JP2005262886A - Method for manufacture of phenol resin-based developer - Google Patents
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Abstract
Description
本発明は、フェノール樹脂系からなる顕色剤の製造方法に関する。さらに詳しくは、特定のフェノール類を反応させる、発色性能や耐水性に優れた感熱記録材料用顕色剤として有用なフェノール樹脂系顕色剤の製造方法に関するものである。 The present invention relates to a method for producing a developer composed of a phenol resin. More specifically, the present invention relates to a method for producing a phenol resin developer useful as a developer for heat-sensitive recording materials, which reacts with specific phenols and has excellent color development performance and water resistance.
従来、フェノール樹脂は、優れた性能から、広範囲な分野で使用されている。また、特殊な構造をしたフェノール樹脂は特殊エポキシ樹脂の原料や感熱・感圧記録材料の顕色剤として用いられている。
たとえば、新規なフェノール三核体として、2,6-ビス［（4-ヒドキシ-2,3,5-トリメチルフェニル）メチル］-4-メチルフェノール（融点２１１℃）が開示されており（特許文献１参照）、その用途の一つとして感熱記録材料への使用が示されている。しかしながら、このトリメチル体を末端につけた場合、たとえば、フルオラン系発色剤と併用し印字した場合、印字色が黒色にならず、濃い赤紫色となり印字としては不鮮明になる。
Conventionally, phenolic resins have been used in a wide range of fields because of their excellent performance. In addition, a phenol resin having a special structure is used as a raw material for a special epoxy resin or a color developer for a heat-sensitive / pressure-sensitive recording material.
For example, 2,6-bis [(4-hydroxy-2,3,5-trimethylphenyl) methyl] -4-methylphenol (melting point: 211 ° C.) is disclosed as a novel phenol trinuclear body (patent document) 1), as one of its applications, its use in a heat-sensitive recording material is shown. However, when this trimethyl compound is attached to the end, for example, when printing is performed in combination with a fluorane color former, the print color does not become black but becomes dark reddish purple and the print becomes unclear.
また、特異なフェノール三核体を混合してなる組成物を用いた感熱記録材料用顕色剤も開示されている（特許文献２参照）。
しかしながら、これらの物質は融点が２００℃以上と高すぎ、感度が鈍くなることより発色の絶対値に劣るという欠点を有する。
また、感熱記録材料用顕色剤としては、ビスフェノールＡやｐ−ヒドロキシ安息香酸エステルなどが用いられているが、前者は、ホルモン撹乱物質としての疑いがあり、また、後者は耐熱性、耐水性などの点で劣ることから、新規な顕色剤の開発が望まれている。
In addition, a developer for a heat-sensitive recording material using a composition formed by mixing a specific phenol trinuclear body is also disclosed (see Patent Document 2).
However, these materials have the disadvantage that the melting point is too high at 200 ° C. or higher, and the absolute value of color development is inferior due to the low sensitivity.
Further, bisphenol A, p-hydroxybenzoic acid ester, and the like are used as color developers for heat-sensitive recording materials. The former is suspected as a hormone disrupting substance, and the latter is heat-resistant and water-resistant. Therefore, development of a new developer is desired.
本発明は、こうした現状に鑑み、顕色剤に対する各種の要求性能を満たし、かつ、人体や環境に対する影響が少ない上、比較的安価に製造しうる、感熱記録材料用顕色剤として有用なフェノール樹脂系顕色剤の製造方法を提供することを目的とするものである。 In view of the present situation, the present invention is a phenol useful as a developer for heat-sensitive recording materials that satisfies various performance requirements for the developer, has little influence on the human body and the environment, and can be produced at a relatively low cost. It aims at providing the manufacturing method of a resin type developer.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、２，６−ジメチロール−ｐ−置換フェノールと、２つのｏ−位およびｐ−位が無置換であるフェノール類と反応させてことにより上記目的に添う感熱記録材料用顕色剤を製造し得ることを見出し、本発明に到達した。 As a result of intensive studies to solve the above problems, the present inventors have reacted 2,6-dimethylol-p-substituted phenol with phenols having two o-positions and no substitution at the p-position. As a result, it has been found that a developer for a heat-sensitive recording material meeting the above-mentioned purpose can be produced, and the present invention has been achieved.
即ち本発明は、一般式（Ｉ）で表される２，６−ジメチロール−ｐ−置換フェノール１モルに対して、一般式（II）で表される２つのｏ−位およびｐ−位が無置換であるフェノール類を２〜１０モル反応させることを特徴とするフェノール樹脂系顕色剤の製造方法である。 That is, the present invention eliminates the two o-positions and p-positions represented by the general formula (II) with respect to 1 mol of the 2,6-dimethylol-p-substituted phenol represented by the general formula (I). The phenol resin developer is produced by reacting 2 to 10 moles of substituted phenols.
（式中、Ｒ1 はハロゲン原子，シアノ基、炭素数１〜１０のアルキル基又はアルコキシル基、若しくは炭素数６〜８のアリール基、Ｒ2 は水素原子，ハロゲン原子，シアノ基又は炭素数１〜４のアルキル基若しくはアルコキシル基を示し、２つのＲ2 は互いに同一でも、異なっていてもよい。） (Wherein R 1 is a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms or an alkoxyl group, or an aryl group having 6 to 8 carbon atoms, R 2 is a hydrogen atom, a halogen atom, a cyano group, or 1 carbon atom) -4 alkyl group or alkoxyl group, and two R 2 s may be the same or different from each other.)
（式中、Ｒ3 は、水素原子，ハロゲン原子，シアノ基又は炭素数１〜４のアルキル基若しくはアルコキシル基を示し、２つのＲ3 は互いに同一でも、異なっていてもよい。） (In the formula, R 3 represents a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or an alkoxyl group, and two R 3 s may be the same or different.)
本発明によれば、適度な融点を有し、白色性、耐熱性、保存安定性に優れるとともに、顕色剤として高い発色性を有し、しかも人体や環境に対する影響が少ないフェノール樹脂系顕色剤を、比較的安価に合成することができる。 According to the present invention, a phenol resin-based developer having an appropriate melting point, excellent whiteness, heat resistance, storage stability, high color developability as a developer, and having little influence on the human body and the environment. The agent can be synthesized relatively inexpensively.
上記一般式（Ｉ）において、Ｒ1 の中、ハロゲン原子としては、塩素原子やフッ素原子などが、炭素数１〜１０のアルキル基としては、メチル基，エチル基，ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，イソブチル基，ｓｅｃ−ブチル基，ｔｅｒｔ−ブチル基が、炭素数１〜１０のアルコキシル基としては、メトキシ基，エポキシ基，ｎ−プロポキシ基、イソプロポキシ基，ｎ−ブトキシ基，イソブトキシ基，ｓｅｃ−ブトキシ基，ｔｅｒｔ−ブトキシ基，ｔｅｒｔ−ブトキシ基、炭素数６〜８のアリール基としてはフェニル基が挙げられる。この中、特に炭素数１〜４のアルキル基が好ましい。
一方、上記一般式（Ｉ）のＲ2 の中、ハロゲン原子，炭素数１〜４のアルキル基及び炭素数１〜４のアルコキシル基としては、上記Ｒ1 の説明において例示したものと同じものを挙げることができる。この中、特に水素原子及び炭素数１〜４のアルキル基が好ましい。
In the general formula (I), in R 1 , a halogen atom is a chlorine atom or a fluorine atom, and an alkyl group having 1 to 10 carbon atoms is a methyl group, an ethyl group, an n-propyl group, or an isopropyl group. , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, as the alkoxyl group having 1 to 10 carbon atoms, methoxy group, epoxy group, n-propoxy group, isopropoxy group, n-butoxy group , Isobutoxy group, sec-butoxy group, tert-butoxy group, tert-butoxy group, and aryl group having 6 to 8 carbon atoms include phenyl group. Among these, an alkyl group having 1 to 4 carbon atoms is particularly preferable.
On the other hand, in R 2 of the general formula (I), the halogen atom, the alkyl group having 1 to 4 carbon atoms, and the alkoxyl group having 1 to 4 carbon atoms are the same as those exemplified in the description of R 1. Can be mentioned. Among these, a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are particularly preferable.
この一般式（Ｉ）で表される２，６−ジメチロール−ｐ−置換フェノールとしては、２，６−ジメチロール−ｐ−クレゾール；２，６−ジメチロール−４−エチルフェノール；２，６−ジメチロール−４−イソプロピルフェノール；２，６−ジメチロール−４−ブチルフェノール；２，６−ジメチロール−３，４，５−トリメチルフェノール；２，６−ジメチロール−ｐ−フェニルフェノールなどを挙げることができる。
これらの中で、２，６−ジメチロール−ｐ−クレゾール、２，６−ジメチロール−ｐ−エチルフェノール、２，６−ジメチロール−４−ブチルフェノール、２，６−ジメチロール−ｐ−フェニルフェノールが好ましく、入手の容易さなどの点から、２，６−ジメチロール−ｐ−クレゾール及び２，６−ジメチロール−４−ブチルフェノールが特に好適である。
Examples of the 2,6-dimethylol-p-substituted phenol represented by the general formula (I) include 2,6-dimethylol-p-cresol; 2,6-dimethylol-4-ethylphenol; 2,6-dimethylol- Examples include 4-isopropylphenol; 2,6-dimethylol-4-butylphenol; 2,6-dimethylol-3,4,5-trimethylphenol; 2,6-dimethylol-p-phenylphenol.
Among these, 2,6-dimethylol-p-cresol, 2,6-dimethylol-p-ethylphenol, 2,6-dimethylol-4-butylphenol, and 2,6-dimethylol-p-phenylphenol are preferable and available. 2,6-dimethylol-p-cresol and 2,6-dimethylol-4-butylphenol are particularly preferred from the standpoint of ease of use.
この一般式（Ｉ）で表される２，６−ジメチロール−ｐ−置換フェノールは、従来公知の方法により製造することができる。例えば水酸基に対して、２，６−位が無置換のｐ−置換フェノールに、アルカリの存在下、ホルムアルデヒドを反応させることにより、２，６−ジメチロール−ｐ−置換フェノールを得ることができる。 The 2,6-dimethylol-p-substituted phenol represented by the general formula (I) can be produced by a conventionally known method. For example, 2,6-dimethylol-p-substituted phenol can be obtained by reacting p-substituted phenol having an unsubstituted 2,6-position with respect to a hydroxyl group in the presence of alkali in the presence of alkali.
一方、（Ｂ）成分の一般式（II）で表される２つのｏ−位およびｐ−位が無置換であるフェノール類において、Ｒ3 の中のハロゲン原子，炭素数１〜４のアルキル基及び炭素数１〜４のアルコキシル基としては、前記一般式（Ｉ）におけるＲ1 において例示したものと同じものを挙げることができる。該Ｒ3 としては水素原子及び炭素数１〜４のアルキル基が好ましい。 On the other hand, in the phenols in which the two o-positions and p-positions represented by the general formula (II) of the component (B) are unsubstituted, a halogen atom in R 3 , an alkyl group having 1 to 4 carbon atoms and the alkoxyl group having 1 to 4 carbon atoms may include the same as those exemplified in R 1 in the general formula (I). R 3 is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
前記一般式（II）で表される２つのｏ−位およびｐ−位が無置換であるフェノール類としては、フェノール、ｍ−クレゾール、３，５−キシレノール、ｍ−エチルフェノールが好適である。その他、ｍ−アミルフェノールなども挙げられるが、モノマーの除去に多大な工数がかかるなど実用的でない。 Phenols that are unsubstituted at the two o-position and p-position represented by the general formula (II) are preferably phenol, m-cresol, 3,5-xylenol, and m-ethylphenol. Other examples include m-amylphenol, which is not practical because it takes a lot of man-hours to remove the monomer.
感熱記録材料用顕色剤としてトリスフェノール化合物（フェノール三核体）を用いることが知られているが、従来の感熱記録材料用顕色剤におけるトリスフェノール化合物は、２，６−ジメチロール−ｐ−置換フェノールとｐ−置換フェノールを反応させて得られるフェノール三核体であり、フェノール三核体を形成するフェノール類が限定されていた。 これに対して本発明では、ｐ−位が水素原子のフェノール類、例えば安価なフェノールを用いることができるので極めて有利である。
また、本発明のように一般式（II）で表される２つのｏ−位およびｐ−位が無置換であるフェノール類である場合には、融点を下げることができるので、取扱いが容易となる。
It is known that a trisphenol compound (phenol trinuclear body) is used as a developer for a heat-sensitive recording material, but a trisphenol compound in a conventional developer for a heat-sensitive recording material is 2,6-dimethylol-p-. It is a phenol trinuclear body obtained by reacting a substituted phenol and a p-substituted phenol, and phenols forming the phenol trinuclear body are limited. In contrast, the present invention is extremely advantageous because phenols having a hydrogen atom at the p-position, for example, inexpensive phenols can be used.
Further, when the two o-positions and p-positions represented by the general formula (II) are unsubstituted phenols as in the present invention, the melting point can be lowered, so that handling is easy. Become.
本発明のフェノール樹脂系顕色剤の製造方法は、前記（Ａ）成分の中から選ばれた一種の化合物１モルに対して、前記（Ｂ）成分の中から選ばれた一種の化合物を２〜１０モル、好ましくは３〜７モルの中で、酸性触媒下、６０〜１２０℃、好ましくは８０〜１００℃で反応させる。反応終了後、常圧〜減圧下で蒸留し、未反応のモノマーを除去することにより、目的のフェノール樹脂系顕色剤を得ることができる。
この時、（Ａ）成分の化合物１モルに対して（Ｂ）成分のモル数が２より小さいと、反応が不均一となり、生成するフェノール樹脂中の融点もしくは軟化点が極めて低くなって、顕色剤として用いる場合、耐熱性に劣る。
また、（Ａ）成分の化合物１モルに対して（Ｂ）成分のモル数が１０より大きいと、結晶性が強くなりすぎ発色性が劣ることとなる。
ここで生成する反応物は、多少の高分子量物も副生成物として出来るものの、特許文献２にて開示されているような特殊な混合を必要とせず、顕色剤に適した融点物質を得ることができる。
In the method for producing a phenol resin developer of the present invention, one kind of compound selected from the above component (B) is added to one mole of one kind of compound selected from the above component (A). The reaction is carried out at 10 to 10 mol, preferably 3 to 7 mol, under an acidic catalyst at 60 to 120 ° C, preferably 80 to 100 ° C. After completion of the reaction, the target phenol resin developer can be obtained by distillation under normal pressure to reduced pressure to remove unreacted monomers.
At this time, if the number of moles of the component (B) is less than 2 with respect to 1 mole of the compound of the component (A), the reaction becomes non-uniform, and the melting point or softening point in the phenol resin to be formed becomes extremely low, which is obvious. When used as a colorant, the heat resistance is poor.
On the other hand, when the number of moles of the component (B) is larger than 10 with respect to 1 mole of the compound of the component (A), the crystallinity becomes too strong and the color developability is poor.
The reaction product produced here can be used as a by-product of some high molecular weight product, but does not require special mixing as disclosed in Patent Document 2 and obtains a melting point material suitable for a developer. be able to.
こうして本発明の方法で得られるフェノール樹脂系顕色剤は、白色性、耐水性、経日安定性に優れ、顕色剤としての高い発色能力を有し、かつ、人体や環境に対する影響が少ない上、比較的安価に製造しうることより、感熱記録材料用顕色剤として極めて有用である。
なお、顕色剤として有用な純物質を多種併用し融点を調整して配合することも考えられるが、こうした混合物の調整は本発明の意図するところではない。
Thus, the phenol resin developer obtained by the method of the present invention is excellent in whiteness, water resistance and stability over time, has high coloring ability as a developer, and has little influence on the human body and the environment. In addition, since it can be produced at a relatively low cost, it is extremely useful as a developer for heat-sensitive recording materials.
In addition, it is conceivable that various pure substances useful as a developer are used in combination, and the melting point is adjusted and mixed, but such adjustment of the mixture is not intended by the present invention.
感熱記録材料において、本発明の方法で得られたフェノール樹脂系顕色剤と組み合わせて使用される発色性化合物等に関しては、特に制限はなく、従来から感熱記録材料における材料として慣用されている物質を用いることができる。発色性化合物として用いられる物質としては、フルオラン系、トリアリールメタン系、スピロ系、フルオレン系化合物などが挙げられる。 In the heat-sensitive recording material, there is no particular limitation on the color-forming compound used in combination with the phenol resin developer obtained by the method of the present invention, and a substance conventionally used as a material in the heat-sensitive recording material Can be used. Examples of the substance used as the color-forming compound include fluorane-based, triarylmethane-based, spiro-based, and fluorene-based compounds.
本発明の方法で得られたフェノール樹脂系顕色剤を用いて感熱記録材料を作成する方法としては、特に制限はなく、従来から公知の方法で作成することができる。具体的には、本発明の方法で得られたフェノール樹脂系顕色剤、発色性化合物、増感剤、結合剤、充填剤、滑剤、酸化防止剤、紫外線吸収剤、界面活性剤、消泡剤などを含む感熱発色層形成用の水性塗工液を常法に従い調整し、紙、プラスチックシート、合成紙などの支持体の上に塗工し、乾燥処理をすることで感熱発色層を形成し、感熱記録材料を作成する。また、必要に応じ、感熱発色層と支持体の間に中間層を設けたり、感熱発色層の上にオーバーコート層を設けてもよい。 There is no restriction | limiting in particular as a method of producing a thermosensitive recording material using the phenol resin type developer obtained by the method of this invention, It can produce by a conventionally well-known method. Specifically, the phenol resin developer, color developing compound, sensitizer, binder, filler, lubricant, antioxidant, ultraviolet absorber, surfactant, antifoam obtained by the method of the present invention. Prepare a heat-sensitive coloring layer by preparing a water-based coating solution for forming a heat-sensitive coloring layer that contains an agent in accordance with conventional methods, coating it on a support such as paper, plastic sheet, or synthetic paper and drying it. Then, a heat-sensitive recording material is prepared. Further, if necessary, an intermediate layer may be provided between the thermosensitive coloring layer and the support, or an overcoat layer may be provided on the thermosensitive coloring layer.
次に本発明を実施例により詳細に説明するが、本発明は以下の実施例により何ら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not limited at all by the following example.
実施例１
フェノール２８２ｇ（３モル）を攪拌機、還流器付フラスコに入れ、６０℃に加熱した。フラスコ中のモノマーが溶解したら、ゆっくりと攪拌を開始し、これに３５重量％塩酸１．０４ｇをゆっくり滴下・混合した。この混合溶液を８０℃に昇温し、そのまま８０℃に保持した。これに更に２，６−ジメチロール−ｐ−クレゾール１６８ｇ（１モル）を、約１時間かけてゆっくりと添加した。２，６−ジメチロール−ｐ−クレゾールの添加が終了したら、内温を１００℃まで昇温し、５時間１００℃で還流・反応させた。反応後、フラスコ内を減圧にし、反応により生じた縮合水および未反応の余剰のモノマーを蒸留し除去した。モノマーを除去し、フェノール樹脂系顕色剤２０７ｇを得た。このもののＤＳＣ（示差熱分析計）による融点は１１３℃であった。
Example 1
Phenol 282 g (3 mol) was placed in a flask equipped with a stirrer and a refluxer and heated to 60 ° C. When the monomer in the flask was dissolved, stirring was started slowly, and 1.04 g of 35 wt% hydrochloric acid was slowly added dropwise and mixed. The mixed solution was heated to 80 ° C. and kept at 80 ° C. as it was. To this, 168 g (1 mol) of 2,6-dimethylol-p-cresol was slowly added over about 1 hour. When the addition of 2,6-dimethylol-p-cresol was completed, the internal temperature was raised to 100 ° C., and the mixture was refluxed and reacted at 100 ° C. for 5 hours. After the reaction, the pressure in the flask was reduced, and the condensed water and unreacted surplus monomer produced by the reaction were distilled off. The monomer was removed to obtain 207 g of a phenol resin developer. The melting point of this product as measured by DSC (differential thermal analyzer) was 113 ° C.
得られたフェノール樹脂系顕色剤を用い、常法により、発色剤、増感剤、無機顔料およびバインダーと共に基紙に塗工し感熱記録紙を作成した。この感熱記録紙を１６０℃２秒間の条件で加熱発色させたところ、濃い黒色に発色した。この発色部について、色差計（ミノルタ社製・ＣＴ−２１０）によりＬａｂ値を測定したところ、Ｌａｂ表記・Ｌ値は２３．５であった。また、作成した感熱記録紙を８０℃２４時間加熱したが、外観上の変化は認められなかった。 Using the obtained phenol resin developer, it was coated on a base paper together with a color former, a sensitizer, an inorganic pigment and a binder by a conventional method to prepare a heat-sensitive recording paper. When this heat-sensitive recording paper was heated and developed under conditions of 160 ° C. for 2 seconds, it developed a dark black color. With respect to this color development portion, the Lab value was measured with a color difference meter (CT-210, manufactured by Minolta Co., Ltd.). The Lab notation and L value were 23.5. Further, the produced thermal recording paper was heated at 80 ° C. for 24 hours, but no change in appearance was observed.
実施例２
フェノール５６４ｇ（６モル）を攪拌機、還流器付フラスコに入れ、６０℃に加熱した。フラスコ中のモノマーが溶解したら、ゆっくりと攪拌を開始し、これに３５重量％塩酸１．０４ｇをゆっくり滴下・混合した。この混合溶液を８０℃に昇温し、そのまま８０℃に保持した。この中に更に２，６−ジメチロール−ｐ−ブチルフェノール２１０ｇ（１モル）を約１時間かけてゆっくりと添加した。２，６−ジメチロール−ｐ−ブチルフェノールの添加が終了したら、１００℃で３時間の還流反応を行なった。以下、実施例１と同様の操作を行い、フェノール樹脂系顕色剤２１６ｇを得た。このもののＤＳＣによる融点は９６℃であった。また、実施例１と同様の方法により感熱記録紙を作成し、発色させたところ、Ｌ値は２３．８であった。
Example 2
Phenol (564 g, 6 mol) was placed in a flask equipped with a stirrer and a refluxer, and heated to 60 ° C. When the monomer in the flask was dissolved, stirring was started slowly, and 1.04 g of 35 wt% hydrochloric acid was slowly added dropwise and mixed. The mixed solution was heated to 80 ° C. and kept at 80 ° C. as it was. To this, 210 g (1 mol) of 2,6-dimethylol-p-butylphenol was slowly added over about 1 hour. When the addition of 2,6-dimethylol-p-butylphenol was completed, a reflux reaction was performed at 100 ° C. for 3 hours. Thereafter, the same operation as in Example 1 was performed to obtain 216 g of a phenol resin developer. The melting point of this product by DSC was 96 ° C. Further, when a heat-sensitive recording paper was prepared and developed in the same manner as in Example 1, the L value was 23.8.
比較例１
２つのｏ−位が無置換であるフェノール類に該当しない２，６−キシレノール６１０ｇ（５モル）を攪拌機、還流器付フラスコに入れ、６０℃に加熱した。フラスコ中のモノマーが溶解したら、ゆっくりと攪拌を開始し、これに３５重量％塩酸１．０４ｇをゆっくり滴下・混合した。この混合溶液を８０℃に昇温し、そのまま８０℃に保持した。この中に更に２，６−ジメチロール−ｐ−クレゾール１６８ｇ（１モル）を約１時間かけてゆっくりと添加した。２，６−ジメチロール−ｐ−クレゾールの添加が終了したら、内温を１００℃まで昇温した。以下、実施例１と同様の操作を行い、白色のフェノール樹脂３００ｇを得た。該フェノール樹脂のＤＳＣによる融点は１７１℃であった。また、実施例１と同様の方法により感熱記録紙を作成し、発色させたところＬ値は３１．８であり、外観上は黒色ではなく茶色であった。
Comparative Example 1
610 g (5 mol) of 2,6-xylenol which does not correspond to the phenols having no substitution at the two o-positions was placed in a flask equipped with a stirrer and a reflux condenser, and heated to 60 ° C. When the monomer in the flask was dissolved, stirring was started slowly, and 1.04 g of 35 wt% hydrochloric acid was slowly added dropwise and mixed. The mixed solution was heated to 80 ° C. and kept at 80 ° C. as it was. Further, 168 g (1 mol) of 2,6-dimethylol-p-cresol was slowly added over about 1 hour. When the addition of 2,6-dimethylol-p-cresol was completed, the internal temperature was raised to 100 ° C. Thereafter, the same operation as in Example 1 was performed to obtain 300 g of a white phenol resin. The melting point of the phenol resin by DSC was 171 ° C. Further, when a thermal recording paper was prepared and colored by the same method as in Example 1, the L value was 31.8, and the appearance was brown instead of black.
比較例２
ｐ−クレゾール１０８０ｇ（１０モル）を攪拌機、還流器付フラスコに入れ、６０℃に加熱した。フラスコ中のモノマーが溶解したら、ゆっくりと攪拌を開始し、これに３５重量％塩酸０．５ｇをゆっくり滴下・混合した。この混合溶液を８０℃に昇温し、そのまま８０℃に保持した。この中に更に２，６−ジメチロール−ｐ−クレゾール８４ｇ（０．５モル）を約１時間かけてゆっくりと添加した。ジメチロール−ｐ−クレゾールの添加が終了したら、内温を１００℃まで昇温した。以下、実施例１と同様の操作を行い、白色のフェノール樹脂１８１ｇを得た。該フェノール樹脂のＤＳＣによる融点は２１１℃であった。また、実施例１と同様の方法により感熱記録紙を作成し、発色させたところ、Ｌ値は３０．４であり、外観は薄めの黒色であった。
Comparative Example 2
1080 g (10 mol) of p-cresol was placed in a flask equipped with a stirrer and a refluxer and heated to 60 ° C. When the monomer in the flask was dissolved, stirring was started slowly, and 0.5 g of 35% by weight hydrochloric acid was slowly added dropwise and mixed. The mixed solution was heated to 80 ° C. and kept at 80 ° C. as it was. Further, 84 g (0.5 mol) of 2,6-dimethylol-p-cresol was slowly added over about 1 hour. When the addition of dimethylol-p-cresol was completed, the internal temperature was raised to 100 ° C. Thereafter, the same operation as in Example 1 was performed to obtain 181 g of a white phenol resin. The melting point of the phenol resin by DSC was 211 ° C. Further, when a thermal recording paper was prepared and colored by the same method as in Example 1, the L value was 30.4 and the appearance was a light black.
比較例３
フェノール９４ｇ（１モル）を攪拌機、還流器付フラスコに入れ、６０℃に加熱した。フラスコ中のモノマーが溶解したら、ゆっくりと攪拌を開始し、これに３５重量％塩酸１．０４ｇをゆっくり滴下・混合した。この混合溶液を８０℃に昇温し、そのまま８０℃に保持した。この中に更に２，６−ジメチロール−ｐ−クレゾール１６８ｇ（１モル）を約１時間かけてゆっくりと添加した。２，６−ジメチロール−ｐ−クレゾールの添加が終了したら、内温を１００℃まで昇温した。以下、実施例１と同様の操作を行い、淡黄透明なフェノール樹脂１５６ｇを得た。該フェノール樹脂のＤＳＣによる測定では融点を示す吸熱は観測されなかった。また、実施例１と同様の方法により感熱記録紙を作成し、作成した感熱記録紙を８０℃２４時間加熱したところ、外観上、黒色に発色し、極めて耐熱性・保存安定性の悪い状態であった。
Comparative Example 3
94 g (1 mol) of phenol was placed in a flask equipped with a stirrer and a refluxer and heated to 60 ° C. When the monomer in the flask was dissolved, stirring was started slowly, and 1.04 g of 35 wt% hydrochloric acid was slowly added dropwise and mixed. The mixed solution was heated to 80 ° C. and kept at 80 ° C. as it was. Further, 168 g (1 mol) of 2,6-dimethylol-p-cresol was slowly added over about 1 hour. When the addition of 2,6-dimethylol-p-cresol was completed, the internal temperature was raised to 100 ° C. Thereafter, the same operation as in Example 1 was performed to obtain 156 g of a pale yellow transparent phenol resin. No endotherm indicating the melting point was observed by DSC measurement of the phenol resin. In addition, a thermal recording paper was prepared by the same method as in Example 1, and when the thermal recording paper thus prepared was heated at 80 ° C. for 24 hours, the appearance turned black, and the heat resistance and storage stability were extremely poor. there were.
Claims (4)
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| JP2005101704A JP2005262886A (en) | 2005-03-31 | 2005-03-31 | Method for manufacture of phenol resin-based developer |
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| JP2005101704A JP2005262886A (en) | 2005-03-31 | 2005-03-31 | Method for manufacture of phenol resin-based developer |
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| JP2002102814A Division JP3733081B2 (en) | 2002-04-04 | 2002-04-04 | Phenolic resin developer |
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