JP5381209B2 - Phenolic resin for rubber composition addition - Google Patents

Phenolic resin for rubber composition addition Download PDF

Info

Publication number
JP5381209B2
JP5381209B2 JP2009070081A JP2009070081A JP5381209B2 JP 5381209 B2 JP5381209 B2 JP 5381209B2 JP 2009070081 A JP2009070081 A JP 2009070081A JP 2009070081 A JP2009070081 A JP 2009070081A JP 5381209 B2 JP5381209 B2 JP 5381209B2
Authority
JP
Japan
Prior art keywords
group
rubber composition
mass
formula
phenol resin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
JP2009070081A
Other languages
Japanese (ja)
Other versions
JP2009173941A (en
Inventor
勝彦 岡崎
光嗣 国田
紀幸 三谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ube Corp
Original Assignee
Ube Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ube Industries Ltd filed Critical Ube Industries Ltd
Priority to JP2009070081A priority Critical patent/JP5381209B2/en
Publication of JP2009173941A publication Critical patent/JP2009173941A/en
Application granted granted Critical
Publication of JP5381209B2 publication Critical patent/JP5381209B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Description

本発明は、ゴム組成物添加用フェノール樹脂、特にタイヤのカーカス部材、コンベヤベルト及びホース等に用いられるゴム組成物に添加される特定構造のフェノール樹脂に関するものである。   The present invention relates to a phenol resin for adding a rubber composition, in particular, a phenol resin having a specific structure added to a rubber composition used for a tire carcass member, a conveyor belt, a hose and the like.

従来、ゴムを高弾性化する手段としては、カーボンブラック等の充填剤を増量したり、加硫剤の硫黄を増量して架橋点を増やす等の手法が知られているが、かかる手法を採るとゴム組成物の耐破壊性等の物性が著しく低下するという問題があった。   Conventionally, as means for increasing the elasticity of rubber, methods such as increasing the filler such as carbon black or increasing the crosslinking point by increasing the sulfur of the vulcanizing agent are employed. In addition, there is a problem that physical properties such as fracture resistance of the rubber composition are remarkably lowered.

これに対し、ゴムの耐破壊性の低下を抑えながらゴムを高弾性化する手段として、ノボラック型又はレゾール型の未変性フェノール樹脂を添加する方法や、トールオイル又はカシューオィル等の不飽和油、或いはキシレン又はメシチレン等の芳香族炭化水素で変性したフェノール樹脂を添加する方法が提案されており、耐破壊性の低下を抑えながらゴム組成物を高弾性化するために広く用いられている(例えば、特許文献1及び2参照)。   On the other hand, as a means to increase the elasticity of rubber while suppressing a decrease in the fracture resistance of rubber, a method of adding a novolak-type or resol-type unmodified phenol resin, an unsaturated oil such as tall oil or cashew oil, or A method of adding a phenol resin modified with an aromatic hydrocarbon such as xylene or mesitylene has been proposed, and is widely used to increase the elasticity of a rubber composition while suppressing a decrease in fracture resistance (for example, (See Patent Documents 1 and 2).

しかしながら、昨今のゴムに対する性能要求は非常に厳しいものがあり、ゴムの耐破壊性の低下を抑えながらゴムを更に高弾性化する必要がある。これに対し、上述の未変性フェノール樹脂や変性フェノール樹脂を添加する方法では、耐破壊性の低下を抑えながらゴムを更に高弾性化するという意味では不充分であり、依然として改良の余地があった。   However, recent performance requirements for rubber are very severe, and it is necessary to further increase the elasticity of rubber while suppressing a decrease in the fracture resistance of the rubber. On the other hand, the above-mentioned method of adding the unmodified phenol resin or the modified phenol resin is insufficient in terms of further increasing the elasticity of the rubber while suppressing a decrease in fracture resistance, and there is still room for improvement. .

特開平5−98081号公報Japanese Patent Laid-Open No. 5-98081 特開2001−226528号公報JP 2001-226528 A

そこで、本発明の目的は、ゴム組成物の耐破壊性の低下を防止しながらゴム組成物の高弾性化が可能なゴム組成物添加用フェノール樹脂を提供することにある。   Therefore, an object of the present invention is to provide a phenol resin for adding a rubber composition, which can increase the elasticity of the rubber composition while preventing a decrease in the fracture resistance of the rubber composition.

本発明者は、上記目的を達成するために鋭意検討した結果、特定構造のフェノール樹脂をゴム組成物に添加することにより、ゴム組成物の耐破壊性の低下を防止しながら、ゴム組成物を著しく高弾性化できることを見出し、本発明を完成させるに至った。   As a result of intensive investigations to achieve the above object, the present inventor has added a phenol resin having a specific structure to the rubber composition, thereby preventing the rubber composition from being deteriorated in breakage resistance. It has been found that the elasticity can be remarkably increased, and the present invention has been completed.

即ち、本発明のゴム組成物添加用フェノール樹脂は、下記式(I):

Figure 0005381209
(式中、R0は、メチル基であり;R1及びR2は、架橋基で、但し、R1及びR2の少なくとも一部は、ビフェニルジメチレン基であり;pは0又は1の整数で、mは1の整数で、R0はヒドロキシル基に対して3位又は4位に結合しており、少なくとも一部のR0はヒドロキシル基に対して3位に結合しており、nは0〜10の数である)で表され、
また、本発明の他のゴム組成物添加用フェノール樹脂は、下記式(I):
Figure 0005381209
(式中、R0は、それぞれ独立して水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくとも一種の官能基であり;R1及びR2は、一部がビフェニルジメチレン基で、残りがメチレン基であり;pは0又は1の整数で、mは1の整数で、nは0〜10の数である)で表され、
また、本発明のフェノール樹脂は、下記式(I):
Figure 0005381209
(式中、R0は、それぞれ独立して水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくとも一種の官能基であり;R1及びR2は、一部がビフェニルジメチレン基で、残りがメチレン基であり;pは0又は1の整数で、mは1の整数で、nは0〜10の数である)で表される。 That is, the phenol resin for adding a rubber composition of the present invention has the following formula (I):
Figure 0005381209
(Wherein R 0 is a methyl group ; R 1 and R 2 are bridging groups, provided that at least a part of R 1 and R 2 is a biphenyldimethylene group; An integer, m is an integer of 1, R 0 is bonded to the hydroxyl group at the 3 or 4 position, at least a portion of R 0 is bonded to the hydroxyl group at the 3 position, n Is a number from 0 to 10),
Another phenol resin for adding a rubber composition of the present invention is represented by the following formula (I):
Figure 0005381209
Wherein R 0 is each independently at least one functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group. R 1 and R 2 are partly a biphenyldimethylene group and the rest are methylene groups; p is an integer of 0 or 1, m is an integer of 1, and n is a number of 0 to 10) Represented by
The phenol resin of the present invention has the following formula (I):
Figure 0005381209
Wherein R 0 is each independently at least one functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group. R 1 and R 2 are partly a biphenyldimethylene group and the rest are methylene groups; p is an integer of 0 or 1, m is an integer of 1, and n is a number of 0 to 10) It is represented by

本発明のゴム組成物添加用フェノール樹脂においては、前記R1及びR2の少なくとも一部がビフェニルジメチレン基であり、[1,1'-ビフェニル]-4,4'-ジメチレン基であることが好ましい。前記R1及びR2の少なくとも一部が[1,1'-ビフェニル]-4,4'-ジメチレン基である場合、該[1,1'-ビフェニル]-4,4'-ジメチレン基の含有量は、全R1及びR2の5モル%以上であるのが好ましい It In the rubber composition for addition phenolic resin of the present invention, at least a portion of the R 1 and R 2 are biphenyl dimethylene group, a [1,1'-biphenyl] -4,4'-dimethylene group Is preferred. When at least a part of R 1 and R 2 is a [1,1′-biphenyl] -4,4′-dimethylene group, the inclusion of the [1,1′-biphenyl] -4,4′-dimethylene group The amount is preferably 5 mol% or more of the total R 1 and R 2 .

本発明のゴム組成物添加用フェノール樹脂の他の好適例においては、前記フェノール樹脂が式(I)で表され、該式(I)中のR0炭素数1〜8のアルキル基であり、pが0である。ここで、前記式(I)中のR0がメチル基であるのが更に好ましいIn another preferable embodiment of the rubber composition added for phenolic resin of the present invention, the phenolic resin is represented by Formula (I), R 0 in the formula (I) is an alkyl group having 1 to 8 carbon atoms Yes, p is 0. Here, it is more preferable that R 0 in the formula (I) is a methyl group.

本発明によれば、特定構造で表され、ゴム組成物に添加することで、ゴム組成物の耐破壊性の低下を防止しながらゴム組成物の高弾性化が可能なゴム組成物添加用フェノール樹脂を提供することができる。   According to the present invention, a phenol for rubber composition addition, which has a specific structure and can be added to a rubber composition, can increase the elasticity of the rubber composition while preventing deterioration of the fracture resistance of the rubber composition. A resin can be provided.

以下に、本発明を詳細に説明する。本発明のゴム組成物添加用フェノール樹脂は、上記式(I)表される。一方、従来のゴム組成物に用いられている下記式(IV):

Figure 0005381209
で表される未変性のフェノール樹脂は、極性の官能基であるフェノール基とフェノール基との距離が短いため、極性の低い天然ゴム及び合成ジエン系ゴム等のゴム成分に対する分散性が低い。このため、フェノール樹脂の偏在した部分がゴム組成物中に存在し、該部分が破壊の基点となりゴム組成物の耐破壊性を低下させていた。 The present invention is described in detail below. Phenolic resin additive rubber composition of the present invention is represented by the above formula (I). On the other hand, the following formula (IV) used in conventional rubber compositions:
Figure 0005381209
Since the distance between the phenol group which is a polar functional group and the phenol group is short, the unmodified phenol resin represented by the formula has a low dispersibility in rubber components such as natural rubber and synthetic diene rubber having low polarity. For this reason, the part where the phenol resin was unevenly distributed existed in the rubber composition, and this part became a starting point of destruction, and the fracture resistance of the rubber composition was lowered.

また、変性フェノール樹脂は、フェノール樹脂を重合した後、該重合体を変性するので、構造的に分子の未端のみが変性され、中央部は未変性のフェノール樹脂と同じである。そのため、分子末端のゴム成分への相溶性は改善されるものの、中央部の相溶性が低いので、充分なゴム物性が得られない。   Further, since the modified phenolic resin is polymerized after the phenolic resin is polymerized, only the molecular end is structurally modified, and the central part is the same as the unmodified phenolic resin. Therefore, although the compatibility of the molecular terminal with the rubber component is improved, the compatibility of the central portion is low, so that sufficient rubber physical properties cannot be obtained.

これに対して、式(I)表されるフェノール樹脂は、複数のフェノール類がメチレン基より大きな2価の基を介して結合した部分を含むため、分子の未端及び中央の双方のゴム成分に対する相溶性が改善されている。一例として、下記式(V):

Figure 0005381209
で表されるフェノール樹脂について述べると、フェノールとキシリレンとが分子単位で結合しているため、未端及び中央の双方のゴム成分に対する相溶性が改善されている。 In contrast, the phenolic resin represented by formula (I), to include a portion in which a plurality of phenols are bonded through a large divalent group from methylene group, non-end and middle of both rubber molecules Compatibility with ingredients is improved. As an example, the following formula (V):
Figure 0005381209
When the phenol resin represented by the formula (1) is described, since the phenol and the xylylene are bonded in a molecular unit, the compatibility with both the unfinished rubber and the central rubber component is improved.

より詳しくは、上記フェノール樹脂は、複数のフェノール類がメチレン基より大きな2価の基を介して結合した部分を含むため、ゴム組成物に従来用いられていた未変性又は変性フェノール樹脂よりも、極性の官能基であるフェノール基とフェノール基との距離が長い部分を含む。そのため、上記フェノール樹脂は、上記未変性及び変性フェノール樹脂よりも極性が低く、(1)ゴム成分中での分散性が改善され、ゴム組成物を大幅に高弾性化することができる。また、上記フェノール樹脂は、ゴム成分中での分散性が良好なため、該フェノール樹脂をゴム組成物に添加しても、ゴム組成物の均一性が維持され、ゴム組成物中に破壊の起点となる部分がなく、そのため、(2)該フェノール樹脂が添加されたゴム組成物は、硬化後の形態が応力に対しより強く、耐破壊性の低下が最小限に抑制されている。   More specifically, since the phenol resin includes a portion in which a plurality of phenols are bonded via a divalent group larger than a methylene group, it is more preferable than an unmodified or modified phenol resin conventionally used in rubber compositions. It includes a portion where the distance between the phenol group and the phenol group which is a polar functional group is long. Therefore, the phenol resin has a lower polarity than the unmodified and modified phenol resins, (1) dispersibility in the rubber component is improved, and the rubber composition can be made highly elastic. In addition, since the phenol resin has good dispersibility in the rubber component, even when the phenol resin is added to the rubber composition, the uniformity of the rubber composition is maintained, and the starting point of destruction in the rubber composition. Therefore, (2) the rubber composition to which the phenol resin is added has a form after curing that is stronger against stress, and a decrease in fracture resistance is minimized.

本発明のゴム組成物添加用フェノール樹脂は、上記式(I)で表される。式(I)において、繰り返し単位数nは、0〜10である。また、式(I)においてR0は、メチル基、或いは、水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくともひとつの官能基であり、好ましくは、炭素数1〜8のアルキル基であり、同一でも異なっていてもよい。ここで、炭素数1〜10のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基等が挙げられ、これらの中でも、メチル基及びエチル基が好ましく、メチル基が更に好ましい。また、炭素数1〜4のアルコキシ基としては、メトキシ基及びエトキシ基が好ましい。なお、R0がメチル基の場合、該メチル基はヒドロキシル基に対して3位又は4位に結合しており、少なくとも一部のメチル基がヒドロキシル基に対して3位に結合しているのが特に好ましい。 The phenol resin for adding a rubber composition of the present invention is represented by the above formula (I). In the formula (I), the number of repeating units n is 0-10. In Formula (I), R 0 is at least one selected from the group consisting of a methyl group , hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group. It is a functional group, preferably an alkyl group having 1 to 8 carbon atoms, which may be the same or different. Here, examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable. Moreover, as a C1-C4 alkoxy group, a methoxy group and an ethoxy group are preferable. When R 0 is a methyl group, the methyl group is bonded to the hydroxyl group at the 3-position or the 4-position, and at least a part of the methyl group is bonded to the hydroxyl group at the 3-position. Is particularly preferred.

式(I)において、pは0又は1の整数で、0であるのが好ましくmは1の整数である。なお、OH、R0、R1及びR2のいずれも結合していない位置には水素が結合している。 In the formula (I), p is an integer of 0 or 1, preferably 0, and m is an integer of 1. Note that hydrogen is bonded to a position where none of OH, R 0 , R 1 and R 2 is bonded.

式(I)おいて、R1及びR2は、架橋基で、但し、R1及びR2の少なくとも一部は、ビフェニルジメチレン基(−CH2−C64−C64−CH2−)であり、互いに同一でも異なってもよい。従来、高弾性化を目的としてゴム組成物に添加されていたフェノール樹脂は、R1及びR2の総てがメチレン基であるが、本発明のゴム組成物添加用フェノール樹脂は、R1及びR2としてメチレン基より大きなビフェニルジメチレン基を含むため、フェノール基同士の距離が長い部分が存在し、前述のような作用を発揮する。 Oite the formula (I), R 1 and R 2 is a bridging group, provided that at least a portion of R 1 and R 2, biphenyl dimethylene group (-CH 2 -C 6 H 4 -C 6 H 4 —CH 2 —), which may be the same or different. Conventionally, a phenol resin that has been added to the rubber composition for the purpose of higher elastification is all of R 1 and R 2 is a methylene group, a rubber composition for addition phenolic resin of the present invention, R 1 and Since R 2 contains a biphenyldimethylene group larger than the methylene group, there is a portion where the distance between the phenol groups is long, and the above-described action is exhibited.

なおビフェニルジメチレン基に、構造異性体、即ち、[1,1'-ビフェニル]-4,4'-ジメチレン基、[1,1'-ビフェニル]-2,2'-ジメチレン基、[1,1'-ビフェニル]-2,3'-ジメチレン基、[1,1'-ビフェニル]-2,4'-ジメチレン基、[1,1'-ビフェニル]-3,3'-ジメチレン基、[1,1'-ビフェニル]-3,4'-ジメチレン基が存在するが、架橋基がこれら構造異性体の一種単独から構成されていてもよいし、架橋基中に複数の構造異性体が混在していてもよい。上記架橋基の中でも、R1及びR2としては[1,1'-ビフェニル]-4,4'-ジメチレン基が好ましく、これら架橋基の割合は、全R1及びR2の5モル%以上(即ち、R1及びR2の総数の5%以上)であるのが好ましく、10モル%以上であるのが更に好ましく、15モル%〜100モル%であるのがより一層好ましい。なお1及びR2が[1,1'-ビフェニル]-4,4'-ジメチレン基であるフェノール樹脂としては、下記式(VI):

Figure 0005381209
で表されるフェノール樹脂が挙げられる。 Note that the biphenyl dimethylene group, structural isomers, i.e., [1,1'-biphenyl] -4,4'-dimethylene group, [1,1'-biphenyl] -2,2'-dimethylene group, [ 1,1′-biphenyl] -2,3′-dimethylene group, [1,1′-biphenyl] -2,4′-dimethylene group, [1,1′-biphenyl] -3,3′-dimethylene group, [1,1′-biphenyl] -3,4′-dimethylene group is present, but the bridging group may be composed of one of these structural isomers alone, or a plurality of structural isomers may be present in the bridging group. It may be mixed. Among the above crosslinking group, the R 1 and R 2, [1,1'-biphenyl] -4,4'-dimethylene group is preferable, the proportion of these crosslinking groups, all R 1 and 5 mole% of R 2 It is preferably above (that is, 5% or more of the total number of R 1 and R 2 ), more preferably 10 mol% or more, and even more preferably 15 mol% to 100 mol%. As the phenolic resin R 1 and R 2 are [1,1'-biphenyl] -4,4'-dimethylene group, the following formula (VI):
Figure 0005381209
The phenol resin represented by these is mentioned.

なお、本発明のゴム組成物添加用フェノール樹脂において、R1及びR2の一部がメチレン基で構成される場合、好ましくは全R1及びR2の5モル%以上が、より好ましくは10モル%以上が、さらに好ましくは20モル%以上が、最も好ましくは50モル%以上が、ビフェニルジメチレン基である。 In addition, in the phenol resin for rubber composition addition of the present invention, when a part of R 1 and R 2 is constituted by a methylene group, preferably 5 mol% or more of all R 1 and R 2 are more preferably 10 More than mol%, more preferably more than 20 mol%, most preferably more than 50 mol% is a biphenyldimethylene group .

また、本発明で使用できる式(I)示されるフェノール樹脂に対し、メチレン架橋したフェノールノボラック樹脂を混合して使用することもできる。ここで、メチレン架橋したフェノールノボラック樹脂としては、例えば、上記式(IV)で示される構造の樹脂、及び下記式(VII):

Figure 0005381209
で示される構造の樹脂が挙げられるが、これらに限定されるものではない。また、メチレン架橋したフェノールノボラック樹脂に用いるフェノール類としては、後述する式(I)表されるフェノール樹脂の製造に用いることができるフェノール類(A)を挙げることができ、式(I)のフェノール樹脂の製造に用いることができるフェノール類が好ましい。式(I)表されるフェノール樹脂と、メチレン架橋したフェノールノボラック樹脂との使用割合は、質量比で95:5〜5:95の範囲が好ましく、10:90〜90:10の範囲が更に好ましく、20:80〜80:20の範囲がより一層好ましく、35:65〜65:35の範囲が最も好ましい。 Further, a methylene-crosslinked phenol novolak resin can be mixed with the phenol resin represented by the formula (I) that can be used in the present invention. Here, as the methylene-crosslinked phenol novolac resin, for example, a resin having a structure represented by the above formula (IV), and the following formula (VII):
Figure 0005381209
Although the resin of the structure shown by these is mentioned, it is not limited to these. As the phenols used in methylene bridged phenol novolak resin, there may be mentioned phenols (A) which can be used in the manufacture of the phenolic resin of the formula (I) described below, the formula of (I) Phenols that can be used for the production of phenol resins are preferred. The proportion of the phenolic resin represented by the formula (I), and methylene bridged phenol novolak resin, a mass ratio of 95: 5 to 5:95 is preferably in the range of 95, 10: 90 to 90: a range of 10 further The range of 20:80 to 80:20 is more preferable, and the range of 35:65 to 65:35 is most preferable.

本発明のゴム組成物添加用フェノール樹脂としては、市販のフェノール樹脂、例えば、明和化成社のMEH-7800、MEH-7851等が使用できる。また、本発明のゴム組成物添加用フェノール樹脂は、以下の方法で合成することもできる。   As the phenol resin for adding a rubber composition of the present invention, commercially available phenol resins such as MEH-7800 and MEH-7851 manufactured by Meiwa Kasei Co., Ltd. can be used. Moreover, the phenol resin for rubber composition addition of this invention is also compoundable with the following method.

上記式(I)表されるフェノール樹脂は、フェノール類(A)と、例えば、1,4-ジアルコキシメチルベンゼン、4,4'-ビス(アルコキシメチル)ビフェニル等の分子中にアルコキシ基を2つ有する化合物、並びに1,4-ジハロゲン化メチルベンゼン、4,4'-ビス(ハロゲン化メチル)ビフェニル等の分子中にハロゲンを2つ有する化合物等の上記架橋基を形成する化合物(B)とを、例えば酸触媒の存在下で縮重合させて合成することができる。ここで、架橋基を形成する化合物(B)において、アルコキシ基としては、炭素数1〜4のアルコキシ基が好ましく、具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられ、これらの中でも、メトキシ基が好ましい。また、ハロゲンとしては、フッ素、塩素、臭素、ヨウ素が挙げられ、これらの中でも塩素が好ましい。また、通常、フェノール類(A)の使用量は、架橋基を形成する化合物(B)の8倍モル以上であればよく、好ましくは9〜50倍モルで、より好ましくは10〜30倍モルである。フェノール類(A)の使用量が架橋基を形成する化合物(B)の8倍モルより少ないと、架橋が過度に進み、目的のフェノール樹脂を安定的に得ることができない。また、フェノール類(A)の使用量が多過ぎると、未反応の原料が多くなり経済的でない。 Phenolic resin represented by the formula (I), phenols and (A), for example, 1,4-dialkoxy-methylbenzene, 4,4'-bis (alkoxymethyl) alkoxy groups in the molecule such as biphenyl Compound having two crosslinkable groups, such as a compound having two halogens in a molecule such as a compound having two, and 1,4-dihalogenated methylbenzene, 4,4′-bis (halogenated methyl) biphenyl, etc. Can be synthesized by, for example, condensation polymerization in the presence of an acid catalyst. Here, in the compound (B) that forms a crosslinking group, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, specifically, a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. Among these, a methoxy group is preferable. In addition, examples of the halogen include fluorine, chlorine, bromine, and iodine. Among these, chlorine is preferable. In general, the amount of the phenols (A) used may be 8 times mol or more, preferably 9 to 50 times mol, more preferably 10 to 30 times mol of the compound (B) forming the crosslinking group. It is. When the amount of the phenols (A) used is less than 8 moles of the compound (B) that forms a crosslinking group, the crosslinking proceeds excessively and the desired phenol resin cannot be stably obtained. Moreover, when there is too much usage-amount of phenols (A), an unreacted raw material increases and it is not economical.

上記式(I)のフェノール樹脂の製造に用いることができるフェノール類(A)としては、フェノール、m-クレゾール(3-メチルフェノール)p-クレゾール(4-メチルフェノール)、エチルフェノール、n-プロピルフェノール、t-ブチルフェノール、オクチルフェノール、ノニルフェノール、フェニルフェノール、キシレノール、メチルプロピルフェノール、ジプロピルフェノール、ジブチルフェノール、グアヤコール、グエトール、トリメチルフェノール、4-ヒドロキシビフェニル、メチロールフェノール、カテコール、レゾルシン、ハイドロキノン等が挙げられる。これらフェノール類には、構造異性体も存在するが、いずれも使用することができる。また、これらフェノール類は、一種単独で用いても、二種以上を混合して用いてもよい。上記フェノール類の中でも、フェノール、クレゾール、キシレノール、4-ヒドロキシビフェニル、メチロールフェノールが好ましく、硬化反応の点から、フェノール及びクレゾールが更に好ましい。   Examples of the phenols (A) that can be used for the production of the phenol resin of the formula (I) include phenol, m-cresol (3-methylphenol), p-cresol (4-methylphenol), ethylphenol, and n-propyl. Examples include phenol, t-butylphenol, octylphenol, nonylphenol, phenylphenol, xylenol, methylpropylphenol, dipropylphenol, dibutylphenol, guaiacol, guetol, trimethylphenol, 4-hydroxybiphenyl, methylolphenol, catechol, resorcin, hydroquinone, etc. . These phenols also have structural isomers, any of which can be used. Moreover, these phenols may be used individually by 1 type, or 2 or more types may be mixed and used for them. Among the above phenols, phenol, cresol, xylenol, 4-hydroxybiphenyl, and methylolphenol are preferable, and phenol and cresol are more preferable from the viewpoint of curing reaction.

上記フェノール樹脂の製造に使用する酸触媒としては、シュウ酸、ギ酸、酢酸、パラトルエンスルホン酸、ジメチル硫酸等の有機酸、塩酸、硫酸等の無機酸が挙げられる。触媒の使用量は、使用するフェノール類の0.01〜1質量%の範囲が好ましい。触媒の使用量が使用するフェノール類の0.01質量%未満では、反応速度が遅く、1質量%を超えると、反応が急激に進行して反応を制御することが困難となる場合がある。   Examples of the acid catalyst used for the production of the phenol resin include organic acids such as oxalic acid, formic acid, acetic acid, p-toluenesulfonic acid and dimethylsulfuric acid, and inorganic acids such as hydrochloric acid and sulfuric acid. The amount of the catalyst used is preferably in the range of 0.01 to 1% by mass of the phenols used. If the amount of the catalyst used is less than 0.01% by mass of the phenols used, the reaction rate is slow, and if it exceeds 1% by mass, the reaction may proceed rapidly and it may be difficult to control the reaction.

反応温度は、使用するフェノール類及び架橋基を形成する化合物の配合割合にもよるが、通常50〜200℃、好ましくは70〜180℃、より好ましくは80〜180℃である。反応温度が低過ぎると重合が進まず、反応温度が高過ぎると反応の制御が難しくなり、目的のフェノールノボラック樹脂を安定的に得ることが困難となる。   The reaction temperature is usually 50 to 200 ° C., preferably 70 to 180 ° C., more preferably 80 to 180 ° C., although it depends on the blending ratio of the phenols to be used and the compound that forms a crosslinking group. If the reaction temperature is too low, the polymerization does not proceed. If the reaction temperature is too high, it becomes difficult to control the reaction, and it becomes difficult to stably obtain the target phenol novolac resin.

また、反応時間は、上記反応温度にもよるが、通常は10時間以内であり、反応圧力に関しては、通常は常圧で行うが、若干の加圧ないし減圧下で反応を行ってもよい。   Although the reaction time depends on the reaction temperature, it is usually within 10 hours, and the reaction pressure is usually normal pressure, but the reaction may be performed under slight pressure or reduced pressure.

具体的に、上記式(V)のフェノール樹脂は、フェノールと1,4-ジアルコキシメチルベンゼン又は1,4-ジハロゲン化メチルベンゼンとを、上記酸触媒の存在下で縮重合させて合成することができ、上記式(VI)で表されるフェノール樹脂は、フェノールと4,4'-ビス(アルコキシメチル)ビフェニル又は4,4'-ビス(ハロゲン化メチル)ビフェニルを、上記酸触媒の存在下で縮重合させて合成することができる。   Specifically, the phenol resin of the formula (V) is synthesized by polycondensation of phenol and 1,4-dialkoxymethylbenzene or 1,4-dihalogenated methylbenzene in the presence of the acid catalyst. The phenol resin represented by the above formula (VI) is obtained by mixing phenol and 4,4′-bis (alkoxymethyl) biphenyl or 4,4′-bis (halogenated methyl) biphenyl in the presence of the acid catalyst. And can be synthesized by condensation polymerization.

本発明のゴム組成物添加用フェノール樹脂の物性については、特に制限はないが、取り扱いの面から、ポリスチレン換算での数平均分子量が800〜5000であるのが好ましく、1000〜3000であるのが更に好ましく、また、軟化点が80℃以上であるのが好ましく、90℃〜140℃であるのが更に好ましい。   The physical properties of the phenol resin for rubber composition addition of the present invention are not particularly limited, but from the viewpoint of handling, the number average molecular weight in terms of polystyrene is preferably 800 to 5000, and preferably 1000 to 3000. Further, the softening point is preferably 80 ° C. or higher, and more preferably 90 ° C. to 140 ° C.

ゴム成分に対し、上記ゴム組成物添加用フェノール樹脂を配合することで、高弾性なゴム組成物が得られる。ここで、ゴム成分としては、天然ゴム(NR);ポリイソプレンゴム(IR)、ブチルゴム(IIR)、ポリブタジエンゴム(BR)及びスチレン-ブタジエン共重合体ゴム(SBR)等の合成ジエン系ゴムが挙げられる。これらゴム成分は、一種単独でも、ブレンドでもよい。上記ゴム組成物における、上記式(I)フェノール樹脂の添加量は、上記ゴム成分100質量部に対して1〜30質量部であり、1〜10質量部の範囲が好ましい。該フェノール樹脂の添加量がゴム成分100質量部に対して1質量部未満では、硬化性能が不充分となる場合があり、30質量部を超えると、ゴム組成物の柔軟性が損なわれる場合がある。 A rubber composition having high elasticity can be obtained by blending the above phenol resin for rubber composition addition with the rubber component. Here, examples of the rubber component include natural rubber (NR); synthetic diene rubbers such as polyisoprene rubber (IR), butyl rubber (IIR), polybutadiene rubber (BR), and styrene-butadiene copolymer rubber (SBR). It is done. These rubber components may be used alone or in a blend. The addition amount of the phenol resin of the formula (I) in the rubber composition is 1 to 30 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the rubber component. If the addition amount of the phenol resin is less than 1 part by mass relative to 100 parts by mass of the rubber component, the curing performance may be insufficient, and if it exceeds 30 parts by mass, the flexibility of the rubber composition may be impaired. is there.

上記ゴム組成物添加用フェノール樹脂をゴム成分に配合する際は、更にメチレン供与体である硬化剤を配合するのが好ましい。但し、前記R0がメチロール基の場合、該フェノール樹脂は自己硬化性なので、硬化剤は不要である。該硬化剤としては、ヘキサメチレンテトラミン、ヘキサメチルメチロールメラミン等が挙げられる。ここで、硬化剤の配合量は、前述した式(I)フェノール樹脂の1〜30質量%の範囲が好ましい。硬化剤の配合量が1質量%未満では、フェノール樹脂の硬化が充分進まず、30質量%を超えると、ゴムの架橋系に悪影響を与える場合がある。 When blending the above-mentioned phenol resin for rubber composition addition into the rubber component, it is preferable to blend a curing agent which is a methylene donor. However, when the R 0 is a methylol group, the phenol resin is self-curing, so that no curing agent is required. Examples of the curing agent include hexamethylenetetramine and hexamethylmethylolmelamine. Here, the amount of curing agent is preferably in the range of 1 to 30% by weight of the phenolic resin of formula (I) described above. When the blending amount of the curing agent is less than 1% by mass, the phenol resin does not sufficiently cure, and when it exceeds 30% by mass, the rubber crosslinking system may be adversely affected.

また、上記ゴム成分には、上記ゴム組成物添加用フェノール樹脂及び硬化剤の他に、ゴム業界で通常使用される配合剤、例えば、充填剤、軟化剤、老化防止剤、加硫剤、加硫促進剤等を用途に応じて適宜配合することができる。上記ゴム組成物は、ロール等の開放式混練機、バンバリーミキサー等の密閉式混練機等の混練り機を用いて混練りすることによって得られ、成形加工後に加硫を行い、各種ゴム製品に適用可能である。例えば、該ゴム組成物は、タイヤ、特にタイヤのカーカス部材、コンベヤベルト及びホース等に用いることができる。   In addition to the above-mentioned phenol resin for adding a rubber composition and a curing agent, the rubber component includes compounding agents usually used in the rubber industry, such as fillers, softeners, anti-aging agents, vulcanizing agents, additives. A sulfur accelerator or the like can be appropriately blended depending on the application. The rubber composition is obtained by kneading using an open kneader such as a roll or a kneader such as a closed kneader such as a Banbury mixer, and vulcanized after molding to produce various rubber products. Applicable. For example, the rubber composition can be used for tires, particularly carcass members of tires, conveyor belts, hoses and the like.

以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。   Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

(合成例1:明和化成製、品名BCrF−2−5)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量2000容量部のガラス製4つ口フラスコに、m-クレゾール酸841質量部(7.787モル:m-クレゾール65モル%及びp-クレゾール35モル%含有)、4,4'-ビスメトキシメチルビフェニル63.9質量部(0.264モル)、42%のホルマリン336.3質量部(4.75モル)及びシュウ酸2.8質量部を加え、内温97℃で15時間反応させた。その後、25%の硫酸0.4質量部を添加し、100℃にて脱水し、170℃まで4時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は130℃で、GPCによるポリスチレン換算数平均分子量(Mn)は1237で、重量平均分子量(Mw)は2057であった。
(Synthesis Example 1: Meiwa Kasei Co., Ltd., product name BCrF-2-5)
To a glass 4-neck flask with a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 841 parts by mass of m-cresolic acid (7.787 mol: 65 mol% of m-cresol and p-cresol) 35 mol% content) 4,4'-bismethoxymethylbiphenyl 63.9 parts by mass (0.264 mol), 42% formalin 336.3 parts by mass (4.75 mol) and oxalic acid 2.8 parts by mass were added, and the internal temperature was 97 ° C for 15 hours. Reacted. Thereafter, 0.4 parts by mass of 25% sulfuric acid was added, dehydrated at 100 ° C., and subjected to demethanol reaction by raising the temperature to 170 ° C. over 4 hours, and then the unreacted components were removed by reduced pressure 40 torr-steaming treatment. Removed. The resulting resin had a softening point of 130 ° C., a polystyrene-reduced number average molecular weight (Mn) by GPC of 1237, and a weight average molecular weight (Mw) of 2057.

(合成例2:明和化成製、品名XCrF−11)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、m-クレゾール酸324質量部(3モル)、p-キシレンジメチルエーテル81質量部(0.488モル)、42%のホルマリン118質量部(1.65モル)及び25%の硫酸0.2質量部を加え、内温97℃で13時間反応させた。その後、100℃にて脱水し、内温を170℃まで4時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は129℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1041で、重量平均分子量(Mw)は2523であった。
(Synthesis Example 2: Meiwa Kasei Co., Ltd., product name XCrF-11)
To a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 324 parts by mass (3 mol) of m-cresolic acid, 81 parts by mass of p-xylene dimethyl ether (0.488) Mol), 118 parts by mass of formalin (42%) (1.65 mol) and 0.2 part by mass of 25% sulfuric acid were added and reacted at an internal temperature of 97 ° C. for 13 hours. Thereafter, dehydration was performed at 100 ° C., and the internal temperature was raised to 170 ° C. over 4 hours to cause demethanol reaction, and then unreacted components were removed by reduced pressure 40 torr-steaming treatment. The softening point of the obtained resin was 129 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1041, and the weight average molecular weight (Mw) was 2523.

(合成例3:明和化成製、品名XBCrF−4)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量2000容量部のガラス製4つ口フラスコに、m-クレゾール酸968質量部(8.962モル)、4,4'-ビスメトキシメチルビフェニル63.9質量部(0.264モル)、p-キシレンジメチルエーテル50.8質量部(0.306モル)、42%のホルマリン339.3質量部(4.75モル)及びシュウ酸2.8質量部を加え、内温97℃で15時間反応させた。その後、50%の硫酸0.6質量部を添加し、100℃にて脱水し、内温を170℃まで6時間かけて昇温することで脱メタノール反応させ、その後、減圧40torr−スチーミング処理で未反応成分を除去した。得られた樹脂の軟化点は130℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1234で、重量平均分子量(Mw)は2005であった。
(Synthesis Example 3: Meiwa Kasei Co., Ltd., product name XBCrF-4)
To a glass 4-necked flask with a capacity of 2000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 968 parts by mass of m-cresolic acid (8.962 mol), 4,4′-bismethoxymethylbiphenyl 63.9 parts by mass (0.264 mol), p-xylene dimethyl ether 50.8 parts by mass (0.306 mol), 42% formalin 339.3 parts by mass (4.75 mol) and 2.8 parts by mass of oxalic acid were added and reacted at an internal temperature of 97 ° C. for 15 hours. . Thereafter, 0.6 parts by mass of 50% sulfuric acid was added, dehydrated at 100 ° C., the internal temperature was raised to 170 ° C. over 6 hours to cause a demethanol reaction, and then the pressure was reduced by 40 torr-steaming treatment. The reaction component was removed. The softening point of the obtained resin was 130 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1234, and the weight average molecular weight (Mw) was 2005.

(合成例4:明和化成製、品名XHF−3M)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに上記式(IV)で表されるノボラック型フェノール樹脂(軟化点94℃、遊離フェノール0.03%)375質量部、4,4'-ビスメトキシメチルビフェニル41.7質量部(0.172モル)を加え、内温120℃で溶解混合させた。その後、10%の硫酸0.4質量部を添加し、内温を175℃まで3時間かけて昇温することで反応させ、その後、減圧下(40torr)で水分を除去した。得られた樹脂の軟化点は124℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は2032で、重量平均分子量(Mw)は8861であった。
(Synthesis example 4: Meiwa Kasei Co., Ltd., product name XHF-3M)
A novolac type phenol resin represented by the above formula (IV) (softening point 94 ° C., free phenol 0.03) on a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer %) 375 parts by mass, 41.7 parts by mass of 4,4′-bismethoxymethylbiphenyl (0.172 mol) was added and dissolved and mixed at an internal temperature of 120 ° C. Thereafter, 0.4 part by mass of 10% sulfuric acid was added, the reaction was carried out by raising the internal temperature to 175 ° C. over 3 hours, and then water was removed under reduced pressure (40 torr). The softening point of the obtained resin was 124 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 2032 and the weight average molecular weight (Mw) was 8861.

(合成例5:明和化成製、品名BHF−3M)
合成例4において、4,4'-ビスメトキシメチルビフェニルに代えてp-キシレンジメチルエーテル41.7質量部(0.251モル)を使用した以外は同様にして反応を行った。得られた樹脂の軟化点は132℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1648で、重量平均分子量(Mw)は27968であった。
(Synthesis Example 5: Meiwa Kasei Co., Ltd., product name BHF-3M)
The reaction was conducted in the same manner as in Synthesis Example 4 except that 41.7 parts by mass (0.251 mol) of p-xylene dimethyl ether was used instead of 4,4′-bismethoxymethylbiphenyl. The softening point of the obtained resin was 132 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1648, and the weight average molecular weight (Mw) was 27968.

(合成例6:明和化成製、品名MEH−7851−4H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部の4つ口ガラス製フラスコに、フェノール188質量部(2モル)、4,4'-ビスメトキシメチルビフェニル331.5質量部(1.37モル)及び50%の硫酸0.23質量部を加え、窒素気流下、内温110℃〜130℃にて3.5時間、さらに165℃にて3時間反応させ、95℃まで冷却した。冷却後、90℃以上の純水500質量部を投入して電気伝導度が50μS/cm以下になるまで水洗した。その後、内温を160℃まで昇温し、減圧−スチーミング処理にて未反応成分を除去した。得られた樹脂の軟化点は130℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1400で、重量平均分子量(Mw)は9178であった。
(Synthesis Example 6: Meiwa Kasei Co., Ltd., product name MEH-7851-4H)
In a four-necked glass flask with a capacity of 1000 parts by volume equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 188 parts by mass of phenol (2 moles) and 331.5 parts by mass of 4,4′-bismethoxymethylbiphenyl (1.37 mol) and 0.23 part by mass of 50% sulfuric acid were added, and the mixture was reacted at an internal temperature of 110 ° C. to 130 ° C. for 3.5 hours and further at 165 ° C. for 3 hours under a nitrogen stream, and cooled to 95 ° C. After cooling, 500 parts by mass of pure water at 90 ° C. or higher was added and washed with water until the electric conductivity reached 50 μS / cm or lower. Thereafter, the internal temperature was raised to 160 ° C., and unreacted components were removed by a reduced pressure-steaming treatment. The softening point of the obtained resin was 130 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1400, and the weight average molecular weight (Mw) was 9178.

(合成例7:明和化成製、品名MEH−7800−3H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、フェノール188質量部(2モル)、p-キシレンジメチルエーテル229.08質量部(1.38モル)、及び50%の硫酸0.16質量部を加え、窒素気流下、内温135℃にて3.5時間、さらに160℃にて1.5時間反応させ、95℃まで冷却した。冷却後、90℃以上の純水500質量部を投入して電気伝導度が30μS/cm以下になるまで水洗した。その後、内温を160℃まで昇温し、減圧−スチーミング処理にて未反応成分を除去した。得られた樹脂の軟化点は95℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は2185で、重量平均分子量(Mw)は20746であった。
(Synthesis Example 7: Meiwa Kasei Co., Ltd., product name MEH-7800-3H)
In a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, 188 parts by mass of phenol (2 mol), 229.08 parts by mass of p-xylene dimethyl ether (1.38 mol), Then, 0.16 parts by mass of 50% sulfuric acid was added, and the mixture was reacted under a nitrogen stream at an internal temperature of 135 ° C. for 3.5 hours and further at 160 ° C. for 1.5 hours, and cooled to 95 ° C. After cooling, 500 parts by mass of pure water at 90 ° C. or higher was added and washed with water until the electric conductivity reached 30 μS / cm or lower. Thereafter, the internal temperature was raised to 160 ° C., and unreacted components were removed by a reduced pressure-steaming treatment. The softening point of the obtained resin was 95 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 2185, and the weight average molecular weight (Mw) was 20,746.

(合成例8:明和化成製、品名MEH−X−5H)
温度計、仕込・留出口、冷却器および撹拌機を備えた容量1000容量部のガラス製4つ口フラスコに、上記式(V)で表されるキシリレン架橋ノボラック樹脂(軟化点87℃、遊離フェノール0.2%)200質量部に対し、上記式(VII)で表されるノボラック型クレゾール樹脂(軟化点155℃、遊離クレゾール1.5%)300質量部を加え、窒素気流下、内温190℃にて溶解混合させた。得られた樹脂の軟化点は133℃であった。GPCによるポリスチレン換算数平均分子量(Mn)は1908で、重量平均分子量(Mw)は13782であった。
(Synthesis Example 8: Meiwa Kasei Co., Ltd., product name MEH-X-5H)
A xylylene cross-linked novolak resin represented by the above formula (V) (softening point 87 ° C., free phenol) was added to a 1000-volume glass four-necked flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer. 0.2%) To 200 parts by mass, add 300 parts by mass of the novolak-type cresol resin (softening point 155 ° C, free cresol 1.5%) represented by the above formula (VII), and dissolve at an internal temperature of 190 ° C under a nitrogen stream. Mixed. The softening point of the obtained resin was 133 ° C. The number average molecular weight (Mn) in terms of polystyrene by GPC was 1908, and the weight average molecular weight (Mw) was 13782.

(実施例1)
表1に示す配合処方に従い、天然ゴム100質量部に対し、HAF級カーボンブラック50質量部、アロマオイル5質量部、ステアリン酸3質量部、亜鉛華4質量部、老化防止剤6PPD[N-(1,3-ジメチルブチル)-N'-フェニル-p-フェニレンジアミン]1質量部、加硫促進剤TBBS[N-t-ブチル-2-ベンゾチアゾールスルフェンアミド]2.2質量部、硫黄5質量部と共に、合成例1で得られたフェノール樹脂を10質量部使用し、更に、ヘキサメチルメチロールメラミン1質量部も併せて混合してゴム組成物を調製した。
Example 1
According to the formulation shown in Table 1, for 100 parts by mass of natural rubber, 50 parts by mass of HAF grade carbon black, 5 parts by mass of aroma oil, 3 parts by mass of stearic acid, 4 parts by mass of zinc oxide, anti-aging agent 6PPD [N- ( 1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine] 1 part by mass, vulcanization accelerator TBBS [N-t-butyl-2-benzothiazolesulfenamide] 2.2 parts by mass, sulfur 5 parts by mass At the same time, 10 parts by mass of the phenol resin obtained in Synthesis Example 1 was used, and 1 part by mass of hexamethylmethylolmelamine was further mixed to prepare a rubber composition.

(実施例2〜8及び比較例1〜2)
実施例1において、合成例1で得られたフェノール樹脂に代えて、合成例2〜8で得られた樹脂を使用する以外は、実施例1と同様にしてゴム組成物を調製した。なお、比較例1で用いたフェノール樹脂は、上記式(IV)で表されるノボラック型フェノール樹脂(品名580、軟化点129℃)であり、比較例2で用いたフェノール樹脂は、上記式(VII)で表されるノボラック型クレゾール樹脂(品名MER−130、軟化点129℃)である。
(Examples 2-8 and Comparative Examples 1-2)
In Example 1, a rubber composition was prepared in the same manner as in Example 1 except that the resins obtained in Synthesis Examples 2 to 8 were used in place of the phenol resin obtained in Synthesis Example 1. The phenol resin used in Comparative Example 1 is a novolak type phenol resin (product name 580, softening point 129 ° C.) represented by the above formula (IV), and the phenol resin used in Comparative Example 2 is the above formula ( VII) is a novolac cresol resin (product name MER-130, softening point 129 ° C.).

次に、実施例1〜8及び比較例1〜2で得られたゴム組成物を145℃で30分間加硫して物性測定用のサンプルを作製し、下記に示す方法で硬度試験、引張試験及び動的粘弾性試験を行った。得られた結果を、比較例1を100として指数表示し、表1に併せて示した。   Next, the rubber compositions obtained in Examples 1 to 8 and Comparative Examples 1 and 2 were vulcanized at 145 ° C. for 30 minutes to prepare samples for measuring physical properties, and the hardness test and tensile test were performed by the methods shown below. And a dynamic viscoelasticity test was performed. The obtained results are shown as an index with Comparative Example 1 being 100, and are also shown in Table 1.

[硬度測定]
上記加硫ゴム組成物について、JIS K6253に準拠してJIS A硬度を測定した。
[Hardness measurement]
The vulcanized rubber composition was measured for JIS A hardness according to JIS K6253.

[引張試験]
上記加硫ゴム組成物からなるJISダンベル状3号形サンプルを用意し、JIS K6251に準拠して25℃で引張試験を行い、切断時伸び、引張強さ、50%伸張時の引張応力を測定した。
[Tensile test]
Prepare a JIS dumbbell-shaped No. 3 sample consisting of the above vulcanized rubber composition, and perform a tensile test at 25 ° C in accordance with JIS K6251 to measure elongation at break, tensile strength, and tensile stress at 50% elongation. did.

[動的粘弾性試験]
上記加硫ゴム組成物について、東洋精機社製スペクトロメーターを用い、歪1%、測定温度25℃にて動的貯蔵弾性率(E’)を測定した。
[Dynamic viscoelasticity test]
About the said vulcanized rubber composition, the dynamic storage elastic modulus (E ') was measured at 1% of distortion, and the measurement temperature of 25 degreeC using the Toyo Seiki spectrometer.

Figure 0005381209
Figure 0005381209

表1の実施例の結果から明らかなように、本発明のゴム組成物添加用フェノール樹脂をゴム組成物に添加することで、切断時伸び、引張強さ及び50%伸長時の引張応力の低下を抑制してゴム組成物の耐破壊性の低下を防止しつつ、動的貯蔵弾性率を向上させ、ゴム組成物を著しく高弾性化できる。   As is apparent from the results of the examples in Table 1, elongation at break, tensile strength, and tensile stress at 50% elongation are reduced by adding the phenol resin for rubber composition addition of the present invention to the rubber composition. The dynamic storage elastic modulus can be improved and the rubber composition can be remarkably increased in elasticity while suppressing the deterioration of the fracture resistance of the rubber composition.

Claims (8)

下記式(I):
Figure 0005381209
(式中、R0は、メチル基であり;R1及びR2は、架橋基で、但し、R1及びR2の少なくとも一部は、ビフェニルジメチレン基であり;pは0又は1の整数で、mは1の整数で、R0はヒドロキシル基に対して3位又は4位に結合しており、少なくとも一部のR0はヒドロキシル基に対して3位に結合しており、nは0〜10の数である)で表されるゴム組成物添加用フェノール樹脂。
Formula (I) below:
Figure 0005381209
(Wherein R 0 is a methyl group; R 1 and R 2 are bridging groups, provided that at least a part of R 1 and R 2 is a biphenyldimethylene group; An integer, m is an integer of 1, R 0 is bonded to the hydroxyl group at the 3 or 4 position, at least a portion of R 0 is bonded to the hydroxyl group at the 3 position, n Is a number from 0 to 10).
下記式(I):
Figure 0005381209
(式中、R0は、それぞれ独立して水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくとも一種の官能基であり;R1及びR2は、一部がビフェニルジメチレン基で、残りがメチレン基であり;pは0又は1の整数で、mは1の整数で、nは0〜10の数である)で表されるゴム組成物添加用フェノール樹脂。
Formula (I) below:
Figure 0005381209
Wherein R 0 is each independently at least one functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group. R 1 and R 2 are partly a biphenyldimethylene group and the rest are methylene groups; p is an integer of 0 or 1, m is an integer of 1, and n is a number of 0 to 10) The phenol resin for rubber composition addition represented by these.
下記式(I):
Figure 0005381209
(式中、R0は、それぞれ独立して水素、炭素数1〜10のアルキル基、炭素数1〜4のアルコキシ基、フェニル基及びメチロール基からなる群から選ばれる少なくとも一種の官能基であり;R1及びR2は、一部がビフェニルジメチレン基で、残りがメチレン基であり;pは0又は1の整数で、mは1の整数で、nは0〜10の数である)で表されるフェノール樹脂。
Formula (I) below:
Figure 0005381209
Wherein R 0 is each independently at least one functional group selected from the group consisting of hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, and a methylol group. R 1 and R 2 are partly a biphenyldimethylene group and the rest are methylene groups; p is an integer of 0 or 1, m is an integer of 1, and n is a number of 0 to 10) A phenolic resin represented by
前記式(I)中のpが0であることを特徴とする請求項1又は2に記載のゴム組成物添加用フェノール樹脂。   The phenol resin for rubber composition addition according to claim 1 or 2, wherein p in the formula (I) is 0. 前記ビフェニルジメチレン基が、[1,1'-ビフェニル]-4,4'-ジメチレン基であることを特徴とする請求項1又は2に記載のゴム組成物添加用フェノール樹脂。   The phenol resin for rubber composition addition according to claim 1 or 2, wherein the biphenyldimethylene group is a [1,1'-biphenyl] -4,4'-dimethylene group. 前記[1,1'-ビフェニル]-4,4'-ジメチレン基の含有量が全R1及びR2の5モル%以上であることを特徴とする請求項5に記載のゴム組成物添加用フェノール樹脂。 The rubber composition addition according to claim 5, wherein the content of the [1,1'-biphenyl] -4,4'-dimethylene group is 5 mol% or more of the total R 1 and R 2 . Phenolic resin. 前記式(I)中のR0が、炭素数1〜8のアルキル基であり、pが0であることを特徴とする請求項2及び4〜6のいずれか1項に記載のゴム組成物添加用フェノール樹脂。 The rubber composition according to any one of claims 2 and 4 to 6, wherein R 0 in the formula (I) is an alkyl group having 1 to 8 carbon atoms, and p is 0. Additive phenolic resin. 前記式(I)中のR0がメチル基であることを特徴とする請求項7に記載のゴム組成物添加用フェノール樹脂。 8. The phenol resin for rubber composition addition according to claim 7, wherein R 0 in the formula (I) is a methyl group.
JP2009070081A 2009-03-23 2009-03-23 Phenolic resin for rubber composition addition Expired - Lifetime JP5381209B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2009070081A JP5381209B2 (en) 2009-03-23 2009-03-23 Phenolic resin for rubber composition addition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2009070081A JP5381209B2 (en) 2009-03-23 2009-03-23 Phenolic resin for rubber composition addition

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP2004111058A Division JP4385831B2 (en) 2004-04-05 2004-04-05 Phenol resin mixture for rubber composition addition

Publications (2)

Publication Number Publication Date
JP2009173941A JP2009173941A (en) 2009-08-06
JP5381209B2 true JP5381209B2 (en) 2014-01-08

Family

ID=41029350

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2009070081A Expired - Lifetime JP5381209B2 (en) 2009-03-23 2009-03-23 Phenolic resin for rubber composition addition

Country Status (1)

Country Link
JP (1) JP5381209B2 (en)

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4170057B2 (en) * 2002-10-07 2008-10-22 株式会社ブリヂストン Rubber composition
JP2004231691A (en) * 2003-01-28 2004-08-19 Bridgestone Corp Pneumatic tire

Also Published As

Publication number Publication date
JP2009173941A (en) 2009-08-06

Similar Documents

Publication Publication Date Title
JP5095681B2 (en) tire
JP4587826B2 (en) Rubber composition for belt layer steel cord and steel cord coated thereby
JP5459047B2 (en) Adhesive rubber composition and pneumatic tire using the same
JP5665475B2 (en) Rubber composition and pneumatic tire using the same
JP6288148B2 (en) Rubber composition
JP2012082323A (en) Rubber composition for tire and pneumatic tire using the same
CN109160986B (en) Modified m-cresol-phenol-formaldehyde resin, preparation method and rubber composition thereof
JP4385831B2 (en) Phenol resin mixture for rubber composition addition
JP4394978B2 (en) Rubber composition for belt layer steel cord and steel cord coated thereby
JP4511231B2 (en) Pneumatic tire
JP2015205950A (en) Rubber composition for tire run-flat reinforced liner and pneumatic run flat tire using the same
WO2018020967A1 (en) Novolac-type cocondensation product to be compounded into rubber, and method for producing said cocondensation product
JP2021165324A (en) Rubber composition for tires and heavy duty tire using the same
JP5381209B2 (en) Phenolic resin for rubber composition addition
JP2007211088A (en) Rubber composition and tire using the same
WO2020262373A1 (en) Rubber composition for tire and pneumatic tire obtained using same
JP6414248B2 (en) Rubber composition
US10696838B2 (en) Rubber compositions containing tackifiers
JP6414249B2 (en) Rubber composition
JP6686324B2 (en) Rubber composition and pneumatic tire using the same
JP7095716B2 (en) Rubber composition for tires and tires using them
JP7095715B2 (en) Rubber composition for tires and tires using them
JP7095657B2 (en) Rubber composition for tires and pneumatic tires using them
JP7095656B2 (en) Rubber composition for tires and pneumatic tires using them
JP2004124011A (en) Rubber composition

Legal Events

Date Code Title Description
A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20090422

A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20090422

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A821

Effective date: 20090410

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20110726

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20110922

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20120410

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20120605

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20130205

A521 Request for written amendment filed

Free format text: JAPANESE INTERMEDIATE CODE: A523

Effective date: 20130220

TRDD Decision of grant or rejection written
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20130903

A61 First payment of annual fees (during grant procedure)

Free format text: JAPANESE INTERMEDIATE CODE: A61

Effective date: 20130916

R150 Certificate of patent or registration of utility model

Ref document number: 5381209

Country of ref document: JP

Free format text: JAPANESE INTERMEDIATE CODE: R150

Free format text: JAPANESE INTERMEDIATE CODE: R150

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

S533 Written request for registration of change of name

Free format text: JAPANESE INTERMEDIATE CODE: R313533

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250