, elasticity and cost.
  • non-conjugated dienes used in EPDM include ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene and the like.
  • the olefin rubber has good adhesion to a coating film formed using the paint of the present invention.
  • diene rubber examples include natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and nitrile rubber.
  • styrene-butadiene rubber and natural rubber are preferably used because they have good adhesion to the coating film formed in the molded article of the present invention.
  • EPM can be crosslinked with a peroxide crosslinking agent to form a crosslinked rubber.
  • EPDM can be crosslinked by either a peroxide crosslinking agent or sulfur, and a crosslinked rubber can be obtained more easily. Further, the diene rubber can be easily vulcanized with sulfur. From the viewpoint of performance, it is particularly preferable to use sulfur-crosslinked EPDM.
  • the crosslinked rubber used in the present invention preferably contains various additives and fillers, inorganic fillers such as carbon black and zinc oxide, process oils such as liquid paraffin, lubricants such as stearic acid, sulfur and peroxides. Vulcanizing agents such as vulcanizing agents, vulcanization aids, anti-aging agents and the like are appropriately blended. What was blended in this way is put into a mold and heated to be crosslinked to obtain a molded product made of a crosslinked rubber.
  • the hardness of the crosslinked rubber is appropriately adjusted according to the use of the molded product, but the A hardness measured in accordance with JIS K6253 is preferably 30 to 90.
  • the adhesiveness of the coating material of the present invention is high even for a crosslinked rubber having a relatively low hardness, and can follow a large deformation.
  • the A hardness is more preferably 85 or less, and even more preferably 80 or less.
  • the A hardness is more preferably 35 or more, and even more preferably 40 or more.
  • the coating material of the present invention contains a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
  • a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride By hydrogenating the diene block, it is possible to form a coating film that hardly deteriorates at high temperatures. Moreover, due to the presence of the hydrogenated diene block, the adhesion to the crosslinked rubber substrate is good.
  • the hydrogenated diene block and the ethylene-propylene- (diene) copolymer may have a similar chemical structure, or may give a molded product with extremely good adhesion of the coating film. Moreover, it is possible to hold
  • the structure of the modified styrene-diene block copolymer hydrogenated product is not particularly limited, and may be a styrene-diene diblock copolymer or a styrene-diene-styrene triblock copolymer.
  • a block copolymer composed of a larger number of blocks may be used.
  • the diene block may be composed of butadiene, isoprene, or a mixture of these.
  • the modified styrene-diene block copolymer hydrogenated product is modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
  • an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride monomer is grafted onto a styrene-diene block copolymer, or a styrene-diene block copolymer is used.
  • Examples thereof include a copolymerization method in which a monomer constituting a polymer and an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride monomer are copolymerized.
  • the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like can be used.
  • the unsaturated carboxylic acid may form a salt in whole or in part.
  • the use of maleic anhydride is preferable because the adhesion to the crosslinked rubber is further improved and the dispersibility of the pigment in the coating film is improved.
  • the content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the modified styrene-diene block copolymer hydrogenated product is 0.2 to the modified styrene-diene block copolymer hydrogenated product. It is preferably ⁇ 5% by weight.
  • the content of the unit derived from the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride is less than 0.2% by weight, the adhesion of the formed coating film to the crosslinked rubber may be lowered. Furthermore, the dispersibility of the pigment in the coating film may be reduced.
  • the content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is more preferably 0.3% by weight or more, and further preferably 0.5% by weight or more.
  • the durability of the coating film may be lowered.
  • the content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is more preferably 4.5% by weight or less, and further preferably 4% by weight or less.
  • the styrene content of the modified styrene-diene block copolymer hydrogenated product is preferably 10 to 40% by weight.
  • the styrene content is more preferably 15% by weight or more.
  • the flexibility may decrease.
  • the styrene content is more preferably 35% by weight or less.
  • the A hardness of the modified styrene-diene block copolymer hydrogenated product used in the present invention is preferably 20 to 90 as measured according to JIS K6253.
  • the A hardness is the A hardness of the raw material modified styrene-diene block copolymer hydrogenated product. If the hardness of the modified styrene-diene block copolymer hydrogenated product is too high, the coating film may be damaged when the crosslinked rubber base material is deformed.
  • the A hardness is more preferably 85 or less, and even more preferably 80 or less. On the other hand, when the hardness is too low, the heat resistance is lowered and the shape retention is also deteriorated.
  • the A hardness is more preferably 30 or more.
  • the MFR of the modified styrene-diene block copolymer hydrogenated product used in the present invention is usually 0.1 to 100 g / 10 min (measured at 230 ° C. and 2.16 kgf).
  • the coating film formed in the present invention contains a pigment together with the modified styrene-diene block copolymer hydrogenated modified with the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride described above.
  • a coating containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment is applied to the surface of the crosslinked rubber, A coating film is formed by removing the liquid medium.
  • the dispersibility of the pigment is good by using the coating material containing the hydrogenated product of the modified styrene-diene block copolymer modified with the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride, the liquid medium, and the pigment. Therefore, the hiding power is improved. In particular, when the crosslinked rubber base material contains carbon black, it is preferable because the hiding power is good.
  • various organic pigments and / or inorganic pigments are used. Examples of organic pigments include azo pigments, quinacridone pigments, phthalocyanine pigments, dioxazine pigments, and the like.
  • inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, carbon black, lead pigments, cadmium pigments, cobalt pigments, iron pigments, chromium pigments, ultramarine blue, and bitumen. Further, a pearl pigment or the like can be used. You may use 1 type or in combination of 2 or more types from these.
  • the paint of the present invention preferably contains a metal powder.
  • the surface of the molded product can be concealed, and a molded product having an excellent appearance can be obtained.
  • the metal powder is not particularly limited as long as the surface of the molded product can be concealed, but aluminum powder, particularly aluminum flake is preferably used from the viewpoint of availability, performance, cost, and the like.
  • the color metallic with pigment is more preferably used.
  • the aluminum powder may be added as a powder, but for safety, it is preferably added to the paint as a paste dispersed in an organic solvent or the like.
  • liquid medium used in the present invention a medium in which a hydrogenated product of a modified styrene-diene block copolymer is dispersed or dissolved is used.
  • an organic solvent capable of dissolving the modified styrene-diene block copolymer hydrogenated product is used.
  • hydrocarbons, esters, ketones, ethers, alcohols, and mixtures thereof are preferably used.
  • hydrocarbons, particularly aromatic hydrocarbons such as toluene and xylene are obtained from the viewpoint that the crosslinked rubber base material is appropriately swollen and the solubility of the modified styrene-diene block copolymer hydrogenated product is good.
  • hydrocarbons, particularly aromatic hydrocarbons such as toluene and xylene are obtained from the viewpoint that the crosslinked rubber base material is appropriately swollen and the solubility of the modified styrene-diene block copolymer hydrogenated product is good.
  • a modified styrene-diene block copolymer hydrogenated dispersion can be obtained.
  • an emulsion is preferable.
  • the solid concentration can be increased at a low concentration.
  • the adhesion to the crosslinked rubber may be reduced.
  • the paint of the present invention contains 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and 50 to 10,000 parts by weight of a liquid medium.
  • the content of the liquid medium in the paint of the present invention needs to be 50 to 10,000 parts by weight with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content of the liquid medium is less than 50 parts by weight, the viscosity of the coating becomes high and it may be difficult to apply the coating. Moreover, there exists a possibility that the thickness of a coating film may not become uniform.
  • the content of the liquid medium is preferably 1000 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content of the liquid medium is preferably 80 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content of the liquid medium is more than 10,000 parts by weight, it takes time to dry, and the working efficiency may be reduced.
  • the content of the liquid medium is preferably 5000 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content of the liquid medium is preferably 500 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the pigment content in the paint of the present invention is 1 to 200 parts by weight per 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. If the pigment content is less than 1 part by weight, the hiding power may be insufficient. In particular, there is a possibility that the concealing force when applied to a crosslinked rubber containing carbon black is insufficient.
  • the pigment content is preferably 2 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When there is more content of a pigment than 200 weight part, there exists a possibility that it may become difficult to paint.
  • the pigment content is preferably 150 parts by weight or less, and more preferably 100 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
  • the content of the metal powder is less than 1 part by weight, the hiding power for the crosslinked rubber may be insufficient.
  • the content of the metal powder is more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more.
  • there is more content of metal powder than 500 weight part there exists a possibility that the intensity
  • the content of the metal powder is more preferably 200 parts by weight or less, and further preferably 100 parts by weight or less.
  • the coating material of the present invention may contain additives other than the modified styrene-diene block copolymer hydrogenated product, the liquid medium, the pigment, and the metal powder.
  • Various inorganic fillers or organic fillers can be blended. In this case, it is important to blend within a range in which the adhesion between the crosslinked rubber and the coating film is not significantly reduced.
  • crosslinking agents such as sulfur, a peroxide, a polyfunctional unsaturated compound, can also be mix
  • the coating material of the present invention does not contain a crosslinking agent.
  • process oils, antioxidants, surfactants, dispersion stabilizers, ultraviolet absorbers, preservatives and the like may be appropriately blended as necessary.
  • the content of components other than the above-described hydrogenated styrene-diene block copolymer, liquid medium, pigment, and metal powder is preferably 30% by weight or less, and 20% by weight. % Or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less.
  • the molded article of the present invention has 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. It can be obtained by applying a coating containing a part to the surface of the crosslinked rubber and removing the liquid medium to form a coating film.
  • a method for applying a coating containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment to the surface of the crosslinked rubber will be described.
  • the method for applying the paint used in the present invention to the surface of the crosslinked rubber is not particularly limited. Spray coating, brush coating, dip coating, etc. can be employed. Among these, spray coating and dip coating are preferable because a uniform coating film can be easily formed on the surface of the crosslinked rubber.
  • the liquid medium is dried.
  • the drying method is not particularly limited, and a heat drying method or the like is employed. Thus, since the said coating film with favorable adhesiveness is formed with respect to the surface of bridge
  • the thickness of the coating film formed on the surface of the crosslinked rubber as described above is not particularly limited, but is preferably 5 to 200 ⁇ m.
  • the thickness of the coating film is more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
  • the thickness of the coating film is more preferably 8 ⁇ m or more.
  • the hydrogenated modified styrene-diene block copolymer used in the present invention is an elastomer that can maintain its form at room temperature, it is not chemically crosslinked and can be dissolved in a liquid medium. Is. Therefore, it is possible to form a coating film only by drying and removing the liquid medium without performing a crosslinking treatment, and the coating film can be formed very easily. Moreover, when the coating material used for this invention is a dispersion liquid, volatilization of the organic solvent at the time of drying can be prevented.
  • the surface of the crosslinked rubber Before applying the paint of the present invention. By performing washing, a coating film having good adhesion can be stably formed.
  • the organic solvent for washing acetone, toluene, isopropanol or the like is used. Water can also be used for cleaning. At this time, the cleaning liquid may contain an acid, an alkali, a surfactant and the like.
  • various primers for rubber may be applied to the surface of the crosslinked rubber, and then the coating material may be applied.
  • the adhesion may be improved, but the manufacturing process becomes complicated, and in some cases, the surface physical properties of the crosslinked rubber may change, which may adversely affect durability against long-term expansion and contraction. So be careful. Therefore, it is preferable to directly apply the paint without applying a primer to the surface of the crosslinked rubber.
  • a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment are added. It is possible to provide a coating method in which the coating material is applied to the surface of the crosslinked rubber, and the liquid medium is removed to form a coating film.
  • the molded article of the present invention thus obtained contains a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and a pigment on the surface of the crosslinked rubber. It is a molded article on which a coating film is formed.
  • the coating film in the molded article of the present invention contains a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic anhydride and a pigment. Furthermore, it is preferable that the coating film contains a metal powder. In addition, the coating film may contain additives other than the modified styrene-diene block copolymer hydrogenated product, the pigment, and the metal powder as long as the effects of the present invention are not impaired. The ratio of each component in the coating film is contained at a ratio corresponding to the content ratio in the paint.
  • the molded product of the present invention has the above-mentioned coating film formed on the surface of the crosslinked rubber as described above.
  • a polyurethane film is further formed on the surface of the coating film.
  • the molded product of the present invention thus obtained can follow large deformations and is excellent in wear resistance.
  • a polyurethane paint to the coating film formed on the surface of the crosslinked rubber, a polyurethane film is formed on the surface of the coating film.
  • the molded product of the present invention having excellent wear resistance can be obtained.
  • the designability of the molded product obtained can also be improved by shaping
  • coat a polyurethane membrane
  • the polyurethane film may be transparent or colored, but from the viewpoint of not hindering the color of the pigment itself contained in the coating film formed on the surface of the crosslinked rubber. Is preferably transparent. Moreover, when a polyurethane membrane
  • the polyurethane paint is applied to the surface of the coating film containing the modified styrene-diene block copolymer hydrogenated with the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and the pigment.
  • Application is a preferred embodiment.
  • the polyurethane paint used for forming the polyurethane film is not particularly limited, but a polyurethane paint having an isocyanate group is preferably used.
  • a polyurethane paint having an isocyanate group By forming a polyurethane film using a polyurethane coating having an isocyanate group, the unsaturated carboxylic acid in the coating film formed on the surface of the crosslinked rubber reacts with the polyurethane coating having the isocyanate group to provide adhesion. It seems to be good.
  • the polyurethane coating having an isocyanate group a one-component moisture curable polyurethane coating or a two-component curable polyurethane coating can be suitably used.
  • a polyurethane resin having an isocyanate group at the end and being cured by reacting with moisture in the air can be used. Since mixing operation is unnecessary, it can be preferably used from the viewpoint of easy handling.
  • a two-component curable polyurethane paint a two-component polyurethane resin that is obtained by mixing and curing a polyisocyanate compound having a plurality of isocyanate groups and polyols at the time of construction can be used.
  • the two-component polyurethane resin may contain a urethane prepolymer having an isocyanate group obtained by a reaction between a polyisocyanate compound and a polyol.
  • an acrylic urethane paint using an acrylic resin having a hydroxyl group (acrylic polyol) as a polyol can also be used as the two-component polyurethane resin.
  • the molded article of the present invention has 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. It is obtained by applying a paint containing a part to the surface of the crosslinked rubber, removing the liquid medium to form a coating film, and then applying a polyurethane paint to the surface of the coating film to form a polyurethane film. it can.
  • a method for forming a polyurethane film by applying a polyurethane paint to the surface of the coating film formed on the surface of the crosslinked rubber will be described.
  • the method for applying the polyurethane paint to the surface of the coating film formed on the surface of the crosslinked rubber is not particularly limited. Spray coating, brush coating, dip coating, etc. can be employed. Among these, spray coating and dip coating are preferable because a uniform polyurethane film can be easily formed. After applying the polyurethane paint, the molded article of the present invention can be obtained by drying and curing as necessary.
  • the thickness of the polyurethane film formed in the molded article of the present invention is preferably 5 to 200 ⁇ m.
  • the thickness of the polyurethane film is more preferably 100 ⁇ m or less, and even more preferably 80 ⁇ m or less.
  • the thickness of the polyurethane film is less than 5 ⁇ m, the wear resistance may be lowered.
  • the thickness of the polyurethane film is more preferably 8 ⁇ m or more.
  • the molded article of the present invention examples include hoses, tubes, tires, vibration-proof rubbers and the like.
  • the portion covered with the coating film may be at least a portion thereof.
  • the resulting molded product has a coating film with good adhesion to the surface of the crosslinked rubber, so that it can follow large deformations and withstand long-term use. it can. Further, by forming the coating film on the surface of the crosslinked rubber, the molded product can be protected or the design of the molded product can be improved. Furthermore, in the molded product in which the polyurethane film is formed on the surface of the coating film, a part of the polyurethane film formed on the surface of the coating film may be a part.
  • the molded product in which the polyurethane film is formed on the surface of the coating film has good adhesion to the surface of the crosslinked rubber, can follow a large deformation, and has excellent wear resistance. Can withstand long-term use. Moreover, the designability of a molded product can also be improved.
  • Example 1a (Production of EPDM sheet) Ethylene-propylene-nonconjugated diene copolymer (EPDM) 100 parts by weight, zinc oxide 5 parts by weight, stearic acid 1 part by weight, carbon black 120 parts by weight, process oil 50 parts by weight, vulcanization accelerator 1.5 parts by weight Then, 1.5 parts by weight of sulfur was kneaded with a mixer and a roll and then formed into a sheet shape, and then vulcanized at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. This was cut into a size of 70 mm ⁇ 100 mm to obtain a rectangular crosslinked EPDM sheet. The obtained crosslinked EPDM sheet had an A hardness of 70 degrees.
  • EPDM Ethylene-propylene-nonconjugated diene copolymer
  • the styrene content is 30 wt%
  • the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf]
  • the A hardness is 84 degrees
  • the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
  • the surface of the crosslinked EPDM sheet prepared by the above method was wiped with acetone to wash the surface. Thereafter, it was dipped in the paint A-1 and then pulled up, allowed to stand at room temperature, and dried.
  • the coating film of the obtained sample was about 30 ⁇ m.
  • the obtained sample was evaluated by the following method.
  • Example 2a (Production of natural rubber sheet) 100 parts by weight of natural rubber (NR), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 50 parts by weight of carbon black, 1 part by weight of a vulcanization accelerator and 2.5 parts by weight of sulfur were kneaded and the same as in Example 1a A rectangular crosslinked natural rubber sheet was obtained by the method described above. The obtained crosslinked natural rubber sheet had an A hardness of 63 degrees.
  • Example 3a (Production of styrene butadiene rubber sheet) 100 parts by weight of styrene butadiene rubber (SBR), 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 50 parts by weight of carbon black, 1 part by weight of vulcanization accelerator and 1.75 parts by weight of sulfur were kneaded, and Example 1a and A rectangular cross-linked styrene butadiene rubber sheet was obtained in the same manner. The obtained crosslinked styrene-butadiene rubber sheet had an A hardness of 64 degrees.
  • SBR styrene butadiene rubber
  • Comparative Example 1a (Preparation of paint B-1) 5 g of a styrene-diene block copolymer hydrogenated product “Tuftec H1062” manufactured by Asahi Kasei Chemicals Corporation was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide and 2 g of quinacridone pigment were added, and the mixture was stirred and dispersed to prepare paint B-1.
  • “Tuftec H1062” is not modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
  • the styrene content is 18% by weight
  • the MFR is 4.5 g / 10 min [230 ° C., 2.16 kgf]
  • the A hardness is 67 degrees.
  • Comparative Example 2a The surface of the crosslinked natural rubber sheet prepared in Example 2a was wiped with acetone and the surface was washed. Thereafter, as in Comparative Example 1a, it was dipped in the paint B-1, lifted, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 ⁇ m. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
  • Comparative Example 3a The surface of the crosslinked styrene butadiene rubber sheet prepared in Example 3a was wiped with acetone to wash the surface. Thereafter, as in Comparative Example 1a, it was dipped in the paint B-1, lifted, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 ⁇ m. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
  • Example 4a Modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Co., Ltd. (styrene content is 30% by weight, MFR is 5.0 g / 10 min [230 ° C., 2 ° C. .16 kgf], A hardness is 84 degrees, the acid value [mgCH 3 ONa / g] indicating the content of maleic anhydride is 10, and the content of maleic anhydride is 1.8% by weight. ) 5 g was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. Even after the stirring was stopped for 15 hours, no aggregation of the pigment was observed with the pigment dispersed.
  • Example 1a The surface of the crosslinked EPDM sheet produced in Example 1a was wiped with acetone and the surface was washed. Thereafter, the film was dipped in the paint prepared in Example 4a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 12 ⁇ m. The obtained samples were evaluated by color measurement.
  • Example 5a Modified styrene-diene block copolymer hydrogenated with maleic anhydride “Tuftec M1943” manufactured by Asahi Kasei Chemicals Corporation (styrene content is 20% by weight, MFR is 8.0 g / 10 min [230 ° C., 2 ° C. .16 kgf], A hardness is 67, acid value indicating the content of maleic anhydride [mgCH 3 ONa / g] is 10, and content of maleic anhydride is 1.8% by weight) 5 g was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. Even after the stirring was stopped for 15 hours, no aggregation of the pigment was observed with the pigment dispersed.
  • Example 3 The surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Example 5a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 25 ⁇ m.
  • Example 1a Furthermore, the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Comparative Example 4a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 10 ⁇ m.
  • Example 1a Furthermore, the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Comparative Example 5a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 10 ⁇ m.
  • Example 4a and Example 5a using the hydrogenated styrene-diene block copolymer had good color measurement results and excellent hiding power against the base rubber.
  • Example 6a 5 g of a modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Corporation was dissolved in 100 cc of toluene. Further, 0.9 g of aluminum flakes and 0.45 g of “Pigment Red 264” were added, and the mixture was stirred and dispersed to prepare paint C-1.
  • the styrene content is 30 wt%
  • the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf]
  • the A hardness is 84 degrees
  • the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
  • the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, it was dipped in the paint C-1 and then pulled up, left at room temperature, and dried.
  • the coating film of the obtained sample was about 20 ⁇ m.
  • Example 6a The sample obtained in Example 6a had good followability to rubber stretch of about 200% and good adhesion. Further, the pigment was uniformly dispersed and the appearance was beautiful.
  • Example 1b (Production of EPDM sheet) 100 parts by weight of ethylene-propylene-nonconjugated diene copolymer (EPDM), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 80 parts by weight of carbon black, 50 parts by weight of process oil, 1.5 parts by weight of vulcanization accelerator Then, 1.5 parts by weight of sulfur was kneaded with a mixer and a roll and then formed into a sheet shape, and then vulcanized at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. This was cut into a size of 25 mm ⁇ 220 mm to obtain a rectangular crosslinked EPDM sheet. The obtained crosslinked EPDM sheet had an A hardness of 65 degrees. In the follow-up test described later, a dumbbell-shaped No. 1 piece was similarly collected from the sheet.
  • EPDM ethylene-propylene-nonconjugated diene copolymer
  • zinc oxide 1 part by weight of ste
  • the styrene content is 30 wt%
  • the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf]
  • the A hardness is 84 degrees
  • the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
  • top coat C-2 100 g of solvent-containing isocyanate group-terminated polyurethane resin “Takenate F707N” manufactured by MC Industrial Co., Ltd. was dissolved in 100 g of polyurethane resin thinner. Furthermore, 2 g of a curing accelerator “Formate S-9” manufactured by MC Industrial Co., Ltd. was added and stirred to prepare a top coat C-2.
  • the surface of the crosslinked EPDM sheet and dumbbell piece produced by the above method was wiped with toluene and the surface was washed. Thereafter, the paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 ⁇ m. Further, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 ⁇ m.
  • the obtained sample was evaluated by the following method.
  • Comparative Example 1b (Preparation of paint B-2) 100 g of hydrogenated styrene-diene block copolymer “Tuftec H1041” manufactured by Asahi Kasei Chemicals Corporation was dissolved in 1600 g of toluene. Further, 18 g of aluminum flakes and 9 g of pigment “Pigment Red 264” were added, and the mixture was stirred and dispersed to prepare paint B-2.
  • “Tuftec H1041” is not modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride.
  • the styrene content is 30% by weight
  • the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf]
  • the A hardness is 84 degrees.
  • Example 1b The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Thereafter, paint B-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 ⁇ m. Further, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 ⁇ m. The obtained sample was evaluated in the same manner as in Example 1b.
  • Comparative Example 2b The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 ⁇ m. The obtained sample was evaluated in the same manner as in Example 1b.
  • Example 2b (Preparation of top coat D-2) Acrylic paint “Polynal No. "500 11 Clear” 100 g is a thinner “No. 5600 "was dissolved in 100 g. Then, the mixture was stirred to prepare a top coating material D-2.
  • Example 1b The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Thereafter, the paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 ⁇ m. Further, the top coating material B-2 was applied by air spray, allowed to stand at room temperature for 10 minutes by flash-out, and then dried at 60 ° C. for 20 minutes. The coating film of the obtained sample was about 30 ⁇ m. The obtained sample was evaluated in the same manner as in Example 1b.
  • Comparative Example 3b The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, the top coating material D-2 was applied by air spray, allowed to stand at room temperature for 10 minutes by flash-out, and then dried at 60 ° C. for 20 minutes. The thickness of the polyurethane film in the obtained sample was about 30 ⁇ m. The obtained sample was evaluated in the same manner as in Example 1b.
  • Example 3b The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 ⁇ m. The obtained sample was evaluated in the same manner as in Example 1b.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A coating material which is to be applied to a crosslinked rubber and which comprises 100 parts by weight of a hydrogenated styrene/diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic anhydride, 50 to 10000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. Thus, a coating material capable of forming a coating film which exhibits excellent tight adhesion to a crosslinked rubber and can follow big deformations and in which a pigment is excellently dispersed is provided.

Description

架橋ゴムに塗装するための塗料、該塗料を塗布して塗膜が形成された成形品及びその製造方法Paint for coating on crosslinked rubber, molded article formed with coating film by applying the paint, and method for producing the same
　本発明は、架橋ゴムに塗装するための塗料、該塗料を塗布して塗膜が形成された成形品及びその製造方法に関する。 The present invention relates to a paint for coating crosslinked rubber, a molded article in which a coating film is formed by applying the paint, and a method for producing the same.
　従来、各種ゴムの表面に、耐候性や放熱性等の機能を付与するために、保護コーティング材料が塗布されてきた。 Conventionally, protective coating materials have been applied to various rubber surfaces to provide functions such as weather resistance and heat dissipation.
　特許文献１には、周囲の温度で硬化可能な二液型液体塗料であって、活性水素含有硬化剤に反応する官能基を含むか、当該官能基が活性水素含有基であるフレキシブル皮膜形成重合体と、前記官能基と反応する硬化成分と、キャリアー液体からなる塗料が記載されている。また、特許文献２には、周囲温度で硬化可能な２部式液状コーティング組成物であって、活性水素含有硬化剤に反応性の官能基をその中に含むか、または当該官能基が活性水素保有基である可撓性フィルム形成性ポリマーと、前記官能基と反応可能な硬化成分と、担体液体と、熱伝導性金属粒子とからなるコーティング組成物が記載されている。これらの塗料は、エラストマー、ゴム製品又はこれらの材料を含む基材の外表面に塗布され、高温で長期間の使用にわたって熱放散を提供することができるとされている。 Patent Document 1 discloses a two-component liquid paint that can be cured at an ambient temperature and includes a functional group that reacts with an active hydrogen-containing curing agent, or the functional group is an active hydrogen-containing group. A paint comprising a coalescence, a curing component that reacts with the functional group, and a carrier liquid is described. Patent Document 2 discloses a two-part liquid coating composition that can be cured at ambient temperature, and contains a reactive functional group in the active hydrogen-containing curing agent, or the functional group is active hydrogen. A coating composition comprising a flexible film-forming polymer as a holding group, a curing component capable of reacting with the functional group, a carrier liquid, and thermally conductive metal particles is described. These paints are said to be able to be applied to the outer surface of elastomers, rubber products or substrates containing these materials and provide heat dissipation over extended periods of use at high temperatures.
　しかしながら、形成される塗膜が架橋されたものであるため、密着性が不足するおそれがあった。さらに、顔料を含む場合には、その分散性が不良となるおそれがあった。 However, since the coating film to be formed is cross-linked, there is a possibility that the adhesion is insufficient. Furthermore, when a pigment is included, the dispersibility may be poor.
　特許文献３には、排気管を車体に懸架するために車体と排気管との間に介装されるマフラーハンガーであって、架橋ゴムからなる成形品の表面が、スチレン－ジエンブロック共重合体水添物及び金属粉末を含有する熱可塑性エラストマー組成物からなる熱反射性皮膜で覆われているマフラーハンガーが記載されている。これにより、密着性、伸縮性の良好な熱反射性皮膜で覆われていて、耐熱性に優れたマフラーハンガーを提供することができるとされている。しかしながら、用途によっては、架橋ゴムに対する密着性が不十分である場合があった。 Patent Document 3 discloses a muffler hanger interposed between a vehicle body and an exhaust pipe in order to suspend the exhaust pipe from the vehicle body, and the surface of a molded product made of a crosslinked rubber is a styrene-diene block copolymer. A muffler hanger covered with a heat-reflective coating made of a thermoplastic elastomer composition containing a hydrogenated product and metal powder is described. Accordingly, it is said that a muffler hanger that is covered with a heat-reflecting film having good adhesion and stretchability and excellent in heat resistance can be provided. However, in some applications, the adhesion to the crosslinked rubber may be insufficient.
　特許文献４には、無水マレイン酸で部分変性したゴムの架橋体、あるいは、無変性のゴムに前記変性ゴムまたは無水マレイン酸で部分変性したＳＥＢＳエラストマー、ポリプロピレン（ＰＰ）、ポリエチレン（ＰＥ）もしくはエチレン酢酸ビニル共重合体（ＥＶＡ）を混合してなる架橋体の表面に、ナイロン、ポリウレタン、ポリ塩化ビニリデン、ポリ塩化ビニルまたはポリフッ化ビニリデンのうちの一種または二種以上の混合物の皮膜を形成させる、ゴムの樹脂皮膜形成方法が記載されている。これによれば、接着剤を用いず、ハロゲン化処理等の表面処理を必要としないため、製造工程の簡素化等ができるとされている。しかしながら、このようにして得られるゴムの耐摩耗性は必ずしも良好ではなく改善が望まれていた。 Patent Document 4 discloses a crosslinked product of rubber partially modified with maleic anhydride, or an SEBS elastomer, polypropylene (PP), polyethylene (PE) or ethylene partially modified with unmodified rubber with the modified rubber or maleic anhydride. Forming a film of one or a mixture of two or more of nylon, polyurethane, polyvinylidene chloride, polyvinyl chloride, or polyvinylidene fluoride on the surface of a crosslinked product obtained by mixing a vinyl acetate copolymer (EVA). A rubber resin film forming method is described. According to this, since an adhesive is not used and a surface treatment such as a halogenation treatment is not required, the manufacturing process can be simplified. However, the abrasion resistance of the rubber thus obtained is not always good, and improvement has been desired.
　また、特許文献５には、ゴム製基材に、水添イソプレン系樹脂のプライマーを塗布し次いでフルオロオレフィン系樹脂、アクリルウレタン樹脂およびアクリル樹脂から選ばれる少なくとも１種を含む上塗り剤を塗布することを特徴とする被覆方法が記載されている。これによれば、ゴム製基材表面に、フルオロオレフィン系樹脂等からなる塗膜を十分密着被覆させることができるとされている。しかしながら、前記ゴム製基材に被覆される上塗り剤に顔料が含まれる場合に、必ずしも顔料の分散性が良好ではなく改善が望まれていた。 In Patent Document 5, a hydrogenated isoprene-based resin primer is applied to a rubber substrate, and then a topcoat containing at least one selected from a fluoroolefin resin, an acrylic urethane resin, and an acrylic resin is applied. A coating method characterized in that is described. According to this, it is said that a coating film made of a fluoroolefin resin or the like can be sufficiently adhered and coated on the surface of the rubber substrate. However, when a pigment is contained in the top coat coated on the rubber substrate, the dispersibility of the pigment is not always good, and improvement has been desired.
特表２００５－５２００１６号公報JP 2005-520016 Gazette 特表２００６－５０２２９０号公報Special table 2006-502290 特開２００９－９０７７８号公報JP 2009-90778 A 特開平６－３２９２５号公報JP-A-6-32925 特開平７－７０３４６号公報JP-A-7-70346
　本発明は、上記課題を解決するためになされたものであり、架橋ゴムに対する密着性が良好で、大きな変形に対する追随が可能であり、顔料の分散性に優れた塗膜を形成できる塗料を提供することを目的とするものである。また、そのような塗料を架橋ゴムからなる成形品の表面に塗布する成形品の製造方法を提供することを目的とするものである。さらに、そのような塗料を塗布して得られた塗膜が形成された成形品を提供することを目的とするものである。 The present invention has been made to solve the above problems, and provides a coating material that has good adhesion to a crosslinked rubber, can follow a large deformation, and can form a coating film excellent in pigment dispersibility. It is intended to do. It is another object of the present invention to provide a method for producing a molded product in which such a paint is applied to the surface of a molded product made of a crosslinked rubber. Furthermore, it aims at providing the molded article in which the coating film obtained by apply | coating such a coating material was formed.
　上記課題は、架橋ゴムに塗装するための塗料であって、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を提供することによって解決される。 The above-mentioned problem is a coating for coating a crosslinked rubber, which is 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, This is solved by providing a paint containing 10,000 parts by weight and 1 to 200 parts by weight of pigment.
　このとき、前記変性スチレン－ジエンブロック共重合体水添物における不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量が、０．２～５重量％であることが好適であり、前記変性スチレン－ジエンブロック共重合体水添物が、無水マレイン酸で変性されたものであることが好適である。 At this time, the content of units derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the modified styrene-diene block copolymer hydrogenated product is preferably 0.2 to 5% by weight. The hydrogenated product of the modified styrene-diene block copolymer is preferably modified with maleic anhydride.
　また、上記課題は、架橋ゴムの表面に、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物及び顔料を含有する塗膜が形成された成形品を提供することによっても解決される。 In addition, the above-mentioned problem is that a coating film containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and a pigment is formed on the surface of the crosslinked rubber. It is also solved by providing goods.
　このとき、前記塗膜の表面に、さらにポリウレタン皮膜が形成されてなることが好適であり、前記塗膜において、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、顔料１～２００重量部を含有することが好適である。また、前記架橋ゴムがオレフィン系ゴム又はジエン系ゴムであることが好適である。 At this time, it is preferable that a polyurethane film is further formed on the surface of the coating film. In the coating film, the modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is used. It is preferable to contain 1 to 200 parts by weight of pigment with respect to 100 parts by weight of the polymer hydrogenated product. In addition, it is preferable that the crosslinked rubber is an olefin rubber or a diene rubber.
　また、上記課題は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を架橋ゴムの表面に塗布し、液状媒体を除去して塗膜を形成することを特徴とする成形品の製造方法を提供することによっても解決される。 Further, the above-mentioned problems are that 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. The present invention can also be solved by providing a method for producing a molded article characterized in that a coating material containing a coating is applied to the surface of a crosslinked rubber and the liquid medium is removed to form a coating film.
　このとき、前記塗膜を形成した後に、該塗膜の表面にポリウレタン塗料を塗布してポリウレタン皮膜を形成することが好適である。 At this time, it is preferable that after forming the coating film, a polyurethane coating is applied to the surface of the coating film to form a polyurethane film.
　本発明の塗料によれば、架橋ゴムに対する密着性が良好で、大きな変形に対する追随が可能であり、顔料の分散性に優れた塗膜を形成することができる。本発明の成形品の製造方法によれば、そのような塗膜を容易に形成することができる。そして、本発明の成形品は、架橋ゴムの表面に対して密着性の良好で、大きな変形に対する追随が可能であり、顔料の分散性に優れた塗膜が形成されている。さらに、塗膜における顔料の分散性が優れているため、成形品の意匠性を向上させることもできる。 According to the coating material of the present invention, it is possible to form a coating film having good adhesion to the crosslinked rubber, capable of following a large deformation, and having excellent pigment dispersibility. According to the method for producing a molded article of the present invention, such a coating film can be easily formed. The molded article of the present invention has good adhesion to the surface of the crosslinked rubber, can follow large deformations, and has a coating film excellent in pigment dispersibility. Furthermore, since the dispersibility of the pigment in a coating film is excellent, the designability of a molded article can also be improved.
　本発明の塗料は、架橋ゴムに塗装するための塗料であって、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物、液状媒体及び顔料を含有する。 The paint of the present invention is a paint for coating a crosslinked rubber, comprising a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment. contains.
　本発明に用いられる架橋ゴムとしては、特に限定されるものではないが、本発明の塗料との接着性の観点から、オレフィン系ゴム及びジエン系ゴムが好適に採用される。 The cross-linked rubber used in the present invention is not particularly limited, but olefin rubber and diene rubber are preferably employed from the viewpoint of adhesion to the paint of the present invention.
　オレフィン系ゴムとしては、エチレン－プロピレン共重合体ゴム（ＥＰＭ）、エチレン－プロピレン－非共役ジエン共重合体ゴム（ＥＰＤＭ）、ブチルゴム等が例示される。その中でもＥＰＭ及びＥＰＤＭが好適なものとして使用される。特に、ＥＰＤＭは加硫が容易で、強度と伸縮性とコストのバランスに優れているので、特に好適である。ＥＰＤＭに用いられる非共役ジエンとしては、エチリデンノルボルネン、１，４－ヘキサジエン、ジシクロペンタジエンなどが例示される。また、後述の実施例にも示されるように、オレフィン系ゴムは、本発明の塗料を用いて形成される塗膜との密着性が良好である。ジエン系ゴムとしては、天然ゴム、ブタジエンゴム、スチレン－ブタジエンゴム、クロロプレンゴム、ニトリルゴムなどが例示される。この中でも、スチレン－ブタジエンゴム、天然ゴムは、本発明の成形品において形成される塗膜との密着性が良好であり、好適に使用される。 Examples of the olefin rubber include ethylene-propylene copolymer rubber (EPM), ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), and butyl rubber. Among them, EPM and EPDM are preferably used. In particular, EPDM is particularly suitable because it is easy to vulcanize and has an excellent balance of strength, elasticity and cost. Examples of non-conjugated dienes used in EPDM include ethylidene norbornene, 1,4-hexadiene, dicyclopentadiene and the like. In addition, as shown in Examples described later, the olefin rubber has good adhesion to a coating film formed using the paint of the present invention. Examples of the diene rubber include natural rubber, butadiene rubber, styrene-butadiene rubber, chloroprene rubber, and nitrile rubber. Among these, styrene-butadiene rubber and natural rubber are preferably used because they have good adhesion to the coating film formed in the molded article of the present invention.
　ＥＰＭは、過酸化物架橋剤で架橋させて架橋ゴムとすることができる。一方、ＥＰＤＭは過酸化物架橋剤によっても、硫黄によっても架橋することができ、より容易に架橋ゴムを得ることができる。また、ジエン系ゴムは硫黄によって容易に加硫することができる。性能面からは、硫黄で架橋されたＥＰＤＭを使用することが特に好ましい。本発明で使用される架橋ゴムは、各種の添加剤やフィラーを含むことが好ましく、カーボンブラックや酸化亜鉛などの無機フィラー、流動パラフィンなどのプロセスオイル、ステアリン酸などの滑剤、硫黄や過酸化物などの加硫剤、加硫助剤、老化防止剤などが適宜配合される。このように配合されたものを型に入れて加熱することによって架橋させ、架橋ゴムからなる成形品が得られる。 EPM can be crosslinked with a peroxide crosslinking agent to form a crosslinked rubber. On the other hand, EPDM can be crosslinked by either a peroxide crosslinking agent or sulfur, and a crosslinked rubber can be obtained more easily. Further, the diene rubber can be easily vulcanized with sulfur. From the viewpoint of performance, it is particularly preferable to use sulfur-crosslinked EPDM. The crosslinked rubber used in the present invention preferably contains various additives and fillers, inorganic fillers such as carbon black and zinc oxide, process oils such as liquid paraffin, lubricants such as stearic acid, sulfur and peroxides. Vulcanizing agents such as vulcanizing agents, vulcanization aids, anti-aging agents and the like are appropriately blended. What was blended in this way is put into a mold and heated to be crosslinked to obtain a molded product made of a crosslinked rubber.
　架橋ゴムの硬度は、成形品の用途に応じて適宜調整されるものであるが、ＪＩＳ　Ｋ６２５３に準じて測定したＡ硬度が３０～９０であることが好ましい。比較的硬度の低い架橋ゴムに対しても本発明の塗料の密着性は高く、大きな変形に対しても追随が可能である。Ａ硬度は、より好適には８５以下であり、さらに好適には８０以下である。一方、硬度が低すぎる場合には、成形品の強度が不十分になりやすく、Ａ硬度は、より好適には３５以上であり、さらに好適には４０以上である。 The hardness of the crosslinked rubber is appropriately adjusted according to the use of the molded product, but the A hardness measured in accordance with JIS K6253 is preferably 30 to 90. The adhesiveness of the coating material of the present invention is high even for a crosslinked rubber having a relatively low hardness, and can follow a large deformation. The A hardness is more preferably 85 or less, and even more preferably 80 or less. On the other hand, if the hardness is too low, the strength of the molded product tends to be insufficient, and the A hardness is more preferably 35 or more, and even more preferably 40 or more.
　本発明の塗料は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物を含有する。ジエンブロックが水添されることによって、高温下で劣化しにくい塗膜を形成することができる。しかも、水添ジエンブロックがあることによって、架橋ゴム基材への密着性が良好である。特に、水添ジエンブロックとエチレン－プロピレン－（ジエン）共重合体とは、その化学構造が似通っているためか、塗膜の密着性がきわめて良好な成形品を与えることができる。また、スチレンブロックを有することによって常温において形態を保持することが可能である。 The coating material of the present invention contains a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. By hydrogenating the diene block, it is possible to form a coating film that hardly deteriorates at high temperatures. Moreover, due to the presence of the hydrogenated diene block, the adhesion to the crosslinked rubber substrate is good. In particular, the hydrogenated diene block and the ethylene-propylene- (diene) copolymer may have a similar chemical structure, or may give a molded product with extremely good adhesion of the coating film. Moreover, it is possible to hold | maintain a form at normal temperature by having a styrene block.
　変性スチレン－ジエンブロック共重合体水添物の構造は特に限定されず、スチレン－ジエンジブロック共重合体であってもよいし、スチレン－ジエン－スチレントリブロック共重合体であってもよいし、それ以上の数のブロックから構成されるブロック共重合体であってもよい。ジエンブロックを構成するのは、ブタジエンであってもよいし、イソプレンであってもよいし、これらを混合使用してもよい。 The structure of the modified styrene-diene block copolymer hydrogenated product is not particularly limited, and may be a styrene-diene diblock copolymer or a styrene-diene-styrene triblock copolymer. A block copolymer composed of a larger number of blocks may be used. The diene block may be composed of butadiene, isoprene, or a mixture of these.
　変性スチレン－ジエンブロック共重合体水添物は不飽和カルボン酸又は不飽和カルボン酸無水物で変性されている。これにより、架橋ゴムとの密着性を良好にし、塗膜における顔料の分散性が良好となる。これらの官能基の導入方法については特に限定されず、例えば、スチレン－ジエンブロック共重合体に、不飽和カルボン酸又は不飽和カルボン酸無水物のモノマーをグラフトさせるグラフト法や、スチレン－ジエンブロック共重合体を構成するモノマーと、不飽和カルボン酸又は不飽和カルボン酸無水物のモノマーとを共重合させる共重合法などを例示できる。不飽和カルボン酸又は不飽和カルボン酸無水物としては、マレイン酸、フマール酸、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、無水マレイン酸、無水イタコン酸等を使用することができる。不飽和カルボン酸は、その全部又は一部が塩を形成していても構わない。中でも無水マレイン酸を使用することで、さらに架橋ゴムとの密着性を良好にし、塗膜における顔料の分散性が良好となるため好ましい。 The modified styrene-diene block copolymer hydrogenated product is modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. Thereby, adhesiveness with crosslinked rubber is made favorable and the dispersibility of the pigment in a coating film becomes favorable. The method for introducing these functional groups is not particularly limited. For example, a graft method in which an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride monomer is grafted onto a styrene-diene block copolymer, or a styrene-diene block copolymer is used. Examples thereof include a copolymerization method in which a monomer constituting a polymer and an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride monomer are copolymerized. As the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, maleic acid, fumaric acid, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic anhydride, itaconic anhydride and the like can be used. The unsaturated carboxylic acid may form a salt in whole or in part. Among these, the use of maleic anhydride is preferable because the adhesion to the crosslinked rubber is further improved and the dispersibility of the pigment in the coating film is improved.
　変性スチレン－ジエンブロック共重合体水添物における不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量は、変性スチレン－ジエンブロック共重合体水添物に対して、０．２～５重量％であることが好ましい。不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量が０．２重量％未満である場合、形成される塗膜の架橋ゴムに対する密着性が低下するおそれがある。さらに、塗膜における顔料の分散性が低下するおそれがある。不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量は０．３重量％以上であることがより好ましく、０．５重量％以上であることがさらに好ましい。不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量が５重量％より多い場合、塗膜の耐久性が低下するおそれがある。不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量は、４．５重量％以下であることがより好ましく、４重量％以下であることが更に好ましい。 The content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the modified styrene-diene block copolymer hydrogenated product is 0.2 to the modified styrene-diene block copolymer hydrogenated product. It is preferably ˜5% by weight. When the content of the unit derived from the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride is less than 0.2% by weight, the adhesion of the formed coating film to the crosslinked rubber may be lowered. Furthermore, the dispersibility of the pigment in the coating film may be reduced. The content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is more preferably 0.3% by weight or more, and further preferably 0.5% by weight or more. When the content of the unit derived from the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride is more than 5% by weight, the durability of the coating film may be lowered. The content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride is more preferably 4.5% by weight or less, and further preferably 4% by weight or less.
　変性スチレン－ジエンブロック共重合体水添物のスチレン含有量が１０～４０重量％であることが好ましい。スチレン含有量が１０重量％未満の場合、耐熱性が低下するとともに、形態保持性も悪化する。スチレン含有量が１５重量％以上であることがより好適である。一方、スチレン含有量が４０重量％より多い場合、柔軟性が低下するおそれがある。スチレン含有量が３５重量％以下であることがより好適である。 The styrene content of the modified styrene-diene block copolymer hydrogenated product is preferably 10 to 40% by weight. When the styrene content is less than 10% by weight, the heat resistance is lowered and the shape retention is also deteriorated. The styrene content is more preferably 15% by weight or more. On the other hand, when the styrene content is more than 40% by weight, the flexibility may decrease. The styrene content is more preferably 35% by weight or less.
　本発明で用いられる変性スチレン－ジエンブロック共重合体水添物のＪＩＳ　Ｋ６２５３に準じて測定したＡ硬度が２０～９０であることが好ましい。ここでのＡ硬度は、原料の変性スチレン－ジエンブロック共重合体水添物のＡ硬度である。変性スチレン－ジエンブロック共重合体水添物の硬度が高すぎる場合には、架橋ゴム基材が変形した時に、塗膜が破損するおそれがある。Ａ硬度は、より好適には８５以下であり、さらに好適には８０以下である。一方、硬度が低すぎる場合、耐熱性が低下するとともに、形態保持性も悪化する。Ａ硬度は、より好適には３０以上である。本発明で用いられる変性スチレン－ジエンブロック共重合体水添物のＭＦＲは、通常０．１～１００ｇ／１０ｍｉｎ（２３０℃、２．１６ｋｇｆで測定）である。 The A hardness of the modified styrene-diene block copolymer hydrogenated product used in the present invention is preferably 20 to 90 as measured according to JIS K6253. Here, the A hardness is the A hardness of the raw material modified styrene-diene block copolymer hydrogenated product. If the hardness of the modified styrene-diene block copolymer hydrogenated product is too high, the coating film may be damaged when the crosslinked rubber base material is deformed. The A hardness is more preferably 85 or less, and even more preferably 80 or less. On the other hand, when the hardness is too low, the heat resistance is lowered and the shape retention is also deteriorated. The A hardness is more preferably 30 or more. The MFR of the modified styrene-diene block copolymer hydrogenated product used in the present invention is usually 0.1 to 100 g / 10 min (measured at 230 ° C. and 2.16 kgf).
　本発明において形成される塗膜は、上記説明した不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物とともに顔料を含有する。後述するように、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物、液状媒体及び顔料を含有する塗料を架橋ゴムの表面に塗布して、液状媒体を除去することにより塗膜が形成される。このように、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物、液状媒体及び顔料を含有する塗料を用いることで、顔料の分散性が良好となるため、隠ぺい力が向上する。特に、架橋ゴム基材がカーボンブラックを含む場合、隠ぺい力が良好となるために好ましい。本発明に用いられる顔料としては、特に限定されないが、目的とする塗膜の色に応じて各種有機系顔料及び／又は無機系顔料が用いられる。有機系顔料としては、アゾ系顔料、キナクリドン系顔料、フタロシアニン系顔料、ジオキサジン系顔料等が挙げられる。無機系顔料としては、酸化チタン、酸化亜鉛、硫化亜鉛、カーボンブラック、鉛系顔料、カドミウム系顔料、コバルト系顔料、鉄系顔料、クロム系顔料、群青、紺青等が挙げられる。さらにパール顔料等を用いることもできる。これらの中から１種又は２種以上を組合わせて用いてもよい。 The coating film formed in the present invention contains a pigment together with the modified styrene-diene block copolymer hydrogenated modified with the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride described above. As described later, a coating containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment is applied to the surface of the crosslinked rubber, A coating film is formed by removing the liquid medium. Thus, the dispersibility of the pigment is good by using the coating material containing the hydrogenated product of the modified styrene-diene block copolymer modified with the unsaturated carboxylic acid or the unsaturated carboxylic acid anhydride, the liquid medium, and the pigment. Therefore, the hiding power is improved. In particular, when the crosslinked rubber base material contains carbon black, it is preferable because the hiding power is good. Although it does not specifically limit as a pigment used for this invention, According to the color of the target coating film, various organic pigments and / or inorganic pigments are used. Examples of organic pigments include azo pigments, quinacridone pigments, phthalocyanine pigments, dioxazine pigments, and the like. Examples of inorganic pigments include titanium oxide, zinc oxide, zinc sulfide, carbon black, lead pigments, cadmium pigments, cobalt pigments, iron pigments, chromium pigments, ultramarine blue, and bitumen. Further, a pearl pigment or the like can be used. You may use 1 type or in combination of 2 or more types from these.
　本発明の塗料は、金属粉末を含有することが好ましい。金属粉末を含有することで、成形品の表面を隠ぺいし、外観に優れた成形品を得ることができる。金属粉末としては、成形品の表面を隠ぺいできるものであれば特に限定されるものではないが、入手のしやすさ、性能、コストなどの面から、アルミニウム粉末、特にアルミニウムフレークが好適に使用される。顔料併用カラーメタリックがより好適に使用される。アルミニウム粉末は、粉末として加えられても良いが、安全性のために、有機溶媒などに分散させたペーストとして塗料に加えることが好ましい。 The paint of the present invention preferably contains a metal powder. By containing the metal powder, the surface of the molded product can be concealed, and a molded product having an excellent appearance can be obtained. The metal powder is not particularly limited as long as the surface of the molded product can be concealed, but aluminum powder, particularly aluminum flake is preferably used from the viewpoint of availability, performance, cost, and the like. The The color metallic with pigment is more preferably used. The aluminum powder may be added as a powder, but for safety, it is preferably added to the paint as a paste dispersed in an organic solvent or the like.
　本発明に用いられる液状媒体としては、変性スチレン－ジエンブロック共重合体水添物を分散又は溶解させるものが用いられる。液状媒体としては、変性スチレン－ジエンブロック共重合体水添物を溶解させることの可能な有機溶剤が使用される。このような有機溶剤としては、炭化水素、エステル、ケトン、エーテル、アルコールや、それらの混合物が好適に用いられる。特に、架橋ゴム基材を適度に膨潤させるとともに、変性スチレン－ジエンブロック共重合体水添物の溶解性が良好であるという点からは、炭化水素、特に、トルエンやキシレンなどの芳香族炭化水素が好適に用いられる。液状媒体として水を使用する場合には、変性スチレン－ジエンブロック共重合体水添物の分散液とすることができる。このとき、エマルジョンとすることが好適である。この場合には、揮発有機物質を使用しないので環境面から好ましく、低濃度で固形分濃度を高くすることもできる。しかしながら、架橋ゴムへの密着性が低下する場合がある。 As the liquid medium used in the present invention, a medium in which a hydrogenated product of a modified styrene-diene block copolymer is dispersed or dissolved is used. As the liquid medium, an organic solvent capable of dissolving the modified styrene-diene block copolymer hydrogenated product is used. As such an organic solvent, hydrocarbons, esters, ketones, ethers, alcohols, and mixtures thereof are preferably used. In particular, hydrocarbons, particularly aromatic hydrocarbons such as toluene and xylene, are obtained from the viewpoint that the crosslinked rubber base material is appropriately swollen and the solubility of the modified styrene-diene block copolymer hydrogenated product is good. Are preferably used. When water is used as the liquid medium, a modified styrene-diene block copolymer hydrogenated dispersion can be obtained. At this time, an emulsion is preferable. In this case, since a volatile organic substance is not used, it is preferable from the viewpoint of the environment, and the solid concentration can be increased at a low concentration. However, the adhesion to the crosslinked rubber may be reduced.
　本発明の塗料は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部及び液状媒体５０～１００００重量部を含有する。 The paint of the present invention contains 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and 50 to 10,000 parts by weight of a liquid medium.
　本発明の塗料における液状媒体の含有量は、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、５０～１００００重量部であることが必要である。液状媒体の含有量が５０重量部未満の場合、塗料の粘度が高くなり、塗装しにくくなるおそれがある。また、塗膜の厚みが均一にならないおそれがある。塗料が溶液である場合、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、液状媒体の含有量は、１０００重量部以上であることが好適である。塗料が分散液である場合、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、液状媒体の含有量は、８０重量部以上であることが好適である。液状媒体の含有量が１００００重量部よりも多い場合、乾燥に時間がかかり、作業効率が低下するおそれがある。塗料が溶液である場合、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、液状媒体の含有量は、５０００重量部以下であることが好適である。塗料が分散液である場合、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、液状媒体の含有量は、５００重量部以下であることが好適である。 The content of the liquid medium in the paint of the present invention needs to be 50 to 10,000 parts by weight with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When the content of the liquid medium is less than 50 parts by weight, the viscosity of the coating becomes high and it may be difficult to apply the coating. Moreover, there exists a possibility that the thickness of a coating film may not become uniform. When the coating material is a solution, the content of the liquid medium is preferably 1000 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When the paint is a dispersion, the content of the liquid medium is preferably 80 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When the content of the liquid medium is more than 10,000 parts by weight, it takes time to dry, and the working efficiency may be reduced. When the coating material is a solution, the content of the liquid medium is preferably 5000 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When the coating material is a dispersion, the content of the liquid medium is preferably 500 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
　本発明の塗料における顔料の含有量は、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、１～２００重量部である。顔料の含有量が１重量部未満の場合、隠ぺい力が不足するおそれがある。特に、カーボンブラック入りの架橋ゴムに塗布する場合の隠ぺい力が不足するおそれがある。変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、顔料の含有量は、２重量部以上であることが好適であり、５重量部以上であることがより好適である。顔料の含有量が２００重量部よりも多い場合、塗装しにくくなるおそれがある。変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、顔料の含有量は、１５０重量部以下であることが好適であり、１００重量部以下であることがより好適である。 The pigment content in the paint of the present invention is 1 to 200 parts by weight per 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. If the pigment content is less than 1 part by weight, the hiding power may be insufficient. In particular, there is a possibility that the concealing force when applied to a crosslinked rubber containing carbon black is insufficient. The pigment content is preferably 2 parts by weight or more and more preferably 5 parts by weight or more with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When there is more content of a pigment than 200 weight part, there exists a possibility that it may become difficult to paint. The pigment content is preferably 150 parts by weight or less, and more preferably 100 parts by weight or less with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product.
　本発明の塗料が金属粉末を含有する場合、その含有量は、変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、１～５００重量部であることが好ましい。金属粉末の含有量が１重量部未満の場合、架橋ゴムに対する隠ぺい力が不足するおそれがある。金属粉末の含有量は、２重量部以上であることがより好適であり、３重量部以上であることがさらに好適である。金属粉末の含有量が５００重量部よりも多い場合、塗膜の強度が低下するおそれがある。さらに、塗装しにくくなるおそれがある。金属粉末の含有量は、２００重量部以下であることがより好適であり、１００重量部以下であることがさらに好適である。 When the paint of the present invention contains metal powder, the content is preferably 1 to 500 parts by weight with respect to 100 parts by weight of the modified styrene-diene block copolymer hydrogenated product. When the content of the metal powder is less than 1 part by weight, the hiding power for the crosslinked rubber may be insufficient. The content of the metal powder is more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more. When there is more content of metal powder than 500 weight part, there exists a possibility that the intensity | strength of a coating film may fall. Furthermore, there is a possibility that it becomes difficult to paint. The content of the metal powder is more preferably 200 parts by weight or less, and further preferably 100 parts by weight or less.
　本発明の効果を阻害しない範囲内であれば、本発明の塗料が、変性スチレン－ジエンブロック共重合体水添物、液状媒体、顔料及び金属粉末以外の添加剤を含有しても構わない。各種の無機フィラー又は有機フィラーを配合することもできるが、この場合、架橋ゴムと塗膜の密着性が大きく低下しない範囲内で配合することが重要である。また、硫黄、過酸化物、多官能不飽和化合物などの架橋剤を配合することもできる。しかしながら、塗布操作の簡略さの観点からも、本発明の塗料が架橋剤を含有しないことが好ましい。さらに、プロセスオイル、酸化防止剤、界面活性剤、分散安定剤、紫外線吸収剤、防腐剤などを適宜必要に応じて配合してもよい。 As long as the effect of the present invention is not impaired, the coating material of the present invention may contain additives other than the modified styrene-diene block copolymer hydrogenated product, the liquid medium, the pigment, and the metal powder. Various inorganic fillers or organic fillers can be blended. In this case, it is important to blend within a range in which the adhesion between the crosslinked rubber and the coating film is not significantly reduced. Moreover, crosslinking agents, such as sulfur, a peroxide, a polyfunctional unsaturated compound, can also be mix | blended. However, also from the viewpoint of simplicity of the coating operation, it is preferable that the coating material of the present invention does not contain a crosslinking agent. Furthermore, process oils, antioxidants, surfactants, dispersion stabilizers, ultraviolet absorbers, preservatives and the like may be appropriately blended as necessary.
　本発明の塗料の固形分のうち、上記した変性スチレン－ジエンブロック共重合体水添物、液状媒体、顔料及び金属粉末以外の成分の含有量は３０重量％以下であることが好ましく、２０重量％以下であることがより好ましく、１０重量％以下であることがさらに好ましく、５重量％以下であることが特に好ましい。 Of the solid content of the coating material of the present invention, the content of components other than the above-described hydrogenated styrene-diene block copolymer, liquid medium, pigment, and metal powder is preferably 30% by weight or less, and 20% by weight. % Or less, more preferably 10% by weight or less, particularly preferably 5% by weight or less.
　本発明の成形品は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を架橋ゴムの表面に塗布し、液状媒体を除去して塗膜を形成することにより得ることができる。まず、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物、液状媒体及び顔料を含有する塗料を、架橋ゴムの表面に塗布する方法について述べる。 The molded article of the present invention has 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. It can be obtained by applying a coating containing a part to the surface of the crosslinked rubber and removing the liquid medium to form a coating film. First, a method for applying a coating containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, a liquid medium and a pigment to the surface of the crosslinked rubber will be described.
　架橋ゴムの表面に対して、本発明に用いられる塗料を塗布する方法は特に限定されない。スプレーコーティング、刷毛塗り、浸漬（ディップ）コーティングなどを採用することができる。中でも、架橋ゴムの表面に対して容易に均一な塗膜を形成できる点から、スプレーコーティングや浸漬コーティングが好適である。本発明では、塗料を塗布した後に、液状媒体を乾燥させる。乾燥方法は特に限定されず、加熱乾燥させる方法などが採用される。このようにして、架橋ゴムの表面に対して密着性の良好な前記塗膜が形成されるため、大きな変形に対しても追随が可能になるとともに、意匠性を向上させることができる。 The method for applying the paint used in the present invention to the surface of the crosslinked rubber is not particularly limited. Spray coating, brush coating, dip coating, etc. can be employed. Among these, spray coating and dip coating are preferable because a uniform coating film can be easily formed on the surface of the crosslinked rubber. In the present invention, after applying the paint, the liquid medium is dried. The drying method is not particularly limited, and a heat drying method or the like is employed. Thus, since the said coating film with favorable adhesiveness is formed with respect to the surface of bridge | crosslinking rubber | gum, while being able to follow large deformation | transformation, design property can be improved.
　上述のようにして架橋ゴムの表面に形成された塗膜の厚さは特に限定されないが、好適には５～２００μｍである。塗膜が厚すぎる場合、コストが上昇するのみならず、架橋ゴム基材への密着性が低下するおそれもある。塗膜の厚さは、より好適には１００μｍ以下であり、さらに好適には８０μｍ以下である。一方、塗膜が薄すぎる場合には、隠ぺい力が低下するおそれがある。また、塗膜の耐久性が低下するおそれがある。塗膜の厚さは、より好適には８μｍ以上である。 The thickness of the coating film formed on the surface of the crosslinked rubber as described above is not particularly limited, but is preferably 5 to 200 μm. When the coating film is too thick, not only the cost increases, but also the adhesion to the crosslinked rubber base material may decrease. The thickness of the coating film is more preferably 100 μm or less, and even more preferably 80 μm or less. On the other hand, when the coating film is too thin, the hiding power may be reduced. Moreover, there exists a possibility that durability of a coating film may fall. The thickness of the coating film is more preferably 8 μm or more.
　本発明で用いられる変性スチレン－ジエンブロック共重合体水添物は、常温で形態を保持することができるエラストマーでありながら、化学的に架橋していないので、液状媒体に溶解することが可能なものである。したがって、特に架橋処理をすることなく液状媒体を乾燥除去するのみで塗膜の形成が可能であり、塗膜の形成が極めて容易である。また、本発明に用いられる塗料が分散液である場合には、乾燥時の有機溶媒の揮散を防ぐことができる。 Although the hydrogenated modified styrene-diene block copolymer used in the present invention is an elastomer that can maintain its form at room temperature, it is not chemically crosslinked and can be dissolved in a liquid medium. Is. Therefore, it is possible to form a coating film only by drying and removing the liquid medium without performing a crosslinking treatment, and the coating film can be formed very easily. Moreover, when the coating material used for this invention is a dispersion liquid, volatilization of the organic solvent at the time of drying can be prevented.
　本発明の塗料を塗布する前に、架橋ゴムの表面を洗浄することが好ましい。洗浄を行うことによって、密着性の良好な塗膜を安定的に形成することができる。洗浄のための有機溶媒としては、アセトン、トルエン、イソプロパノールなどが使用される。洗浄のために水を用いることもできる。このとき洗浄液に、酸、アルカリ及び界面活性剤等が含まれていても良い。 It is preferable to wash the surface of the crosslinked rubber before applying the paint of the present invention. By performing washing, a coating film having good adhesion can be stably formed. As the organic solvent for washing, acetone, toluene, isopropanol or the like is used. Water can also be used for cleaning. At this time, the cleaning liquid may contain an acid, an alkali, a surfactant and the like.
　前記塗料の塗布に先立って、架橋ゴムの表面に、ゴム用の各種プライマーを塗布してから、前記塗料を塗布してもよい。そうすることによって密着性を改善できる場合があるが、製造工程が煩雑になるし、場合によってはむしろ架橋ゴムの表面物性が変化して、長期間の伸縮に対する耐久性に悪影響を及ぼす場合もあるので注意が必要である。したがって、架橋ゴムの表面にプライマーを施すことなく塗料を直接塗布することが好適である。特にプライマーを塗布しなくても、十分な密着性が得られることも本発明の有利な効果の一つである。 Prior to application of the coating material, various primers for rubber may be applied to the surface of the crosslinked rubber, and then the coating material may be applied. By doing so, the adhesion may be improved, but the manufacturing process becomes complicated, and in some cases, the surface physical properties of the crosslinked rubber may change, which may adversely affect durability against long-term expansion and contraction. So be careful. Therefore, it is preferable to directly apply the paint without applying a primer to the surface of the crosslinked rubber. In particular, it is one of the advantageous effects of the present invention that sufficient adhesion can be obtained without applying a primer.
　上述のように、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を架橋ゴムの表面に塗布し、液状媒体を除去して塗膜を形成する塗装方法を提供することができる。このようにして得られる本発明の成形品は、架橋ゴムの表面に、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物及び顔料を含有する塗膜が形成された成形品である。 As described above, 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment are added. It is possible to provide a coating method in which the coating material is applied to the surface of the crosslinked rubber, and the liquid medium is removed to form a coating film. The molded article of the present invention thus obtained contains a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride and a pigment on the surface of the crosslinked rubber. It is a molded article on which a coating film is formed.
　本発明の成形品における塗膜は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物及び顔料を含有する。さらに、塗膜が金属粉末を含有していることが好ましい。また、本発明の効果を阻害しない範囲内であれば、塗膜が、変性スチレン－ジエンブロック共重合体水添物、顔料及び金属粉末以外の添加剤を含有しても構わない。塗膜における各成分の割合は、上記塗料中の含有比率に対応する割合で含有させる。 The coating film in the molded article of the present invention contains a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic anhydride and a pigment. Furthermore, it is preferable that the coating film contains a metal powder. In addition, the coating film may contain additives other than the modified styrene-diene block copolymer hydrogenated product, the pigment, and the metal powder as long as the effects of the present invention are not impaired. The ratio of each component in the coating film is contained at a ratio corresponding to the content ratio in the paint.
　本発明の成形品は、上述のように架橋ゴムの表面に前記塗膜が形成されてなる。ここで、前記塗膜の表面に、さらにポリウレタン皮膜が形成されてなることが本発明の好適な実施態様である。こうして得られた本発明の成形品は、大きな変形に対しても追随が可能になるとともに、耐摩耗性に優れている。後述するように、架橋ゴムの表面に形成された前記塗膜に対してポリウレタン塗料を塗布することにより、該塗膜の表面にポリウレタン皮膜が形成される。このように、ポリウレタン皮膜が形成されることにより、耐摩耗性に優れた本発明の成形品を得ることができる。また、ポリウレタン皮膜の成形により、得られる成形品の意匠性を向上させることもできる。ポリウレタン皮膜は透明であってもよいし、色が付されていてもよいが、架橋ゴムの表面に形成された前記塗膜に含まれる顔料自体の色を阻害しないようにする観点から、ポリウレタン皮膜は透明であることが好ましい。また、ポリウレタン皮膜が透明である場合、得られる成形品に光沢感を与えることができる。 The molded product of the present invention has the above-mentioned coating film formed on the surface of the crosslinked rubber as described above. Here, it is a preferred embodiment of the present invention that a polyurethane film is further formed on the surface of the coating film. The molded product of the present invention thus obtained can follow large deformations and is excellent in wear resistance. As will be described later, by applying a polyurethane paint to the coating film formed on the surface of the crosslinked rubber, a polyurethane film is formed on the surface of the coating film. Thus, by forming a polyurethane film, the molded product of the present invention having excellent wear resistance can be obtained. Moreover, the designability of the molded product obtained can also be improved by shaping | molding a polyurethane membrane | film | coat. The polyurethane film may be transparent or colored, but from the viewpoint of not hindering the color of the pigment itself contained in the coating film formed on the surface of the crosslinked rubber. Is preferably transparent. Moreover, when a polyurethane membrane | film | coat is transparent, glossiness can be given to the molded article obtained.
　また、後述する実施例１ｂと比較例２ｂにおける塗布性能の評価結果からも分かるように、架橋ゴムの表面に直接ポリウレタン塗料を塗布した場合、大きなはじきが発生し、外観状態が良好ではなかったことを本発明者らは確認している。したがって、本発明のように、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物及び顔料を含有する塗膜の表面に対して、ポリウレタン塗料を塗布することが好適な実施態様である。 In addition, as can be seen from the evaluation results of the coating performance in Example 1b and Comparative Example 2b described later, when the polyurethane paint was directly applied to the surface of the crosslinked rubber, a large repellency occurred and the appearance was not good. The present inventors have confirmed. Therefore, as in the present invention, the polyurethane paint is applied to the surface of the coating film containing the modified styrene-diene block copolymer hydrogenated with the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and the pigment. Application is a preferred embodiment.
　本発明において、上記ポリウレタン皮膜を形成する際に用いられるポリウレタン塗料としては、特に限定されないが、イソシアネート基を有するポリウレタン塗料が好適に使用される。イソシアネート基を有するポリウレタン塗料を用いてポリウレタン皮膜を形成することにより、架橋ゴムの表面に形成された塗膜中の不飽和カルボン酸等と該イソシアネート基を有するポリウレタン塗料とが反応して密着性が良好になると考えられる。イソシアネート基を有するポリウレタン塗料としては、１液湿気硬化型ポリウレタン塗料や２液硬化型ポリウレタン塗料を好適に用いることができる。 In the present invention, the polyurethane paint used for forming the polyurethane film is not particularly limited, but a polyurethane paint having an isocyanate group is preferably used. By forming a polyurethane film using a polyurethane coating having an isocyanate group, the unsaturated carboxylic acid in the coating film formed on the surface of the crosslinked rubber reacts with the polyurethane coating having the isocyanate group to provide adhesion. It seems to be good. As the polyurethane coating having an isocyanate group, a one-component moisture curable polyurethane coating or a two-component curable polyurethane coating can be suitably used.
　１液湿気硬化型ポリウレタン塗料としては、末端にイソシアネート基を有し、空気中の水分と反応して硬化するポリウレタン樹脂などを用いることができる。混合操作が不要であるため取扱いが容易である等の観点から好適に使用することができる。また、２液硬化型ポリウレタン塗料として、イソシアネート基を複数有するポリイソシアネート化合物とポリオール類とを施工時に混合して硬化させる２液型のポリウレタン樹脂などを用いることができる。前記２液型のポリウレタン樹脂には、ポリイソシアネート化合物とポリオールとの反応により得られるイソシアネート基を有するウレタンプレポリマーを含んでいても構わない。また、ポリオール類として水酸基を有するアクリル樹脂（アクリルポリオール）を用いたアクリルウレタン塗料を前記２液型のポリウレタン樹脂として用いることもできる。 As the one-component moisture-curable polyurethane coating, a polyurethane resin having an isocyanate group at the end and being cured by reacting with moisture in the air can be used. Since mixing operation is unnecessary, it can be preferably used from the viewpoint of easy handling. Further, as the two-component curable polyurethane paint, a two-component polyurethane resin that is obtained by mixing and curing a polyisocyanate compound having a plurality of isocyanate groups and polyols at the time of construction can be used. The two-component polyurethane resin may contain a urethane prepolymer having an isocyanate group obtained by a reaction between a polyisocyanate compound and a polyol. In addition, an acrylic urethane paint using an acrylic resin having a hydroxyl group (acrylic polyol) as a polyol can also be used as the two-component polyurethane resin.
　本発明の成形品は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を架橋ゴムの表面に塗布し、液状媒体を除去して塗膜を形成した後に、該塗膜の表面にさらにポリウレタン塗料を塗布してポリウレタン皮膜を形成することにより得ることができる。以下、架橋ゴムの表面に形成された前記塗膜の表面にポリウレタン塗料を塗布してポリウレタン皮膜を形成する方法について述べる。 The molded article of the present invention has 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, and 1 to 200 parts by weight of a pigment. It is obtained by applying a paint containing a part to the surface of the crosslinked rubber, removing the liquid medium to form a coating film, and then applying a polyurethane paint to the surface of the coating film to form a polyurethane film. it can. Hereinafter, a method for forming a polyurethane film by applying a polyurethane paint to the surface of the coating film formed on the surface of the crosslinked rubber will be described.
　架橋ゴムの表面に形成された前記塗膜の表面に対して、ポリウレタン塗料を塗布する方法は特に限定されない。スプレーコーティング、刷毛塗り、浸漬（ディップ）コーティングなどを採用することができる。中でも、容易に均一なポリウレタン皮膜を形成できる点から、スプレーコーティングや浸漬コーティングが好適である。ポリウレタン塗料を塗布した後に、必要に応じて乾燥させてから硬化させることで本発明の成形品を得ることができる。 The method for applying the polyurethane paint to the surface of the coating film formed on the surface of the crosslinked rubber is not particularly limited. Spray coating, brush coating, dip coating, etc. can be employed. Among these, spray coating and dip coating are preferable because a uniform polyurethane film can be easily formed. After applying the polyurethane paint, the molded article of the present invention can be obtained by drying and curing as necessary.
　本発明の成形品において形成されるポリウレタン皮膜の厚さは、好適には５～２００μｍである。ポリウレタン皮膜の厚さが２００μｍを超える場合、コストが上昇するのみならず、前記塗膜への密着性が低下するおそれもある。ポリウレタン皮膜の厚さは、より好適には１００μｍ以下であり、さらに好適には８０μｍ以下である。一方、ポリウレタン皮膜の厚さが５μｍ未満の場合、耐摩耗性が低下するおそれがある。ポリウレタン皮膜の厚さは、より好適には８μｍ以上である。 The thickness of the polyurethane film formed in the molded article of the present invention is preferably 5 to 200 μm. When the thickness of the polyurethane film exceeds 200 μm, not only the cost increases, but also the adhesion to the coating film may decrease. The thickness of the polyurethane film is more preferably 100 μm or less, and even more preferably 80 μm or less. On the other hand, when the thickness of the polyurethane film is less than 5 μm, the wear resistance may be lowered. The thickness of the polyurethane film is more preferably 8 μm or more.
　こうして得られる本発明の成形品としては、ホース、チューブ、タイヤ、防振ゴム等が例示される。本発明の成形品において、塗膜で覆われる部分はその少なくとも一部分であればよい。得られた成形品は、架橋ゴムの表面に対して密着性の良好な塗膜が形成されているため、大きな変形に対しても追随が可能になるとともに、長期間の使用にも耐えることができる。また、架橋ゴムの表面に前記塗膜を形成することによって、成形品を保護したり、成形品の意匠性を向上させたりすることができる。さらに、前記塗膜の表面にポリウレタン皮膜が形成されてなる成形品においては、該塗膜の表面にポリウレタン皮膜が形成されてなる部分が一部分であっても構わない。このように、前記塗膜の表面にポリウレタン皮膜が形成されてなる成形品は、架橋ゴムの表面に対する密着性が良好で、大きな変形に対する追随が可能であり、耐摩耗性に優れているため、長期間の使用にも耐えることができる。また、成形品の意匠性を向上させることもできる。 Examples of the molded article of the present invention thus obtained include hoses, tubes, tires, vibration-proof rubbers and the like. In the molded article of the present invention, the portion covered with the coating film may be at least a portion thereof. The resulting molded product has a coating film with good adhesion to the surface of the crosslinked rubber, so that it can follow large deformations and withstand long-term use. it can. Further, by forming the coating film on the surface of the crosslinked rubber, the molded product can be protected or the design of the molded product can be improved. Furthermore, in the molded product in which the polyurethane film is formed on the surface of the coating film, a part of the polyurethane film formed on the surface of the coating film may be a part. Thus, the molded product in which the polyurethane film is formed on the surface of the coating film has good adhesion to the surface of the crosslinked rubber, can follow a large deformation, and has excellent wear resistance. Can withstand long-term use. Moreover, the designability of a molded product can also be improved.
　以下、実施例を用いて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１ａ
（ＥＰＤＭシートの作製）
　エチレン－プロピレン－非共役ジエン共重合体（ＥＰＤＭ）１００重量部、酸化亜鉛５重量部、ステアリン酸１重量部、カーボンブラック１２０重量部、プロセスオイル５０重量部、加硫促進剤１．５重量部及び硫黄１．５重量部をミキサー及びロールで混練してから、シート形状に成形した後に、１６０℃で１０分間加硫して、厚さ２ｍｍの架橋ゴムシートを得た。これを７０ｍｍ×１００ｍｍの寸法に切り出して長方形の架橋ＥＰＤＭシートを得た。得られた架橋ＥＰＤＭシートのＡ硬度は７０度であった。 Example 1a
(Production of EPDM sheet)
Ethylene-propylene-nonconjugated diene copolymer (EPDM) 100 parts by weight, zinc oxide 5 parts by weight, stearic acid 1 part by weight, carbon black 120 parts by weight, process oil 50 parts by weight, vulcanization accelerator 1.5 parts by weight Then, 1.5 parts by weight of sulfur was kneaded with a mixer and a roll and then formed into a sheet shape, and then vulcanized at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. This was cut into a size of 70 mm × 100 mm to obtain a rectangular crosslinked EPDM sheet. The obtained crosslinked EPDM sheet had an A hardness of 70 degrees.
（塗料Ａ－１の作製）
　旭化成ケミカルズ株式会社製の無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物『タフテックＭ１９１３』５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇ及びキナクリドン顔料２ｇを添加、攪拌し分散させ塗料Ａ－１を作製した。ここで『タフテックＭ１９１３』において、スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４度であり、無水マレイン酸の含有量を示す酸価［ｍｇＣＨ３ＯＮａ/ｇ］は１０であり、無水マレイン酸の含有量は１．８重量％である。 (Preparation of paint A-1)
5 g of a modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Corporation was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide and 2 g of quinacridone pigment were added, stirred and dispersed to prepare paint A-1. Here, in “Tuftec M1913”, the styrene content is 30 wt%, the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf], the A hardness is 84 degrees, and the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
（塗料の塗装、及び乾燥方法）
　上記方法で作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、塗料Ａ－１に浸漬してから引き上げ、室温にて静置して、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料を以下の方法で評価した。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet prepared by the above method was wiped with acetone to wash the surface. Thereafter, it was dipped in the paint A-1 and then pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The obtained sample was evaluated by the following method.
［密着性碁盤目試験］
　ＪＩＳ　Ｋ　５６００－５－６（塗膜の機械的性質－付着性　クロスカット法）による。カッターナイフを用い、ゴムシート上の塗膜を貫通してゴム素地に達する切り傷を、１ｍｍ間隔で碁盤目状に（１０×１０）付けた。この碁盤目の上にセロハン粘着テープを気泡等が入らないように貼り、指先でこすって塗膜に密着させた後、塗装面に対して４５度方向にテープを素早く引っ張って剥がした。その後、塗膜の剥離状況を観察した。結果は、「塗膜残り目数／１００」で表した。このとき、各碁盤目で区切られた塗膜の面積の内、５％以上剥れている場合を剥れとみなした。結果を表１に示す。 [Adhesion cross-cut test]
According to JIS K 5600-5-6 (mechanical properties of coating film-adhesive cross-cut method). Using a cutter knife, cuts reaching the rubber substrate through the coating film on the rubber sheet were made in a grid pattern (10 × 10) at intervals of 1 mm. A cellophane adhesive tape was affixed to the grid so that air bubbles and the like did not enter and rubbed with a fingertip to adhere to the coating film, and then the tape was quickly pulled in a direction of 45 degrees with respect to the painted surface. Then, the peeling state of the coating film was observed. The result was expressed as “number of remaining coating films / 100”. At this time, the case where 5% or more of the area of the coating film divided by each grid was peeled was regarded as peeling. The results are shown in Table 1.
［繰り返し密着試験］
　［密着性碁盤目試験］と同様の方法により、セロハン粘着テープによる剥離試験を繰り返し行った。剥離を１０回、３０回、５０回行った時の結果を、それぞれ「塗膜残り目数／１００」で表した。このとき、各碁盤目で区切られた塗膜の面積の内、５％以上剥れている場合を剥れとみなした。結果を表２に示す。 [Repeated adhesion test]
In the same manner as in [Adhesion cross cut test], a peel test using a cellophane adhesive tape was repeated. The results when peeling was performed 10 times, 30 times, and 50 times were expressed as “number of remaining coating films / 100”, respectively. At this time, the case where 5% or more of the area of the coating film divided by each grid was peeled was regarded as peeling. The results are shown in Table 2.
実施例２ａ
（天然ゴムシートの作製）
　天然ゴム（ＮＲ）１００重量部、酸化亜鉛５重量部、ステアリン酸１重量部、カーボンブラック５０重量部、加硫促進剤１重量部及び硫黄２．５重量部を混練し、実施例１ａと同様の方法で長方形の架橋天然ゴムシートを得た。得られた架橋天然ゴムシートのＡ硬度は６３度であった。 Example 2a
(Production of natural rubber sheet)
100 parts by weight of natural rubber (NR), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 50 parts by weight of carbon black, 1 part by weight of a vulcanization accelerator and 2.5 parts by weight of sulfur were kneaded and the same as in Example 1a A rectangular crosslinked natural rubber sheet was obtained by the method described above. The obtained crosslinked natural rubber sheet had an A hardness of 63 degrees.
（塗料の塗装、及び乾燥方法）
　上記方法で作製した架橋天然ゴムシートの表面をアセトンで拭い表面を洗浄した。その後、実施例１ａと同様に塗料Ａ－１に浸漬してから引き上げ、室温にて静置して、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料の密着性碁盤目試験の結果を表１に示す。 (Painting and drying methods)
The surface of the cross-linked natural rubber sheet produced by the above method was wiped with acetone to wash the surface. Thereafter, it was dipped in the coating material A-1 as in Example 1a, then pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
実施例３ａ
（スチレンブタジエンゴムシートの作製）
　スチレンブタジエンゴム（ＳＢＲ）１００重量部、酸化亜鉛３重量部、ステアリン酸１重量部、カーボンブラック５０重量部、加硫促進剤１重量部及び硫黄１．７５重量部を混練し、実施例１ａと同様の方法で長方形の架橋スチレンブタジエンゴムシートを得た。得られた架橋スチレンブタジエンゴムシートのＡ硬度は６４度であった。 Example 3a
(Production of styrene butadiene rubber sheet)
100 parts by weight of styrene butadiene rubber (SBR), 3 parts by weight of zinc oxide, 1 part by weight of stearic acid, 50 parts by weight of carbon black, 1 part by weight of vulcanization accelerator and 1.75 parts by weight of sulfur were kneaded, and Example 1a and A rectangular cross-linked styrene butadiene rubber sheet was obtained in the same manner. The obtained crosslinked styrene-butadiene rubber sheet had an A hardness of 64 degrees.
（塗料の塗装、及び乾燥方法）
　上記方法で作製した架橋スチレンブタジエンゴムシートの表面をアセトンで拭い表面を洗浄した。その後、実施例１ａと同様に塗料Ａ－１に浸漬してから引き上げ、室温にて静置して、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料の密着性碁盤目試験の結果を表１に示す。 (Painting and drying methods)
The surface of the crosslinked styrene butadiene rubber sheet produced by the above method was wiped with acetone and the surface was washed. Thereafter, it was dipped in the coating material A-1 as in Example 1a, then pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
比較例１ａ
（塗料Ｂ－１の作製）
　旭化成ケミカルズ株式会社製スチレン－ジエンブロック共重合体水添物『タフテックＨ１０６２』５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇ及びキナクリドン顔料２ｇを添加、攪拌し分散させ塗料Ｂ－１を作製した。ここで『タフテックＨ１０６２』は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性されていない。『タフテックＨ１０６２』において、スチレン含有量は１８重量％であり、ＭＦＲは４．５ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は６７度である。 Comparative Example 1a
(Preparation of paint B-1)
5 g of a styrene-diene block copolymer hydrogenated product “Tuftec H1062” manufactured by Asahi Kasei Chemicals Corporation was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide and 2 g of quinacridone pigment were added, and the mixture was stirred and dispersed to prepare paint B-1. Here, “Tuftec H1062” is not modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. In “Tuftec H1062”, the styrene content is 18% by weight, the MFR is 4.5 g / 10 min [230 ° C., 2.16 kgf], and the A hardness is 67 degrees.
（塗料の塗装、及び乾燥方法）
　実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、塗料Ｂ－１に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料の密着性碁盤目試験の結果を表１に、繰り返し密着試験の結果を表２に示す。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint B-1, lifted, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1, and the results of the repeated adhesion test are shown in Table 2.
比較例２ａ
　実施例２ａで作製した架橋天然ゴムシートの表面をアセトンで拭い表面を洗浄した。その後、比較例１ａと同様に塗料Ｂ－１に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料の密着性碁盤目試験の結果を表１に示す。 Comparative Example 2a
The surface of the crosslinked natural rubber sheet prepared in Example 2a was wiped with acetone and the surface was washed. Thereafter, as in Comparative Example 1a, it was dipped in the paint B-1, lifted, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
比較例３ａ
　実施例３ａで作製した架橋スチレンブタジエンゴムシートの表面をアセトンで拭い表面を洗浄した。その後、比較例１ａと同様に塗料Ｂ－１に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約３０μｍであった。得られた試料の密着性碁盤目試験の結果を表１に示す。 Comparative Example 3a
The surface of the crosslinked styrene butadiene rubber sheet prepared in Example 3a was wiped with acetone to wash the surface. Thereafter, as in Comparative Example 1a, it was dipped in the paint B-1, lifted, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 30 μm. The results of the adhesion cross-cut test of the obtained sample are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　密着性碁盤目試験の結果から、無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物を含有する塗料Ａ－１の密着性が優れていることがわかった。特にＮＲにおいては、スチレン－ジエンブロック共重合体水添物を含有する塗料Ｂ－１と比較して顕著に密着性が向上した。また、繰り返し密着試験の結果から、ＥＰＤＭに対して無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物を含有する塗料Ａ－１の密着性が塗料Ｂ－１より優れていることがわかった。 From the results of the cross-cut adhesion test, it was found that the paint A-1 containing the hydrogenated product of the modified styrene-diene block copolymer modified with maleic anhydride was excellent. Particularly in the case of NR, the adhesion was remarkably improved as compared with the coating material B-1 containing a hydrogenated styrene-diene block copolymer. Further, from the results of the repeated adhesion test, the adhesion of the coating A-1 containing the modified styrene-diene block copolymer hydrogenated with maleic anhydride with respect to EPDM is superior to the coating B-1. I understood it.
実施例４ａ
　旭化成ケミカルズ株式会社製無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物『タフテックＭ１９１３』（スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４度であり、無水マレイン酸の含有量を示す酸価［ｍｇＣＨ３ＯＮａ/ｇ］は１０であり、無水マレイン酸の含有量は１．８重量％である）５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇを添加、攪拌し分散させ、攪拌停止１５時間後の状態を目視で確認した。攪拌停止１５時間後も、顔料が分散された状態で、顔料の凝集は見られなかった。 Example 4a
Modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Co., Ltd. (styrene content is 30% by weight, MFR is 5.0 g / 10 min [230 ° C., 2 ° C. .16 kgf], A hardness is 84 degrees, the acid value [mgCH 3 ONa / g] indicating the content of maleic anhydride is 10, and the content of maleic anhydride is 1.8% by weight. ) 5 g was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. Even after the stirring was stopped for 15 hours, no aggregation of the pigment was observed with the pigment dispersed.
　実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、実施例４ａで調製した塗料に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約１２μｍであった。得られた試料を色測定により評価した。 The surface of the crosslinked EPDM sheet produced in Example 1a was wiped with acetone and the surface was washed. Thereafter, the film was dipped in the paint prepared in Example 4a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 12 μm. The obtained samples were evaluated by color measurement.
［色測定］
　コニカミノルタ製ＣＲ－３００色彩色差計にて、室温、蛍光灯下で測定した。測定結果は、同一試料の５箇所の測定値の平均値を用いた。 [Color measurement]
The measurement was performed at room temperature under a fluorescent lamp using a Konica Minolta CR-300 color difference meter. As the measurement result, the average value of the measurement values at five locations of the same sample was used.
　結果を表３に示す。測定結果は、Ｌ＊＝６５．１２、ａ＊＝－１．７７、ｂ＊＝－８．２４であった。 The results are shown in Table 3. The measurement results were L * = 65.12, a * = − 1.77, and b * = − 8.24.
実施例５ａ
　旭化成ケミカルズ株式会社製無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物『タフテックＭ１９４３』（スチレン含有量は２０重量％であり、ＭＦＲは８．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は６７であり、無水マレイン酸の含有量を示す酸価［ｍｇＣＨ３ＯＮａ/ｇ］は１０であり、無水マレイン酸の含有量は１．８重量％である）５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇを添加、攪拌し分散させ、攪拌停止１５時間後の状態を目視で確認した。攪拌停止１５時間後も、顔料が分散された状態で、顔料の凝集は見られなかった。 Example 5a
Modified styrene-diene block copolymer hydrogenated with maleic anhydride “Tuftec M1943” manufactured by Asahi Kasei Chemicals Corporation (styrene content is 20% by weight, MFR is 8.0 g / 10 min [230 ° C., 2 ° C. .16 kgf], A hardness is 67, acid value indicating the content of maleic anhydride [mgCH 3 ONa / g] is 10, and content of maleic anhydride is 1.8% by weight) 5 g was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. Even after the stirring was stopped for 15 hours, no aggregation of the pigment was observed with the pigment dispersed.
　さらに実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、実施例５ａで調製した塗料に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約２５μｍであった。得られた試料を色測定により評価した。結果を表３に示す。測定結果は、Ｌ＊＝７９．９３、ａ＊＝－１．４４、ｂ＊＝－５．３２であった。 Further, the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Example 5a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 25 μm. The obtained samples were evaluated by color measurement. The results are shown in Table 3. The measurement results were L * = 79.93, a * = − 1.44, and b * = − 5.32.
比較例４ａ
　旭化成ケミカルズ株式会社製スチレン－ジエンブロック共重合体水添物『タフテックＨ１０４１』（スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４である）５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇを添加、攪拌し分散させ、攪拌停止１５時間後の状態を目視で確認した。攪拌停止１５時間後では、顔料が凝集し、沈殿がみられた。 Comparative Example 4a
Asahi Kasei Chemicals Co., Ltd. styrene-diene block copolymer hydrogenated product “Tuftec H1041” (styrene content is 30 wt%, MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf], A hardness 5) was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. After 15 hours of stirring, the pigment aggregated and precipitation was observed.
　さらに実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、比較例４ａで作製した塗料に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約１０μｍであった。得られた試料を色測定により評価した。結果を表３に示す。測定結果は、Ｌ＊＝３４．１２、ａ＊＝－０．３７、ｂ＊＝－２．４２であった。 Furthermore, the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Comparative Example 4a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 10 μm. The obtained samples were evaluated by color measurement. The results are shown in Table 3. The measurement results were L * = 34.12, a * = − 0.37, and b * = − 2.42.
比較例５ａ
　旭化成ケミカルズ株式会社製スチレン－ジエンブロック共重合体水添物『タフテックＨ１０６２』（スチレン含有量は１８重量％であり、ＭＦＲは４．５ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度６７である）５ｇをトルエン１００ｃｃに溶解させた。さらに酸化チタン２ｇを添加、攪拌し分散させ、攪拌停止１５時間後の状態を目視で確認した。攪拌停止１５時間後では、顔料が凝集し、沈殿がみられた。 Comparative Example 5a
Asahi Kasei Chemicals Co., Ltd. styrene-diene block copolymer hydrogenated product “Tuftec H1062” (styrene content is 18% by weight, MFR is 4.5 g / 10 min [230 ° C., 2.16 kgf], A hardness 67) was dissolved in 100 cc of toluene. Further, 2 g of titanium oxide was added, stirred and dispersed, and the state after 15 hours of stirring was visually confirmed. After 15 hours of stirring, the pigment aggregated and precipitation was observed.
　さらに実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、比較例５ａで調製した塗料に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約１０μｍであった。得られた試料を色測定により評価した。結果を表３に示す。測定結果は、Ｌ＊＝３５．１２、ａ＊＝－０．３４、ｂ＊＝－２．２９であった。 Furthermore, the surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, the film was dipped in the paint prepared in Comparative Example 5a, pulled up, allowed to stand at room temperature, and dried. The coating film of the obtained sample was about 10 μm. The obtained samples were evaluated by color measurement. The results are shown in Table 3. The measurement results were L * = 35.12, a * = − 0.34, and b * = − 2.29.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　変性スチレン－ジエンブロック共重合体水添物を用いた、実施例４ａ及び実施例５ａは、色測定の結果が良好であり、基材ゴムに対する隠ぺい力が優れていた。 Example 4a and Example 5a using the hydrogenated styrene-diene block copolymer had good color measurement results and excellent hiding power against the base rubber.
実施例６ａ
　旭化成ケミカルズ株式会社製無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物『タフテックＭ１９１３』５ｇをトルエン１００ｃｃに溶解させた。さらにアルミニウムフレーク０．９ｇ及び『Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６４』０．４５ｇを添加、攪拌し分散させ塗料Ｃ－１を作製した。ここで『タフテックＭ１９１３』において、スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４度であり、無水マレイン酸の含有量を示す酸価［ｍｇＣＨ３ＯＮａ/ｇ］は１０であり、無水マレイン酸の含有量は１．８重量％である。 Example 6a
5 g of a modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Corporation was dissolved in 100 cc of toluene. Further, 0.9 g of aluminum flakes and 0.45 g of “Pigment Red 264” were added, and the mixture was stirred and dispersed to prepare paint C-1. Here, in “Tuftec M1913”, the styrene content is 30 wt%, the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf], the A hardness is 84 degrees, and the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
（塗料の塗装、及び乾燥方法）
　実施例１ａで作製した架橋ＥＰＤＭシートの表面をアセトンで拭い表面を洗浄した。その後、塗料Ｃ－１に浸漬してから引き上げ、室温にて静置、乾燥した。得られた試料の塗膜は約２０μｍであった。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet prepared in Example 1a was wiped with acetone to wash the surface. Thereafter, it was dipped in the paint C-1 and then pulled up, left at room temperature, and dried. The coating film of the obtained sample was about 20 μm.
　実施例６ａで得られた試料は２００％程度のゴムの伸張に対して追従性が良好であり、密着性も良好であった。また、顔料が均一に分散しており、外観が美麗であった。 The sample obtained in Example 6a had good followability to rubber stretch of about 200% and good adhesion. Further, the pigment was uniformly dispersed and the appearance was beautiful.
実施例１ｂ
（ＥＰＤＭシートの作製）
　エチレン－プロピレン－非共役ジエン共重合体（ＥＰＤＭ）１００重量部、酸化亜鉛５重量部、ステアリン酸１重量部、カーボンブラック８０重量部、プロセスオイル５０重量部、加硫促進剤１．５重量部及び硫黄１．５重量部をミキサー及びロールで混練してから、シート形状に成形した後に、１６０℃で１０分間加硫して、厚さ２ｍｍの架橋ゴムシートを得た。これを２５ｍｍ×２２０ｍｍの寸法に切り出して長方形の架橋ＥＰＤＭシートを得た。得られた架橋ＥＰＤＭシートのＡ硬度は６５度であった。後述する追従性試験では、同じくシートからダンベル状1号形片を採取した。 Example 1b
(Production of EPDM sheet)
100 parts by weight of ethylene-propylene-nonconjugated diene copolymer (EPDM), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 80 parts by weight of carbon black, 50 parts by weight of process oil, 1.5 parts by weight of vulcanization accelerator Then, 1.5 parts by weight of sulfur was kneaded with a mixer and a roll and then formed into a sheet shape, and then vulcanized at 160 ° C. for 10 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. This was cut into a size of 25 mm × 220 mm to obtain a rectangular crosslinked EPDM sheet. The obtained crosslinked EPDM sheet had an A hardness of 65 degrees. In the follow-up test described later, a dumbbell-shaped No. 1 piece was similarly collected from the sheet.
（塗料Ａ－２の作製）
　旭化成ケミカルズ株式会社製の無水マレイン酸で変性された変性スチレン－ジエンブロック共重合体水添物『タフテックＭ１９１３』１００ｇをトルエン１６００ｇに溶解させた。さらにアルミニウムフレーク１８ｇ及び顔料『Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６４』９ｇを添加、攪拌し分散させ塗料Ａ－２を作製した。ここで『タフテックＭ１９１３』において、スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４度であり、無水マレイン酸の含有量を示す酸価［ｍｇＣＨ３ＯＮａ/ｇ］は１０であり、無水マレイン酸の含有量は１．８重量％である。 (Preparation of paint A-2)
100 g of modified styrene-diene block copolymer hydrogenated product “Tuftec M1913” modified with maleic anhydride manufactured by Asahi Kasei Chemicals Corporation was dissolved in 1600 g of toluene. Further, 18 g of aluminum flakes and 9 g of pigment “Pigment Red 264” were added, and the mixture was stirred and dispersed to prepare paint A-2. Here, in “Tuftec M1913”, the styrene content is 30 wt%, the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf], the A hardness is 84 degrees, and the maleic anhydride content The acid value [mgCH 3 ONa / g] is 10 and the content of maleic anhydride is 1.8% by weight.
（上塗り塗料Ｃ－２の作製）
　エムシー工業株式会社製の溶剤含有イソシアネート基末端ポリウレタン樹脂『タケネートＦ７０７Ｎ』１００ｇをポリウレタン樹脂用シンナー１００ｇに溶解させた。さらにエムシー工業株式会社製の硬化促進剤『フォーメート　Ｓ-９』２ｇを添加、攪拌し上塗り塗料Ｃ－２を作製した。 (Preparation of top coat C-2)
100 g of solvent-containing isocyanate group-terminated polyurethane resin “Takenate F707N” manufactured by MC Industrial Co., Ltd. was dissolved in 100 g of polyurethane resin thinner. Furthermore, 2 g of a curing accelerator “Formate S-9” manufactured by MC Industrial Co., Ltd. was added and stirred to prepare a top coat C-2.
（塗料の塗装、及び乾燥方法）
　上記方法で作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。その後、塗料Ａ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料の塗膜の厚みは約２０μｍであった。さらに、上塗り塗料Ｃ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料におけるポリウレタン皮膜の厚みは約３０μｍであった。得られた試料を以下の方法で評価した。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet and dumbbell piece produced by the above method was wiped with toluene and the surface was washed. Thereafter, the paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 μm. Further, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 μm. The obtained sample was evaluated by the following method.
［耐摩耗性試験］
　摩擦堅牢度試験機にて白綿布はＪＩＳ　Ｌ０８０３準拠の綿３－１号を用い、おもり重量１０００ｇ、摩擦速度は３０回／ｍｉｎ、試験環境温度は２３℃で行った。塗膜が摩耗し、ゴムの素地が現れた時点で試験を終了した。耐摩耗性試験における試験上限回数を１万回とした。結果を表４に示す。 [Abrasion resistance test]
In the friction fastness tester, white cotton cloth conforming to JIS L0803 was used, and the weight was 1000 g, the friction speed was 30 times / min, and the test environment temperature was 23 ° C. The test was terminated when the coating was worn and a rubber substrate appeared. The upper limit number of tests in the wear resistance test was 10,000. The results are shown in Table 4.
［密着性碁盤目試験と繰り返し密着試験］
　実施例１ａと同様の方法により、密着性碁盤目試験と繰り返し密着試験を行った。得られた結果を表４に示す。 [Adhesion cross cut test and repeated adhesion test]
By the same method as in Example 1a, an adhesion cross-cut test and a repeated adhesion test were performed. Table 4 shows the obtained results.
［塗膜追従性試験］
　塗料を塗布したダンベル片（標線間４０ｍｍ）を精密万能試験機にて１０ｍｍ／ｍｉｎの速度で引張り、塗膜の状態を観察した。塗膜に破れが発生するまで行い、その時の伸度、塗膜の剥離状態の程度で評価した。結果を表４に示す。 [Film followability test]
A dumbbell piece (40 mm between marked lines) coated with the paint was pulled at a speed of 10 mm / min with a precision universal testing machine, and the state of the coating film was observed. The test was performed until the coating film was broken, and the degree of elongation at that time and the degree of peeling of the coating film were evaluated. The results are shown in Table 4.
［塗布性能評価］
　上塗り塗料の塗布性を塗布後のつやの差異、つやむらの程度、厚さのむら、しわ、つぶ、くぼみ、流れ、はじき、泡、膨れ、割れ、はがれ、白化などの外観状態で評価した。結果を表４に示す。表４において、外観状態が良好であった場合を「ａ」、大きなはじきなどで外観状態が良好ではなかった場合を「ｂ」と評価した。 [Evaluation of coating performance]
The applicability of the top coating was evaluated based on the appearance conditions such as the difference in gloss after application, the degree of gloss unevenness, the thickness unevenness, wrinkles, crushing, dents, flow, repelling, foam, swelling, cracking, peeling, and whitening. The results are shown in Table 4. In Table 4, the case where the appearance state was good was evaluated as “a”, and the case where the appearance state was not good due to large repelling was evaluated as “b”.
比較例１ｂ
（塗料Ｂ－２の作製）
　旭化成ケミカルズ株式会社製スチレン－ジエンブロック共重合体水添物『タフテックＨ１０４１』１００ｇをトルエン１６００ｇに溶解させた。さらにアルミニウムフレーク１８ｇ及び顔料『Ｐｉｇｍｅｎｔ　Ｒｅｄ　２６４』９ｇを添加、攪拌し分散させ塗料Ｂ－２を作製した。ここで『タフテックＨ１０４１』は、不飽和カルボン酸又は不飽和カルボン酸無水物で変性されていない。『タフテックＨ１０４１』において、スチレン含有量は３０重量％であり、ＭＦＲは５．０ｇ／１０ｍｉｎ［２３０℃、２．１６ｋｇｆ］であり、Ａ硬度は８４度である。 Comparative Example 1b
(Preparation of paint B-2)
100 g of hydrogenated styrene-diene block copolymer “Tuftec H1041” manufactured by Asahi Kasei Chemicals Corporation was dissolved in 1600 g of toluene. Further, 18 g of aluminum flakes and 9 g of pigment “Pigment Red 264” were added, and the mixture was stirred and dispersed to prepare paint B-2. Here, “Tuftec H1041” is not modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. In “Tuftec H1041”, the styrene content is 30% by weight, the MFR is 5.0 g / 10 min [230 ° C., 2.16 kgf], and the A hardness is 84 degrees.
（塗料の塗装、及び乾燥方法）
　実施例１ｂで作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。その後、塗料Ｂ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料の塗膜の厚みは約２０μｍであった。さらに、上塗り塗料Ｃ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料におけるポリウレタン皮膜の厚みは約３０μｍであった。得られた試料を実施例１ｂと同様の方法で評価した。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Thereafter, paint B-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 μm. Further, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 μm. The obtained sample was evaluated in the same manner as in Example 1b.
比較例２ｂ
　実施例１ｂで作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。そして、上塗り塗料Ｃ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料におけるポリウレタン皮膜の厚みは約３０μｍであった。得られた試料を実施例１ｂと同様の方法で評価した。 Comparative Example 2b
The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, the top coat C-2 was applied by air spray, allowed to stand at room temperature and dried. The thickness of the polyurethane film in the obtained sample was about 30 μm. The obtained sample was evaluated in the same manner as in Example 1b.
実施例２ｂ
（上塗り塗料Ｄ－２の作製）
　大橋化学工業株式会社製のアクリル塗料『ポリナールＮｏ．５００　１１　クリヤー』１００ｇを大橋化学工業株式会社製の合成樹脂塗料用シンナー『Ｎｏ．５６００』１００ｇに溶解させた。そして、攪拌し上塗り塗料Ｄ－２を作製した。 Example 2b
(Preparation of top coat D-2)
Acrylic paint “Polynal No. "500 11 Clear" 100 g is a thinner "No. 5600 "was dissolved in 100 g. Then, the mixture was stirred to prepare a top coating material D-2.
（塗料の塗装、及び乾燥方法）
　実施例１ｂで作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。その後、塗料Ａ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料の塗膜の厚みは約２０μｍであった。さらに、上塗り塗料Ｂ－２をエアースプレー塗布し、フラッシュアウトで１０ｍｉｎ室温にて静置した後、６０℃で２０ｍｉｎの乾燥をした。得られた試料の塗膜は約３０μｍであった。得られた試料を実施例１ｂと同様の方法で評価した。 (Painting and drying methods)
The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Thereafter, the paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 μm. Further, the top coating material B-2 was applied by air spray, allowed to stand at room temperature for 10 minutes by flash-out, and then dried at 60 ° C. for 20 minutes. The coating film of the obtained sample was about 30 μm. The obtained sample was evaluated in the same manner as in Example 1b.
比較例３ｂ
　実施例１ｂで作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。そして、上塗り塗料Ｄ－２をエアースプレー塗布し、フラッシュアウトで１０ｍｉｎ室温にて静置した後、６０℃で２０ｍｉｎの乾燥をした。得られた試料におけるポリウレタン皮膜の厚みは約３０μｍであった。得られた試料を実施例１ｂと同様の方法で評価した。 Comparative Example 3b
The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, the top coating material D-2 was applied by air spray, allowed to stand at room temperature for 10 minutes by flash-out, and then dried at 60 ° C. for 20 minutes. The thickness of the polyurethane film in the obtained sample was about 30 μm. The obtained sample was evaluated in the same manner as in Example 1b.
実施例３ｂ
　実施例１ｂで作製した架橋ＥＰＤＭシートとダンベル片の表面をトルエンで拭い表面を洗浄した。そして、塗料Ａ－２をエアースプレー塗布し、室温にて静置して、乾燥した。得られた試料の塗膜の厚みは約２０μｍであった。得られた試料を実施例１ｂと同様の方法で評価した。 Example 3b
The surface of the crosslinked EPDM sheet and dumbbell pieces prepared in Example 1b was wiped with toluene and the surface was washed. Then, paint A-2 was applied by air spray, allowed to stand at room temperature, and dried. The thickness of the coating film of the obtained sample was about 20 μm. The obtained sample was evaluated in the same manner as in Example 1b.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　表４の結果から、無水マレイン酸で変性された変性スチレン-ジエンブロック共重合体水添物を含有する塗料Ａ－２にポリウレタン塗料を上塗りすると、密着性が優れ、耐摩耗性も優れていることがわかった。これは、無水マレイン酸で変性されていない塗料Ｂ－２を使用した比較例１ｂと比較して、耐摩耗性が顕著に現れている。この結果は、静的な密着試験では判定できない密着性が向上していることを示す。 From the results shown in Table 4, when the polyurethane coating is overcoated on the coating A-2 containing the modified styrene-diene block copolymer hydrogenated with maleic anhydride, the adhesion is excellent and the wear resistance is also excellent. I understood it. As compared with Comparative Example 1b using the coating material B-2 not modified with maleic anhydride, the wear resistance is remarkably exhibited. This result shows that the adhesion which cannot be determined by the static adhesion test is improved.

Claims (9)

  1. 　架橋ゴムに塗装するための塗料であって、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料。 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium, A paint containing 1 to 200 parts by weight of pigment.
  2. 　前記変性スチレン－ジエンブロック共重合体水添物における不飽和カルボン酸又は不飽和カルボン酸無水物に由来する単位の含有量が、０．２～５重量％である請求項１記載の塗料。 2. The paint according to claim 1, wherein the content of the unit derived from the unsaturated carboxylic acid or unsaturated carboxylic acid anhydride in the modified styrene-diene block copolymer hydrogenated product is 0.2 to 5% by weight.
  3. 　前記変性スチレン－ジエンブロック共重合体水添物が、無水マレイン酸で変性されたものである請求項１又は２記載の塗料。 The paint according to claim 1 or 2, wherein the hydrogenated product of the modified styrene-diene block copolymer is modified with maleic anhydride.
  4. 　架橋ゴムの表面に、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物及び顔料を含有する塗膜が形成された成形品。 Molded product in which a coating film containing a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or unsaturated carboxylic acid anhydride and a pigment is formed on the surface of the crosslinked rubber.
  5. 　前記塗膜の表面に、さらにポリウレタン皮膜が形成されてなる請求項４記載の成形品。 The molded article according to claim 4, wherein a polyurethane film is further formed on the surface of the coating film.
  6. 　前記塗膜において、不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部に対して、顔料１～２００重量部を含有する請求項４又は５記載の成形品。 The coating film contains 1 to 200 parts by weight of a pigment with respect to 100 parts by weight of a hydrogenated product of a modified styrene-diene block copolymer modified with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride. Or the molded article of 5.
  7. 　前記架橋ゴムがオレフィン系ゴム又はジエン系ゴムである請求項４～６のいずれか記載の成形品。 The molded article according to any one of claims 4 to 6, wherein the crosslinked rubber is an olefin rubber or a diene rubber.
  8. 　不飽和カルボン酸又は不飽和カルボン酸無水物で変性された変性スチレン－ジエンブロック共重合体水添物１００重量部、液状媒体５０～１００００重量部及び顔料１～２００重量部を含有する塗料を架橋ゴムの表面に塗布し、液状媒体を除去して塗膜を形成することを特徴とする成形品の製造方法。 Crosslinking a paint containing 100 parts by weight of a modified styrene-diene block copolymer hydrogenated with an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, 50 to 10,000 parts by weight of a liquid medium and 1 to 200 parts by weight of a pigment. A method for producing a molded article, characterized in that a coating film is formed by applying to a rubber surface and removing a liquid medium.
  9. 　前記塗膜を形成した後に、該塗膜の表面にポリウレタン塗料を塗布してポリウレタン皮膜を形成する請求項８記載の成形品の製造方法。 The method for producing a molded article according to claim 8, wherein after forming the coating film, a polyurethane coating is formed on the surface of the coating film by applying a polyurethane paint.
PCT/JP2012/050330 2011-01-12 2012-01-11 Coating material to be applied to crosslinked rubber, molded article coated with the coating material, and process for producing same WO2012096281A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012552738A JP5825610B2 (en) 2011-01-12 2012-01-11 Molded product having a coating film formed on the surface of a crosslinked rubber and method for producing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-003795 2011-01-12
JP2011003795 2011-01-12
JP2011182331 2011-08-24
JP2011-182331 2011-08-24

Publications (1)

Publication Number Publication Date
WO2012096281A1 true WO2012096281A1 (en) 2012-07-19

Family

ID=46507179

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/050330 WO2012096281A1 (en) 2011-01-12 2012-01-11 Coating material to be applied to crosslinked rubber, molded article coated with the coating material, and process for producing same

Country Status (2)

Country Link
JP (1) JP5825610B2 (en)
WO (1) WO2012096281A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3412689A4 (en) * 2016-02-02 2019-09-11 Zeon Corporation Block-copolymer hydride having acid anhydride group and use thereof
KR20200014371A (en) * 2017-05-31 2020-02-10 베이 머트리얼스, 엘엘씨 Double Shell Dental Instruments And Materials Composition
JP2020186301A (en) * 2019-05-13 2020-11-19 住友ゴム工業株式会社 Paint composition for tire
US11999141B2 (en) 2022-12-02 2024-06-04 Bay Materials, Llc. Dual shell dental appliance and material constructions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63139953A (en) * 1986-12-02 1988-06-11 Mitsubishi Petrochem Co Ltd Primer composition
JPH0632925A (en) * 1992-07-13 1994-02-08 Polytec Design:Kk Method for forming resinous coating on rubber
JPH0770346A (en) * 1993-09-01 1995-03-14 Asahi Glass Co Ltd Coating method
JP2001220531A (en) * 2000-02-09 2001-08-14 Jsr Corp Coating composition and coated melded article
JP2007112832A (en) * 2005-10-18 2007-05-10 Konishi Co Ltd Primer composition
JP2009090778A (en) * 2007-10-05 2009-04-30 Marugo Rubber Ind Co Ltd Muffler hanger and manufacturing method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2670581B2 (en) * 1988-10-19 1997-10-29 三井石油化学工業株式会社 Primer composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63139953A (en) * 1986-12-02 1988-06-11 Mitsubishi Petrochem Co Ltd Primer composition
JPH0632925A (en) * 1992-07-13 1994-02-08 Polytec Design:Kk Method for forming resinous coating on rubber
JPH0770346A (en) * 1993-09-01 1995-03-14 Asahi Glass Co Ltd Coating method
JP2001220531A (en) * 2000-02-09 2001-08-14 Jsr Corp Coating composition and coated melded article
JP2007112832A (en) * 2005-10-18 2007-05-10 Konishi Co Ltd Primer composition
JP2009090778A (en) * 2007-10-05 2009-04-30 Marugo Rubber Ind Co Ltd Muffler hanger and manufacturing method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3412689A4 (en) * 2016-02-02 2019-09-11 Zeon Corporation Block-copolymer hydride having acid anhydride group and use thereof
KR20200014371A (en) * 2017-05-31 2020-02-10 베이 머트리얼스, 엘엘씨 Double Shell Dental Instruments And Materials Composition
JP2020522405A (en) * 2017-05-31 2020-07-30 ベイ マテリアルズ エルエルシー Double shell dental equipment and material composition
KR102602064B1 (en) * 2017-05-31 2023-11-15 베이 머트리얼스, 엘엘씨 Double shell dental instrument and material composition
JP7448295B2 (en) 2017-05-31 2024-03-12 ベイ マテリアルズ エルエルシー Double shell dental device and material composition
JP2020186301A (en) * 2019-05-13 2020-11-19 住友ゴム工業株式会社 Paint composition for tire
JP7251303B2 (en) 2019-05-13 2023-04-04 住友ゴム工業株式会社 tire paint composition
US11999141B2 (en) 2022-12-02 2024-06-04 Bay Materials, Llc. Dual shell dental appliance and material constructions

Also Published As

Publication number Publication date
JP5825610B2 (en) 2015-12-02
JPWO2012096281A1 (en) 2014-06-09

Similar Documents

Publication Publication Date Title
EP1549720B1 (en) Flexible emissive coatings for elastomer substrates
TWI262205B (en) Room temperature curable functionalized HNBR coating
CN105378018B (en) Adhesive composition
CN105378015B (en) Bonding sheet and its application
JP4717463B2 (en) Aqueous dispersion and laminate
JP5952812B2 (en) Primer composition and adhesive tape
TWI655251B (en) Primer-free coating composition, preparation method thereof and articles containing the same
KR20020069161A (en) Aqueous coating composition
EP2135895A1 (en) Thermoplastic elastomer composition and method for producing the same
KR20080081079A (en) Coating material
JP5825610B2 (en) Molded product having a coating film formed on the surface of a crosslinked rubber and method for producing the same
JP5411027B2 (en) Water dispersion
CA2492866A1 (en) Ambient cured coatings and coated rubber products therefrom
WO2011021725A1 (en) Coating composition for sliding members
JP2009108128A (en) Aqueous dispersion
JP2008056772A (en) Aqueous coating agent for ethylene-propylene rubber
JP2006176615A (en) Coating agent for polyolefin-based resin molded article and molded article coated therewith
CN106715565B (en) Vulcanized rubber surface treating agent
EP1431358A1 (en) Coating composition for elastomers
JP6507817B2 (en) Water-based coating agent
CN110054943A (en) For reducing rubber surface coefficient of friction and the molybdenum disulfide nano coating of abrasion and preparation method thereof
CA1071036A (en) Method of compounding rubber
JP6937024B2 (en) Sealing material, its manufacturing method, and coating composition for sealing material
JP5011986B2 (en) Polypropylene laminate, method for producing the same, and coating material used therefor
JP2008195742A (en) Water-based pigment paste and water-based coating material composition

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12734233

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2012552738

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12734233

Country of ref document: EP

Kind code of ref document: A1