JP5998079B2 - Anti-curing agent for unvulcanized rubber and method for producing non-vulcanized rubber having been subjected to anti-adhesion - Google Patents
Anti-curing agent for unvulcanized rubber and method for producing non-vulcanized rubber having been subjected to anti-adhesion Download PDFInfo
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- JP5998079B2 JP5998079B2 JP2013043244A JP2013043244A JP5998079B2 JP 5998079 B2 JP5998079 B2 JP 5998079B2 JP 2013043244 A JP2013043244 A JP 2013043244A JP 2013043244 A JP2013043244 A JP 2013043244A JP 5998079 B2 JP5998079 B2 JP 5998079B2
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- Prior art keywords
- adhesion
- unvulcanized rubber
- mass
- rubber
- adhesive
- Prior art date
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/346—Clay
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
本発明は、未加硫ゴム同士の密着を防止するための防着剤と、これを用いた防着処理済み未加硫ゴムの製造方法に関する。 The present invention relates to an adhesion preventive agent for preventing adhesion between unvulcanized rubbers, and a method for producing an adhesion-treated unvulcanized rubber using the same.
例えば天然ゴム(NR)、ブタジエンゴム(BR)などのゴムの生産加工の現場においては、シート状などに成形された未加硫ゴムを、次の成形、加硫等の工程に移行するまでの間、積み重ねたり、折り畳んだりして貯蔵することがある。このような貯蔵時において、未加硫ゴム同士が密着してしまうことを防止する目的で、未加硫ゴムの表面に防着剤(密着防止剤)を付着させることが行われている(例えば特許文献1参照。)。 For example, in the field of production and processing of rubber such as natural rubber (NR) and butadiene rubber (BR), unvulcanized rubber molded into a sheet or the like is transferred to the next molding and vulcanization process. In the meantime, they may be stacked or folded for storage. At the time of such storage, for the purpose of preventing the unvulcanized rubber from adhering to each other, an adhesion preventing agent (adhesion preventing agent) is adhered to the surface of the unvulcanized rubber (for example, (See Patent Document 1).
防着剤を未加硫ゴムの表面に付着させる方法として、2〜3質量%程度の濃度で防着剤を水に分散させた懸濁液を用いるウェット法がある。ウェット法では、シート状などに成形された後の高温状態(例えば80〜150℃)にある未加硫ゴムに対して懸濁液をシャワー設備により散布したり、懸濁液の入った槽に高温状態の未加硫ゴムを短時間浸漬(ディップ)したりして、未加硫ゴムの表面に懸濁液を付着させる。付着した懸濁液中の水分は、未加硫ゴムの熱により急速に蒸発、乾燥し、それにより、未加硫ゴムの表面に防着剤の被膜が形成される。 As a method of attaching the anti-adhesive to the surface of the unvulcanized rubber, there is a wet method using a suspension in which the anti-adhesive is dispersed in water at a concentration of about 2 to 3% by mass. In the wet method, a suspension is sprayed with shower equipment on unvulcanized rubber in a high temperature state (for example, 80 to 150 ° C.) after being formed into a sheet or the like, or in a tank containing the suspension. The suspension is attached to the surface of the unvulcanized rubber by dipping the unvulcanized rubber in a high temperature state for a short time. Moisture in the adhering suspension is rapidly evaporated and dried by the heat of the unvulcanized rubber, thereby forming a film of an adhesion-preventing agent on the surface of the unvulcanized rubber.
しかしながら、このようなウェット法においては、防着剤懸濁液と未加硫ゴムの表面との濡れ性が不充分であったり、濡れ性が比較的良好であったとしても、高温状態にある未加硫ゴムの熱で懸濁液が急速に乾燥される条件下では、懸濁液が乾燥過程ではじかれたりして、未加硫ゴムの表面にムラなく防着剤を付着させることは困難であった。防着剤の付着ムラがあると、防着性能を充分に発揮させることは難しい。 However, in such a wet method, even if the wettability between the adhesion-suspending agent suspension and the surface of the unvulcanized rubber is insufficient or the wettability is relatively good, the wet method is in a high temperature state. Under conditions where the suspension is rapidly dried by the heat of the unvulcanized rubber, the suspension is repelled in the drying process, and the adhesion agent is not evenly adhered to the surface of the unvulcanized rubber. It was difficult. If there is uneven adhesion of the anti-adhesive agent, it is difficult to fully exhibit the anti-adhesion performance.
また、近年、防着剤を使用する作業現場では、作業性の向上が求められており、具体的には、懸濁液中の防着剤濃度を低くして、ゴム表面に付着させる防着剤の量を低減する方法などがとられている。また、未加硫ゴムの表面に付着した防着剤は、次工程でゴム中に練り込まれるため、未加硫ゴムに付着させる防着剤の量を出来るだけ少量とし、防着剤がゴムの物性に悪影響を及ぼさないようにすることが好ましい。
ところが、このように防着剤濃度が低い懸濁液を使用した場合には、防着剤濃度が高い懸濁液を使用した場合よりも、防着剤の付着ムラによる防着性能低下が顕著となる傾向にあった。
さらに最近では、ゴム種の多様化により表面状態の複雑な未加硫ゴムが増加しており、防着剤がより付着しにくいケースが認められるようになってきている。
Also, in recent years, work sites where anti-adhesive agents are used have been required to improve workability. Specifically, the anti-adhesive agents are adhered to the rubber surface by reducing the concentration of the anti-adhesive agent in the suspension. A method of reducing the amount of the agent is taken. Also, since the anti-adhesive agent adhering to the surface of the unvulcanized rubber is kneaded into the rubber in the next step, the amount of the anti-adhesive agent adhering to the unvulcanized rubber is made as small as possible, and the anti-adhesive agent is the rubber. It is preferable not to adversely affect the physical properties.
However, when a suspension with a low concentration of the anti-adhesive agent is used in this way, the deterioration of the anti-adhesion performance due to uneven adhesion of the anti-adhesive agent is more significant than when a suspension with a high concentration of the anti-adhesive agent is used. There was a tendency to become.
More recently, the diversification of rubber types has increased the number of unvulcanized rubbers with complex surface conditions, and cases have been recognized in which adherents are less likely to adhere.
本発明は上記事情に鑑みてなされたもので、防着剤を防着剤懸濁液として使用した場合に、前記防着剤懸濁液が未加硫ゴムの表面に対して良好な濡れ性を示し、かつ、前記防着剤懸濁液の乾燥時には未加硫ゴムの表面に前記防着剤がムラなく付着する優れた付着性を示し、そのため、懸濁液の防着剤濃度を低くして使用した場合でも良好な防着性能を発揮する未加硫ゴム用防着剤の提供を課題とする。 The present invention has been made in view of the above circumstances, and when the anti-adhesive agent is used as an anti-adhesive suspension, the anti-adhesive suspension has good wettability with respect to the surface of the unvulcanized rubber. In addition, when the anti-adhesive agent suspension is dried, the anti-adhesive agent adheres uniformly to the surface of the unvulcanized rubber and exhibits excellent adhesion. It is an object of the present invention to provide an anti-vulcanized rubber anti-adhesive agent that exhibits good anti-adhesion performance even when used as an adhesive.
本発明者らは、未加硫ゴム表面に対する防着剤懸濁液の濡れ性と防着剤の付着性に着目し、これらの向上が、優れた防着性能の付与に繋がることを見出し、本発明を完成するに至った。
本発明の未加硫ゴム用防着剤は、Na型モンモリロナイトを60質量%以上含有するベントナイト(A)を未加硫ゴム用防着剤の総質量に対して50〜90質量%と、アニオン界面活性剤(B)と、下記式(1)で表されるノニオン界面活性剤(C)とを含有し、前記(B)の質量/前記(C)の質量で表される質量比が、0.15〜0.65であることを特徴とする。
本発明の防着処理済み未加硫ゴムの製造方法は、未加硫ゴムの表面に、前記未加硫ゴム用防着剤を付着させる工程を有することを特徴とする。
The inventors of the present invention have focused on the wettability of the adhesive suspension to the unvulcanized rubber surface and the adhesion of the adhesive, and found that these improvements lead to the provision of excellent adhesion performance. The present invention has been completed.
The anti-curing agent for unvulcanized rubber of the present invention comprises 50 to 90% by mass of bentonite (A) containing Na-type montmorillonite at 60% by mass or more based on the total mass of the unvulcanized rubber anti-corrosive agent, It contains the surfactant (B) and the nonionic surfactant (C) represented by the following formula (1), and the mass ratio represented by the mass of (B) / the mass of (C) It is 0.15-0.65, It is characterized by the above-mentioned.
The method for producing an adhesion-treated unvulcanized rubber according to the present invention is characterized by including a step of adhering the adhesion agent for unvulcanized rubber to the surface of the unvulcanized rubber.
本発明の未加硫ゴム用防着剤は、防着剤を防着剤懸濁液として使用した場合に、前記防着剤懸濁液が未加硫ゴムの表面に対して良好な濡れ性を示し、かつ、前記防着剤懸濁液の乾燥時には未加硫ゴムの表面に前記防着剤がムラなく付着する優れた付着性を示す。そのため、懸濁液の防着剤濃度を低くして使用した場合でも良好な防着性能を発揮する。 The anti-curing agent for unvulcanized rubber of the present invention has good wettability with respect to the surface of the unvulcanized rubber when the anti-sticking agent is used as an anti-sticking agent suspension. In addition, when the anti-adhesive agent suspension is dried, the anti-adhesive agent adheres uniformly to the surface of the unvulcanized rubber. For this reason, even when the suspension is used at a low concentration of the anti-sticking agent, it exhibits good anti-sticking performance.
以下、本発明を詳細に説明する。
本発明の未加硫ゴム用防着剤(本明細書では、単に防着剤という場合がある)は、例えばシート状に成形された未加硫ゴムの表面に付着して被膜を形成し、貯蔵時などにおけるシート状の未加硫ゴム同士の密着を防止するものである。
本発明の防着剤は、Na型モンモリロナイトをベントナイト(A)中、60質量%以上含有するベントナイト(A)を防着剤の総質量に対して50〜90質量%と、アニオン界面活性剤(B)と、特定のノニオン界面活性剤(C)とを含有する粉体組成物であり、通常、前記防着剤が水に分散した防着剤懸濁液の形態で、未加硫ゴムの表面に適用される。
Hereinafter, the present invention will be described in detail.
The unvulcanized rubber anti-adhesive agent of the present invention (in the present specification, sometimes simply referred to as an anti-adhesive agent), for example, adheres to the surface of the unvulcanized rubber formed into a sheet to form a film, This prevents the sheet-like unvulcanized rubber from adhering to each other during storage.
The anti-adhesive agent of the present invention comprises 50 to 90% by mass of an anionic surfactant containing 50% by mass or more of bentonite (A) containing Na-type montmorillonite in the bentonite (A) with respect to the total mass of the anti-adhesive agent. B) and a specific nonionic surfactant (C), which is a powder composition, usually in the form of an anti-adhesive suspension in which the anti-adhesive is dispersed in water, Applied to the surface.
[(A)成分]
本発明では、(A)成分として、Na型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有するベントナイト(A)を使用する。前記ベントナイト(A)は、防着剤の防着性を担う成分であって、ベントナイト(A)中のNa型モンモリロナイトの含有量はベントナイトの総質量に対して90質量%以上であることがより好ましい。Na型モンモリロナイトの含有量がベントナイトの総質量に対して60質量%未満のベントナイトを用いた防着剤は、未加硫ゴムの表面に対する付着性が不充分であり、そのため、未加硫ゴムに優れた防着性能を付与することができない。ベントナイト(A)は、Na型モンモリロナイト以外に、石英、クリストバライト、長石類、炭酸塩鉱物などを含有し、これら不純物の総質量がベントナイトの総質量に対して40質量%を超えると付着性が低下する。
なお、ベントナイト(A)中のNa型モンモリロナイトの含有量は、X線回折により測定される値である。
[(A) component]
In this invention, the bentonite (A) which contains Na type montmorillonite 60 mass% or more with respect to the total mass of bentonite is used as (A) component. The said bentonite (A) is a component which bears the anti-adhesion property of an anti-adhesive agent, Comprising: It is more preferable that content of Na type montmorillonite in bentonite (A) is 90 mass% or more with respect to the total mass of bentonite. preferable. An anti-adhesive agent using bentonite having a Na-type montmorillonite content of less than 60% by mass with respect to the total mass of bentonite has insufficient adhesion to the surface of the unvulcanized rubber. Excellent anti-adhesion performance cannot be imparted. Bentonite (A) contains quartz, cristobalite, feldspar, carbonate minerals, etc. in addition to Na-type montmorillonite. Adhesion decreases when the total mass of these impurities exceeds 40% by mass with respect to the total mass of bentonite. To do.
The content of Na-type montmorillonite in bentonite (A) is a value measured by X-ray diffraction.
[(B)成分]
本発明では、(B)成分として、アニオン界面活性剤を用いる。
アニオン界面活性剤(B)は、本発明の未加硫ゴム用防着剤を防着剤懸濁液としたときに、ベントナイト(A)中のNa型モンモリロナイトに効果的に吸着し、前記Na型モンモリロナイトを前記防着剤懸濁液中で薄片状に均一に分散させるとともに、未加硫ゴムの表面に対する前記防着剤懸濁液の表面張力を低下させて、前記防着剤懸濁液と未加硫ゴムの表面との濡れ性を向上させる作用を奏するものと推察される。
(B)成分として具体的には、
(1)高級脂肪酸塩、アルキルエーテルカルボン酸塩、ポリオキシアルキレンエーテルカルボン酸塩、アルキル(又はアルケニル)アミドエーテルカルボン酸塩、アシルアミノカルボン酸塩等のカルボン酸型アニオン界面活性剤、
(2)高級アルコール硫酸エステル塩、ポリオキシアルキレン高級アルコール硫酸エステル塩、アルキルフェニルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、グリセリン脂肪酸エステルモノ硫酸エステル塩等の硫酸エステル型アニオン界面活性剤、
(3)アルカンスルホン酸塩、α−オレフィンスルホン酸塩、直鎖アルキルベンゼンスルホン酸塩、α−スルホ脂肪酸エステル塩、ジアルキルスルホコハク酸塩等のスルホン酸型アニオン界面活性剤、
(4)アルキルリン酸エステル塩、ポリオキシアルキレンアルキルリン酸エステル塩、ポリオキシアルキレンアルキルフェニルリン酸エステル塩、グリセリン脂肪酸エステルモノリン酸エステル塩等のリン酸エステル型アニオン界面活性剤等が挙げられる。
[Component (B)]
In the present invention, an anionic surfactant is used as the component (B).
The anionic surfactant (B) effectively adsorbs to the Na-type montmorillonite in the bentonite (A) when the anti-vulcanized rubber anti-adhesive agent of the present invention is used as an anti-adhesive suspension. The type montmorillonite is uniformly dispersed in the form of flakes in the anti-adhesive agent suspension, and the surface tension of the anti-adhesive agent suspension with respect to the surface of the unvulcanized rubber is reduced, whereby the anti-adhesive agent suspension It is surmised that it has the effect of improving the wettability with the surface of the unvulcanized rubber.
Specifically, as the component (B),
(1) Carboxylic acid type anionic surfactants such as higher fatty acid salts, alkyl ether carboxylates, polyoxyalkylene ether carboxylates, alkyl (or alkenyl) amide ether carboxylates, acylaminocarboxylates,
(2) Sulfate-type anionic surface activity such as higher alcohol sulfate, polyoxyalkylene higher alcohol sulfate, alkylphenyl ether sulfate, polyoxyalkylene alkylphenyl ether sulfate, glycerin fatty acid ester monosulfate Agent,
(3) sulfonic acid type anionic surfactants such as alkane sulfonate, α-olefin sulfonate, linear alkylbenzene sulfonate, α-sulfo fatty acid ester salt, dialkyl sulfosuccinate,
(4) Phosphate ester type anionic surfactants such as alkyl phosphate ester salts, polyoxyalkylene alkyl phosphate ester salts, polyoxyalkylene alkyl phenyl phosphate ester salts, glycerin fatty acid ester monophosphate ester salts, and the like.
高級脂肪酸とは、炭素数6〜20の脂肪酸を意味し、高級アルコールとは、炭素数6〜20のアルコールを意味する。
アニオン界面活性剤の対イオンは、ナトリウム、カリウム等のアルカリ金属、モノエタノールアミン、ジエタノールアミン等のアルカノールアミンが好ましい。これらは、1種のみを単独で使用してもよく、2種以上を併用してもよい。すなわち、アニオン界面活性剤の塩としては、ナトリウム、カリウム等のアルカリ金属との塩、モノエタノールアミン、ジエタノールアミン等のアルカノールアミンとの塩等が好ましい。
アニオン界面活性剤としては、未加硫ゴムの表面との濡れ性により優れる防着剤懸濁液が得られることから、ジアルキルスルホコハク酸塩が好ましく、ジオクチルスルホサクシネートNa塩がより好ましい。
The higher fatty acid means a fatty acid having 6 to 20 carbon atoms, and the higher alcohol means an alcohol having 6 to 20 carbon atoms.
The counter ion of the anionic surfactant is preferably an alkali metal such as sodium or potassium, or an alkanolamine such as monoethanolamine or diethanolamine. These may be used alone or in combination of two or more. That is, the salt of the anionic surfactant is preferably a salt with an alkali metal such as sodium or potassium, or a salt with an alkanolamine such as monoethanolamine or diethanolamine.
As the anionic surfactant, a dialkylsulfosuccinate is preferable, and a dioctylsulfosuccinate Na salt is more preferable because an anti-adhesive suspension excellent in wettability with the surface of the unvulcanized rubber can be obtained.
[(C)成分]
本発明では、(C)成分として、式(1)で表されるノニオン界面活性剤(すなわち、ポリオキシアルキレンアルキルエーテルを意味する)を用いる。式(1)のノニオン界面活性剤は、(B)成分であるアニオン界面活性剤とともに、未加硫ゴムの表面に対する前記防着剤懸濁液の表面張力を低下させることに加えて、未加硫ゴムの表面への前記防着剤の付着性を効果的に高める作用を奏するものと推察される。
[Component (C)]
In the present invention, a nonionic surfactant represented by the formula (1) (that means a polyoxyalkylene alkyl ether) is used as the component (C). The nonionic surfactant of the formula (1), together with the anionic surfactant which is the component (B), reduces the surface tension of the anti-adhesive agent suspension relative to the surface of the unvulcanized rubber, It is presumed that the effect of effectively increasing the adhesion of the adhesion-preventing agent to the surface of the vulcanized rubber is exhibited.
式中、Rは、炭素数が8〜18の脂肪族炭化水素基を示す。Rの脂肪族炭化水素基は、直鎖状でも分岐鎖状でもよい。また、飽和、不飽和のいずれであってもよい。Rの炭素数は、(A)成分の分散性に優れる点から、好ましくは12〜16であり、12〜13がさらに好ましい。 In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms. The aliphatic hydrocarbon group for R may be linear or branched. Moreover, either saturated or unsaturated may be sufficient. The carbon number of R is preferably 12 to 16 and more preferably 12 to 13 from the viewpoint of excellent dispersibility of the component (A).
AOは炭素数2〜4のオキシアルキレン基を示し、nはAOの平均付加モル数である。
nは、1〜8が好ましく、1〜5がより好ましい。
nが1未満では界面活性能が低下し、(A)成分の分散性が低下する。nが1〜8の範囲で、(A)成分の分散性が向上し、更に、未加硫ゴム表面の疎水性が高い場合にも被覆に充分な粘弾性を与えることで付着性を向上させるものと考えられる。nが8を超えると、親水性が高くなりすぎて適性を欠いてしまう。
AO represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the average added mole number of AO.
n is preferably from 1 to 8, and more preferably from 1 to 5.
When n is less than 1, the surface activity decreases, and the dispersibility of component (A) decreases. When n is in the range of 1 to 8, the dispersibility of the component (A) is improved, and the adhesion is improved by giving sufficient viscoelasticity to the coating even when the hydrophobicity of the unvulcanized rubber surface is high. It is considered a thing. When n exceeds 8, the hydrophilicity becomes too high and lacks suitability.
炭素数2〜4のオキシアルキレン基とは、炭素数2〜4のアルキレンオキサイドが付加してなる基であって、エチレンオキサイドが付加してなるオキシエチレン基(EO)、プロピレンオキサイドが付加してなるオキシプロピレン基(PO)、ブチレンオキサイドが付加してなるオキシブチレン基(BO)があるが、(AO)nは、少なくともオキシエチレン基を含む。(AO)nが、オキシエチレン基(EO)と、オキシプロピレン基(PO)および/またはオキシブチレン基(BO)とを含む場合は、これらの基はブロック状に配列していても、ランダムに配列していてもよい。好ましい(AO)nは、親水性、疎水性のバランスに優れる点から、オキシエチレン基(EO)のみからなる。 The oxyalkylene group having 2 to 4 carbon atoms is a group formed by adding an alkylene oxide having 2 to 4 carbon atoms, and an oxyethylene group (EO) formed by adding ethylene oxide or propylene oxide. There are oxypropylene groups (PO) and oxybutylene groups (BO) formed by addition of butylene oxide, and (AO) n contains at least an oxyethylene group. (AO) When n contains an oxyethylene group (EO) and an oxypropylene group (PO) and / or an oxybutylene group (BO), these groups are randomly arranged even if they are arranged in a block shape. It may be arranged. Preferable (AO) n consists of only an oxyethylene group (EO) from the viewpoint of excellent balance between hydrophilicity and hydrophobicity.
このようなノニオン界面活性剤(C)としては、例えば、下記のものが挙げられる。
・式(1)中のRが炭素数13の分岐状、かつ飽和型の脂肪族炭化水素基であって、nが3であり、かつAOがEOであるノニオン界面活性剤(以下、C13EO3と表記することがある。)。このようなノニオン界面活性剤(C)としては、ライオン(株)製、「レオコールTD−30(純度100%)」がある。
・式(1)中のRが炭素数13の分岐状、かつ飽和型の脂肪族炭化水素基であって、nが3であり、かつAOとしてEOが2モル、POが1モル付加したノニオン界面活性剤(以下、C13EO2/PO1と表記することがある。)。このようなノニオン界面活性剤(C)としては、青木油脂工業(株)製、「ファインサーフTDP−0201R(純度100%)」がある。
・式(1)中のRが炭素数18の直鎖状、かつ飽和型の脂肪族炭化水素基であって、nが5であり、かつAOがEOであるノニオン界面活性剤(以下、C18EO5と表記することがある。)。このようなノニオン界面活性剤(C)としては、青木油脂工業(株)製、「ブラウノンSR−705(純度100%)」)がある。
これらのなかでもより好ましくは、C13EO3、C13EO2/PO1である。
As such nonionic surfactant (C), the following are mentioned, for example.
A nonionic surfactant (hereinafter referred to as C13EO3) in which R in the formula (1) is a branched and saturated aliphatic hydrocarbon group having 13 carbon atoms, n is 3, and AO is EO. May be indicated.) As such a nonionic surfactant (C), there is “Leocor TD-30 (purity 100%)” manufactured by Lion Corporation.
-Nonion in which R in formula (1) is a branched and saturated aliphatic hydrocarbon group having 13 carbon atoms, n is 3, and 2 mol of EO and 1 mol of PO are added as AO Surfactant (hereinafter sometimes referred to as C13EO2 / PO1). As such a nonionic surfactant (C), there is “Finesurf TDP-0201R (purity 100%)” manufactured by Aoki Oil & Fat Co., Ltd.
A nonionic surfactant (hereinafter referred to as C18EO5) in which R in the formula (1) is a linear and saturated aliphatic hydrocarbon group having 18 carbon atoms, n is 5, and AO is EO. May be written.) Examples of such nonionic surfactant (C) include “Brownon SR-705 (purity 100%)” manufactured by Aoki Oil & Fat Co., Ltd.).
Among these, C13EO3 and C13EO2 / PO1 are more preferable.
[任意成分]
本発明の防着剤には、上述の(A)〜(C)成分の他に、必要に応じて、消泡剤、濡れ性補助剤、滑剤(滑り剤)、粘性補助剤などの添加剤が任意成分として含まれていてもよい。
消泡剤としては特に限定はないが、例えば、ヒマシ油、ゴマ油、アマニ油、動植物油などの油脂系消泡剤;ステアリン酸イソアミル、コハク酸ジステアリル、エチレングリコールジステアレート、ステアリン酸ブチルなどの脂肪酸エステル系消泡剤;ポリオキシアルキレンモノハイドリックアルコールジ−t−アミルフェノキシエタノール、3−ヘプタノール、2−エチルヘキサノールなどのアルコール系消泡剤;ジ−t−アミルフェノキシエタノール、3−ヘプチルセロソルブ、ノニルセロソルブ、3−ヘプチルカルビトールなどのエーテル系消泡剤;トリブチルオスフェート、トリス(ブトキシエチル)フォスフェートなどのリン酸エステル系消泡剤;ジアミルアミンなどのアミン系消泡剤;ポリアルキレンアミド、アシレートポリアミンなどのアミド系消泡剤;鉱物油;シリコーン油;などが挙げられる。上記消泡剤を1種以上、使用できる。
[Optional ingredients]
In addition to the above-mentioned components (A) to (C), the anti-adhesive agent of the present invention may contain additives such as antifoaming agents, wettability aids, lubricants (slip agents), and viscosity aids as necessary. May be included as an optional component.
There are no particular limitations on the antifoaming agent, but for example, oil-based antifoaming agents such as castor oil, sesame oil, linseed oil, animal and vegetable oils; isoamyl stearate, distearyl succinate, ethylene glycol distearate, butyl stearate, etc. Fatty acid ester-based antifoaming agents; alcohol-based antifoaming agents such as polyoxyalkylene monohydric alcohol di-t-amylphenoxyethanol, 3-heptanol, 2-ethylhexanol; di-t-amylphenoxyethanol, 3-heptylcellosolve, Ether-type antifoaming agents such as nonyl cellosolve and 3-heptylcarbitol; Phosphate-based antifoaming agents such as tributyl osphate and tris (butoxyethyl) phosphate; Amine-based antifoaming agents such as diamylamine; Acylate polyami Amide-based defoaming agent and the like; mineral oils; silicone oil; and the like. One or more of the above antifoaming agents can be used.
濡れ性補助剤としてはアルコール類が挙げられ、特に限定はないが、例えば、メタノール、エタノール、ヘキサノール、グリセリン、1,3−ブタンジオール、プロピレングリコール、ジプロピレングリコール、ペンチレングリコール、ヘキシレングリコール、ポリエチレングリコール、ソルトール、マルチトール、スクロース、エリスリトール、キシリトール等が挙げられ、1種以上を使用できる。 Examples of the wettability aid include alcohols, and are not particularly limited. For example, methanol, ethanol, hexanol, glycerin, 1,3-butanediol, propylene glycol, dipropylene glycol, pentylene glycol, hexylene glycol, Examples thereof include polyethylene glycol, saltol, maltitol, sucrose, erythritol, xylitol and the like, and one or more kinds can be used.
滑剤としては金属石ケン類が挙げられ、特に限定はないが、例えば、ラウリン酸マグネシウム、ラウリン酸カルシウム、ラウリン酸亜鉛、ミリスチン酸マグネシウム、ミリスチン酸カルシウム、ミリスチン酸亜鉛、パルミチン酸マグネシウム、パルミチン酸カルシウム、パルミチン酸亜鉛、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸亜鉛、トリオクタデカン酸アルミニウム、ジオクタデカン酸アルミニウム、モノオクタデカン酸アルミニウム、オクタデカン酸カルシウム、オクタデカン酸亜鉛、オクタデカン酸マグネシウム、オクタデカン酸バリウム等からなる粒子が挙げられ、1種以上を使用できる。なお、ここに記載された金属石ケン類は、非水溶性塩であり、一般にアニオン界面活性剤には該当しないものである。
また、滑剤としてはさらに、例えば、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム等の炭酸塩;カオリン、ケイ酸アルミニウム、ケイ酸カルシウム、クレー、タルク、マイカ、セリサイト等のケイ酸塩;硫酸カルシウム、硫酸バリウム等の硫酸塩;シリカ、アルミナ、酸化マグネシウム、三酸化アンチモン、酸化チタン、ホワイトカーボン、酸化鉄等の金属酸化物;水酸化アルミニウム、水酸化マグネシウム、水酸化鉄等の金属水酸化物;ベンガラ;カーボンブラック;グラファイト等の無機粉体類も挙げられ、1種以上を使用できる。
Examples of the lubricant include metal soaps, and are not particularly limited. For example, magnesium laurate, calcium laurate, zinc laurate, magnesium myristate, calcium myristate, zinc myristate, magnesium palmitate, calcium palmitate, Particles consisting of zinc palmitate, magnesium stearate, calcium stearate, zinc stearate, aluminum trioctadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecanoate, zinc octadecanoate, magnesium octadecanoate, barium octadecanoate, etc. 1 or more types can be used. The metal soaps described here are water-insoluble salts and generally do not correspond to anionic surfactants.
Further, as the lubricant, for example, carbonates such as calcium carbonate, magnesium carbonate, barium carbonate; silicates such as kaolin, aluminum silicate, calcium silicate, clay, talc, mica, sericite; calcium sulfate, sulfuric acid Sulfates such as barium; metal oxides such as silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon and iron oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide; bengara Carbon black; inorganic powders such as graphite are also included, and one or more kinds can be used.
粘性補助剤としては、水溶性高分子類が挙げられ、特に限定はないが、例えば、蛋白類、ポリアクリル酸、ポリアクリル酸ナトリウム、ポリアクリルアミド、ポリビニルアルコール、ポリビニルピロリドン、ポリエチレングリコール、ポリエチレンオキシド、水溶性ウレタン樹脂、水溶性メラミン樹脂、水溶性エポキシ樹脂、水溶性ブタジエン樹脂、水溶性フェノール樹脂等の合成水溶性高分子;キサンタンガム、グアーガム、ウェランガム、ローカストビーンガム、ダイユータンガム、タマリンドガム、タマリンドシードガム、トラガントガム、アラビアガム、カラギーナン、ラムザンガム、サクシノグリカン、タラガム、ジェランガム、カラヤガム、ペクチン、アルギン酸誘導体、セルロースエーテル類等の天然水溶性高分子が挙げられ、これらを1種以上使用できる。
また、防着剤には、その粉体流動を抑制するなどの目的で、水を含有させてもよい。その場合、水の含有量は、例えば防着剤の総質量に対して2〜3質量%程度である。
Examples of the viscosity auxiliary agent include water-soluble polymers and are not particularly limited. For example, proteins, polyacrylic acid, sodium polyacrylate, polyacrylamide, polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethylene oxide, Synthetic water-soluble polymers such as water-soluble urethane resin, water-soluble melamine resin, water-soluble epoxy resin, water-soluble butadiene resin, water-soluble phenol resin; xanthan gum, guar gum, welan gum, locust bean gum, diyutan gum, tamarind gum, tamarind Examples include natural water-soluble polymers such as seed gum, tragacanth gum, gum arabic, carrageenan, rhamzan gum, succinoglycan, tara gum, gellan gum, karaya gum, pectin, alginic acid derivatives, and cellulose ethers. These can be used 1 or more.
The anti-adhesive agent may contain water for the purpose of suppressing the powder flow. In that case, content of water is about 2-3 mass% with respect to the total mass of an adhesion preventive agent, for example.
[防着剤および防着処理済み未加硫ゴム]
本発明の防着剤は、Na型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有するベントナイト(A)を防着剤の総質量に対して50〜90質量%と、アニオン界面活性剤(B)と、式(1)で表されるノニオン界面活性剤(C)とを含有する。
ベントナイト(A)は、防着性を担う成分であるため、防着剤中の含有量が防着剤の総質量に対して50質量%未満では、防着性が低下する。一方、防着剤中の含有量が防着剤の総質量に対して90質量%を超えると、相対的に(B)成分および(C)成分の含有量が少なくなるため、未加硫ゴムの表面に対する防着剤懸濁液の濡れ性、および付着性が低下し、その結果、充分な防着性が得られない。防着剤中のベントナイト(A)のより好ましい含有量は、防着剤の総質量に対して60〜80質量%である。
なお、ベントナイトには、水を含んだ状態で流通するものもあるが、本明細書においてベントナイト(A)の含有量といった場合、前記含有量は、水の量を含まない値である。
[Anti-curing agent and non-vulcanized rubber with anti-deposition treatment]
The anti-adhesive agent of the present invention comprises 50 to 90% by mass of bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more based on the total mass of the bentonite, and an anionic surfactant. (B) and the nonionic surfactant (C) represented by Formula (1) are contained.
Since bentonite (A) is a component responsible for adhesion, the adhesion is reduced when the content in the adhesion is less than 50% by mass relative to the total mass of the adhesion. On the other hand, when the content in the anti-adhesive agent exceeds 90% by mass with respect to the total mass of the anti-adhesive agent, the contents of the component (B) and the component (C) are relatively reduced. As a result, the wettability and adhesion of the suspension of the anti-adhesive agent to the surface of the resin deteriorate, and as a result, sufficient anti-adhesive properties cannot be obtained. The more preferable content of bentonite (A) in the anti-adhesive agent is 60 to 80% by mass with respect to the total mass of the anti-adhesive agent.
In addition, some bentonite circulates in a state containing water, but in the present specification, when the content of bentonite (A) is referred to, the content is a value not including the amount of water.
防着剤中における(C)成分の質量に対する(B)成分の質量の質量比(B)/(C)は、0.15〜0.65が好ましい。このような質量比であると、本発明の防着剤を防着剤懸濁液として使用した場合に、前記防着剤懸濁液が未加硫ゴムの表面に対して良好な濡れ性を示し、かつ、高温状態にある未加硫ゴムの表面で前記防着剤懸濁液が脱水、乾燥されるときに、前記防着剤懸濁液が前記未加硫ゴムの表面でハジかれることなく表面にムラなく付着する優れた防着剤が得られる。このように防着剤懸濁液と未加硫ゴムとの濡れ性と付着性とが共に優れると、防着剤懸濁液の防着剤濃度を低くした場合でも、未加硫ゴムに対して良好な防着性能を付与することができる。前記質量比が0.15未満では、(B)成分であるアニオン界面活性剤が相対的に少ないことに起因して、防着剤懸濁液と未加硫ゴムとの濡れ性が不充分となる。一方、0.65を超えると、(C)成分である特定のノニオン界面活性剤が相対的に少ないことに起因して、防着剤の未加硫ゴムの表面に対する付着性が不充分となる。質量比(B)/(C)は、好ましくは0.20〜0.50である。 The mass ratio (B) / (C) of the mass of the component (B) to the mass of the component (C) in the anti-adhesive agent is preferably 0.15 to 0.65. With such a mass ratio, when the anti-adhesive agent of the present invention is used as an anti-adhesive suspension, the anti-adhesive suspension exhibits good wettability with respect to the surface of the unvulcanized rubber. And when the anti-adhesive suspension is dehydrated and dried on the surface of the unvulcanized rubber in a high temperature state, the anti-adhesive suspension is removed from the surface of the unvulcanized rubber. And an excellent anti-adhesive that adheres uniformly to the surface. Thus, when both the wettability and adhesion between the anti-adhesive suspension and the unvulcanized rubber are excellent, even when the concentration of the anti-adhesive suspension is reduced, And good adhesion performance can be imparted. When the mass ratio is less than 0.15, the wettability between the anti-adhesive suspension and the unvulcanized rubber is insufficient due to the relatively small amount of the anionic surfactant as the component (B). Become. On the other hand, when it exceeds 0.65, due to the relatively small amount of the specific nonionic surfactant as the component (C), the adhesion of the anti-adhesive agent to the surface of the unvulcanized rubber becomes insufficient. . The mass ratio (B) / (C) is preferably 0.20 to 0.50.
防着剤中における(A)成分の質量に対する、(B)成分および(C)成分の総質量の質量比((B)+(C))/(A)は、0.05以上が好ましく、より好ましくは0.15〜0.30である。前記質量比が上記下限値未満となると、防着剤懸濁液と未加硫ゴムの表面との濡れ性、防着剤の未加硫ゴムの表面に対する付着性のいずれもが不充分となり、良好な防着性能を付与できなくなる傾向にある。一方、質量比((B)+(C))/(A)が大きくなっても、上述の濡れ性や付着性は低下しないが、界面活性剤の量が相対的に多くなることに起因して、防着剤懸濁液の調製時や前記防着剤懸濁液を未加硫ゴムに付着させた際に起泡し、泡トラブルが発生する可能性がある。また、界面活性剤は高価であるため、コスト面でも有利ではない。これらの点からは、質量比((B)+(C))/(A)は0.30以下であることが好ましい。 The mass ratio ((B) + (C)) / (A) of the total mass of the component (B) and the component (C) to the mass of the component (A) in the anti-adhesive agent is preferably 0.05 or more, More preferably, it is 0.15-0.30. When the mass ratio is less than the above lower limit, the wettability between the surface of the anti-adhesive agent suspension and the unvulcanized rubber, the adhesion of the anti-adhesive agent to the surface of the unvulcanized rubber is insufficient, There is a tendency that it is impossible to impart good adhesion performance. On the other hand, even if the mass ratio ((B) + (C)) / (A) is increased, the above-mentioned wettability and adhesion are not lowered, but the amount of the surfactant is relatively increased. In addition, foaming troubles may occur during the preparation of the anti-sticking agent suspension or when the anti-sticking agent suspension is adhered to the unvulcanized rubber. Further, since the surfactant is expensive, it is not advantageous in terms of cost. From these points, the mass ratio ((B) + (C)) / (A) is preferably 0.30 or less.
本発明の防着剤は、(A)〜(C)成分と、必要に応じて配合される任意成分とを混合することにより製造できる。混合に用いる装置としては、撹拌羽根を容器内に備えた構成の装置などを使用できる。具体的には、リボン型混合機、垂直スクリュー型混合機等の揺動撹拌または撹拌を行える粉体混合機を挙げることができる。また、撹拌装置が複数組み合わされたスーパーミキサー(株式会社カワタ製)、ハイスピードミキサー(株式会社深江製)、ニューグラムマシン(株式会社セイシン企業製)、SVミキサー(株式会社神鋼環境ソリューション社製)等の多機能粉体混合機なども使用できる。また、ジョークラッシャー、ジャイレトリークラッシャー、コーンクラッシャー、ロールクラッシャー、インパクトクラッシャー、ハンマークラッシャー、ロッドミル、ボールミル、振動ロッドミル、振動ボールミル、円盤型ミル、ジェットミル、サイクロンミルなどの乾式粉砕機を用いてもよい。
また、(A)〜(C)成分、任意成分のうち、液体成分を少なくとも1種使用する場合には、前記液体成分を液体成分以外の混合物に対して吹付けたり散布したりするスプレー装置、シャワー装置などを併用してもよい。
The anti-adhesive agent of this invention can be manufactured by mixing (A)-(C) component and the arbitrary component mix | blended as needed. As an apparatus used for mixing, an apparatus having a configuration in which a stirring blade is provided in a container can be used. Specific examples include a powder mixer that can perform rocking stirring or stirring, such as a ribbon-type mixer and a vertical screw-type mixer. In addition, a super mixer (manufactured by Kawata Co., Ltd.), a high speed mixer (manufactured by Fukae Co., Ltd.), a Newgram machine (manufactured by Seishin Enterprise Co., Ltd.), and an SV mixer (manufactured by Shinko Environmental Solution Co., Ltd.) Multifunctional powder mixers such as can also be used. Also, dry crushers such as jaw crusher, gyratory crusher, cone crusher, roll crusher, impact crusher, hammer crusher, rod mill, ball mill, vibration rod mill, vibration ball mill, disk type mill, jet mill, cyclone mill, etc. Good.
Moreover, when using at least 1 type of liquid component among (A)-(C) component and arbitrary components, the spray apparatus which sprays or sprays the said liquid component with respect to mixtures other than a liquid component, You may use a shower apparatus etc. together.
本発明の防着処理済み未加硫ゴムの製造方法は、上述した防着剤を未加硫ゴムの表面に付着させる工程を有する。このようにして製造された防着処理済み未加硫ゴムは、積み重ねたり、折り畳んだりして貯蔵されても、未加硫ゴム同士が密着してしまうことがない。
付着させる工程としては、防着剤を水に分散させた防着剤懸濁液を未加硫ゴムの表面に付着させる懸濁液付着工程と、未加硫ゴムの表面の防着剤懸濁液を乾燥して、防着剤からなる被膜を未加硫ゴムの表面に形成する乾燥工程とを有する工程が好ましい。このような工程は、ウェット法と呼ばれることがある。
The method for producing an adhesion-treated unvulcanized rubber according to the present invention includes a step of adhering the above-mentioned adhesion preventing agent to the surface of the unvulcanized rubber. Even if the non-vulcanized rubber that has been subjected to the adhesion treatment manufactured in this way is stored by being stacked or folded, the unvulcanized rubber does not adhere to each other.
The adhesion process includes a suspension adhesion process in which an anti-adhesive suspension in which an anti-adhesive is dispersed in water is adhered to the surface of the unvulcanized rubber, and an anti-adhesive suspension on the surface of the unvulcanized rubber. A step having a drying step of drying the liquid and forming a film made of an anti-adhesive agent on the surface of the unvulcanized rubber is preferable. Such a process is sometimes called a wet method.
懸濁液付着工程では、シート状などに成形された時の熱により例えば80〜150℃程度の高温状態にある未加硫ゴムに対して、防着剤懸濁液を付着させることが好ましい。 In the suspension attaching step, it is preferable to attach the anti-adhesive agent suspension to the unvulcanized rubber at a high temperature of, for example, about 80 to 150 ° C. by heat when it is formed into a sheet or the like.
懸濁液付着工程の具体的方法としては、例えば、防着剤懸濁液を未加硫ゴムにシャワー装置で散布する方法、防着剤懸濁液の入った槽に未加硫ゴムを短時間浸漬するディップ法が挙げられる。また、塗布装置を用いて防着剤懸濁液を未加硫ゴムに塗布する方法などを採用してもよく、これらの方法を適宜併用してもよい。 Specific methods of the suspension adhesion step include, for example, a method of spraying the anti-adhesive suspension on the unvulcanized rubber with a shower device, and a short method of unvulcanized rubber in the tank containing the anti-adhesive suspension. There is a dipping method in which the immersion is performed for a time. Moreover, the method of apply | coating anti-adhesive agent suspension to unvulcanized rubber using an application | coating apparatus may be employ | adopted, and these methods may be used together suitably.
以上説明したように、本発明の防着剤は、Na型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有し、付着性に優れるベントナイト(A)を防着剤の総質量に対して50〜90質量%を含有したうえで、アニオン界面活性剤(B)と、式(1)で表されるノニオン界面活性剤(C)とを含んでいる。そして、ノニオン界面活性剤(C)の含有量に対するアニオン界面活性剤(B)の含有量の質量比(B)/(C)が、好ましくは0.15〜0.65である。そのため、前記防着剤は、防着剤懸濁液として使用される場合、前記防着剤の濃度が防着剤懸濁液の総質量に対して1.0〜1.5質量%の低濃度で使用することができ、前記低濃度で使用しても、前記防着剤からなる均一な被膜を未加硫ゴムの表面に形成でき、未加硫ゴムに対して優れた防着性能を付与する。 As described above, the anti-adhesive agent of the present invention contains Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite, and bentonite (A) having excellent adhesiveness with respect to the total mass of the anti-adhesive agent. After containing 50-90 mass%, the anionic surfactant (B) and the nonionic surfactant (C) represented by Formula (1) are included. And mass ratio (B) / (C) of content of anionic surfactant (B) with respect to content of nonionic surfactant (C) becomes like this. Preferably it is 0.15-0.65. Therefore, when the antiadhesive is used as an antiadhesive suspension, the concentration of the antiadhesive is as low as 1.0 to 1.5% by mass relative to the total mass of the antiadhesive suspension. It can be used at a low concentration, and even when used at the low concentration, it can form a uniform film composed of the anti-adhesive agent on the surface of the unvulcanized rubber, and has excellent anti-adhesion performance against the unvulcanized rubber. Give.
本発明の防着剤がこのような効果を奏する理由は、次のように推察できる。
防着剤を構成する(B)成分のアニオン界面活性剤は、前記防着剤を防着剤懸濁液としたときに、ベントナイト(A)中のNa型モンモリロナイトに効果的に吸着し、前記Na型モンモリロナイトを前記防着剤懸濁液中で薄片状に均一に分散させるとともに、未加硫ゴムの表面に対する前記防着剤懸濁液の表面張力を低下させるものと考えられる。よって、(B)成分を含む本発明の防着剤から調製された防着剤懸濁液は、未加硫ゴムの表面との濡れ性に優れるだけでなく、Na型モンモリロナイトを高い分散状態で保持しており、未加硫ゴムの表面を効率的に覆えるものと考えられる。
The reason why the anti-adhesive agent of the present invention has such an effect can be presumed as follows.
The anionic surfactant of the component (B) constituting the anti-adhesive agent is effectively adsorbed on Na-type montmorillonite in bentonite (A) when the anti-adhesive agent is used as an anti-adhesive suspension, It is considered that Na-type montmorillonite is uniformly dispersed in the form of flakes in the above-mentioned anti-adhesive suspension, and the surface tension of the above-mentioned anti-adhesive suspension with respect to the surface of the unvulcanized rubber is reduced. Therefore, the anti-sticking agent suspension prepared from the anti-sticking agent of the present invention containing the component (B) is not only excellent in wettability with the surface of the unvulcanized rubber, but also in a highly dispersed state of Na-type montmorillonite. It is considered that the surface of the unvulcanized rubber can be efficiently covered.
一方、防着剤を構成する(C)成分のノニオン界面活性剤は、(B)成分であるアニオン界面活性剤とともに作用して、未加硫ゴムの表面に対する前記防着剤懸濁液の表面張力を低下させることに加えて、(A)成分であるベントナイトの前記防着剤懸濁液中における分散性を制御し、未加硫ゴムの表面を覆った防着剤懸濁液が乾燥脱水されていく過程で、防着剤懸濁液の粘弾性を高めて、未加硫ゴム表面への防着剤の付着性を効果的に高めているものと推察される。そのため、未加硫ゴムの表面を覆った防着剤懸濁液中の防着剤は、一旦付着した後に乾燥過程で未加硫ゴム表面ではじかれることなく、未加硫ゴムの表面にムラなく付着して、均一な被膜を形成するものと考えられる。 On the other hand, the nonionic surfactant of component (C) that constitutes the anti-adhesive agent acts together with the anionic surfactant as the component (B), and the surface of the anti-adhesive suspension with respect to the surface of the unvulcanized rubber In addition to lowering the tension, the dispersion of the bentonite component (A) in the above-described anti-adhesive suspension is controlled, and the anti-adhesive suspension covering the surface of the unvulcanized rubber is dried and dehydrated. In the course of the process, it is presumed that the adhesion of the adhesion preventing agent to the unvulcanized rubber surface is effectively enhanced by increasing the viscoelasticity of the adhesion preventing agent suspension. For this reason, the anti-adhesive agent in the anti-adhesive suspension covering the surface of the unvulcanized rubber does not repel the surface of the unvulcanized rubber during the drying process after adhering to the surface. It is thought that it adheres and forms a uniform film.
このように本発明の防着剤は、防着性を担う成分としてNa型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有するベントナイト(A)を含有することに加えて、上述のような作用を奏するアニオン界面活性剤(B)とノニオン界面活性剤(C)とを特定の比率で含有する。
よって、本発明の防着剤を、防着剤懸濁液として使用した場合に、未加硫ゴムの表面に対して前記防着剤懸濁液が良好な濡れ性を示し、かつ、前記防着剤懸濁液の乾燥時には未加硫ゴムの表面に前記防着剤がムラなく付着する優れた付着性を示し、そのため、懸濁液の防着剤濃度を低くして使用した場合でも、未加硫ゴムに対して良好な防着性能を付与することができる。
Thus, in addition to containing bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite as a component responsible for adhesion, the depositing agent of the present invention is as described above. An anionic surfactant (B) and a nonionic surfactant (C) that exhibit a specific action are contained in a specific ratio.
Therefore, when the anti-adhesive agent of the present invention is used as an anti-adhesive suspension, the anti-adhesive agent suspension exhibits good wettability with respect to the surface of the unvulcanized rubber, and When the adhesive suspension is dried, the anti-adhesive agent adheres to the surface of the unvulcanized rubber evenly and exhibits excellent adhesion. Therefore, even when the suspension is used with a low concentration of the anti-adhesive agent, Good adhesion performance can be imparted to unvulcanized rubber.
本発明の防着剤が適用可能なゴム種には特に制限はなく、未加硫のゴムであればよい。
ゴム種としては、例えば、天然ゴム(NR)、ブタジエンゴム(BR)、スチレンブタジエンゴム(SBR)、IIR(ブチルゴム)、EPDM(エチレンプロピレンゴム)等のゴムや、これらのうちの複数種が混合されたゴムが挙げられる。また、防着剤が付与される未加硫ゴムは、加硫剤(硫黄等。)や、ゴムに対して一般に使用される各種添加物(老化防止剤、加硫促進剤、カーボンブラック等。)等を含有できる。
本発明の1つの側面は、Na型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有するベントナイト(A)を組成物の総質量に対して50〜90質量%と、アニオン界面活性剤(B)と、前記式(1)で表されるノニオン界面活性剤(C)とを含有し、前記(B)の質量/前記(C)の質量で表される質量比が、0.15〜0.65である組成物に関する。
本発明の別の側面は、Na型モンモリロナイトをベントナイトの総質量に対して60質量%以上含有するベントナイト(A)を組成物の総質量に対して50〜90質量%と;ジアルキルスルホコハク酸塩、より好ましくはジオクチルスルホサクシネートNa塩であるアニオン界面活性剤(B)と;前記式(1)で表され、式(1)中のRが炭素数13の分岐状、かつ飽和型の脂肪族炭化水素基であって、nが3であり、かつAOがEOであるノニオン界面活性剤、前記式(1)で表され、式(1)中のRが炭素数13の分岐状、かつ飽和型の脂肪族炭化水素基であって、nが3であり、かつAOとしてEOが2モル、POが1モル付加したノニオン界面活性剤、および前記式(1)で表され、式(1)中のRが炭素数18の直鎖状、かつ飽和型の脂肪族炭化水素基であって、nが5であり、かつAOがEOであるノニオン界面活性剤からなる群より選択させる少なくとも1種のノニオン界面活性剤(C)とを含有し、前記(B)の質量/前記(C)の質量で表される質量比が、0.15〜0.65である組成物に関する。
本発明のまた別の側面は、消泡剤、濡れ性補助剤、滑剤(滑り剤)および粘性補助剤からなる群より選択される少なくとも1種の添加剤を更に含有する、上記側面のいずれか1つの組成物に関する。
本発明のまた別の側面は、上記側面のいずれか1つの組成物の未加硫ゴムの防着のための使用に関する。
There are no particular restrictions on the type of rubber to which the adhesion-preventing agent of the present invention can be applied, as long as it is an unvulcanized rubber.
Examples of rubber types include natural rubber (NR), butadiene rubber (BR), styrene butadiene rubber (SBR), IIR (butyl rubber), EPDM (ethylene propylene rubber), and a mixture of these. The rubber which was made is mentioned. In addition, the unvulcanized rubber to which the adhesion-preventing agent is applied is a vulcanizing agent (sulfur etc.) and various additives generally used for rubber (anti-aging agent, vulcanization accelerator, carbon black, etc.). ) And the like.
One aspect of the present invention is that the bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite is 50 to 90% by mass with respect to the total mass of the composition, an anionic surfactant ( B) and the nonionic surfactant (C) represented by the formula (1), and the mass ratio represented by the mass of (B) / the mass of (C) is 0.15 to 0.15. Relates to the composition being 0.65.
Another aspect of the present invention is that the bentonite (A) containing Na-type montmorillonite in an amount of 60% by mass or more with respect to the total mass of bentonite is 50 to 90% by mass with respect to the total mass of the composition; More preferably, an anionic surfactant (B) which is a dioctylsulfosuccinate Na salt; represented by the formula (1), wherein R in the formula (1) is a branched and saturated aliphatic group having 13 carbon atoms. A nonionic surfactant having a hydrocarbon group, n of 3 and AO of EO, represented by the formula (1), wherein R in the formula (1) is branched and saturated with 13 carbon atoms Type non-ionic surfactant having n type of 3 and 2 mol of EO and 1 mol of PO as AO, and the formula (1) R is straight and saturated with 18 carbon atoms At least one nonionic surfactant (C) selected from the group consisting of nonionic surfactants, wherein n is 5, and AO is EO, It is related with the composition whose mass ratio represented by the mass of B) / the mass of said (C) is 0.15-0.65.
Another aspect of the present invention is any one of the above aspects, further comprising at least one additive selected from the group consisting of an antifoaming agent, a wettability aid, a lubricant (slipper), and a viscosity aid. Relates to one composition.
Yet another aspect of the present invention relates to the use of any one of the above aspects for the prevention of unvulcanized rubber.
以下、本発明について、実施例を挙げて具体的に説明する。
[製造例]
Na型モンモリロナイト含有量が表1に示す値となるように、ベントナイト(A−1)(クニミネ工業(株)製「クニピア−F」、Na型モンモリロナイト含有量:98.5質量%(クニピアF製品安全チェックシート(MSDS)に記載を参照。))に対して、下記方法で調製したベントナイト副鉱物を混合し、Na型モンモリロナイト含有量の異なる6種類のベントナイト(A−2)〜(A−6)を(A)成分として調製した。
Hereinafter, the present invention will be specifically described with reference to examples.
[Production example]
Bentonite (A-1) (“Kunipia-F” manufactured by Kunimine Kogyo Co., Ltd., Na-type montmorillonite content: 98.5% by mass (Kunipia F product) so that the Na-type montmorillonite content becomes the value shown in Table 1. 6) Bentonite (A-2) to (A-6) having different Na-type montmorillonite contents mixed with a bentonite sub-mineral prepared by the following method. ) Was prepared as component (A).
(ベントナイト副鉱物の調製方法)
ベントナイト(クニミネ工業(株)製「クニゲルV−1」)の5質量%水分散液を調製し、これを一日放置し、固形分を沈殿させた。ついで、固形分が沈殿した液を遠心分離(回転数:約5000rpm、30分間)し、沈殿物を回収した。
ついで、この沈殿物の5質量%水分散液を調製し、上述と同様の方法による固形分の沈殿、遠心分離、沈殿の回収という一連の操作をさらに2回繰り返し、得られた沈殿物を減圧乾燥後、メノウ乳鉢で微粉砕した。こうして得られた粉体を「ベントナイト副鉱物」とした。
ベントナイト副鉱物をX線回折により分析した結果、前記ベントナイト副鉱物は、石英、クリストバライト、長石、炭酸塩鉱物等を主に含むこと、また、2θ=7°付近に出現するNa型モンモリロナイト由来の回折ピーク強度から求めたNa型モンモリロナイト含有量(残存量)は、検出限界の1質量%以下であることが確認された。
Na型モンモリロナイト含有量(残存量)を定量した際のX線回折の分析条件は下記のとおりである。
(Method for preparing bentonite secondary mineral)
A 5% by mass aqueous dispersion of bentonite (“Kunigel V-1” manufactured by Kunimine Kogyo Co., Ltd.) was prepared and allowed to stand for one day to precipitate a solid content. Next, the liquid in which the solid content was precipitated was centrifuged (rotation speed: about 5000 rpm, 30 minutes), and the precipitate was collected.
Next, a 5% by mass aqueous dispersion of this precipitate is prepared, and the series of operations of solid content precipitation, centrifugation, and precipitation recovery by the same method as described above is repeated twice more, and the resulting precipitate is decompressed. After drying, it was pulverized in an agate mortar. The powder thus obtained was designated as “bentonite secondary mineral”.
As a result of analyzing the bentonite minor mineral by X-ray diffraction, the bentonite minor mineral mainly contains quartz, cristobalite, feldspar, carbonate mineral, etc., and diffraction derived from Na-type montmorillonite appearing near 2θ = 7 °. It was confirmed that the content (residual amount) of Na-type montmorillonite determined from the peak intensity was 1% by mass or less of the detection limit.
The analysis conditions for X-ray diffraction when the Na-type montmorillonite content (residual amount) is quantified are as follows.
X線回折分析条件
・測定装置:X’Pert PRO MRD(PANalytical社製)
・ターゲット:Cu
・管電圧:45kV
・管電流:40mA
・スキャン軸:ゴニオ
・スキャン範囲:5°〜60°
・ステップサイズ:0.03°
・ステップ時間:12.7秒
・発散スリット:1/2°
・散乱スリット:1°
・受光スリット:なし
X-ray diffraction analysis conditions / measurement device: X'Pert PRO MRD (manufactured by PANalytical)
・ Target: Cu
・ Tube voltage: 45kV
・ Tube current: 40 mA
・ Scan axis: Goniometer ・ Scan range: 5 ° -60 °
・ Step size: 0.03 °
・ Step time: 12.7 seconds ・ Divergent slit: 1/2 °
・ Scatter slit: 1 °
・ Reception slit: None
なお、ベントナイト副鉱物の原料として用いた「クニゲルV−1」は、文献〔ベントナイトの鉱物組成分析(日本原子力学会誌)P.1055−1058〕によれば、スメクタイトの含有量が46〜49質量%とされている。ここでのスメクタイトとは、モンモリロナイトのことである。 “Kunigel V-1” used as a raw material for bentonite sub-minerals is described in the literature [Mineral composition analysis of bentonite (Journal of the Atomic Energy Society of Japan) 1055-1058], the smectite content is 46 to 49 mass%. The smectite here is montmorillonite.
[実施例1〜18、比較例1〜9]
表2〜4に示す質量比率で、(A)〜(C)成分と、滑剤としてのステアリン酸カルシウム(任意成分:日油(株)製、カルシウムステアレート(純度100%))とを混練して、均一粉体からなる各例の防着剤を調製した。そして、得られた各防着剤を水道水に攪拌しながら加え、防着剤の濃度が防着剤懸濁液の総質量に対して1質量%である防着剤懸濁液を調製した。
得られた各例の防着剤懸濁液(濃度1質量%)を用いて、下記の評価を行った。
[Examples 1 to 18, Comparative Examples 1 to 9]
Kneading components (A) to (C) and calcium stearate as a lubricant (optional component: manufactured by NOF Corporation, calcium stearate (purity 100%)) at mass ratios shown in Tables 2 to 4 In each case, an anti-adhesive agent comprising a uniform powder was prepared. And each obtained anti-adhesive was added to tap water, stirring, and prepared the anti-adhesive suspension whose density | concentration of an anti-adhesive is 1 mass% with respect to the total mass of an anti-adhesive suspension. .
The following evaluation was performed using the obtained anti-adhesive agent suspension (concentration 1% by mass) of each example.
各例で用いた(B)成分および(C)成分は以下のとおりである。
(B−1):ジオクチルスルホサクシネートNa塩(日本サイテックインダストリーズ(株)製、「エアロゾルGPG(純度70%)」)
(B−2):アルキル基の炭素数が12〜20であるアルキルベンゼンスルホン酸ナトリウム塩(ライオン(株)製、「リポランPB(純度95%)」)
(B−3):ステアリン酸Na塩(大日化学工業(株)製、「ダイワックスNA(純度100%))
The components (B) and (C) used in each example are as follows.
(B-1): Dioctylsulfosuccinate Na salt (Nippon Cytec Industries, Ltd., “Aerosol GPG (purity 70%)”)
(B-2): Alkylbenzenesulfonic acid sodium salt having 12 to 20 carbon atoms in the alkyl group (manufactured by Lion Corporation, “Lipolane PB (purity 95%)”)
(B-3): Na stearate (manufactured by Dainichi Chemical Co., Ltd., “Die Wax NA (purity 100%))
(C−1):ライオン(株)製、「レオコールTD−30(純度100%)」
(C−2):青木油脂工業(株)製、「ファインサーフTDP−0201R(純度100%)」
(C−3):青木油脂工業(株)製、「ブラウノンSR−705(純度100%)」
(C−4):比較品であって、式(1)において、Rが炭素数12の直鎖、飽和型、n=9、AO=EOのノニオン界面活性剤、ライオン(株)製、「レオックスCC−90(純度98%)」
(C-1): “Leocor TD-30 (100% purity)” manufactured by Lion Corporation
(C-2): Aoki Yushi Kogyo Co., Ltd., "Fine Surf TDP-0201R (purity 100%)"
(C-3): Aoki Yushi Kogyo Co., Ltd., “Brownon SR-705 (purity 100%)”
(C-4): Comparative product, wherein in formula (1), R is a linear, saturated, n = 9, AO = EO nonionic surfactant having 12 carbon atoms, manufactured by Lion Corporation, “ Leox CC-90 (purity 98%) "
<評価>
各種評価には、評価用ゴムとして下記の未加硫NR/BRゴムを用いた。
(未加硫NR/BRゴム)
NR(RSS♯3)70質量部とBR(JSR(株)製、「BR−01」)30質量部の合計100質量部に対して、ホワイトカーボン(東ソー・シリカ(株)製、「ニップシールVN−3」)10質量部と、ISAFブラック(東海カーボン(株)製、「シースト6」)30質量部と、JSRAROMA(プロセスオイル)(日本サン石油(株)製、「アロマ790」)15質量部と、亜鉛華(ハクスイテック(株)製、亜鉛華2種)3質量部と、ステアリン酸(日油(株)製、椿)1質量部と、6PPD(大内新興化学工業(株)製、老化防止剤「ノクラック6C」、N−フェニル−N’−(1,3−ジメチルブチル)−p−フェニレンジアミン)1質量部、CBS(大内新興化学工業(株)製、加硫促進剤「ノクセラーCZ−G」、N−シクロヘキシル−2−ベンゾチアゾリルスルフェンアミド)1質量部、硫黄(鶴見化学(株)製)1.5質量部を配合した(合計162.5質量部)未加硫NR/BRゴム。
<Evaluation>
For various evaluations, the following unvulcanized NR / BR rubber was used as a rubber for evaluation.
(Unvulcanized NR / BR rubber)
For a total of 100 parts by mass of 70 parts by mass of NR (RSS # 3) and 30 parts by mass of BR (manufactured by JSR Co., Ltd., “BR-01”), White Carbon (Tosoh Silica Co., Ltd., “Nip Seal VN -3 ") 10 parts by mass, ISAF black (Tokai Carbon Co., Ltd.," Seast 6 ") 30 parts by mass, JSRAROMA (Process Oil) (Nihon Sun Oil Co., Ltd.," Aroma 790 ") 15 parts by mass Parts, 3 parts by weight of zinc white (Hakusuitec Co., Ltd., 2 types of zinc white), 1 part by weight of stearic acid (manufactured by NOF Corporation, cocoon), 6PPD (manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.) , Anti-aging agent “NOCRACK 6C”, 1 part by mass of N-phenyl-N ′-(1,3-dimethylbutyl) -p-phenylenediamine), CBS (manufactured by Ouchi Shinsei Chemical Co., Ltd., vulcanization accelerator) "Noxeller CZ-G", N- Unvulcanized NR / BR rubber in which 1 part by mass of cyclohexyl-2-benzothiazolylsulfenamide) and 1.5 parts by mass of sulfur (manufactured by Tsurumi Chemical Co., Ltd.) were blended (total 162.5 parts by mass).
(1)濡れ性の評価
上記の未加硫ゴム(未加硫NR/BRゴム)を温度80〜120℃のオープンロールで練り出してゴムシート(厚さ:5〜8mm、60cm×15cm)とし、練り出された直後の前記ゴムシートを各例で得られた防着剤懸濁液(温度40℃)1Lに約1秒間浸漬した。その後、ゴムシートをすばやく垂直に引き上げ、室温下で静置し、約3秒間経過後にゴムシートの表面を写真撮影した。得られた写真を観察して、ゴムシートの表面積を100%とした際の濡れている部分の面積の割合(%)を求め、その値から濡れ性を下記1〜5の5段階で判定した。濡れている部分の面積が大きい方が、濡れ性に優れている。結果を表2〜4に示す。
1:0%
2:0を超え50%未満
3:50%以上90%未満
4:90%以上100%未満(合格)
5:100%(合格)
(1) Evaluation of wettability The unvulcanized rubber (unvulcanized NR / BR rubber) is kneaded with an open roll at a temperature of 80 to 120 ° C. to obtain a rubber sheet (thickness: 5 to 8 mm, 60 cm × 15 cm). The rubber sheet immediately after kneading was immersed in 1 L of an anti-adhesive suspension (temperature 40 ° C.) obtained in each example for about 1 second. Thereafter, the rubber sheet was quickly pulled up vertically and allowed to stand at room temperature. After about 3 seconds, the surface of the rubber sheet was photographed. By observing the obtained photograph, the ratio (%) of the area of the wet part when the surface area of the rubber sheet was set to 100% was determined, and the wettability was determined from the value in the following 5 stages. . The larger the area of the wet part, the better the wettability. The results are shown in Tables 2-4.
1%
2: 0 and less than 50% 3: 50% or more and less than 90% 4: 90% or more and less than 100% (pass)
5: 100% (pass)
(2)付着性の評価
上記(1)のようにして濡れ性を評価した直後(すなわち、ゴムシートの表面を写真撮影した直後)から、さらに室温下で静置し、90秒間経過後に再び、ゴムシートの表面を写真撮影した。得られた写真を観察して、ゴムシートの表面積を100%とした際の、防着剤乾燥被膜で覆われている部分の面積(被膜面積)の割合(%)、ならびに被膜の均質性(一様の膜厚で覆われている)の両面から、下記1〜5の5段階で判定した。結果を表に示す。
1:被膜面積が0%
2:被膜面積が0を超え40%未満
3:被膜面積が40%以上70%未満
4:被膜面積が70%以上100%未満であって、且つ、被膜が縦て縞状やマダラ状でない均質被膜である(合格)。
5:被膜面積が100%であって、且つ、皮膜が縦て縞状やマダラ状でない均質皮膜である(合格)。
(2) Evaluation of adhesiveness Immediately after evaluating the wettability as described in (1) above (that is, immediately after taking a picture of the surface of the rubber sheet), it is allowed to stand still at room temperature, and again after 90 seconds, The surface of the rubber sheet was photographed. By observing the obtained photograph, the ratio (%) of the area (coating area) of the portion covered with the dry coating of the anti-adhesive agent when the surface area of the rubber sheet is 100%, and the homogeneity of the coating ( It was determined in five stages from 1 to 5 below. The results are shown in the table.
1: 0% coating area
2: The coating area exceeds 0 and less than 40% 3: The coating area is 40% or more and less than 70% 4: The coating area is 70% or more and less than 100%, and the coating is not vertically striped or madrid It is a film (pass).
5: The coating area is 100%, and the coating is a homogeneous coating that is not vertically striped or madrid (pass).
上記のように、80〜120℃のオープンロールで練り出され、表面が高温状態にあるゴムを防着剤懸濁液に、ごく短時間(約1秒間)浸漬させただけで、引き上げた直後に優れた濡れ性を示し、且つ、付着した防着剤懸濁液から水分が急速に蒸発しても、縦て縞状、マダラ状などのムラのない、均一な薄膜状態で防着剤がゴム表面に残存できる状態を合格点とした。 As described above, immediately after pulling out the rubber, which has been kneaded with an open roll at 80 to 120 ° C. and having a high-temperature surface in an anti-adhesive suspension for a very short time (about 1 second). In addition, even if moisture rapidly evaporates from the attached anti-adhesive suspension, the anti-adhesive agent can be applied in a uniform thin film state with no unevenness such as vertical stripes and madras. The state that can remain on the rubber surface was regarded as a passing score.
(3)防着性能の評価
上記の未加硫ゴム(未加硫NR/BRゴム)を温度80〜120℃のオープンロールで練り出してゴムシート(厚さ:5〜8mm、60cm×15cm)とし、練り出された直後の前記ゴムシートを各例で得られた防着剤懸濁液(温度40℃)1Lに約1秒間浸漬した。その後、ゴムシートをすばやく垂直に引き上げ、室温下において垂直状態で静置し、自然乾燥した。
その後、ゴムシートを6cm×15cmにカットして2枚を重ね合わせて積層状態とし、その積層状態にある試験片に対して、一方の面から垂直方向に1t/m2の荷重をかけ、60℃、12時間放置した。
その後、試験片を室温に戻し、引張り試験機〔AGS−500D型、SHIMADZU〕を用いて180°剥離試験を行い、引っ張り速度300mm/minで剥離抗力(N/cm)を測定した。測定された剥離抗力の値を表2〜4に記載する。
(3) Evaluation of adhesion prevention performance Rubber sheet (thickness: 5-8 mm, 60 cm × 15 cm) by kneading the above unvulcanized rubber (unvulcanized NR / BR rubber) with an open roll at a temperature of 80-120 ° C. The rubber sheet immediately after being kneaded was immersed in 1 L of the anti-adhesive suspension (temperature 40 ° C.) obtained in each example for about 1 second. Thereafter, the rubber sheet was quickly pulled up vertically, allowed to stand in a vertical state at room temperature, and naturally dried.
Thereafter, the rubber sheet was cut into 6 cm × 15 cm, and the two sheets were laminated to form a laminated state. A load of 1 t / m 2 was applied to the test piece in the laminated state in the vertical direction from one surface, and 60 The mixture was left at 12 ° C. for 12 hours.
Then, the test piece was returned to room temperature, a 180 ° peel test was performed using a tensile tester [AGS-500D type, SHIMADZU], and the peel resistance (N / cm) was measured at a pulling speed of 300 mm / min. The measured peel resistance values are listed in Tables 2-4.
剥離抗力が2.0N/cm以下の場合、大きな負荷なくゴムシートを剥がすことができ、防着性能は良好であると判断できる。剥離抗力が2.0N/cm超の場合、ゴムシートを剥がす時の負荷が大きく、防着性能は不良であると判断できる。さらに剥離抗力が3.0N/cm超の場合、ゴムシートは密着しており、通常の作業現場での剥離は困難であると判断できる。 When the peel resistance is 2.0 N / cm or less, the rubber sheet can be peeled off without a large load, and it can be determined that the adhesion prevention performance is good. When the peel resistance is more than 2.0 N / cm, it can be determined that the load when peeling the rubber sheet is large and the adhesion prevention performance is poor. Furthermore, when the peeling resistance is more than 3.0 N / cm, the rubber sheet is in close contact, and it can be judged that peeling at a normal work site is difficult.
表中の各成分の配合量(質量比率%)は、純分換算で計算した値である。 The compounding amount (mass ratio%) of each component in the table is a value calculated in terms of pure content.
表2〜3に示されているように、実施例1〜18で得られた各防着剤懸濁液は、高温状態にある未加硫ゴムの表面への濡れ性、付着性がいずれも4点以上の合格点であり、優れていた。具体的には、実施例1〜18で得られた各防着剤懸濁液によれば、80〜120℃のオープンロールで練り出され、表面が高温状態にあるゴムをごく短時間(約1秒間)浸漬させただけで、引き上げた直後に優れた濡れ性を示し、且つ、付着した防着剤懸濁液から水分が急速に蒸発しても、縦て縞状、マダラ状などのムラのない、均一な薄膜状態の防着剤乾燥被膜を高い面積割合でゴム表面に形成できた。そして、このように濡れ性と付着性とに優れた実施例1〜18の防着剤懸濁液で処理された未加硫ゴムは、重ねられて荷重を加えられた後でも、剥離抗力がいずれも2N/cm以下と低く、高い防着性能が付与されていた。
以上のことから、良好な濡れ性と付着性とを兼ね備えていることが、優れた防着性能の付与に繋がることが明らかとなった。
As shown in Tables 2-3, each of the anti-sticking agent suspensions obtained in Examples 1 to 18 has both wettability and adhesion to the surface of the unvulcanized rubber in a high temperature state. It was a passing score of 4 points or more and was excellent. Specifically, according to each of the anti-adhesive suspensions obtained in Examples 1 to 18, the rubber whose surface is in a high temperature state is kneaded with an open roll at 80 to 120 ° C. for a very short time (about 1 sec) shows excellent wettability immediately after pulling up, and even if moisture rapidly evaporates from the adhered suspension of adhesion, unevenness such as vertical stripes and madras A uniform thin film of the anti-adhesive agent dried film having no area could be formed on the rubber surface at a high area ratio. And the unvulcanized rubber treated with the adhesion-preventing agent suspensions of Examples 1 to 18 having excellent wettability and adhesion as described above has a peeling resistance even after being overlaid and loaded. All of them were as low as 2 N / cm or less, and high adhesion performance was imparted.
From the above, it has been clarified that having both good wettability and adhesion leads to the provision of excellent anti-adhesion performance.
これに対して、表4に示されているように、比較例1〜9で得られた各防着剤懸濁液は、濡れ性、付着性の少なくとも一方が3点以下であって良好ではなく、そのため、防着性能も良好ではないという結果であった。例えば、Na型モンモリロナイト含有量の低いベントナイト(A)を用いた比較例1、2では、濡れ性および付着性が悪かった。比較例3では、ベントナイト(A)量が少ないために濡れ性は良好だが付着性が悪く、比較例4では、ベントナイト(A)量が過剰でありアニオン界面活性剤(B)とノニオン界面活性剤(C)が少ないために濡れ性が悪く、付着性も悪かった。また、ノニオン界面活性剤として、オキシアルキレン基の平均付加モル数が多いものを用いた比較例5では、ノニオン界面活性剤(C)の親水性が高く、濡れ性、付着性が不充分であった。ノニオン界面活性剤(C)を含まない比較例6では、濡れ性は優れるものの付着性が悪かった。アニオン界面活性剤(B)を含まない比較例7では、濡れ性と付着性が極めて悪く、そのため、防着性能の評価において、試験片を構成する2枚のゴムシート同士が強く密着してしまい、上記条件の180°剥離試験では剥離することできず、試験片の破断も認められた。また、(B)/(C)が小さい比較例8では濡れ性が悪く、(B)/(C)が大きい比較例9では付着性が特に悪かった。
また、付着性については、比較例3や比較例6では、乾燥被膜で覆われている部分の面積の割合は高いが、縦て縞状のムラが認められ、比較例4では、乾燥被膜で覆われている部分の面積の割合が低いことに加えて、マダラ状のムラが認められた。
このように実施例1〜18の防着剤懸濁液は、防着剤として、Na型モンモリロナイトを60質量%以上含有するベントナイト(A)と、アニオン界面活性剤(B)と、特定のノニオン界面活性剤(C)とを含有し、(B)/(C)で表される質量比が、0.15〜0.65であるものを用いているため、未加硫ゴムの表面に対して良好な濡れ性を示し、かつ、乾燥時には未加硫ゴムの表面にムラなく付着する優れた付着性を示し、そのため、懸濁液の防着剤濃度が1質量%と低くても、未加硫ゴムに対して良好な防着性能を付与できることが明らかであった。
On the other hand, as shown in Table 4, each of the anti-adhesive suspensions obtained in Comparative Examples 1 to 9 is not good because at least one of wettability and adhesion is 3 points or less. Therefore, the result was that the adhesion preventing performance was not good. For example, in Comparative Examples 1 and 2 using bentonite (A) having a low Na-type montmorillonite content, wettability and adhesion were poor. In Comparative Example 3, since the amount of bentonite (A) is small, the wettability is good but the adhesion is poor. In Comparative Example 4, the amount of bentonite (A) is excessive, and the anionic surfactant (B) and the nonionic surfactant Since there was little (C), wettability was bad and adhesiveness was also bad. Further, in Comparative Example 5 using a nonionic surfactant having a large average added mole number of oxyalkylene groups, the nonionic surfactant (C) has high hydrophilicity and insufficient wettability and adhesion. It was. In Comparative Example 6 containing no nonionic surfactant (C), the wettability was excellent, but the adhesion was poor. In Comparative Example 7 not containing the anionic surfactant (B), wettability and adhesion were extremely poor, and therefore, in the evaluation of the anti-adhesion performance, the two rubber sheets constituting the test piece were in close contact with each other. In the 180 ° peel test under the above conditions, the test piece could not be peeled off, and the test piece was also broken. Further, Comparative Example 8 having a small (B) / (C) had poor wettability, and Comparative Example 9 having a large (B) / (C) had particularly poor adhesion.
In addition, regarding the adhesion, in Comparative Example 3 and Comparative Example 6, the ratio of the area of the portion covered with the dry film is high, but vertical striped unevenness is observed. In Comparative Example 4, the dry film is In addition to the low area ratio of the covered part, spotted irregularities were observed.
Thus, the anti-adhesive suspensions of Examples 1 to 18 are bentonite (A) containing 60% by mass or more of Na-type montmorillonite, an anionic surfactant (B), and a specific nonion as the anti-adhesive agent. The surfactant (C) is contained and the mass ratio represented by (B) / (C) is 0.15 to 0.65, so that the surface of the unvulcanized rubber is used. It exhibits good wettability and exhibits excellent adhesion that adheres to the surface of the unvulcanized rubber evenly when dried. Therefore, even if the concentration of the anti-sticking agent in the suspension is as low as 1% by mass, It was clear that good adhesion performance could be imparted to the vulcanized rubber.
なお、以上の本実施例では、未加硫ゴムのゴムとしてNR/BRゴムを用いたが、一般的なNR、SBR、BR、IIR、EPDM等のゴムを用いた場合でも、上記実施例および比較例と同様の結果が得られる。 In the above embodiment, NR / BR rubber is used as the rubber of the unvulcanized rubber. However, even when rubber such as general NR, SBR, BR, IIR, EPDM is used, the above embodiment and Results similar to those of the comparative example are obtained.
本発明の未加硫ゴム用防着剤は、防着剤を防着剤懸濁液として使用した場合、かかる懸濁液の防着剤濃度を低くして使用しても、未加硫ゴムに対して良好な防着性能を発揮する。 The anti-curing agent for unvulcanized rubber according to the present invention, when the anti-sticking agent is used as an anti-sticking agent suspension, the unvulcanized rubber is used even if the anti-sticking agent concentration of the suspension is lowered. Excellent adhesion performance.
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TWI732919B (en) * | 2016-08-09 | 2021-07-11 | 日商獅王特殊化學股份有限公司 | Anti-adhesive composition for unvulcanized rubber |
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JP7262630B2 (en) * | 2017-05-12 | 2023-04-21 | ライオン・スペシャリティ・ケミカルズ株式会社 | Anti-adhesion agent for unvulcanized rubber and anti-adhesion agent aqueous dispersion for unvulcanized rubber |
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US20200255604A1 (en) * | 2017-09-11 | 2020-08-13 | Lion Specialty Chemicals Co., Ltd. | Unvulcanized rubber anti-tack agent, production method for anti-tack liquid, and anti-tack liquid production device |
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