JP6501498B2 - Rubber paint - Google Patents
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- JP6501498B2 JP6501498B2 JP2014226631A JP2014226631A JP6501498B2 JP 6501498 B2 JP6501498 B2 JP 6501498B2 JP 2014226631 A JP2014226631 A JP 2014226631A JP 2014226631 A JP2014226631 A JP 2014226631A JP 6501498 B2 JP6501498 B2 JP 6501498B2
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- 239000003973 paint Substances 0.000 title claims description 63
- 229920001971 elastomer Polymers 0.000 title claims description 34
- 239000005060 rubber Substances 0.000 title claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 52
- 239000000463 material Substances 0.000 claims description 48
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 26
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 26
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 239000007822 coupling agent Substances 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 19
- 235000010215 titanium dioxide Nutrition 0.000 claims description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 235000011187 glycerol Nutrition 0.000 claims description 13
- 239000000049 pigment Substances 0.000 claims description 9
- 239000004014 plasticizer Substances 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 7
- 238000010073 coating (rubber) Methods 0.000 claims description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims 1
- 239000011354 acetal resin Substances 0.000 claims 1
- 229920006324 polyoxymethylene Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 description 41
- 229920005989 resin Polymers 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 40
- 239000011248 coating agent Substances 0.000 description 38
- 238000000576 coating method Methods 0.000 description 38
- 238000004073 vulcanization Methods 0.000 description 25
- 238000007639 printing Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 238000000465 moulding Methods 0.000 description 14
- 238000003825 pressing Methods 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 230000002411 adverse Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000008602 contraction Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 206010040844 Skin exfoliation Diseases 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000012461 cellulose resin Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 206010008428 Chemical poisoning Diseases 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Paints Or Removers (AREA)
Description
本発明はゴム材料、特にタイヤのトレッドに好適に用いることができるゴム用塗料に関する。 The present invention relates to a rubber material, in particular to a paint for rubber that can be suitably used for the tread of a tire.
鉄鋼材製造工場や自動車工場などでは、古くから鋼板や鋼材部品の表面に材質・用途等を示す文字・記号や加工位置を指示するライン等をマーキングするためにマーキング用の塗料が使用されている。 In steel and steel manufacturing plants and automobile plants, marking paints have long been used to mark the surface of steel plates and steel parts with letters and symbols indicating materials and applications and lines indicating processing positions. .
現在ではゴム材料もマーキングの対象であり、例えば、タイヤのトレッドは、タイヤ本体に取り付ける前に当該トレッドの仕様等が未加硫状態のトレッドにマーキングされており、仕様がマーキングされた未加硫状態のトレッドをタイヤ本体に巻き付けて、成形金型に入れた後、加熱して加硫反応によりタイヤ本体と一体化させて取り付けられる。 At present, rubber materials are also subject to marking, and for example, the tread of a tire is marked on the tread of an unvulcanized state such as the specification of the tread before being attached to the tire main body, and the unvulcanized is marked of the specification. After the tread in the above state is wound around the tire body and placed in a molding die, it is heated to be integrated with the tire body by a vulcanization reaction and attached.
鋼板や鋼材部品の表面に使用するマーキング塗料は、セルロース樹脂やアクリル樹脂が溶剤として用いられるため比較的硬い塗膜が形成される。 Since a marking resin used on the surface of a steel plate or steel component is made of a cellulose resin or an acrylic resin as a solvent, a relatively hard coating film is formed.
しかしながら、セルロース樹脂やアクリル樹脂を溶剤とした塗料を未加硫ゴム材料に使用すると、塗膜がゴム材料の伸縮に対して追従できずに亀裂や剥離が生じる場合があり、また、前記加硫反応による取り付け成形工程においては、塗膜が成形金型に付着したり、剥離したりする場合がある。 However, when a paint containing cellulose resin or acrylic resin as a solvent is used as the unvulcanized rubber material, the coating film may not follow the expansion and contraction of the rubber material, which may cause cracking or peeling, and the above-mentioned vulcanization In the mounting and forming step by reaction, the coating film may adhere to or peel off from the molding die.
そこで、未加硫のゴム材料に使用する塗料には、生ゴムをガソリン、ゴム揮発油、灯油等の石油系溶剤に溶かし顔料を加えた塗料や、ゴムのエマルジョン（ラテックス）を使用し、ゴムの伸縮に追従できるように柔軟性を備えた塗料が使用されている。 Therefore, paints used for unvulcanized rubber materials are paints made of crude rubber dissolved in petroleum solvents such as gasoline, rubber volatile oil, kerosene, etc. Paints containing pigments and emulsions of rubber (latex) are used. Flexible paint is used so that it can follow expansion and contraction.
しかし、通常、タイヤ製造工場におけるトレッドのマーキングには、成形直後の８０℃〜１００℃のトレッドにマーキングが行われ、その後、すぐに冷水によって冷却されるため、トレッドに使用できるマーキング用の塗料には、ゴムの伸縮に追従できる柔軟性に加えて、高温のゴム材料でも滲まず鮮明に付着する性質、速乾性、冷水に溶解しない性質を備えることが必要である。 However, marking of the tread in a tire manufacturing plant is usually performed on a tread at 80 ° C. to 100 ° C. immediately after molding, and then, immediately after cooling by cold water, the coating for marking that can be used for the tread In addition to the flexibility capable of following the expansion and contraction of the rubber, it is necessary that the high-temperature rubber material has a property to be attached without blurring and to have a quick-drying property and a property not to dissolve in cold water.
また、トレッドはタイヤ本体に巻き付けられて、成形金型に入れられ、約１８０℃の加硫反応によってタイヤ本体と一体化させて取り付けられるため、当該加硫反応による取り付け成形工程において塗料が成形金型に付着して残留しないという性質も要求される。 In addition, since the tread is wound around the tire body, placed in a molding die, and integrally attached to the tire body by a vulcanization reaction at about 180 ° C., the paint is formed in the mounting molding step by the vulcanization reaction. It is also required that it adheres to the mold and does not remain.
加えて、マーキングは印字装置の細いノズルから塗料を噴射してトレッドの表面に点状の塗料を付着させて行うため、作業効率上、ノズルの目詰まりを起こし難い塗料であることが好ましく、また、目詰まりを起こした場合には容易に目詰まりを解消できる性質も要求される。 In addition, since marking is carried out by spraying paint from the thin nozzles of the printing apparatus to make point paint adhere to the surface of the tread, it is preferable that the paint is less likely to cause clogging of the nozzles in terms of work efficiency. Also, when clogging occurs, the property of being able to easily eliminate the clogging is also required.
前述とおり、タイヤのトレッドに使用できるマーキング用の塗料には通常のゴム用塗料に加えて多くの性質が要求されるため、トレッドに好適に使用できる塗料の開発が望まれている。 As described above, since a coating for marking that can be used for the tread of a tire is required to have many properties in addition to a conventional coating for rubber, development of a coating that can be suitably used for the tread is desired.
特許文献１に記載のゴム系塗料は、溶剤に沸点の高い白灯油を混入した溶剤を使用いるため、８０℃〜１４０℃でも使用できる塗料である。
しかしながら、溶剤が可燃性であるため、火災の危険性があり、また、ＶＯＣ（揮発性有機溶剤）を含むので、人体や環境に悪影響を及ぼし、有機溶剤中毒予防法における規制の対象にもなっている。したがって、販売者や購入者は取り扱いに注意を払う必要があるという問題がある。
The rubber-based paint described in Patent Document 1 is a paint that can be used even at 80 ° C. to 140 ° C. because it uses a solvent in which white kerosene having a high boiling point is mixed with the solvent.
However, since the solvent is flammable, there is a risk of fire, and since it contains VOC (volatile organic solvent), it has an adverse effect on the human body and the environment, and is also subject to the regulations under the Organic Solvent Poisoning Prevention Act. ing. Therefore, there is a problem that sellers and buyers need to pay attention to handling.
特許文献２記載の塗料は、被膜形成成分がワックス類、シリコーンオイル、樹脂類、ゴム類、油脂、脂肪酸及びその誘導体であるので、高温のゴム材料への使用には適さず、また、マーキング用の印字装置ノズルの目詰まりが起こりやすく、目詰まりが起こった場合には界面活性剤で溶解させなければならないといった問題がある。
また、実施例に記載の溶剤は揮発性が高く人体や環境に悪影響を及ぼし、かつ、火災の危険性もあるといった問題がある。
The paint described in Patent Document 2 is not suitable for use in high-temperature rubber materials because the film-forming component is waxes, silicone oils, resins, rubbers, oils and fats, fatty acids and derivatives thereof, and for marking There is a problem that the nozzle of the printing apparatus tends to be clogged, and if clogged, it has to be dissolved with a surfactant.
In addition, the solvents described in the examples are highly volatile, adversely affecting human bodies and the environment, and causing fire hazards.
そこで、本発明者は、トレッドのマーキングに好適に用いることができる塗料、即ち、ゴム材料が高温でも滲まず鮮明に付着して速乾性があり、冷水によって溶解しない性質を備えると共に、ゴムの伸縮に追従する柔軟性を有して、高温の加硫反応による取り付け成形工程においても塗膜に亀裂や剥離が生じず、かつ、成形金型に塗料が付着せず、更には、印字装置のノズルの目詰まりを起こし難く、また、容易に目詰まりを解消させることができ、加えて、火災のおそれがなく、人体や環境に悪影響を及ぼさない塗料を提供することを技術的課題として鋭意研究を行った結果、ケン化度が８９〜９９mol％のポリビニルアルコールのアセタール化樹脂（以下「アセタール化ＰＶＡ樹脂」と言うこともある）３〜１０重量％と顔料とカップリング剤と可塑剤と水とを含有させた塗料とすることで、前記技術的課題を解決できるという刮目すべき知見を得て、本発明を完成させた。 Therefore, the present inventors have found that a paint that can be suitably used for marking the tread, that is, the rubber material has the property of being rapidly attached without sharp bleeding even at high temperatures and having a property of not dissolving in cold water, The coating film does not crack or peel off even in the mounting and forming process due to the high temperature vulcanization reaction, and the paint does not adhere to the molding die, and furthermore, the nozzle of the printing apparatus Research has been conducted with the aim of providing paint that does not easily cause clogging, can be easily eliminated, and that there is no risk of fire and does not adversely affect the human body or the environment As a result, 3 to 10 wt% of polyvinyl alcohol acetalized resin having a saponification degree of 89 to 99 mol% (hereinafter sometimes referred to as "acetalized PVA resin"), pigment and cuprin With paint which contains the agent and plasticizer and water to obtain knowledge should Katsumoku that can solve the technical problems, and completed the present invention.
前記技術的課題は次のとおり、本発明によって解決できる。 The above technical problems can be solved by the present invention as follows.
本発明は、ケン化度が８９〜９９mol％のポリビニルアルコールのアセタール化樹脂３〜１０重量％と顔料３〜１０重量％とカップリング剤１〜２重量％と可塑剤１〜２重量％と水とを含有してなるゴム用塗料である。
The present invention comprises 3 to 10% by weight of an acetalized resin of polyvinyl alcohol having a saponification degree of 89 to 99% by mol, 3 to 10% by weight of a pigment , 1 to 2% by weight of a coupling agent and 1 to 2% by weight of a plasticizer And a rubber coating comprising
また本発明は、前記顔料がチタン白である前記ゴム用塗料である。 The present invention, the pigment is Ru said rubber paint der titanium white.
また、本発明は、前記カップリング剤がチタネート系またはアルミネート系である前記ゴム用塗料である。 Further, the present invention, the coupling agent is Ru said rubber paint der a titanate or aluminate-based.
また、本発明は、前記可塑剤がグリセリン、エチレングリコール、プロピレングリコールである前記ゴム用塗料である。 Further, the present invention, the plasticizer is glycerin, ethylene glycol, Ru said rubber paint der propylene glycol.
本発明によれば、低温のゴム材料はもちろん、８０℃〜１００℃の高温のゴム材料でも滲まず鮮明に付着して速乾性があり、冷水に塗料が溶解せず、ゴムの伸縮に追従する柔軟性があり、また、高温(約１８０℃)の加硫反応による取り付け成形工程においても塗膜に亀裂や剥離が生じることがなく、かつ、塗料は全てゴム側に付着して成形金型には付着しないゴム用塗料になる。
また、印字装置ノズルの目詰まりを起こし難く、たとえ目詰まりした場合であっても温水により容易に解消することができるため、作業効率の良いゴム用塗料になる。
According to the present invention, low-temperature rubber materials as well as high-temperature rubber materials of 80 ° C. to 100 ° C. do not blur and adhere sharply and have quick drying properties, and the paint does not dissolve in cold water and follows the expansion and contraction of rubber It is flexible, and no cracks or peelings occur in the coating film even in the attachment molding process due to the high temperature (about 180 ° C.) vulcanization reaction, and all the paint adheres to the rubber side to form a molding die Is a non-stick rubber paint.
In addition, since the nozzles of the printing apparatus are not easily clogged and can be easily eliminated by the warm water even when clogged, it becomes a paint for rubber with good working efficiency.
本発明のゴム用塗料には、ケン化度が８９〜９９mol％のポリビニルアルコールのアセタール化樹脂を使用するので、低温はもちろんのこと、８０℃〜１００℃の高温のゴム材料であっても表面に滲まず鮮明に付着し、素早く乾燥塗膜になって速乾性があり、冷水によって塗料が溶解することがない。 Since the acetalized resin of polyvinyl alcohol having a saponification degree of 89 to 99 mol% is used in the coating material for rubber of the present invention, not only low temperature but also high temperature rubber material of 80 ° C. to 100 ° C. It does not blur on the surface, adheres sharply, quickly becomes a dry coating, and dries quickly, and the paint does not dissolve in cold water.
また、アセタール化ＰＶＡ樹脂を使用しているので、冷水には溶解しないが、６０℃以上の温水には溶解するから、たとえ印字装置のノズルが目詰まりした場合であっても温水で溶解させることで容易に目詰まりを解消することができる。 In addition, because it uses acetalized PVA resin, it does not dissolve in cold water, but it dissolves in warm water of 60 ° C or higher. Therefore, even if the nozzle of the printing apparatus is clogged, it should be dissolved with warm water Can easily eliminate clogging.
また、溶剤が水なので、火災の心配や、人体や環境へ悪影響を及ぼすことがなく簡便に使用することができる。 In addition, since the solvent is water, it can be used conveniently without fear of fire, adverse effects on the human body and the environment.
さらに、顔料をチタン白とすることで、白色度の高い塗料にすることができる。 Furthermore, the Pigments With titanium white, can be a high degree of whiteness paint.
また、カップリング剤がチタネート系又はアルミネート系であれば、ポットライフが十分に確保できるため、マーキング用の塗料として適した性質となり、また、塗料とゴム材料との密着性を増加させることもできる。 Further, if the mosquitoes coupling agent is a titanate or aluminate-based, since the pot life can be sufficiently ensured, it becomes properties suitable as a coating material for marking, also to increase the adhesion between the coating and the rubber material it can.
また、可塑剤がグリセリン、エチレングリコール及びプロピレングリコールであれば、乾燥塗膜が固くなり過ぎず柔軟性のある塗料となり、塗膜の亀裂や剥離を抑制することができる。 Further, if the answer is Y plasticizer is glycerin, ethylene glycol and propylene glycol, dry film becomes paint flexible not too hard, it is possible to suppress cracking and peeling of the coating film.
本発明におけるゴム用塗料に使用できるケン化度が８９〜９９mol％のポリビニルアルコールのアセタール化樹脂は特に限定されるものではないが、好適に使用できるものとしてゴーゼネックス（登録商標）Z−１００（日本合成化学株式会社製）を挙げることができる。 The acetalized resin of polyvinyl alcohol having a degree of saponification of 89 to 99 mol%, which can be used as the coating material for rubber in the present invention, is not particularly limited, but Gozenex Z® Z-100 (Japan) can be suitably used. Synthetic Chemical Co., Ltd.) can be mentioned.
本発明におけるアセタール化ＰＶＡ樹脂の含有量は、３〜１０重量％が好ましい。３重量％より少なければ、塗膜の強度が弱くなり、冷水で塗料が剥離する虞があり、１０重量％を超えると粘性が上がって作業効率が悪くなると共に、塗膜が固くなって、高温の加硫反応による成形工程において塗膜が剥離する虞があるからである。 The content of the acetalized PVA resin in the present invention is preferably 3 to 10% by weight. If the amount is less than 3% by weight, the strength of the coating is weakened, and the paint may peel off with cold water, and if it exceeds 10% by weight, the viscosity is increased to deteriorate the working efficiency and the coating becomes hard and high temperature This is because there is a possibility that the coating film may peel off in the molding step by the vulcanization reaction.
本発明に使用できる顔料としては、チタン白、亜鉛華、硫酸バリウムを挙げることができるが、特にチタン白が好ましい。 Examples of pigments that can be used in the present invention include titanium white, zinc white and barium sulfate, with titanium white being particularly preferable.
本発明における顔料の含有量は３〜１０重量％が好ましい。３重量％より少なければ白色度が低下するので識別性が低下する虞があり、１０重量％を超えれば塗膜が固くなって、高温の加硫反応による成形工程において塗膜が剥離する虞があるからである。 The content of the pigment in the present invention is preferably 3 to 10% by weight. If the amount is less than 3% by weight, the whiteness may be reduced, so the identification may be reduced. If the amount is more than 10% by weight, the coating may become hard and the coating may be peeled off in the molding process due to the high temperature vulcanization reaction It is because there is.
本発明に使用できるカップリング剤としては、チタネート系、アルミネート系及びシランカップリング剤を用いることができるがチタネート系、アルミネート系のカップリング剤が好ましい。 As a coupling agent which can be used in the present invention, titanate type, aluminate type and silane coupling agents can be used, but titanate type and aluminate type coupling agents are preferable.
アミン、アルデヒド等の架橋剤は架橋反応がすぐに始まるので、ポットライフが短く、マーキング用のゴム用塗料に使用するのは好ましくない。 Crosslinking agents such as amines and aldehydes have a short pot life and are not preferable for use in rubber coatings for marking because the crosslinking reaction starts immediately.
カップリング剤の含有量としては１〜２重量％が好ましい。１重量％より少なければ塗料が成形金型に付着する虞があり、２重量％を超えれば、冷水によって塗料が溶解する虞があるからである。 The content of the coupling agent is preferably 1 to 2% by weight. If the amount is less than 1% by weight, the paint may adhere to the molding die, and if it exceeds 2% by weight, the paint may be dissolved by cold water.
本発明における可塑剤は、グリセリン、エチレングリコール、プロピレングリコールが好ましい。 The plasticizer in the present invention is preferably glycerin, ethylene glycol or propylene glycol.
可塑剤の含有量は、１〜２重量％が好ましい。１重量％より少なければ塗膜が剥離する虞があり、２重量％を超えると冷水に溶解する虞があるからである。 The content of the plasticizer is preferably 1 to 2% by weight. If the amount is less than 1% by weight, the coating may be peeled off. If the amount is more than 2% by weight, it may be dissolved in cold water.
(実施例１)
ケン化度が８９〜９９ｍｏｌ％のポリビニルアルコールのアセタール化樹脂としてゴーセネックス（登録商標）Ｚ-１００（日本合成化学株式会社製）２０重量％を水に分散させ撹拌しながら９０℃まで加熱して溶解させる。（以下この水溶液を「アセタール化ＰＶＡ樹脂水溶液」と言う。）
Example 1
As an acetalization resin of polyvinyl alcohol having a degree of saponification of 89 to 99 mol%, 20% by weight of Gaunexex® Z-100 (manufactured by Japan Synthetic Chemical Co., Ltd.) is dispersed in water and dissolved while heating to 90 ° C while stirring Let (Hereinafter, this aqueous solution is referred to as "acetalized PVA resin aqueous solution".)
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白５重量％を水に投入し混合分散させ、１.５重量％のオルガチックス(登録商標)ＴＣ−３１０（マツモトファインケミカル株式会社製）(以下の実施例、比較例においては「チタネート系カップリング剤」と言う)と２重量％のグリセリンを添加して均一にした塗料を作成した。この塗料を印字装置ＰＪ−１Ｂ（マークテック株式会社社製）で８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
25% by weight of an aqueous acetalized PVA resin solution (5% by resin amount) and 5% by weight of titanium white are added to water, mixed and dispersed, and 1.5% by weight of Organics (registered trademark) TC-310 (manufactured by Matsumoto Fine Chemical Co., Ltd.) ) (Hereinafter referred to as "titanate based coupling agent" in the following examples and comparative examples) and 2% by weight of glycerin were added to prepare a uniform coating. Mark the unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. with this printer with printing device PJ-1B (manufactured by Marktec Co., Ltd.), spray water immediately after that, and visually observe the state of the coated film Observed.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（実施例２）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と２重量％のエチレングリコールを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Example 2)
25% by weight of acetalized PVA resin aqueous solution (5% of resin amount) and 10% by weight of titanium white are added to water, mixed and dispersed, and 1.5% by weight of a titanate coupling agent and 2% by weight of ethylene glycol are added The paint was made uniform.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
(実施例３)
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、１.５重量％のプレンアクト(登録商標)ＡＬ−Ｍ（味の素ファインテクノ株式会社製）（以下の実施例、比較例においては「アルミネート系カップリング剤」と言う）と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Example 3)
25% by weight of an aqueous acetalized PVA resin solution (5% resin amount) and 10% by weight of titanium white are added to water, mixed and dispersed, and 1.5% by weight of Prenact (registered trademark) AL-M (manufactured by Ajinomoto Fine Techno Co., Ltd.) ) (Hereinafter referred to as "aluminate coupling agent" in the following examples and comparative examples) and 2 wt% of glycerin were added to prepare a uniform coating.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
(比較例１)
アセタール化ＰＶＡ樹脂水溶液１０重量％（樹脂量２％）とチタン白５重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 1)
10% by weight of acetalized PVA resin aqueous solution (2% of resin amount) and 5% by weight of titanium white are added to water, mixed and dispersed, and 1.5% by weight of a titanate coupling agent and 2% by weight of glycerin are added An even paint was made. This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例２）
アセタール化ＰＶＡ樹脂水溶液６０重量％（樹脂量１２％）とチタン白５重量％を水に投入し混合分散させ、１．５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行ったが粘度が高いためマーキングができなかった。
そこで刷毛でマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 2)
Add 60% by weight of an aqueous solution of acetalized PVA resin (12% resin amount) and 5% by weight of titanium white into water, mix and disperse, add 1.5% by weight of a titanate coupling agent and 2% by weight of glycerin. An even paint was made.
Marking was performed on an unvulcanized tread material (50 mm × 50 mm) which was heated at 80 ° C. by the printing apparatus PJ-1B, but the marking could not be performed because the viscosity was high.
Therefore, marking was carried out with a brush, and immediately after that, water was sprayed to visually observe the state of the coating.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例３）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１５重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 3)
Add 25% by weight of acetalized PVA resin aqueous solution (5% resin amount) and 15% by weight of titanium white into water, mix and disperse, add 1.5% by weight of a titanate coupling agent and 2% by weight of glycerin. An even paint was made.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例４）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、２重量％のプロピレングリコールを添加し均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 4)
A 25% by weight aqueous solution of acetalized PVA resin (5% resin amount) and 10% by weight of titanium white were added to water, mixed and dispersed, and 2% by weight of propylene glycol was added to form a uniform coating.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例５）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、１．５重量％のアルミネート系カップリング剤を添加して均一にした塗料を作成した。この塗料を印字装置ＰＪ−１Ｂ（マークテック社製）で８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 5)
A 25% by weight aqueous solution of acetalized PVA resin (5% resin content) and 10% by weight titanium white are added to water, mixed and dispersed, and a 1.5% by weight aluminate coupling agent is added to make uniform paint Created. This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by a printing apparatus PJ-1B (manufactured by Marktec Co., Ltd.), and water was sprayed immediately after that to observe the state of the coated film.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例６）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白２重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 6)
Add 25% by weight of an aqueous acetalized PVA resin solution (5% resin amount) and 2% by weight of titanium white into water, mix and disperse, add 1.5% by weight of a titanate coupling agent and 2% by weight of glycerin. An even paint was made.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例７）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、０．５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 7)
Add 25% by weight of acetalized PVA resin aqueous solution (5% of resin amount) and 10% by weight of titanium white into water, mix and disperse, add 0.5% by weight of a titanate coupling agent and 2% by weight of glycerin. An even paint was made.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例８）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、３重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 8)
Add 25% by weight of an aqueous acetalized PVA resin solution (5% resin amount) and 10% by weight of titanium white into water, mix and disperse, add 3% by weight of a titanate coupling agent and 2% by weight of glycerin and make uniform Made the paint.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例９）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と０．５重量％のエチレングリコールを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 9)
Add 25% by weight of an aqueous acetalized PVA resin solution (5% resin amount) and 10% by weight of titanium white to water, mix and disperse, and mix 1.5% by weight of a titanate coupling agent and 0.5% by weight of ethylene glycol An additive was added to make the paint uniform.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例１０）
アセタール化ＰＶＡ樹脂水溶液２５重量％（樹脂量５％）とチタン白１０重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と３重量％のエチレングリコールを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
(Comparative example 10)
Add 25% by weight of acetalized PVA resin aqueous solution (5% resin amount) and 10% by weight of titanium white into water, mix and disperse, add 1.5% by weight of a titanate coupling agent and 3% by weight of ethylene glycol The paint was made uniform.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
（比較例１１）
ケン化度が８６.５〜８９ｍｏｌ％未満のポリビニールアルコールのアセタール化樹脂として、ゴーセノール(登録商標)ＧＬ−０５（日本合成化学株式会社製）を２０％、水に分散させ撹拌しながら９０℃まで加熱して溶解させる(以下この水溶液を「アセタール化ＰＶＡ樹脂２水溶液」という)。
(Comparative example 11)
As an acetalization resin of polyvinyl alcohol having a degree of saponification of less than 86.5 to 89 mol%, GOOSENOL® GL-05 (manufactured by Japan Synthetic Chemical Co., Ltd.) 20% dispersed in water and stirred at 90 ° C. The solution is heated to dissolve (hereinafter this aqueous solution is referred to as “acetalized PVA resin 2 aqueous solution”).
アセタール化ＰＶＡ樹脂２水溶液２５重量％（樹脂量５％）とチタン白５重量％を水に投入し混合分散させ、１.５重量％のチタネート系カップリング剤と２重量％のグリセリンを添加して均一にした塗料を作成した。
この塗料を印字装置ＰＪ−１Ｂで８０℃に加熱した未加硫トレッド材（50ｍｍ×50ｍｍ）にマーキングを行い、直後に水を噴霧して塗膜の状態を目視で観察した。
その後、鋼製成形金型で未加硫トレッド材（50ｍｍ×50ｍｍ）を挟んで圧力をかけて１８０℃で２０分加熱して加硫反応を行った後、金型への付着の有無を目視により確認した。
25% by weight (5% resin amount) of an aqueous solution of acetalized PVA resin 2 and 5% by weight of titanium white are added to water, mixed and dispersed, and 1.5% by weight of a titanate coupling agent and 2% by weight of glycerin are added The paint was made uniform.
This paint was marked on an unvulcanized tread material (50 mm × 50 mm) heated to 80 ° C. by the printing apparatus PJ-1B, and water was sprayed immediately after that to observe the state of the coating film visually.
After that, a vulcanizing reaction is carried out by applying pressure on both sides of an unvulcanized tread material (50 mm × 50 mm) and heating at 180 ° C. for 20 minutes to perform a vulcanization reaction, and then visually observe the presence or absence of adhesion to the mold. It confirmed by.
実施例１〜３及び比較例１〜１１の配合比率を表１に示す。 The compounding ratios of Examples 1 to 3 and Comparative Examples 1 to 11 are shown in Table 1.
実施例１〜３及び比較例１〜１１の水冷時の状態及び加硫反応後の金型への塗料の付着の有無について目視によって評価した結果を表２に示す。 The results obtained by visually evaluating the condition during water cooling of Examples 1 to 3 and Comparative Examples 1 to 11 and the presence or absence of the adhesion of the paint to the mold after the vulcanization reaction are shown in Table 2.
表２の水冷時の状態は、塗料が溶解しない場合には○、一部溶解する場合には△、溶解する場合には×で表わす。
また、金型への塗料の付着は、付着がない場合には○、付着がある場合には×で表わす。
なお、その他の評価は備考に記載した。
The state at the time of water cooling in Table 2 is represented by ○ when the paint is not dissolved, Δ when it is partially dissolved, and x when it is dissolved.
Further, the adhesion of the paint to the mold is represented by 場合 when there is no adhesion and by × when there is adhesion.
Other evaluations are described in the remarks.
表２に示したとおり、本発明のゴム用塗料は８０℃のゴム材料でも表面に付着して速乾性があり、冷水によっても溶解せず、かつ、１８０℃で２０分間の加硫反応による成形工程においても塗料が成形金型に付着しない塗料である。 As shown in Table 2, the coating material for rubber of the present invention adheres to the surface even at 80 ° C. and is fast drying, does not dissolve even in cold water, and forms by a vulcanization reaction at 180 ° C. for 20 minutes Also in the process, the paint does not adhere to the molding die.
本発明におけるゴム用塗料は、高温のゴム材料であっても滲まず鮮明に付着し、速乾性があり、冷水によって溶解せず、かつ、高温の加硫反応による成形工程においても成形金型に塗料が付着しない塗料であり、タイヤのトレッドに好適に用いることができる。
また、冷水には溶解しないが、６０℃以上の温水には溶解するため、たとえ印字装置のノズルが目詰まりしたとしても温水により容易に目詰まりを解消でき、加えて、石油系溶剤やＶＯＣを含有しないため人体及び環境に悪影響を及ぼさないゴム用塗料であるから、本発明は産業上の利用可能性が高い発明である。
The coating material for rubber in the present invention does not blur even if it is a high temperature rubber material, adheres clearly, is quick-drying, does not dissolve in cold water, and does not dissolve in a molding die even in a molding process by a high temperature vulcanization reaction. It is a paint to which the paint does not adhere, and can be suitably used for the tread of a tire.
In addition, since it does not dissolve in cold water but dissolves in warm water of 60 ° C or higher, even if the nozzle of the printing apparatus is clogged, the hot water can be easily eliminated from the clogging, and additionally, petroleum solvents and VOCs The present invention is a highly industrially applicable invention because it is a rubber coating that does not adversely affect human bodies and the environment because it is not contained.
Claims (4)
The paint for rubber according to any one of claims 1 to 3 , wherein the plasticizer is glycerin, ethylene glycol or propylene glycol.
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