JP2006089551A - Method for producing boron-modified resol phenolic resin composition - Google Patents
Method for producing boron-modified resol phenolic resin composition Download PDFInfo
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本発明は、硬化物に優れた耐熱性や難燃性を与え、溶解性や成形性に優れたホウ素変性レゾール型フェノール樹脂組成物の製造方法に関する。 The present invention relates to a method for producing a boron-modified resol-type phenol resin composition that imparts excellent heat resistance and flame retardancy to a cured product and is excellent in solubility and moldability.
フェノール樹脂は各種の優れた特性を生かして主に成形材料、積層材料、摩擦材料、塗料などの用途に広く使用されている。しかし、近年、各用途での要求性能が高度化するにつれ、特に耐熱性及び難燃性において要求される高いレベルに対して十分に対応できなくなってきている。耐熱性、難燃性を向上させる手段としては、フェノール樹脂をホウ酸で変性することが有効であることは古くから知られている。例えば、レゾール型フェノール樹脂にホウ酸を添加し、溶融状態で反応させる方法が報告されている(特許文献1及び特許文献2参照)。しかし、この方法ではレゾール型フェノール樹脂とホウ酸とを、例えば110℃以上の高温で溶解させ、次いでこの加熱下で共縮合させるため、レゾール型フェノール樹脂の熱硬化が進行してしまい、得られたホウ素変性フェノール樹脂の溶剤溶解性が大きく低下するという欠点があった。
また、レゾール型フェノール樹脂とホウ酸とをメタノールに溶解して得られるワニスが報告されている(特許文献3参照)。しかし、メタノールを溶剤とした場合、メタノールとホウ素との反応により低沸点のホウ酸エステルを生成し気化するため、最終硬化物に含まれるホウ素含有量が低下したり、またワニスの保存安定性が悪く、商品としての実用性が乏しい。更に、メタノールに溶解できるホウ酸変性レゾール型フェノール樹脂は低分子量のレゾール型フェノール樹脂に限られており、このような低分子量の変性樹脂を用いて得られた硬化物は力学物性が低い欠点を有する。
Phenol resins are widely used mainly for applications such as molding materials, laminated materials, friction materials, paints, etc. by making use of various excellent properties. However, in recent years, as the required performance in each application has become more sophisticated, it has become impossible to sufficiently cope with the high level required particularly in heat resistance and flame retardancy. As a means for improving heat resistance and flame retardancy, it has long been known that it is effective to modify a phenol resin with boric acid. For example, a method has been reported in which boric acid is added to a resol type phenol resin and reacted in a molten state (see Patent Document 1 and Patent Document 2). However, in this method, the resol type phenol resin and boric acid are dissolved at a high temperature of, for example, 110 ° C. or higher, and then co-condensed under this heating. In addition, the solvent solubility of the boron-modified phenol resin is greatly reduced.
In addition, a varnish obtained by dissolving a resol type phenolic resin and boric acid in methanol has been reported (see Patent Document 3). However, when methanol is used as the solvent, a low-boiling borate ester is generated and vaporized by the reaction between methanol and boron, so that the boron content in the final cured product is reduced and the storage stability of the varnish is reduced. It is bad and the practicality as a product is poor. Furthermore, boric acid-modified resol type phenol resins that can be dissolved in methanol are limited to low molecular weight resol type phenol resins, and cured products obtained using such low molecular weight modified resins have the disadvantage of low mechanical properties. Have.
本発明は、硬化後に耐熱性と難燃性を有し、且つ溶解性や成形性に優れたホウ素変性レゾール型フェノール樹脂組成物の製造方法を提供することにある。 An object of the present invention is to provide a method for producing a boron-modified resol type phenolic resin composition having heat resistance and flame retardancy after curing, and excellent in solubility and moldability.
本発明者は、前記目的を達成すべく、鋭意検討を重ねた結果、アミド系有機溶剤中においてレゾール型フェノール樹脂とホウ酸系化合物とを低温で反応させて得られたホウ素変性レゾール型フェノール樹脂溶液をそのままワニスとして用いることによりその硬化物に優れた耐熱性や難燃性を与え、溶解性や成形性を併せ持つフェノール樹脂組成物を得ることができ、本発明を完成するに至った。
即ち、本発明は、フェノール類とアルデヒト類とを塩基性触媒存在下で反応して得られる固形レゾール型フェノール樹脂(A)と、ホウ酸系化合物(B)とを、アミド系溶剤(C)に溶解させ、(A)と(B)とを(A)が硬化しない温度で反応させることを特徴とするホウ素変性レゾール型フェノール樹脂組成物の製造方法を提供する。
As a result of intensive studies to achieve the above object, the present inventor has obtained a boron-modified resol type phenol resin obtained by reacting a resol type phenol resin and a boric acid type compound in an amide organic solvent at a low temperature. By using the solution as a varnish as it is, a cured resin can be provided with excellent heat resistance and flame retardancy, and a phenol resin composition having both solubility and moldability can be obtained, and the present invention has been completed.
That is, the present invention provides a solid resol-type phenol resin (A) obtained by reacting phenols and aldehydes in the presence of a basic catalyst, and a boric acid compound (B), an amide solvent (C). A method for producing a boron-modified resol-type phenol resin composition is provided, which comprises dissolving (A) and (B) at a temperature at which (A) does not cure.
本発明は、従来の方法に比べてより優れた溶解性及び塗膜形成や製膜性などに優れた成形性を有するホウ素変性レゾール型フェノール樹脂組成物を製造できる。即ち、熱硬化した成分を殆ど含まないで且つ高濃度のホウ素変性レゾール型フェノール樹脂組成物の製造方法を提供することができる。更に本発明は、レゾール型フェノール樹脂が硬化しない温度、即ち60℃未満、特に室温程度の反応温度で反応せしめることができるため、エネルギーコストが低減されるメリットを有する。更に、ホウ酸変性時に不均一な熱硬化反応が生じないため、耐熱性・難燃性の向上にも優れている。 INDUSTRIAL APPLICABILITY The present invention can produce a boron-modified resol-type phenolic resin composition having superior solubility and moldability superior to conventional methods, such as film formation and film formation. That is, it is possible to provide a method for producing a high-concentration boron-modified resol-type phenol resin composition that hardly contains thermosetting components. Furthermore, the present invention has a merit that the energy cost is reduced because the reaction can be performed at a temperature at which the resol type phenolic resin is not cured, that is, a reaction temperature of less than 60 ° C., particularly about room temperature. Furthermore, since a non-uniform thermosetting reaction does not occur at the time of boric acid modification, it is excellent in improving heat resistance and flame retardancy.
本発明で用いるレゾール型フェノール樹脂(A)としては、フェノール類とアルデヒド類のモル比が好ましくは1:1〜1:2になるように配合し、アルカリ触媒、特に好ましくはアンモニア水溶液存在下で反応させ、減圧蒸留により水を除去して得られる高分子量のものが用いられる。得られたレゾール型フェノール樹脂のGPCの数平均分子量は250以上が好ましく、より好ましくは300〜800である。かかる分子量が上記範囲であれば、得られる変性樹脂の硬化物の力学物性が良好で、実用性が高い。又、得られる樹脂組成物の溶剤溶解性も充分で、ワニスとしての使用に適する。また、レゾール型フェノール樹脂に含まれる水の量は好ましくとしては4質量%以下、より好ましくは2質量%以下である。水の含有量が4質量%を超えると、ホウ素変性レゾール型フェノール樹脂の合成において加水分解反応を生じる恐れがあるため、好ましくない。 The resol type phenolic resin (A) used in the present invention is blended so that the molar ratio of phenols and aldehydes is preferably 1: 1 to 1: 2, and in the presence of an alkaline catalyst, particularly preferably an aqueous ammonia solution. A high molecular weight product obtained by reacting and removing water by distillation under reduced pressure is used. The number average molecular weight of GPC of the obtained resol type phenol resin is preferably 250 or more, more preferably 300 to 800. When the molecular weight is in the above range, the cured product of the resulting modified resin has good mechanical properties and high practicality. In addition, the resulting resin composition has sufficient solvent solubility and is suitable for use as a varnish. The amount of water contained in the resol type phenol resin is preferably 4% by mass or less, more preferably 2% by mass or less. If the water content exceeds 4% by mass, hydrolysis reaction may occur in the synthesis of the boron-modified resol type phenol resin, which is not preferable.
ここでフェノール類としては、フェノール、クレゾール、キシレノール、m-クレゾール、m-エチルフェノール、レゾルシン、カテコール、ヒドロキノン及びビスフェノールAなどが挙げられ、これらを単独または２種以上組み合わせて使用できる。また、アルデヒド類としては、ホルマリン、パラホルムアルデヒド、トリオキサン、アセトアルデヒド、ベンズアルデヒドなどが挙げられ、これらを単独または２種以上組み合わせて使用できる。 Here, examples of phenols include phenol, cresol, xylenol, m-cresol, m-ethylphenol, resorcin, catechol, hydroquinone, bisphenol A, and the like, and these can be used alone or in combination of two or more. Examples of aldehydes include formalin, paraformaldehyde, trioxane, acetaldehyde, benzaldehyde and the like, and these can be used alone or in combination of two or more.
本発明で用いるホウ酸系化合物(B)としては、ホウ酸およびホウ酸エステル、ホウ酸エステルの部分重縮合物が用いられる。ホウ酸およびホウ酸エステルとしては、一般式(1)
B(OR)n(OH)3-n (1)
(式中、nは0〜3までの整数、RはCmH2m+1のアルキル基であり、mは1〜10の整数を表す。)で表わされるものが用いられる。ホウ酸としては、具体的には、例えばオルトホウ酸、メタホウ酸、四ホウ酸、およびそれらの混合物が挙げられ、また、ホウ酸エステルとしては、具体的には、例えばホウ酸トリメチル、ホウ酸トリエチル、ホウ酸トリプロピル、ホウ酸トリブチル等が挙げられる。これらのホウ酸及びホウ酸エステルは、単独又は2種以上組み合わせて使用できる。また、それらの部分加水分解物や部分重縮合物も単独又は併用して用いることができる。上記の中ではホウ酸が最も好ましく用いられる。なお、前記の部分重縮合物は、一般式(1)で表されるホウ酸エステルを、水、溶剤、及び必要により酸又は塩基触媒と共に混合攪拌する方法によって得ることができる。
As the boric acid compound (B) used in the present invention, boric acid, boric acid esters, and partial polycondensates of boric acid esters are used. As boric acid and boric acid ester, general formula (1)
B (OR) n (OH) 3-n (1)
(Wherein n is an integer from 0 to 3, R is an alkyl group of CmH2m + 1, and m is an integer from 1 to 10). Specific examples of the boric acid include orthoboric acid, metaboric acid, tetraboric acid, and mixtures thereof. Specific examples of the boric acid ester include trimethyl borate and triethyl borate. , Tripropyl borate, tributyl borate and the like. These boric acid and boric acid ester can be used alone or in combination of two or more. Moreover, those partial hydrolysates and partial polycondensates can be used alone or in combination. Of these, boric acid is most preferably used. The partial polycondensate can be obtained by a method in which the borate ester represented by the general formula (1) is mixed and stirred with water, a solvent, and, if necessary, an acid or a base catalyst.
本発明で使用するホウ酸系化合物(B)の添加量は、ホウ酸系化合物中に含まれるホウ素量のレゾール型フェノール樹脂(A)に対する質量%で規定される。例えば、フェノール樹脂100gに対してホウ酸を10g用いた場合にはホウ素含有量は1.75質量%である。
即ち、レゾール型フェノール樹脂(A)に対するホウ酸系化合物(B)の量は、ホウ素の(A)に対する割合が好ましくは0.1〜5質量%、より好ましくは0.3〜4質量%、特に好ましくは0.5〜3質量%となるように用いられる。かかるホウ素含有量が0.1〜5質量%の場合、得られる硬化物の耐熱性や難燃性が向上し、且つ該樹脂組成物の粘度が低くて、含浸剤やコーディング材などとして好適に用いられる。
The addition amount of the boric acid compound (B) used in the present invention is defined by mass% of the boron content contained in the boric acid compound with respect to the resol type phenol resin (A). For example, when 10 g of boric acid is used per 100 g of phenol resin, the boron content is 1.75% by mass.
That is, the amount of the boric acid compound (B) with respect to the resol type phenol resin (A) is preferably 0.1 to 5% by mass, more preferably 0.3 to 4% by mass, and particularly preferably 0.5% of the ratio of boron to (A). It is used so that it may become ~ 3 mass%. When the boron content is 0.1 to 5% by mass, the heat resistance and flame retardancy of the resulting cured product are improved, and the viscosity of the resin composition is low, so that it is suitably used as an impregnating agent or a coding material. .
本発明で用いるアミド系溶剤(C)としては、原料のレゾール型フェノール樹脂及びホウ酸系化合物及び反応生成物ホウ素変性レゾール型フェノール樹脂を溶解するようなものが用いられる。具体的には、N,N-ジメチルホルムアミド、N-メチルピロリドン、N,N-ジメチルアセトアミド、ジメチルスルホキシドが好ましく用いられ、最も好ましくはN,N-ジメチルホルムアミド、N-メチルピロリドンである。尚、用いるアミド系溶剤(C)の量は原料であるレゾール型フェノール樹脂及びホウ酸系化合物を各々溶解できる量であれば良く、必ずしも限定されないが、得られるホウ素変性レゾール型フェノール樹脂組成物溶液の適正粘度範囲から、レゾール型フェノール樹脂及びホウ酸系化合物の合計100質量部に対して溶剤が50〜500質量部となるように用いることが好ましい。 As the amide solvent (C) used in the present invention, a solvent which dissolves the raw material resol type phenol resin, boric acid type compound and reaction product boron modified resol type phenol resin is used. Specifically, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide and dimethyl sulfoxide are preferably used, and most preferably N, N-dimethylformamide and N-methylpyrrolidone. The amount of the amide solvent (C) to be used is not limited as long as it is an amount capable of dissolving the resol type phenol resin and boric acid type compound as raw materials, but the boron-modified resol type phenol resin composition solution to be obtained is not necessarily limited. From the proper viscosity range, the solvent is preferably used in an amount of 50 to 500 parts by mass with respect to 100 parts by mass in total of the resol type phenolic resin and boric acid compound.
本発明におけるホウ素変性レゾール型フェノール樹脂の製造は、例えば次のようにして行うことができる。まず、フェノール類1モルに対してアルデヒド類1〜2モルを塩基性触媒の存在下で反応させ、得られる初期縮合物を静置分離して、初期縮合物中の水分を2〜15質量%にし、しかる後脱水、脱フェノール及び縮合反応を行い、レゾール型固形フェノール樹脂を得る。次いで、得られたレゾール型フェノール樹脂にホウ酸のN,N-ジメチルホルムアミド（DMF）溶液を加え、両者を室温(25℃)で15時間反応させ、目的とするホウ素変性レゾール型フェノール樹脂組成物を得ることができる。
本発明のホウ素変性レゾール型フェノール樹脂組成物の製造においては、レゾール型フェノール樹脂とホウ酸系化合物との反応温度が重要となる。反応温度としては、60℃未満の低温が好ましく、より好ましくは15〜50℃、更に好ましくは20〜40℃、特に好ましくは室温(20〜30℃)である。また、反応時間は反応温度により異なるが、通常1〜24時間である。60℃を超える温度ではホウ素変性時にフェノール樹脂の架橋反応が生じて好ましくない。
The production of the boron-modified resol-type phenol resin in the present invention can be performed, for example, as follows. First, 1 to 2 mol of aldehyde is reacted with 1 mol of phenol in the presence of a basic catalyst, and the resulting initial condensate is allowed to stand and be separated, so that the water content in the initial condensate is 2 to 15% by mass. Thereafter, dehydration, dephenolization and condensation are carried out to obtain a resol-type solid phenol resin. Next, an N, N-dimethylformamide (DMF) solution of boric acid was added to the obtained resol type phenol resin, and both were reacted at room temperature (25 ° C.) for 15 hours to obtain the desired boron-modified resol type phenol resin composition. Can be obtained.
In the production of the boron-modified resol type phenol resin composition of the present invention, the reaction temperature between the resol type phenol resin and the boric acid compound is important. The reaction temperature is preferably a low temperature of less than 60 ° C, more preferably 15 to 50 ° C, still more preferably 20 to 40 ° C, and particularly preferably room temperature (20 to 30 ° C). Moreover, although reaction time changes with reaction temperature, it is 1 to 24 hours normally. A temperature exceeding 60 ° C. is not preferable because a crosslinking reaction of the phenol resin occurs at the time of boron modification.
上述の製造方法で得られたホウ素変性レゾール型フェノール樹脂組成物は、そのままワニスとして耐熱性塗料、耐熱性結合材などとして有効に利用することができる。例えば、本発明のホウ素変性フェノール樹脂組成物からなる紙基材積層板を得るには、上述のホウ素変性樹脂ワニスを結合材としてクラフト紙、リンター紙、ガラス布、ガラス不織布、ポリエステル布、アラミド繊維布、帆布などの紙基材に塗布含浸させて、乾燥して得られた積層材料に銅箔を加えて熱プレスすることにより積層成形する方法が挙げられる。
本発明のホウ素変性レゾール型フェノール樹脂組成物は、良溶剤の中、低温で均一に反応して得られるため、耐熱性、難燃性を有するだけでなく、優れた溶解性及び塗膜形成や製膜性などに優れた成形性をも有し、含浸剤やコーティング材などとして好適に用いられる。これに対して、従来の溶融法では、ホウ酸変性時に一般に樹脂の溶融温度以上に加熱するため、レゾール型フェノール樹脂の熱硬化が部分的に進行してしまい、溶剤溶解性が極端に低下し、実用性に乏しくなる。また、ホウ酸変性時の溶融粘度が高く、均一に反応しにくいため、耐熱性と難燃性の向上にも悪影響を与える。
The boron-modified resol-type phenol resin composition obtained by the above-described production method can be effectively used as it is as a varnish as a heat-resistant paint, a heat-resistant binder or the like. For example, in order to obtain a paper base laminate comprising the boron-modified phenolic resin composition of the present invention, kraft paper, linter paper, glass cloth, glass nonwoven fabric, polyester cloth, aramid fiber using the above boron-modified resin varnish as a binder. Examples of the method include laminating by applying a copper foil to a laminated material obtained by applying and impregnating a paper base material such as cloth or canvas and drying, followed by hot pressing.
The boron-modified resol type phenolic resin composition of the present invention is obtained by uniformly reacting at a low temperature in a good solvent, so that it not only has heat resistance and flame retardancy, but also has excellent solubility and coating film formation. It also has excellent moldability such as film forming properties, and is suitably used as an impregnating agent or a coating material. On the other hand, in the conventional melting method, when the boric acid is modified, generally, the resin is heated to a temperature higher than the melting temperature of the resin, so that the thermosetting of the resol type phenol resin partially proceeds and the solvent solubility is extremely lowered. , Become less practical. Moreover, since the melt viscosity at the time of boric acid modification is high and it is difficult to react uniformly, it also has an adverse effect on the improvement of heat resistance and flame retardancy.
本発明を実施例によって更に具体的に説明する。また、以下の実施例において、ガラス転移温度及び貯蔵弾性率は、固体動的粘弾性測定装置(レオメトリックス・ファーイースト株式会社製RSA-2)を用い、測定周波数1Hz、昇温速度2℃/分で測定した。なお、ガラス転移温度(Tg)はtanδピーク温度とした。ホウ素含有量はPerkn Elmer社製 Optima 3300DVを用いて、プラズマ発光(ICP)の測定を行い、予めホウ酸を用いて作成しておいた検量線により定量した。組成物の溶液粘度は、山一電機株式会社製VM-100A振動式粘度計を用いて室温で測定した。 The present invention will be described more specifically with reference to examples. Further, in the following examples, the glass transition temperature and the storage elastic modulus were measured using a solid dynamic viscoelasticity measuring device (RSA-2 manufactured by Rheometrics Far East Co., Ltd.), a measurement frequency of 1 Hz, and a heating rate of 2 ° C. / Measured in minutes. The glass transition temperature (Tg) was tan δ peak temperature. The boron content was measured by plasma emission (ICP) using an Optima 3300DV manufactured by Perkn Elmer, and quantified by a calibration curve prepared in advance using boric acid. The solution viscosity of the composition was measured at room temperature using a VM-100A vibratory viscometer manufactured by Yamaichi Electronics Co., Ltd.
(実施例1)
加熱冷却ジャケット、攪拌機及び減圧脱水装置を備えた反応釜にフェノール1000質量部、41.5%ホルマリン1072質量部を加え、攪拌を開始した。25%アンモニア水200質量部を加え、70℃まで昇温し、遊離ホルムアルデヒドが1%になるまで反応させた。そして、反応釜の温度を50℃以下に冷却し、30分間静置分離を行い、上層水750質量部を除去した。続いて、得られたこの初期縮合樹脂を95〜100℃、減圧度700〜750mmHgで脱水、脱フェノールを行い、融点71℃、150℃におけるゲルタイム110秒、水分1%の固形レゾール型フェノール樹脂Aを得た。
得られたレゾール型フェノール樹脂A 100質量部とホウ酸6.8質量部をDMFに溶解させ、室温で15時間攪拌して反応した。これにより得られたホウ素変性レゾール型フェノール樹脂組成物の粘度は1450cpであった。また、この変性樹脂組成物をガラス板上にキャストして80℃で乾燥した後、150℃、180℃各1時間熱硬化させて得られた硬化フィルムはクラック、気泡、しわなどもなく、良好な表面形態を示した。これに対して、下記の比較例1で得られたホウ素変性樹脂はDMFに溶解せず、キャスト膜を作れなかった。
更に、上記のホウ素変性樹脂組成物を型に注ぎ、乾燥、熱硬化させて、幅6mm、厚み1mm の注型板を作製し、動的粘弾性測定を行った。得られた貯蔵弾性率(E’)及びtanδピーク温度(Tg)を表2に示す。なお、表2には下記の比較例2の未変性のレゾール型フェノール樹脂の硬化物結果も併せて示す。比較例2では、貯蔵弾性率(E’)が270℃で大きく低下したのに対し、実施例1のE’では270℃まで殆ど低下しなかった。また、実施例1で得られた硬化物のガラス転移温度(Tg)も比較例2より高い。ホウ素変性レゾール型フェノール樹脂硬化物の耐熱性が大きく向上していることが明らかとなった。
(Example 1)
1000 parts by mass of phenol and 1072 parts by mass of 41.5% formalin were added to a reaction kettle equipped with a heating / cooling jacket, a stirrer, and a vacuum dehydrator, and stirring was started. 200 parts by mass of 25% aqueous ammonia was added, the temperature was raised to 70 ° C., and the reaction was continued until the free formaldehyde became 1%. Then, the temperature of the reaction kettle was cooled to 50 ° C. or lower, and the mixture was allowed to stand for 30 minutes to remove 750 parts by mass of the upper layer water. Subsequently, the obtained initial condensation resin was dehydrated and dephenoled at 95 to 100 ° C. and a degree of vacuum of 700 to 750 mmHg. Got.
100 parts by mass of the obtained resol type phenolic resin A and 6.8 parts by mass of boric acid were dissolved in DMF, and the mixture was reacted at room temperature for 15 hours with stirring. The viscosity of the boron-modified resol type phenolic resin composition obtained in this manner was 1450 cp. Moreover, the cured film obtained by casting this modified resin composition on a glass plate and drying at 80 ° C. and then thermosetting at 150 ° C. and 180 ° C. for 1 hour each is good without cracks, bubbles, wrinkles, etc. Surface morphology. In contrast, the boron-modified resin obtained in Comparative Example 1 below did not dissolve in DMF, and a cast film could not be made.
Further, the above boron-modified resin composition was poured into a mold, dried and thermally cured to produce a cast plate having a width of 6 mm and a thickness of 1 mm, and dynamic viscoelasticity measurement was performed. The obtained storage elastic modulus (E ′) and tan δ peak temperature (Tg) are shown in Table 2. Table 2 also shows the results of curing the unmodified resol type phenol resin of Comparative Example 2 below. In Comparative Example 2, the storage elastic modulus (E ′) significantly decreased at 270 ° C., whereas in E ′ of Example 1, it hardly decreased to 270 ° C. Further, the glass transition temperature (Tg) of the cured product obtained in Example 1 is also higher than that of Comparative Example 2. It was revealed that the heat resistance of the boron-modified resol type phenolic resin cured product was greatly improved.
(比較例1)
実施例1で得られたレゾール型フェノール樹脂A 100質量部にホウ酸6.8質量部を加え、110℃に昇温した。窒素気流下、溶融状態で1時間20分攪拌して反応した。得られたホウ素変性樹脂はDMFに溶かしたところ、完全に溶解しなかった。また、X線回折を測定したところ、未反応のホウ酸が検出された。変性反応がまだ終わっていない内にレゾール型フェノール樹脂の熱硬化はすでに進行してしまったことが明かとなった。
(Comparative Example 1)
6.8 parts by mass of boric acid was added to 100 parts by mass of the resol type phenol resin A obtained in Example 1, and the temperature was raised to 110 ° C. The reaction was stirred for 1 hour and 20 minutes in a molten state under a nitrogen stream. When the obtained boron-modified resin was dissolved in DMF, it was not completely dissolved. Further, when X-ray diffraction was measured, unreacted boric acid was detected. It was revealed that the thermosetting of the resol type phenolic resin had already progressed before the modification reaction was finished.
(比較例2)
実施例1で得られたレゾール型フェノール樹脂Aを熱プレスにより成形板を作製し、150℃、180℃各1時間熱処理して動的粘弾性測定を行った。その結果を表2に示す。
(Comparative Example 2)
A molded plate was prepared by hot pressing the resol-type phenol resin A obtained in Example 1, and heat-treated at 150 ° C. and 180 ° C. for 1 hour, and dynamic viscoelasticity was measured. The results are shown in Table 2.
(実施例2)
実施例１で得られた固形レゾールフェノール樹脂Ａ 100質量部とホウ酸4.7質量部をＤＭＦに溶解させ、実施例1と同様にしてホウ素変性フェノール樹脂組成物及びその硬化物を調製した。その結果を表1に示す。
(Example 2)
100 parts by mass of the solid resol phenol resin A obtained in Example 1 and 4.7 parts by mass of boric acid were dissolved in DMF, and a boron-modified phenol resin composition and a cured product thereof were prepared in the same manner as in Example 1. The results are shown in Table 1.
Claims (4)
B(OR)n(OH)3-n
(式中、nは0〜3までの整数、RはCmH2m+1のアルキル基であり、mは1〜10の整数を表す。)である請求項1叉は2に記載のホウ素変性レゾール型フェノール樹脂組成物の製造方法。 The boric acid compound (B)
B (OR) n (OH) 3-n
The boron-modified resol type according to claim 1 or 2, wherein n is an integer of 0 to 3, R is an alkyl group of CmH2m + 1, and m is an integer of 1 to 10. A method for producing a phenol resin composition.
The boron-modified resol type phenol resin according to any one of claims 1 to 3, wherein an amount of boron contained in the boric acid compound (B) is 0.1 to 5% by mass with respect to the resol type phenol resin (A). A method for producing the composition.
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| KR20160025077A (en) * | 2014-08-25 | 2016-03-08 | (주)엘지하우시스 | Modified resol type phenolic resin, method of producing the same and thermosetting composition |
| CN109942767A (en) * | 2019-03-29 | 2019-06-28 | 中国科学院化学研究所 | A kind of boron hydridization O-phthalic itrile group phenolic resin and its preparation method and application |
| JP2020063362A (en) * | 2018-10-17 | 2020-04-23 | 住友ベークライト株式会社 | Adhesive composition for wet friction material |
| CN117362916A (en) * | 2023-11-14 | 2024-01-09 | 山东永创材料科技有限公司 | Modified phenolic resin and preparation method thereof |
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