CN100446990C - Developer for recording materials - Google Patents

Abstract

The present invention provides a developer which contains a triphenolic compound (B) being a triphenolic compound (A) of the general formula (1) satisfying the requirements: (a) an OH group is present at one or more of 4- and 4'-positions of the left and right aromatic rings and (b) at least one of the substituents adjacent to at least one OH group on the left or right aromatic rings is hydrogen and which exhibits high sensitivity and shelf stability of images and less fog in non-image areas; and color forming materials and thermal recording materials made by using the same.

Description

Developer for recording materials

Technical field

The present invention relates to developer for recording materials, use the quality material compositions of described developer and use the recording materials of described quality material compositions.

Background technology

Known up to now a large amount of service recorder energy for example the chemistry of heat, pressure etc. become color system.In described system, exist for a long time with regard to known one-tenth color system, it generally includes separately by colourless or light leuco dye (leuco dye) and becomes color system with two components that the developer of quality is formed by contacting with described leuco dye, and described one-tenth color system is widely used in the recording materials for a long time.The example of this recording materials comprises photosensitive recording material of the pressure sensitive recording material of working pressure energy, the thermal recording medium that uses heat energy, use luminous energy or the like.

The pressure sensitive recording material of working pressure energy belongs to the general already used recording materials that are similar to conventional paper.The pressure sensitive recording material obtains usually in the following manner: leuco dye is dispersed in the emulsion that contains the described leuco dye particle of several microns sizes in the suitable medium with preparation; Preparation afterwards comprises the microencapsulation material of these dye particles; This microencapsulation material is applied on the matrix with the preparation upper paper, and the developer layer that will contain developer is applied on the other matrix with preparation lower floor paper; These paper are stacked on top of each other so that the surface of the surface of described microcapsules coating and developer coating faces with each other.Be applied on the pressure sensitive recording material that so obtains when writing down pressure, bump pressure etc., described microcapsules rupture discharges the microcapsules inclusion that contains leuco dye, contact with described developer thereby described leuco dye is transferred in the developer layer, thereby described leuco dye and the described developer generation chemical reaction of quality that is used for are with document image.

In these years, the thermal photography method of using heat energy to write down has been widely used in the multiple massaging device.The thermal recording medium that is used in the thermal photography method all has excellent character in many aspects as recording materials, and it is highly sensitive that for example its whiteness height, outward appearance and sense of touch approach conventional paper and quality.Hot recording method have its equipment size little, need not plant maintenance and do not produce noise because of superiority.Therefore hot recording method has been found the application that enlarges at the wide spectrum that comprises surveying record instrument, facsimile machine, printer, computer terminal and be used for the automatic machine of label, bill etc.

The thermal photography method adopts following proposal usually: be arranged on the recording materials that make on the matrix, will be applied to as the heat of record energy by heat head, brand, laser etc. the temperature-sensitive component is contacted with each other on recording materials thereby wherein use by the one-tenth chromatograph that will mainly contain two temperature-sensitive components, thereby carry out record by quality.In many cases, as the temperature-sensitive component, leuco dye that the quality material is for example colourless or light and acid developer for example phenolic compounds are united use.Use the example of the recording materials of these components to comprise and for example use crystal violet lactone, two (4 '-hydroxy phenyl) propane of 2-(bisphenol-A: BPA) as the electrothermal sensitive recording paper (referring to for example patent documentation 1) of developer as colour former and 2.

Give electron compound and be subjected to electron compound respectively mainly with the leuco dye and the developer that act in this recording method.These compounds have outward appearance that excellent character thereby they have the white of being almost separately up to contacting with one another, but can obtain multiple highdensity quality color immediately by it is contacted with each other, and are for example red, orange, yellow, green, blue and black.Yet on the other hand, the picture steadiness of the one-tenth color image of these compounds is poor, thereby the one-tenth color image that so the obtains disappearance of can fading in time, and exposes in the sun that the short period will make its disappearance of fading or fade.Therefore, thirst for very much these compounds are improved.

In these years, along with the variation of tape deck, especially plant bulk reduce quickening with speed, special require be low-yield down quality ability (sensitivity) and write down the picture steadiness of quality.For the quality ability that improves under low-yield is improved the thermal response of thermal recording medium usually; But usually can have problems when the thermal response of thermal recording medium is improved makes even also can produce blushing (quality) phenomenon at the not heating part of recording medium in non-image areas.Up to now, for the blushing phenomenon of improvement non-image areas and the picture steadiness of document image under the situation of not damaging thermal response some kinds of methods have been proposed.Especially, BPA is doing well aspect the blushing of thermal response and non-image areas and cheap, and therefore BPA has been used as developer for a long time and widely to be applied to that picture steadiness to document image requires be not in the so strict general temperature-sensitive paper in practice.Yet in these years,, therefore consider to have impelled the research that replaces BPA with other developer from the angle of Environmental security problem because BPA is the endocrine material of a kind of interference.

On the other hand, be primarily aimed at the pressure sensitive recording material, so far after deliberation use the technology (referring to patent documentation 2) of the condensation polymer of phenolic compounds and aldehyde as developer.The problem that exists when such developer is used as thermal recording medium is an insufficient sensitivity, although the picture steadiness of document image as a rule is excellent.Therefore, carried out multiple research, thereby used above-mentioned condensation polymer and improve sensitivity in conjunction with phenolic compounds by uniting in order to address this problem.For example, disclose a kind of thermal photography method, wherein the condensation polymer of phenolic compounds and aldehyde and free phenol are united use (referring to patent documentation 3).This thermal photography method unites the condensation polymer of phenolic compounds and aldehyde and the substituted phenol compound of monomer as developer, and the eutectic point of described developer is lower than any component, thereby has improved thermal response; Yet consider still not enough and have a problem of using other developer and can causing producing blushing to the further improvement of sensitivity by uniting from actual angle in non-image areas through improved thermal response like this.

As selection, condensation degree as the condensation polymer by control phenolic compounds and aldehyde improves sensitivity of method, disclose a kind of be characterised in that comprise one or more 2,2 '-methylene diphenol compound (bisphenol compound) is as the heat-sensitive sheet of developer, wherein said compound respectively by phenolic compounds and aldehyde according to 2 molecules the former: the 1 molecule latter's ratio condensation obtains (referring to patent documentation 4).Even yet the thermal response of this heat-sensitive sheet is satisfactory relatively, but the picture steadiness of document image is poor, and the blushing in non-image areas is still a problem, so this sheet still can not reach any realistic scale.On the other hand, in order to improve the picture steadiness of document image, proposed a kind of by comprising the thermal recording medium developer (referring to patent documentation 5) that above-mentioned bisphenol compound is made as the key component and the composition of at least a polyphenolic substance (for example three phenolic compounds to five phenolic compounds) that adds.Yet when using described polyphenolic substance with the level of the image stabilization sexual satisfaction practical application that is able to make document image, sensitivity be reduced to can not obtain that the related industries field requires with use the resulting suitable sensitivity of BPA.

Attempted using three phenolic compounds as developer (referring to patent documentation 6) in addition, but three phenolic compounds that are used for this situation have up to 200 ℃ respectively or higher fusing point usually, and can not provide and by well-content compatibility between the picture steadiness of suitable sensitivity of the sensitivity of BPA gained and document image, described compatibility is a problem to be solved in the present invention.With regard to this thinking, also attempted using two or more described three phenolic compounds that mix, improved (referring to patent documentation 7) thereby can make the eutectic point of the mixture that so obtains be low to moderate 150～200 ℃ and sensitivity.Yet contain the picture steadiness that triphenol compound compositions that this phenol that replaces by condensation contraposition on the ortho position of OH group obtains can not provide enough sensitivity and enough document image, the situation of the developer of this and patent documentation 6 is similar.Proposed a kind of as the novel triphenol compound structure of selecting, wherein the phenol that replaces of contraposition by the methylene on the ortho position that is positioned at its OH group with other alkyl phenol condensation so that these alkyl phenols carry out condensation (referring to patent documentation 8) respectively in the contraposition of its OH group; Yet be similar to above-mentioned situation, do not obtain the enough sensitivity and the picture steadiness of document image.

Patent documentation 1:U.S. patent No.3539375

Patent documentation 2:JP-B-42-20144

Patent documentation 3:JP-A-48-58842

Patent documentation 4: Japan Patent No.1712000

Patent documentation 5: international open No.02/098674

Patent documentation 6:JP-A-06-115255

Patent documentation 7:JP-A-2001-96926

Patent documentation 8:JP-A-09-278695

Summary of the invention

The purpose of this invention is to provide that a kind of picture steadiness with the sensitivity suitable with the sensitivity of BPA, document image is outstanding, the blushing in the non-image areas is low and the developer of easy preparation; The quality material compositions that comprises described developer; With the recording materials, particularly thermal recording medium that use described quality material compositions.

Carried out extensive studies in order to address the above problem, the inventor finds can to address the above problem by the composition that use comprises as the phenolic compounds with ad hoc structure of developer for recording materials as a result.This discovery causes having finished the present invention.More particularly, the present invention includes the aspect of following (1)～(12):

(1) a kind of developer that comprises three phenolic compounds (B) that belong to three phenolic compounds (A) class of representing by following general formula (1):

[formula 1]

R wherein _aFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _bFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and R _bGroup can be identical or different; R _cFor be selected from hydrogen atom, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and two or more R if present, _cGroup can be identical or different; M and n represent 1～5 integer respectively,

Wherein said three phenolic compounds (B) have:

(a) the OH group on one of 4-and 4 '-position in laying respectively at left aromatic ring and right aromatic ring at least; With

(b) with at left aromatic ring conduct substituent at least one hydrogen atom adjacent with nuclear substituted at least one the OH group of right aromatics.

(2) according to the developer of (1), the content that wherein belongs to three phenolic compounds (A) and do not meet three phenolic compounds (C) of three phenolic compounds (B) is 30 weight % or still less.

(3), it is characterized in that the ratio of the content of the content of described three phenolic compounds (B) and described three phenolic compounds (A) is 0.5 or bigger according to each developer in (1) and (2).

(4) each developer in basis (1)～(3), the content of wherein said three phenolic compounds (A) is 20 weight % or more.

(5) each developer in basis (1)～(4), it contains the condensation product that is obtained by at least a condensation in the phenolic compounds of the amphyl of the contraposition replacement of following general formula (2) representative and following general formula (3) representative,

[formula 2]

R wherein _dFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _eFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and R _eGroup can be identical or different;

[formula 3]

R wherein _fFor be selected from hydrogen atom, hydroxyl, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and R _fGroup can be identical or different,

Wherein, for the condensation product total amount, the condensation product components contents that is different from described three phenolic compounds (A) that is included in the described condensation product is 50 weight % or littler.

(6) each developer in basis (1)～(5) is characterized in that the R in the formula (1) _cGroup all is a hydrogen atom.

(7) each developer in basis (1)～(6) is characterized in that the R in the formula (3) _fGroup all is a hydrogen atom.

(8) each developer in basis (1)～(7), it comprises can be so that colourless or light dyestuff former forms other developer of color.

(9) a kind of quality material compositions that is used for recording materials, it contains colourless or light dyestuff former and according to each developer in (1)～(8).

(10) according to the quality material compositions that is used for recording materials of (9), it further comprises emulsion.

(11) a kind of by the recording materials that form according to each the quality material compositions that is used for recording materials in (9) and (10) are set on matrix.

(12) according to the recording materials of (11), wherein said recording materials are thermal recording medium.

The thermal recording medium of developer of the present invention and the described developer of use can obtain the picture steadiness excellence of highly sensitive and image and the low thermal recording medium of blushing in this external non-image areas with low cost, and all these improved character are difficult to obtain up to now.

Preferred forms of the present invention

Developer of the present invention contains three phenolic compounds (B), it belongs to three phenolic compounds (A) with following structure: wherein the phenol nuclear of contraposition replacement connects by the methylene on the ortho position that is positioned at its OH group and other two phenol nuclear bonds, as shown in general formula (1), described three phenolic compounds (B) be characterised in that have at least in laying respectively at left aromatic ring and right aromatic ring the OH group on one of 4-and 4 '-position and with at left aromatic ring conduct substituent at least one hydrogen atom adjacent with nuclear substituted at least one the OH group of right aromatics.

Three phenolic compounds importantly of the present invention (B) have an OH group on one of 4-and 4 '-position in laying respectively at left aromatic ring and right aromatic ring at least.For example, do not laying respectively at 4-and 4 ' in left aromatic ring and the right aromatic ring-locational OH group and only laying respectively at when having the OH group on 2-and 2 '-position in left aromatic ring and the right aromatic ring when described three phenolic compounds (B) do not have, because described center aromatic ring is present on the ortho position of these OH groups by methylene, therefore the OH group that plays a major role in each comfortable quality spatially can be subjected to the influence of the group of adjacent keyed jointing, therefore becomes the picture steadiness of chromatic sensitivity and document image to become very not satisfactory.

In addition importantly in three phenolic compounds of the present invention (B), and be hydrogen atom at left aromatic ring at least one substituting group adjacent with nuclear substituted at least one the OH group of right aromatics.Herein, " substituting group adjacent " with the OH group be meant be connected to separately with two adjacent with the carbon atom of OH group keyed jointing in aromatic ring carbon atoms on substituting group or atom.When with a left side that is present in described three phenolic compounds (A) and right aromatic ring on adjacent all substituting groups of OH group all be when being different from the group of hydrogen atom and described three phenolic compounds (A) and being used as reagent composition in the quality material compositions, be difficult to obtain to have the quality material compositions of the picture steadiness of enough sensitivity and enough document image because relevant OH group with can be subjected to the substituent obstruction adjacent with relevant OH group as the interaction between the leuco dye of quality component.

To more specifically describe three phenolic compounds of the present invention (B).

In general formula (1), R _aFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _aBe preferably ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, dodecyl, cyclohexyl, phenyl, α-Jia Jibianji and α, α '-dimethyl benzyl, more preferably n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclohexyl, phenyl, α-Jia Jibianji or α, α '-dimethyl benzyl.

R _bFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom; Preferably hydrogen atom or methyl in these groups, and described R _bGroup can be identical or different.

R _cFor be selected from hydrogen atom, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and be preferably hydrogen atom, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, dodecyl, cyclohexyl or phenyl; Described R _cGroup can be identical or different, and particularly preferably be wherein all R _cGroup is the situation of hydrogen atom.

Herein, respectively do for oneself 1～5 integer of m and n, and represent respectively at the number of the nuclear substituted OH group of left aromatics with at the number of the nuclear substituted OH group of right aromatics; Usually, when the number of described OH group increases, water-soluble increase and be tending towards producing following problems: by in water dispersion medium, developer mixed generation quality effect in the stage for preparing the quality material compositions with leuco dye, perhaps in moisture resistance test, in non-image areas, produce blushing, so m and n are preferably 1 or 2 separately.

In developer of the present invention, three phenolic compounds (B) are necessary component; But for the fusing point that reduces described developer and the chromatic sensitivity that becomes that improves the recording materials that obtain thus, relevant developer can comprise that as component three phenolic compounds (C) that are different from described necessary component it belongs to three phenolic compounds (A) but does not meet three phenolic compounds (B).If the content height of three phenolic compounds (C) in the described developer, find so sometimes the retention of quality performance and document image is had a negative impact, therefore the content of described three phenolic compounds (C) is preferably 30wt% or still less, 25wt% or still less more preferably, more preferably 20wt% or still less.Consider from the angle of the effective ways of preparation developer, preferably as described three phenolic compounds (C) be for example resemble the OH group only being arranged on a left side and 2-and the 2 '-position of right aromatic ring, corresponding to the compound of the isomers of described three phenolic compounds (B), this be because, as described later, described compound can prepare the identical chemical operation of three phenolic compounds (B) and prepare simultaneously with three phenolic compounds (B) according to being used to.

When developer of the present invention contains above-mentioned three phenolic compounds (B) and (C) time, the ratio of the content of the content of three phenolic compounds (B) and three phenolic compounds (A) is preferably 0.5 or bigger in the described developer.The content of three phenolic compounds (B) is high more, then easy more realization advantageous effects of the present invention.The ratio of the content of three phenolic compounds (B) more preferably 0.6 or bigger.

As will be described, developer of the present invention can contain the multiple component that is different from above-mentioned three phenolic compounds (A) component, as long as advantageous effects of the present invention can not suffer damage.But, obtain required performance effectively in order to make developer of the present invention, relevant developer preferably with 20wt% or bigger, more preferably 50wt%, further preferred 70wt% or bigger amount contain three phenolic compounds (A).

Method for preparation three phenolic compounds of the present invention (B) does not have special theoretic restriction.The method of multiple phenolic compounds and aldehyde being carried out condensation is considered to short-cut method usually.Yet according to described method, when attempt to obtain as among the present invention, when having three phenolic compounds of different phenol nuclears, the condensation product of gained can be the mixture that comprises a large amount of phenol condensation products, and three phenolic compounds (B) that therefore are difficult to prepare effectively hope.At least a compound condensation in the amphyl of the contraposition replacement of therefore preferably general formula (2) being represented and the phenolic compounds of general formula (3) representative.

By the control reaction condition, can relatively easily make the condensation product that makes by said method become three phenolic compounds (B) and mixture (C).This means that single chemical operation can prepare three phenolic compounds (B) and (C) simultaneously, the advantage of avoiding in the complex operations described in the prior art part is provided, wherein synthetic separately in advance in the prior art have similar molecular structure and dystectic polyphenolic substance, afterwards these materials mixed as developer.The profitability that the conduct of said method is selected is even when described condensation product mixture contains condensation product (hereinafter suitably the being called condensation by-product) component of non-three phenolic compounds (A), and the condensation product of gained also almost can use and needn't carry out any special purifying and lock out operation to remove these condensation by-product components when being used for developer.Beyond any doubt, in order further to improve the performance of described developer, can carry out purifying etc. according to the method that the back will be described.

It should be noted that the example of the accessory substance mentioned can comprise herein: the amphyl that is replaced by the contraposition of the desirable compound of general formula (1) representative and general formula (2) representative reacts and the high molecular weight component that obtains; The dimerization that in the preparation process of the amphyl that above-mentioned contraposition replaces, contains and/or the dihydroxy methyl compound of trimerization; And the component that obtains by the condensation reaction between the phenolic compounds of monohydroxy methyl compound and general formula (3) representative.

In this case, the content of above-mentioned condensation by-product is preferably 50wt% or littler in developer of the present invention.When relevant content during greater than this 50wt%, depend on the application of recording materials, produce following problems sometimes: can not obtain enough hear resistances, tend to occur in the adverse effects such as blushing of non-image areas, this is because due to the fusing point of the fusing initial temperature of the reduction of described developer and reduction.The content of described condensation by-product is 20wt% or littler, more preferably 10wt% or littler, 5wt% or littler more preferably more preferably.

Be used among the above-mentioned preparation method and be the compound that the dihydroxy methylation by corresponding contraposition substituted phenol obtains by the amphyl that the contraposition of general formula (2) representative replaces.In general formula (2), R _dFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _dBe preferably ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, dodecyl, cyclohexyl, phenyl, α-Jia Jibianji or α, α '-dimethyl benzyl, more preferably n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group, cyclohexyl, phenyl, α-Jia Jibianji or α, α '-dimethyl benzyl.R _eFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and described R _eGroup can be identical or different, wherein preferably hydrogen atom or methyl.

The methylated examples for compounds of described dihydroxy can comprise: 2,6-dihydroxy methyl-4-methylphenol, 2,6-dihydroxy methyl-4-ethyl-phenol, 2,6-dihydroxy methyl-4-n-pro-pyl phenol, 2,6-dihydroxy methyl-4-isopropyl-phenol, 2,6-dihydroxy methyl-4-tert-butyl phenol, 2,6-dihydroxy methyl-4-sec-butyl phenol, 2,6-dihydroxy methyl-4-dodecyl phenol, 2,6-dihydroxy methyl-3,4, the 5-pseudocuminol, 2,6-dihydroxy methyl-4-cyclohexylphenol, 2,6-dihydroxy methyl-4-metoxyphenol, 2,6-dihydroxy methyl-4-butoxy phenol, 2,6-dihydroxy methyl-4-tert-amyl phenol, 2,6-dihydroxy methyl-4-phenylphenol, 2,6-dihydroxy methyl-4-(α-Jia Jibianji) phenol, 2,6-dihydroxy methyl-3 methyl 4 isopropyl phenol and 2,6-dihydroxy methyl-4-(α, α '-dimethyl benzyl) phenol.

The dihydroxy methylation of the phenol that described contraposition replaces can be undertaken by common method; For example, phenol and formaldehyde that contraposition is replaced react in the presence of water and base catalyst, with sour neutralize or the acidification reaction product to obtain desirable product.

On the other hand, the phenolic compounds of the amphyl reaction that replaces with above-mentioned contraposition is represented by general formula (3).In general formula (3), R _fFor be selected from hydrogen atom, hydroxyl, halogen atom, cyano group, have 1～18 carbon atom alkyl, have the cycloalkyl of 5～10 carbon atoms and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl; Described R _fGroup can be identical or different.

In the phenolic compounds of molecular structure, use wherein R with formula (3) representative _fGroup suitably is those compounds of hydrogen atom, and can obtain following three phenolic compounds (A): wherein in each three phenolic compounds be hydrogen atom at a left side at least one substituting group adjacent with nuclear substituted at least one the OH group of right aromatics.Therefore condensation reaction height in the contraposition of the phenolic compounds OH group in the formula of formula (3) representative can relatively easily obtain to have three phenolic compounds (A) of OH group at least one of 4-and the 4 '-position of a left side and right phenyl ring.

The example of described phenolic compounds can comprise: phenol, orthoresol, metacresol, 2-ethyl-phenol, 3-ethyl-phenol, 2-isopropyl-phenol, 3-isopropyl-phenol, 2-sec-butyl phenol, 2-tert-butyl phenol, 3-tert-butyl phenol, 2-phenylphenol, 3-phenylphenol, 2-chlorophenol, 3-chlorophenol, 2-bromophenol, 3-bromophenol, 2-cyanophenol, 3-cyanophenol, 2,3-xylenol, catechol and resorcinol.

From considering preferably only on 3-position and/or 5-position, have substituent phenol and all separately R in these materials by the performance of the developer of its gained, cheap price and the angle that obtains easily _fGroup is the not substituted phenol of hydrogen atom.Catechol and resorcinol have two OH groups respectively, therefore help obtaining highly sensitive developer, but on the other hand, tend to occur following problems: make its water-soluble increase owing to containing many hydrophily substituting groups in its molecule, thereby in described developer and leuco dye mix with the stage that forms the quality material compositions, form color in water dispersion medium, perhaps in the moisture resistance test, appear at the blushing in the non-image areas.Therefore, when using these phenolic compounds preferred selecting type (2) representative, substituent R wherein _dAnd R _eThe amphyl that replaces for the contraposition of high hydrophobicity.

Reagent composition of the present invention can prepare according to amphyl and the above-mentioned phenolic compounds that method well known in the art uses above-mentioned contraposition to replace.For example, in the presence of suitable acid catalyst, react each other, cause the condensation reaction between the two to contain the condensation product of three phenolic compounds (A) of general formula (1) representative thus as key component with generation by amphyl and a kind of above-mentioned phenolic compounds of heating with a kind of above-mentioned contraposition replacement of scheduled volume.In this condensation reaction, described phenolic compounds has high response usually on the contraposition of the OH group shown in the formula (3) and ortho position, therefore can be so that relatively easily three phenolic compounds (A) that obtain as mentioned above become the mixture of being made up of three phenolic compounds (B) and three phenolic compounds (C).

By regulating the content that described three phenolic compounds be used for condensation reaction simultaneously and the mol ratio of the amphyl of described contraposition replacement can be controlled above-mentioned condensation by-product in the developer.For example, when the content that makes described condensation by-product is 50wt% or more hour, the consumption of preferred described phenolic compounds be 10 times of mole of the amphyl that replaces of contraposition or more, be preferably 20 times or more.As optional method, the amphyl that contraposition replaces can be infeeded in the reaction system that contains the described phenolic compounds that sets in advance continuously.

The condensation product that so obtains can use as developer according to it; Yet especially when requiring the purity of developer, described condensation product can be as developer after using any one conventional purification process purifying, described conventional purification process comprises: wherein described condensation product once is dissolved in the good solvent, then this solution is added in poor solvent with the method that is settled out described condensation product again, wherein with the method for the described product of solvent wash that can other condensation product of solvent with wherein add solvent and it is dissolved in wherein and the method that is recrystallized of cooling then by heating in described product.

As can be by other developer that can form color, the amphyl that can enumerate, hydroxybenzoic acid derivative, salicyclic acid derivatives, solsonylurea compounds, urea-carbamate compounds etc. by general formula (4) representative with the colourless or light dyestuff former that developer of the present invention is united use.To the instantiation of these compounds be described below, but other above-mentioned developer is not limited to these examples.

[formula 4]

Wherein, each hydrogen atom that is keyed on the aromatic ring can be replaced by the phenyl of hydroxyl, alkyl, aryl, alkoxyl, phenyl and replacement; A is for being selected from-CR ¹R ²-,-SO ₂-,-O-,-CO-,-CONH-,-NH-,-OCOO-,-NHCONH-,-NHCOO-,-CH (COOR ³)-,-C (C F ₃) ₂-,-OCH ₂CH ₂The group of O-and cyclohexylidene; R ¹R ²And R ³Represent hydrogen atom, alkyl or phenyl separately; B is the group that is selected from the group of hydroxyl, alkoxyl and following formula (5) representative:

[formula 5]

Wherein p is 1～7 integer.

Example by the described amphyl of general formula (4) representative can comprise 2, two (4 '-hydroxy phenyl) propane of 2-, 2, two (hydroxy phenyl) butane of 2-, 2, two (hydroxy phenyl) heptane of 2-, 4,4 '-(1,3-dimethyl-butylidene) bis-phenol, 1, the 1-bis(4-hydroxyphenyl)cyclohexane, two (4-hydroxy phenyl) butyl acetate, two (4-hydroxy phenyl) acetic acid benzyl ester, 4,4 '-(1,3-dimethyl-butylidene) bis-phenol, 2,4-dihydroxy-2 '-methoxybenzoyl aniline, two (4-hydroxy phenyl) n-butyl acetate, 1-(4-carboxyl-3-hydroxyphenoxy)-2-(4-methoxyl group phenoxy group) ethane, 4,4 '-dihydroxy-diphenyl sulfone, two (3-methyl-4-hydroxy phenyl) sulfone, 4-hydroxy phenyl-4 '-methyl phenyl sulfone, 3-chloro-4-hydroxy phenyl-4 '-methyl phenyl sulfone, 3,4-dihydroxy phenyl-4 '-methyl phenyl sulfone, 2,4 '-dihydroxy-diphenyl sulfone, two (3-pi-allyl-4-hydroxy phenyl) sulfone, 4-hydroxyl-4 '-isopropoxy diphenyl sulfone, 4-hydroxy phenyl-4 '-benzyloxy phenylsulfone, 4-isopropyl phenyl-4 '-hydroxy phenyl sulfone, two (2-methyl-3-tert-butyl-hydroxy phenyl) sulfide, 1-(4 '-methoxyl group phenoxy group)-2-(3 '-hydroxyl-4 '-carboxyl phenoxy group) ethane, contain 4, (Nipon Soda Co., Ltd. makes 4 '-[oxygen two (ethyleneoxy group-to the phenylene sulfone)] xenol: D-90) as the developer of key component.

The example of described hydroxybenzoic acid derivative can comprise 4-methyl hydroxybenzoate, 4-nipagin A, 4-butoben, 4-hydroxy benzoic acid benzyl ester, 4-hydroxybenzoic acid (4 '-chloro benzyl) ester, 1, two (4 '-hydroxybenzoic acid) ethyl esters, 1 of 2-, two (4 '-hydroxybenzoic acid) pentyl esters and 1 of 5-, 6-two (the own ester of 4 '-hydroxybenzoic acid).

The example of described salicyclic acid derivatives can comprise: 4-n-octyloxy salicylic acid, 4-n-butoxy salicylic acid, 4-n-pentyloxy salicylic acid, 3-n-dodecane oxygen base salicylic acid, the positive hot acyloxy salicylic acid of 3-, 4-carbonyl octyloxy aminosalicylic acid and positive hot acyloxy carbonylamino salicylic acid of 4-and slaine thereof.

The example of described solsonylurea compounds can also comprise the compound that contains at least one arlysulfonylamino urea groups; for example 4; 4 '-two (p-toluenesulfonyl amino carbonyl amino) diphenyl methane, 4; 4 '-two (p-toluenesulfonyl amino carbonyl amino) diphenyl sulfide, 4,4 '-two (p-toluenesulfonyl amino carbonyl amino) diphenyl ether and N-(p-toluenesulfonyl)-N '-phenylurea.

For urea-carbamate compounds, its definition can be found in WO 00/14058 A and JP-A-2002-332271, and the example can comprise the developer UU that is made by Asahi Kasei Corp..

Other developer that these and developer of the present invention use simultaneously can two or more unite use with it as required.Other developer of these of small scale can have the picture steadiness of the document image of satisfied sensitivity and satisfaction usually simultaneously; Those that can have these character under satisfied condition simultaneously can relate to the high and therefore defective of deficiency in economic performance of price.Yet these other developers and developer of the present invention are mixed or unite use can obtain in fact satisfactory performance aspect the blushing of the picture steadiness of sensitivity, document image, non-image areas and the economic benefit.

The quality material compositions that is used for the excellence of recording materials can be by developer of the present invention and dyestuff former preparation.As the dyestuff former that is used for this situation, can use the known chemical substance in quality material field that is used in pressure sensitive recording material and the thermal recording medium, and be not particularly limited for described precursor.Yet preferably common colourless or light leuco dye, for example triarylmethane leuco dye, fluoran leuco dye, fluorenes leuco dye and diphenyl-methane leuco dye.

Listed the example of typical leuco dye below.

(1) triaryl methane compounds

3, two (right-the dimethylaminophenyl)-6-dimethylamino 2-benzofuranones (crystal violet lactone) of 3-, 3, two (right-dimethylaminophenyl) the 2-benzofuranones of 3-, 3-(right-dimethylaminophenyl)-3-(1,2-dimethyl indole-3-yl) 2-benzofuranone, 3-(right-dimethylaminophenyl)-3-(2 methyl indole-3-yl) 2-benzofuranone, 3-(right-dimethylaminophenyl)-3-(2-phenylindone-3-yl) 2-benzofuranone, 3,3-two (1,2-dimethyl indole-3-yl)-5-dimethylamino 2-benzofuranone, 3,3-two (1,2-dimethyl indole-3-yl)-6-dimethylamino 2-benzofuranone, 3, two (9-ethyl carbazole-3-the yl)-5-dimethylamino 2-benzofuranones of 3-, 3, two (2-phenylindone-3-yl)-5-dimethylamino 2-benzofuranones of 3-and 3-be right-dimethylaminophenyl-3-(1-methylpyrrole-2-yl)-6-dimethylamino 2-benzofuranone.

(2) diphenyl-methane compound

4,4-Bis-dimethylamino phenyl benzhydryl benzylic ether, the colourless auramine of N-halogenophenyl, N-2,4, the colourless auramine of 5-trichlorophenyl etc.

(3) xanthene compound

Rhodamine B anilino-lactams, rhodamine B-right-chloroanilino lactams, 3-dimethylamino-6-methyl-7-(m-trifluoromethyl anilino-) fluorane, 3-diethylamino-6-methyl-fluorane, 3-diethylamino-7-methyl-fluorane, 3-diethylamino-7-chloro-fluorane, 3-diethylamino-7-dibenzyl amino fluorane, 3-diethylamino-6-methyl-7-chlorine fluorane, the amino fluorane of 3-diethylamino-7-octyl group, 3-diethylamino-7-phenyl fluorane, 3-diethylamino-6-methyl-7-anilino fluorane, 3-diethylamino-6-methyl-7-is to the toluidine fluorane, toluidine fluorane between 3-diethylamino-6-methyl-7-, 3-diethylamino-6-chloro-7-methyl fluoran, 3-diethylamino-7-(3,4-dichloro-benzenes amido) fluorane, 3-diethylamino-7-(2-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-diethylamino-6-methyl-7-(2, the 6-xylidino) fluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-ethoxycarbonyl propyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-tolyl) amino-6-methyl-7-phenethyl fluorane, 3-diethylamino-7-(adjacent fluorine) anilino fluorane, 3-diethylamino-7-trifluoromethylbenzene amido fluorane, 3-diethylamino-7-(4-nitrobenzene amido) fluorane, 3-diethylamino-6-methyl-7-(m-trifluoromethyl anilino-) fluorane, 3-diethylamino-6-methyl-7-(neighbour-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-(right-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-(ortho-fluorophenyl amido) fluorane, 3-diethylamino-6-methyl-7-(right-the n-butylbenzene amido) fluorane, the amino fluorane of 3-diethylamino-6-methyl-7-n-octyl, 3-diethylamino-6-chloro-7-anilino fluorane, 3-diethylamino-6-ethoxyethyl group-7-anilino fluorane, 3-diethylamino-benzo [a] fluorane, 3-diethylamino-benzo [c] fluorane, 3-diethylamino-6-methyl-7-benzylamino fluorane, 3-diethylamino-6-methyl-7-dibenzyl amino fluorane, the amino fluorane of 3-diethylamino-7-two (right-methyl-benzyl), the amino fluorane of 3-diethylamino-6-methyl-7-diphenyl methyl, 3-diethylamino-7-dinaphthyl methylamino fluorane, 10-diethylamino-4-dimethylamino benzo [a] fluorane, 3-diethylamino-7,8-benzo fluorane, 3-diethylamino-6-methyl-7-(-the trichloro-benzenes amido) fluorane, 3-diethylamino-7-(neighbour-chloroanilino) fluorane, 3-dibutylamino-7-(neighbour-chloroanilino) fluorane, 3-diethylamino-6-methyl-7-(2 ', 4 '-dimethyl benzene amido) fluorane, 3-(N, the N-diethylamino)-5-methyl-7-(N, the N-dibenzyl amino) fluorane, morpholinyl-7-(N-propyl group trifluoromethylbenzene amido) fluorane, 3-pyrrolidinyl-7-trifluoromethylbenzene amido fluorane, 3-diethylamino-5-chloro-7-(N-benzyl-trifluoromethylbenzene amido) fluorane, 3-pyrrolidines generation-7-(two-right-chlorphenyl) methylamino fluorane, 3-diethylamino-5-chloro-7-(α-phenylethyl amino) fluorane, 3-(N-ethyl-N-is to toluidino)-7-(α-phenylethyl amino) fluorane, 3-diethylamino-7-(O-methoxy carbonyl phenyl ethyl) fluorane, 3-diethylamino-5-methyl-7-(α-phenylethyl amino) fluorane, the amino fluorane of 3-diethylamino-7-piperidino, 2-chloro-3-(N-methyl toluidino)-7-(right-N-butyl benzene amido) fluorane, 3-(N-ethyl-N-cyclohexyl amino)-5,6-benzo-7-Alpha-Naphthyl amino-4 '-bromo fluorane, 3-diethylamino-6-methyl-7-(2,4, the 6-trimethylphenyl) (mesitydino)-4 ', 5 '-benzo fluorane, 3-dibutylamino-6-methyl fluoran, 3-dibutylamino-6-methyl-7-chloro fluorane, 3-dibutylamino-6-methyl-7-anilino fluorane, 3-dibutylamino-6-methyl-7-is to the toluidine fluorane, 3-dibutylamino-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-dibutylamino-6-methyl-7-(m-trifluoromethyl anilino-) fluorane, 3-dibutylamino-6-methyl-7-(o-chloraniline base) fluorane, 3-dibutylamino-6-methyl-7-(parachloroanilinum base) fluorane, 3-dibutylamino-6-methyl-7-(adjacent fluoroanilino) fluorane, 3-dibutylamino-7-(adjacent fluoroanilino) fluorane, 3-dibutylamino-6-methyl-7-(right-the n-butylbenzene amido) fluorane, the amino fluorane of 3-dibutylamino-6-methyl-7-n-octyl, 3-dibutylamino-6-chloro-7-anilino fluorane, 3-dibutylamino-6-ethoxyethyl group-7-anilino fluorane, 3-two n-pentyls amino-6-methyl-7-anilino fluorane, 3-two n-pentyls amino-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-two n-pentyls amino-6-methyl-7-(m-trifluoromethyl anilino-) fluorane, 3-two n-pentyls amino-6-methyl-7-(o-chloraniline base) fluorane, 3-two n-pentyls amino-6-methyl-7-(parachloroanilinum base) fluorane, 3-two n-pentyls amino-6-methyl-7-(adjacent fluoroanilino) fluorane, 3-pyrrolidinyl-6-methyl-7-anilino fluorane, 3-piperidino-6-methyl-7-anilino fluorane, 3-cyclohexyl amino-6-chloro fluorane, 3-dimethylamino-5,7-dimethyl fluorane, 3-(N-methyl-N-isopropyl amyl group amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-n-pro-pyl amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-amyl group amino)-6-methyl-7-anilino fluorane, 3-(N, N-two n-pentyl amino)-6-methyl-7-anilino fluorane, 3-(N-methyl-N-isopropyl propyl group amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-n-pro-pyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isopropyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-normal-butyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isobutylamino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-is to the toluidine fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(m-trifluoromethyl anilino-) fluorane, 3-(N-ethyl-N-n-hexyl amino)-6-methyl-7-(o-chloraniline base) fluorane, 3-(N-ethyl-N-isopentyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-isopentyl amino)-6-chloro-7-anilino fluorane, 3-(N-ethyl-N-3-methyl butyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-is to toluidino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-is to toluidino)-6-methyl-7-(to toluidine) fluorane, 3-(N-ethyl-N-is to toluidino)-6-methyl-7-(neighbour, right-the dimethyl benzene amido) fluorane, 3-(N-ethyl-N-tetrahydrofurfuryl amino)-6-methyl-7-anilino fluorane, 3-(N-cyclohexyl-N-methylamino)-6-methyl-7-anilino fluorane, 3-(N-cyclohexyl-N-methylamino)-7-anilino fluorane, 3-(N-ethyl-N-3-methoxy-propyl amino)-6-methyl-7-anilino fluorane, 3-(N-ethyl-N-3-ethoxycarbonyl propyl amino)-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-dimethylamino-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-diethylamino-6-methyl-7-anilino fluorane, 2-(4-oxa-hexyl)-3-dipropyl amino-6-methyl-7-anilino fluorane, 3, two (diethylamino) fluorane-γ of 6--(2 '-nitro) anilino-lactams, 3, two (diethylamino) fluorane-γ of 6--(3 '-nitro) anilino-lactams, 3, two (diethylamino) fluorane-γ of 6--(4 '-nitro) anilino-lactams and 3, two (diethylamino) fluorane-γ of 6--anilino-lactams.

(4) thiazine compounds

Benzoyl leukomethylene, right-nitro benzoyl leukomethylene etc.

(5) spiro-compound

3-methylspiro dinaphthopyran, 3-ethyl spiral shell dinaphthopyran, 3,3-dichloro spiral shell dinaphthopyran, 3-benzyl spiral shell dinaphthopyran, 3-methyl naphtho--(3-methoxyl group benzo) spiro-pyrans, 3-propyl group spirobenzopyran etc.

In addition, can enumerate following compounds: 3 with near infrared absorption zone etc., two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino 2-benzofuranone), 3-diethylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino 2-benzofuranone), 3, two (diethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dimethylamino 2-benzofuranone), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino 2-benzofuranone), 3-dibutylamino-6-diethylamino fluorenes-9-spiral shell-3 '-(6 '-dimethylamino 2-benzofuranone), 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-diethylamino 2-benzofuranone), 3-diethylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-diethylamino 2-benzofuranone), 3-dibutylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-diethylamino 2-benzofuranone), 3, two (diethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-diethylamino 2-benzofuranone), 3, two (dimethylamino) fluorenes of 6--9-spiral shell-3 '-(6 '-dibutylamino 2-benzofuranone), 3-dibutylamino-6-diethylamino fluorenes-9-spiral shell-3 '-(6 '-diethylamino 2-benzofuranone), 3-diethylamino-6-dimethylamino fluorenes-9-spiral shell-3 '-(6 '-dibutylamino 2-benzofuranone) and 3, two [2-(4-dimethylaminophenyl)-2-(4-methoxyphenyl) vinyl]-4 of 3-, 5,6,7-tetrachloro 2-benzofuranone.

In these compounds, consider from the picture steadiness angle of sensitivity and document image, particularly preferably be triarylmethane leuco dye, fluoran leuco dye, fluorenes leuco dye and diphenyl-methane leuco dye.These leuco dyes can two or more unite use with it as required.

With respect to the dyestuff former of 100 weight portions, the consumption of developer is generally 5～1000 weight portions, preferred 10～500 weight portions, more preferably 30～300 weight portions in quality material compositions of the present invention.When the amount of described developer hour, become color density low and be not suitable for practical application.When the amount of described developer is too big, become the color density value of reaching capacity and unfavorable economically.

When quality material compositions of the present invention is used as thermal recording medium, for the sensitivity that improves described recording materials can contain emulsion in the quality material compositions.Usually the emulsion chemical substance that can melt for heating, and preferably have 60～180 ℃, especially preferred 80～140 ℃ fusing point.The example of described emulsion can comprise: stearmide and emulsion thereof, palmitamide Shan Yu acid amides, N-methylol stearmide, the betanaphthyl benzylic ether, N-stearyl urea, N, N '-distearyl urea, β-naphthoic acid phenylester, 1-hydroxyl-2-naphthoic acid phenylester, betanaphthol-(right-methyl-benzyl) ether, 1, the 4-dimethoxy-naphthalene, 1-methoxyl group-4-benzyloxy naphthalene, the stearic uride of N-, right-benzylbiphenyl, 1, the 2-biphenoxyl ethane, 1,2-two (-methylphenoxy) ethane, 1,2-hexichol oxygen ylmethyl benzene, 1,2-two (3, the 4-3,5-dimethylphenyl) ethane, 1-phenoxy group-2-(4-chlorophenoxy) ethane, 1,4-butanediol phenyl ether, dimethyl terephthalate (DMT), terephthalic acid (TPA) dibenzyl ester, between-terphenyl, dibenzyl oxalate, oxalic acid two-right-methyl-benzyl ester and oxalic acid two (right-the benzyl chloride base) ester.

In addition, owing to can improve the sensitivity of described recording materials very effectively, therefore following compounds is preferred: 4,4 '-dimethoxy-benzophenone, 4,4 '-dichloro benzophenone, 4,4 '-difluoro benzophenone, diphenyl sulfone, 4,4 '-dichloro diphenylsulfone, 4,4 '-difluorodiphenyl base sulfone, 4,4 '-dichloro diphenyl disulphide, diphenylamines, 2-methyl-4-methoxy diphenylamine, N, N '-diphenyl-p-phenylenediamine (PPD), 1-(N-phenyl amino) naphthalene, 1,3-diphenyl-1,3-propanedione etc.

It is preferred in these compounds that what use is diphenyl sulfone, oxalic acid two-right-methyl-benzyl ester, P-hydroxybenzoic acid benzyl ester, betanaphthyl benzylic ether, to benzylbiphenyl, 1,2-two (-methylphenoxy) ethane, 1,2-hexichol oxygen ylmethyl benzene ,-terphenyl and stearmide.

Above-mentioned emulsion can use separately or two or more unite use with it.With respect to the described dyestuff former of 100 weight portions, the consumption of described emulsion is generally 0～1000 weight portion, preferred 0～500 weight portion, more preferably 1～300 weight portion.When sensitization dosage hour, the thermal response that is difficult to improve recording materials.When sensitization dosage is too big, thermal response value of reaching capacity and unfavorable economically.

As mentioned above, quality material compositions of the present invention contains as the dyestuff former of its key component and developer of the present invention, and goes back usability photo etching simultaneously as required; Randomly as required, described quality material compositions can further contain other following additives, for example lubricant, adhesive, filler, dispersant and picture steadiness imparting agent.

Add lubricant and be in order to prevent effects such as the first-class wearing and tearing of heat, adhesion, it is to be 70 ℃ or higher for the material of solid and fusing point under conventional temperature; The example can comprise wax, for example from the wax and the synthetic wax in animal or plant source; Higher fatty acids and slaine thereof; Higher fatty acid amides; With the higher fatty acids anilide.The instantiation of described wax can comprise: vegetable wax, Brazil wax, shellac, paraffin, montan wax, oxidized paraffin wax, Tissuemat E and oxidic polyethylene; The instantiation of described higher fatty acids and slaine thereof can comprise stearic acid with behenic acid and slaine thereof, i.e. zinc stearate, calcium stearate; The instantiation of described higher fatty acid amides can comprise oleamide, N-methyl stearmide, mustard acid amides, methylol Shan Yu acid amides, di-2-ethylhexylphosphine oxide stearmide and ethylenebisstearamide; The instantiation of described higher fatty acids anilide can comprise stearic acid anilide and linoleic acid anilide.

These lubricants consumption is separately chosen wantonly, but is preferably two times of used leuco dye or still less.

The instantiation that can be used for the present invention's adhesive can comprise: water-soluble substances, for example methylcellulose, the methoxyl group cellulose, hydroxyethylcellulose, carboxymethyl cellulose, sodium carboxymethylcellulose, cellulose, polyvinyl alcohol, carboxyl-modified polyethylene alcohol, sulfonic acid group-modified polyethylene alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, the starch or derivatives thereof, casein, gelatin, water-soluble isoprene rubber, the alkali metal salt of phenylethylene/maleic anhydride copolymer, the alkali metal salt of different (or two different) butylene/copolymer-maleic anhydride; Hydrophobic polymer emulsion, vinyl chloride/vinyl acetate co-polymer, polystyrene, polyacrylate, polyurethane, styrene/butadiene copolymers, styrene/butadiene copolymers, the phenylethylene/butadiene/acrylic copolymer of carboxylated and the composite particulate material of making by silica gel and acrylic resin with polyvinyl acetate.

The instantiation that can be used for the present invention's filler can comprise: calcium carbonate, magnesium carbonate, magnesia, silica, white carbon, talcum, clay, alumina, magnesium hydroxide, aluminium hydroxide, aluminium oxide, barium sulfate, polystyrene resin and urea-formalin resin.With respect to the leuco dye of 100 weight portions, the addition of described filler is 0～1000 weight portion, preferred 0～500 weight portion, more preferably 0～300 weight portion.

The instantiation that can be used for the present invention's dispersant can comprise: water-soluble polymer, for example alkali metal salt of polyvinyl alcohol, carboxylic acid-modified polyethylene alcohol, sulfonic acid-modified polyethylene alcohol, methylcellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose and phenylethylene/maleic anhydride copolymer; Anion surfactant, for example the naphthalene sulfonate of condensation, polyoxyethylene alkyl ether sulfuric acid are (for example, polyoxyethylene lauryl ether sodium sulfovinate, polyoxyethylene alkyl ether sodium sulfovinate and polyoxyethylene alkyl phenyl ether sodium sulfovinate), sulfosuccinic acid dialkyl sodium, alkylphosphonic (for example, alkyl phosphoric acid diethanol amine and alkyl phosphate potassium) and specific carboxylic acid polyalcohol; Non-ionic surface active agent, for example polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene sorbitan carboxylate, mono fatty acid glyceride and cithrol; And cationic surfactant, for example dicyandiamide polyamine, tertiary ammonium salt and quaternary ammonium salt.Particularly preferably be alkali metal salt, methylcellulose and the polyoxyethylene alkyl ether sodium sulfovinate of polyvinyl alcohol, carboxylic acid-modified polyethylene alcohol, sulfonic acid-modified polyethylene alcohol, styrene/maleic acid in these compounds.These dispersants can use separately separately or use as its mixture.

The picture steadiness imparting agent that is used for the present invention is meant for example additive of image stabilizing agent, light stabilizer and antioxidant.These picture steadiness imparting agents and quality material of the present invention are united the photostability that use can improve described quality material, thus the recording materials that obtain having excellent photostability.Image stabilizing agent as the preferred embodiment of picture steadiness imparting agent used among the present invention for example can comprise: hindered phenol compound, for example 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,1,3-three (2-methyl-4-hydroxyl-5-cyclohexyl phenyl) butane, 4,4 '-butylidene two (the 2-tert-butyl group-5-methylphenol), 4,4 '-thiobis (the 2-tert-butyl group-5-methylphenol), 2,2 '-thiobis (the 6-tert-butyl group-4-methylphenol) and 2,2 '-di-2-ethylhexylphosphine oxide (the 6-tert-butyl group-4-methylphenol); With 4-benzyloxy-4 '-(2-methyl glycidyl oxygen base) diphenyl sulfone, 4,4 '-diglycidyl oxygen base diphenyl sulfone, 1,4-diglycidyl oxygen base benzene, 2,2 '-di-2-ethylhexylphosphine oxide (4, the 6-di-tert-butyl-phenyl) phosphate sodium, 2-propanol derivative and salicyclic acid derivatives.Usually, with respect to the dyestuff former of 100 weight portions, these image stabilizing agents consumption separately is preferably 5～1000 weight portions, more preferably 10～500 weight portions.When the amount of described image stabilizing agent surpassed 5 weight portions, photostability was satisfactory and become color density also high.When described image stabilizing agent surpassed 1000 weight portions, the effect of photostability did not improve and is also unfavorable economically in addition.

Can improve brightness by in quality material compositions of the present invention, adding fluorescent dye in addition.Can use multiple compound well known in the art as fluorescent dye, described examples for compounds can comprise stilbene derivative, coumarin derivative, pyrazoline derivative, bis-styrylbiphenyl derivative, Naphthalamide derivatives and dibenzoxazine derivative.Though described fluorescent dye is not limited to these examples, preferred especially diaminourea Stilbene disulfonic acid derivatives.With respect to the solid total content of described quality material, the consumption of described fluorescent dye is preferably 0.01～3 weight %, more preferably in 0.1～2 weight % scope.When the consumption of described fluorescent dye surpassed 3 weight %, described sometimes quality material can variable color, and when the consumption of described fluorescent dye during less than 0.01 weight %, for the effect decline of brightness.

Quality material compositions of the present invention can be used for multiple recording materials for example thermal recording medium, pressure sensitive recording material, is particularly suitable for thermal recording medium.

Thermal recording medium has wherein the structure that will be arranged on by the heat sensitive recording layer that heating can form color on the matrix usually.More particularly, developer, dyestuff former, thermographic compound and other material are mixed with dispersion, and described dispersion liquid is applied on the matrix to form heat sensitive recording layer with other necessary component.In the preparation of described dispersion liquid, the meticulous pulverizing of compound that one or more is belonged to these independent components with sand mill etc. in containing the aqueous solution of dispersant is to produce dispersion liquid.The granularity of the discrete particles in dispersion liquid preferably in 0.1～10 mu m range, about 1 μ m more preferably.

When developer of the present invention is used to thermal recording medium, be adjusted to 0.05 μ m or bigger and be 5 μ m or littler by particle mean size with the developer particle of meticulous pulverizing, can obtain satisfactory aspect the thermal response and on the picture steadiness of quality document image also gratifying thermal recording medium.When particle mean size during less than 0.05 μ m, the picture steadiness of non-image areas reduces, and when particle mean size during greater than 5 μ m, the sensitivity variation of thermal recording medium.Particle mean size is 0.1 μ m or bigger and be 3 μ m or littler more preferably.

When developer of the present invention carries out wet-milling when broken in water-bearing media, the fluid temperature of used water-bearing media is preferably 60 ℃ or lower.When fluid temperature is 60 ℃ or when higher, described developer can change and assembles according to other condition, probably can cause the blushing in the non-image areas and the sensitivity of used thermal recording medium to reduce.

When described developer is pulverized, preferably under 5～10 neutral pH, pulverize., when the hot coating liquid of preparation, can cause inorganic pigment and other material to decompose, thereby probably can cause sensitivity to reduce less than for 5 for pH in the pulverization, and for pH greater than 10, developer can change and the sensitivity reduction sometimes.

With regard to pulverizing described developer, by described developer and the meticulous together pulverizing of above-mentioned emulsion (pulverizing altogether) can be obtained favourable effect: with the independent component of the meticulous pulverizing of difference, situation about being blended together is again afterwards compared, the sensitivity of thermal recording medium is further improved and the stability of its document image also is further improved, although its reason is not clear.

As the matrix that is used for heat sensitive recording layer, main use paper, but can randomly use following non-paper material: multiple yarn fabric and adhesive-bonded fabric, synthetic resin film, laminated paper, synthetic paper, metal forming and combine the composite sheet of these materials according to purpose.The basis weight of matrix wishes to be 40g/m ²～200g/m ²And wish by applying heat with mechanical calender, soft calender, super calender etc. and pressure comes matrix is carried out surface-processing, because wish that as thermal recording medium matrix has high as far as possible flatness, just, wish that matrix has excellent surface smoothness and flatness.

The surface p H of described matrix is preferably 3～12.When the surface p H of matrix less than 3 the time, tend to appear at the blushing in the non-image areas, and when surface p H surpassed 12, developer can change and become the color density reduction sometimes.Surface p H more preferably 5～9, more preferably 6～8.

Described heat sensitive recording layer can be made of single layer or a plurality of layer.For example, single quality component can be included in respectively in the layer to form sandwich construction.On heat sensitive recording layer, can be provided with by single layer or a plurality of layers of protective layer of forming, perhaps can will be arranged between matrix and the heat sensitive recording layer by single layer or a plurality of layers of intermediate layer of forming.Heat sensitive recording layer can obtain by apply mixture that makes by mixing water dispersion liquid and adhesive etc. and the layer that so forms by drying afterwards on matrix, and wherein said aqueous dispersions is by obtaining independent quality component and the meticulous pulverizing of other component.

Quality material of the present invention can be used as multiple thermal recording medium, and is especially suitable for use as thermo magnetic recording material, thermosensitive recording label, polychrome thermal recording medium, laser-mark thermal recording medium.When described thermal recording medium is the thermo magnetic recording material, be preferably on the one side that the heat sensitive recording layer that wherein contains developer is set at matrix and magnetic recording layer is set at form on the another side.Magnetic recording layer in the thermo magnetic recording material is for example by being applied in coating material on the matrix and the dry layer that so forms forms, and wherein said coating material is by with barium ferrite, strontium ferrite, Co-γ-Fe ₂O ₂, γ-Fe ₂O ₂Deng ferromagnetic powder be dispersed in the aqueous binders of forming by aqueous emulsion resin etc. and make.In this case, can add multiple additives according to purpose, comprise antistatic additive for example carbon graphite, as the wax of lubricant, in order to the coloring pigment of regulating color with as the PEO of the softening agent of filming.Thermo magnetic recording material of the present invention is suitable as the thermo magnetic recording material that is used for traffic ticket, other bill, prepaid card etc.

When described thermal recording medium is thermosensitive recording label, be preferably on the one side that the heat sensitive recording layer that wherein contains developer is set at matrix and adhesive layer is set at form on the another side.The adhesive layer of described thermal recording medium contains the contact adhesive as key component, and the example of described contact adhesive can comprise synthetic rubber latex adhesive, acrylic emulsion adhesive, natural rubber solvent cement, acrylic acid solvent cement and siloxane solvent adhesive; Particularly preferably be the acrylic emulsion adhesive in these compounds.

In addition, when back layer (back coating) is set between the adhesive layer of prepared according to the methods of the invention thermosensitive recording label and the matrix as required, the crimping of thermosensitive recording label is stretched, can prevent its electrostatic interaction and can control its coefficient of friction.For the coating liquid component that is used for back layer, its using method etc., can adopt the method identical with forming heat sensitive recording layer.

When the preparation thermosensitive recording label, the order of operating for coating is not particularly limited.Yet some possible situations for example are: wherein heat sensitive recording layer is arranged on the one side of matrix, back coating is set afterwards and adhesive layer further is set to prepare the situation of relevant label on another side; Wherein back coating is arranged on the face of matrix, heat sensitive recording layer is arranged on the another side afterwards and the situation of adhesive layer further is set on the coating overleaf.For the method that is used for being provided with on the coating overleaf adhesive layer, to carry out on the dry back coating after the liquid that is used to form adhesive layer can being applied directly to, the liquid that perhaps will be used to form adhesive layer is applied in and will carries out afterwards on the dry peeling paper, and described peeling paper can be laminated on the back side-coat side of the thermal recording medium that adhesive layer also is not set on it.Can improve thermal response by being arranged between heat sensitive recording layer and the matrix by single layer or a plurality of layers of intermediate layer of forming.Mainly for example water-soluble polymer and latex are formed by organic and inorganic pigment, microballoon and aqueous binders in described intermediate layer; Can use with heat sensitive recording layer in used similar organic and inorganic pigment and aqueous binders.Also be not particularly limited for the method that forms the intermediate layer, can use and be used to form the similar method of method of heat sensitive recording layer.The heat sensitive recording layer of thermosensitive recording label contains quality material and the adhesive as its key component, and wherein said quality material is based on by the contact of the caused material of heating and be carried out to colour response, and can be according to adding crosslinking agent, pigment and emulsion.Under this applicable cases, water-soluble or water-dispersed resin can be used for temperature-sensitive and become the contained adhesive of chromatograph.Yet prerequisite prerequisite is when the dispersion liquid of the dispersion liquid of adhesive and leuco dye and reagent composition mixes, and the mixed solution that so obtains can not form color, highly viscous state takes place to assemble or change into; The superficial layer of the heat sensitive recording layer that necessary in addition is forms is tough and tensile and the effect that sensitiveness descends can not occur.Become the solids content of chromatograph with respect to temperature-sensitive, temperature-sensitive becomes the combined amount of the adhesive in the chromatograph to be preferably 5～20%; Combined amount can cause the low defective of strength of coating less than 5%, and combined amount surpasses 20% problem that can cause sensitivity to reduce.In addition, become the resistance to water of chromatograph can use the crosslinking agent that is used for cured resin in order to improve temperature-sensitive.

When thermal recording medium is the polychrome thermal recording medium, be preferably on the one side that the heat sensitive recording layer of wherein being made up of at least two layers is set at matrix and one deck at least of heat sensitive recording layer contains the form of developer of the present invention.Can use following material and other material as matrix: the synthetic paper that makes by following method: wherein kneading vistanex and white inorganic pigment under heating, extrude the mixture of gained and carry out longitudinal stretching from mould afterwards, thereby will be formed one or two layer in each face by the film lamination that vistanex and white inorganic pigment are made on each face of the mixture of described drawn, the laminate of cross directional stretch gained is to prepare translucent or opaque synthetic paper; The film that makes by following method: wherein for example polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, polyvinyl chloride, polystyrene and polyester use separately or use as its mixture thermoplastic resin separately, selected one or more resins of kneading under heating, extrude from mould afterwards, with the material biaxial orientation extruded with the preparation film; The opaque coating that makes by following method: wherein one or more and the white inorganic pigment with these resins mixes, and makes the mixture biaxial orientation with the preparation opaque coating afterwards; Can use the paper of making by paper pulp fiber in addition, for example high-quality paper, ordinary quality paper, coil paper, recycled writing paper and coated paper.In order to reach satisfied image uniformity, preferably for providing coating, the matrix of being made by paper pulp fiber also is coated with heat-sensitive layer then in advance.

Form as the polychrome thermal recording medium, what can enumerate is following polychrome thermal recording medium: wherein have different two heat sensitive recording layers that become color temperatures and form the color of different tones and be formed on the one side of matrix by lamination, go up wherein that heat sensitive recording layer contains colour developing/reducing agent or reversible developer and time heat sensitive recording layer contains developer of the present invention.In this material, colour developing/the reducing agent that is used for heat sensitive recording layer shows coloring function when being heated at low temperatures, show the decolouring function when at high temperature being heated, and for containing acidic-group with coloring function and the amphoteric compound with basic group of decolouring function.Described acidic-group by phenolic hydroxyl group or carboxyl as representative instance, and basic group by amino as representative instance.Described colour developing/reducing agent can contain the basic group as functional group, but preferably contains the basic group as the part of salt compound, for example complex between phenol carboxylic acid compound and the amines.The instantiation of described colour developing/reducing agent can comprise following compounds.The example that constitutes the phenol carboxylic acid compound of colour developing/reducing agent can comprise 2 hydroxybenzoic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 3,4-dihydroxy-benzoic acid, 3,5-dihydroxy-benzoic acid, 2,3-dihydroxy-benzoic acid, 2,4-dihydroxy-benzoic acid, 2,5-dihydroxy-benzoic acid, 2,6-dihydroxy-benzoic acid, gallic acid, two (4-hydroxy phenyl) acetic acid and 3, two (4-hydroxy phenyl) propionic acid of 3-.The example that forms the amines of salt or complex with the phenol carboxylic acid compound can comprise octylame, nonyl amine, decyl amine, lauryl amine, tetradecylamine, heptadecyl amine, stearic amine, Shan Yu base amine, 3-METHOXY PROPYL AMINE and hexamethylene diamine.

Reversible developer is for phenolic compounds for example or have the phosphinic acid compounds of the aliphatic hydrocarbyl of 8 or more a plurality of carbon atoms.The instantiation of this reversible developer can comprise following compounds; But described reversible developer is not limited to these examples, and for reversible developer without limits, as long as its reagent that shows coloring function when heating at low temperatures and show the decolouring function when at high temperature heating.Above-mentioned instantiation can comprise 4-(octadecane sulfenyl) phenol, 4-(docosane sulfenyl) phenol, 4-(octadecane oxygen base) phenol, 4-(docosane oxygen base) phenol, N-octadecyl-4-hydroxybenzamide, 4 '-hydroxyl behenic acid anilide, N-(4-hydroxy phenyl)-N '-n-octadecane base urea and docosyl phosphonic acids.When using polychrome thermal recording medium and thermo printer etc. to write down, under low temperature hot stamping brush, have only low temperature to become chromatograph to form color, and become chromatograph to decolour at the low temperature that has only high temperature to become chromatograph to form color under the elevated temperature heat printing and being printed in the part.

Another kind is had the developer of image stabilization of very high recording picture and developer of the present invention and unite use and can make the object that is used for laser labelling, it is provided as the sufficient and highly stable quality document image of color density; Therefore consider its advantageous particularly from the long preservation angle of record.The object that is used for laser labelling preferably contains the recording sensitivity improver at its hot recording layer.Recording sensitivity improver as available can use the material that can absorb the laser that is used to shine.The instantiation of this material can comprise multiple inorganic compound for example aluminium hydroxide and silicate mineral, and described silicate mineral comprises wollastonite, bentonite, mica (muscovite, bronze mica), calcium silicates, talcum, kaolin, clay, fayalite, hornblend and albite.Particularly preferably be aluminium hydroxide, muscovite, wollastonite and kaolin.Described inorganic compound can use separately separately or as it two or more mixture and use.

Usage ratio between dyestuff former described in the heat sensitive recording layer and recording sensitivity improver can suitably be selected according to the type of used dyestuff former and used recording sensitivity improver, is not particularly limited for described ratio.Yet with respect to the quality material of 100 weight portions, described recording sensitivity improver can use with 10～5000 weight portions, preferred 100～2000 weight portions usually.With respect to the total amount of the solid contents in the relevant layer, the ratio of the dyestuff former in the heat sensitive recording layer, developer and recording sensitivity improver can be set in respectively in the following ranges: for dyestuff former is 5～30 weight %, preferred 10～25 weight %; Be 10～60 weight %, be preferably 20～50 weight % for developer; For the recording sensitivity improver is 5～40 weight %, preferred 10～30 weight %.In order further to improve the sensitivity of the object that is used for laser labelling, can also in heat sensitive recording layer, contain emulsion mentioned above.

The quality marking composition contains above-mentioned colourless or light dyestuff former, developer and recording sensitivity improver and aqueous binders and the water as its necessary component; Sneak into multiple auxiliary agent as required to produce relevant composition.The example of the auxiliary agent of Shi Yonging can comprise in this case: dispersant, for example sodium salt of dioctyl sodium sulphosuccinate, neopelex, laruyl alcohol sulfuric ester and the slaine of aliphatic acid; Screening agent is titanium oxide for example; Defoamer; Viscosity modifier; Fluorescent dye; And colouring agent.Have no particular limits for the matrix of printing (applying) quality marking composition thereon, as long as described matrix needs mark.The example of described matrix can comprise the specific part of food containers, packaging material and electronic unit, and will be bonded in the object label matrix for example on these above-mentioned objects.As label matrix, suitably use paper and other material for example paper and synthetic paper, metal deposited film, metal and the wood materials of stationery and synthetic paper, synthetic resin film, plastics, metal-deposition as required.The quality marking composition can prepare in the following manner: with adhesive dissolving or be dispersed in water or contain in the solvent of water as key component; With quality material, developer, recording sensitivity improver etc., if necessary, with for example dissolving such as ball mill, grater, sand mill or be dispersed in water or contain in the solvent of water as key component of dispersal device, so that for example at water or contain dispersant and for example in the aqueous solvent of polyvinyl alcohol independent component is handled together or respectively, thereby make a dispersion liquid or a plurality of dispersion liquid; Be generally about 2 μ or littler and be preferably about 1 μ or littler through the particle mean size of each component after the dispersion treatment; Then adhesive and dispersion liquid are mixed to generate the quality marking composition.The solids content of described quality marking composition is 20～70 weight %, be preferably 30～65 weight % orders of magnitude.

The quality marking composition can be applied directly on the described matrix, perhaps be applied on the matrix of carrying out the coating of surface treatment or bottom in advance.For example roll coater, notch board coating machine, nick plate coating machine, knife type coater or flush coater carry out described applying can to adopt suitable apparatus for coating.The thickness of film (the hot recording layer) of gained can be made into 1～4 μ m usually after coating and drying.When thickness during less than 1 μ m, be used for the quality character variation of laser irradiation and simultaneously described filming tend to peel off, and when thickness during, be used for availability and dry property that label bonds and tend to be lowered greater than 4 μ m.Comprise linear velocity according to the coating condition, change desiccation and can at room temperature carry out, also can under heating, carry out making heat sensitive recording layer not form under the condition of color.At the object that is used for laser labelling protective layer is set by on its heat sensitive recording layer, applying transparent limpid coating liquid.Described limpid coating liquid is the Aquo-composition of being made up of aqueous binders, water and other material.

By irradiating laser on the heat sensitive recording layer of the formation like this of the object that is used for mark, heat its illuminated part, therefore described developer and the dyestuff former formation color that reacts each other promptly produces mark.Energy for irradiating laser is not particularly limited, but considers to be preferably 1.4J (joule)/cm from destroying the angle of filming ²Or it is littler.On the other hand, owing to can not obtain to be used to produce low-energy device, thereby not clear for the lower limit of quality, but have been found that 0.4J/cm ²Energy be enough to carry out abundant quality.Therefore, the irradiation energy scope that is used for quality is set in 0.4～1.4J/cm ²In, particularly suitable is 0.45～1.2J/cm ²As the laser that is used in the irradiation, suitable is pulse laser or scan laser, and as the type of laser instrument, any of gas laser, excimer laser and semiconductor laser can use.Particularly, can enumerate carbon dioxide gas laser, mixed gas laser, YAG laser instrument, ruby laser etc.

Label as the object that is used for laser labelling can be made in the following manner: as required with paper and other material for example paper and synthetic paper, synthetic resin film, plastics, metal deposition paper and synthetic paper, metal deposited film, metal etc. suitably as label matrix; According to said method, on selected each label matrix, form heat sensitive recording layer and protective layer.The application of the label that obtains comprises all spectra that label has up to now been used, the especially preferred application relevant with electric component with food, medical product, cosmetics, publication and electronics.As the packaging material of the object that is used for laser labelling is by using said method to the multiple normally used packaging material object that provides heat sensitive recording layer and protective layer to make such as box body, wrapping paper, parcel for example, is paper and other material for example paper and synthetic paper, synthetic resin film, plastics, metal deposition paper and synthetic paper, metal deposited film, metal, glass and wood materials as matrix suitably wherein.The application of these packaging material comprises all spectra that packaging material have up to now been used, the especially preferred application relevant with electric component with food, medical product, cosmetics, publication and electronics.Container as the object that is used for laser labelling of the present invention uses glass, plastics and metal as matrix, and by using said method on these matrix, to provide heat sensitive recording layer and protective layer to make respectively.These containers can be used for all spectra that container has up to now been used, and for example relevant with food containers field comprises the bottle, rice steamer formula food containers and the instant food container that are used for drinks and pick-me-up; Cosmetics containers; The medical product container; And cosmetic product.

To describe particularly the present invention based on embodiment, comparative example and reference example now.But embodiments of the invention are not limited to these embodiment.In following explanation, " part " refers to that " weight portion " and " % " refers to " weight % ".

At first the method for analyzing and estimate the performance of each material that will study in embodiment, comparative example and the reference example is described.

The measurement of the content of three phenolic compounds and proportion of composing in＜the developer 〉

(Hitachi High-Technologies Corp. makes: L-7100) measure with high performance liquid chromatography under following condition.

Post: Cadenza CD-C18 (Intact Co., Ltd. makes, the ODS post)

Colour-developing solvent (volume ratio): in following mixed solvent, carry out gradient and handle.

CH ₃CN/H ₂O (containing 0.15% ammonium acetate)=3/7 to 7/3 (40 minutes), 7/3 to 9.6/0.4 (10 minutes) subsequently

Internal standard compound matter: pyrene

Flow velocity: 1ml/min

Detector: UV 254nm

＜fusing point is measured 〉

(Sibata Scientific Technology Ltd. makes, and is to measure under the 1 ℃/min at temperature rise rate B-545), and will begin temperature as fusing point by the fusing that visual examination is determined with the fusing point measurement mechanism.

＜one-tenth colour test 〉

Use Ohkura Electric Co., Ltd. the hot stamping brush experimental rig of making (TH-PMD) is that 2.4V, pulse width are that 1.5 milliseconds and printing energy are that the thermal recording medium to appointment is carried out to colour test under the condition of 0.34mj/dot applying voltage, and wherein said hot stamping brush experimental rig has been equipped the heat KJT-256-8MGF1 that Kyocera Corp. makes.(Kollmorgen Corp. makes, and RD917) the one-tenth color part of surveying record material is to obtain into color density (OD value) with the Macbeth reflection densitometer.

＜heat-resistance test 〉

Based on following formula, by be provided with in the hot air circulate drier of quality thermal recording medium under 60 ℃ after 24 hours with before the color density that becomes obtain into the color density storage rate.

Become color density storage rate (%)=(the one-tenth color density after 60 ℃ are placed 24 hours down/before placement one-tenth color density) * 100

＜moisture resistance test 〉

Based on following formula, by with the quality thermal recording medium 40 ℃ with 90%RH humidity under constant temperature and constant humidity degree chamber in place 24 hours after with before the color density that becomes obtain into the color density storage rate.

Become color density storage rate=(%) (the one-tenth color density that becomes color density/before placement after under 40 ℃ and 90%RH, placing 24 hours) * 100

Result based on above-mentioned test and measurement estimates the performance of recording materials by following method.

[evaluation of sensitivity]

Based on following standard, estimate sensitivity by the one-tenth color density that in above-mentioned one-tenth colour test, obtains (OD value); Be worth that high sensitivity is good more more.

Zero: OD value: greater than 1.05

△: OD value: 0.90～1.05

*: OD value: less than 0.90

[evaluation of the blushing in the non-image areas]

Based on following standard, by in above-mentioned one-tenth colour test, estimating blushing degree in the non-image areas through the OD value of the non-one-tenth color part of the thermal recording medium measured.The blushing degree that is worth in the low more non-image areas is good more.In addition, also the thermal recording medium through above-mentioned heat-resistance test and moisture-resistant test is carried out the evaluation of the blushing of non-image areas according to identical mode.

Zero: OD value: less than 0.10

△: OD value: 0.10～0.16

*: OD value: greater than 0.16

[hear resistance evaluation]

Based on following standard, by the one-tenth color density storage rate that in above-mentioned heat-resistance test, obtains, for the hear resistance of each picture appraisal as the image stability sex index of recording picture.Be worth that high-fire resistance is good more more.

Zero: OD value: greater than 80%

△: OD value: 80%～50%

*: OD value: less than 50%

[moisture resistance evaluation]

Based on following standard, by the one-tenth color density storage rate that in above-mentioned moisture resistance test, obtains, for the moisture resistance of each picture appraisal as the image stability sex index of recording picture.Be worth that high moisture is good more more.

Zero: OD value: greater than 70%

△: OD value: 70%～50%

*: OD value: less than 50%

Embodiment 1

In flask, put into 20g toluene and 48.0g (510mmol) phenol as phenolic compounds, put into 2 of amphyl that 5.0g (25.6mmol) replaces as contraposition in this external flask, 6-dihydroxy methyl-4-isopropyl-phenol, the mixture that stirring so obtains is to dissolve.Under 30 ℃ in this solution, adding 0.12g (0.63mmol) p-methyl benzenesulfonic acid monohydrate under the stirring condition, stirred described solution then 5 minutes, make it 60 ℃ of down reactions 2 hours afterwards.It is 6 that the reaction solution that washes gained with water makes its pH, removes phenol as the toluene of solvent and excessive use then to obtain the condensation product as developer of the present invention under the pressure that reduces.In the developer of gained, the content of three phenolic compounds (A) is 90%, and the content of remaining phenol is 0.4%, and remaining is made up of other condensation by-product, and the content of three phenolic compounds (C) is 16%, and fusing point is 130 ℃.

Next, use the coating vibrating machine developer of 2g gained to be pulverized 12 hours so that itself and 2.5% polyvinyl alcohol water solution (Nippon Synthetic Chemical Industry Co., Ltd. manufacturing; Trade name: " Gohseran L-3266 ") disperses together, thereby obtain dispersion liquid.In addition, use sand mill (container volume: 400ml; Aimex Co., Ltd. makes) under the rotating speed of 2000rpm, 70g was pulverized 3 hours so that its polyvinyl alcohol water solution with 130g 8% disperses as the 3-dibutylamino-6-methyl-7-anilino fluorane of leuco dye, thereby obtain dispersion liquid.In addition, use sand mill (container volume: 400ml; Aimex Co., Ltd. makes) under the rotating speed of 2000rpm with 70g as the betanaphthyl benzylic ether of emulsion (Ueno Fine Chemicals Industry, Ltd. makes; Trade name: " BON ") pulverized 3 hours so that its polyvinyl alcohol water solution with 130g 5.4% disperses, thereby obtain dispersion liquid.In addition, thus 10g calcium carbonate mixed with 30g water and stirs described mixture and it is disperseed to make dispersion liquid with agitator.

Next, by following ingredients being mixed the coating liquid that obtains to contain quality material compositions of the present invention under stirring condition, wherein " part " is that solids content according to drying provides: 30 parts of developer dispersions; 15 parts of 3-dibutylamino-6-methyl-7-anilino fluorane dispersion liquids; 30 parts of betanaphthyl benzylic ether dispersion liquids; 20 parts of calcium carbonate disperse liquid; 10 part of 16% (solid content concentration) zinc stearate dispersion liquid; Polyvinyl alcohol with 7 part 15%.

It is 50g/m that the coating liquid that will so obtain with spreading rod (excellent No.10) is applied in basis weight ²Basic paper on.Paper through coating is handled to make thermal recording medium with super calender in dry back.The applied amounts of coating liquid is 3g/m based on dry weight ²Thermal recording medium to gained carries out the results are shown in the table 1 of performance evaluation.

Embodiment 2

Obtain condensation product as developer of the present invention according to the step of embodiment 1, different is that 6-dihydroxy methyl-4-sec-butyl phenol replaces 5.0g (25.6mmol) 2,6-dihydroxy methyl-4-isopropyl-phenol with 5.4g (25.6mmol) 2.In the developer of gained, the content of three phenolic compounds (A) is 89%, and the content of remaining phenol is 0.2%, and remaining is made up of other condensation by-product, and the content of three phenolic compounds (C) is 19%, and fusing point is 120 ℃.

Use the developer of gained and contain the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side according to the step preparation of embodiment 1.What so obtain the results are shown in the table 1.

Embodiment 3

In flask, put into 48.0g (510mmol) phenol, put into 5.0g (25.6mmol) 2 in this external flask, 6-dihydroxy methyl-4-tert-butyl phenol, the mixture that stirring so obtains is to dissolve.Under 30 ℃ in the hydrochloric acid that in this solution, adds 0.074g (0.73mmol) 36% under the stirring condition, stirred described solution then 5 minutes, make it 60 ℃ of down reactions 2 hours afterwards.It is 6 that the reaction solution that washes gained with water makes its pH, removes the phenol of excessive use to obtain the condensation product as developer of the present invention then under the pressure that reduces.In the developer of gained, the content of three phenolic compounds (A) is 86%, and the content of remaining phenol is 0.6%, and remaining is made up of other condensation by-product, and the content of three phenolic compounds (C) is 12%, and fusing point is 126 ℃.In addition, in this developer, add toluene, and to stir mixture, the cooling so obtain and filter to obtain three phenolic compounds (A) wherein under heating be that the content of 97% and three phenolic compounds (C) is the developer of 12% purifying.The fusing point of the developer of purifying is 132 ℃.

Use the developer of gained and contain the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side according to the step preparation of embodiment 1.What so obtain the results are shown in the table 1.

Embodiment 4

By heating the developer that obtains among the embodiment 2 is dissolved in toluene, cooling is recrystallized with the developer that obtains being recrystallized then, and wherein the content that all has three phenolic compounds (B) of OH group in 4-and the 4 '-position that lays respectively on a left side and the right aromatic ring is 92%.The fusing point of the developer of recrystallization is 200 ℃.Fully mix by the mixture that 4-hydroxyl-4 '-the isopropoxy diphenyl sulfone is formed that developer and 0.4g by 1.6g recrystallization are added as another developer and to prepare new developer.Use described new developer and preparation contains the quality material compositions according to the step of embodiment 1 coating liquid, the benchmark test of the line item material of going forward side by side.What so obtain the results are shown in the table 1.

Embodiment 5

By to by 1.6g Bis P-PC (Honshu Chemical Industry Co., Ltd. makes; Purity: 98%; Fusing point: 210 ℃) and 0.4g add as another developer 4, the mixture that 4 '-dihydroxy-diphenyl sulfone is formed fully mixes and prepares new developer, wherein said Bis P-PC is for all having three phenolic compounds (B) of OH group in 4-and the 4 '-position that lays respectively on a left side and the right aromatic ring, and it is by 2, and the condensation between 6-dihydroxy methyl-4-methylphenol and the phenol obtains.Use described new developer and preparation contains the quality material compositions according to the step of embodiment 1 coating liquid, the benchmark test of the line item material of going forward side by side.What so obtain the results are shown in the table 1.

Embodiment 6

As developer of the present invention, obtain 2 according to the step of embodiment 1, the condensation product of 6-dihydroxy methyl-4-isopropyl-phenol and phenol, different is is set at 7.3g (78mmol) with the consumption of phenol.In the developer of gained, the content of three phenolic compounds (A) is 55%, and the content of other condensation by-product is that the content of 44% and three phenolic compounds (C) is 11%.Result according to fusing point is measured observes fusing to a certain degree developer near 50 ℃, the fusing effect continues gradually and do not observe any definite fusing point then.Use described new developer and preparation contains the quality material compositions according to the step of embodiment 1 coating liquid, the benchmark test of the line item material of going forward side by side.What so obtain the results are shown in the table 1.

＜comparative example 1 〉

Use is three phenolic compounds, be wherein the MtrisPC of all paracresol rings three phenolic compounds (C) of keyed jointing by the methylene on the ortho position of its OH group (Honshu ChemicalIndustry Co., Ltd. makes; Purity: 96%; Fusing point: 215 ℃), and contains the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side according to the step among the embodiment 1 preparation as developer.What so obtain the results are shown in the table 1.

＜comparative example 2 〉

Mainly contained the condensation product of three phenolic compounds (C) according to the step of embodiment 1, different is to use 2, and 6-dihydroxy methyl-4-ethyl-phenol replaces 2, and 6-dihydroxy methyl-4-isopropyl-phenol also uses paracresol to replace phenol.The condensation product of gained is recrystallized with methyl iso-butyl ketone (MIBK), and the content that records three phenolic compounds (C) then is 98% and to record fusing point be 203 ℃.The MtrisPC and the above-mentioned condensation product of 0.6g after recrystallization that 1.4g are used as another developer in comparative example 1 are fully smashed to pieces so that it mixes in mortar, thereby obtain another developer.Use the developer so obtain and contain the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side according to the step preparation of embodiment 1.What so obtain the results are shown in the table 1.

＜comparative example 3 〉

Obtain mainly to contain the condensation product of three phenolic compounds (C) according to the step of embodiment 1, wherein in described three phenolic compounds (C) with at a left side all groups adjacent, be methyl with the nuclear substituted OH group of right aromatics, different is to use 2,6-dihydroxy methyl-4-methylphenol replaces 2,6-dihydroxy methyl-4-isopropyl-phenol also uses 2, and the 6-xylenols replaces phenol.In described condensation product, the content of three phenolic compounds (C) be 95% and fusing point be 183 ℃.Preparation contains the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side as developer and according to the step of embodiment 1 to use described condensation product.What so obtain the results are shown in the table 1.

＜comparative example 4 〉

Obtain condensation product according to the step of embodiment 1, different is is set at 2.4g (25.6mmol) with the consumption of phenol.In the condensation product of gained, the content of three phenolic compounds (A) is 15%, and the content of other condensation by-product is that the content of 84% and three phenolic compounds (C) is 3%.The result who measures according to fusing point observes fusing to a certain degree near 40 ℃, and the fusing effect continues gradually and do not observe any definite fusing point then.Preparation contains the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side as developer and according to the step of embodiment 1 to use described condensation product.What so obtain the results are shown in the table 1.

＜reference example 1 〉

For as a reference, use widely used up to now BPA to contain the coating liquid of quality material compositions, the benchmark test of the line item material of going forward side by side as developer and according to the step preparation of embodiment 1.What so obtain the results are shown in the table 1.

Result shown in the table 1 shows to use to have those suitable performances that obtain with using BPA aspect the blushing of thermal recording medium in sensitivity, non-image areas that developer of the present invention obtains and the picture steadiness of recording picture (hear resistance), and the picture steadiness of this external recording picture (moisture resistance) aspect has than using resulting those more performance of BPA.On the contrary, show aspect the blushing of the thermal recording medium that uses the developer of comparative example as can be seen and obtain in non-image areas and use BPA and those suitable performances of obtaining, but showing aspect the image stabilization of sensitivity and recording picture than using resulting those the worse performances of BPA.

The industry practicality

The thermal recording medium of developer of the present invention and the described developer of use provides can be cheap Ground replaces the thermal recording medium of BPA, and therefore has very much value in commercial Application.

Claims (17)

1. one kind comprises the developer that belongs to by the triphenol compd B of the triphenol compd A class of following formula 1 representative:

Formula 1

R wherein _aFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _bFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and R _bGroup can be identical or different; R _cFor be selected from hydrogen atom, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and work as R _cWhen group is two, these two R _cGroup can be identical or different, works as R _cGroup is during more than two, these R _cComparing between two in the group can be identical or different; M and n represent 1～5 integer respectively,

Wherein said triphenol compd B has:

A is the OH group on one of 4-and 4 '-position in laying respectively at left aromatic ring and right aromatic ring at least; With

B with at left aromatic ring conduct substituent at least one hydrogen atom adjacent with nuclear substituted at least one the OH group of right aromatics.

2. according to the developer of claim 1, the content that wherein belongs to the triphenol compd A and do not meet the triphenol Compound C of triphenol compd B is 30 weight % or still less.

3. according to the developer of claim 1, the content that it is characterized in that described triphenol compd B is 0.5 or bigger with the ratio of the content of described triphenol compd A.

4. according to the developer of claim 2, the content that it is characterized in that described triphenol compd B is 0.5 or bigger with the ratio of the content of described triphenol compd A.

5. according to each developer in the claim 1～4, the content of wherein said triphenol compd A is 20 weight % or more.

6. according to each developer in the claim 1～4, it contains the condensation product that at least a condensation in the phenolic compounds of amphyl that the contraposition by 2 representatives of following formula replaces and following formula 3 representatives obtains,

Formula 2

R wherein _dFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _eFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and R _eGroup can be identical or different;

Formula 3

R wherein _fFor be selected from hydrogen atom, hydroxyl, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and R _fGroup can be identical or different,

Wherein, for the condensation product total amount, the condensation product components contents that is different from described triphenol compd A that is included in the described condensation product is 50 weight % or littler.

7. according to the developer of claim 5, it contains the condensation product that at least a condensation in the phenolic compounds of being represented by the amphyl of the contraposition replacement of following formula 2 representatives and following formula 3 obtains,

Formula 2

R wherein _dFor being selected from the alkyl with 1～18 carbon atom, cycloalkyl, alkoxyl, halogen atom and having the aralkyl of 7～14 carbon atoms respectively and the group of aryl with 1～4 carbon atom with 5～10 carbon atoms; R _eFor be selected from hydrogen atom, have 1～4 carbon atom alkyl, have the alkoxyl of 1～4 carbon atom and the group of halogen atom, and R _eGroup can be identical or different;

Formula 3

R wherein _fFor be selected from hydrogen atom, hydroxyl, halogen atom, cyano group, have 1～18 carbon atom alkyl, have 5～10 carbon atoms cycloalkyl, have the alkoxyl of 1～4 carbon atom and have the aralkyl of 7～14 carbon atoms respectively and the group of aryl, and R _fGroup can be identical or different,

Wherein, for the condensation product total amount, the condensation product components contents that is different from described triphenol compd A that is included in the described condensation product is 50 weight % or littler.

8. according to each developer in the claim 1～4, it is characterized in that the R in the formula 1 _cGroup all is a hydrogen atom.

9. according to the developer of claim 7, it is characterized in that the R in the formula 1 _cGroup all is a hydrogen atom.

10. according to each developer in the claim 1～4, it is characterized in that the R in the formula 3 _fGroup all is a hydrogen atom.

11., it is characterized in that the R in the formula 3 according to the developer of claim 9 _fGroup all is a hydrogen atom.

12. according to each developer in the claim 1～4, it comprises can be so that colourless or light dyestuff former forms other developer of color.

13. according to the developer of claim 11, it comprises can be so that colourless or light dyestuff former forms other developer of color.

14. a quality material compositions that is used for recording materials, it contains colourless or light dyestuff former and according to each developer in the claim 1～13.

15. according to the quality material compositions that is used for recording materials of claim 14, it further comprises emulsion.

16. one kind by being provided with the recording materials that form according to each the quality material compositions that is used for recording materials in claim 14 and 15 on matrix.

17. according to the recording materials of claim 16, wherein said recording materials are thermal recording medium.