JP2022165704A - Oil-in-water type emulsion of energy-ray curable resin composition and heat-sensitive recording material - Google Patents

Abstract

To provide: a heat-sensitive recording material excellent in high transparency, high glossiness, storage stability of a color recording portion, and thermal head aptitude; an oil-in-water type emulsion of an energy ray curable resin composition, which does not use nonylphenol that gives unfavorable influence on a human body and an environment; and a heat-sensitive recording material formed by coating the same.SOLUTION: An oil-in-water type emulsion comprising: a resin (A) having an ethylenically unsaturated group in the molecule; a reactive surfactant (B) comprising polyoxyethylene mono(3-butenyl) ether or an ether of a polyoxyethylene and β-methylstyrene whose aromatic ring is substituted with a 1-phenylethyl group, the polyoxyethylene having one terminal substituted with an anionic hydrophilic group selected from -(CH2)a-SO3M, -(CH2)b-COOM, -PO3M2, and -CO-CH2-CH-(SO3M)-COOM; a pigment component (C) having an average particle size of 5 μm or less, and a lubricant component (D) having an average particle size of 1.5 μm or less.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an oil-in-water emulsion of an energy ray-curable resin composition, and a thermosensitive recording material having a cured film layer of the energy ray-curable resin composition as an overcoat layer.

A heat-sensitive recording material is generally prepared by separately dispersing a leuco dye and a developer such as a phenolic compound into fine particles, mixing the two, and then adding a binder, a sensitizer, a filler, a lubricant, and the like. A coating liquid obtained by adding additives is applied to paper, film, synthetic paper, etc. When heated, one or both of the leuco dye and the color developer melt and come into contact with each other, causing a chemical reaction that develops color. It is for recording. A thermal printer or the like having a built-in thermal head is used for coloring such a heat-sensitive recording material. Compared to other recording methods, this thermal recording method has the following advantages: (1) no noise during recording, (2) no need for developing and fixing, (3) maintenance-free, and (4) relatively low mechanical Due to its low cost and other features, it is widely used in the field of facsimiles, computer output, printers such as calculators, recorders for medical measurement, automatic ticket vending machines, thermal recording labels, and the like.

2. Description of the Related Art In recent years, as the applications of thermal recording materials have expanded, the diversification and performance enhancement of recording apparatuses have progressed, and the required quality of thermal recording materials has become higher. For example, writing aptitude, printing aptitude, prevention of generation of head residue, and the like can be mentioned. In addition, the color development recording part (printing, image, pattern, etc.) are required to have storage stability. Furthermore, in the case of a transmissive thermosensitive recording medium using a synthetic resin film such as a polyethylene terephthalate film as a support, high transparency and surface gloss are required.

From the viewpoint of improving the above problem, a protective layer (overcoat layer) is generally provided on the thermosensitive recording layer. For example, Patent Document 1 discloses a protective layer formed using a hydrophobic polymer compound emulsion or the like. Further, in Patent Document 2, an intermediate layer is formed on a heat-sensitive recording layer using an emulsion of a water-soluble polymer compound or a hydrophobic polymer compound, and an oil-based paint having a hydrophobic polymer compound as a resin component is applied thereon. A heat-sensitive recording material having a surface layer is disclosed. However, although these heat-sensitive recording materials are improved in the storage stability of the color-developed recording portion, the surface gloss is considerably low.

On the other hand, Patent Documents 3 to 8 propose various heat-sensitive recording materials in which an overcoat layer containing a resin cured by irradiating an ultraviolet-curable compound with ultraviolet rays is provided on the heat-sensitive recording layer. Further, in Patent Document 9, for the purpose of obtaining a heat-sensitive recording material excellent in high-speed recording properties, high glossiness, heat-sensitive recording itself and color image storability, a hydrophilic polymer having an ethylenically unsaturated group is disclosed. Disclosed is an oil-in-water emulsion of an energy ray-curable resin composition containing a resin as an emulsifier and also containing a filler, suitable for an overcoat layer of a heat-sensitive recording material. However, the emulsifier used in Patent Document 9 has a problem in that it has a nonylphenol structure. This is because nonylphenol has been reported to be toxic to endocrine system organs as an endocrine hormone substance with estrogenic activity (Non-Patent Documents 1 and 2, European Directives 2003/53/EC and 76/769/EEC). Supplement I No. 46). Also in Japan, in August 2001, the Endocrine Disrupting Substances Review Committee confirmed the endocrine disrupting action of nonylphenol and pointed out that nonylphenol is a causative agent of environmental problems such as cancer and malformation. In addition, nonylphenol is strongly irritating to the eyes, skin, and respiratory system (Non-Patent Documents 3-4), and it was also found in skin irritation tests that prolonged exposure time shows corrosiveness to the skin. ing. For this reason, it has been strongly desired to use an emulsifier that does not contain a nonylphenol structure in the overcoat layer of a heat-sensitive recording material that comes into direct contact with the skin.

Patent Document 10 discloses an oil-in-water energy ray-curable resin composition suitable for an overcoat layer of a heat-sensitive recording material, which contains a hydrophilic resin having an ethylenically unsaturated group and no nonylphenol structure as an emulsifier. A drop emulsion is disclosed. However, the example of the thermal recording material with high glossiness in the same document causes recording failure and head residue adhesion in sticking evaluation and/or head residue adhesion evaluation, and satisfactory results for thermal head suitability are not necessarily obtained.

Patent Document 11 discloses an oil-in-water energy ray-curable resin composition suitable for an overcoat layer of a heat-sensitive recording material, which contains a hydrophilic resin having an ethylenically unsaturated group and no nonylphenol structure as an emulsifier. A drop emulsion is disclosed. However, regarding the evaluation of thermal head aptitude carried out in the same document, it is assumed that it will be used under more severe conditions when it is actually used. There has been a demand for improved performance. Insufficient thermal head aptitude may lead to serious problems in actual use, such as poor printing and destruction of the thermal head.
Thus, none of the heat-sensitive recording materials that have been proposed so far can satisfy all of the requirements for high transparency, high glossiness, storage stability of color-developed recording areas, and suitability for thermal heads, and new improvements are needed. Met.

JP-A-56-146794 JP-A-58-199189 JP-A-2-192988 JP-A-6-344664 JP-A-7-40658 JP-A-8-142508 JP-A-9-156222 JP-A-9-220855 Japanese Patent Application Laid-Open No. 2000-160060 JP-A-2000-327952 WO2020-039601

Laws, S. C. et al. , Estrogenic activity of octylphenol, nonylphenol, bisphenol A and methoxychlor in rats. , Toxicol Sci. , 54(1), 154-167 (2000) Lee, P. C. , Disruption of male reproductive tract development by administration of the xenoestrogen, nonylphenol, to male newborn rats. , Endocrine, 9(1), 105-111 (1998) U.S.A. S. Coast Guard, Department of Transportation. CHRIS Hazardous Chemical Data. U.S.A. S. Coast Guard. WashingtonD. C. (1985) Masayuki Ikeda et al. , Two cases of leucoderma, presumably due to nonyl- or octylphenol in synthetic detergents. Ind. Health 8(4), 192-196 (1970)

An object of the present invention is to solve the problems of the prior art described above, and more specifically, to form a heat-sensitive recording material which is excellent in high transparency, high glossiness, storage stability of the color-developing recording portion, and suitability for thermal heads. and is prepared without using an emulsifier having a nonylphenol structure that adversely affects the human body and the environment. intended to provide

The present inventor has completed the present invention as a result of earnest studies to achieve the above object.

That is, the present invention
[1] A resin (A) having an ethylenically unsaturated group in the molecule, a reactive surfactant (B) represented by formula (1) or (2), and a pigment component having an average particle size of 5 μm or less (C) and an oil-in-water emulsion of an energy ray-curable resin composition containing (C) and a lubricant component (D) having an average particle size of 1.5 μm or less,

（式中、Ｒは水素原子またはメチル基を表し、Ａは炭素数２～４のアルキレン基を表し、ｍは２～８０の範囲にある平均付加モル数を表す）

(Wherein, R represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and m represents the average added mole number in the range of 2 to 80)

（式中、ｎ１は平均値で１～３の置換基数を表し、ｎ２は０～１００の範囲にある平均付加モル数を表し、Ｔは水素原子または－（ＣＨ_２）_ａ－ＳＯ_３Ｍ、－（ＣＨ_２）_ｂ－ＣＯＯＭ、－ＰＯ_３Ｍ_２、及び－ＣＯ－ＣＨ_２－ＣＨ－（ＳＯ_３Ｍ）－ＣＯＯＭから選ばれるアニオン性親水基を表す。これらの式中、ａ及びｂはそれぞれ０～４の数を表し、Ｍはそれぞれ、水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム残基、又はアルカノールアミン残基を表す）、好ましくは、本発明の水中油滴型エマルションはノニルフェノール構造を有する化合物を含まない、
［２］前記反応性界面活性剤（Ｂ）の少なくとも１種が、式（２）においてＴが水素原子または－ＳＯ_３ＮＨ_４で表される化合物である［１］に記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［３］前記反応性界面活性剤（Ｂ）として、式（１）で表される化合物と、Ｔが－ＳＯ_３ＮＨ_４である式（２）で表される化合物とを含む、［１］に記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［４］前記反応性界面活性剤（Ｂ）として、Ｔが水素原子である式（２）で表される化合物と、Ｔが－ＳＯ_３ＮＨ_４である式（２）で表される化合物とを含む、［１］に記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［５］前記顔料成分（Ｃ）が無機顔料であり、その含有量がエネルギー線硬化型樹脂組成物の全固形分に対し０．５～５０質量％である［１］乃至［４］のいずれか一つに記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［６］前記顔料成分（Ｃ）が、炭酸カルシウムである［１］乃至［５］のいずれか一つに記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［７］前記滑剤成分（Ｄ）が高級脂肪酸の金属塩であり、その含有量がエネルギー線硬化型樹脂組成物の全固形分に対し０．１～３０質量％である［１］乃至［６］のいずれか一つに記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［８］前記滑剤成分（Ｄ）が、ステアリン酸亜鉛である、［１］乃至［７］のいずれか一つに記載のエネルギー線硬化型樹脂組成物の水中油滴型エマルション、
［９］［１］乃至［８］のいずれか一つに記載の水中油滴型エマルションから成るオーバーコート剤、
［１０］支持体上に感熱記録層及びオーバーコート層を有する感熱記録材料において、オーバーコート層が［９］に記載のオーバーコート剤の硬化膜層から成ることを特徴とする感熱記録材料、
［１１］［１０］に記載の感熱記録材料のＨＡＺＥ値が２５以下、かつ光沢度が７５以上であることを特徴とする感熱記録材料、
に関する。

(Wherein, n1 represents the average number of substituents of 1 to 3, n2 represents the average number of added moles in the range of 0 to 100, T is a hydrogen atom or -(CH ₂ ) _a -SO ₃ M, —(CH ₂ ) _b —COOM, —PO ₃ M ₂ , and —CO—CH ₂ —CH—(SO ₃ M)—COOM, in which a and b are Each represents a number from 0 to 4, and each M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, or an alkanolamine residue), preferably the oil-in-water emulsion of the present invention does not contain compounds with a nonylphenol structure,
[2] The energy beam-curable type according to [1], wherein at least one of the reactive surfactants (B) is a compound in which T is a hydrogen atom or —SO ₃ NH ₄ in formula (2). an oil-in-water emulsion of a resin composition,
[3] The reactive surfactant (B) includes a compound represented by formula (1) and a compound represented by formula (2) in which T is —SO ₃ NH ₄ , [1] oil-in-water emulsion of the energy beam-curable resin composition according to
[4] As the reactive surfactant (B), a compound represented by the formula (2) in which T is a hydrogen atom and a compound represented by the formula (2) in which T is —SO ₃ NH ₄ The oil-in-water emulsion of the energy ray-curable resin composition according to [1], comprising
[5] Any one of [1] to [4], wherein the pigment component (C) is an inorganic pigment, and the content thereof is 0.5 to 50% by mass based on the total solid content of the energy ray-curable resin composition. An oil-in-water emulsion of the energy beam-curable resin composition according to any one of the above,
[6] The oil-in-water emulsion of the energy beam-curable resin composition according to any one of [1] to [5], wherein the pigment component (C) is calcium carbonate;
[7] The lubricant component (D) is a metal salt of a higher fatty acid, and the content thereof is 0.1 to 30% by mass relative to the total solid content of the energy ray-curable resin composition [1] to [6] ] An oil-in-water emulsion of the energy ray-curable resin composition according to any one of
[8] The oil-in-water emulsion of the energy beam-curable resin composition according to any one of [1] to [7], wherein the lubricant component (D) is zinc stearate.
[9] An overcoat agent comprising the oil-in-water emulsion according to any one of [1] to [8],
[10] A heat-sensitive recording material having a heat-sensitive recording layer and an overcoat layer on a support, wherein the overcoat layer comprises a cured film layer of the overcoat agent according to [9].
[11] A heat-sensitive recording material according to [10], which has a HAZE value of 25 or less and a glossiness of 75 or more;
Regarding.

The present invention comprises a resin (A) having an ethylenically unsaturated group in the molecule, a reactive surfactant (B) represented by formula (1) or formula (2), and a pigment having an average particle size of 5 μm or less. By combining the component (C) with the lubricant component (D) having an average particle size of 1.5 μm or less, thermal recording with high transparency, high glossiness, storage stability of the color recording portion, and excellent suitability for thermal heads. An oil-in-water emulsion of an energy beam-curable resin composition that is suitable for forming materials and prepared without using an emulsifier having a nonylphenol structure that adversely affects the human body and the environment, and obtained by applying the same A heat-sensitive recording material could be provided.

Below, the present invention will be described in detail based on embodiments. It should be noted that the invention is not limited by the embodiments shown below.
As described above, the present invention comprises a resin (A) having an ethylenically unsaturated group in the molecule, a reactive surfactant (B) represented by formula (1) or formula (2), and an average particle size An oil-in-water emulsion of an energy ray-curable resin composition containing a pigment component (C) having an average particle size of 5 μm or less and a lubricant component (D) having an average particle size of 1.5 μm or less, an overcoat agent using the same, and It relates to a heat-sensitive recording material produced by coating it on a support.

In one embodiment of the present invention, the resin (A) having an ethylenically unsaturated group in the molecule is preferably liquid at room temperature. acrylates are more preferred. The amount used is preferably 2 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the energy ray-curable resin composition, in consideration of film performance such as film-forming property, coating film strength, and gloss. % range.

In one embodiment of the present invention, the acrylates include a monofunctional monomer having one (meth)acryloyl group, a bifunctional monomer having two (meth)acryloyl groups, an oligomer having a (meth)acryloyl group, It is roughly classified into polyfunctional monomers having 3 or 4 or more (meth)acryloyl groups, but since high film-forming ability, film hardness, and high heat resistance are required, It is desirable that the main component is a polyfunctional monomer or oligomer having

In one embodiment of the present invention, when the number of (meth)acryloyl groups is two or less, the desired heat resistance cannot be obtained because the crosslink density is not sufficient. However, for the purpose of imparting flexibility to the film and preventing curling and cracking, 0 to 100 parts by weight per 100 parts by weight of a polyfunctional monomer or oligomer having three or more (meth)acryloyl groups may be contained. It is preferably contained in an amount of 20 to 80 parts by mass, and particularly preferably in an amount of 30 to 70 parts by mass. Also, as the number of (meth)acryloyl groups increases, the crosslink density increases and the heat resistance is further improved, but the flexibility of the film is impaired and curling and cracking occur. Preferably, those containing 50% by mass or more of these as main components are particularly preferable. Rather than using these materials alone, it is preferable to use two or more resins together in consideration of heat resistance, flexibility, and curability.

In one embodiment of the present invention, the monofunctional monomer is not particularly limited, but specific examples thereof include N,N-dimethylaminomethyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hydroxybutyl (Meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-decyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate , phenoxypolyethylene glycol (meth)acrylate, lauryl (meth)acrylate, phenylglycidyl ether (meth)acrylate, acryloylmorpholine and the like.

In one embodiment of the present invention, the bifunctional monomer is not particularly limited, but specific examples include ethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, neopentyl glycol diacrylate, acrylate, tripropylene glycol diacrylate, di(meth)acrylate of alkylene oxide adduct of bisphenol A, tetraethylene glycol diacrylate, neopentyl glycol hydroxypivalate diacrylate, 1,4-butanediol di(meth)acrylate, 1 ,6-hexanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate, 1,16-hexadecanediol di(meth)acrylate, 1,20 -eicosandiol di(meth)acrylate, isopentyldiol di(meth)acrylate, 3-ethyl-1,8-octanediol di(meth)acrylate and the like.

In one embodiment of the present invention, the oligomer is not particularly limited, but specific examples include epoxy (meth) acrylate, saturated polyester/styrene, polyethylene (meth) acrylate, polyether (meth) ) acrylate, silicon (meth)acrylate, polybutadiene (meth)acrylate, polyene/thiol, polystyrylethyl (meth)acrylate, polyamide (meth)acrylate and the like.

In one embodiment of the present invention, the polyfunctional monomer is not particularly limited, but specific examples thereof include trimethylolpropane tri(meth)acrylate, trimethyloloctane tri(meth)acrylate, tri Methylolpropane polyethoxytri(meth)acrylate, trimethylolpropane polypropoxytri(meth)acrylate, polymethylolpropane polyethoxypolypropoxytri(meth)acrylate, tris[(meth)acryloyloxyethyl]isocyanate, pentaerythritol tri(meth)acrylate ) acrylate, pentaerythritol polyethoxy tetra (meth) acrylate, pentaerythritol polypropoxy tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, di pentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified tris[(meth)acryloyloxyethyl]isocyanate, and the like.

The reactivity of the reactive surfactant (B) represented by formula (1) or formula (2) used in the present invention means that it contains a reactive double bond, and the monomer and the reactive surfactant each other It means to undergo a polymerization reaction. That is, the reactive surfactant (B) acts as an emulsifier for the resin (A) having an ethylenically unsaturated group in the molecule, and is covalently bonded to a part of the polymer when cured with an energy ray. . Therefore, there is almost no free surfactant, and the resulting film has improved water resistance and thermal head suitability.

The reactive surfactant (B) used in the present invention is generally a compound having a (polymerizable) ethylenically unsaturated double bond and a group exhibiting surface activity, particularly an ethylenically unsaturated double bond and an interface It is a compound in which a group exhibiting active properties is directly attached to a benzene ring and does not contain a nonylphenol structure. Reactive surfactant (B) replaces a substitutable group or atom (e.g., hydrogen atom) in the surfactant with a group having an ethylenically unsaturated double bond (e.g., vinyl group, allyl group) A compound is preferred. Surfactants mean compounds exhibiting surface-active properties (preferably normal surfactants), such as anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. do. The molecular weight (number average molecular weight) of the reactive surfactant (B) may be 100-15,000, preferably 150-5,000. Among these, the reactive surfactant (B) used in the present invention is preferably represented by the following formula (1) or (2).

（式中、Ｒは水素原子またはメチル基を表し、Ａは炭素数２～４のアルキレン基を表し、ｍは２～８０の範囲にある平均付加モル数を表す）

(Wherein, R represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and m represents the average added mole number in the range of 2 to 80)

（式中、ｎ１は平均値で１～３の置換基数を表し、ｎ２は０～１００の範囲にある平均付加モル数を表し、Ｔは水素原子または－（ＣＨ_２）_ａ－ＳＯ_３Ｍ、－（ＣＨ_２）_ｂ－ＣＯＯＭ、－ＰＯ_３Ｍ_２、及び－ＣＯ－ＣＨ_２－ＣＨ－（ＳＯ_３Ｍ）－ＣＯＯＭから選ばれるアニオン性親水基を表す。これらの式中、ａ及びｂはそれぞれ０～４の数を表し、Ｍはそれぞれ、水素原子、アルカリ金属原子、アルカリ土類金属原子、アンモニウム残基、又はアルカノールアミン残基を表す）

(Wherein, n1 represents the average number of substituents of 1 to 3, n2 represents the average number of added moles in the range of 0 to 100, T is a hydrogen atom or -(CH ₂ ) _a -SO ₃ M, —(CH ₂ ) _b —COOM, —PO ₃ M ₂ , and —CO—CH ₂ —CH—(SO ₃ M)—COOM, in which a and b are each represents a number from 0 to 4, and each M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, or an alkanolamine residue)

R in general formula (1) is a hydrogen atom or a methyl group, preferably a methyl group.

The (AO) _m chain portion in the general formula (1) is an addition polymer of one or more of ethylene oxide, propylene oxide and butylene oxide as an alkylene oxide having 2 to 4 carbon atoms, and the polymerization form is particularly It is not limited, and may be a homopolymer of one type of alkylene oxide, a random copolymer of two or more types of alkylene oxide, or a combination of a random adduct thereof and a block copolymer.

An oxyethylene group is particularly preferred as the alkylene oxide. When two or more alkylene oxides are selected, one of them is preferably ethylene oxide, and the (AO) _m chain portion preferably contains 50 to 100 mol% of oxyethylene groups, more preferably 60 It is a (poly)oxyalkylene chain containing up to 100 mol %.

The reactive surfactant (B) represented by the above general formula (1) can be obtained by a conventionally known method and is not particularly limited. In addition, it can be easily obtained from commercial products, and examples thereof include Latemul PD-420, PD-430, PD-450 manufactured by Kao Corporation.

n1 in the general formula (2) is preferably in the range of 1 to 3, more preferably in the range of 1 to 2 as an average value.

The (C ₂ H ₄ O) _n2 chain portion in the general formula (2) is an addition polymer of ethylene oxide, and the degree of polymerization n2 represents the number of moles of ethylene oxide added, and has an average value in the range of 0 to 100. The preferred range of the average number of added moles is usually 0.1 or more, preferably 1 or more, more preferably 3 or more, and particularly preferably 10 or more. Moreover, the upper limit is preferably 90 or less, more preferably 80 or less, and particularly preferably 50 or less. More specifically, when T in the general formula (2) is a hydrogen atom, the degree of polymerization n2 is preferably in the range of 30 or more and 50 or less. Further, when T is an ionic hydrophilic group, the degree of polymerization n2 is preferably a number in the range of 0 or more and 50 or less, more preferably a number in the range of 10 or more and 30 or less.

In the surfactant represented by the general formula (2), the content of ethylene oxide groups in the (C ₂ H ₄ O) _n2 chain and the degree of polymerization n2 determine the degree of hydrophilicity or hydrophobicity of the surfactant. Although variable, it is preferable to appropriately design the composition of the (C ₂ H ₄ O) _n2 chain portion according to the type of resin (A) having an ethylenically unsaturated group in the molecule to be used.

T in the general formula (2) is a hydrogen atom, -(CH ₂ ) _a -SO ₃ M, -(CH ₂ ) _b -COOM, -PO ₃ M ₂ and -CO-CH ₂ -CH-(SO ₃ M)-COOM represents an anionic hydrophilic group, wherein a and b each represent a number from 0 to 4; M represents a hydrogen atom, an alkali metal atom such as lithium, sodium or potassium, an alkaline earth metal atom such as magnesium or calcium, or an ammonium or alkanolamine residue. Examples of ammonium include ammonium of ammonia, ammonium of alkylamines such as monomethylamine and dipropylamine, and examples of alkanolamine residues include monoethanolamine residues, diethanolamine residues, triethanolamine residues, and the like. residues and the like. Among these anionic hydrophilic groups, a group represented by —SO ₃ M is preferred. These may be used individually by 1 type, and may use 2 or more types together.

The reactive surfactant (B) represented by the general formula (2) can be obtained by a conventionally known method and is not particularly limited. In addition, it can be easily obtained from commercial products, for example, Aqualon AR-10, AR-20, AR-1025, AR-2020, AN-5065 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. can be mentioned.

As the reactive surfactant (B) used in the present invention, anionic surfactants, cationic surfactants, nonionic surfactants and the like can be used without particular limitation. The surfactant (B) can satisfactorily complete emulsification even when used alone, but as long as it does not impair the desired effects of the present invention, and a nonionic surfactant may be used in combination, and when two or more surfactants are selected, one of them is preferably a nonionic surfactant.

The amount of either one of the general formula (1) or the formula (2) used, or the amount of use when the reactive surfactant (B) represented by the general formulas (1) and (2) is used in combination, Considering film physical properties such as emulsion stability, water resistance, and heat resistance, it is preferably in the range of 2 to 40% by mass, more preferably 4 to 20% by mass, based on the total mass of the energy ray-curable resin composition. be. When the reactive surfactant (B) represented by general formula (1) and formula (2) is used in combination, the mixing ratio is preferably 51:49 to 99:1, more preferably 70:30 to 95. :5.

When T in the general formula (2) is an ionic hydrophilic group, the reactive surfactant (B) is a kind of anionic emulsifier. A group in which T is -SO ₃ M is preferred, and more preferably T is an ammonium sulfonate base (-SO ₃ NH ₄ ).

The present invention contains a pigment component (C) having an average particle size of 5 μm or less. The particle size is preferably smaller than the film thickness of the overcoat layer, and more preferably about 0.01 to 5 μm as an average particle size. Also, considering the stability of the emulsion and the glossiness of the coating film, the amount used is preferably 0.5 to 50% by mass, more preferably 1 to 30% by mass, based on the total mass of the energy ray-curable resin composition. %.

In one embodiment of the present invention, as the pigment component (C), calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, kaolin, calcined kaolin, lithopone, talc, clay, magnesium hydroxide, aluminum hydroxide, oxide Titanium, zinc oxide, aluminum oxide, barium sulfate, diatomaceous earth, acid clay, bentonite, synthetic aluminum silicate, inorganic pigments such as surface-treated calcium carbonate and silica; urea-formalin resin, silicone resin, styrene-methacrylic acid copolymer resin , polystyrene resins, organic pigments such as raw starch particles, etc., inorganic pigments are preferred, and calcium carbonate, silica, aluminum hydroxide, and calcined kaolin are more preferred from the viewpoint of ease of miniaturization and gloss, and calcium carbonate is particularly preferred. These are used singly or in combination of two or more.

In one embodiment of the present invention, a phosphate is used as a dispersant, and a dispersion of the pigment component (C) can be prepared in advance and used. The phosphate is not particularly limited, but specific examples thereof include primary sodium phosphate, secondary sodium phosphate, tertiary sodium phosphate, sodium pyrophosphate, sodium acid pyrophosphate, tripolyphosphate sodium hexametaphosphate, sodium tetrapolyphosphate, sodium hexametaphosphate, sodium hexametaphosphate, or potassium salts, calcium salts, magnesium salts thereof, and the like, and the content thereof is preferably 0.5 to the pigment component (C). 01 to 20 mass %, more preferably 0.1 to 15 mass %.

The present invention contains a lubricant component (D) having an average particle size of 1.5 μm or less. The particle size is more preferably about 0.01 to 1.5 μm as an average particle size, considering the thermal head suitability of the coating film. The amount used is preferably 0.1 to 30% by mass, more preferably 0% by mass, based on the total mass of the energy ray-curable resin composition, considering the stability of the emulsion and the gloss and transparency of the coating film. .2 to 15% by mass.

In one embodiment of the present invention, the lubricant component (D) includes tetrafluoride resin, stearic acid-modified silicone oil, aspartic acid ester derivatives, and metal salts of higher fatty acids such as zinc stearate, magnesium stearate, and calcium stearate. , stearic acid amide, higher fatty acid amide such as polyoxyethylene stearic acid amide, higher fatty acid ester such as polyoxyethylene sorbitol stearate, liquid paraffin, vegetable oil, animal oil, sorbitan ester, polyoxyethylene sorbitol fatty acid ester, polyglycerin fatty acid Ester etc. are mentioned. Among these, metal salts of higher fatty acids are preferred, and zinc stearate is particularly preferred, in terms of high lubricating function and release effect, high anti-sticking quality, and high anti-sticking effect. These are used singly or in combination of two or more.

In one embodiment of the present invention, for the purpose of improving the leveling property of the coating liquid, the energy ray-curable resin composition of the present invention contains an acrylic copolymer, silicone oil, an alkyl group, an amino group, an epoxy group, A silicone oil modified with a fluorine group, a carboxyl group, a hydroxyl group, a mercapto group, an acrylic group, or a methacrylic group, a fluorosurfactant, or the like can be added. A small amount of an emulsifying/dispersing agent may also be added for the purpose of improving the emulsifying power. These may be used individually by 1 type, or may use 2 or more types together. The content of these components is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, relative to the total mass of the energy ray-curable resin composition.

In one embodiment of the present invention, wax can be contained in the energy ray-curable resin composition of the present invention for the purpose of further reducing scum adhesion to the thermal head. Examples of waxes include various natural waxes such as montan wax, paraffin wax, carnauba wax and rice wax, and various synthetic waxes such as polyethylene wax. More than one type may be used together. The content ratio thereof is preferably 0 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.05 to 1% by mass, relative to the total mass of the energy ray-curable resin composition. is.

The energy ray-curable resin composition used in the present invention may be omitted when cured by electron beams, but when cured by ultraviolet rays, a photopolymerization initiator may be added, and if necessary, a photopolymerization accelerator may be added. use.

In one embodiment of the present invention, the photopolymerization initiator includes an α-hydroxyketone polymerization initiator, an α-aminoketone polymerization initiator, an acylphosphine oxide polymerization initiator, an oxime polymerization initiator, and a sulfonium salt polymerization initiator. Polymerization initiators, iodonium salt-based polymerization initiators, diazonium salt-based polymerization initiators, ferrocenium salt-based polymerization initiators, etc. may be mentioned, and α-hydroxyketone-based polymerization initiators are preferred in terms of curability, yellowing, and odor. .

In one embodiment of the present invention, the photopolymerization accelerator includes N-methyldiethylethanolamine, triethanolamine, diethanolamine, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, N,N- Amine compounds such as diethyl-p-aminobenzonitrile, phosphorus compounds such as tri-n-butylphosphine, chlorine compounds such as hexachloroethane, and Michler's ketone can be used alone or in combination of two or more.

The mixing ratio of these photopolymerization initiators and photopolymerization accelerators is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, relative to the total mass of the energy ray-curable resin composition. %.

The energy ray-curable resin composition used in the present invention may optionally contain various additives other than those described above by appropriately selecting the type and amount used. Examples include polymers, antifoaming agents, UV absorbers, antioxidants, polymerization inhibitors, antistatic agents, fluorescent dyes, and the like.

The emulsion of the present invention can be produced, for example, as follows. That is, the reactive surfactant (B) represented by Formula (1) or Formula (2) is dissolved or dispersed in water. Then, if necessary, a photopolymerization initiator, a photopolymerization accelerator, and other additives are added to the liquid of the resin (A) having an ethylenically unsaturated group in the molecule, and the liquid is stirred while the formula (1 ) or the solution or dispersion of the reactive surfactant (B) represented by formula (2) is gradually added, and emulsified using a high-speed stirrer such as a homogenizer, homomixer, sand mill, or a microfluidizer. - By dispersing, an oil-in-water emulsion of the energy ray-curable resin composition of the present invention is obtained.

The pigment component (C) having an average particle size of 5 μm or less and the lubricant component (D) having an average particle size of 1.5 μm or less used in the present invention are added in advance to the resin (A) having an ethylenically unsaturated group in the molecule. Alternatively, an aqueous dispersion is prepared by dispersing it in water together with a dispersant in advance, and it is added to the resin (A) having an ethylenically unsaturated group in the molecule, or it is made into a suspension and then energy ray-curable. It may be added to the oil-in-water emulsion of the resin composition.

When it is added in advance to the resin (A) having an ethylenically unsaturated group in the molecule, it is dispersed in the resin (A) having an ethylenically unsaturated group in the molecule with a dispersing machine such as a ball mill, a roll mill, a sand mill, or a dissolver. , A photopolymerization initiator, a photopolymerization accelerator, and other additives are added as necessary. As dispersants for pigment component (C) and lubricant component (D), polycarboxylic acid-based dispersants, silane coupling agents, titanate-based coupling agents, silicone-based dispersants such as modified silicone oil, and organic copolymer-based dispersants can be used. It is also possible to use a dispersant or the like in combination. The blending ratio of these can be 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the composition. Resin (A) having an ethylenically unsaturated group in the molecule containing pigment component (C) thus obtained or lubricant component (D) and reactive interface represented by formula (1) or formula (2) The solution or dispersion of the active agent (B) is mixed, emulsified and dispersed by the method described above to obtain the oil-in-water emulsion of the present invention.

When a wax is used, it is added in advance to the resin (A) having an ethylenically unsaturated group in the molecule, or a suspension of the wax is added to the oil-in-water emulsion of the energy ray-curable resin composition. Just do it.

The solid content in the oil-in-water emulsion of the energy ray-curable resin composition thus obtained is 20 to 80% by mass, more preferably 30 to 70% by mass. An oil-in-water emulsion of this energy ray-curable resin composition is stable over time, and an emulsion diluted with water as necessary for coating is also stable.

The method for forming a cured film of the oil-in-water emulsion of the energy ray-curable resin composition is not particularly limited, but according to one embodiment of the present invention, bar coater coating, air knife coating, By gravure coating, offset printing, flexographic printing, screen printing, etc., it is coated on paper, synthetic paper, or film by a method known per se, dried, and then applied by irradiating energy rays such as ultraviolet rays and electron beams. Cure the film. At that time, when curing with an electron beam, an electron beam accelerator having an energy of 100 to 500 eV is preferable. On the other hand, when curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, etc. is used as a light source. It is preferable to have suitable light emitting properties. Irradiation conditions vary depending on the type of lamp, the type of resin (A) having an ethylenically unsaturated group in the molecule, the amount added, the temperature of the base material, the oxygen concentration, etc., and the amount of light and the arrangement of the light source, for example, a high-pressure mercury lamp. When using , it is preferable to cure by irradiating 1 to 4 times with a lamp having a light quantity of 80 to 200 W/cm at a conveying speed of 5 to 60 m/min.

In the heat-sensitive recording material of the present invention, a heat-sensitive recording layer containing at least a color-forming compound and a color-developing compound and the energy beam-curable resin composition described above are coated on one side of a support as an overcoat agent. It has an overcoat layer in this order.

<Support>
The shape, structure, size, material, etc. of the support used in the present invention are not particularly limited, and can be appropriately selected according to the purpose. The structure may be a single layer structure or a laminated structure, and the size may be appropriately selected according to the size of the heat-sensitive recording material. can.

Examples of the support include paper, synthetic paper, film, and the like. In the case of a transmissive thermosensitive recording medium, it is preferable to use a transparent support, and specific examples thereof include polypropylene. films, polyethylene films, polyethylene terephthalate films, polystyrene films, vinyl chloride films and the like. Among these, polyethylene film and polyethylene terephthalate film are preferable, and polyethylene terephthalate film is particularly preferable, from the viewpoint of strength and ease of processing.

The average thickness of the support is not particularly limited and can be appropriately selected depending on the intended purpose.

The transparent support may be subjected to corona discharge treatment or conductive treatment with a conductive agent.

<Thermal recording layer>
The heat-sensitive recording layer generally contains a colorless or light-colored color-forming compound, a color-developing compound, and optionally a sensitizer, a storage-improving agent, binders and fillers described below, and other additives. Containing things, etc.

The color-developing compound used in the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper or heat-sensitive recording paper. In one embodiment of the present invention, examples of color-forming compounds include fluorane-based compounds, triarylmethane-based compounds, spiro-based compounds, diphenylmethane-based compounds, thiazine-based compounds, lactam-based compounds, fluorene-based compounds, and vinylphthalide-based compounds. Fluorane compounds are preferred.

The fluoran compound is not particularly limited, but specific examples include 3-diethylamino-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane , 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isopentylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilinofluorane, 3-[N-ethyl-N-(3-ethoxypropyl)amino]-6-methyl-7-anilino Fluorane, 3-(N-ethyl-N-hexylamino)-6-methyl-7-anilinofluorane, 3-dipentylamino-6-methyl-7-anilinofluorane, 3-(N-methyl- N-propylamino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-tetrahydrofurylamino)-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl- 7-(p-chloroanilino)fluorane, 3-diethylamino-6-methyl-7-(p-fluoroanilino)fluorane, 3-[N-ethyl-N-(p-tolyl)amino]-6-methyl-7 -anilinofluorane, 3-diethylamino-6-methyl-7-(p-toluidino)fluorane, 3-diethylamino-7-(o-chloroanilino)fluorane, 3-dibutylamino-7-(o-chloroanilino)fluorane, 3-diethylamino-7-(o-fluoroanilino)fluorane, 3-dibutylamino-7-(o-fluoroanilino)fluorane, 3-diethylamino-7-(3,4-dichloroanilino)fluorane, 3- pyrrolidino-6-methyl-7-anilinofluorane, 3-diethylamino-6-chloro-7-ethoxyethylaminofluorane, 3-diethylamino-6-chloro-7-anilinofluorane, 3-diethylamino-7- Chlorofluorane, 3-diethylamino-7-methylfluorane, 3-diethylamino-7-octylfluorane, 3-[N-ethyl-N-(p-tolyl)amino]-6-methyl-7-phenethylfluorane , 2-methyl-6-(Np-tolyl-N-ethylamino)fluorane (RED520), 9-(N-ethyl-N-isopentylamino)spiro[benzo[a]xanthene-12,3′- phthalide] (RED500), 2'-anilino- 6'-(N-ethyl-N-isopentylamino)-3'-methylspiro[phthalido-3,9'-xanthene] (S-205), 2'-anilino-6'-(N,N-dipentane- 1-ylamino)-3′-methyl-3H-spiro[isobenzofuran-1,9′-xanthene]-3-one (Black305), 2′-anilino-6′-(dibutylamino)-3′-methylspiro[ phthalide-3,9′-xanthene] (Black400), 2′-anilino-6′-[N-ethyl-N-(4-tolyl)amino]-3′-methyl-3H-spiro[isobenzofuran-1, 9′-xanthene]-3-one (ETAC), 6-(diethylamino)-2-[(3-trifluoromethyl)anilino]xanthene-9-spiro-3′-phthalide (Black100), 1-ethyl-8 -[N-ethyl-N-(4-methylphenyl)amino]-2,2,4-trimethyl-1,2-dihydrospiro[11H-chromeno[2,3,-g]quinoline-11,3′- phthalide] (H-1046), 3-dibutylamino-6-methyl-7-bromofluorane, 3-[4-(diethylamino)phenyl]-3-(1-ethyl-2-methyl-1H-indole-3 -yl)-1(3H)-isobenzofuranone (Blue 502) and the like, preferably 3-dibutylamino-6-methyl-7-anilinofluorane.

Triarylmethane-based compounds are not particularly limited, but specific examples thereof include 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet lactone or CVL). , 3,3-bis(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2-dimethylaminoindol-3-yl)phthalide, 3-(p-dimethylaminophenyl) )-3-(2-methylindol-3-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2-phenylindol-3-yl)phthalide, 3,3-bis(1,2- dimethylindol-3-yl)-5-dimethylaminophthalide, 3,3-bis(1,2-dimethylindol-3-yl)-6-dimethylaminophthalide, 3,3-bis(9-ethylcarbazole -3-yl)-5-dimethylaminophthalide, 3,3-(2-phenylindol-3-yl)-5-dimethylaminophthalide, 3-p-dimethylaminophenyl-3-(1-methylpyrrole -2-yl)-6-dimethylaminophthalide, 3-(4-diethylamino-2-methylphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (Blue200), 3-[4-(diethylamino)-2-hexyloxyphenyl]-3-(1-ethyl-2-methylindol-3-yl)-4-azaphthalide (Blue203), 3-(4-diethylamino-2-methyl Phenyl)-3-(1-ethyl-2-methyl-1H-indol-3-yl)-4-azaphthalide (Blue220), 7-(4-diethylamino-2-ethoxyphenyl)-7-(1-ethyl-2 -methyl-1H-indol-3-yl)furo[3,4-b]pyridin-5(7H)-one (Blue63) and the like.

Spiro-based compounds are not particularly limited, but specific examples include 3-methylspirodinaphthopyran, 3-ethylspirodinaphthopyran, 3,3'-dichlorospirodinaphthopyran, 3-benzyl Spirodinaphthopyran, 3-propylspirobenzopyran, 3-methylnaphtho-(3-methoxybenzo)spiropyran, 1,3,3-trimethyl-6-nitro-8′-methoxyspiro(indoline-2,2′-benzopyran ) and the like; diphenylmethane compounds are not particularly limited, but specific examples thereof include N-halophenyl-leuco auramine, 4,4-bis-dimethylaminophenylbenzhydrylbenzyl ether, N-2, 4,5-trichlorophenyl leuco auramine and the like; thiazine compounds are not particularly limited, but specific examples thereof include benzoyl leucomethylene blue, p-nitrobenzoyl leuco methylene blue and the like; lactam compounds are particularly limited Specific examples thereof include rhodamine B anilinolactam, rhodamine B-p-chloroanilinolactam, etc.; fluorene compounds are not particularly limited, but specific examples include: 3,6-bis(dimethylamino)fluorene spiro(9,3′)-6′-dimethylaminophthalide, 3,6-bis(dimethylamino)fluorene spiro(9,3′)-6′-pyrrolidinophthalide de, 3-dimethylamino-6-diethylaminofluorene spiro(9,3′)-6′-pyrrolidinophthalide, etc.; the vinylphthalide compound is not particularly limited, but specific examples thereof include 3- [2,2-bis(4-diethylaminophenyl)vinyl]-6-dimethylaminophthalide (H-3035), 3,3-bis[2-(4-dimethylaminophenyl)-2-(4-methoxyphenyl ) Vinyl]-4,5,6,7-tetrachlorophthalide (NIR Black 78), and the like. These color-developing compounds can be used alone or in combination.

The color-developing compound used in the present invention is not particularly limited as long as it is generally used for pressure-sensitive recording paper or heat-sensitive recording paper. In one embodiment of the present invention, the color-developing compound includes, for example, phenol derivatives, benzotriazole derivatives, saccharin derivatives, sulfonamide derivatives, malonamide derivatives, thiourea derivatives, sulfonylurea derivatives, amino group-substituted diphenylsulfone derivatives, aromatic carboxylic acid derivatives, diphenylurea derivatives and the like.

A phenol derivative means a compound having a hydroxy group directly bonded to a benzene ring in the molecule, and those known per se can be used. Specific examples include α-naphthol, β-naphthol, p-octylphenol, 4-tert-octylphenol, p-tert-butylphenol, p-phenylphenol, 1,1-bis(p-hydroxyphenyl)propane, 2, 2-bis(p-hydroxyphenyl)propane (also known as bisphenol A or BPA), 2,2-bis(p-hydroxyphenyl)butane, 1,1-bis(p-hydroxyphenyl)cyclohexane, 4,4'- thiobisphenol, 4,4'-cyclo-hexylidenediphenol, 2,2'-bis(2,5-dibromo-4-hydroxyphenyl)propane, 4,4'-isopropylidenebis(2-tert-butylphenol) , 2,2′-methylenebis(4-chlorophenol), 4,4′-dihydroxydiphenylsulfone, 4-hydroxy-4′-methoxydiphenylsulfone, 4-hydroxy-4′-ethoxydiphenylsulfone, 4-hydroxy-4 '-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxydiphenylsulfone, 4-hydroxy-4'-vinyloxydiphenylsulfone, 4-hydroxy-4'-butoxydiphenylsulfone, 4-hydroxy-4'- Benzyloxydiphenylsulfone, 2,4'-dihydroxydiphenylsulfone, 3,3'-diallyl-4,4'-dihydroxydiphenylsulfone, 4-hydroxy-4'-allyloxydiphenylsulfone, bis(4-hydroxyphenyl)acetic acid methyl, butyl bis(4-hydroxyphenyl)acetate, benzyl bis(4-hydroxyphenyl)acetate, 2,4-dihydroxy-2'-methoxybenzanilide and the like.

Benzotriazole derivatives are not particularly limited, but specific examples thereof include benzotriazole, 5-methyl-1H-benzotriazole, 4-methyl-1H-benzotriazole, phenyl-6benzotriazole, phenyl- 5-benzotriazole, chloro-5-benzotriazole, chloro-5-methylbenzotriazole, chloro-5-isopropyl-7-methyl-4-benzotriazole, bromo-5-benzotriazole and the like.

The saccharin derivative is not particularly limited, but specific examples thereof include saccharin, 1-bromosaccharin, 1-nitrosaccharin, 1-aminosaccharin and the like.

The sulfonamide derivative is not particularly limited, but specific examples thereof include methanylanilide, N-phenyl-4-aminobenzenesulfonamide, neourilone, N-phenyl-3-nitrobenzenesulfonamide, N-(4 -methyl-2-nitrophenyl)benzenesulfonamide, N-(2-methoxyphenyl)-p-toluenesulfonamide, N-(4-methoxyphenyl)-p-toluenesulfonamide, N-(2-chlorophenyl)- p-toluenesulfonamide, N-(4-methylphenyl)-4-methylbenzenesulfonamide, N-(2-methylphenyl)-p-toluenesulfonamide, N-phenylbenzenesulfonamide, 4-bromo-4' -methylbenzenesulfonanilide, N-(4-bromophenyl)benzenesulfonamide, N-(3-nitrophenyl)benzenesulfonamide, N-(4-nitrophenyl)-4-methylbenzenesulfonamide, N-(4 -methylphenyl)benzenesulfonamide, N-phenyl-p-toluenesulfonamide, N-phenylbenzenesulfonamide and the like.

Malonamide derivatives are not particularly limited, but specific examples thereof include N,N'-bis(2-hydroxy-5-phenyl)phenyl-malonamide, N,N'-diphenylmalonamide, N, N'-bis(2,4,6-tribromophenyl)malonamide, N,N'-bis(2-aminophenyl)malonamide, N,N'-bis(m-trifluoromethylphenyl)malonamide, N,N '-bis(m-trifluoromethylphenyl)α, α-dichloromalonamide, diethylmalondianilide and the like.

The thiourea derivative is not particularly limited, but specific examples include 1,3-bis(4-methylphenyl)thiourea, 1,3-bisphenylthiourea, 1,3-bis( 4-chlorophenyl)thiourea, 1,3-bis(4-methoxyphenyl)thiourea, N,N'-bis(3-chlorophenyl)thiourea, 1,3-bis(3-methoxyphenyl)thiourea, 1 , 3-bis(3-methylphenyl)thiourea, 1,3-bis(4-benzylphenyl)thiourea, 1,3-bis(4-bromophenyl)thiourea, 1-phenyl-3-butylthiourea, 1-phenyl-3-ethylthiourea and the like.

The sulfonylurea derivative is not particularly limited, but specific examples thereof include N-(p-toluenesulfonyl)-N'-(3-n-butylaminosulfonylphenyl)urea, N-(p-toluene sulfonyl)-N'-(4-trimethylacetophenyl)urea, N-(benzenesulfonyl)-N'-(3-p-toluenesulfonyloxyphenyl)urea, N-(p-toluenesulfonyl)-N'-( 3-p-toluenesulfonylphenyl)urea, N-(p-toluenesulfonyl)-N'-(3-phenylsulfonyloxyphenyl)urea, tolbutamide, chlorpropamide and the like.

The diphenylsulfone derivative substituted with an amino group is not particularly limited, but specific examples thereof include 2-aminodiphenylsulfone, 2,2'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , 4,4′-diaminodiphenylsulfone, and the like.

The aromatic carboxylic acid derivative is not particularly limited, but specific examples include benzyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, dibenzyl 4-hydroxyphthalate, and dimethyl 4-hydroxyphthalate. , ethyl 5-hydroxyisophthalate, 3,5-di-tert-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, aromatic carboxylic acids or polyvalent metal salts thereof, and the like.

The diphenylurea derivative is not particularly limited, but specific examples thereof include 1,3-diphenylurea, 1-phenyl-3-(o-tolyl)urea, 1-phenyl-3-(m- tolyl)urea, 1-phenyl-3-(p-tolyl)urea, 1-(2-methoxyphenyl)-3-phenylurea, 1-(3-methoxyphenyl)-3-phenylurea, 1-(4- Methoxyphenyl)-3-phenylurea, 2-(3-phenylureido)phenylacetate, 3-(3-phenylureido)phenylacetate, 4-(3-phenylureido)phenylacetate, 2-(3-phenylureido) Phenylbenzoate, 3-(3-phenylureido)phenylbenzoate, 4-(3-phenylureido)phenylbenzoate, 2-(3-phenylureido)phenylacrylate, 3-(3-phenylureido)phenylacrylate, 4-( 3-phenylureido)phenyl acrylate, N-[2-(3-phenylureido)phenyl]acetamide, N-[3-(3-phenylureido)phenyl]acetamide, N-[4-(3-phenylureido)phenyl ] Acetamide, N-[2-(3-phenylureido)phenyl]benzamide, N-[3-(3-phenylureido)phenyl]benzamide, N-[4-(3-phenylureido)phenyl]benzamide, N- [2-(3-phenylureido)phenyl]benzenesulfonamide, N-[3-(3-phenylureido)phenyl]benzenesulfonamide, N-[4-(3-phenylureido)phenyl]benzenesulfonamide, [ 2-(3-phenylureido)phenyl] = 4-methylbenzenesulfonate, [3-(3-phenylureido)phenyl] = 4-methylbenzenesulfonate, [4-(3-phenylureido)phenyl] = 4 -methylbenzenesulfonate and the like.

In one embodiment of the present invention, a sensitizer (heat-fusible compound) may be included, and specific examples of the sensitizer (heat-fusible compound) include waxes such as animal and plant waxes and synthetic waxes. Higher fatty acids, higher fatty acid amides, higher fatty acid anilides, naphthalene derivatives, aromatic ethers, aromatic carboxylic acid derivatives, aromatic sulfonic acid ester derivatives, carbonic acid or oxalic acid diester derivatives, biphenyl derivatives, terphenyl derivatives, sulfone derivatives , aromatic ketone derivatives, and aromatic hydrocarbon compounds.

Waxes are not particularly limited, but specific examples thereof include Japan wax, carnauba wax, shellac, paraffin, montan wax, paraffin oxide, polyethylene wax, and polyethylene oxide. Although not limited, specific examples thereof include stearic acid, behenic acid and the like. Higher fatty acid amides are not particularly limited, but specific examples include stearic acid amide and oleic acid. amide, N-methylstearic acid amide, erucic acid amide, methylolbehenic acid amide, methylenebisstearic acid amide, ethylenebisstearic acid amide, etc., and the higher fatty acid anilide is not particularly limited, but its specific Examples thereof include stearic acid anilide, linoleic acid anilide, etc. Naphthalene derivatives are not particularly limited, but specific examples thereof include 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 1-hydroxy Examples include phenyl naphthoic acid, 2,6-diisopropylnaphthalene, etc. The aromatic ether is not particularly limited, but specific examples thereof include 1,2-diphenoxyethane, 1,4-diphenoxy butane, 1,2-bis(3-methylphenoxy)ethane, 1,2-bis(4-methoxyphenoxy)ethane, 1,2-bis(3,4-dimethylphenyl)ethane, 1-phenoxy-2-( 4-chlorophenoxy)ethane, 1-phenoxy-2-(4-methoxyphenoxy)ethane, 1,2-diphenoxymethylbenzene, diphenyl glycol and the like, and the aromatic carboxylic acid derivative is not particularly limited. Specific examples thereof include p-hydroxybenzoic acid benzyl ester, p-benzyloxybenzoic acid benzyl ester, terephthalic acid dibenzyl ester, etc. The aromatic sulfonate derivative is not particularly limited. Specific examples thereof include p-toluenesulfonic acid phenyl ester, phenylmesitylenesulfonate, 4-methylphenylmesitylenesulfonate, 4-tolylmesitylenesulfonate, etc. Carbonic acid or oxalic acid diester derivatives are particularly Specific examples include, but are not limited to, diphenyl carbonate, dibenzyl oxalate, di(4-chlorobenzyl) oxalate, di(4-methylbenzyl) oxalate, and the like. Although the biphenyl derivative is not particularly limited, specific examples thereof include p-benzylbiphenyl, p-allyloxybiphenyl, etc., and the terphenyl derivative is not particularly limited. , Specific examples thereof include m-terphenyl and the like, and the sulfone derivative is not particularly limited, but specific examples include p-toluenesulfonamide, benzenesulfonanilide, p-toluenesulfonanilide, , diphenylsulfone and the like, and the aromatic ketone derivative is not particularly limited, but specific examples thereof include 4,4'-dimethylbenzophenone, dibenzoylmethane, etc., and aromatic hydrocarbon compounds is not particularly limited, but specific examples thereof include p-acetotoluidine and the like.

One embodiment of the present invention may also contain a preservative, specific examples of which are 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2 '-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol ), 4,4′-butylidenebis(6-tert-butyl-m-cresol), 1-[α-methyl-α-(4′-hydroxyphenyl)ethyl]-4-[α′,α′-bis( 4′-hydroxyphenyl)ethyl]benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5 -tert-butylphenyl)butane, tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanurate, 4,4'-thiobis(3-methylphenol), 4,4'-dihydroxy- 3,3′,5,5′-Tetrabromodiphenylsulfone, 4,4′-dihydroxy-3,3′,5,5′-tetramethyldiphenylsulfone, 2,2-bis(4-hydroxy-3,5 -dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane and other hindered phenol compounds, 1 , 4-diglycidyloxybenzene, 4,4'-diglycidyloxydiphenylsulfone, 4-benzyloxy-4'-(2-methylglycidyloxy)diphenylsulfone, diglycidyl terephthalate, cresol novolak type epoxy resin, phenol novolak type Epoxy resins, epoxy compounds such as bisphenol A type epoxy resins, N,N'-di-2-naphthyl-p-phenylenediamine, sodium of 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate or polyvalent metal salts, bis(4-ethyleneiminocarbonylaminophenyl)methane and the like. For example, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-ethyl-6-tert-butylphenol), 2,2′-ethylidenebis(4,6-di -tert-butylphenol), 4,4'-thiobis(2-methyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 1-[α-methyl-α -(4'-hydroxyphenyl)ethyl]-4-[α',α'-bis(4'-hydroxyphenyl)ethyl]benzene, 1,1,3-tris(2-methyl-4-hydroxy-5- Cyclohexylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocyanate Nurate, 4,4'-thiobis(3-methylphenol), 4,4'-dihydroxy-3,3',5,5'-tetrabromodiphenylsulfone, 4,4'-dihydroxy-3,3',5 ,5′-tetramethyldiphenylsulfone, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2- Hindered phenol compounds such as bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,4-diglycidyloxybenzene, 4,4'-diglycidyloxydiphenylsulfone, 4-benzyloxy-4'-( Epoxy compounds such as 2-methylglycidyloxy)diphenylsulfone, diglycidyl terephthalate, cresol novolak type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, N,N'-di-2-naphthyl-p-phenylenediamine , sodium or polyvalent metal salt of 2,2′-methylenebis(4,6-di-tert-butylphenyl) phosphate, bis(4-ethyleneiminocarbonylaminophenyl)methane, ureaurethane compound (manufactured by Chemipro Kasei Co., Ltd.) color compound UU, etc.), and a diphenylsulfone crosslinked compound represented by the following formula (3) or a mixture thereof.

（式中、ａは０～６の整数である。）

(Wherein, a is an integer of 0 to 6.)

In one embodiment of the present invention, a binder may be included, and specific examples of the binder include methylcellulose, methoxycellulose, hydroxyethylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, cellulose derivatives such as cellulose, polyvinyl alcohol (PVA), ), carboxy-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, silyl-modified polyvinyl alcohol, diacetone-modified polyvinyl alcohol, acetoacetyl-modified polyvinyl alcohol, polyvinyl alcohol with various degrees of saponification and polymerization, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid Soda, starch and its derivatives, sulfosuccinates such as dioctyl sodium sulfosuccinate, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, fatty acid salts, casein, gelatin, water-soluble isoprene rubber, styrene/maleic anhydride Water-soluble substances such as alkali salts of polymers, alkali salts of iso(or diiso)butylene/maleic anhydride copolymers, or (meth)acrylic acid ester copolymers, styrene/(meth)acrylic acid ester copolymers Union, polyurethane, polyester polyurethane, polyether polyurethane, polyvinyl acetate, ethylene/vinyl acetate copolymer, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinylidene chloride, polystyrene, styrene/butadiene (SB) Copolymer, carboxylated styrene/butadiene (SB) copolymer, styrene/butadiene/acrylic acid copolymer, acrylonitrile/butadiene (NB) copolymer, carboxylated acrylonitrile/butadiene (NB) copolymer, colloidal Examples include hydrophobic polymer emulsions such as composite particles of silica and (meth)acrylic resin.

In one embodiment of the present invention, fillers may be included, and specific examples of fillers include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, kaolin, calcined kaolin, lithopone, talc, clay, Magnesium hydroxide, aluminum hydroxide, titanium oxide, zinc oxide, aluminum oxide, barium sulfate, diatomaceous earth, acid clay, bentonite, synthetic aluminum silicate, inorganic pigments such as surface-treated calcium carbonate and silica; urea-formalin resin, silicone Examples include resins, styrene-methacrylic acid copolymer resins, polystyrene resins, and organic pigments such as raw starch particles.

In one embodiment of the present invention, various additives other than those mentioned above can be included, for example, metal salts of higher fatty acids such as zinc stearate and calcium stearate for the purpose of preventing thermal head wear and sticking, UV absorbers such as phenol derivatives, benzophenone-based compounds, benzotriazole-based compounds, various cross-linking agents, surfactants, antifoaming agents, and the like for imparting antioxidation or antiaging effects are exemplified.

In the present invention, the composition ratio of each component of the thermosensitive recording layer is not particularly limited. 1 to 70% by mass, preferably 10 to 50% by mass of a developer compound; 0 to 80% by mass of a sensitizer, usually 0 to 30% by mass of a storage-improving agent, and a binder. usually 1 to 90% by mass, fillers are usually 0 to 80% by mass, and other lubricants, UV absorbers, cross-linking agents, surfactants, and antifoaming agents are each in arbitrary proportions, for example, each is usually 0 to 30% by mass. % (mass % is the solid content conversion mass ratio of each component in the thermosensitive recording layer).

The heat-sensitive recording layer of the present invention is prepared by using the above materials, for example, by the following method. According to one embodiment of the present invention, for example, water is used as a dispersion medium, and a color-forming compound and a color-developing compound are added, if necessary, together with a binder and other additives, to a ball mill, an attritor, or a sand mill. , a dispersion liquid pulverized and dispersed by a dispersing machine such as a high-pressure jet mill, and, if necessary, a coating liquid for a heat-sensitive recording layer prepared by mixing and stirring binders, fillers, and other additives, A support having a heat-sensitive recording layer is obtained by coating one side of the support with a dry weight of 1 to 20 g/m ² and drying.

There are no particular restrictions on the method of applying each of the above coating liquids onto the support, but according to one embodiment of the present invention, bar coating, air knife coating, variver blade coating, pure blade coating, and rod blade coating are used. Any known coating method such as coating, short dwell coating, curtain coating, die coating, etc. may be used. Each coating liquid may be applied and dried one by one to form each layer, or the same coating liquid may be applied in two or more layers. Furthermore, simultaneous multi-layer coating may be performed in which two or more layers are coated simultaneously.

<Middle layer>
In the heat-sensitive recording material, in order to prevent mixing of each layer and block harmful gases (oxygen, ozone, etc.) and components contained in the protective layer to the storage stability of the uncolored portion (background) and the colored recording portion, Alternatively, in order to improve glossiness, an intermediate layer may be provided on the color development side of the support having the heat-sensitive recording layer.

The intermediate layer is a layer provided between two layers and does not include a thermosensitive recording layer. Specifically, when two or more different types of thermosensitive recording layers are provided on the color developing surface side having the thermosensitive recording layer of the support, the thermosensitive recording layers (in the case of having a plurality of thermosensitive recording layers) means the heat-sensitive recording layer farthest from the support) and the overcoat layer.

The intermediate layer contains at least one resin selected from water-soluble resins and water-dispersible resins, as well as fillers and other additives according to the purpose and need.

As the water-soluble resin contained in the intermediate layer, any resin can be used as long as it exhibits barrier properties and does not impair the heat-sensitive recording properties and glossiness. Specifically, fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, carboxy-modified polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfone-modified polyvinyl alcohol, silanol-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, etc., having a polymerization degree of 200 to 2500. Water-soluble polymeric substances such as modified polyvinyl alcohol, hydroxyethyl cellulose, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as acetyl cellulose, (meth)acrylic acid ester, acrylic acid ester and/or methacrylic acid ester and styrene and/or acetic acid Vinyl copolymer, acrylamide/acrylic acid ester copolymer, acrylamide/acrylic acid ester/methacrylic acid terpolymer, colloidal silica composite acrylic acid ester copolymer, colloidal silica composite styrene/acrylic acid ester copolymer Acrylic acid ester-based resins such as polymers can be mentioned, but are not limited to these.

As the water-dispersible resin contained in the intermediate layer, any resin can be used as long as it exhibits barrier properties and does not impair the heat-sensitive recording properties and glossiness. Specifically, polyvinyl acetate, polyurethane, polyacrylic acid, polyacrylate, polyolefin, vinyl chloride-vinyl acetate copolymer, polybutyl methacrylate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer , styrene-butadiene copolymers, and styrene-butadiene-acrylic copolymers. Incidentally, the water-insoluble polymer may be used in the form of a latex.

The particle size distribution of the dispersed particles is not particularly limited, and may have a wide particle size distribution or a monodisperse particle size distribution.

Incidentally, even those materials which cannot impart barrier properties to the intermediate layer by themselves can be used in the intermediate layer by adding a cross-linking agent or the like to increase the barrier properties. As such a cross-linking agent, any agent may be used as long as it does not reduce the heat-sensitive recording properties and glossiness. , melamine resin, diglycidyl-based dimethylol urea such as glycerin diglycidyl ether, ammonium persulfate, ferric chloride, magnesium chloride, ammonium zirconium carbonate, hydrazine-based compounds, polyamide-epichlorohydrin-based compounds, and the like. is not limited to The amount of the cross-linking agent to be added may be appropriately adjusted according to the desired performance, and is, for example, about 0.05 to 0.35 parts per part of the resin component.

Specific examples of the filler include calcium carbonate, magnesium carbonate, magnesium oxide, silica, white carbon, kaolin, calcined kaolin, lithopone, talc, clay, magnesium hydroxide, aluminum hydroxide, titanium oxide, zinc oxide, and aluminum oxide. , barium sulfate, diatomaceous earth, acid clay, bentonite, synthetic aluminum silicate, inorganic pigments such as surface-treated calcium carbonate and silica; urea-formalin resin, styrene-methacrylic acid copolymer resin, polystyrene resin, organic such as raw starch particles A pigment etc. are mentioned.

Further, various additives other than those mentioned above can be used in the intermediate layer. , carnauba wax, polyethylene wax and other waxes, phenol derivatives for imparting antioxidant or anti-aging effects, UV absorbers such as benzophenone compounds and benzotriazole compounds, various surfactants, antifoaming agents, etc. mentioned.

In forming the intermediate layer, at least one resin selected from a water-soluble resin or a water-dispersible resin, and optionally a pigment and other additives are used in combination to form a coating solution for the intermediate layer, and the heat-sensitive recording layer A support having a heat-sensitive recording layer and an intermediate layer is obtained by coating and drying so that the solid content mass becomes 0.5 to 5 g/m ² .

In forming the intermediate layer, the resin is 50 to 100% by mass, the filler is usually 0 to 50% by mass, and other lubricants, waxes, ultraviolet absorbers, surfactants, and antifoaming agents are each in arbitrary proportions. , for example, each is usually used in an amount of 0 to 30 mass % (mass % is the mass ratio of each component in the intermediate layer). Further, in the heat-sensitive recording material of the present invention, a resin, a filler and other additives known per se may be used in combination with the above components.

The method for applying each of the intermediate layer coating liquids onto the thermosensitive recording layer is not particularly limited, but according to one embodiment of the present invention, bar coating, air knife coating, variver blade coating, pure blade coating are used. Any of the known coating methods such as coating, rod blade coating, short dwell coating, curtain coating, die coating, etc. may be used. Each coating liquid may be applied and dried one by one to form each layer, or the same coating liquid may be applied in two or more layers. Furthermore, simultaneous multi-layer coating may be performed in which two or more layers are coated simultaneously.

In the heat-sensitive recording material of the present invention, an oil-in-water emulsion of the energy ray-curable resin composition of the present invention is applied as a coating liquid for an overcoat layer on the heat-sensitive recording layer or intermediate layer obtained by the above method. By a method known per se, such as coater coating, air knife coating, gravure coating, offset printing, flexographic printing, screen printing, etc., the coating is applied, dried, and then irradiated with energy rays such as ultraviolet rays and electron beams. It is obtained by curing the film to form an overcoat layer. The coating amount of the coating solution for the overcoat layer is not particularly limited. Due to the problem of film cracking, it is usually preferably 0.5 to 10 g/m ² , more preferably 1 to 5 g/m ² . When curing the coating film with an electron beam, an electron beam accelerator having an energy of 100 to 500 eV is preferred. On the other hand, when curing with ultraviolet rays, an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, a UV-LED lamp, etc. is used as a light source, and the amount of light, the arrangement of the light source, etc. are determined as necessary. When a high-pressure mercury lamp is used, it is preferable to cure by irradiating 1 to 4 times with a lamp having a light quantity of 80 to 200 W/cm at a conveying speed of 5 to 60 m/min.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples. "Parts" in the examples are parts by mass, and "%" in the description of solutions is mass %.

[Example 1] Preparation of heat-sensitive recording material (Formation of heat-sensitive recording layer)
A mixture of the following composition was measured using a bead mill (Labostar Mini LMZ015, manufactured by Ashizawa Finetech Co., Ltd.), and a median particle size measured by a laser diffraction/scattering particle size distribution analyzer (Microtrac MT3300EXII, manufactured by Microtrac Bell Co., Ltd.). was pulverized and dispersed so as to have a diameter of 0.5 μm to prepare a dispersion liquid [A] of a color developing compound.

[A] Liquid:
Bis (3-allyl-4-hydroxyphenyl) sulfone having an α-type crystal form (see JP-A-11-29549) 30.0 parts modified polyvinyl alcohol (Gohsenex L-3266 manufactured by Mitsubishi Chemical Corporation)
20% aqueous solution 15.0 parts Water 55.0 parts

A mixture of the following composition was measured using a bead mill (Labostar Mini LMZ015, manufactured by Ashizawa Finetech Co., Ltd.), and a median particle size measured by a laser diffraction/scattering particle size distribution analyzer (Microtrac MT3300EXII, manufactured by Microtrac Bell Co., Ltd.). was pulverized and dispersed so as to have a particle size of 0.5 μm to prepare a dispersion liquid [B] of a color-developing compound.
[B] Liquid:
3-dibutylamino-6-methyl-7-anilinofluorane 30.0 parts denatured polyvinyl alcohol (Mitsubishi Chemical Corporation Gohsenex L-3266)
20% aqueous solution 15.0 parts Water 55.0 parts

Next, [A] solution, [B] solution and 48% modified styrene/butadiene copolymer latex were mixed in the following composition to prepare a thermosensitive recording layer coating solution. A transparent film (polyethylene terephthalate film, Cosmoshine A4100 manufactured by Toyobo Co., Ltd., thickness 50 μm) was used as a support, and the resulting coating solution was applied on one side of the film so that the dry mass was 7 g/m ² , and dried. Thus, a heat-sensitive recording material of the present invention was produced.
[A] Liquid 20.0 parts [B] Liquid 10.0 parts 48% modified styrene-butadiene copolymer latex 16.7 parts Water 53.3 parts

(Formation of intermediate layer)
Next, an intermediate layer coating solution having the following composition was coated on the thermosensitive recording layer so that the dry weight was 2 g/m ² and dried to prepare a thermosensitive recording material with an intermediate layer.
25% ethylene/acrylic acid copolymer emulsion 40.7 parts 5% bentonite aqueous dispersion 20.0 parts Water 39.3 parts

(Formation of overcoat layer)
First, calcium carbonate is dispersed in a mixture of dipentaerythritol hexaacrylate and EO-modified bisphenol A.diacrylate, and then a photopolymerization initiator is added and mixed. Next, an aqueous solution in which Latemul PD-450 and Aqualon AR-20 are dissolved is gradually added, emulsified and dispersed, and then a zinc stearate dispersion is added to obtain an energy ray-curable composition of the present invention having the following composition. An oil-in-water emulsion of the resin composition was prepared to obtain an overcoat layer coating liquid of Example 1. This overcoat layer coating solution is coated on the heat-sensitive recording material with the intermediate layer by using a bar coater so that the dry weight is 3 g/m ² , dried, and then applied to the coated surface in an air atmosphere. The energy ray-curable resin composition was cured by irradiating once at a conveyer speed of 20 m/min using an ultraviolet irradiator having a high-pressure mercury lamp of 80 W/cm, and a heat-sensitive recording material of Example 1 was obtained.
Dipentaerythritol hexaacrylate 26.0 parts EO-modified bisphenol A diacrylate 10.0 parts α-hydroxyketone initiator
(Omnirad 184 manufactured by IGM Resins) 4.0 parts Calcium carbonate (Luminous manufactured by Maruo Calcium Co., Ltd.,
Average particle size 0.5 μm or less) 4.0 parts reactive surfactant (Latemul PD-450 manufactured by Kao Corporation,
Concentration 100%, R = methyl group in formula (1)) 3.3 parts Reactive surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Aqualon AR-20,
Concentration 97%, T=SO ₃ NH ₄ in formula (2), n2=20) 1.0 parts Zinc stearate dispersion (Hymicron L-111 manufactured by Chukyo Yushi Co., Ltd.,
Concentration 20%, average particle size 0.3 μm or less) 8.5 parts Water 43.2 parts

[Example 2]
An oil-in-water emulsion and a heat-sensitive recording material of Example 2 were obtained in the same manner as in Example 1, except that the overcoat layer coating liquid of Example 1 was changed to the following composition.
Dipentaerythritol hexaacrylate 26.0 parts EO-modified bisphenol A diacrylate 10.0 parts α-hydroxyketone initiator (OMnirad 184 manufactured by IGM Resins)
4.0 parts calcium carbonate (Luminous manufactured by Maruo Calcium Co., Ltd., average particle size 0.5 μm or less)
4.0 parts reactive surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Aqualon AN-5065,
Concentration 65%, T = hydrogen atom, n2 = 50 in formula (2)) 5.0 parts reactive surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Aqualon AR-20,
Concentration 97%, T=SO ₃ NH ₄ in formula (2), n2=20) 1.0 parts Zinc stearate dispersion (Hymicron L-111 manufactured by Chukyo Yushi Co., Ltd.,
Concentration 20%, average particle size 0.3 μm or less) 8.5 parts Water 41.5 parts

[Comparative Example 1]
An oil-in-water emulsion and a heat-sensitive recording material of Comparative Example 1 were obtained in the same manner as in Example 1, except that the overcoat layer coating liquid of Example 1 was changed to the following composition.
Dipentaerythritol hexaacrylate 26.0 parts EO-modified bisphenol A diacrylate 10.0 parts α-hydroxyketone initiator (OMnirad 184 manufactured by IGM Resins)
4.0 parts calcium carbonate (Luminous manufactured by Maruo Calcium Co., Ltd., average particle size 0.5 μm or less)
4.0 parts reactive surfactant (Daiichi Kogyo Seiyaku Co., Ltd. Aqualon RN-50,
Ingredient name: Polyoxyethylene nonylpropenyl phenyl ether and
Polyoxyethylene nonylphenyl ether, concentration 65%) 5.0 parts Reactive surfactant (Antox MS-60 manufactured by Nippon Nyukazai Co., Ltd.,
Ingredient name: Bis (polyoxyethylene polycyclic phenyl ether)
Methacrylate sulfate, concentration 90%) 1.0 parts Water 50.0 parts

[Comparative Example 2]
An oil-in-water emulsion and a heat-sensitive recording material of Comparative Example 2 were obtained in the same manner as in Example 1, except that the zinc stearate dispersion in the overcoat layer coating solution of Example 1 was omitted.

[Comparative Example 3]
Example 1 except that in the overcoat layer coating solution of Example 1 above, the zinc stearate dispersion was removed and 0.5 parts of polyethylene wax emulsion (Polylon L-788 manufactured by Chukyo Yushi Co., Ltd., concentration 31%) was used. In the same manner as above, an oil-in-water emulsion and a heat-sensitive recording material of Comparative Example 3 were obtained.

[Comparative Example 4]
Comparative Example 4 was carried out in the same manner as in Example 1 except that in the overcoat layer coating solution of Example 1 above, 0.5 parts of polyethylene wax emulsion (Polylon L-788 manufactured by Chukyo Yushi Co., Ltd., concentration 31%) was used in combination. An oil-in-water emulsion and a heat sensitive recording material were obtained.

[Comparative Example 5]
An oil-in-water emulsion and a heat-sensitive recording material of Comparative Example 5 were obtained in the same manner as in Example 2, except that the zinc stearate dispersion in the overcoat layer coating liquid of Example 2 was omitted.

[Comparative Example 6]
Example 2 except that in the overcoat layer coating solution of Example 2 above, the zinc stearate dispersion was excluded and 0.5 parts of polyethylene wax emulsion (Polylon L-788 manufactured by Chukyo Yushi Co., Ltd., concentration 31%) was used. In the same manner as above, an oil-in-water emulsion and a heat-sensitive recording material of Comparative Example 6 were obtained.

[Comparative Example 7]
Comparative Example 7 was carried out in the same manner as in Example 2 except that 0.5 parts of polyethylene wax emulsion (Polylon L-788 manufactured by Chukyo Yushi Co., Ltd., concentration 31%) was used in the overcoat layer coating solution of Example 2 above. An oil-in-water emulsion and a heat sensitive recording material were obtained.

[Presence or absence of surfactant having a nonylphenol structure]
Table 1 above summarizes the components used in Examples 1 and 2 and Comparative Examples 1 to 7. Regarding the reactive surfactant (B), the presence or absence of a surfactant having a nonylphenol structure Descriptions are based on descriptions in relevant product catalogs and SDSs (Safety Data Sheets).

[Evaluation of emulsion state]
Each of the obtained oil-in-water emulsions was allowed to stand at room temperature, and the stability was evaluated according to the following criteria by visually observing the state of water separation and oil floating. The results are shown in Table 2 below.
◯: Stable emulsion with no water separation or oil floating.
Δ: Slight water separation or oil floating is observed, but redispersibility is good.
x: Remarkable separation of the oil phase and the water phase is observed, and the emulsification is broken.

[Evaluation of Thermal Head Suitability (Noise)]
For each of the obtained thermal recording materials, a checkered pattern was printed using a thermal printer (high quality label printer BP-4000) manufactured by Ishida Co., Ltd. 136, 144, 152, 161, 169, 178, 186, 194 μJ/dot in order to print a total of 12 points continuously, thermal head: BHP6417FS-SE manufactured by TDK Corporation). Printer noise caused by adhesion of the protective layer of the thermal recording material to the printer head during printing was evaluated according to the following criteria. The results are shown in Table 2 below.
A: No or almost no noise.
(triangle|delta): Noise arises.
x: Loud noise.

[Evaluation of Thermal Head Suitability (Print Length Ratio)]
For each of the obtained thermal recording materials, a checkered pattern was printed using a thermal printer (high quality label printer BP-4000) manufactured by Ishida Co., Ltd. 136, 144, 152, 161, 169, 178, 186, 194 μJ/dot in order to print a total of 12 points continuously, thermal head: BHP6417FS-SE manufactured by TDK Corporation). The print length ratio at the time of printing was obtained by the following formula (I). The results are shown in Table 2 below.
Print length ratio (%) = (print length for each thermal recording material)/(normal print length) x 100 (I)
The print length is the length of print from the print start part to the print last part when a specific print pattern is printed by a printer. On the other hand, if the sticking property is poor, the same part of the thermal recording material is printed in duplicate, and meandering of the thermal recording material occurs, resulting in a short print length and a low print length ratio. .

[Evaluation of thermal head aptitude (head residue resistance)]
Solid printing was performed on each of the obtained thermal recording materials using a thermal paper printing evaluation tester TH-M2/PP manufactured by Okura Engineering Co., Ltd. (applied voltage: 19 V, pulse width: 1.4 msec, applied energy : 0.54 mJ/dot, thermal head: LH4114WK manufactured by Toshiba Hokuto Electronics Co., Ltd.). The state of deposits on the thermal head after printing was visually observed and evaluated according to the following criteria. The results are shown in Table 2 below.
◯: There is no deposit or almost no deposit.
Δ: Deposits are present.
x: A lot of deposits.

[Storage stability test (plasticizer resistance test)]
A vinyl chloride wrap film (containing a plasticizer) is wrapped around a glass plate twice, and a checkered pattern (printing part applied energy is 169 μJ/dot, thermal head: BHP6417FS-SE manufactured by TDK Corporation). It was left at 40° C. for 24 hours while being double wrapped with the same vinyl chloride wrap film. Before and after the test, the density of the color-developed recording portion of the heat-sensitive recording material was measured using a fluorescence spectrodensitometer FD-7 manufactured by Konica Minolta. Colorimetry was performed under the conditions of illuminant C as an observation light source, standard illuminant A as a density illumination condition, ISO Status A as a density status, and a viewing angle of 2 degrees. The results are shown in Table 2 below. The results were evaluated according to the following criteria based on the survival rate calculated by the following formula (II).
Residual rate (%)=(Density of color-developed recorded portion of thermal recording material after test)/(Density of color-developed recorded portion of thermal recording material before test)×100 (II)
○: The residual rate is 95% or more, and the plasticizer resistance is very good. △: The residual rate is 80% or more and less than 95%, but there is no practical problem in the plasticizer resistance.
x: Residual rate is less than 80%, and there is a problem with plasticizer resistance.

[Storage stability test (oil resistance test)]
Using a thermal printer manufactured by Ishida Co., Ltd. (high quality label printer BP-4000), the above Example 1 printed with a checkered pattern (energy applied to the printing unit is 169 μJ / dot, thermal head: BHP6417FS-SE manufactured by TDK Corporation) and 2. Three drops of salad oil were dropped on the color-developing recording portions of the heat-sensitive recording materials obtained in Comparative Examples 1 to 7 and allowed to stand at 40° C. for 24 hours. Before and after the test, the density of the color-developed recording portion of the heat-sensitive recording material was measured using a fluorescence spectrodensitometer FD-7 manufactured by Konica Minolta. Colorimetry was performed under the conditions of illuminant C as an observation light source, standard illuminant A as a density illumination condition, ISO Status A as a density status, and a viewing angle of 2 degrees. The results are shown in Table 2 below. The results were evaluated according to the following criteria based on the survival rate calculated by the following formula (III).
Residual rate (%) = (Density of color-developed recording portion of thermal recording material after test)/(Density of color-developed recording portion of thermal recording material before test) x 100 (III)
○: The residual rate is 95% or more, and the oil resistance is very good. △: The residual rate is 80% or more and less than 95%, but the oil resistance is practically no problem.
x: Residual rate is less than 80%, and there is a problem with oil resistance.

[Evaluation of transparency]
The HAZE values of the heat-sensitive recording materials obtained in Examples 1 and 2 and Comparative Examples 1 to 7 were measured with a haze meter manufactured by Tokyo Denshoku Co., Ltd. (product name: Automatic Haze Meter TG-H3DPK). The results are shown in Table 2 below. Incidentally, the smaller the HAZE value, the higher the transparency and the better, and practically, it is required to be 25 or less.

[Example 3]
A white polyethylene terephthalate film (Lumirror E22 #188 manufactured by Toray Industries, Inc., thickness 188 μm) was used instead of a transparent polyethylene terephthalate film (Cosmoshine A4100 manufactured by Toyobo Co., Ltd., thickness 50 μm) as the support in Example 1 above, and thermal recording was performed. A test film of Example 3 was obtained in the same manner as in Example 1, except that the oil-in-water emulsion described in Example 1 was coated directly onto the support without a layer or intermediate layer.

[Example 4]
A test film of Example 4 was obtained in the same manner as in Example 3, except that the oil-in-water emulsion described in Example 2 was used instead of the oil-in-water emulsion in Example 3 above.

[Comparative Examples 8 to 14]
Test films of Comparative Examples 8 to 14 were prepared in the same manner as in Example 3 except that the oil-in-water emulsions described in Comparative Examples 1 to 7 were used instead of the oil-in-water emulsions in Example 3 above. Obtained.

[Glossiness evaluation]
The 60° gloss Gs (60°) (JIS Z 8741) of each test film was measured with a gloss meter manufactured by Nippon Denshoku Co., Ltd. (trade name: handy gloss meter PG-II). Table 3 shows the results. It should be noted that the larger the value, the higher the glossiness and the better.

From the results of Tables 1 and 2, the oil-in-water emulsion of the energy beam-curable resin composition of the present invention using the reactive surfactant represented by formula (1) or formula (2) has a nonylphenol structure. Comparative Example 1 using a conventionally known oil-in-water emulsion described in Patent Document 9 and a conventionally known oil-in-water emulsion described in Patent Document 11. Compared with Examples 2 and 5, the emulsion stability is comparable. Further, the thermosensitive recording material of the present invention having the cured film layer of the energy ray-curable resin composition as an overcoat layer was excellent in thermal head suitability (noise, print length ratio, head residue resistance) in Comparative Examples 1, 2, It is found to be better than 3, 5 and 6. On the other hand, although the results in terms of thermal head suitability are the same as those of Comparative Examples 4 and 7, the results in Table 3 show that the oil-in-water emulsions obtained in Comparative Examples 4 and 7 were applied to a white polyethylene terephthalate film. Comparing Comparative Examples 11 and 14, which correspond to the 60° glossiness after being directly coated on the surface, with Examples 3 and 4, Examples 3 and 4 are superior, and the heat-sensitive recording material of the present invention is superior. It turns out to be excellent.

From the above results, the oil-in-water emulsion of the energy ray-curable resin composition of the present invention does not contain a surfactant having a nonylphenol structure, so it is more friendly to the human body and the environment than conventionally known emulsions. In addition, it can be said that it is suitable for forming a thermal recording material that is more excellent in thermal head aptitude while maintaining high transparency, high glossiness, and high storage stability of the color-developed recording portion.

Claims (11)

A resin (A) having an ethylenically unsaturated group in the molecule, a reactive surfactant (B) represented by formula (1) or formula (2), and a pigment component (C) having an average particle size of 5 μm or less and a lubricant component (D) having an average particle size of 1.5 µm or less.

(Wherein, R represents a hydrogen atom or a methyl group, A represents an alkylene group having 2 to 4 carbon atoms, and m represents the average added mole number in the range of 2 to 80)

(Wherein, n1 represents the average number of substituents of 1 to 3, n2 represents the average number of added moles in the range of 0 to 100, T is a hydrogen atom or -(CH ₂ ) _a -SO ₃ M, —(CH ₂ ) _b —COOM, —PO ₃ M ₂ , and —CO—CH ₂ —CH—(SO ₃ M)—COOM, in which a and b are each represents a number from 0 to 4, and each M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium residue, or an alkanolamine residue). Preferably, the oil-in-water emulsion of the present invention does not contain a compound having a nonylphenol structure. The energy ray-curable resin composition according to [1], wherein at least one of the reactive surfactants (B) is a compound represented by formula (2) in which T is a hydrogen atom or —SO ₃ NH ₄ . of oil-in-water emulsion. [1], wherein the reactive surfactant (B) includes a compound represented by formula (1) and a compound represented by formula (2) in which T is —SO ₃ NH ₄ An oil-in-water emulsion of an energy ray-curable resin composition. The reactive surfactant (B) includes a compound represented by the formula (2) in which T is a hydrogen atom and a compound represented by the formula (2) in which T is —SO ₃ NH ₄ , An oil-in-water emulsion of the energy ray-curable resin composition according to [1]. Any one of [1] to [4], wherein the pigment component (C) is an inorganic pigment, and the content thereof is 0.5 to 50% by mass with respect to the total solid content of the energy ray-curable resin composition. 2. An oil-in-water emulsion of the energy ray-curable resin composition according to 1. The oil-in-water emulsion of the energy ray-curable resin composition according to any one of [1] to [5], wherein the pigment component (C) is calcium carbonate. Any one of [1] to [6], wherein the lubricant component (D) is a metal salt of a higher fatty acid, and the content thereof is 0.1 to 30% by mass relative to the total solid content of the energy ray-curable resin composition. An oil-in-water emulsion of the energy ray-curable resin composition according to any one of the above. The oil-in-water emulsion of the energy beam-curable resin composition according to any one of [1] to [7], wherein the lubricant component (D) is zinc stearate. An overcoat agent comprising the oil-in-water emulsion according to any one of [1] to [8]. A heat-sensitive recording material having a heat-sensitive recording layer and an overcoat layer on a support, wherein the overcoat layer comprises a cured film layer of the overcoat agent described in [9]. A heat-sensitive recording material according to [10], wherein the heat-sensitive recording material has a HAZE value of 25 or less and a glossiness of 75 or more.