JP5147166B2 - Halogenated alkylphenol / formaldehyde co-condensation resin crosslinking agent - Google Patents
Halogenated alkylphenol / formaldehyde co-condensation resin crosslinking agent Download PDFInfo
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Description
本発明は、可塑剤を含有したハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂からなる樹脂架橋剤に関するものである。 The present invention relates to a resin crosslinking agent comprising a halogenated alkylphenol-formaldehyde cocondensation resin containing a plasticizer.
樹脂架橋剤には従来からフレーク状または粒子状のレゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂が用いられているが、ゴムへの分散性が悪いことが知られている。樹脂架橋剤をゴムに充分分散させる為には、樹脂の軟化点以上の温度で混練するのが好ましいが、混練温度が１２０℃以上となるとゴムの架橋反応が開始しだし、均一なゴム組成物が得られなくなる。このため樹脂架橋剤は軟化点が１１５℃以下のものが一般的に用いられている。 Conventionally, flaky or particulate resol-type alkylphenol-formaldehyde cocondensation resins have been used as the resin crosslinking agent, but it is known that the dispersibility in rubber is poor. In order to sufficiently disperse the resin cross-linking agent in the rubber, it is preferable to knead at a temperature equal to or higher than the softening point of the resin. However, when the kneading temperature is 120 ° C. or higher, the rubber cross-linking reaction starts and a uniform rubber composition is obtained. Cannot be obtained. For this reason, a resin crosslinking agent having a softening point of 115 ° C. or lower is generally used.
樹脂架橋剤を微粉末状にして用いるか、樹脂架橋剤の軟化点を低くすると分散性が改良されることが知られているが、微粉化すると、保管中に樹脂同士の互着（ブロッキング）が生じて実使用に耐えられない。
樹脂架橋剤の計量、ゴムとの混練作業工程での粉塵防止と、樹脂架橋剤のけを向上させる方法として、樹脂架橋剤とゴムとのマスターバッチを作成する方法が開示されている。（特許文献１）
It is known that the resin cross-linking agent is used in the form of fine powder or the softening point of the resin cross-linking agent is lowered, so that dispersibility is improved. Will not be able to withstand actual use.
As a method for measuring the resin cross-linking agent, preventing dust in the kneading operation step with the rubber, and improving the resin cross-linking agent, a method of creating a master batch of the resin cross-linking agent and rubber is disclosed. (Patent Document 1)
一方において近年環境汚染防止が社会的課題となっており、製品中の不純物、残留原料、残留溶剤の削減が求められている。樹脂架橋剤の製造において、原料であるアルキルフェノールの残留量を分離削減するのはなかなか困難であり、縮合反応をできるだけ完結させる方法で残留量を削減するのが製造コスト的にも好ましい方法である。しかしながらこの方法では必然的に得られる樹脂架橋剤の軟化点が高くなり、ゴムへの分散性の低下が生じてしまう欠点がある。 On the other hand, prevention of environmental pollution has become a social issue in recent years, and reduction of impurities, residual raw materials and residual solvents in products has been demanded. In the production of a resin cross-linking agent, it is difficult to separate and reduce the residual amount of alkylphenol as a raw material, and it is preferable from the viewpoint of production cost to reduce the residual amount by a method that completes the condensation reaction as much as possible. However, this method inevitably has a drawback that the softening point of the obtained resin cross-linking agent is increased and the dispersibility in rubber is lowered.
本発明の目的は、軟化点がゴムの架橋反応温度より低く、ゴムへの分散性、ゴムの架橋性能および樹脂架橋剤保管時の耐ブロッキング性が従来品と同等性能を有し、かつ、従来品より残留溶媒、残留未反応アルキルフェノールについて大幅に低減された樹脂架橋剤を提供する事である。 The object of the present invention is that the softening point is lower than the crosslinking reaction temperature of rubber, the dispersibility in rubber, the crosslinking performance of rubber and the blocking resistance during storage of the resin crosslinking agent have the same performance as conventional products, and It is to provide a resin cross-linking agent that is greatly reduced in terms of residual solvent and residual unreacted alkylphenol.
本発明者らは課題解決に向けて鋭意検討した結果、ハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂に可塑剤を含有させる事で、本発明の目的が達成できる事を見出した。 As a result of intensive studies aimed at solving the problems, the present inventors have found that the object of the present invention can be achieved by adding a plasticizer to the halogenated alkylphenol / formaldehyde cocondensation resin.
以下本発明について詳細に説明する。
本発明の樹脂架橋剤は硫黄架橋可能な全てのゴムに適用可能であり、具体的ゴムとしては、天然ゴム、ＳＢＲ、イソプレンゴム、ＮＢＲ、ブチルゴム、ＥＰＤＭ、ＣＲ等が挙げられる。
The present invention will be described in detail below.
The resin crosslinking agent of the present invention can be applied to all rubbers capable of sulfur crosslinking, and specific rubbers include natural rubber, SBR, isoprene rubber, NBR, butyl rubber, EPDM, CR and the like.
本発明に用いられるハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂とは、レゾール型アルキルフェノール・ホルムアルデヒド共縮合樹脂をハロゲン化剤でハロゲン化した樹脂であり、主成分は式（４）により表される。
本発明で使用されるハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂は、例えば、プラスチック材料講座１５「フェノール樹脂」（日刊工業新聞社 刊）等に記載の公知の方法で合成可能なアルキルフェノール・ホルムアルデヒド共縮合樹脂にハロゲン化水素（ＨＸ）を反応させることにより得られ、アルキル基（Ｒ）の炭素数は１〜２０のものが好適に使用される。ハロゲン化共縮合樹脂の分子量はポリスチレン換算重量平均分子量が１０００〜５０００のものが通常用いられる。また環境汚染防止の観点から、アルキルフェノール・ホルムアルデヒド共縮合樹脂中には、原料であるアルキルフェノールの残留量及び反応等に用いる溶媒の残留量は少ない程好ましく、具体的にはそれぞれ１重量％未満のものを選択して使用される。 The halogenated alkylphenol / formaldehyde cocondensation resin used in the present invention is, for example, an alkylphenol / formaldehyde cocondensation resin that can be synthesized by a known method described in Plastic Material Course 15 “Phenolic Resin” (published by Nikkan Kogyo Shimbun). And an alkyl group (R) having 1 to 20 carbon atoms is preferably used. As the molecular weight of the halogenated cocondensation resin, those having a polystyrene-reduced weight average molecular weight of 1000 to 5000 are usually used. From the viewpoint of preventing environmental pollution, it is preferable that the residual amount of alkylphenol as a raw material and the residual amount of the solvent used for the reaction in the alkylphenol / formaldehyde cocondensation resin is smaller, and specifically, less than 1% by weight respectively. Used to select.
本発明に用いられるハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂化合物としては、例えば、クレゾール・ホルムアルデヒド共縮合樹脂、エチルフェノール・ホルムアルデヒド共縮合樹脂、ブチルフェノール・ホルムアルデヒド共縮合樹脂、オクチルフェノール・ホルムアルデヒド共縮合樹脂、ブチルフェノール・オクチルフェノール・ホルムアルデヒド共縮合樹脂等のレゾール型共縮合樹脂の塩素、臭素、ヨウ素などのハロゲン化樹脂が挙げられ、市販品としては、例えば、タッキロール２５０（臭素化アルキルフェノール・ホルムアルデヒド共縮合樹脂 田岡化学工業社製））等が挙げられる。 Examples of the halogenated alkylphenol / formaldehyde cocondensation resin compound used in the present invention include cresol / formaldehyde cocondensation resin, ethylphenol / formaldehyde cocondensation resin, butylphenol / formaldehyde cocondensation resin, octylphenol / formaldehyde cocondensation resin, butylphenol Examples include halogenated resins such as chlorine, bromine and iodine of resol type cocondensation resins such as octylphenol / formaldehyde cocondensation resin. Commercially available products include, for example, Tacrol 250 (brominated alkylphenol / formaldehyde cocondensation resin Taoka Chemical Co., Ltd.) Manufactured)) and the like.
本発明のハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂中の可塑剤の含有量は、１〜３０重量％であり、２〜２０重量％が好ましい範囲である。該可塑剤の含有量が１重量％未満であれば軟化点の低減効果が認められず、３０重量％を超えると本発明の共縮合樹脂のブロッキングを生じ、また、架橋ゴムの硬度の減少を招き、好ましくない。 The content of the plasticizer in the halogenated alkylphenol / formaldehyde cocondensation resin of the present invention is 1 to 30% by weight, and 2 to 20% by weight is a preferred range. If the content of the plasticizer is less than 1% by weight, the effect of reducing the softening point is not observed. Invited, not preferable.
本発明における可塑剤は、特に限定はないが、ハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂及びゴムの両方に相溶性の良いものが好ましい。
可塑剤として具体的にはリン酸誘導体が挙げられ、これらの例としてリン酸エステル等が挙げられる。
上記可塑剤のうち、式（１）
The plasticizer in the present invention is not particularly limited, but those having good compatibility with both the halogenated alkylphenol-formaldehyde cocondensation resin and the rubber are preferable.
Specific examples of the plasticizer include phosphoric acid derivatives. Examples of these include phosphate esters.
Of the plasticizers, the formula (1)
ハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂と可塑剤との混合方法は、ハロゲン化アルキルフェノール・ホルムアルデヒド共縮合樹脂の有機溶剤溶液に可塑剤を均一に溶解させた後に有機溶剤を留去させる方法が最も簡便な方法であるが、樹脂の軟化点以上の温度で有機溶剤を用いずに可塑剤と混合する方法も可能である。
本発明の樹脂架橋剤の軟化点は、縮合樹脂の分子量、残留アルキルフェノール量、残留溶媒量、可塑剤の添加量によって決まり、樹脂架橋剤の軟化点が８５〜１１５℃のものが使用され、９０〜１１０℃のものが好ましい。軟化点が８５℃より低いと保管中に樹脂同士の互着が生じやすくなるため、本発明の樹脂架橋剤を低温で保管する必要性が生じ、また１１５℃より高いとゴムのコンパウンド作成時の混練温度が高温となりゴムの架橋反応が部分的に開始されてコンパウンドの品質低下が生じる。
The simplest method for mixing the halogenated alkylphenol / formaldehyde cocondensation resin and the plasticizer is to uniformly dissolve the plasticizer in the organic solvent solution of the halogenated alkylphenol / formaldehyde cocondensation resin and then distill the organic solvent off. Although it is a method, the method of mixing with a plasticizer without using an organic solvent at the temperature more than the softening point of resin is also possible.
The softening point of the resin cross-linking agent of the present invention is determined by the molecular weight of the condensation resin, the amount of residual alkylphenol, the amount of residual solvent, the amount of plasticizer added, and the softening point of the resin cross-linking agent is 85 to 115 ° C. The thing of -110 degreeC is preferable. If the softening point is lower than 85 ° C., mutual adhesion between the resins tends to occur during storage. Therefore, it becomes necessary to store the resin cross-linking agent of the present invention at a low temperature. The kneading temperature becomes high and the rubber cross-linking reaction is partially initiated, resulting in a deterioration in the quality of the compound.
本発明の樹脂架橋剤の使用量に特に制限は無いが、通常、ゴム１００重量部に対して、１〜５０重量部、好ましくは３〜３０重量部使用される。
また本発明の樹脂架橋剤は、ＣＲ、塩化スズ、ベンゼンスルフォン酸、酸化カルシュウム、モレキュラーシーブといった架橋促進剤の併用も可能である。
Although there is no restriction | limiting in particular in the usage-amount of the resin crosslinking agent of this invention, Usually, 1-50 weight part with respect to 100 weight part of rubber | gum, Preferably 3-30 weight part is used.
The resin cross-linking agent of the present invention can be used in combination with cross-linking accelerators such as CR, tin chloride, benzenesulfonic acid, calcium oxide, and molecular sieve.
本発明の樹脂架橋剤を用いた時の架橋温度は、従来の樹脂架橋剤と同じ温度領域が適用可能である。具体的には１２０〜２３０℃において、ゴムの種類に応じた適切な温度が選択される。
本発明の樹脂架橋剤は、薬栓、ブラダー、コンデンサーパッキン、タイヤチューブ、インナーライナー、ホース、チューブ、ガスケット、自動車内装材、家電部品等に使用されるゴム製品、ＴＰＥ製品に好適に使用される。
As the crosslinking temperature when the resin crosslinking agent of the present invention is used, the same temperature region as that of the conventional resin crosslinking agent can be applied. Specifically, an appropriate temperature according to the type of rubber is selected at 120 to 230 ° C.
The resin cross-linking agent of the present invention is suitably used for rubber products and TPE products used in medicine plugs, bladders, condenser packings, tire tubes, inner liners, hoses, tubes, gaskets, automobile interior materials, home appliance parts, etc. .
本発明により、軟化点がゴムの架橋反応温度より低く、ゴムへの分散性、ゴムの架橋性能および樹脂架橋剤保管時の耐ブロッキング性が従来品と同等性能を有し、かつ、従来品より残留溶媒、残留未反応アルキルフェノールについて大幅に低減された樹脂架橋剤が得られる。 According to the present invention, the softening point is lower than the crosslinking reaction temperature of rubber, the dispersibility to rubber, the crosslinking performance of rubber and the blocking resistance during storage of the resin crosslinking agent have the same performance as the conventional product, and A resin cross-linking agent having a greatly reduced residual solvent and residual unreacted alkylphenol is obtained.
本発明の詳細を、実施例と比較例により本発明を具体的に説明する。本発明はこれらの例によって何ら限定されるものではない。 The details of the present invention will be specifically described with reference to Examples and Comparative Examples. The present invention is not limited by these examples.
下記の方法により樹脂架橋剤の評価をおこなった。
「残留溶剤、残留アルキルフェノ−ルの測定」
樹脂架橋剤１ｇに、内部標準物質としてアニソールを０．１ｇ加え、アセトン２０ｍｌに溶解させ、ガスクロマトグラフィーで測定した。
「軟化点の測定」
ＪＩＳ Ｋ２２０７準拠
「耐ブロッキング性の測定」
フレーク状の樹脂架橋剤を口径４cmの円筒に厚さ３cmになるように投入し、上部に厚さ１mm、径４cmのプラッスチック板と３６０gの荷重を載せ、４５℃のオーブン中で一週間静置後にフレーク同士のブロッキング状態の観察を行った。ブロッキング部分が５％以上のものを×とした。
「分散性の測定」
東洋精機ラボプラストミル・ローラーミキサー（チャンバー容量６０cc）を用いて、下記配合のゴムコンパウンド５０ｇを設定温度９０℃、１５分混練で作成した。得られたコンパウンドをロールで厚さ０．５mmにシート成形し、目視で凝集物の有無を観察した。凝集物の無い物を分散性〇とし、凝集物があるものを分散性×とした。
＜配合＞ポリサーブチル４０２ １００重量部
ＨＡＦカーボン ５０重量部
ステアリン酸 １重量部
亜鉛華 ５重量部
樹脂架橋剤 ４０重量部
「オシレーティング・レオメータによる架橋特性の測定」
(株)東洋精機製作所製ロータレスレオメータ使用。
測定温度１８０℃、振幅角度３°で測定。
The resin crosslinking agent was evaluated by the following method.
"Measurement of residual solvent and residual alkylphenol"
0.1 g of anisole as an internal standard substance was added to 1 g of a resin crosslinking agent, dissolved in 20 ml of acetone, and measured by gas chromatography.
"Measurement of softening point"
JIS K2207 compliant "Measurement of blocking resistance"
A flake-shaped resin cross-linking agent is put into a cylinder with a diameter of 4 cm so as to have a thickness of 3 cm, a plastic plate with a thickness of 1 mm and a diameter of 4 cm and a load of 360 g are placed on the top, and left in an oven at 45 ° C. for one week. Later, the blocking state of flakes was observed. Those having a blocking portion of 5% or more were evaluated as x.
"Measurement of dispersibility"
Using a Toyo Seiki Lab Plast Mill roller mixer (chamber capacity 60 cc), 50 g of a rubber compound having the following composition was prepared by kneading at a set temperature of 90 ° C. for 15 minutes. The obtained compound was formed into a sheet having a thickness of 0.5 mm with a roll, and the presence or absence of aggregates was visually observed. The thing without an aggregate was made into dispersibility (circle), and the thing with an aggregate was made into dispersibility x.
<Formulation> Polycerbutyl 402 100 parts by weight HAF carbon 50 parts by weight Stearic acid 1 part by weight Zinc white 5 parts by weight Resin crosslinking agent 40 parts by weight "Measurement of crosslinking characteristics with an oscillating rheometer"
Uses a rotary rheometer manufactured by Toyo Seiki Seisakusho.
Measured at a measurement temperature of 180 ° C and an amplitude angle of 3 °.
公知の方法に従って、ホルムアルデヒドとアルキルフェノールの１種であるｐ−オクチルフェノールを原料とし、アルカリ触媒を用いてｐ−オクチルフェノールの残留量が１.０％未満のレゾール型樹脂を合成し、減圧下にトルエンを留去し、臭化水素と反応させ、臭素化アルキルフェノール・ホルムアルデヒド共縮合樹脂を得た。続いてその共縮合樹脂に、可塑剤であるトリ（２−エチルヘキシル）ホスフェートを樹脂１００重量部に対して８重量部加えて、樹脂架橋剤Ａを得た。
得られた樹脂架橋剤Ａの、残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、耐ブロッキング性、分散性を測定して表１に記載した。
ポリサー・ブチル４０２（１００重量部）、ＨＡＦカーボン（５０重量部）、ステアリン酸（１重量部）、亜鉛華（５重量部）、樹脂架橋剤Ａ（１２重量部）の配合コンパウンドをロールを用いて通常の混練方法で作成した。得られたコンパウンドのオシレーティング・レオメータによる架橋特性を１８０℃、６０分の条件下に測定し、表２に記載した。
According to a known method, p-octylphenol, which is one of formaldehyde and alkylphenols, is used as a raw material, a resole resin having a residual amount of p-octylphenol of less than 1.0% is synthesized using an alkali catalyst, and toluene is added under reduced pressure. Distilled off and reacted with hydrogen bromide to obtain a brominated alkylphenol-formaldehyde cocondensation resin. Subsequently, 8 parts by weight of tri (2-ethylhexyl) phosphate as a plasticizer was added to the co-condensation resin with respect to 100 parts by weight of the resin to obtain a resin crosslinking agent A.
The obtained resin cross-linking agent A was measured for residual solvent amount, residual p-octylphenol amount, softening point, blocking resistance and dispersibility, and listed in Table 1.
Using a roll of compounded compound of Policer butyl 402 (100 parts by weight), HAF carbon (50 parts by weight), stearic acid (1 part by weight), zinc white (5 parts by weight), and resin cross-linking agent A (12 parts by weight) And prepared by a conventional kneading method. The resulting compound was measured for cross-linking properties with an oscillating rheometer at 180 ° C. for 60 minutes and listed in Table 2.
トリ（２−エチルヘキシル）ホスフェートの配合量を４重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｂを合成した。得られた樹脂Ｂの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、耐ブロッキング性、分散性、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表１〜２に示した。 Resin crosslinking agent B was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 4 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.
トリ（２−エチルヘキシル）ホスフェートの配合量を２重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｃを合成した。得られた樹脂Ｃの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、耐ブロッキング性、分散性、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表１〜２に示した。 Resin crosslinking agent C was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 2 parts by weight. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.
（比較例１）
トリ（２−エチルヘキシル）ホスフェートを配合しない以外は実施例１と同様にして樹脂架橋剤Ｄを合成した。得られた樹脂Ｄの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、耐ブロッキング性、分散性、オシレーティング・レオメータによる架橋特性を実施例１と同様にして測定した結果を表１〜２に示した。
(Comparative Example 1)
Resin crosslinking agent D was synthesized in the same manner as in Example 1 except that tri (2-ethylhexyl) phosphate was not blended. Tables 1 and 2 show the results of measuring the amount of residual solvent, the amount of residual p-octylphenol, the softening point, the blocking resistance, the dispersibility, and the crosslinking characteristics with an oscillating rheometer in the same manner as in Example 1. Indicated.
（比較例２）
トリ（２−エチルヘキシル）ホスフェートの配合量を２０重量部に変更する以外は実施例１と同様にして樹脂架橋剤Ｅを合成した。得られた樹脂Ｅの残留溶剤量、残留ｐ-オクチルフェノール量、軟化点、耐ブロッキング性、分散性について測定した結果を表１に示す。
樹脂架橋剤Ｅについては、耐ブロッキング性の評価結果が×であったのでオシレーティング・レオメータによる架橋特性は測定しなかった。
(Comparative Example 2)
Resin crosslinking agent E was synthesized in the same manner as in Example 1 except that the amount of tri (2-ethylhexyl) phosphate was changed to 20 parts by weight. Table 1 shows the results of measurement of the residual solvent amount, residual p-octylphenol amount, softening point, blocking resistance, and dispersibility of the obtained resin E.
With respect to the resin crosslinking agent E, the evaluation result of the blocking resistance was x, so the crosslinking characteristics with an oscillating rheometer were not measured.
Ｔ（９０）：加硫曲線から求められた、トルクの最大値と最小値との差の９０％に達するまでの時間（分）
ＭＬ ：加硫曲線から求められた、トルクの最小値（ｋｇ・ｃｍ）
ＭＨ ：加硫曲線から求められた、トルクの最大値（ｋｇ・ｃｍ）
T (90): Time (minutes) required to reach 90% of the difference between the maximum and minimum torque values determined from the vulcanization curve
ML: Minimum torque value (kg · cm) obtained from the vulcanization curve
MH: Maximum value of torque (kg · cm) obtained from vulcanization curve
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| JPS5938245A (en) * | 1982-08-27 | 1984-03-02 | Yokohama Rubber Co Ltd:The | Crosslinking agent composition for rubber |
| JPH0611777B2 (en) * | 1986-04-26 | 1994-02-16 | 住友デユレズ株式会社 | Method for producing phenol resin |
| JP3413897B2 (en) * | 1992-12-17 | 2003-06-09 | 住友化学工業株式会社 | Co-condensate and rubber composition containing the same |
| JP3521948B2 (en) * | 1993-12-17 | 2004-04-26 | 田岡化学工業株式会社 | Resin vulcanizing agent for rubber and production method thereof |
| JPH09255745A (en) * | 1996-03-25 | 1997-09-30 | Sumitomo Bakelite Co Ltd | Production of phenol resin |
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