CA1188971A - Marks for use in rubber articles - Google Patents
Marks for use in rubber articlesInfo
- Publication number
- CA1188971A CA1188971A CA000422654A CA422654A CA1188971A CA 1188971 A CA1188971 A CA 1188971A CA 000422654 A CA000422654 A CA 000422654A CA 422654 A CA422654 A CA 422654A CA 1188971 A CA1188971 A CA 1188971A
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- Prior art keywords
- rubber
- mark
- weight
- thickness
- chromatic
- Prior art date
- Legal status (The legal status 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 status listed.)
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Abstract
Abstract of the Disclosure A mark for use in rubber article is disclosed, which comprises a chromatic rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated poly-ethylene rubber and having a thickness of 0.1 to 1.5 mm, an antioxidant-migration film barrier selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film and having a thickness of 3 to 100 µm, and an adhesive layer of thermoplastic polyester or polyurethane having a thickness of 0.005 to 0.5 mm.
Description
This invention relates to chromatic marks for use in rubber articles provided with an an-tioxidant-migra~ion fil~ barrier having an excellent flex resist-ance which hardly cause color failure and have excellent flex resistance and wea~her resistance.
Heretofore, there have been made various studies on a technic for adhering a chromatic mark to rubber articles after vulcaniza-tion, particularly tires.
For instance, there is practically no problem on the adhesion between the vlllcanized rubber and the mark when using the technic as disclosed in Japanese Patent Applica~
tion Publication No. 36,910/77. In this case, however, the stain resistance of the mark is considerably poor, so that the antioxidant migrates from the vulcanized ru~ber of the rubber article into the mark in a short period to cause color failure o~ the mark. Moreover, such a color failure can be prevented by using a stainproof antioxidant, but the antioxidative performance of this stainproof antioxidant is considerably inferior to that of a-n amine-series antioxidan-t having a strongest staining property, so that the stainproof antiox:idant cannot generally be used only for preventing the color fa:ilure of the chromatic mark.
Now, there have been made many studies in order to prevent the color failure of the chromatic mark when using an amine-series antioxi.dant or the like having a strong staining property to rubber articles. Among them, a method as disclosed in Japanese Pa-tent laid open No. 56-13~,006 is excellent in the effect of preventing the color failure, but it has some drawbacks that small
Heretofore, there have been made various studies on a technic for adhering a chromatic mark to rubber articles after vulcaniza-tion, particularly tires.
For instance, there is practically no problem on the adhesion between the vlllcanized rubber and the mark when using the technic as disclosed in Japanese Patent Applica~
tion Publication No. 36,910/77. In this case, however, the stain resistance of the mark is considerably poor, so that the antioxidant migrates from the vulcanized ru~ber of the rubber article into the mark in a short period to cause color failure o~ the mark. Moreover, such a color failure can be prevented by using a stainproof antioxidant, but the antioxidative performance of this stainproof antioxidant is considerably inferior to that of a-n amine-series antioxidan-t having a strongest staining property, so that the stainproof antiox:idant cannot generally be used only for preventing the color fa:ilure of the chromatic mark.
Now, there have been made many studies in order to prevent the color failure of the chromatic mark when using an amine-series antioxi.dant or the like having a strong staining property to rubber articles. Among them, a method as disclosed in Japanese Pa-tent laid open No. 56-13~,006 is excellent in the effect of preventing the color failure, but it has some drawbacks that small
- 2 -7~
scratches are innumcrably formed on the surface of the mark due to the presence of a metal foil disposed on the mark, and that when a tire provided with such a mark is run at a state of insufficient internal pressure for a long time, the me-tal foil is broken by fatigue to form a breaking nucleus, from which crack grows up to an outer rubber layer of -the tire.
It is, therefore, an object of the invention to provide a chromatic mark for use in rubber articles which eliminates the aforementioned drawbacks, prevents the color failure, and considerably improves -the beautiful appearance, flex resistance and weather resistance~
According to the inven-tion, there is provided a mark for use in rubber articles comprising a chromatic rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content and having a thickness of 0.1 to ].5 mm, an antioxidant-migration film barrier selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film and having a thickness of 3 to 100 ~Im, and an adhesive layer selected from thermoplastic polyes-ters and thermoplastic polyurethanes and having a thickness of 0.005 to 0.5 mm.
In the preferred embodiment of the invention, the mark has a three-layer structure obtained by laminating the chromatic rubber composition layer, the antioxidant-migration film barrier and the adhesive layer in this order, or a four-layer structure obtained by laminating the chromatic rubber composition layer, the adhesive layer, the antioxiclant-migration film barrier and the adhesive layer in this order, or a six-layer structure obtained by laminating the chromatic rubber composition layer, the adhesive layer, the antioxidan-t-migration film barrier~ a shock-absorbing rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated poly-ethylene rubber per 100 parts by weight of total rubber content and having a ~hickness of 0.1 to 1.5 mm, and ~he adhesive layer in this order.
In another preferred embodiment of the invention, the mark for use in rubber articles is compose~ of a ~our-layer laminate obtained by laminating a chromatic rubber composition layer containing not less than 50 parts by weight of chlorosulfonated polyethylene rubber with a chlorine content of not less than 30% by weigh-t per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1~0 ~m, a ny:Lon copolymer film barrier having a thickness of 0.008 to 0.3 mtrl and a softening point of 100 to 180C~ a shock-absorbing rubber composition layer containing not less than 50 parts by weight of chlorosulona-ted polyethylene rubber with a chlorine content of not less than 30% by weight per --100 parts by weight of total rubber content and having a thickness of 0.1 to 1.5 mm, and an aclhesive layer of thermoplastic polyester or thermoplastic polyurethane having a thickness of 0.OOS to 0.2 mm and a softening point of ~0 to 200C in this order, and has a total thickness of Q.25 to 3.0 mm.
7~
According to the invention, it is favorable in practice that the outer surface of the mark is pro-tected by providing a protective coating on the surface o~ the chromatic rubber composition layer. Further, it is preferable ~o form an indicative print on the surface of the chroma~ic rubber composition layer from viewpoints of expressiveness, beautiful appearance and labor-saving.
Moreover, the term "chromatic" color -used herein means to be a color having either a lightness or a saturation or both. If the chromatic color has the lightness as in white, gray or the like, it has not necessarily the saturation. And also, if -the chromatic color is black and has a brightness or the like and is different from black color of the tire in the color tone, it may be used as a mark.
The invention will be described in greater de tail below.
In the chromatic rubber composition layer and the shock-absorbing rubber composition layer according to the invention, chloroprene rubber and chlorosulfonated polyethylene rwbber are used as a rubber component because they have a considerably e~cellent weather resistance, ~mong them, the use of chlorosulfonated polyethylene rubber is more preferable because it is excellent in the adhesion to polyester film, nylon copolymer film, thermo-plastic polyester and thermoplastic polyurethane.
The chloroprene rubber is preferable -to have a grade that the crystallization is slow and the change of hardness at low temperature is small. The chloro-
scratches are innumcrably formed on the surface of the mark due to the presence of a metal foil disposed on the mark, and that when a tire provided with such a mark is run at a state of insufficient internal pressure for a long time, the me-tal foil is broken by fatigue to form a breaking nucleus, from which crack grows up to an outer rubber layer of -the tire.
It is, therefore, an object of the invention to provide a chromatic mark for use in rubber articles which eliminates the aforementioned drawbacks, prevents the color failure, and considerably improves -the beautiful appearance, flex resistance and weather resistance~
According to the inven-tion, there is provided a mark for use in rubber articles comprising a chromatic rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content and having a thickness of 0.1 to ].5 mm, an antioxidant-migration film barrier selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film and having a thickness of 3 to 100 ~Im, and an adhesive layer selected from thermoplastic polyes-ters and thermoplastic polyurethanes and having a thickness of 0.005 to 0.5 mm.
In the preferred embodiment of the invention, the mark has a three-layer structure obtained by laminating the chromatic rubber composition layer, the antioxidant-migration film barrier and the adhesive layer in this order, or a four-layer structure obtained by laminating the chromatic rubber composition layer, the adhesive layer, the antioxiclant-migration film barrier and the adhesive layer in this order, or a six-layer structure obtained by laminating the chromatic rubber composition layer, the adhesive layer, the antioxidan-t-migration film barrier~ a shock-absorbing rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated poly-ethylene rubber per 100 parts by weight of total rubber content and having a ~hickness of 0.1 to 1.5 mm, and ~he adhesive layer in this order.
In another preferred embodiment of the invention, the mark for use in rubber articles is compose~ of a ~our-layer laminate obtained by laminating a chromatic rubber composition layer containing not less than 50 parts by weight of chlorosulfonated polyethylene rubber with a chlorine content of not less than 30% by weigh-t per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1~0 ~m, a ny:Lon copolymer film barrier having a thickness of 0.008 to 0.3 mtrl and a softening point of 100 to 180C~ a shock-absorbing rubber composition layer containing not less than 50 parts by weight of chlorosulona-ted polyethylene rubber with a chlorine content of not less than 30% by weight per --100 parts by weight of total rubber content and having a thickness of 0.1 to 1.5 mm, and an aclhesive layer of thermoplastic polyester or thermoplastic polyurethane having a thickness of 0.OOS to 0.2 mm and a softening point of ~0 to 200C in this order, and has a total thickness of Q.25 to 3.0 mm.
7~
According to the invention, it is favorable in practice that the outer surface of the mark is pro-tected by providing a protective coating on the surface o~ the chromatic rubber composition layer. Further, it is preferable ~o form an indicative print on the surface of the chroma~ic rubber composition layer from viewpoints of expressiveness, beautiful appearance and labor-saving.
Moreover, the term "chromatic" color -used herein means to be a color having either a lightness or a saturation or both. If the chromatic color has the lightness as in white, gray or the like, it has not necessarily the saturation. And also, if -the chromatic color is black and has a brightness or the like and is different from black color of the tire in the color tone, it may be used as a mark.
The invention will be described in greater de tail below.
In the chromatic rubber composition layer and the shock-absorbing rubber composition layer according to the invention, chloroprene rubber and chlorosulfonated polyethylene rwbber are used as a rubber component because they have a considerably e~cellent weather resistance, ~mong them, the use of chlorosulfonated polyethylene rubber is more preferable because it is excellent in the adhesion to polyester film, nylon copolymer film, thermo-plastic polyester and thermoplastic polyurethane.
The chloroprene rubber is preferable -to have a grade that the crystallization is slow and the change of hardness at low temperature is small. The chloro-
3~ sulfonated polyethylene rubber is preferable to have 7~
a chlorine content o-f ~5 to 43% by weight, preferably 30 to 43/0 by weight. When the chlorine conten-t is less than 25% by weight~ the adhesion to adjoining layers lowers.
In the rubber compositions, at least one of chloroprene rubber and chlorosulfonated polyethylene rubber is compounded in an amount of not less than 30 parts by weight, preferably not less than 50 parts by weight per 100 parts by weight of total rubber content, to which may be aclded at least one diene rubber selected from acryloni-trile-butadiene copolymer rwbber, synthetic polyisoprene rubber, natural rubber, polybutadiene rubber, butadiene-styrene copolymer rubber, butyl rubber, halogenate~ butyl rubber and the like in such an amount that the effect o chloroprene rubber cr chlorosulfonated polyethylene rubber is not damaged.
The chromatic rubber composition layer and the shock-absorbing rubber composition layer are Eavorable -to have a hardness (measured at 30~C by a spring hardness test (A-type~ according to JIS K-6301) of not more than 70 in order to improve the flex resisLance.
These rubber composi-tions may contain a filler for chromatic color such as silicic anhydride, calcium carbonate, magnesium carbonate, talc, iron oxide, bentonite., zinc white, diatomaceous earth, china clay, clay alumina, titanium oxide and ~he like, or may contain additives usually used in rubber industry such as vulcanizing agent, vulcanization accelera-tor~ an-tioxidant~
softener, wax and the like. Furthermore~ they may contain carbon black, if necessary.
In the chlorosulfonated polyethylene rubber i7~
composition, a combination of magnesium oxide ~magnesia~
usually used as a pigment~ thiuram-series vulcanization accelerator and sulfur or a combination of magnesium oxide (magnesia), pentaerythritol, thiuram-series vulcanization accelerator and sulfur is preferably used as a vulcanizing system. In this case, litharge may be used as a metal oxide.
As the thiuram-series vulcanization accelerator, use may be made of accelerator DPTI (dipentamethylene-thiuram tetrasulfide), accelerator TMTD (tetrame~hylthiuram disulfide) and the like.
The shock-absorbing rubber composition layer serves to surface the chromatic rubber composition layer for the improvement of beautiful appearance and to mitigate strain if the rubber article is repeatedly subjected to such a strain. Therefore~ the shock-absorbing rubber composition layer may have the same composition as in the chromatic rubber composition layer if the hardness of the former layer is low, but is most preferable to be macle darlc, particularly black Erom viewpoint o the surfacing of the chromatic rubber composition layer.
The antioxidant-migration film barrier to be used in the invention acts ~o advan-tageously intercept the migration of the staining amine-series antioxidant from the rubber article and is selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film.
As the polyes-ter film are used films produced by using a polyester or a blend of two or more polyester as mentioned below. As the polyester, mention may be 7~
made of polybisphenol A terephthalate, polyethylene terephthalate, polybu~ylene terephthalate, poly-~1,4,7-trioxa-3,3,5,5-tetrafl-uoroheptamethylenecarbonyl-1,3~
phenylenehexafluorotrimethylene-1,3-phenylenecarbonyl), poly-(1,4,7-trioxa-3,3,5,5-tetrafluoroheptamethyleneiso-phthaloyl), poly-(1,4,7-trioxa-3,3,595-tetrafluorohepta-methylene-5-pentyloxyisophthaloyl), poly-(oxyadipoyloxy-2,6-dichloro-1,4-phenyleneisopropylidene-3,5-dichloro~
phenylene), poly-(oxyadipoyloxy-3,3',5,5'-tetramechyl-4,4-biphenylene), poly-(oxyadipoyloxydecamethylene), poly-(oxyadipoyloxy-2,6 dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,4-phenylene), poly-(oxyadi.poyloxy~
phenyleneisopropylidene l,4-phenylene), poly-(oxyadi-poyloxy-2,6-diphenyl-1,4-phenylenemethylene-3,5-diphenyl-1,4-phenylene), poly-(oxy-5-butyl-1,3-phenyleneoxyiso-phthaloyl), poly-(oxydibutyltinoxyadipoyl), poly-(oxydi-butyltinoxyfumaroyl), poly-(oxydibutyltinoxyterephthaloyl), poly-(oxycarbonyl-3,3'-biphenylene-carbonyl.oxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly-(oxycarbonyl-:I,4-~yclohexylenecarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly-(oxycarbonyl-2,6-naph-thylenecarbonyl-oxydecamethylene), poly-(oxyethyleneoxycarbonyl-1,4-cyclo-hexylenecarbonyl), poly-(oxyethyleneoxycarbonyl-2,2'-dimethyl-4,4'-~iphenylenecarbonyl)~ poly-(oxyethyl.eneoxy-carbonyl-1,1,3-trimethylindan-3,5-irene-1,4-phenylene-carbonyl), poly (oxyethyleneoxycarbonyl~1,4-naphthylene-carbonyl), poly-(oxyethyleneoxycarbonyl-1~5-naphthylene-carbonyl), poly-(oxyethyleneoxycarbony~i-2,6-naphthylene-carbonyl~, poly-(oxyethyleneoxycarbonyl-2,7-naphthylene-carbonyl), pol.y-(oxyethyleneoxycarbonyl-1,4-phenylene-9~iL
sec-butylidene-l 7 4-phenylenecarbonyl), poly-(oxyethylene-- oxycarbonyl-1,4-naphthylenecarbonyl), poly(oxyethylene-oxycarbonyl-1,5-naphthylenecarbonyl), poly-(oxyethylene-oxycarbonyl-2,6-naphthylenecarbonyl), poly-(oxyethylene-oxyisophthaloyl), poly-(oxy-5-ethyl-1~3-phenyleneoxyiso-phthaloyl), poly-~oxyisophthaloyloxy-2-methyl-1,4-phenyleneisopropylidene-3-methyl-1,4-phenylene), poly-(oxy-2,2,~,4-tetramethyl~1,3-cyclobutyleneoxycarbonyl-trans-1,4-cyclohexylenecarbonyl~, poly-(oxy-5-methyl-1,3-phenyleneoxyisoph-thaloyl), poly-~oxyterephthaloyloxy-methylene-1,4-cyclohexylenemethylene), poly-(oxytere-phthaloyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) and the like.
Among these polyester films~ -the use of poly-ethylene terephthalate is most preferable in view of the balance between the film strength and the effect of intercepting antioxidant migra-tion.
As the nylon film, use may be made of nylon-6 film, nylon-6,6 film, nylon~ Eilm, nylon-12 film, ny:lon copolymer film and the like.
The nylon copolymer :Eilm is obt.ained by polymerizing two or more nylon homopolymers, and basical]y by co-condensation polymerization of caprolactam with at least one other nylon salt. As the other nylon salt are used nylon-6,6 salt, nylon-6,10 salt and the like.
The nylon copolymer film is preferably used as the antioxidant-migration film barrier because i-t is high in the flexibility due to the drop of crystallizability and good in the adhesion to the chromatic rubber composition 3Q layer and the shock-absorbing rubber com-position layer.
According ~o the invention, the -thermoplastic polyure~hane or thermoplas~ic polyester is laminated on either side of ~he antioxidan~-migration film barrier to form an aflhesive layer for r-ubber article or rubber composition layer, which serves not only for the bonding between the chromatic rubber c~mposition layer and the antioxidant-migration film barrier and the bonding between the mark and the rubber article, but also to mitigate permanent strain applied to the antioxidant~migration film barrier. In the lat~er case9 when the rubber article is subjected to repetitive strain, residual strain (or permanent strain) remains only in the antioxidant-migration film barrier of the mark bonded to the rubber article because this barrier has no rubbery elasticity and as a result, i-f compression strain is applied to both ends of the mark, small wrinkles are produced in the barrier, so that it is necessary to use ~he thermoplastic polyurethane or thermoplastic polyester having a flexible rubbery elasticity capable of sufficiently following ~o the occurrence of wrinkles.
Therefore, the thermoplastic polyurethane or polyester is preferable to have a hardness at 30C within a range of 60 to 96. Furthermore, -the thermoplastic polyurethane or polyes~er is preferabl~ to have a softening point of 80C to 200C. When the softening point is less than 80C, it is apt to cause the peeling at boundary between the rubber article and the mark if ~he tempera-t-ure of the rubber article rises to 70-80C For instance, when the rubber article is a tire, it is possible that the temperature of the adhesive joint reaches to 60-70C
' 10 -during the rwnning of -the tire exposed to light in summer season, so that there is a fear of producing the peeling of the mark from the tire. On the other hand, when the softening point exceeds 200~C, the hardness may become too high. Furthermore, the temperature of 200C is an upper limit for readily performing the sticking of the mark in general homes, above which the surface of -the rubber article is deterioratecl.
According to the invention, the thermoplastic polyester having the aforementioned softening point range is a single polyester or a blend of polyesters. In the thermoplastic polyester blend, the control of the softening point can be performed by properly selecting the blend ratio of polyesters, for exalTlple 9 the blend ratio of polyethylene terephthalate, polybutylene terephthalate and polyethylene isophthalate. Particularly, when using a polyester having a low softening point, -the control of ~he softening point is perEormed by adding thereto a liquid polyester (trade name: Sansosizer P-1500A, made by Shinnippon Rika K.K.).
In the thermoplastic polyurethane, the softening point is usually controlled by changing the molecular weight of the polyurethane. Moreover, the control of the softening point may be performed by changing the branching degree of the molecular chain or by properly blending few kinds of polyure-thanes.
Alternatively, the softening point and hardness of the thermoplastic polyester or polyurethane may be controlled by the addition of a plasticizer~ a filler and the like.
In the mark according to the invention, an adhesive may be used between the adjoining layers such as chromatic rubber composition layer, antioxidant-migration film barrier, adhesive layer of thermoplastic polyurethane or polyester and the like. For instance, when a combination of phenol resin and nitrile ru'bber or a combination of phenol resin and neoprene is ~sed as the adhesive between the polyester film and the thermoplastic polyester layer, the bonding power is considerably increased.
The invention will be described in detail with reference to the accompanying drawings, wherein:
Fig. l is a partially perspective view of an embodiment of the tire provided with t'he mark according to the invention;
Fig. 2 is a perspective view of an embodiment of the mark according to the invention;
Figs. 3 to 6 are sectional views of various embodiments of the mark according to the invention, respectively; and Figs. 7 and 8 are sectional views of embodiments of the mark according to the prior art, respectively.
In Fig. 1 is`shown an embodiment of applying a mark 1 as shown, for example, in Fig. 2 to a sidewall of a tire. Such a mark l has a laminate structure of 3 to 6 layers as shown in Figs. 3 to 6. E'or instance, the mark l of Fig. 3 has a four-layer structure o'btained by laminating a chromatic rubber composition layer 2, an adhesive layer 3 of thermoplastic polyurethane or thermoplastic polyester, an antioxidant-migration film barrier 4 and an adhesive layer 6 in this order viewed from the outer surface of the mark, while the mark 1 of Fig. 4 has a six-layer structure obtained by laminating a chromatic rubber composition layer 2, an adhesive layer 3, an antioxidant-migration film barrier 4, an adhesive layer 3t, a shock-absorbing rwbber composition layer 5 and an adhesive layer 6 in this order.
According to the invention, the mark 1 is bonded to the surace of the rubber article 7 by heating under pressure through the adhesive layer 6 of thermo-plastic polyurethane or polyester. In this case, the bonding between the mark and the rubber article i5 perfonned at a temperature above 100C under pressure by a proper heating means such as heat press, radiation, laser, infrared ray or the like.
In the mark according to the invention, the reason why the thickness of each layer constituting the mark and the total thickness of these layers are limited to the ranges as previously mentioned is as fol]ows.
The chromatic rubber composition layer 2 has a thickness of 0.1 to 1.0 mm. When the thickness is less than 0.1 mm, the handling is possible in laboratory but very difficult in industry. While, when the thickness exceeds 1.0 mm, not only the production cost becomes vainly higher, but also the total thickness of the mark becomes excessive, so that it is not favorable in view of industrialization and beau~iful appearance.
As the antioxidan-t-migration film barrier 4 is used the film having a high modulus of elasticity as previously mentioned. Thereforeg when using the film having a thickness of more -than 100 ~m, if the rubber article provided with the mark is s-ubjected to repetitive strain, cracks occur in the boundary between the mark and the rubber article and grow therefrom. On the other hand, when the thickness is less than 3 ~m, the film strength becomes ~oo low and there is a high risk of producing the breaking of the film during the manufacture of the mark. For -this reason, the thickness of the antioxidant migration film barrier should be within a range of 3 to 100 ~m. Preferably, the thickness of this barrier is 3 to 15 ~m in view of the flex resistance of the mark.
The thickness of the adhesive layer 3, 3', 6 composed of thermoplastic polyester or polyurethane is 0.005 to 0.5 mm, preferably 0.005 to 0.2 mrn) more particularly 0.01 to 0.03 mm. When the thickness is less than 0.005 mm, satisfactory bonding power cannot be obtained, while when the thickness exceecls 0.5 mm, extra amount of the thermoplastic polyester or poly~lrethane 2~ sticks out of the mark during the heat bonding, resulting in the dama~e of the beautiful appearance.
The shock-absorbing rubber composition layer 5 has a thickness of 0.1 to 1.5 mm. I~hen the thickness is less than 0.1 mm~ the two func-tions as men-tioned above cannot be achieved, while when the thickness exceeds 1.5 ~m, strain-mitigating effect is sufficiently satisfied, but the thickness itself becomes excessiveS resulting in ~.he damage of the beautiful appearance and the increase of the production cost.
The mark according to the invention has a total ~1~85~
thickness of 0.25 ~o 3.0 mm. When the total thickness is less than 0.25 mm, the mark is deficient in the three-dimensional appearance, while when the total thickness exceeds 3.0 mm, not only the production cost becomes vainly higher, but also the mark is liable to suffer external damages in view of the beautiful appearance.
For instance, when the mark is applied to the tire, the total thickness is most preferable to be about 0.4 to 1.2 mm.
As the another embodiments of the invention~
the mark of Fig. 5 has a three-layer structure obtained by laminating a chromatic rubber composition layer 2, an antioxidant-migration film barrier 4 and an adhesive layer 6 in this order viewed -from -the outer su~face of the mark, while the mark of Fig. 6 has a four-layer structure obtained by laminating a chromatic rubber composition layer 2, an antioxidant-migration film barrier
a chlorine content o-f ~5 to 43% by weight, preferably 30 to 43/0 by weight. When the chlorine conten-t is less than 25% by weight~ the adhesion to adjoining layers lowers.
In the rubber compositions, at least one of chloroprene rubber and chlorosulfonated polyethylene rubber is compounded in an amount of not less than 30 parts by weight, preferably not less than 50 parts by weight per 100 parts by weight of total rubber content, to which may be aclded at least one diene rubber selected from acryloni-trile-butadiene copolymer rwbber, synthetic polyisoprene rubber, natural rubber, polybutadiene rubber, butadiene-styrene copolymer rubber, butyl rubber, halogenate~ butyl rubber and the like in such an amount that the effect o chloroprene rubber cr chlorosulfonated polyethylene rubber is not damaged.
The chromatic rubber composition layer and the shock-absorbing rubber composition layer are Eavorable -to have a hardness (measured at 30~C by a spring hardness test (A-type~ according to JIS K-6301) of not more than 70 in order to improve the flex resisLance.
These rubber composi-tions may contain a filler for chromatic color such as silicic anhydride, calcium carbonate, magnesium carbonate, talc, iron oxide, bentonite., zinc white, diatomaceous earth, china clay, clay alumina, titanium oxide and ~he like, or may contain additives usually used in rubber industry such as vulcanizing agent, vulcanization accelera-tor~ an-tioxidant~
softener, wax and the like. Furthermore~ they may contain carbon black, if necessary.
In the chlorosulfonated polyethylene rubber i7~
composition, a combination of magnesium oxide ~magnesia~
usually used as a pigment~ thiuram-series vulcanization accelerator and sulfur or a combination of magnesium oxide (magnesia), pentaerythritol, thiuram-series vulcanization accelerator and sulfur is preferably used as a vulcanizing system. In this case, litharge may be used as a metal oxide.
As the thiuram-series vulcanization accelerator, use may be made of accelerator DPTI (dipentamethylene-thiuram tetrasulfide), accelerator TMTD (tetrame~hylthiuram disulfide) and the like.
The shock-absorbing rubber composition layer serves to surface the chromatic rubber composition layer for the improvement of beautiful appearance and to mitigate strain if the rubber article is repeatedly subjected to such a strain. Therefore~ the shock-absorbing rubber composition layer may have the same composition as in the chromatic rubber composition layer if the hardness of the former layer is low, but is most preferable to be macle darlc, particularly black Erom viewpoint o the surfacing of the chromatic rubber composition layer.
The antioxidant-migration film barrier to be used in the invention acts ~o advan-tageously intercept the migration of the staining amine-series antioxidant from the rubber article and is selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film.
As the polyes-ter film are used films produced by using a polyester or a blend of two or more polyester as mentioned below. As the polyester, mention may be 7~
made of polybisphenol A terephthalate, polyethylene terephthalate, polybu~ylene terephthalate, poly-~1,4,7-trioxa-3,3,5,5-tetrafl-uoroheptamethylenecarbonyl-1,3~
phenylenehexafluorotrimethylene-1,3-phenylenecarbonyl), poly-(1,4,7-trioxa-3,3,5,5-tetrafluoroheptamethyleneiso-phthaloyl), poly-(1,4,7-trioxa-3,3,595-tetrafluorohepta-methylene-5-pentyloxyisophthaloyl), poly-(oxyadipoyloxy-2,6-dichloro-1,4-phenyleneisopropylidene-3,5-dichloro~
phenylene), poly-(oxyadipoyloxy-3,3',5,5'-tetramechyl-4,4-biphenylene), poly-(oxyadipoyloxydecamethylene), poly-(oxyadipoyloxy-2,6 dimethyl-1,4-phenyleneisopropylidene-3,5-dimethyl-1,4-phenylene), poly-(oxyadi.poyloxy~
phenyleneisopropylidene l,4-phenylene), poly-(oxyadi-poyloxy-2,6-diphenyl-1,4-phenylenemethylene-3,5-diphenyl-1,4-phenylene), poly-(oxy-5-butyl-1,3-phenyleneoxyiso-phthaloyl), poly-(oxydibutyltinoxyadipoyl), poly-(oxydi-butyltinoxyfumaroyl), poly-(oxydibutyltinoxyterephthaloyl), poly-(oxycarbonyl-3,3'-biphenylene-carbonyl.oxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly-(oxycarbonyl-:I,4-~yclohexylenecarbonyloxy-1,4-phenyleneisopropylidene-1,4-phenylene), poly-(oxycarbonyl-2,6-naph-thylenecarbonyl-oxydecamethylene), poly-(oxyethyleneoxycarbonyl-1,4-cyclo-hexylenecarbonyl), poly-(oxyethyleneoxycarbonyl-2,2'-dimethyl-4,4'-~iphenylenecarbonyl)~ poly-(oxyethyl.eneoxy-carbonyl-1,1,3-trimethylindan-3,5-irene-1,4-phenylene-carbonyl), poly (oxyethyleneoxycarbonyl~1,4-naphthylene-carbonyl), poly-(oxyethyleneoxycarbonyl-1~5-naphthylene-carbonyl), poly-(oxyethyleneoxycarbony~i-2,6-naphthylene-carbonyl~, poly-(oxyethyleneoxycarbonyl-2,7-naphthylene-carbonyl), pol.y-(oxyethyleneoxycarbonyl-1,4-phenylene-9~iL
sec-butylidene-l 7 4-phenylenecarbonyl), poly-(oxyethylene-- oxycarbonyl-1,4-naphthylenecarbonyl), poly(oxyethylene-oxycarbonyl-1,5-naphthylenecarbonyl), poly-(oxyethylene-oxycarbonyl-2,6-naphthylenecarbonyl), poly-(oxyethylene-oxyisophthaloyl), poly-(oxy-5-ethyl-1~3-phenyleneoxyiso-phthaloyl), poly-~oxyisophthaloyloxy-2-methyl-1,4-phenyleneisopropylidene-3-methyl-1,4-phenylene), poly-(oxy-2,2,~,4-tetramethyl~1,3-cyclobutyleneoxycarbonyl-trans-1,4-cyclohexylenecarbonyl~, poly-(oxy-5-methyl-1,3-phenyleneoxyisoph-thaloyl), poly-~oxyterephthaloyloxy-methylene-1,4-cyclohexylenemethylene), poly-(oxytere-phthaloyloxy-1,4-phenyleneisopropylidene-1,4-phenylene) and the like.
Among these polyester films~ -the use of poly-ethylene terephthalate is most preferable in view of the balance between the film strength and the effect of intercepting antioxidant migra-tion.
As the nylon film, use may be made of nylon-6 film, nylon-6,6 film, nylon~ Eilm, nylon-12 film, ny:lon copolymer film and the like.
The nylon copolymer :Eilm is obt.ained by polymerizing two or more nylon homopolymers, and basical]y by co-condensation polymerization of caprolactam with at least one other nylon salt. As the other nylon salt are used nylon-6,6 salt, nylon-6,10 salt and the like.
The nylon copolymer film is preferably used as the antioxidant-migration film barrier because i-t is high in the flexibility due to the drop of crystallizability and good in the adhesion to the chromatic rubber composition 3Q layer and the shock-absorbing rubber com-position layer.
According ~o the invention, the -thermoplastic polyure~hane or thermoplas~ic polyester is laminated on either side of ~he antioxidan~-migration film barrier to form an aflhesive layer for r-ubber article or rubber composition layer, which serves not only for the bonding between the chromatic rubber c~mposition layer and the antioxidant-migration film barrier and the bonding between the mark and the rubber article, but also to mitigate permanent strain applied to the antioxidant~migration film barrier. In the lat~er case9 when the rubber article is subjected to repetitive strain, residual strain (or permanent strain) remains only in the antioxidant-migration film barrier of the mark bonded to the rubber article because this barrier has no rubbery elasticity and as a result, i-f compression strain is applied to both ends of the mark, small wrinkles are produced in the barrier, so that it is necessary to use ~he thermoplastic polyurethane or thermoplastic polyester having a flexible rubbery elasticity capable of sufficiently following ~o the occurrence of wrinkles.
Therefore, the thermoplastic polyurethane or polyester is preferable to have a hardness at 30C within a range of 60 to 96. Furthermore, -the thermoplastic polyurethane or polyes~er is preferabl~ to have a softening point of 80C to 200C. When the softening point is less than 80C, it is apt to cause the peeling at boundary between the rubber article and the mark if ~he tempera-t-ure of the rubber article rises to 70-80C For instance, when the rubber article is a tire, it is possible that the temperature of the adhesive joint reaches to 60-70C
' 10 -during the rwnning of -the tire exposed to light in summer season, so that there is a fear of producing the peeling of the mark from the tire. On the other hand, when the softening point exceeds 200~C, the hardness may become too high. Furthermore, the temperature of 200C is an upper limit for readily performing the sticking of the mark in general homes, above which the surface of -the rubber article is deterioratecl.
According to the invention, the thermoplastic polyester having the aforementioned softening point range is a single polyester or a blend of polyesters. In the thermoplastic polyester blend, the control of the softening point can be performed by properly selecting the blend ratio of polyesters, for exalTlple 9 the blend ratio of polyethylene terephthalate, polybutylene terephthalate and polyethylene isophthalate. Particularly, when using a polyester having a low softening point, -the control of ~he softening point is perEormed by adding thereto a liquid polyester (trade name: Sansosizer P-1500A, made by Shinnippon Rika K.K.).
In the thermoplastic polyurethane, the softening point is usually controlled by changing the molecular weight of the polyurethane. Moreover, the control of the softening point may be performed by changing the branching degree of the molecular chain or by properly blending few kinds of polyure-thanes.
Alternatively, the softening point and hardness of the thermoplastic polyester or polyurethane may be controlled by the addition of a plasticizer~ a filler and the like.
In the mark according to the invention, an adhesive may be used between the adjoining layers such as chromatic rubber composition layer, antioxidant-migration film barrier, adhesive layer of thermoplastic polyurethane or polyester and the like. For instance, when a combination of phenol resin and nitrile ru'bber or a combination of phenol resin and neoprene is ~sed as the adhesive between the polyester film and the thermoplastic polyester layer, the bonding power is considerably increased.
The invention will be described in detail with reference to the accompanying drawings, wherein:
Fig. l is a partially perspective view of an embodiment of the tire provided with t'he mark according to the invention;
Fig. 2 is a perspective view of an embodiment of the mark according to the invention;
Figs. 3 to 6 are sectional views of various embodiments of the mark according to the invention, respectively; and Figs. 7 and 8 are sectional views of embodiments of the mark according to the prior art, respectively.
In Fig. 1 is`shown an embodiment of applying a mark 1 as shown, for example, in Fig. 2 to a sidewall of a tire. Such a mark l has a laminate structure of 3 to 6 layers as shown in Figs. 3 to 6. E'or instance, the mark l of Fig. 3 has a four-layer structure o'btained by laminating a chromatic rubber composition layer 2, an adhesive layer 3 of thermoplastic polyurethane or thermoplastic polyester, an antioxidant-migration film barrier 4 and an adhesive layer 6 in this order viewed from the outer surface of the mark, while the mark 1 of Fig. 4 has a six-layer structure obtained by laminating a chromatic rubber composition layer 2, an adhesive layer 3, an antioxidant-migration film barrier 4, an adhesive layer 3t, a shock-absorbing rwbber composition layer 5 and an adhesive layer 6 in this order.
According to the invention, the mark 1 is bonded to the surace of the rubber article 7 by heating under pressure through the adhesive layer 6 of thermo-plastic polyurethane or polyester. In this case, the bonding between the mark and the rubber article i5 perfonned at a temperature above 100C under pressure by a proper heating means such as heat press, radiation, laser, infrared ray or the like.
In the mark according to the invention, the reason why the thickness of each layer constituting the mark and the total thickness of these layers are limited to the ranges as previously mentioned is as fol]ows.
The chromatic rubber composition layer 2 has a thickness of 0.1 to 1.0 mm. When the thickness is less than 0.1 mm, the handling is possible in laboratory but very difficult in industry. While, when the thickness exceeds 1.0 mm, not only the production cost becomes vainly higher, but also the total thickness of the mark becomes excessive, so that it is not favorable in view of industrialization and beau~iful appearance.
As the antioxidan-t-migration film barrier 4 is used the film having a high modulus of elasticity as previously mentioned. Thereforeg when using the film having a thickness of more -than 100 ~m, if the rubber article provided with the mark is s-ubjected to repetitive strain, cracks occur in the boundary between the mark and the rubber article and grow therefrom. On the other hand, when the thickness is less than 3 ~m, the film strength becomes ~oo low and there is a high risk of producing the breaking of the film during the manufacture of the mark. For -this reason, the thickness of the antioxidant migration film barrier should be within a range of 3 to 100 ~m. Preferably, the thickness of this barrier is 3 to 15 ~m in view of the flex resistance of the mark.
The thickness of the adhesive layer 3, 3', 6 composed of thermoplastic polyester or polyurethane is 0.005 to 0.5 mm, preferably 0.005 to 0.2 mrn) more particularly 0.01 to 0.03 mm. When the thickness is less than 0.005 mm, satisfactory bonding power cannot be obtained, while when the thickness exceecls 0.5 mm, extra amount of the thermoplastic polyester or poly~lrethane 2~ sticks out of the mark during the heat bonding, resulting in the dama~e of the beautiful appearance.
The shock-absorbing rubber composition layer 5 has a thickness of 0.1 to 1.5 mm. I~hen the thickness is less than 0.1 mm~ the two func-tions as men-tioned above cannot be achieved, while when the thickness exceeds 1.5 ~m, strain-mitigating effect is sufficiently satisfied, but the thickness itself becomes excessiveS resulting in ~.he damage of the beautiful appearance and the increase of the production cost.
The mark according to the invention has a total ~1~85~
thickness of 0.25 ~o 3.0 mm. When the total thickness is less than 0.25 mm, the mark is deficient in the three-dimensional appearance, while when the total thickness exceeds 3.0 mm, not only the production cost becomes vainly higher, but also the mark is liable to suffer external damages in view of the beautiful appearance.
For instance, when the mark is applied to the tire, the total thickness is most preferable to be about 0.4 to 1.2 mm.
As the another embodiments of the invention~
the mark of Fig. 5 has a three-layer structure obtained by laminating a chromatic rubber composition layer 2, an antioxidant-migration film barrier 4 and an adhesive layer 6 in this order viewed -from -the outer su~face of the mark, while the mark of Fig. 6 has a four-layer structure obtained by laminating a chromatic rubber composition layer 2, an antioxidant-migration film barrier
4, a shock-absorbing rubber composition layer 5 and an adhesive layer 6 in this order.
In case of applying no adhesive layer to either side of the antioxidant~migration film barrier 4 as shown in Fig. 6, nylon copolymer film is preferably use~ as the barrier 4 because the nylon copolymer film is an antioxidant-migration barrier having high flexibility and crack propagation resistance. ~hen usi~g the nylon copolymer film, the thickness of the barrier should be within a range of 0.003 to 0.3 mm. When the thickness is less than 0.003 ~m, the migration of the antioxidant cannot sufficiently be intercepted~ while when the thickness exceeds 0.3 mm, the tensile force of the film itself &~
becomes too large and the stress concentration is increased when the rubber article is subjected to repetiti.ve strain and consequently there is cawsed the peeling between the nylon copolymer film barrier 4 and the shock-absorbing rubher composition layer 5. Moreover, the thickness of the nyl.on copolymer film is preferable within a range of 0.008 to 0.3 ~ because when the th;.ckness is less than 0.008 mm, the nylon copolymer film is apt to stick to rol].s or -the like and becomes bad in the workability.
The lamination of the chromatic r-ubber composi-ti.on layer 2, nylon copolymer film barrier 4 and the shock-absorbing rubber composit~on layer S may easily be performed, for example, by press cwring or the like, and also the lamination of the shock-absorbing rubber composi-tion layer 5 to the adhesive layer 6 may easily be performed by roll press or the like. Moreover, the lamination of these layers can be carried out by many well-known methods in addition to the above lami.nation method.
As apparent from the above, the marks for use in rubber articles according to the invention have another significant merit that the industrial production thereof can be performed in the absence of a solvent. ~ecause, when a solvent type adhesive is applied to the surface of each of the layers constituting -the mark~ it is very difficult ~o obtain a laminate having a uniform thickness due to the swelling o:E the layer with solvent.
The mark 1 according to the invention may be bonded to the rubber article 7 as follows: tha-t is, a surface portion of the rubber artlcle 7 to be bonded with the mark 1 is first treated with a surface-treating liquid such as a solution of N,N'-dichlorosulfonamide compound in acetone or ~he like and then the adhesive layer 6 of the mark 1 is contacted with the treated surface portion of the rubber article 7 and heat-pressed thereto by means of a hot iron. The temperature of the iron is usually within a range of 150 to 200C, but it is not intended as limitation thereof.
According to the invention, the hardness is measured by a spring hardness test (A-type) according to JIS K-6301, and the softening point of nylon copolymer, thermoplastic polyurethane or thermoplastic polyester is measured by a Vicat softening temperature -test according to JIS K-7~06 under the following conditions:
Measuring device : thermomechanical analyzer ~TMA-TMS-l~ UU-l), made by Perkin Elmer Corp.
Temperature rising ra-te : 0.62C/min Sample form : cubic body of
In case of applying no adhesive layer to either side of the antioxidant~migration film barrier 4 as shown in Fig. 6, nylon copolymer film is preferably use~ as the barrier 4 because the nylon copolymer film is an antioxidant-migration barrier having high flexibility and crack propagation resistance. ~hen usi~g the nylon copolymer film, the thickness of the barrier should be within a range of 0.003 to 0.3 mm. When the thickness is less than 0.003 ~m, the migration of the antioxidant cannot sufficiently be intercepted~ while when the thickness exceeds 0.3 mm, the tensile force of the film itself &~
becomes too large and the stress concentration is increased when the rubber article is subjected to repetiti.ve strain and consequently there is cawsed the peeling between the nylon copolymer film barrier 4 and the shock-absorbing rubher composition layer 5. Moreover, the thickness of the nyl.on copolymer film is preferable within a range of 0.008 to 0.3 ~ because when the th;.ckness is less than 0.008 mm, the nylon copolymer film is apt to stick to rol].s or -the like and becomes bad in the workability.
The lamination of the chromatic r-ubber composi-ti.on layer 2, nylon copolymer film barrier 4 and the shock-absorbing rubber composit~on layer S may easily be performed, for example, by press cwring or the like, and also the lamination of the shock-absorbing rubber composi-tion layer 5 to the adhesive layer 6 may easily be performed by roll press or the like. Moreover, the lamination of these layers can be carried out by many well-known methods in addition to the above lami.nation method.
As apparent from the above, the marks for use in rubber articles according to the invention have another significant merit that the industrial production thereof can be performed in the absence of a solvent. ~ecause, when a solvent type adhesive is applied to the surface of each of the layers constituting -the mark~ it is very difficult ~o obtain a laminate having a uniform thickness due to the swelling o:E the layer with solvent.
The mark 1 according to the invention may be bonded to the rubber article 7 as follows: tha-t is, a surface portion of the rubber artlcle 7 to be bonded with the mark 1 is first treated with a surface-treating liquid such as a solution of N,N'-dichlorosulfonamide compound in acetone or ~he like and then the adhesive layer 6 of the mark 1 is contacted with the treated surface portion of the rubber article 7 and heat-pressed thereto by means of a hot iron. The temperature of the iron is usually within a range of 150 to 200C, but it is not intended as limitation thereof.
According to the invention, the hardness is measured by a spring hardness test (A-type) according to JIS K-6301, and the softening point of nylon copolymer, thermoplastic polyurethane or thermoplastic polyester is measured by a Vicat softening temperature -test according to JIS K-7~06 under the following conditions:
Measuring device : thermomechanical analyzer ~TMA-TMS-l~ UU-l), made by Perkin Elmer Corp.
Temperature rising ra-te : 0.62C/min Sample form : cubic body of
5 mm side Indenter : column with a sectional area of 1.000~0.015 mm~
(contact surface of column top is flat) Load : It is adjustecl to apply a pressure of 20 g/~n2 to the inden-ter top.
In the latter case, the softening temperature is defined by a temperature when the indenter is entered into the sample by 1 ~n.
The following examples are given in illustration of the invention and are not intended as limitations 9;7~
there~f.
In these examples, properties on the marlc were evaluated by the following test methods.
1~ Drum test for crack propagation resistance The tire provided with the mark and subjected to an internal pressure oE 1.7 kg/cm2 was run on a drum at a speed of 60 km/hr under JIS 130%
load over a clistance of 20,000 km. Thereafter, the presence of cracks was observed at the mark and the boundary between the mark and the tire.
2~ Stainproof test The tire provided with the mark was left to stand in a ventilatable oven at ~0C for one week and then exposed to a ultraviolet ray with a xenon lamp of 500 W output. Thereafter, the presence of color failure of the mark was observed.
3) Durability test The tire (tire size: 165 SR 13) provided with 10 marks per tire was mounted to a passenge-r car with a displacement of 1~500 CC9 which was run over a distance of 41,330 km. Thereafter, the presence of mark peeling was observed. The property was evaluated by the number of tires exhibiting the partial or whole mark peeling.
4~ Drum test under low internal pressure The tire provided with 10 marks per tire and subjected to an internal press-wre of 1.2 kg/cm2 wa~ run on a drum a-t a speed of 60 km/hr under JIS
100% load over a distance of 20,000 km. Thereafter, the presence of cracking of mark and cracking at -the boundary between the mar'k and the tire sidewall was observed.
Examples 1 to 10, Prior Art 1 to 2 At first, there were prepared five rubber compositions having a compounding recipe (unit: par-t by weight) as shown in the following Table l. The white rubber compositions of Rubber Composition Nos. 1 and 2 were used in a chromatic rubber composi~ion layer, while the carbon black-containing rubber compositions of Kubber Composition Nos. 3 to 5 were used in a shock-absorbing rubber composition layer.
The materials and trade names of the antioxidant-migration film layer and adhesive layer to be used were shown in the following Table 2.
lS Then, twelve marks as shown in the following Table 3 were manufac-twred by using the materials of Tables l and 2.
In Examples l to 4, the laminate sheet for the mar'k was o'btained by bonding the adhesive layer having a predetermined thick~ess to the rubber composition sheet press-cured into a predetermined thickness at 155C for 30 minutes and the antioxiclant-migration film 'barrier having a predetermined thickness wi-th hot rolls.
'Ln Examples 5 and 6 9 the laminate sheet for the mark was obtained by adhering the antioxidan~-migration film barrier to the uncured white rubber composition, press-curing it into a predetermined thickness at 155C
for 30 minutes, and bonding the adhesive layer thereto with hot rolls.
Ln Examples 7 to 10, the laminate sheet for the 3~ ~
mark was obtained by adhering the antioxidant-migration film barrier and uncured shock-absorbing ru~ber composition to the uncured white rubber composition, press-curing it into a predetermined thi.ckness at 155C for 30 mi.nutes, and bonding the adhesive layer thereto with hot rolls.
In the prior art 13 the laminate sheet for the mark was obtained by bonding the thermoplastic polyurethane having a thickness of 20 ~m to the white ru~ber composition sheet press-cured into a thickness of 0.7 ~m at 155~C for 30 minutes with ho-t rolls.
In the prior art 2, the laminate sheet for the mark was obtained by adhering aluminum foil to the uncurecl shock-absorbing rubber composition, press-curing it at 155C for 30 minutes and bonding the thermoplastic poly-urethane having a thickness of 20 ~m thereto with hot rolls.
Then, marks were manufactured by stamping out circle bodies of 30 mm diameter from each of these laminate sheets with a knife.
The thus obtained marks were heat-bondecl to a sidewall of a radial tire for passenger car in an amount of 10 marks per tire by means of an iron heated at 160C.
In this case, the sidewall of the radial tire for passenger car (tire size: 165 S~ 13) was previously treated with a surface-treating liquid consisting of a solution of N,N'-dichlorobenzene sulfonamide in acetone as disclosed in Japanese Patent Application Publication No. 36,910/77 prior to the heat bonding of the mark.
The drum test for crack propagation resistance, stainproof test, durability test and drum test under low 3 ~ 7~
internal pressure as previously mentioned were made with respect to each of twelve tires provided wi-th ~he mark to obtain results as shown in Table 3.
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In the marks, particularly chromatic mark according to the invent;.on, the migration of antioxidant from rubber article is substantially completely prevented by using polyester film, nylon ~ilm~ vinylidene chloride film or vinylidene chloride-vinyl chloride copolymer film which considerably advantageously prevents the migration of staining antioxidant, particularly a~ine-series antioxidant. Furthermore, this film has a swfEicient performance of preventing the migrati.on of antioxi.dant even when the thickness is fairly thin, so that the thickness and rigidity of the mark as a whole can be reduced. As a result, not only the beautiful appearance but also the flex resistance, resistance to external damage and resistance to peeling from rubber article are considerably improved, and also the weather resistance is excellent.
Furthermore, according to the invention, the chromatic rubber composition layer (2), anti.oxidant-migration film barrier (4), shock-absorbing -rubber compos.ition layer (5) and adhesive layer (3, 3', 6), each of w:hich having excellent functional proper~ies, are properly combined into a laminate structwre of 3 to 6 layers, whereby the flex resistance and weather resis-tance, which have never been improved in the prior art, are considerably advantageously improved in addition to the improvement of beautiful appearance and the prevention o:E
color failure, and also the bonding treatment can simply be performed.
The marks according to the invention are preferable as decoration for tires, particularly radial 7~
tires for passenger cars, but may be widely applied ~o rubber articles requiring a flex resistance, such as large hoses, conveyor belts, belts for power transmission, oil fences and the like.
s
(contact surface of column top is flat) Load : It is adjustecl to apply a pressure of 20 g/~n2 to the inden-ter top.
In the latter case, the softening temperature is defined by a temperature when the indenter is entered into the sample by 1 ~n.
The following examples are given in illustration of the invention and are not intended as limitations 9;7~
there~f.
In these examples, properties on the marlc were evaluated by the following test methods.
1~ Drum test for crack propagation resistance The tire provided with the mark and subjected to an internal pressure oE 1.7 kg/cm2 was run on a drum at a speed of 60 km/hr under JIS 130%
load over a clistance of 20,000 km. Thereafter, the presence of cracks was observed at the mark and the boundary between the mark and the tire.
2~ Stainproof test The tire provided with the mark was left to stand in a ventilatable oven at ~0C for one week and then exposed to a ultraviolet ray with a xenon lamp of 500 W output. Thereafter, the presence of color failure of the mark was observed.
3) Durability test The tire (tire size: 165 SR 13) provided with 10 marks per tire was mounted to a passenge-r car with a displacement of 1~500 CC9 which was run over a distance of 41,330 km. Thereafter, the presence of mark peeling was observed. The property was evaluated by the number of tires exhibiting the partial or whole mark peeling.
4~ Drum test under low internal pressure The tire provided with 10 marks per tire and subjected to an internal press-wre of 1.2 kg/cm2 wa~ run on a drum a-t a speed of 60 km/hr under JIS
100% load over a distance of 20,000 km. Thereafter, the presence of cracking of mark and cracking at -the boundary between the mar'k and the tire sidewall was observed.
Examples 1 to 10, Prior Art 1 to 2 At first, there were prepared five rubber compositions having a compounding recipe (unit: par-t by weight) as shown in the following Table l. The white rubber compositions of Rubber Composition Nos. 1 and 2 were used in a chromatic rubber composi~ion layer, while the carbon black-containing rubber compositions of Kubber Composition Nos. 3 to 5 were used in a shock-absorbing rubber composition layer.
The materials and trade names of the antioxidant-migration film layer and adhesive layer to be used were shown in the following Table 2.
lS Then, twelve marks as shown in the following Table 3 were manufac-twred by using the materials of Tables l and 2.
In Examples l to 4, the laminate sheet for the mar'k was o'btained by bonding the adhesive layer having a predetermined thick~ess to the rubber composition sheet press-cured into a predetermined thickness at 155C for 30 minutes and the antioxiclant-migration film 'barrier having a predetermined thickness wi-th hot rolls.
'Ln Examples 5 and 6 9 the laminate sheet for the mark was obtained by adhering the antioxidan~-migration film barrier to the uncured white rubber composition, press-curing it into a predetermined thickness at 155C
for 30 minutes, and bonding the adhesive layer thereto with hot rolls.
Ln Examples 7 to 10, the laminate sheet for the 3~ ~
mark was obtained by adhering the antioxidant-migration film barrier and uncured shock-absorbing ru~ber composition to the uncured white rubber composition, press-curing it into a predetermined thi.ckness at 155C for 30 mi.nutes, and bonding the adhesive layer thereto with hot rolls.
In the prior art 13 the laminate sheet for the mark was obtained by bonding the thermoplastic polyurethane having a thickness of 20 ~m to the white ru~ber composition sheet press-cured into a thickness of 0.7 ~m at 155~C for 30 minutes with ho-t rolls.
In the prior art 2, the laminate sheet for the mark was obtained by adhering aluminum foil to the uncurecl shock-absorbing rubber composition, press-curing it at 155C for 30 minutes and bonding the thermoplastic poly-urethane having a thickness of 20 ~m thereto with hot rolls.
Then, marks were manufactured by stamping out circle bodies of 30 mm diameter from each of these laminate sheets with a knife.
The thus obtained marks were heat-bondecl to a sidewall of a radial tire for passenger car in an amount of 10 marks per tire by means of an iron heated at 160C.
In this case, the sidewall of the radial tire for passenger car (tire size: 165 S~ 13) was previously treated with a surface-treating liquid consisting of a solution of N,N'-dichlorobenzene sulfonamide in acetone as disclosed in Japanese Patent Application Publication No. 36,910/77 prior to the heat bonding of the mark.
The drum test for crack propagation resistance, stainproof test, durability test and drum test under low 3 ~ 7~
internal pressure as previously mentioned were made with respect to each of twelve tires provided wi-th ~he mark to obtain results as shown in Table 3.
7~
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In the marks, particularly chromatic mark according to the invent;.on, the migration of antioxidant from rubber article is substantially completely prevented by using polyester film, nylon ~ilm~ vinylidene chloride film or vinylidene chloride-vinyl chloride copolymer film which considerably advantageously prevents the migration of staining antioxidant, particularly a~ine-series antioxidant. Furthermore, this film has a swfEicient performance of preventing the migrati.on of antioxi.dant even when the thickness is fairly thin, so that the thickness and rigidity of the mark as a whole can be reduced. As a result, not only the beautiful appearance but also the flex resistance, resistance to external damage and resistance to peeling from rubber article are considerably improved, and also the weather resistance is excellent.
Furthermore, according to the invention, the chromatic rubber composition layer (2), anti.oxidant-migration film barrier (4), shock-absorbing -rubber compos.ition layer (5) and adhesive layer (3, 3', 6), each of w:hich having excellent functional proper~ies, are properly combined into a laminate structwre of 3 to 6 layers, whereby the flex resistance and weather resis-tance, which have never been improved in the prior art, are considerably advantageously improved in addition to the improvement of beautiful appearance and the prevention o:E
color failure, and also the bonding treatment can simply be performed.
The marks according to the invention are preferable as decoration for tires, particularly radial 7~
tires for passenger cars, but may be widely applied ~o rubber articles requiring a flex resistance, such as large hoses, conveyor belts, belts for power transmission, oil fences and the like.
s
Claims (16)
1. A mark for use in rubber article comprising a chromatic rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1.5 mm, an antioxidant-migration film barrier selected from polyester film, nylon film, vinylidene chloride film and vinylidene chloride-vinyl chloride copolymer film and having a thickness of 3 to 100 µm, and an adhesive layer selected from thermoplastic polyesters and thermoplastic polyurethanes and having a thickness of 0.005 to 0.5 mm.
2. A mark for use in rubber article according to claim 1, wherein said mark has a three-layer structure obtained by laminating said chromatic rubber composition layer, said antioxidant-migration film barrier and said adhesive layer in this order.
3. A mark for use in rubber article according to claim 1, wherein said mark has a four-layer structure obtained by laminating said chromatic rubber composition layer, said adhesive layer, said antioxidant-migration film barrier and said adhesive layer in this order.
4. A mark for use in rubber article according to claim 1, wherein said mark further comprises a shock-absorbing rubber composition layer containing not less than 30 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1.5 mm.
5. A mark for use in rubber article according to claim 4, wherein said mark has a six-layer structure obtained by laminating said chromatic rubber composition layer, said adhesive layer, said antioxidant-migration film barrier, said adhesive layer, said shock-absorbing rubber composition layer and said adhesive layer in this order.
6. A mark for use in rubber article according to claim 1, wherein said mark has a total thickness of 0.25 to 3.0 mm.
7. A mark for use in rubber article according to claim 1, wherein said chlorosulfonated polyethylene rubber has a chlorine content of 25 to 43% by weight.
8. A mark for use in rubber article according to claim 7, wherein said chlorine content is 30 to 43% by weight.
9. A mark for use in rubber article according to claim 1, wherein said thermoplastic polyester and thermo-plastic polyurethane have a softening point of 80 to 200°C.
10. A mark for use in rubber article according to claim 1, wherein said thermoplastic polyester and thermo-plastic polyurethane have a hardness of 60° to 96° as measured at 30°C by a spring hardness test (A-type) according to JIS K-6301.
11. A mark for use in rubber article according to claim 1, wherein said chromatic rubber composition layer has a hardness of not more than 70° as measured at 30°C
by a spring hardness test (A-type) according to JIS K-6301
by a spring hardness test (A-type) according to JIS K-6301
12. A mark for use in rubber article according to claim 1, wherein said chromatic rubber composition layer contains not less than 50 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content.
13. A mark for use in rubber article according to claim 4, wherein said shock-absorbing rubber composition layer contains not less than 50 parts by weight of at least one of chloroprene rubber and chlorosulfonated polyethylene rubber per 100 parts by weight of total rubber content.
14. A mark for use in rubber article according to claim 1, wherein said chromatic rubber composition layer is provided at its surface with a protective coating.
15. A mark for use in rubber article according to claim 1, wherein said chromatic rubber composition layer is provided at its surface with an indicative print.
16. A mark for use in rubber article comprising a four-layer structure obtained by laminating a chromatic rubber composition layer containing not less than 50 parts by weight of chlorosulfonated polyethylene rubber with a chlorine content of not less than 30% by weight per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1.0 mm, a nylon copolymer film barrier having a thickness of 0.008 to 0.3 mm and a softening point of 100 to 180°C, a shock-absorbing rubber composition layer containing not less than 50 parts by weight of chlorosulfonated polyethylene rubber with a chlorine content of not less than 30% by weight per 100 parts by weight of total rubber content and having a thickness of 0.1 to 1.5 mm and an adhesive layer of thermoplastic polyester or thermoplastic polyurethane having a thickness of 0.005 to 0.2 mm and a softening point of 80 to 200°C in this order, and having a total thickness of 0.25 to 3.0 mm.
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27,130/82 | 1982-03-01 | ||
| JP2713082U JPS58130728U (en) | 1982-03-01 | 1982-03-01 | Labels for rubber products |
| JP70,079/82 | 1982-05-15 | ||
| JP7007982U JPS58175042U (en) | 1982-05-15 | 1982-05-15 | Highly flexible signs for rubber products |
| JP7451182U JPS58180038U (en) | 1982-05-21 | 1982-05-21 | Label piece for pasting on the surface of rubber articles |
| JP74,511/82 | 1982-05-21 | ||
| JP1536883U JPS59121210U (en) | 1983-02-07 | 1983-02-07 | Signs with excellent bending and weather resistance |
| JP15,368183 | 1983-02-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1188971A true CA1188971A (en) | 1985-06-18 |
Family
ID=27456367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000422654A Expired CA1188971A (en) | 1982-03-01 | 1983-03-01 | Marks for use in rubber articles |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1188971A (en) |
-
1983
- 1983-03-01 CA CA000422654A patent/CA1188971A/en not_active Expired
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