JP2001310560A - Recording material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a recording material having a commercially usable water resisting property in which a coated layer and fibers are easily separated in a releasing and decomposing process in a waste-paper recycling treatment. SOLUTION: An undercoat layer, which contains a filler and a polymer having a water-insoluble and alkali-soluble properties as main components, is provided between a paper support and a thermal color forming layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a recording material, and more particularly, to a heat-sensitive recording material, a heat-sensitive magnetic recording material, and a heat-transfer type magnetic recording material having improved disintegration properties in a used paper recycling process after use and recovery. It is about.

[0002]

2. Description of the Related Art Thermosensitive recording paper is an application of recording paper in which a colorless leuco dye, which is usually colorless or pale, and a color developing agent such as an organic acidic substance develop a color by a melting reaction when heated. Examples thereof are disclosed in Japanese Patent Publication No. Sho 43-4160 and Japanese Patent Publication No. 45-14039, and are well known.

[0003] These thermosensitive recording papers have been applied to a wide range of fields, such as measuring recorders, terminal printers such as computers, facsimile machines, automatic ticket vending machines, and bar code labels. As the performance has been improved, the required quality of the heat-sensitive recording paper has become higher.

On the other hand, due to the recent increase in the movement of resource conservation, papers contained in municipal garbage have been particularly highlighted, and paper garbage discharged from offices and factories in particular has spurred an increase in the total amount of garbage. I have. Therefore, it is desired to collect such waste paper and use it as a raw material for recycled paper.

[0005] However, thermosensitive recording paper is not yet available at present.
It is considered a contraindication to purchase used paper. this is,
This is because the heat-sensitive recording layer component used in the heat-sensitive recording paper, which cannot be completely separated during the waste paper recycling process and is mixed in the recycled paper, re-colors when the recycled paper is heated and dried, thereby lowering the whiteness of the recycled paper. .

One of the reasons why the heat-sensitive coloring layer component is mixed is as follows.
The heat dissipating property (the property of peeling and decomposing) of the heat-sensitive coloring layer from the support (paper) at the time of recycling waste paper of the heat-sensitive recording paper is poor. This raises the wet strength of the paper support in order to prevent paper breakage in the coating machine when applying the thermosensitive coloring layer forming liquid to the paper support of the thermosensitive recording paper and to increase the water resistance to external moisture. Due to the use of wet strength agents in the paper support.

Therefore, since the paper support is added with a wet strength enhancer to withstand moisture adhesion, that is, wet under water absorption and does not shrink, the paper support does not shrink wet. The thermosensitive coloring layer is difficult to disintegrate.

[0008] Therefore, when the heat-sensitive recording paper mixed in ordinary waste paper is supposed to be regenerated, it is preferable that the heat-sensitive coloring layer be disintegrated quickly, and in that sense, a heat-sensitive recording paper having a low wet strength is required. However, such a thermosensitive recording paper having a low wet strength has a problem in that the paper support cannot withstand the tension applied by the coating machine during the coating process of the thermosensitive coloring layer component, and the paper is cut off, thereby reducing the productivity of stopping the machine. There is a conflicting problem of inviting.

Regarding the recycling of waste paper including thermal recording paper, for example, JP-A-63-135585 describes
A method is described in which a step of neutralizing after disaggregation, a flotation step, a dehydration / concentration step also serving as washing, and a step of disaggregating remaining undisintegrated fibers by a high-speed disintegrator are described. JP-A-63-1
No. 82487 proposes to add an organic solvent. In addition, Japanese Patent Application Laid-Open No. Hei 3-248884 discloses a method of adding an antifoaming agent after deflocculation of an alkali and washing it.

However, any of these methods is intended to solve the problem of recoloring of the heat-sensitive recording paper, but solves the problem of the difficulty in disintegration of the heat-sensitive recording paper itself, which is a problem at the time of recycling the used heat-sensitive recording paper. Has not been done.

[0011] Again, the recycling of waste paper is as follows:
In general, the paper is disintegrated in an alkaline aqueous solution having a pH of 9 to 11 as in papermaking. In this case, the solid component that is difficult to be decomposed or divided may be removed as dust or may be directly transferred to papermaking. It is preferable to remove the dust as dust, but if the heat-sensitive coloring layer component is adhered to the paper fiber without clearly separating the paper support and the heat-sensitive coloring layer, it is inappropriate to use this for papermaking.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks, that is, to prevent paper breakage in a coating machine when applying a coating liquid to a paper support and to reduce water resistance during use. It is an object of the present invention to provide a recording material which can improve the disintegration and facilitate the disintegration at the time of regenerating decomposition.

According to the present invention, there is firstly provided a thermosensitive recording material comprising an undercoat layer and a thermosensitive coloring layer mainly composed of a leuco dye and a color developer which are sequentially laminated on one surface of a support, A heat-sensitive recording material is provided, wherein the coat layer contains a filler and a water-insoluble alkali-soluble polymer as main components.

Second, a filler is further provided on the thermosensitive coloring layer.
The heat-sensitive recording material according to the first aspect, further comprising a protective layer mainly containing a crosslinking agent and a water-soluble polymer compound.

Third, the heat-sensitive recording material according to the above-mentioned first, characterized in that a protective layer mainly containing a filler, a crosslinking agent and a water-insoluble alkali-soluble polymer is further provided on the heat-sensitive recording layer. Is provided.

Fourth, the backing layer having a filler and a water-insoluble alkali-soluble polymer as main components is provided on the other surface of the support. A thermal recording material is provided.

Fifth, on the other surface of the support or on the back coat layer provided thereon, an adhesive layer and a release liner,
Alternatively, there is provided the heat-sensitive recording material according to any one of the above first to fourth, wherein a linerless pressure-sensitive adhesive layer is laminated.

Sixth, a magnetic recording layer containing a magnetic material is provided on one surface of the support, and an undercoat layer, a thermosensitive coloring layer mainly containing a leuco dye and a developer are provided on the other surface of the support. Are provided, wherein the undercoat layer comprises a filler and a water-insoluble alkali-soluble polymer as main components.

A seventh aspect of the present invention is the thermosensitive magnetic device according to the sixth aspect, wherein an undercoat layer containing a filler and a water-insoluble alkali-soluble polymer as main components is provided between the support and the magnetic recording layer. A recording material is provided.

Eighth, a filler is further provided on the thermosensitive coloring layer.
The heat-sensitive recording material according to the sixth or seventh aspect, further comprising a protective layer mainly containing a crosslinking agent and a water-soluble polymer compound.

Ninth, a filler is further provided on the thermosensitive coloring layer.
The heat-sensitive magnetic recording material according to the sixth or seventh aspect, further comprising a protective layer comprising a crosslinking agent and a water-insoluble alkali-soluble polymer as main components.

Tenthly, there is provided a thermal transfer type magnetic recording material in which a magnetic recording layer containing a magnetic material is provided on one surface of a support, and an undercoat layer and a receiving layer are laminated on the other surface of the support. A thermal transfer type magnetic recording material is provided, wherein the undercoat layer comprises a filler and a water-insoluble alkali-soluble polymer as main components.

An eleventh aspect of the present invention is the thermal transfer type of the tenth aspect, wherein an undercoat layer containing a filler and a water-insoluble alkali-soluble polymer as main components is provided between the support and the magnetic recording layer. A magnetic recording material is provided.

A water-resistant layer (for example, a layer containing a sizing agent) for preventing water from entering is originally provided on the coated side surface of a paper support used for a heat-sensitive recording material, a heat-sensitive or thermal transfer-type magnetic recording material, or the like. However, in the present invention, the undercoat layer containing the water-insoluble alkali-soluble polymer itself can serve both the function and the layer.

Considering the reproduction of the recording material, the water-soluble polymer seems to be more preferable than the water-insoluble alkali-soluble polymer in terms of disaggregation at the time of reproduction. To wake up
There is a problem that the water resistance at the time of use is lowered, and when a normal water-insoluble polymer is used, waterproofing, that is, prevention of water intrusion, paper cutting and water resistance are preferable, but there is a problem that it cannot be disaggregated at the time of reproduction. . The present invention solves such a disadvantage.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The recording material of the present invention is characterized in that the polymer constituting the undercoat layer coated on the support (paper) is water-insoluble, so that the water used in coating the thermosensitive coloring layer component, the adhesive layer component, etc. To prevent infiltration of paper, prevent paper breakage, and improve water resistance during normal use.

On the other hand, at the time of regenerative decomposition, since the above-mentioned polymer constituting the undercoat layer is alkali-soluble, the undercoat layer is melted by the disaggregation treatment, and the heat-sensitive coloring layer or more on the undercoat layer is easily peeled off. It is very convenient because all of the material, ie, dust, is removed, and only paper quality can be separated and obtained (gain). Therefore, recycled paper that has good recycling efficiency, does not contain impurities, and does not develop color when recycled and dried. The effect is obtained.

In the recording material of the present invention, it is preferable to provide a protective layer on the heat-sensitive recording layer for the purpose of improving the matching property of a thermal head or the like and enhancing the storage stability of a recorded image. When the same material as the undercoat layer, that is, composed of a filler and a water-insoluble alkali-soluble polymer as main components, increases water resistance during normal use and dissolves during regeneration decomposition, without preventing water intrusion. Smooth infiltration of water occurs and promotes disintegration from the undercoat layer. It is preferable that a crosslinking agent is added to this protective layer.

Further, a back coat layer may be provided on the back surface of the support, and this back coat layer is preferably made of the same material as the above-mentioned undercoat layer. The layer provided on the back coat layer can be easily peeled off by the defibration treatment. If necessary, an adhesive layer and a release paper for sealing may be provided on the back coat layer, or a thermal adhesive layer (linerless adhesive layer) which exhibits adhesiveness by heat may be provided. It may be. In this case, the peeling layer does not have to be removed in advance at the time of reproduction, and if there is, there is no problem because the peeling is easy.

The "water-insoluble alkali-soluble polymer" used as a binder of the undercoat layer and the backcoat layer of the present invention is not particularly limited, but is not soluble in water but is immersed in and contacted with an aqueous alkali solution. Preferred are those that dissolve or swell and that dissolve or swell the coating film with a 1% aqueous solution of NaOH. Specific examples include acrylate (co) polymers, styrene / acrylic copolymers, epoxy resins, polyvinyl acetate, polyvinylidene chloride, polyvinyl chloride, and derivatives thereof.

The filler used in combination with the water-insoluble alkali-soluble polymer is not particularly limited. The amount of the filler to be used with respect to the water-insoluble alkali-soluble polymer is 1 to 1 part by weight of the alkali-soluble polymer in terms of solid content. ５０50 parts by weight, preferably 5-30 parts by weight.
When the amount is less than this range, there are problems such as coatability during production and drying properties, and when the amount is too large, the support, the heat-sensitive coloring layer, the adhesiveness with the pressure-sensitive adhesive layer or the heat-sensitive adhesive layer, the fading of the color image, the water Problems such as dissolution of the layer during immersion occur.

As the filler, a well-known organic or inorganic filler is usually used, but a hollow particle filler may also be used. In particular, since the hollow particle filler has good heat insulating properties, it has an effect of blocking the transfer of heat from the heat-sensitive coloring layer to the support, thereby increasing the heat sensitivity of the heat-sensitive coloring layer.

In the heat-sensitive recording material of the present invention, the undercoat layer and the backcoat layer may be provided, if necessary, with conventionally known water-soluble polymers, water-proofing agents, surfactants, heat-soluble substances and other auxiliary substances. Agents can be used.

The leuco dye used in the thermosensitive coloring layer of the present invention is used alone or as a mixture of two or more kinds. As such a leuco dye, those applied to this kind of thermosensitive material can be arbitrarily applied. For example, leuco compounds of dyes such as triphenylmethane type, fluoran type, phenothiazine type, auramine type, spiropyran type and indolinophthalide type are preferably used. Specific examples of such leuco dyes include, for example, those shown below.

3,3-bis (p-dimethylaminophenyl) -phthalide, 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (also known as crystal violet lactone), 3,3-bis ( p-dimethylaminophenyl) -6-diethylaminophthalide 3,
3-bis (p-dimethylaminophenyl) -6-chlorophthalide, 3,3-bis (p-dibutylaminophenyl) phthalide, 3-cyclohexylamino-6-chlorofluoran, 3-dimethylamino-5,7-dimethyl Fluoran, 3-dienitylamino-7-chlorofluoran, 3-diethylamino-7-methylfluoran, 3-
Diethylamino-7,8-benzfluoran, 3-diethylamino-6-methyl-7-chlorofluoran, 3-
(Np-tolyl-N-ethylamino) -6-methyl-
7-anilinofluoran,

3-pyrrolidino-6-methyl-7-anilinofluoran, 2- {N- (3'-trifluoromethylphenyl) amino} -6-diethylaminofluoran, 2- {3,6-bis ( Diethylamino) -9- (o
-Chloroanilino) lactam xanthylbenzoate {3
-Diethylamino-6-methyl-7- (m-trichloromethylanilino) fluoran, 3-diethylamino-7
-(O-chloroanilino) fluoran, 3-di-n-butylamino-7- (o-chloroanilino) fluoran,
3-N-methyl-N, n-amylamino-6-methyl-
7-anilinofluoran, 3-N-methyl-N-cyclohexylamino-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7-anilinofluoran, 3- (N, N -Diethylamino) -5-methyl-7- (N, N-dibenzylamino) fluoran,

Benzoylleucomethylene blue, 6'-
Chloro-8'-methoxy-benzoindolino-spiropyran, 6'-bromo-3'-methoxy-benzoindolino-spiropyran, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2 ' -Methoxy-5 '
-Chlorophenyl) phthalide, 3- (2'-hydroxy-4'-dimethylaminophenyl) -3- (2'-methoxy-5'-nitrophenyl) phthalide, 3- (2'-
(Hydroxy-4'-diethylaminophenyl) -3-
(2′-methoxy-5′-methylphenyl) phthalide,
3- (2'-methoxy-4'-dimethylaminophenyl) -3- (2'-hydroxy-4'-chloro-5'-
Methylphenyl) phthalide,

3- (N-ethyl-N-tetrahydrofurfuryl) amino-6-methyl-7-anilinofluoran, 3-N-ethyl-N- (2-ethoxypropyl) amino-6-methyl-7 -Anilinofluoran, 3-N-
Ethyl-N-isobutyl-6-methyl-7-anilinofluoran, 3-morpholino-7- (N-propyl-trifluoromethylanilino) fluoran, 3-pyrrolidino-7-m-trifluoromethylanilinofur Oran, 3
-Diethylamino-5-chloro-7- (N-benzyl-
(Trifluoromethylanilino) fluoran, 3-pyrrolidino-7- (di-p-chlorophenyl) methylaminofluoran, 3-diethylamino-5-chloro-7- (α
-Phenylethylamino) fluoran, 3- (N-ethyl-p-toluidino) -7- (α-phenylethylamino) fluoran, 3-diethylamino-7- (o-methoxycarbonylphenylamino) fluoran, 3-diethylamino- 5-methyl-7- (α-phenylethylamino) fluoran, 3-diethylamino-7-piperidinofluoran, 2-chloro-3- (N-methyltoluidino) -7- (pn-butylanilino) fluoran, 3
-(N-methyl-N-isopropylamino) -6-methyl-7-anilinofluoran, 3-di-n-butylamino-6-methyl-7-anilinofluoran,

3,6-bis (dimethylamino) fluorenespiro (9,3 ')-6'-dimethylaminophthalide, 3- (N-benzyl-N-cyclohexylamino)
-5,6-benzo-7-α-naphthylamino-4′-bromofluoran, 3-diethylamino-6-chloro-7
-Anilinofluoran, 3-diethylamino-6-methyl-7-mesitidino-4 ', 5'-benzofluoran,
3-N-methyl-N-isopropyl-6-methyl-7-
Anilinofluoran, 3-N-ethyl-N-isoamyl-6-methyl-7-anilinofluoran, 3-diethylamino-6-methyl-7- (2 ′, 4′-dimethylanilino) fluoran and the like.

As the developer used in the present invention, various electron-accepting substances which react with the leuco dye upon heating to develop the color are applied. Specific examples thereof are as follows. Examples thereof include phenolic substances, organic or inorganic acidic substances, and esters and salts thereof.

Gallic acid, salicylic acid, 3-isopropylsalicylic acid, 3-cyclohexylsalicylic acid, 3,5-
Di-tert-butylsalicylic acid, 3,5-di-α-methylbenzylsalicylic acid, 4,4′-isopropylidene diphenol, 1,1′-isopropylidenebis (2-
Chlorophenol), 4,4′-isopropylidenebis (2,6-dibromophenol), 4,4′-isopropylidenebis (2,6-dichlorophenol),
4'-isopropylidenebis (2-methylpheno-
4,4′-isopropylidenepis (2,6-dimethylphenol), 4,4′-isopropylidenebis (2-tert-butylphenol), 4,4′-se
c-butylidene diphenol, 4,4′-cyclohexylidenebisphenol, 4,4′-cyclohexylidenebis (2-methylphenol),

4-tert-butylphenol, 4-phenylphenol, 4-hydroxydiphenoxide, α
Naphthol, β-naphthol, 3,5-xylenol, thymol, methyl-4-hydroxybenzoate,
4-hydroxyacetophenone, novolak-type phenol resin, 2,2′-thiobis (4,6-dichlorophenol), catechol, resorcin hydroquinone, pyrogallol, phloroglysin, phloroglysin carboxylic acid, 4-tert-octyl catechol,

2,2'-methylenebis (4-chlorophenol), 2,2'-methylenebis (4-methyl-6
(tert-butylphenol) 2,2'-dihydroxydiphenyl, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, butyl p-hydroxybenzoate, benzyl p-hydroxybenzoate, p-hydroxybenzoic acid-p- Chlorobenzyl, p-hydroxybenzoic acid-c-chlorobenzyl, p-hydroxybenzoic acid-p
-Methylbenzyl, n-octyl p-hydroxybenzoate,

Benzoic acid, zinc salicylate, 1-hydroxy-2-naphthoic acid, 2-hydroxy-6-naphthoic acid, zinc 2-hydroxy-6-naphthoate, 4-hydroxydiphenylsulfone, 4-hydroxy-4 ' -Chlorodiphenylsulfonebis (4-hydroxyphenyl)
Sulfide, 2-hydroxy-p-toluic acid, 3,5
-Zinc di-tert-butylsalicylate, 3,5-di-
tin tert-butylsalicylate,

Tartaric acid, oxalic acid, maleic acid, citric acid, succinic acid, stearic acid, 4-hydroxyphthalic acid, boric acid, thiourea derivatives, 4-hydroxythiophenol derivatives,

Ethyl bis (4-hydroxyphenyl) acetate, n-propyl bis (4-hydroxyphenyl) acetate, n-butyl bis (4-hydroxyphenyl) acetate,
Phenyl bis (4-hydroxyphenyl) acetate, benzyl bis (4-hydroxyphenyl) acetate, bis (4-hydroxyphenyl) acetate
Hydroxyphenyl) phenethyl acetate, bis (3-methyl-4-hydroxyphenyl) acetic acid, methyl bis (3-methyl-4-hydroxyphenyl) acetate, n-propyl bis (3-methyl-4-hydroxyphenyl) acetate,

1,7-bis (4-hydroxyphenylthio) 3,5-dioxaheptane, 1,5-bis (4-hydroxyphenylthio) 3-oxapentane, dimethyl 4-hydroxyphthalate, 4-hydroxy -4'-methoxydiphenylsulfone, 4-hydroxy-4'-ethoxydiphenylsulfone, 4-hydroxy-4'-isopropoxydiphenylsulfone, 4-hydroxy-4 '
-Propoxydiphenylsulfone, 4-hydroxy-
4'-butoxydiphenyl sulfone, 4-hydroxy-
4'-isobutoxydiphenyl sulfone, 4-hydroxy-4, -sec-butoxydiphenyl sulfone, 4-
Hydroxy-4'-tert-butoxydiphenylsulfone, 4-hydroxy-4'-benzyloxydiphenylsulfone, 4-hydroxy-4'-phenoxydiphenylsulfone, 4-hydroxy-4 '-(m-methylbenzyloxy) diphenylsulfone , 4-hydroxy-4 '
-(P-methylbenzyloxy) diphenyl sulfone, 4
-Hydroxy-4 '-(o-methylbenzyloxy) diphenylsulfone, 4-hydroxy-4'-(p-chlorobenzyloxy) diphenylsulfone and the like.

In the heat-sensitive coloring layer of the present invention, together with the leuco dye and the developer, if necessary, auxiliary additives commonly used in this type of heat-sensitive recording material, for example, a water-soluble polymer and / or Alternatively, an aqueous emulsion type resin, a filler, a heat-fusible substance, a surfactant and the like can be used in combination.

In this case, examples of the filler include inorganic fine particles such as calcium carbonate, silica, zinc oxide, titanium oxide, aluminum hydroxide, zinc hydroxide, barium sulfate, clay, talc, and surface-treated calcium and silica. In addition to powder, organic fine powder such as urea-formalin resin, styrene-methacrylic acid copolymer, and polystyrene resin can be used.

Examples of the heat-fusible substance include higher fatty acids or their esters, amides and metal salts, various waxes, condensates of aromatic carboxylic acids and amines, benzoic acid phenyl esters, higher linear glycols. , 3,4
-Dialkyl epoxy-hexahydrophthalate, higher ketones, p-benzylbiphenyl, and other heat-fusible organic compounds having a melting point of about 50 to 200 ° C.

In the recording material of the present invention, a conventional resin can be used in place of the above-mentioned resin (water-insoluble alkali-soluble polymer) for the protective layer, but the use of a water-insoluble alkali-soluble polymer is preferred. Is desirable as described above. Here, as the conventional resin, for example, polyvinyl alcohol, cellulose derivative, starch and its derivative, carboxyl group-modified polyvinyl alcohol, polyacrylic acid and its derivative, styrene-acrylic acid copolymer and its derivative, poly (meth) acrylamide And their derivatives, styrene-acrylic acid-acrylamide copolymer, amino group-modified polyvinyl alcohol, epoxy-modified polyvinyl alcohol, polyethyleneimine, aqueous polyester, aqueous polyurethane, isobutylene-maleic anhydride copolymer and its derivatives Resins, polyesters, polyurethanes, acrylate polymers or copolymers, styrene-acrylic copolymers, epoxy resins, polyvinyl acetate, polyvinylidene chloride, polyvinyl chloride and these Conductor and the like.

In the protective layer of the present invention, conventionally used auxiliary additives, for example, a filler, a surfactant, a heat-fusible substance (or a lubricant), a pressure coloring inhibitor and the like can be used in combination. Further, a water-proofing agent can be contained.
In this case, specific examples of the filler and the heat-fusible substance include those similar to those exemplified in relation to the thermosensitive coloring layer.

The magnetic recording layer mainly comprises a magnetic powder and a binder resin. Generally, the magnetic powder, the binder resin, and a small amount of additives are mixed using a solvent, and the mixture is applied onto the undercoat layer. Formed by

The magnetic powder includes CrO ₂ , γ-Fe ₂ O ₃ , C
o-γ-Fe ₂ O ₃ and BaO-γ-Fe ₂ O ₃ . Examples of the binder resin include polyvinyl alcohol, a coated vinyl-vinyl acetate copolymer, polyurethane, and nitrocellulose.

The receiving layer of the receiving paper for thermal transfer is a layer for receiving a thermal transfer image from a sublimation type or hot melt type ink ribbon, and generally contains a white pigment and a binder resin as main components. As the white pigment, fine powders such as calcium carbonate, silica, white carbon, titanium oxide, urea-formalin resin, and polystyrene are used. The binder resin can be variously selected depending on the type of the thermal transfer ink ribbon and the intended use, but a polyacrylic resin, a polyester resin, a polyurethane resin, a polyvinyl resin, an epoxy resin, or the like is used.

[0056]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In addition, all the parts and% shown below are based on weight.

(Example 1) (Solution A) 40 parts of aluminum hydroxide 2.5 parts of a 2.5% aqueous solution of an alkali salt of itaconic acid-modified polyvinyl alcohol 4 parts 40% of a water-insoluble alkali-soluble acrylic resin (manufactured by E-Tech; N412-N) 5 parts of water and 51 parts of water were mixed and stirred to prepare an undercoat layer coating liquid.

(Solution B) 3-N-cyclohexyl-N-methylamino-6-methyl-7anilinofluoran 5 parts 1,4-bis (2-vinyloxyethoxy) benzene 10 parts Calcium carbonate 15 parts Itaconic acid 15 parts of a 10% aqueous solution of an alkali salt of a modified polyvinyl alcohol 15 parts of water 15 parts of the above composition was pulverized by a sand mill so that the average particle size became 2 μm or less. (Liquid C) 4-hydroxy-4'-isopropoxydiphenylsulfone 25 parts 1,1,3-tris (3-tert-butyl-4-hydroxy-6-methylphenyl) butane 5 parts Itaconic acid-modified polyvinyl alcohol alkali The above composition was pulverized with a sand mill so that the average particle size became 2 μm or less. Next, 100 parts of the liquid B and 100 parts of the liquid C were mixed and stirred to prepare a thermosensitive coloring layer coating liquid.

Subsequently, an undercoat layer coating liquid and a thermosensitive coloring layer coating liquid were sequentially applied to the surface of a high-quality paper having a basis weight of 130 g / m ² , and dried to obtain an adhesion amount of 8.0 g / m ^2. And a thermosensitive coloring layer of 6.0 g / m ² were laminated to prepare a thermosensitive recording material of the present invention.

(Example 2) (D solution) Silica 1 part Alkaline salt of itaconic acid-modified polyvinyl alcohol 10% aqueous solution 1 part 10% aqueous solution of silicon-modified polyvinyl alcohol 10 parts Polyamide epichlorohydrin resin 12.5% aqueous solution 1 part Water 7 The parts were mixed and stirred to prepare a protective layer coating liquid.

This protective layer coating solution was applied to the thermosensitive coloring layer of Example 1.
The coating amount after drying is 4.0 g / m. ^TwoApply dry so that
After drying, a heat-sensitive recording material of the present invention was prepared.

(Example 3) (Solution E) Aluminum hydroxide 20 parts 2.5% aqueous solution of an alkali salt of itaconic acid-modified polyvinyl alcohol 2 parts 40% solution of a water-insoluble alkali-soluble acrylic resin (manufactured by E-Tech; N412-N 10 parts of water and 68 parts of water were mixed and stirred to prepare a back coat layer coating liquid.

Next, as in Example 2, the undercoat layer, the thermosensitive coloring layer and the protective layer were coated on the surface of the high-quality paper having a basis weight of 60 g / m ² to obtain a coating amount of 8.0 g / m ² , 6 after drying. 0.0 g /
m ² , 4.0 g / m ^2, and the coated amount after drying the back coat layer on the back surface of the high-quality paper is 4.0 g / m 2.
^The resultant was coated and dried so as to obtain No. ² , thereby obtaining a heat-sensitive recording material of the present invention. The back surface of the obtained heat-sensitive recording material was treated at 30 ° C. in an environment of 7 ° C.
After storage for one day, an acrylic pressure-sensitive adhesive layer and a release paper were sequentially provided on the back coat layer on the back surface of the support to obtain a thermosensitive recording label of the present invention.

(Comparative Example 1) A comparative heat-sensitive recording material was obtained in the same manner as in Example 2, except that the water-insoluble alkali-soluble acrylic resin (N412-N, manufactured by Etec) was removed from the undercoat layer coating solution. Was.

(Comparative Example 2) In Example 2, the water-insoluble alkali-soluble acrylic resin (N412-N, manufactured by Etec) used in the undercoat layer coating solution was subjected to SBR.
(Nippon A & L Co., Ltd .: Smartex PA-91
Comparative heat-sensitive recording material was obtained in the same manner except that the above-mentioned method was replaced with (59).

(Comparative Example 3) In Example 3, the water-insoluble alkali-soluble acrylic resin (manufactured by E-Tech; N412-N) used in the undercoat layer coating solution and the backcoat layer coating solution was subjected to SBR (Japan A & L). (Manufactured by SMARTEX PA-9159).

(Comparative Example 4) In Example 2, a water-insoluble alkali-soluble acrylic resin (N412-N, manufactured by E-Tech Co., Ltd.) of the undercoat layer coating solution was applied to SBR (Smartex PA-9159, manufactured by Nippon A & L Co., Ltd.). Alternatively, except for the water-insoluble alkali-soluble acrylic resin (N-412-N, manufactured by Etec) of the coating liquid for the back coat layer, a 2.5% aqueous solution of an alkali salt of itaconic acid-modified polyvinyl alcohol was changed from 2 parts to 12 parts. A comparative heat-sensitive recording label was obtained in the same manner except for the above.

(Example 4) In Example 1, (Solution A)
The water-insoluble alkali-soluble acrylic resin (N412-N manufactured by E-Tech) used in the undercoat layer solution was converted into a water-insoluble alkali-soluble SBR (manufactured by Nippon A & L):
A heat-sensitive recording material of the present invention was obtained in the same manner except that SMARTEX PA-9157) was used.

Next, each of the heat-sensitive recording materials and the heat-sensitive recording labels obtained as described above was subjected to the following confirmation tests.
The results are shown in Table 1.

[Table 1]

(1) Water resistance: After immersing each heat-sensitive recording material in water at room temperature for 16 hours, the front and back surfaces are rubbed ten times with a finger, and the presence or absence of peeling of the coating layer is visually determined. ○ ・ ・ ・ ・ ・ ・ ・ No peeling of coating layer △ ・ ・ ・ ・ ・ ・ ・ Peeling of coating layer (with resistance) × ・ ・ ・ ・ ・ ・ ・ Peeling of coating layer (no resistance)

(2) Water resistance of pressure-sensitive adhesive labels: The release paper of each heat-sensitive label was peeled off, immersed in water at room temperature for 16 hours, and then the pressure-sensitive adhesive layer was rubbed ten times with a finger, and the peeling of the pressure-sensitive adhesive was visually observed. judge. ○ ・ ・ ・ ・ ・ ・ ・ ・ ・ No peeling of adhesive △ ・ ・ ・ ・ ・ ・ ・ Peeling of coating layer (with resistance) × ・ ・ ・ ・ ・ ・ ・ Peeling of coating layer (no resistance)

(3) Disintegration property: 1) Put 25 g of a sample in 500 ml of warm water at 40 ° C.
2) 0.5 g of NaOH, 1.0 g of water glass, 0.5 g of hydrogen peroxide, 0.05 g of deinking agent and 0.05 g of stirring were added, and the mixture was further stirred for 15 seconds. 3) Left in a 55 ° C. warm bath for 1 hour. 4) 2 liters of water. In addition, the mixture was filtered and washed (three times) with a 60-mesh wire net. 5) The amount of non-fibrous material was visually determined. ..Materials other than fibrous are available.

The following can be seen from Table 1. Examples 1 and 4 show that when the water-insoluble alkali-soluble polymer of the present invention was used for the undercoat layer, not only water resistance but also defibration properties were good. Example 1 has the same characteristics as the undercoat layer even if the protective layer is present, as in Example 2.
It can be seen that the same effect as described above is obtained. From Example 3, it can be seen that the water-insoluble alkali-soluble polymer of the present invention is used for the undercoat layer and the backcoat layer, so that both the front and back surfaces have good water resistance and defibration properties.

In Comparative Example 1, the water-insoluble alkali-soluble polymer of the present invention was used for the protective layer, but the water-insoluble alkali-soluble polymer of the present invention was not used for the undercoat layer, and the water-soluble polymer (itacon Acid-modified PV
Since only A) is used, the disintegration is poor and the water resistance is slightly poor.

In Comparative Example 2, the water-insoluble alkali-soluble polymer of the present invention was used for the protective layer, but SBR was used for the undercoat layer instead of the water-insoluble alkali-soluble polymer of the present invention, Has a poor disaggregation property at the time of reproduction.

In Comparative Example 3, a back coat layer and an adhesive layer were further provided on the one in Comparative Example 2, but SBR was used for the back coat layer without using the water-insoluble alkali-soluble polymer of the present invention. Therefore, the surface shows the same characteristics as in Comparative Example 2, and the back surface (the surface of the adhesive layer) has good water resistance but poor disintegration.

In Comparative Example 4, a back coat layer and an adhesive layer were further provided on Comparative Example 2, but the water-insoluble alkali-soluble polymer of the present invention was not used in the back coat layer. Since (itaconic acid-modified PVA) is used, the surface shows the same characteristics as Comparative Example 2, and the back (adhesive layer side) has good disintegration but poor water resistance.

Example 5 (Solution F) 100 parts of BaO-γ-Fe ₂ O ₃ 70 parts of polyvinyl alcohol (10% solution) 20 parts of carbon black (38% solution) 60 parts of water 60 parts manufactured by HORIBA, Ltd. The magnetic layer dispersion is prepared using a sand grinder so that the median diameter of the particle size distribution measuring device LA-700 becomes 6 μm. 250 parts of this F solution, 30 parts of polyvinyl alcohol (10% solution), 100 parts of vinylidene chloride emulsion (49% solution), and 20 parts of water
The parts were mixed and stirred to prepare a magnetic recording layer coating liquid.

Subsequently, on a high-quality paper having a basis weight of 157 g / m ² ,
The undercoat layer of Example 1 (however, 20 g /
After providing the drying) was m ^2, and the coating was applied to the magnetic recording layer coating solution so as to 90 g / m ² in Wet, after orientation central magnetic field in face-to-face orientation machine 5000 G, dryer To form a magnetic recording layer.

Next, on the surface of the support opposite to the magnetic recording layer,
The same undercoat layer, thermosensitive coloring layer and protective layer as in Examples 1 and 2 were each applied after drying at a coating weight of 8.0 g / m ² ,
Coating and drying were performed at 6.0 g / m ² and 4.0 g / m ² to obtain a heat-sensitive magnetic recording material of the present invention.

(Example 6) (Solution G) Calcium carbonate (oil absorption: 50 m1 / 100 g) 100 parts Polyvinyl alcohol (10% solution) 100 parts Water 350 parts A mixture having the above composition was mixed with a sand grinder to obtain 1 to 3 parts.
Disperse for time to prepare a receiving layer dispersion. 550 parts of this receiving layer dispersion, polyvinyl alcohol (10% solution) 1
50 parts, urethane-modified SBR emulsion 180 parts (4
2% solution, glass transition point: 50 ° C, urethane modification degree:
50%) and 150 parts of water were mixed and stirred to prepare a receiving layer coating liquid.

Subsequently, the same undercoat layer coating liquid as in Example 1 and the above-described receiving layer coating liquid were dried on the support surface opposite to the magnetic recording layer obtained in the same manner as in Example 4, respectively. Is applied and dried so that the coating amount is 8.0 g / m ² and 5.0 g / m ² , and then the surface smoothness of the receiving layer is 500 s.
Then, a calendering process was performed to obtain a thermal transfer type magnetic recording material.

Comparative Example 5 Comparative heat-sensitive magnetic recording was performed in the same manner as in Example 5, except that the water-insoluble alkali-soluble acrylic resin (N412-N, manufactured by Etec) was removed from the undercoat layer coating solution. The material was obtained.

(Comparative Example 6) In Example 5, the water-insoluble alkali-soluble acrylic resin (manufactured by E-Tech; N412-N) used in the undercoat layer coating solution was subjected to SBR.
(Nippon A & L Co., Ltd .: Smartex PA-91
A comparative heat-sensitive magnetic recording material was obtained in the same manner as in the above except that 59) was used.

Comparative Example 7 A comparative thermal transfer type magnet was prepared in the same manner as in Example 6 except that the water-insoluble alkali-soluble acrylic resin (N412-N, manufactured by E-Tech Co.) was removed from the coating solution of the Angou coat layer. A recording material was obtained.

Comparative Example 8 In Example 6, the water-insoluble alkali-soluble acrylic resin (E412; N412-N) used in the coating liquid for the backcoat layer was replaced with SBR (manufactured by Nippon A & L Co., Ltd .: Smarttex PA-915).
A comparative thermal transfer type magnetic recording material was obtained in the same manner except for replacing the item 9).

Next, the same confirmation test as in Examples 1 to 4 and Comparative Examples 1 to 4 was performed on each of the heat-sensitive magnetic recording materials and the thermal transfer-type magnetic recording materials obtained as described above. It was shown to. The evaluation criteria here are the same as those described in Table 1.

[Table 2]

As can be seen from the results shown in Table 2, the heat-sensitive and transfer-type magnetic recording materials of the present invention have a practical level of water resistance without peeling of the coating layer when immersed in water, and have a high level of recyclability in waste paper recycling processing. The coating layer and the fibers can be easily separated in the defibration process.

[0089]

According to the recording material of the present invention, a layer comprising a filler and a water-insoluble alkali-soluble polymer as main components is provided on the surface of a paper support. Therefore, even if a wet strength enhancer is added to the paper support. The coating of the thermosensitive coloring layer coating solution can be performed smoothly. In addition, the disintegration treatment with an alkali solution can be performed favorably, and as a result, recycled paper having high whiteness can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B41M 5/26 101H (72) Inventor Kazuhiro Uchimura 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company F-term in Ricoh (reference) 2H026 AA07 BB02 BB21 DD01 DD32 DD48 DD55 DD57 DD58 FF01 FF15 FF25 FF27 2H111 AA22 AA26 AA27 CA03 CA04 CA05 CA33

Claims (11)

[Claims] 1. An undercoat layer on one side of a support,
What is claimed is: 1. A thermosensitive recording material comprising a thermosensitive coloring layer comprising a leuco dye and a color developer as main components, wherein said undercoat layer comprises a filler and a water-insoluble alkali-soluble polymer as main components. material. 2. The heat-sensitive recording material according to claim 1, further comprising a protective layer containing a filler, a crosslinking agent, and a water-soluble polymer compound as main components on the heat-sensitive coloring layer. 3. The heat-sensitive recording material according to claim 1, wherein a protective layer mainly comprising a filler, a crosslinking agent and a water-insoluble alkali-soluble polymer is further provided on the heat-sensitive coloring layer. 4. The heat-sensitive recording according to claim 1, wherein a back coat layer containing a filler and a water-insoluble alkali-soluble polymer as main components is provided on the other surface of the support. material. 5. An adhesive material layer and a release liner or a linerless adhesive material layer are laminated on the other surface of the support or on the back coat layer provided thereon. 5. The heat-sensitive recording material according to any one of 4. 6. A magnetic recording layer containing a magnetic material is provided on one surface of a support, and an undercoat layer and a thermosensitive coloring layer containing leuco dye and a developer as main components are laminated on the other surface of the support. A heat-sensitive magnetic recording material according to claim 1, wherein said undercoat layer comprises a filler and a water-insoluble alkali-soluble polymer as main components. 7. The heat-sensitive magnetic recording material according to claim 6, wherein an undercoat layer containing a filler and a water-insoluble alkali-soluble polymer as main components is provided between the support and the magnetic recording layer. 8. The heat-sensitive magnetic recording material according to claim 6, wherein a protective layer containing a filler, a crosslinking agent and a water-soluble polymer as main components is further provided on the heat-sensitive coloring layer. . 9. The heat-sensitive magnetic recording material according to claim 6, further comprising a protective layer mainly containing a filler, a crosslinking agent, and a water-insoluble alkali-soluble polymer, on the heat-sensitive coloring layer. . 10. A thermal transfer magnetic recording material comprising: a magnetic recording layer containing a magnetic material provided on one surface of a support; and an undercoat layer and a receiving layer laminated on the other surface of the support. A thermal transfer type magnetic recording material characterized in that the layer comprises a filler and a water-insoluble alkali-soluble polymer as main components. 11. The thermal transfer type magnetic recording material according to claim 10, wherein an undercoat layer containing a filler and a water-insoluble alkali-soluble polymer as main components is provided between the support and the magnetic recording layer.