【発明の詳細な説明】
く産業上の利用分野〉
本発明はレジノイド砥石に間し、更に詳しくは砥石の製
造から使用に到るまでの品質保持を図るための経時劣化
の少ないレジノイド砥石に関する．く従来の技術〉
一般鋳鉄、ステンレス鋼等の高硬度物質を研削または切
断するには酸化アルミナを主原料とする比較的粗い砥粒
と熱硬化性フェノール樹脂を結合剤として加熱成形した
レジノイド砥石を用いるのが通常である．
この場合、結合剤に熱硬化性フェノール樹脂を使用して
いる為、レジノイド砥石を長期間保管しておくと、砥粒
と熱硬化性フェノール樹脂との結合力が低下し、砥粒の
性能が著しく低下する等の問題点があった．
く発明が解決しようとする課題〉
本発明は従来の砥石製造から使用に到るまでの保存期閏
での経時劣化の少ないレジノイド砥石を提供することを
目的とする．
く問題点を解決するための手段〉
本発明者らは上記目的を達成するために鋭意検討した結
果、レジノイド砥石の結合剤である熱硬化性フェノール
樹脂のノボラックタイプ（ヘキサメチレンテトラミンを
含む．）及び／またはレゾールタイブの少なくともｌ種
にシランカップリング剤を配合し、これを成形すること
により長期保存による経時劣化の少ないレジノイド砥石
を得ることを見い出し本発明に到った．
以下に本発明を詳しく説明する．
本発明に使用される熱硬化性フェノール樹脂はレゾール
型フェノール樹脂及びノボラック型フェノール樹脂があ
る．レゾール型フェノール樹脂についてはフェノール、
クレゾール、キシレノール、ビスフェノール等のフェノ
ール類とホルマリン、パラホルムアルデヒド等のホルム
アルデヒド源となる物質とを水酸化ナトリウム、水酸化
カルシウム等のアルカリ金属、アルカリ土類金属水酸化
物及び酸化カルシウム等のアルカリ金属、アルカリ土類
金属酸化物及びアンモニア等のアミン化合物より成る塩
基性触媒の１種またはそれ以上を併用して反応させるこ
とにより得られる．
ノボラック型樹脂についてはフェノール、クレゾール、
キシレノール、ビスフェノール等のフェノール類とホル
マリン、バラホルムアルデヒド等のホルムアルデヒド源
となる物質とを塩酸、硫酸、シュウ酸等の酸を１種また
はそれ以上を併用して反応させることにより得られる．
更に、得れた樹脂にヘキサメチレンテトラミンを添加し
、これを粉砕して、粉末状熱硬化型のノボラック樹脂を
得ることが出来る．
シランカップリング剤としてはアミノシラン系カップリ
ング剤を用いる．アミノシランはシランカップリング剤
の側鎖、または末端に１個以上のアミノ基を有するもの
である．
又、アミノシランのフェノール樹脂に対する添加量はフ
ェノール樹脂固形分１００！量部に対して、アミノシラ
ン０．２〜１５１Ｈ１部が望ましい．アミノシランの添
加量が０．２重量部より少ないと経時劣化に対する効果
は顕著に現れず、１５！ｌ量部以上添加してもその効果
は変わらない．本発明で使用される砥粒については溶融
アルミナを主成分とするもの炭化珪素を主成分とするも
の等があるが、溶融アルミナを主成分とするものが望ま
しい．
砥粒の大きさは２０μ〜３ｍｍまでの物が使用される．
その他の充填物としては氷晶石、硫化鉄、酸化鉄、硫酸
バリウム等の無機フィラーを用いることも出来る．
本発明はアミノシランを含有する上記フェノール樹脂を
バインダーとし、砥粒等を混練り、成形、填成した経時
劣化の少ないレジノイド砥石である．く作用〉
砥石の長期保存による経時劣化は熱硬化性フェノール樹
脂結合剤の種類によっても差はあるが、熱硬化性フェノ
ール樹脂結合剤に７ミノシランを含冑させることにより
、砥石成形時１６０℃〜２００℃の焼成時において、ア
ミノシランが架橋剤あるいは架橋触媒として働き、熱硬
化性フェノール樹脂結合剤の劣化現象を防止し、経時劣
化の少ないレジノイド砥石が得られる．
く実施例〉
次に実施例により本発明を説明する．例中の部、％は特
に断わりのない限り重量基準である．尚、本発明はかか
る実施例に限定されるものではない．
合成例ｌ
フェノール１０００部、８６％のバラホルム４０８部を
還流器付きの３ｇの３つロフラスコに仕込、６．５％の
カセイソーダｆｆＪ液１０８部を加え、内温８０℃で反
応し、２６℃における粘度が５６０ｃｐになったところ
で３０℃まで冷却し固形分７２％のレゾール樹脂１６１
６部を得、これにアミノシラン（商品名ｒＳ １−ＫＢ
Ｅ−９０３Ｊ信越化学株式会社１！）６３部を添加し、
均一混合してレゾール樹脂Ａを得た．
合成例２
フェノール１ ０００部、５０％ホルムアルデヒロ
ド水溶液５２２部を還流器付きの２Ｑの４つフラスコに
仕込、シュウ酸２水和物５部を加え、還流させながら３
時間反応した後、内温２００℃まで昇温し、未反応モノ
マー等を除去し、樹脂の軟化点が１０５℃になったとこ
ろで内温を１５０℃まで冷却し、アミノシラン１３部を
添加し、均一混合して樹脂１０２０部を得た．次いでこ
の樹脂１００部に対してヘキサメチレンテトラミン１０
部を加え、混合粉砕し、粉末ノボラック樹ｆ＃Ｂを得た
．
合成例３
フェノール１０００部、８６％のバラホルムアルデヒド
４０８部を還流器付き３２の３つ口フラスコに仕込、６
．５％のカセイソーダ’？Ｊ ｔ（ｌ １ ０ ８部を
加え、内温８０℃で反応し、２５℃における粘度が５５
０ｃｐになったところで３０℃まで冷却し固形分７２％
のレゾール樹脂ＣＩ５１６部を得た．
合成例４
フェノール１０００部、５０％ホルムアルデヒド水溶液
５２２部を還流器付き２＄１の４つ口フラスコに仕込、
シュウ酸２水和物５部を加え、還流させながら３時間反
応した後、内温２００℃まで昇温し、未反応モノマー等
を除去し、軟化点がｌ０５℃になったところで取り出し
、樹脂１００７部を得た．次いでこの樹脂１００部に対
しヘキサメチレンテトラミン１０部を加え混合粉砕し、
粉末ノボラック樹脂Ｄを得た．
合成例５
合成例１と同様の条件で反応し、３０℃まで冷却し、固
形分７２％のレゾール樹脂１５１６部を得、これにアミ
ノシラン３０部を添加し、均一混合してレゾール樹１１
ｉＩＥを得た．
合成例６
合成例Ｉと同様の条件で反応し、３０℃まで冷却し、固
形分７２％のレゾール樹！１５１６部を得、これにアミ
ノシラン１３２部を添加し、均一混合してレゾール樹脂
Ｆを得た．
実施例１
砥粒Ａ３０＃１０００部とレゾール型フェノール樹ＮＡ
５０部をスピードミキサーで約１分混合した後、粉末状
ノボラック型フェノール樹１ｒｇＤ１５０部を添加し、
粉が良く入るまで混練りして排出し、樹脂被覆砥粒を得
た．
次いで１５Ｘ１５Ｘ１５０ｍｍ， 密度２．４０ｇ／
ｃｎ？のテストビースを成形し、内温１８０℃、６時間
で焼成し成形した．
実施例２
砥粒Ａ３０＃１０００部とレゾール型フェノール樹脂Ｐ
Ｌ−４８０５ （群栄化学工業１１）５０部をスピード
ミキサーで約１分混合した後、粉末状ノボラック型フェ
ノール樹１！ｉｒ８１５０部を添加−し、粉が良く入る
まで混練りして排出し、樹脂被覆延粒を得た．実施例ｌ
と同様にし成形し、焼成した．実施例３
砥粒Ａ３０＃１０００部とレゾール型フェノール樹１１
ＷＣ５０部をスピードミキサーで約１分混合した後、粉
末状ノボラック型フェノール樹脂Ｄ１５０部を添加し、
実施例ｌと同様の操作をした．実施例４
砥粒Ａ３０＃１０００部とレゾール型フェノール樹脂Ｐ
Ｌ−４８０５ ５０部をスピードミキサーで約ｌ分混
合した後、粉末状ノボラック型フェノール樹脂Ｄ１５０
部を添加し、実施例１と同様の操作をした．
実施例５
砥粒Ａ３０＃１０００部とレゾール型フェノール樹脂Ｅ
５０部をスピードミキサーで約１分混合した後、粉末状
ノボラック型フェノール樹脂ＰＧ−４５５１ （群栄化
学工業株式会社＄！）１５０部を添加し、実施例１と同
様の操作をした．実施例６
砥粒Ａ３０＃１０００部とレゾール型フェノール樹脂Ａ
５０部をスピードミキサーで約１分混合した後、粉末状
ノボラック型フェノール樹脂ＰＧ−４５５１ １５０
部を添加し、実施例ｌと同様の操作をした．
実施例７
砥粒Ａ３０＃１０００部とレゾール型フェノール樹１’
ｉｔＦ５０部をスピードミキサーで約１分混練りした後
、粉末状ノボラック型フェノール樹脂ＰＣ−４５５１
１５０部を添加し、実施例１と同様の操作をした．
実施例８
砥粒Ａ３０＃１０００部とレゾール型フエノール樹脂Ｃ
５０部をスピードミキサーで約１分混合した後、粉末状
ノボラック型フェノール樹脂ＰＧ−４５５１ １５０
部を添加し、実施例１と同様の操作をした。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a resinoid grindstone, and more particularly to a resinoid grindstone that exhibits little deterioration over time in order to maintain quality from the production of the grindstone until its use. Conventional technology: To grind or cut high-hardness materials such as general cast iron and stainless steel, a resinoid grinding wheel made by heat-forming relatively coarse abrasive grains made mainly of alumina oxide and a thermosetting phenolic resin as a binder is used. It is usually used. In this case, since thermosetting phenolic resin is used as the binder, if the resinoid grinding wheel is stored for a long period of time, the bonding force between the abrasive grains and the thermosetting phenolic resin will decrease, and the performance of the abrasive grains will deteriorate. There were problems such as a significant drop in performance. Problems to be Solved by the Invention The purpose of the present invention is to provide a resinoid grindstone that exhibits less deterioration over time during the storage period from conventional grindstone manufacture to use. Means for Solving the Problems In order to achieve the above object, the present inventors conducted extensive studies and found that a novolak type thermosetting phenolic resin (containing hexamethylenetetramine) is used as a binder for resinoid grinding wheels. The present inventors have discovered that by blending a silane coupling agent with at least one type of resol type and molding the resulting resin, a resinoid grindstone that exhibits less deterioration over time due to long-term storage can be obtained, and has thus arrived at the present invention. The present invention will be explained in detail below. The thermosetting phenolic resins used in the present invention include resol type phenolic resins and novolac type phenolic resins. For resol type phenolic resin, phenol,
Phenols such as cresol, xylenol, and bisphenol and formaldehyde source substances such as formalin and paraformaldehyde are combined with alkali metals such as sodium hydroxide, calcium hydroxide, alkaline earth metal hydroxides, and alkali metals such as calcium oxide. It is obtained by reacting with one or more basic catalysts consisting of alkaline earth metal oxides and amine compounds such as ammonia. For novolac type resins, phenol, cresol,
It is obtained by reacting phenols such as xylenol and bisphenol with a formaldehyde source such as formalin and formaldehyde in combination with one or more acids such as hydrochloric acid, sulfuric acid, and oxalic acid.
Furthermore, by adding hexamethylenetetramine to the obtained resin and pulverizing it, a powdered thermosetting novolak resin can be obtained. An aminosilane coupling agent is used as the silane coupling agent. Aminosilane is a silane coupling agent that has one or more amino groups in the side chain or at the end. Also, the amount of aminosilane added to the phenol resin is 100% of the solid content of the phenol resin! Preferably, the amount of aminosilane is 0.2 to 151H1 part. If the amount of aminosilane added is less than 0.2 parts by weight, the effect on aging deterioration will not be noticeable, and 15! Even if more than 1 part is added, the effect remains the same. The abrasive grains used in the present invention include those whose main component is fused alumina and those whose main component is silicon carbide, but those whose main component is fused alumina are preferable. The size of the abrasive grains used is from 20μ to 3mm. Other fillers that can be used include inorganic fillers such as cryolite, iron sulfide, iron oxide, and barium sulfate. The present invention is a resinoid abrasive wheel that exhibits little deterioration over time and is made by using the above-mentioned phenolic resin containing aminosilane as a binder, kneading it with abrasive grains, molding it, and filling it. Effects> Although the deterioration over time due to long-term storage of the whetstone varies depending on the type of thermosetting phenolic resin binder, by incorporating 7-minosilane into the thermosetting phenolic resin binder, the whetstone can be heated to 160°C or more during molding. During firing at 200°C, aminosilane acts as a crosslinking agent or crosslinking catalyst, preventing the deterioration of the thermosetting phenolic resin binder, resulting in a resinoid grinding wheel that shows little deterioration over time. Examples> Next, the present invention will be explained using examples. Parts and percentages in the examples are based on weight unless otherwise specified. Note that the present invention is not limited to such embodiments. Synthesis Example 1 1000 parts of phenol and 408 parts of 86% baraform were placed in a 3 g three-bottle flask equipped with a reflux device, 108 parts of 6.5% caustic soda FFJ solution was added, and the reaction was carried out at an internal temperature of 80°C, followed by a reaction at 26°C. When the viscosity reached 560 cp, it was cooled to 30°C and resol resin 161 with a solid content of 72% was added.
6 parts were obtained, to which aminosilane (trade name rS 1-KB
E-903J Shin-Etsu Chemical Co., Ltd. 1! ) 63 parts were added,
Resol resin A was obtained by uniformly mixing. Synthesis Example 2 1,000 parts of phenol and 522 parts of a 50% formaldehyde aqueous solution were placed in four 2Q flasks equipped with a reflux device, 5 parts of oxalic acid dihydrate was added, and 3 parts of phenol was added while refluxing.
After reacting for a period of time, the internal temperature was raised to 200°C, unreacted monomers, etc. were removed, and when the softening point of the resin reached 105°C, the internal temperature was cooled to 150°C, 13 parts of aminosilane was added, and a uniform The mixture was mixed to obtain 1020 parts of resin. Then, 10 parts of hexamethylenetetramine was added to 100 parts of this resin.
1.5% of the powder was added, mixed and pulverized to obtain a powdered novolac tree f#B. Synthesis Example 3 1000 parts of phenol and 408 parts of 86% rose formaldehyde were charged into a 32 mm three-necked flask equipped with a reflux device, and 6
．． 5% caustic soda'? J t (l 1 0 8 parts was added, the reaction was carried out at an internal temperature of 80°C, and the viscosity at 25°C was 55
When it reaches 0 cp, cool it down to 30℃ and reduce the solid content to 72%.
516 parts of resol resin CI were obtained. Synthesis Example 4 1000 parts of phenol and 522 parts of a 50% formaldehyde aqueous solution were charged into a 2 $1 four-necked flask equipped with a reflux device.
After adding 5 parts of oxalic acid dihydrate and reacting for 3 hours under reflux, the internal temperature was raised to 200°C, unreacted monomers etc. were removed, and when the softening point reached 105°C, it was taken out and the resin 1007 I got the department. Next, 10 parts of hexamethylenetetramine was added to 100 parts of this resin, mixed and ground.
Powder novolak resin D was obtained. Synthesis Example 5 The reaction was carried out under the same conditions as in Synthesis Example 1, and the mixture was cooled to 30°C to obtain 1516 parts of resol resin with a solid content of 72%. To this, 30 parts of aminosilane was added and mixed uniformly to obtain resol resin 11.
I got iIE. Synthesis Example 6 Reaction was carried out under the same conditions as in Synthesis Example I, cooled to 30°C, and a resol tree with a solid content of 72% was obtained! 1516 parts were obtained, and 132 parts of aminosilane was added thereto and mixed uniformly to obtain resol resin F. Example 1 1000 parts of abrasive grain A30 and resol type phenolic tree NA
After mixing 50 parts with a speed mixer for about 1 minute, 150 parts of powdered novolac type phenol tree 1rgD was added,
The powder was kneaded until well incorporated and then discharged to obtain resin-coated abrasive grains. Then 15X15X150mm, density 2.40g/
cn? A test bead was molded and fired at an internal temperature of 180°C for 6 hours. Example 2 1000 parts of abrasive grain A30 and resol type phenolic resin P
After mixing 50 parts of L-4805 (Gunei Chemical Industry 11) with a speed mixer for about 1 minute, powdered novolac type phenol tree 1! 8,150 parts of ir was added, kneaded until the powder was incorporated well, and then discharged to obtain resin-coated granules. Example l
It was molded and fired in the same manner as above. Example 3 Abrasive grain A30 #1000 parts and resol type phenol tree 11
After mixing 50 parts of WC with a speed mixer for about 1 minute, 150 parts of powdered novolac type phenolic resin D was added.
The same operation as in Example 1 was performed. Example 4 1000 parts of abrasive grain A30 and resol type phenolic resin P
After mixing 50 parts of L-4805 for about 1 minute with a speed mixer, powdered novolac type phenolic resin D150
The same procedure as in Example 1 was carried out. Example 5 1000 parts of abrasive grain A30 and resol type phenolic resin E
After mixing 50 parts with a speed mixer for about 1 minute, 150 parts of powdered novolac type phenolic resin PG-4551 (Gun-ei Chemical Industry Co., Ltd. $!) was added, and the same operation as in Example 1 was performed. Example 6 1000 parts of abrasive grain A30 and resol type phenolic resin A
After mixing 50 parts with a speed mixer for about 1 minute, powdered novolac type phenolic resin PG-4551 150
The same procedure as in Example 1 was carried out. Example 7 1000 parts of abrasive grain A30 and resol type phenol tree 1'
After kneading 50 parts of itF with a speed mixer for about 1 minute, powdered novolak type phenolic resin PC-4551 was mixed.
150 parts were added and the same operation as in Example 1 was carried out. Example 8 1000 parts of abrasive grain A30 and resol type phenolic resin C
After mixing 50 parts with a speed mixer for about 1 minute, powdered novolac type phenolic resin PG-4551 150
The same procedure as in Example 1 was carried out.
上記により得た樹脂被覆砥粒の型特性試験結果を表１に
記す．
く発明の効果〉
以上のごとく、本発明によりレジノイド砥石性能の代表
的な特性項目である常態強度や熱閘強度の低下をまねく
ことなく、経時劣化の目安となる耐水強度を大幅に向上
させる、すなわち経時劣化の少ないレジノイド砥石を得
ることが出来る．出願人 群栄化学工業株式会社Table 1 shows the mold characteristic test results for the resin-coated abrasive grains obtained above. Effects of the Invention> As described above, the present invention significantly improves water resistance strength, which is a measure of deterioration over time, without causing a decrease in normal strength and heat lock strength, which are typical characteristic items of resinoid grinding wheel performance. In other words, it is possible to obtain a resinoid grindstone with little deterioration over time. Applicant Gunei Chemical Industry Co., Ltd.