JP4878610B2 - Diphenylsulfone crosslinkable compound, developer for thermal recording and thermal recording material - Google Patents
Diphenylsulfone crosslinkable compound, developer for thermal recording and thermal recording material Download PDFInfo
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- JP4878610B2 JP4878610B2 JP2008178707A JP2008178707A JP4878610B2 JP 4878610 B2 JP4878610 B2 JP 4878610B2 JP 2008178707 A JP2008178707 A JP 2008178707A JP 2008178707 A JP2008178707 A JP 2008178707A JP 4878610 B2 JP4878610 B2 JP 4878610B2
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- heat
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- recording material
- sensitive recording
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- 239000000463 material Substances 0.000 title claims description 66
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 title claims description 59
- 150000001875 compounds Chemical class 0.000 title claims description 34
- 238000004132 cross linking Methods 0.000 claims description 15
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- 239000007795 chemical reaction product Substances 0.000 description 25
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- 239000011347 resin Substances 0.000 description 15
- -1 p-hydroxyphenylsulfonyl Chemical group 0.000 description 14
- 238000003860 storage Methods 0.000 description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
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- NRPKURNSADTHLJ-UHFFFAOYSA-N octyl gallate Chemical compound CCCCCCCCOC(=O)C1=CC(O)=C(O)C(O)=C1 NRPKURNSADTHLJ-UHFFFAOYSA-N 0.000 description 1
- 235000010387 octyl gallate Nutrition 0.000 description 1
- 239000000574 octyl gallate Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 150000002990 phenothiazines Chemical class 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000002294 quinazolinyl group Chemical class N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- 235000021067 refined food Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000004961 triphenylmethanes Chemical class 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Landscapes
- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、ジフェニルスルホン架橋型化合物、感熱記録用顕色物質及び感熱記録材料に関する。さらに詳しくは、本発明は、画像部の保存性と未発色部の保存性に優れた感熱記録材料を与えることのできる顕色物質として有用な新規なジフェニルスルホン架橋型化合物、該架橋型化合物からなる感熱記録用顕色物質、及び該顕色物質を用いてなる、前記の優れた性状を有する感熱記録材料に関する。 The present invention relates to a diphenylsulfone crosslinking compound, a thermal recording developer, and a thermal recording material. More specifically, the present invention relates to a novel diphenylsulfone crosslinkable compound useful as a developer capable of providing a heat-sensitive recording material excellent in storability of an image area and storability of an uncolored area, from the crosslinkable compound. The present invention relates to a heat-sensitive recording developer and a heat-sensitive recording material comprising the developer and having the above-described excellent properties.
感熱記録材料は、一般に支持体上に電子供与性の無色若しくは淡色の染料前駆体と、電子受容性の顕色物質とを主成分とする感熱発色層を設けたもので、熱ヘッド、熱ペン、レーザー光などで加熱することにより、染料前駆体と顕色物質とが瞬時に反応し、記録材料が得られる。このような感熱記録材料は、古くより開発が進められ、例えば、紙面に特殊な塗被を施して、通常は無色であるが、加熱又は赤外線照射により顕色する組成物からなる熱感応性複写シートとして、反応顕色成分が、ラクトン、ラクタム又はサルトン型の無着色染料ベース、有機酸及び熱可融性物質よりなる熱感応性複写シートが提案されている（特許文献１）。また、耐湿性及びプリント安定性が改良され、耐湿性の改良により、塗布された記録形成成分の乾燥及び作製中における着色を防ぐことができる感熱記録材料として、記録形成ユニットが、クリスタル・バイオレット・ラクトン及びフェノール性物質を有する支持体シート材料よりなり、該フェノール性物質は室温では固体、サーモグラフ温度では液化又は気化し、ラクトンと反応して記録を生じ、該ラクトン及びフェノール性物質はポリビニルアルコール中に分散している感熱記録材料が提案されている（特許文献２）。
このような感熱記録材料は、比較的簡易な装置で記録が得られ、保守が容易であること、騒音の発生が少ないことなどの利点があり、各種携帯端末などのサーマルプリンター、超音波エコーなどに付属する医療画像プリンター、心電図や分析機器などのサーモペンレコーダー、航空券、乗車券、商品のＰＯＳラベルなどに利用されている。
A heat-sensitive recording material generally comprises a heat-sensitive color-developing layer mainly comprising an electron-donating colorless or light-colored dye precursor and an electron-accepting developer on a support. By heating with laser light or the like, the dye precursor and the developer react instantaneously to obtain a recording material. Such heat-sensitive recording materials have been developed for a long time. For example, a heat-sensitive copying material made of a composition that is usually colorless by applying a special coating to the paper surface, but develops color by heating or infrared irradiation. As a sheet, there has been proposed a heat-sensitive copying sheet in which a reaction developing component is composed of a lactone, lactam or sultone type non-colored dye base, an organic acid and a heat-fusible substance (Patent Document 1). In addition, as a heat-sensitive recording material that has improved moisture resistance and print stability, and can prevent coloration during drying and production of the applied record-forming components by improving the moisture resistance, the record-forming unit has crystal violet, It comprises a support sheet material having a lactone and a phenolic substance. The phenolic substance is solid at room temperature, liquefied or vaporized at a thermographic temperature, and reacts with the lactone to produce a recording. The lactone and phenolic substance are polyvinyl alcohol. A heat-sensitive recording material dispersed therein has been proposed (Patent Document 2).
Such heat-sensitive recording materials have advantages such that recording can be obtained with a relatively simple device, maintenance is easy, noise generation is low, thermal printers such as various portable terminals, ultrasonic echoes, etc. It is used for medical image printers, thermopen recorders such as electrocardiograms and analytical instruments, air tickets, boarding tickets, and POS labels for products.
感熱記録材料には、発色性に優れ、低熱量で高濃度に発色すること、得られた画像の保存性に優れること、未発色部の白度が保持されることなどのさまざまな特性が要求される。特に、電子レンジ加工食品ラベル、駐車券、配送ラベル、チケットなどには、記録画像の信頼性が重視されるために、耐油性、耐湿性、耐熱性などの保存性が要求される。このために、感熱記録材料の顕色剤として、さまざまな化合物が検討されている。
例えば、高感度で地肌のかぶりが少なく、記録像の保存性、とりわけ、耐水性、耐可塑剤性に優れた感熱記録材料が得られる顕色剤として、α,α'−ビス[４−(ｐ−ヒドロキシフェニルスルホニル)フェノキシ]−ｐ−キシレン、α,α'−ビス[４−(ｐ−ヒドロキシフェニルスルホニル)フェノキシ]−ｍ−キシレン若しくはα,α'−ビス[４−(ｐ−ヒドロキシフェニルスルホニル)フェノキシ]−ｏ−キシレンを含有する感熱記録材料が提案されている（特許文献３）。また、発色画像の保存安定性、特に、耐可塑剤性、耐油性、耐光性、耐湿熱性に優れた感熱記録材料の顕色剤として、ジヒドロキシジフェニルスルホンとアルキレンジクロライドやα,α'−ジクロロキシレンなどとの反応物であるジフェニルスルホン架橋型化合物が例示されている（特許文献４）。しかし、これらの感熱記録材料は、未発色部の耐熱性が不十分であり、また、顕色剤の高保存性という要求が十分に満たされているとは言えない。
For example, α, α′-bis [4- () is a color developer that provides a heat-sensitive recording material with high sensitivity and little fogging of the background, and excellent storage stability of recorded images, in particular, water resistance and plasticizer resistance. p-hydroxyphenylsulfonyl) phenoxy] -p-xylene, α, α′-bis [4- (p-hydroxyphenylsulfonyl) phenoxy] -m-xylene or α, α′-bis [4- (p-hydroxyphenyl) A heat-sensitive recording material containing sulfonyl) phenoxy] -o-xylene has been proposed (Patent Document 3). In addition, as a developer for heat-sensitive recording materials with excellent storage stability of color images, especially plasticizer resistance, oil resistance, light resistance, and heat and humidity resistance, dihydroxydiphenyl sulfone and alkylene dichloride and α, α'-dichloroxylene A diphenylsulfone cross-linking compound that is a reaction product with the above is exemplified (Patent Document 4). However, these heat-sensitive recording materials have insufficient heat resistance of the uncolored portion, and it cannot be said that the requirement for high storage stability of the developer is sufficiently satisfied.
本発明は、このような事情のもとで、画像部の保存性、特に耐湿熱性、耐油性に優れ、さらに、未発色部の保存性、特に耐熱性にも優れた感熱記録材料を与えることのできる顕色物質として有用な新規なジフェニルスルホン誘導体、このものからなる感熱記録用顕色物質、及び該顕色物質を用いてなる上記の優れた性状を有する感熱記録材料を提供することを目的としてなされたものである。 Under such circumstances, the present invention provides a heat-sensitive recording material that is excellent in storage stability of an image area, particularly moisture heat resistance and oil resistance, and also excellent in storage stability of an uncolored area, particularly heat resistance. An object of the present invention is to provide a novel diphenylsulfone derivative useful as a developer capable of developing, a developer for thermal recording comprising the same, and a thermosensitive recording material having the above-described excellent properties using the developer. It was made as.
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、特定の構造を有するジフェニルスルホン架橋型化合物により、その課題を解決し得ることを見出し、この知見に基づいて本発明を完成するに至った。
すなわち、本発明は、
［１］一般式（１）
で表されるジフェニルスルホン架橋型化合物、
［２］上記一般式（１）で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質、及び
［３］上記一般式（１）で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質と、無色又は淡色のロイコ染料からなる発色物質とを含有する感熱発色層を支持体上に設けてなることを特徴とする感熱記録材料、
を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have found that the problem can be solved by a diphenylsulfone bridged compound having a specific structure, and the present invention has been completed based on this finding. It came to do.
That is, the present invention
[1] General formula (1)
Diphenylsulfone crosslinkable compound represented by:
[2] A heat-sensitive recording developer composed of a diphenylsulfone crosslinkable compound represented by the general formula (1), and [3] a thermosensitive recording composed of a diphenylsulfone crosslinkable compound represented by the general formula (1). A heat-sensitive recording material, comprising: a heat-sensitive color-developing material, and a color-developing material comprising a colorless or light-colored leuco dye;
Is to provide.
本発明によれば、画像部の保存性、特に耐湿熱性、耐油性に優れ、さらに、未発色部の保存性、特に耐熱性にも優れた感熱記録材料を与えることのできる顕色物質として有用な新規なジフェニルスルホン架橋型化合物、このものからなる感熱記録用顕色物質、及び該顕色物質を用いてなる上記の優れた性状を有する感熱記録材料を提供することができる。 According to the present invention, it is useful as a developer capable of providing a heat-sensitive recording material that is excellent in storage stability of an image area, in particular heat and moisture resistance, and oil resistance, and also excellent in storage stability of an uncolored area, particularly heat resistance. It is possible to provide a novel diphenylsulfone cross-linking compound, a heat-sensitive recording color developer comprising the same, and a heat-sensitive recording material having the above-described excellent properties using the color developing material.
まず、本発明のジフェニルスルホン架橋型化合物について説明する。
［ジフェニルスルホン架橋型化合物］
本発明のジフェニルスルホン架橋型化合物は、新規物質であって、一般式（１）
で表される構造を有している。
このジフェニルスルホン架橋型化合物は、特に感熱記録材料における顕色物質として有用である。
一般式（１）で表されるジフェニルスルホン架橋型化合物の製造方法に特に制限はなく、例えば、ジヒドロキシジフェニルスルホンと４,４'−ビス(ハロメチル)ビフェニル（ハロメチルとしては、クロロメチル又はブロモメチルが好ましい。）とを、塩基性物質の存在下に、溶剤を用いて脱ハロゲン化水素反応させることにより製造することができる。反応温度としては、５０℃以上、溶剤の還流温度以下であることが好ましい。反応温度が５０℃未満であると、反応の終了までに長時間を要するおそれがある。反応温度が溶剤の還流温度を超えると、耐圧性の反応容器が必要になり、経済性が損なわれるおそれがある。
反応に用いるジヒドロキシジフェニルスルホンとしては、例えば、４,４'−ジヒドロキシジフェニルスルホン、２,４'−ジヒドロキシジフェニルスルホン、２,２'−ジヒドロキシジフェニルスルホン、これらの混合物などを挙げることができる。これらの中で、４,４'−ジヒドロキシジフェニルスルホンと２,４'−ジヒドロキシジフェニルスルホンの混合物は、画像部の保存性、特に耐湿熱性、耐油性に優れ、さらに、未発色部の耐熱性を有する顕色物質を得ることができるので特に好適に用いることができる。
First, the diphenylsulfone crosslinked compound of the present invention will be described.
[Diphenylsulfone crosslinking compound]
The diphenylsulfone cross-linking compound of the present invention is a novel substance having the general formula (1)
It has the structure represented by these.
This diphenylsulfone cross-linking compound is particularly useful as a developer in a heat-sensitive recording material.
There is no restriction | limiting in particular in the manufacturing method of the diphenylsulfone bridge | crosslinking type compound represented by General formula (1), For example, dihydroxy diphenyl sulfone and 4,4'-bis (halomethyl) biphenyl (As halomethyl, chloromethyl or bromomethyl is preferable. .) Can be produced by a dehydrohalogenation reaction using a solvent in the presence of a basic substance. The reaction temperature is preferably 50 ° C. or higher and the solvent reflux temperature or lower. If the reaction temperature is less than 50 ° C, it may take a long time to complete the reaction. When the reaction temperature exceeds the reflux temperature of the solvent, a pressure-resistant reaction vessel is required, and the economy may be impaired.
Examples of dihydroxydiphenyl sulfone used in the reaction include 4,4′-dihydroxydiphenyl sulfone, 2,4′-dihydroxydiphenyl sulfone, 2,2′-dihydroxydiphenyl sulfone, and mixtures thereof. Among these, the mixture of 4,4′-dihydroxydiphenylsulfone and 2,4′-dihydroxydiphenylsulfone is excellent in the storage stability of the image area, in particular, the heat and oil resistance, and the heat resistance of the uncolored area. Since it can obtain the developer which has, it can use especially suitably.
用いる塩基性物質としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、トリエチルアミン、ピリジンなどを挙げることができる。
用いる溶剤としては、例えば、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、イソブタノールなどのアルコール類；エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコールなどのグリコール類；グリコール類のモノアルキルエーテル類；グリコール類のジアルキルエーテル類；アセトン、メチルエチルケトンなどのケトン類；アセトニトリル、プロピオニトリルなどのニトリル類；テトラヒドロフランなどのエーテル類；酢酸メチル、炭酸ジメチル、炭酸プロピレンなどのエステル類；Ｎ−メチルホルムアミド、Ｎ,Ｎ−ジメチルホルムアミドなどのアミド類；ジメチルスルホキシドなどのスルホキシド類、これらの混合溶剤などを挙げることができる。
Examples of the basic substance to be used include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, pyridine and the like.
Examples of the solvent to be used include alcohols such as methanol, ethanol, propanol, isopropanol, butanol and isobutanol; glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol; monoalkyl ethers of glycols; glycols Dialkyl ethers; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; ethers such as tetrahydrofuran; esters such as methyl acetate, dimethyl carbonate and propylene carbonate; N-methylformamide, N, N -Amides such as dimethylformamide; sulfoxides such as dimethyl sulfoxide; and mixed solvents thereof.
本発明において、一般式（１）におけるｎは、１〜１０の整数である。ｎが１０を超えると、一般式（１）で表される当該架橋型化合物中に存在する末端ヒドロキシル基の濃度が低下して、顕色物質としての効果が低下するおそれがある。
一般式（１）で表されるジフェニルスルホン架橋型化合物の製造において、ジヒドロキシジフェニルスルホンとビス(ハロメチル)ビフェニルとのモル比は、１０：３〜１０：１０であることが好ましく、１０：５〜１０：８であることがより好ましい。ジヒドロキシジフェニルスルホン１０モルに対するビス(ハロメチル)ビフェニルの量が３モル未満であると、得られる架橋型化合物の縮合度が上がりにくく、反応混合物中の未反応のジヒドロキシジフェニルスルホンの量が増加するおそれがある。ジヒドロキシジフェニルスルホン１０モルに対するビス(ハロメチル)ビフェニルの量が１０モルを超えると、反応生成物中の末端ヒドロキシル基の濃度が低下するおそれがある。
ジヒドロキシジフェニルスルホンと４,４'−ビス(ハロメチル)ビフェニルの縮合反応をジヒドロキシジフェニルスルホンが過剰の状態で行うと、反応混合物には未反応のジヒドロキシジフェニルスルホンが混在する場合がある。混在するジヒドロキシジフェニルスルホンは、精製によりジフェニルスルホン架橋型化合物から分離除去することができ、あるいは、ジヒドロキシジフェニルスルホン自体が顕色物質としての性能を有するので、ジフェニルスルホン架橋型化合物から分離除去することなく、そのまま感熱記録用顕色物質として使用することもできる。ただし、ジヒドロキシジフェニルスルホンの含有量が多いと、得られる感熱記録材料の保存性が低下するおそれがある。
本発明はまた、前記一般式（１）で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質をも提供する。
In this invention, n in General formula (1) is an integer of 1-10. If n exceeds 10, the concentration of the terminal hydroxyl group present in the cross-linked compound represented by the general formula (1) is lowered, and the effect as a developer may be lowered.
In the production of the diphenylsulfone crosslinked compound represented by the general formula (1), the molar ratio of dihydroxydiphenylsulfone and bis (halomethyl) biphenyl is preferably 10: 3 to 10:10, and 10: 5 More preferably, it is 10: 8. If the amount of bis (halomethyl) biphenyl with respect to 10 mol of dihydroxydiphenylsulfone is less than 3 mol, the degree of condensation of the resulting cross-linked compound is difficult to increase, and the amount of unreacted dihydroxydiphenylsulfone in the reaction mixture may increase. is there. If the amount of bis (halomethyl) biphenyl with respect to 10 moles of dihydroxydiphenylsulfone exceeds 10 moles, the concentration of terminal hydroxyl groups in the reaction product may decrease.
When the condensation reaction of dihydroxydiphenylsulfone and 4,4′-bis (halomethyl) biphenyl is carried out in an excess of dihydroxydiphenylsulfone, unreacted dihydroxydiphenylsulfone may be mixed in the reaction mixture. Dihydroxy diphenyl sulfone present in the mixture can be separated and removed from the diphenyl sulfone cross-linked compound by purification, or the dihydroxy diphenyl sulfone itself has a performance as a developer, so that it can be separated and removed from the diphenyl sulfone cross-linked compound. It can also be used as a color developing material for thermal recording as it is. However, if the content of dihydroxydiphenyl sulfone is large, the storage stability of the resulting heat-sensitive recording material may be lowered.
The present invention also provides a color developer for thermal recording comprising the diphenylsulfone crosslinking type compound represented by the general formula (1).
次に、本発明の感熱記録材料について説明する。
［感熱記録材料］
本発明の感熱記録材料は、前記一般式（１）で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質と、無色又は淡色のロイコ染料からなる発色物質とを含有する感熱発色層を支持体上に設けてなることを特徴とする。
（発色物質）
本発明において、発色物質として用いる無色又は淡色のロイコ染料に特に制限はなく、例えば、フルオラン誘導体、キナゾリン誘導体、フタリド誘導体、トリフェニルメタン誘導体、フェノチアジン誘導体などを挙げることができる。これらのロイコ染料の中で、フルオラン誘導体は、発色性が良好なので特に好適に用いることができる。フルオラン誘導体であるロイコ染料としては、例えば、３−ジエチルアミノ−６−メチル−７−アニリノフルオラン、３−ジエチルアミノ−６−メチル−７−(２',４'−ジメチルアニリノ)フルオラン、３−ジエチルアミノ−６−メチル−７−クロロフルオラン、３−ジブチルアミノ−６−メチル−７−アニリノフルオラン、３−ジアミルアミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−メチル−Ｎ−プロピル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−メチル−Ｎ−ブチル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−メチル−Ｎ−アミル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−メチル−Ｎ−シクロヘキシル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−エチル−Ｎ−プロピル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−エチル−Ｎ−アミル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−エチル−Ｎ−イソアミル)アミノ−６−メチル−７−アニリノフルオラン、３−[Ｎ−エチル−Ｎ−(４−メチルフェニル)]アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−エチル−Ｎ−シクロヘキシル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−ペンチル−Ｎ−シクロヘキシル)アミノ−６−メチル−７−アニリノフルオラン、３−(Ｎ−ヘキシル−Ｎ−イソアミル)アミノ−６−メチル−７−アニリノフルオラン、３−ジエチル−Ｎ−ブチルアミノ−７−(２'−フルオロアニリノ)フルオラン、３−(Ｎ−メチル−Ｎ−シクロヘキシル)アミノ−６−クロロフルオラン、３−ピロジリル−７−ジベンジルアミノフルオラン、３−ビス(ジフェニルアミノ)フルオラン、３−ジエチルアミノ−６−クロロ−７−アニリノフルオラン、３−ジエチルアミノ−７−(２'−クロロアニリノ)フルオラン、３−ジブチルアミノ−７−(２'−クロロアニリノ)フルオラン、３−ジエチルアミノ−７−クロロフルオラン、３−ブチルアミノ−７−(２'−クロロアニリノ)フルオラン、３−ジエチルアミノ−６−エトキシエチル−７−アニリノフルオラン、３−ジエチルアミノ−７−ジベンジルアミノフルオランなどを挙げることができる。感熱発色層に含有させる発色物質の量は、目的とする感熱記録材料の特性に応じて適宜選択することができる。
Next, the heat-sensitive recording material of the present invention will be described.
[Thermal recording material]
The heat-sensitive recording material of the present invention comprises a heat-sensitive color developing layer comprising a heat-sensitive recording developer composed of a diphenylsulfone cross-linked compound represented by the general formula (1) and a color developing material composed of a colorless or light leuco dye. Is provided on a support.
(Coloring substance)
In the present invention, the colorless or light leuco dye used as the coloring substance is not particularly limited, and examples thereof include a fluorane derivative, a quinazoline derivative, a phthalide derivative, a triphenylmethane derivative, and a phenothiazine derivative. Among these leuco dyes, fluorane derivatives are particularly suitable because they have good color developability. Examples of leuco dyes that are fluorane derivatives include 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7- (2 ′, 4′-dimethylanilino) fluorane, 3 -Diethylamino-6-methyl-7-chlorofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3-diamilamino-6-methyl-7-anilinofluorane, 3- (N-methyl) -N-propyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-butyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N -Amyl) amino-6-methyl-7-anilinofluorane, 3- (N-methyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-pro L) Amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-amyl) amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N-isoamyl) Amino-6-methyl-7-anilinofluorane, 3- [N-ethyl-N- (4-methylphenyl)] amino-6-methyl-7-anilinofluorane, 3- (N-ethyl-N -Cyclohexyl) amino-6-methyl-7-anilinofluorane, 3- (N-pentyl-N-cyclohexyl) amino-6-methyl-7-anilinofluorane, 3- (N-hexyl-N-isoamyl) Amino-6-methyl-7-anilinofluorane, 3-diethyl-N-butylamino-7- (2′-fluoroanilino) fluorane, 3- (N-methyl-N-cyclohexyl) amino-6 Chlorofluorane, 3-pyrodyryl 7-dibenzylaminofluorane, 3-bis (diphenylamino) fluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-7- (2′-chloroanilino) fluorane, 3-dibutylamino -7- (2'-chloroanilino) fluorane, 3-diethylamino-7-chlorofluorane, 3-butylamino-7- (2'-chloroanilino) fluorane, 3-diethylamino-6-ethoxyethyl-7-anilinofluor Examples thereof include uranium and 3-diethylamino-7-dibenzylaminofluorane. The amount of the color developing material to be contained in the thermosensitive coloring layer can be appropriately selected according to the characteristics of the target thermosensitive recording material.
（顕色物質）
本発明においては、前記一般式（１）で表されるジフェニルスルホン架橋型化合物を顕色物質として単独で用いることもできるが、従来公知な顕色物質と併用して用いることもできる。本発明で用いる前記一般式（１）で表されるジフェニルスルホン架橋型化合物と従来公知な顕色物質とを併用して用いることで、従来公知な顕色物質の発色性を損なうことなく、画像部の保存性と未発色部の保存性をより向上させることが可能となる。
使用できる従来公知の顕色物質に特に制限はないが、例えば、α−ナフトール、β−ナフトール、４−オクチルフェノール、ｐ−ｔ−オクチルフェノール、ｐ−ｔ−ブチルフェノール、ｐ−フェニルフェノール、１,１−ビス(４−ヒドロキシフェニル)プロパン、２,２−ビス(４−ヒドロキシフェニル)プロパン、２,２−ビス(３−メチル−４−ヒドロキシフェニル)プロパン、２,２−ビス(３−フェニル−４−ヒドロキシフェニル)プロパン、２,２−ビス(３,４−ジヒドロキシフェニル)プロパン、２,２−ビス(２−クロロ−４−ヒドロキシフェニル)プロパン、２,２−ビス(２,５−ジブロモ−４−ヒドロキシフェニル)プロパン、２,２−ビス(２−ヒドロキシフェニル)プロパン、２,２−ビス(３−ｔ−ブチル−４−ヒドロキシフェニル)プロパン、２,２−ビス(ｐ−ヒドロキシフェニル)ブタン、１,１,３−トリス(２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル)ブタン、１,１,３−トリス(２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル)ブタン、１,６−ビス(４,−ヒドロキベンゾイルオキシメチル)ヘキサン、１,１−ビス(４−ヒドロキシフェニル)シクロヘキサン、１,１−ビス(４−ヒドロキシフェニル)−１−フェニルエタン、ビス(２−ヒドロキシ−４−クロロフェニル)メタン、ビス(４−ヒドロキシフェニル)メタン、１,３−ビス(４−ヒドロキシクミル)ベンゼン、１,４−ビス(４−ヒドロキシクミル)ベンゼン、１,４−ビス(４'−ヒドロキベンゾイルオキシメチル)ベンゼン、１,４−ビス(４,−ヒドロキベンゾイルオキシメチル)シクロヘキサン、１,３−ビス(３'−ヒドロキベンゾイルオキシメチル)シクロヘキサン、１,２−ビス(２'−ヒドロキベンゾイルオキシメチル)シクロヘキサン、α,α−ビス(４−ヒドロキシフェニル)−α−メチルトルエン、４,４'−チオビスフェノール、４,４'−チオビス(２−メチルフェノール)、４,４'−チオビス(２−クロロフェノール)、４,４'−チオビス(６−ターシャリーブチル−２−メチルフェノール)、１,７−ビス(４−ヒドロキシフェニルチオ)−３,５−ジオキサヘプタン、１,５−ビス(４−ヒドロキシフェニルチオ)−３−オキサペンタン、１,３−ビス(４−ヒドロキシフェニルチオ)−プロパン、１,３−ビス(４−ヒドロキシフェニルチオ)−２−ヒドロキシプロパン、４,４'−ジフェノールスルホキシド、４,４'−ジヒドロキシジフェニルスルホン、２,４'−ジヒドロキシジフェニルスルホン、３,３'−ジアリル−４,４'−ジフェノールスルホン、４−アリルオキシ−４'−ヒドロキシジフェニルスルホン、４−ベンジルオキシ−４'−ヒドロキシジフェニルスルホン、４−イソプロポキシ−４'−ヒドロキシジフェニルスルホン、４−プロポキシ−４'−ヒドロキシジフェニルスルホン、４−メチル−４'−ヒドロキシジフェニルスルホン、４−メチル−３',４'−ジヒドロキシジフェニルスルホン、４,４'−ジヒドロキシジフェニルスルホンジエチルエーテル縮合物、ビス(４−ヒドロキシフェニル)酢酸メチル、ビス(４−ヒドロキシフェニル)酢酸ブチル、ビス(４−ヒドロキシフェニル)酢酸ベンジル、ｐ−ヒドロキシ安息香酸ベンジル、ｐ−ヒドロキシ安息香酸エチル、ｐ−ヒドロキシ安息香酸イソプロピル、４−ヒドロキシフタル酸ジベンジル、４−ヒドロキシフタル酸ジメチル、５−ヒドロキシイソフタル酸エチル、３,５−ジ−ｔ−ブチルサリチル酸、没食子酸ステアリル、没食子酸ラウリル、没食子酸オクチル、Ｎ,Ｎ'−ジフェニルチオ尿素、Ｎ,Ｎ'−ジ(ｍ−クロロフェニル)チオ尿素、Ｎ−(ｐ−トルエンスルホニル)−Ｎ'−(３−ｐ−トルエンスルホニルオキシフェニル)尿素、Ｎ−(ｐ−トルエンスルホニル)−Ｎ'−(ｐ−ブトキシフェニル)尿素、Ｎ−(ｐ−トルエンスルホニル)−Ｎ'−フェニル尿素、２−ヒドロキシ−３−ナフトエ酸、２−ヒドロキシ−１−ナフトエ酸、１−ヒドロキシ−２−ナフトエ酸などを挙げることができる。
これらの顕色物質は、１種を単独で併用させることができ、あるいは、２種以上を組み合わせて併用させることもできる。
(Developer)
In the present invention, the diphenylsulfone crosslinking compound represented by the general formula (1) can be used alone as a developer, but can also be used in combination with a conventionally known developer. By using the diphenylsulfone crosslinking type compound represented by the general formula (1) used in the present invention in combination with a conventionally known developer, an image can be obtained without impairing the color developability of the conventionally known developer. It is possible to further improve the storage stability of the part and the storage stability of the non-colored part.
Although there is no restriction | limiting in particular in the conventionally well-known developer which can be used, For example, (alpha)-naphthol, (beta) -naphthol, 4-octylphenol, pt-octylphenol, pt-butylphenol, p-phenylphenol, 1,1- Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4) -Hydroxyphenyl) propane, 2,2-bis (3,4-dihydroxyphenyl) propane, 2,2-bis (2-chloro-4-hydroxyphenyl) propane, 2,2-bis (2,5-dibromo- 4-hydroxyphenyl) propane, 2,2-bis (2-hydroxyphenyl) propane, 2,2-bis (3-tert-butyl-4-hydroxyphenyl) propane, 2,2- Bis (p-hydroxyphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-) 5-cyclohexylphenyl) butane, 1,6-bis (4, -hydroxybenzoyloxymethyl) hexane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1- Phenylethane, bis (2-hydroxy-4-chlorophenyl) methane, bis (4-hydroxyphenyl) methane, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) Benzene, 1,4-bis (4′-hydroxybenzoyloxymethyl) benzene, 1,4-bis (4, -hydroxybenzoyloxymethyl) cyclohexane, 1,3-bis (3′-hydroxyben) Yloxymethyl) cyclohexane, 1,2-bis (2′-hydroxybenzoyloxymethyl) cyclohexane, α, α-bis (4-hydroxyphenyl) -α-methyltoluene, 4,4′-thiobisphenol, 4,4 '-Thiobis (2-methylphenol), 4,4'-thiobis (2-chlorophenol), 4,4'-thiobis (6-tertiarybutyl-2-methylphenol), 1,7-bis (4- Hydroxyphenylthio) -3,5-dioxaheptane, 1,5-bis (4-hydroxyphenylthio) -3-oxapentane, 1,3-bis (4-hydroxyphenylthio) -propane, 1,3- Bis (4-hydroxyphenylthio) -2-hydroxypropane, 4,4'-diphenol sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 2,4'-dihydroxydiphenyl sulfone 3,3′-diallyl-4,4′-diphenolsulfone, 4-allyloxy-4′-hydroxydiphenylsulfone, 4-benzyloxy-4′-hydroxydiphenylsulfone, 4-isopropoxy-4′-hydroxydiphenylsulfone 4-propoxy-4′-hydroxydiphenylsulfone, 4-methyl-4′-hydroxydiphenylsulfone, 4-methyl-3 ′, 4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfone diethyl ether condensate, Methyl bis (4-hydroxyphenyl) acetate, butyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, benzyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, isopropyl p-hydroxybenzoate , 4-hydroxyphthalic acid diben Dimethyl, 4-hydroxyphthalate, ethyl 5-hydroxyisophthalate, 3,5-di-t-butylsalicylic acid, stearyl gallate, lauryl gallate, octyl gallate, N, N′-diphenylthiourea, N, N′-di (m-chlorophenyl) thiourea, N- (p-toluenesulfonyl) -N ′-(3-p-toluenesulfonyloxyphenyl) urea, N- (p-toluenesulfonyl) -N ′-(p -Butoxyphenyl) urea, N- (p-toluenesulfonyl) -N′-phenylurea, 2-hydroxy-3-naphthoic acid, 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, etc. be able to.
These developers can be used alone or in combination of two or more.
（増感剤）
本発明の感熱記録材料においては、感熱発色層にさらに増感剤を含有させることができる。用いる増感剤に特に制限はないが、例えば、ステアリン酸アミド、パルミチン酸アミドなどの脂肪酸アミド類；１,２−ジフェノキシエタン、１,２−ビス(４−メチルフェノキシ)エタン、１,２−ビス(３−メチルフェノキシ)エタン、１,２−ビス(フェノキシメチル)ベンゼン、１,３−ビス(フェノキシメチル)ベンゼン、１,４−ビス(フェノキシメチル)ベンゼン、１,２−ビス(３−メチルフェノキシメチル)ベンゼン、１,３−ビス(３−メチルフェノキシメチル)ベンゼン、１,４−ビス(３−メチルフェノキシメチル)ベンゼン、１,２−ビス(４−メチルフェノキシメチル)ベンゼン、１,３−ビス(４−メチルフェノキシメチル)ベンゼン、１,４−ビス(４−メチルフェノキシメチル)ベンゼン、２−ベンジルオキシナフタレン、シュウ酸ジベンジル、シュウ酸ジ(４−メチルベンジル)、シュウ酸ジ(４−クロロベンジル)、４−アセチルベンジル、Ｎ−フェニルトルエンスルホンアミド、トルエンスルホンサンナフチル、ｐ−ベンジルビフェニル、ｍ−テルフェニル、４,４'−ジプロポキシジフェニルスルホン、４,４'−ジイソプロポキシジフェニルスルホン、４,４'−ジアリルオキシジフェニルスルホン、２,４'−ジプロポキシジフェニルスルホン、２,４'−ジイソプロポキシジフェニルスルホン、２,４'−ジアリルオキシジフェニルスルホン、ｐ−ベンジルオキシ安息香酸ベンジル、テレフタル酸ベンジルなどを挙げることができる。これらの増感剤は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
(Sensitizer)
In the heat-sensitive recording material of the present invention, a sensitizer can be further contained in the heat-sensitive coloring layer. The sensitizer to be used is not particularly limited, and examples thereof include fatty acid amides such as stearamide and palmitic acid amide; 1,2-diphenoxyethane, 1,2-bis (4-methylphenoxy) ethane, 1,2 -Bis (3-methylphenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, 1,3-bis (phenoxymethyl) benzene, 1,4-bis (phenoxymethyl) benzene, 1,2-bis (3 -Methylphenoxymethyl) benzene, 1,3-bis (3-methylphenoxymethyl) benzene, 1,4-bis (3-methylphenoxymethyl) benzene, 1,2-bis (4-methylphenoxymethyl) benzene, , 3-bis (4-methylphenoxymethyl) benzene, 1,4-bis (4-methylphenoxymethyl) benzene, 2-benzyloxynaphthalene, dibenzyl oxalate, oxalic acid Di (4-methylbenzyl), oxalic acid di (4-chlorobenzyl), 4-acetylbenzyl, N-phenyltoluenesulfonamide, toluenesulfonsannaphthyl, p-benzylbiphenyl, m-terphenyl, 4,4′- Dipropoxydiphenylsulfone, 4,4′-diisopropoxydiphenylsulfone, 4,4′-diallyloxydiphenylsulfone, 2,4′-dipropoxydiphenylsulfone, 2,4′-diisopropoxydiphenylsulfone, 2,4 Examples include '-diallyloxydiphenylsulfone, benzyl p-benzyloxybenzoate, and benzyl terephthalate. These sensitizers can be used individually by 1 type, or can also be used in combination of 2 or more type.
（画像安定剤）
本発明の感熱記録材料においては、感熱発色層にさらに画像安定化剤を含有させることができる。用いる画像安定化剤に特に制限はなく、例えば、４−ベンジルオキシ−４'−(２−メチルグリシジルオキシ)−ジフェニルスルホン、４,４'−ジグリシジルオキシジフェニルスルホン、４,４'−ブチリデンビス(３−メチル−６−ｔ−ブチルフェノール)、２,２'−ジ−ｔ−ブチル−５,５'−ジメチル−４,４'−スルホニルフェノール、１,１,３−トリス(２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル)ブタン、１,１,３−トリス(２−メチル−４−ヒドロキシ−５−シクロヘキシルフェニル)ブタン、ポリヒドロキシ安息香酸などのポリエステル構造を有する化合物、ウレアウレタンなどのウレタン構造を有する物質、ポリ(フェニルスルホン)エーテルなどのポリエーテル構造を有する物質などを挙げることができる。これらの画像安定化剤は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
(Image stabilizer)
In the heat-sensitive recording material of the present invention, an image stabilizer can be further contained in the heat-sensitive coloring layer. The image stabilizer used is not particularly limited, and examples thereof include 4-benzyloxy-4 ′-(2-methylglycidyloxy) -diphenylsulfone, 4,4′-diglycidyloxydiphenylsulfone, 4,4′-butylidenebis ( 3-methyl-6-tert-butylphenol), 2,2′-di-tert-butyl-5,5′-dimethyl-4,4′-sulfonylphenol, 1,1,3-tris (2-methyl-4 -Hydroxy-5-t-butylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, compounds having a polyester structure such as polyhydroxybenzoic acid, urea urethane, etc. And a substance having a urethane structure, a substance having a polyether structure such as poly (phenylsulfone) ether, and the like. These image stabilizers can be used alone or in combination of two or more.
（填料、その他添加剤）
本発明の感熱記録材料においては、必要に応じて、感熱発色層に填料を含有させることができる。用いる填料としては、例えば、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、クレー、タルク、酸化チタン、水酸化アルミニウム、酸化亜鉛、水酸化亜鉛、硫酸バリウム、表面処理されたシリカなどの無機填料や、ポリスチレンマイクロボール、ナイロンパウダー、尿素−ホルマリン樹脂フィラー、シリコーン樹脂粒子、セルロース粉、スチレン／メタクリル酸共重合体粒子、塩化ビニリデン系樹脂粒子、スチレン／アクリル共重合体粒子、プラスチック球状中空微粒子などの有機填料などを挙げることができる。
本発明の感熱記録材料においては、必要に応じて、他の添加剤を感熱発色層に含有させることができる。含有させる添加剤としては、例えば、ステアリン酸エステルワックス、ポリエチレンワックス、ステアリン酸亜鉛などの滑剤、２−ヒドロキシ−４−ベンジルオキシベンゾフェノンなどのベンゾフェノン系の紫外線吸収剤、ベンゾトリアゾール、２−(２'−ヒドロキシ−５'−メチルフェニル)ベンゾトリアゾールなどのトリアゾール系紫外線吸収剤、グリオキザールなどの耐水化剤、分散剤、消泡剤、酸化防止剤、蛍光染料などを挙げることができる。
(Fillers, other additives)
In the heat-sensitive recording material of the present invention, a filler can be contained in the heat-sensitive coloring layer as required. Examples of the filler used include inorganic fillers such as silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, clay, talc, titanium oxide, aluminum hydroxide, zinc oxide, zinc hydroxide, barium sulfate, and surface-treated silica. And polystyrene microballs, nylon powder, urea-formalin resin filler, silicone resin particles, cellulose powder, styrene / methacrylic acid copolymer particles, vinylidene chloride resin particles, styrene / acrylic copolymer particles, plastic spherical hollow particles, etc. And organic fillers.
In the heat-sensitive recording material of the present invention, other additives can be contained in the heat-sensitive color developing layer as necessary. Examples of the additive to be contained include lubricants such as stearic acid ester wax, polyethylene wax and zinc stearate, benzophenone-based ultraviolet absorbers such as 2-hydroxy-4-benzyloxybenzophenone, benzotriazole, and 2- (2 ′ Examples thereof include triazole-based ultraviolet absorbers such as -hydroxy-5'-methylphenyl) benzotriazole, water-proofing agents such as glyoxal, dispersants, antifoaming agents, antioxidants, and fluorescent dyes.
（感熱記録材料の製造）
本発明の感熱記録材料の製造方法に特に制限がなく、例えば、発色物質、顕色物質、増感剤、画像安定化剤及び必要に応じて添加するその他の成分を、適当な結合剤とともに、水媒体などの媒体中に分散させて感熱発色層の分散液（塗布液）を調製し、この塗布液を支持体上に塗布し、乾燥することにより製造することができる。発色物質、顕色物質、増感剤を含有する分散液は、発色物質を含有する分散液、顕色物質を含有する分散液及び増感剤を含有する分散液をそれぞれ個別に調製したのち、これらの分散液を混合することにより調製することが好ましい。
各分散液中において、発色物質、顕色物質及び増感剤は、微粒子化して分散していることが望ましいので、これらの分散液の調製には、サンドミル、ボールミルなどを用いることが好ましい。
(Manufacture of thermal recording materials)
There is no particular limitation on the method for producing the heat-sensitive recording material of the present invention. For example, a coloring substance, a developer, a sensitizer, an image stabilizer, and other components added as necessary, together with an appropriate binder, It can be produced by dispersing in a medium such as an aqueous medium to prepare a dispersion liquid (coating liquid) of the thermosensitive coloring layer, applying the coating liquid on a support, and drying. A dispersion containing a color former, a developer, and a sensitizer is prepared separately for each of a dispersion containing a color former, a dispersion containing a developer, and a dispersion containing a sensitizer. It is preferable to prepare by mixing these dispersions.
In each dispersion liquid, it is desirable that the color developing substance, the color developing substance, and the sensitizer are dispersed in fine particles. Therefore, it is preferable to use a sand mill, a ball mill, or the like for the preparation of these dispersion liquids.
＜結合剤＞
使用する結合剤に特に制限はなく、例えば、ヒドロキシエチルセルロース、メチルセルロース、メトキシセルロース、エチルセルロース、カルボキシメチルセルロースなどのセルロース誘導体；ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、スルホン変性ポリビニルアルコール、シリコーン変性ポリビニルアルコール、アマイド変性ポリビニルアルコールなどのポリビニルアルコール類；ゼラチン、カゼイン、澱粉、アルギン酸などの天然高分子類；ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリメタクリル酸エステル、塩化ビニル／酢酸ビニル共重合体、エチレン／酢酸ビニル共重合体、酢酸ビニル／アクリル酸エステル共重合体、ポリアクリルアミド、アクリルアミド／アクリル酸エステル共重合体、アクリルアミド／アクリル酸エステル／メタクリル酸三元共重合体、イソブチレン／無水マレイン酸共重合体、スチレン／アクリル酸エステル共重合体、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル系共重合体、スチレン／無水マレイン酸共重合体、メチルビニルエーテル／無水マレイン酸共重合体、カルボキシ変性ポリエチレン、ポリビニルアルコール／アクリルアミドブロック共重合体、ポリビニルピロリドン、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂、ポリウレタン、ポリアミド樹脂、石油樹脂、テルペン樹脂などを挙げることができる。これらの結合剤は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
<Binder>
The binder to be used is not particularly limited, and examples thereof include cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, methoxy cellulose, ethyl cellulose, carboxymethyl cellulose; polyvinyl alcohol, carboxy modified polyvinyl alcohol, sulfone modified polyvinyl alcohol, silicone modified polyvinyl alcohol, amide modified polyvinyl. Polyvinyl alcohols such as alcohol; natural polymers such as gelatin, casein, starch and alginic acid; polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polymethacrylic acid ester, vinyl chloride / vinyl acetate copolymer, ethylene / Vinyl acetate copolymer, vinyl acetate / acrylic acid ester copolymer, polyacrylamide, acrylamide / acrylic acid ester copolymer Acrylamide / acrylic acid ester / methacrylic acid terpolymer, isobutylene / maleic anhydride copolymer, styrene / acrylic acid ester copolymer, styrene / butadiene copolymer, styrene / butadiene / acrylic copolymer, styrene / Maleic anhydride copolymer, methyl vinyl ether / maleic anhydride copolymer, carboxy-modified polyethylene, polyvinyl alcohol / acrylamide block copolymer, polyvinylpyrrolidone, melamine-formaldehyde resin, urea-formaldehyde resin, polyurethane, polyamide resin, petroleum Examples thereof include resins and terpene resins. These binders can be used individually by 1 type, or can also be used in combination of 2 or more type.
＜支持体、アンダーコート層、バックコート層＞
本発明の感熱記録材料に使用する支持体には特に制限はなく、例えば、中性紙や酸性紙などの紙、合成紙、古紙パルプを用いた再生紙、フィルム、不織布、織布などを挙げることができる。
本発明の感熱記録材料においては、支持体上に、さらに、シリカ、炭酸カルシウム、カオリン、焼成カオリン、ケイソウ土、クレー、タルク、酸化チタン、水酸化アルミニウム、酸化亜鉛、水酸化亜鉛、硫酸バリウム、表面処理されたシリカなどの無機填料や、ポリスチレンマイクロボール、ナイロンパウダー、尿素−ホルマリン樹脂フィラー、シリコーン樹脂粒子、セルロース粉、スチレン／メタクリル酸共重合体粒子、塩化ビニリデン系樹脂粒子、スチレン／アクリル共重合体粒子、プラスチック球状中空微粒子などの有機填料などを含むアンダーコート層やバックコート層を設けることが好ましい。アンダーコート層やバックコート層を設けることにより、断熱層として作用し、サーマルヘッド等からの熱エネルギーの効率的活用による感度向上をもたらすことができる。特に、プラスチック球状中空微粒子を含むアンダーコート層やバックコート層は、熱感度を効果的に向上させることができるので好適に用いられる。
<Support, undercoat layer, backcoat layer>
The support used for the heat-sensitive recording material of the present invention is not particularly limited, and examples thereof include paper such as neutral paper and acid paper, synthetic paper, recycled paper using waste paper pulp, film, nonwoven fabric, woven fabric, and the like. be able to.
In the heat-sensitive recording material of the present invention, on the support, silica, calcium carbonate, kaolin, calcined kaolin, diatomaceous earth, clay, talc, titanium oxide, aluminum hydroxide, zinc oxide, zinc hydroxide, barium sulfate, Surface-treated inorganic fillers such as silica, polystyrene microballs, nylon powder, urea-formalin resin filler, silicone resin particles, cellulose powder, styrene / methacrylic acid copolymer particles, vinylidene chloride resin particles, styrene / acrylic copolymer It is preferable to provide an undercoat layer or a backcoat layer containing organic fillers such as polymer particles and plastic spherical hollow fine particles. By providing an undercoat layer or a backcoat layer, it can act as a heat insulating layer, and can improve sensitivity by efficiently using thermal energy from a thermal head or the like. In particular, an undercoat layer or a backcoat layer containing plastic spherical hollow fine particles can be suitably used because it can effectively improve thermal sensitivity.
なお、プラスチック球状中空微粒子とは、熱可塑性樹脂を殻としており、内部に空気その他の気体を含有してすでに発泡状態となっている微小中空粒子であり、平均粒子径は０.２〜２０μｍ程度のものである。この平均粒子径(粒子外径)が０.２μｍより小さいものは、任意の中空率にすることが難しいなどの生産上の問題があってコスト面で難点があり、逆に２０μｍより大きいものは塗布乾燥後の表面平滑性が低下するためにサーマルヘッドとの密着性が低下し、熱感度向上効果が低下する。従って、該粒子は粒子径が前記範囲にあると共に粒子径のバラツキが少ないものが好ましい。さらにこのプラスチック球状中空微粒子は、その断熱効果を勘案すると中空率は、４０％以上のものが好ましく、９０％以上のものが更に好ましい。中空率が低いものは、断熱効果が不充分なためサーマルヘッドからの熱エネルギーが支持体を通じて感熱記録材料の外へ放出され、熱感度向上効果が劣る。なお、ここで言う「中空率」とは、中空微粒子の外径と内径の比であり、下記で表されるものである。
中空率（％）＝[(中空微粒子の内径)／(中空微粒子の外径)]×１００
プラスチック球状中空微粒子は、前記したように熱可塑性樹脂を穀とするものであるが、該樹脂としては、ポリスチレン、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリ酢酸ビニル、ポリアクリル酸エステル、ポリアクリロニトリル、ポリブタジエンあるいはそれらの共重合体樹脂などが挙げられる。これらの中でも、特に塩化ビニリデンとアクリロニトリルを主体とする共重合体樹脂が好ましい。
In addition, the plastic spherical hollow fine particles are fine hollow particles having a thermoplastic resin as a shell, containing air or other gas inside and already foamed, and an average particle size of about 0.2 to 20 μm. belongs to. If the average particle diameter (particle outer diameter) is smaller than 0.2 μm, there are production problems such as difficulty in making an arbitrary hollow ratio, which is difficult in terms of cost. Since the surface smoothness after coating and drying is lowered, the adhesion with the thermal head is lowered, and the effect of improving the thermal sensitivity is lowered. Therefore, it is preferable that the particles have a particle size in the above range and have little variation in particle size. Further, the plastic spherical hollow fine particles preferably have a hollow ratio of 40% or more, and more preferably 90% or more, considering the heat insulating effect. Those having a low hollowness have insufficient heat insulation effect, so that heat energy from the thermal head is released to the outside of the heat-sensitive recording material through the support, resulting in poor heat sensitivity improvement effect. The “hollow ratio” referred to here is the ratio of the outer diameter to the inner diameter of the hollow fine particles, and is expressed below.
Hollow ratio (%) = [(inner diameter of hollow fine particles) / (outer diameter of hollow fine particles)] × 100
As described above, the plastic spherical hollow fine particles are made from a thermoplastic resin as a grain. Examples of the resin include polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylate, polyacrylonitrile, and polybutadiene. Or those copolymer resins etc. are mentioned. Among these, a copolymer resin mainly composed of vinylidene chloride and acrylonitrile is particularly preferable.
アンダーコート層やバックコート層に使用する結合剤に特に制限はなく、例えば、ヒドロキシエチルセルロース、メチルセルロース、メトキシセルロース、エチルセルロース、カルボキシメチルセルロースなどのセルロース誘導体；ポリビニルアルコール、カルボキシ変性ポリビニルアルコール、スルホン変性ポリビニルアルコール、シリコーン変性ポリビニルアルコール、アマイド変性ポリビニルアルコールなどのポリビニルアルコール類；ゼラチン、カゼイン、澱粉、アルギン酸などの天然高分子類；ポリアクリル酸、ポリアクリル酸エステル、ポリ酢酸ビニル、ポリメタクリル酸エステル、塩化ビニル／酢酸ビニル共重合体、エチレン／酢酸ビニル共重合体、酢酸ビニル／アクリル酸エステル共重合体、ポリアクリルアミド、アクリルアミド／アクリル酸エステル共重合体、アクリルアミド／アクリル酸エステル／メタクリル酸三元共重合体、イソブチレン／無水マレイン酸共重合体、スチレン／アクリル酸エステル共重合体、スチレン／ブタジエン共重合体、スチレン／ブタジエン／アクリル系共重合体、スチレン／無水マレイン酸共重合体、メチルビニルエーテル／無水マレイン酸共重合体、カルボキシ変性ポリエチレン、ポリビニルアルコール／アクリルアミドブロック共重合体、ポリビニルピロリドン、メラミン−ホルムアルデヒド樹脂、尿素−ホルムアルデヒド樹脂、ポリウレタン、ポリアミド樹脂、石油樹脂、テルペン樹脂などを挙げることができる。 There are no particular limitations on the binder used for the undercoat layer and the backcoat layer, for example, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, methoxy cellulose, ethyl cellulose, carboxymethyl cellulose; polyvinyl alcohol, carboxy-modified polyvinyl alcohol, sulfone-modified polyvinyl alcohol, Polyvinyl alcohols such as silicone-modified polyvinyl alcohol and amide-modified polyvinyl alcohol; natural polymers such as gelatin, casein, starch and alginic acid; polyacrylic acid, polyacrylic acid ester, polyvinyl acetate, polymethacrylic acid ester, vinyl chloride / Vinyl acetate copolymer, ethylene / vinyl acetate copolymer, vinyl acetate / acrylate copolymer, polyacrylamide, acrylic Mido / acrylic acid ester copolymer, acrylamide / acrylic acid ester / methacrylic acid terpolymer, isobutylene / maleic anhydride copolymer, styrene / acrylic acid ester copolymer, styrene / butadiene copolymer, styrene / Butadiene / acrylic copolymer, styrene / maleic anhydride copolymer, methyl vinyl ether / maleic anhydride copolymer, carboxy-modified polyethylene, polyvinyl alcohol / acrylamide block copolymer, polyvinyl pyrrolidone, melamine-formaldehyde resin, urea Examples include formaldehyde resin, polyurethane, polyamide resin, petroleum resin, and terpene resin.
本発明の感熱記録材料においては、さらに必要に応じて、感熱発色層の上に、セルロース誘導体、ポリビニルアルコール類などの水溶性樹脂や、スチレン−ブタジエン共重合体、テルペン樹脂などの水溶性エマルジョンや非水溶性樹脂、それらの樹脂に填料、イソシアネート類、不飽和化合物などのモノマーやオリゴマーと架橋剤を加えてオーバーコート層を形成することができる。
本発明の感熱記録材料は、色調の異なる発色物質をそれぞれ感熱発色層として多層形成した多色感熱記録材料とすることができる。
本発明の感熱記録材料は、画像部の保存性、特に耐湿熱性、耐油性に優れ、さらに、未発色部の保存性、特に耐熱性にも優れるなどの特徴を有し、例えば、電子レンジ加工食品ラベル、駐車券、配送ラベル、チケットなどの記録画像の保存性が要求される分野において、特に好適に用いることができる。
In the heat-sensitive recording material of the present invention, if necessary, a water-soluble resin such as a cellulose derivative or polyvinyl alcohol, a water-soluble emulsion such as a styrene-butadiene copolymer or a terpene resin, An overcoat layer can be formed by adding monomers or oligomers such as fillers, isocyanates, unsaturated compounds, and crosslinking agents to water-insoluble resins and those resins.
The heat-sensitive recording material of the present invention can be a multi-color heat-sensitive recording material in which color-forming substances having different color tones are formed in multiple layers as heat-sensitive color forming layers.
The heat-sensitive recording material of the present invention has characteristics such as excellent storage stability of the image area, particularly moisture and heat resistance, and oil resistance, and also excellent storage stability of the non-colored area, particularly heat resistance. The present invention can be particularly suitably used in a field where storability of recorded images such as food labels, parking tickets, delivery labels, and tickets is required.
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、実施例において、反応生成物の組成は、下記の条件によるゲルパーミエーションクロマトグラフィーにより求めた。
クロマトグラフ：東ソー(株)、ＨＬＣ−８１２０ＧＰＣ
カラム：直径７.８ｍｍ×長さ３０ｍｍ、１本：Ｓｈｏｄｅｘ Ａｓａｈｉｐａｋ ＧＦ−３１０ＨＱ
カラム温度：４０℃
移動相：ジメチルホルムアミド
流量：０.５ｍＬ／分
検出器：ＲＩ
また、実施例及び比較例において、作製した感熱記録材料の性能は、次の方法により評価した。
（１）耐油性
作製した感熱記録材料に、感熱印字装置［(株)大倉電気製］を用いて、印字電圧２０Ｖ、パルス巾３ｍｓで発色させ、発色させた部分（画像部）の色濃度を反射濃度計［マクベス社製、「ＲＤ−９１８」］を用いて測定する。次に、画像部に綿実油を一滴垂らし、２０℃、６５％ＲＨで２４時間放置したのち色濃度を測定した。
（２）耐湿熱性
作製した感熱記録材料に、感熱印字装置［(株)大倉電気製］を用いて、印字電圧２０Ｖ、パルス巾３ｍｓで発色させ、発色させた部分（画像部）の色濃度を反射濃度計［マクベス社製、「ＲＤ−９１８」］を用いて測定する。次に、６０℃、８０％ＲＨで２４時間放置したのち色濃度を測定した。
（３）耐熱性
作製した感熱記録材料の、発色させていない部分（未発色部）の色濃度を反射濃度計［マクベス社製、「ＲＤ−９１８」］を用いて測定する。次に、８０℃または１００℃で２４時間放置したのち、色濃度を測定した。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples, the composition of the reaction product was determined by gel permeation chromatography under the following conditions.
Chromatograph: Tosoh Corporation, HLC-8120GPC
Column: 7.8 mm in diameter x 30 mm in length, one: Shodex Asahipak GF-310HQ
Column temperature: 40 ° C
Mobile phase: Dimethylformamide Flow rate: 0.5 mL / min Detector: RI
In the examples and comparative examples, the performance of the produced thermosensitive recording material was evaluated by the following method.
(1) Oil resistance Using the thermal printing device [manufactured by Okura Electric Co., Ltd.] on the produced thermal recording material, color was developed at a printing voltage of 20 V and a pulse width of 3 ms, and the color density of the colored part (image part) was determined. Measurement is performed using a reflection densitometer [manufactured by Macbeth, “RD-918”]. Next, a drop of cottonseed oil was dropped on the image area and allowed to stand at 20 ° C. and 65% RH for 24 hours, and then the color density was measured.
(2) Humidity and heat resistance Using the thermal printing device [manufactured by Okura Electric Co., Ltd.], the produced thermosensitive recording material was developed with a printing voltage of 20 V and a pulse width of 3 ms, and the color density of the colored portion (image part) was determined. Measurement is performed using a reflection densitometer [manufactured by Macbeth, “RD-918”]. Next, after being left for 24 hours at 60 ° C. and 80% RH, the color density was measured.
(3) Heat resistance The color density of a non-colored portion (uncolored portion) of the produced heat-sensitive recording material is measured using a reflection densitometer [Macbeth Co., Ltd. “RD-918”]. Next, after leaving at 80 ° C. or 100 ° C. for 24 hours, the color density was measured.
実施例１
反応容器に、４,４'−ジヒドロキシジフェニルスルホン（純度９９.８質量％）３５ｇ（０.１４モル）、２,４'−ジヒドロキシジフェニルスルホン（純度９６.５質量％）１５ｇ（０.０６モル）及びジメチルホルムアミド２００ｇを仕込み、溶解させた。次に、水酸化ナトリウム１４ｇ（０.３５モル）を加え、７０℃に加熱し、４,４'−ビス(クロロメチル)ビフェニル３８ｇ（０.１５モル）をジメチルホルムアミド１２０ｇに溶解させた溶液を、０.５時間かけて滴下した。滴下終了後、１１０℃に加熱してさらに５時間反応した。反応終了後、反応混合物を、０.１質量％塩酸２,０００ｇ中に３０℃で０.５時間かけて徐々に添加したのち、さらに２時間撹拌した。析出した結晶をろ別し、水洗した。次に、反応容器に得られた結晶と２０質量％メタノール水溶液５００ｇを仕込み、７０℃で２時間加熱したのち、２５℃に冷却して析出した結晶をろ別し、水洗、乾燥したところ、反応生成物７０ｇが得られた。得られた反応生成物はゲルパーミエーションクロマトグラフィーで分析したところ、前記一般式（１）においてｎが１〜９である次のような組成であった。
ｎ＝０（分子量２５０） ：保持時間１２.９分：ピーク面積比 ４.９％
ｎ＝１（分子量６７８） ：保持時間１２.０分：ピーク面積比２３.２％
ｎ＝２（分子量１,１０６）：保持時間１１.２分：ピーク面積比２３.７％
ｎ＝３（分子量１,５３４）：保持時間１０.７分：ピーク面積比１９.１％
ｎ＝４（分子量１,９６２）：保持時間１０.４分：ピーク面積比１２.７％
ｎ＝５（分子量２,３９０）：保持時間１０.０分：ピーク面積比 ７.３％
ｎ＝６（分子量２,８１８）：保持時間 ９.７分：ピーク面積比 ３.３％
ｎ＝７（分子量３,２４６）：保持時間 ９.４分：ピーク面積比 １.２％
ｎ＝８（分子量３,６７４）：保持時間 ９.２分：ピーク面積比 ０.３％
ｎ＝９（分子量４,１０２）：保持時間 ８.９分：ピーク面積比 ０.１％
Example 1
In a reaction vessel, 35 g (0.14 mol) of 4,4′-dihydroxydiphenylsulfone (purity 99.8% by mass), 15 g (0.06 mol) of 2,4′-dihydroxydiphenylsulfone (purity 96.5% by mass) ) And 200 g of dimethylformamide were charged and dissolved. Next, 14 g (0.35 mol) of sodium hydroxide was added and heated to 70 ° C. to obtain a solution in which 38 g (0.15 mol) of 4,4′-bis (chloromethyl) biphenyl was dissolved in 120 g of dimethylformamide. The solution was added dropwise over 0.5 hours. After completion of the dropwise addition, the mixture was heated to 110 ° C. and further reacted for 5 hours. After completion of the reaction, the reaction mixture was gradually added to 2,000 g of 0.1% by mass hydrochloric acid at 30 ° C. over 0.5 hours, and then stirred for another 2 hours. The precipitated crystals were separated by filtration and washed with water. Next, the crystals obtained in a reaction vessel and 500 g of a 20% by weight aqueous methanol solution were charged, heated at 70 ° C. for 2 hours, cooled to 25 ° C., and the precipitated crystals were filtered off, washed with water and dried. 70 g of product was obtained. When the obtained reaction product was analyzed by gel permeation chromatography, it had the following composition in which n is 1 to 9 in the general formula (1).
n = 0 (molecular weight 250): Retention time 12.9 minutes: Peak area ratio 4.9%
n = 1 (molecular weight 678): retention time 12.0 minutes: peak area ratio 23.2%
n = 2 (molecular weight 1,106): retention time 11.2 minutes: peak area ratio 23.7%
n = 3 (molecular weight 1,534): retention time 10.7 minutes: peak area ratio 19.1%
n = 4 (molecular weight 1,962): retention time 10.4 minutes: peak area ratio 12.7%
n = 5 (molecular weight 2,390): retention time 10.0 minutes: peak area ratio 7.3%
n = 6 (molecular weight 2,818): retention time 9.7 minutes: peak area ratio 3.3%
n = 7 (molecular weight 3,246): retention time 9.4 minutes: peak area ratio 1.2%
n = 8 (molecular weight 3,674): retention time 9.2 minutes: peak area ratio 0.3%
n = 9 (molecular weight 4,102): retention time 8.9 minutes: peak area ratio 0.1%
実施例２
水酸化ナトリウム１４ｇ（０.３５モル）の代わりに９.２ｇ（０.２３モル）を、４,４'−ビス(クロロメチル)−１,１'−ビフェニル３８ｇ（０.１５モル）の代わりに２５.３ｇ（０.１モル）を使用した以外は、実施例１と同様にして、反応生成物５２ｇを得た。
得られた反応生成物の組成はｎ＝０：ピーク面積比８.９％、ｎ＝１：ピーク面積比３９.８％、ｎ＝２：ピーク面積比２６.８％、ｎ＝３：ピーク面積比１２.１％、ｎ＝４：ピーク面積比５.０％、ｎ＝５：ピーク面積比２.１％、ｎ＝６：ピーク面積比０.５％、ｎ＝７：ピーク面積比０.３％、ｎ＝８：ピーク面積比０.２％であった。
実施例３
４,４'−ジヒドロキシジフェニルスルホン（純度９９.８質量％）３５ｇ（０.１４モル）の代わりに５０ｇ（０.２モル）を使用し、２,４'−ジヒドロキシジフェニルスルホンを使用しなかった以外は実施例１と同様にして反応生成物６９ｇを得た。得られた反応生成物の組成はｎ＝０：ピーク面積比４.７％、ｎ＝１：ピーク面積比２４.１％、ｎ＝２：ピーク面積比２３.１％、ｎ＝３：ピーク面積比１８.８％、ｎ＝４：ピーク面積比１２.５％、ｎ＝５：ピーク面積比７.２％、ｎ＝６：ピーク面積比３.５％、ｎ＝７：ピーク面積比１.５％、ｎ＝８：ピーク面積比０.４％、ｎ＝９：ピーク面積比０.２％であった。
実施例４
２,４'−ジヒドロキシジフェニルスルホン（純度９６.５質量％）１５ｇ（０.０６モル）の代わりに５０ｇ（０.２モル）を使用し、４,４'−ジヒドロキシジフェニルスルホンを使用しなかった以外は、実施例１と同様にして、反応生成物６５ｇを得た。得られた反応生成物の組成はｎ＝０：ピーク面積比５.０％、ｎ＝１：ピーク面積比２３.０％、ｎ＝２：ピーク面積比２３.５％、ｎ＝３：ピーク面積比１９.０％、ｎ＝４：ピーク面積比１３.０％、ｎ＝５：ピーク面積比７.０％、ｎ＝６：ピーク面積比４.０％、ｎ＝７：ピーク面積比１.１％、ｎ＝８：ピーク面積比０.４％、ｎ＝９：ピーク面積比０.２％であった。
実施例１〜４の結果を、第１表に示す。
Example 2
Instead of 14 g (0.35 mol) of sodium hydroxide, 9.2 g (0.23 mol) was substituted for 38 g (0.15 mol) of 4,4′-bis (chloromethyl) -1,1′-biphenyl. In the same manner as in Example 1 except that 25.3 g (0.1 mol) was used, 52 g of a reaction product was obtained.
The composition of the obtained reaction product is n = 0: peak area ratio 8.9%, n = 1: peak area ratio 39.8%, n = 2: peak area ratio 26.8%, n = 3: peak Area ratio 12.1%, n = 4: Peak area ratio 5.0%, n = 5: Peak area ratio 2.1%, n = 6: Peak area ratio 0.5%, n = 7: Peak area ratio 0.3%, n = 8: The peak area ratio was 0.2%.
Example 3
Instead of 35 g (0.14 mol) of 4,4′-dihydroxydiphenylsulfone (purity 99.8% by weight), 50 g (0.2 mol) was used and 2,4′-dihydroxydiphenylsulfone was not used. Except for the above, 69 g of a reaction product was obtained in the same manner as in Example 1. The composition of the reaction product obtained was n = 0: peak area ratio 4.7%, n = 1: peak area ratio 24.1%, n = 2: peak area ratio 23.1%, n = 3: peak. Area ratio 18.8%, n = 4: peak area ratio 12.5%, n = 5: peak area ratio 7.2%, n = 6: peak area ratio 3.5%, n = 7: peak area ratio The ratios were 1.5%, n = 8: peak area ratio of 0.4%, and n = 9: peak area ratio of 0.2%.
Example 4
Instead of 15 g (0.06 mol) of 2,4′-dihydroxydiphenylsulfone (purity 96.5% by mass), 50 g (0.2 mol) was used and no 4,4′-dihydroxydiphenylsulfone was used. Except for the above, 65 g of reaction product was obtained in the same manner as in Example 1. The composition of the obtained reaction product is n = 0: peak area ratio 5.0%, n = 1: peak area ratio 23.0%, n = 2: peak area ratio 23.5%, n = 3: peak. Area ratio 19.0%, n = 4: peak area ratio 13.0%, n = 5: peak area ratio 7.0%, n = 6: peak area ratio 4.0%, n = 7: peak area ratio The ratios were 1.1%, n = 8: peak area ratio of 0.4%, and n = 9: peak area ratio of 0.2%.
The results of Examples 1 to 4 are shown in Table 1.
実施例５
３−ジブチルアミノ−６−メチル−７−アニリノフルオラン１０質量部、１０質量％ポリビニルアルコール水溶液１０質量部及び水３０質量部を、サンドミルを用いて４時間微粉砕して分散させることにより、発色物質分散液（Ａ液）を調製した。実施例１で得られた反応生成物１０質量部、１０質量％ポリビニルアルコール水溶液１０質量部及び水３０質量部を、サンドミルを用いて３時間微粉砕して分散させることにより、顕色物質分散液（Ｂ液）を調製した。シリカ［水沢化学(株)製、「ミズカシル(登録商標)Ｐ−５２７」］１０質量部、１０質量％ポリビニルアルコール水溶液１０質量部及び水３０質量部を、サンドミルを用いて３時間微粉砕して分散させることにより、シリカ分散液（Ｃ液）を調製した。ステアリン酸亜鉛１０質量部、１０質量％ポリビニルアルコール水溶液１０質量部及び水３０質量部を、サンドミルを用いて３時間微粉砕して分散させることにより、ステアリン酸亜鉛分散液（Ｄ液）を調製した。非発泡性プラスチック微小中空粒子［固形分２４質量％、平均粒径３μｍ、中空率９０％］４０質量部、スチレン／ブタジエン共重合体ラテックス［日本ゼオン(株)製、「Ｎｉｐｏｌ(登録商標)ＬＸ４３０」］１０質量部及び水５０質量部を、ディスパーを用いて撹拌混合することにより、樹脂液（Ｅ液）を調製した。
次に、Ａ液５質量部、Ｂ液２０質量部、Ｃ液２０質量部及びＤ液２.５質量部を、ディスパーを用いて撹拌混合し発色層の塗布液を調製した。また、Ｃ液５質量部及びＥ液１０質量部を、ディスパーを用いて撹拌混合しアンダーコート層の塗布液を調製した。
坪量６０ｇ／ｍ2の上質紙に、アンダーコート層の塗布液を乾燥塗布量が３ｇ／ｍ2となるように塗布し、乾燥してアンダーコート塗布紙を得た。このアンダーコート層上に、発色層の塗布液を乾燥塗布量が５ｇ／ｍ2となるように塗布し、乾燥し、０.９８ＭＰａの圧力でカレンダー処理して本発明の感熱記録材料を作製し、評価を行った。
Example 5
By dispersing 10 parts by weight of 3-dibutylamino-6-methyl-7-anilinofluorane, 10 parts by weight of a 10% by weight aqueous polyvinyl alcohol solution and 30 parts by weight of water using a sand mill for 4 hours, A coloring substance dispersion (liquid A) was prepared. The developer dispersion obtained by pulverizing and dispersing 10 parts by mass of the reaction product obtained in Example 1 and 10 parts by mass of a 10% by weight aqueous polyvinyl alcohol solution and 30 parts by mass of water using a sand mill for 3 hours. (Liquid B) was prepared. 10 parts by mass of silica [manufactured by Mizusawa Chemical Co., Ltd., “Mizukasil (registered trademark) P-527”], 10 parts by mass of 10% by mass aqueous polyvinyl alcohol solution and 30 parts by mass of water were pulverized for 3 hours using a sand mill. A silica dispersion (liquid C) was prepared by dispersing. A zinc stearate dispersion (liquid D) was prepared by pulverizing and dispersing 10 parts by weight of zinc stearate, 10 parts by weight of a 10% by weight polyvinyl alcohol aqueous solution and 30 parts by weight of water using a sand mill for 3 hours. . Non-foaming plastic micro hollow particles [solid content 24% by mass, average particle size 3 μm, hollow rate 90%] 40 parts by mass, styrene / butadiene copolymer latex [manufactured by Nippon Zeon Co., Ltd., “Nipol (registered trademark) LX430 The resin liquid (E liquid) was prepared by stirring and mixing 10 mass parts and 50 mass parts of water using a disper.
Next, 5 parts by mass of A liquid, 20 parts by mass of B liquid, 20 parts by mass of C liquid, and 2.5 parts by mass of D liquid were stirred and mixed using a disper to prepare a coating solution for a coloring layer. Moreover, 5 mass parts of C liquid and 10 mass parts of E liquid were stirred and mixed using the disper, and the coating liquid of the undercoat layer was prepared.
The high-quality paper having a basis weight 60 g / m 2, by coating a coating solution for undercoat layer so as to have a dry coating amount of the 3 g / m 2, to obtain an undercoat coated paper and dried. On this undercoat layer, a color layer coating solution is applied so that the dry coating amount is 5 g / m 2 , dried, and calendered at a pressure of 0.98 MPa to produce the thermosensitive recording material of the present invention. And evaluated.
実施例６
実施例１で得られた反応生成物の代わりに、実施例２で得られた反応生成物を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録紙を作製し、評価を行った。
実施例７
実施例１で得られた反応生成物の代わりに、実施例３で得られた反応生成物を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録紙を作製し、評価を行った。
実施例８
実施例１で得られた反応生成物の代わりに、実施例４で得られた反応生成物を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録紙を作製し、評価を行った。
Example 6
Heat sensitive in the same manner as in Example 5 except that the developer dispersion (Liquid B) was prepared using the reaction product obtained in Example 2 instead of the reaction product obtained in Example 1. Recording paper was prepared and evaluated.
Example 7
Heat sensitive in the same manner as in Example 5 except that the developer dispersion (Liquid B) was prepared using the reaction product obtained in Example 3 instead of the reaction product obtained in Example 1. Recording paper was prepared and evaluated.
Example 8
Heat sensitive in the same manner as in Example 5 except that the developer dispersion (Liquid B) was prepared using the reaction product obtained in Example 4 instead of the reaction product obtained in Example 1. Recording paper was prepared and evaluated.
実施例９
実施例１で得られた反応生成物１０質量部の代わりに、実施例１で得られた反応生成物７質量部、４−アリルオキシ−４'−ヒドロキシジフェニルスルホン３質量部を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録材料を作製し、評価を行った。
実施例１０
実施例１で得られた反応生成物１０質量部の代わりに、実施例１で得られた反応生成物７質量部、４,４'−ジヒドロキシジフェニルスルホン３質量部を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録材料を作製し、評価を行った。
実施例１１
実施例１で得られた反応生成物１０質量部の代わりに、実施例１で得られた反応生成物７質量部、２,４'−ジヒドロキシジフェニルスルホン３質量部を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録材料を作製し、評価を行った。
Example 9
Instead of 10 parts by mass of the reaction product obtained in Example 1, 7 parts by mass of the reaction product obtained in Example 1 and 3 parts by mass of 4-allyloxy-4′-hydroxydiphenyl sulfone were used as a developer. A heat-sensitive recording material was prepared and evaluated in the same manner as in Example 5 except that the dispersion (liquid B) was prepared.
Example 10
Instead of 10 parts by mass of the reaction product obtained in Example 1, 7 parts by mass of the reaction product obtained in Example 1 and 3 parts by mass of 4,4′-dihydroxydiphenylsulfone were used as a developer dispersion. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 5 except that (Liquid B) was prepared.
Example 11
Instead of 10 parts by mass of the reaction product obtained in Example 1, 7 parts by mass of the reaction product obtained in Example 1 and 3 parts by mass of 2,4′-dihydroxydiphenyl sulfone were used as a developer dispersion. A thermosensitive recording material was prepared and evaluated in the same manner as in Example 5 except that (Liquid B) was prepared.
比較例１
実施例１で得られた反応生成物の代わりに、４,４'−ジヒドロキシジフェニルスルホンを用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録材料を作製し、評価を行った。
比較例２
実施例１で得られた反応生成物の代わりに、４,４'−ジヒドロキシジフェニルスルホンとビス(２−クロロエチル)エーテルの重縮合物（両末端フェノール性ヒドロキシル基）［日本曹達(株)製、「Ｄ−９０」］を用いて顕色物質分散液（Ｂ液）を調製した以外は、実施例５と同様にして感熱記録材料を作製し、評価を行った。
実施例５〜１１及び比較例１〜２の感熱記録材料の評価結果を第２表に示す。
Comparative Example 1
A heat-sensitive recording material was prepared in the same manner as in Example 5 except that the developer dispersion (Liquid B) was prepared using 4,4′-dihydroxydiphenylsulfone instead of the reaction product obtained in Example 1. Were prepared and evaluated.
Comparative Example 2
Instead of the reaction product obtained in Example 1, 4,4′-dihydroxydiphenylsulfone and bis (2-chloroethyl) ether polycondensate (both terminal phenolic hydroxyl groups) [manufactured by Nippon Soda Co., Ltd., A thermosensitive recording material was produced and evaluated in the same manner as in Example 5 except that the developer dispersion (liquid B) was prepared using “D-90”].
The evaluation results of the heat-sensitive recording materials of Examples 5 to 11 and Comparative Examples 1 and 2 are shown in Table 2.
第２表に見られるように、比較例１または比較例２で用いた化合物を顕色物質として用いた感熱記録材料に比べて、本発明の化合物を顕色物質として用いた実施例５〜１１の感熱記録材料は、画像部の耐油性、耐湿熱性および、未発色部の耐熱性に優れていることが明らかである。 As can be seen in Table 2, Examples 5 to 11 using the compound of the present invention as the developer compared to the heat-sensitive recording material using the compound used in Comparative Example 1 or Comparative Example 2 as the developer. It is apparent that this heat-sensitive recording material is excellent in the oil resistance of the image area, the heat and moisture resistance, and the heat resistance of the uncolored area.
本発明のジフェニルスルホン架橋型化合物は新規物質であって、感熱記録材料の顕色物質として有用である。また、顕色物質に当該ジフェニルスルホン架橋型化合物を用いた本発明の感熱記録材料は、画像部の耐油性、耐湿熱性、及び、未発色部の耐熱性に優れ、電子レンジ加工食品ラベル、駐車券、配送ラベル、チケットなどの記録画像の保存性が要求される分野において、特に好適に用いることができる。 The diphenylsulfone cross-linking compound of the present invention is a novel substance and is useful as a color developing substance for heat-sensitive recording materials. In addition, the heat-sensitive recording material of the present invention using the diphenylsulfone cross-linking compound as the developer is excellent in oil resistance of the image area, heat and humidity resistance of the image area, and heat resistance of the uncolored area. It can be particularly suitably used in a field where record image storability such as a ticket, a delivery label, and a ticket is required.
Claims (3)
で表されるジフェニルスルホン架橋型化合物。 General formula (1)
A diphenylsulfone crosslinking compound represented by the formula:
で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質。 General formula (1)
A developer for heat-sensitive recording comprising a diphenylsulfone cross-linking compound represented by the formula:
で表されるジフェニルスルホン架橋型化合物からなる感熱記録用顕色物質と、無色又は淡色のロイコ染料からなる発色物質とを含有する感熱発色層を支持体上に設けてなることを特徴とする感熱記録材料。
General formula (1)
A thermosensitive color-developing material comprising a diphenylsulfone cross-linking compound represented by the formula (1) and a color-developing material comprising a colorless or light leuco dye are provided on a support. Recording material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008178707A JP4878610B2 (en) | 2008-07-09 | 2008-07-09 | Diphenylsulfone crosslinkable compound, developer for thermal recording and thermal recording material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008178707A JP4878610B2 (en) | 2008-07-09 | 2008-07-09 | Diphenylsulfone crosslinkable compound, developer for thermal recording and thermal recording material |
Related Parent Applications (1)
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| JP2007125343A Division JP2008280283A (en) | 2007-05-10 | 2007-05-10 | Diphenylsulfone cross-linkable compound, color-developing material for heat-sensitive recording and heat-sensitive recording material |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009255494A (en) * | 2008-03-25 | 2009-11-05 | Nicca Chemical Co Ltd | Heat-sensitive recording material |
| JP2010052375A (en) * | 2008-08-29 | 2010-03-11 | Nicca Chemical Co Ltd | Color developer substance for thermosensitive recording and thermosensitive recording material |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5118600B2 (en) * | 2008-10-17 | 2013-01-16 | 日華化学株式会社 | Thermal recording material |
| JP2010149372A (en) * | 2008-12-25 | 2010-07-08 | Nicca Chemical Co Ltd | Thermosensitive recording material |
| JP2015085520A (en) * | 2013-10-28 | 2015-05-07 | 王子ホールディングス株式会社 | Thermosensitive recording medium |
| KR20240027041A (en) | 2021-06-30 | 2024-02-29 | 닛카카가쿠가부시키가이샤 | Thermal recording material and method of manufacturing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3544218B2 (en) * | 1993-11-30 | 2004-07-21 | 株式会社三光開発科学研究所 | Sulfonyl compound, method for producing the same, and heat-sensitive recording material using the same |
| JP3913820B2 (en) * | 1995-10-31 | 2007-05-09 | 日本曹達株式会社 | Diphenylsulfone cross-linking compound and recording material using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009255494A (en) * | 2008-03-25 | 2009-11-05 | Nicca Chemical Co Ltd | Heat-sensitive recording material |
| JP2010052375A (en) * | 2008-08-29 | 2010-03-11 | Nicca Chemical Co Ltd | Color developer substance for thermosensitive recording and thermosensitive recording material |
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| JP2008303225A (en) | 2008-12-18 |
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