CN101528476A - Writing implement and writing implement set - Google Patents
Writing implement and writing implement set Download PDFInfo
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- CN101528476A CN101528476A CNA200780038859XA CN200780038859A CN101528476A CN 101528476 A CN101528476 A CN 101528476A CN A200780038859X A CNA200780038859X A CN A200780038859XA CN 200780038859 A CN200780038859 A CN 200780038859A CN 101528476 A CN101528476 A CN 101528476A
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Abstract
Provided are a writing instrument produced at a lower cost than conventional thermochromic writing instruments utilizing frictional heat, slim like a pencil and not bulky because it contains an ink directly in a barrel thereof, and excellent in portability; and a set of the writing instruments. The writing instrument 1 is obtained by directly filling a barrel thereof with an ink 2 which becomes colorless or colored, or undergoes a color change by heating and an ink follower 5 following the ink with its consumption; firmly fixing a writing tip portion 3 to the end of the barrel directly or via a relay member; and disposing a friction body 6 having an elasticity at the rear end portion of the barrel. The writing instrument set has a plurality of the writing instruments respectively different from each other in color tone.
Description
Technical field
The present invention relates to writing implement.In particular, the present invention relates to writing implement and writing implement set, the person's handwriting that described writing implement and writing implement set produce is by applying frictional heat and become colorless or coloured, or change color takes place.
Background technology
Traditionally, use the pencil or the propelling pencil of solid pen core (as lead) to be used as the writing implement that produces erasable person's handwriting, and described person's handwriting can go by enough erased by rubber.Writing implement as the ink that directly contains the generation change color of being heated in it has disclosed such thermochromism writing implement, and it changes the color (for example, referring to patent documentation 1) of person's handwriting by the frictional heat that is produced by friction piece.
By utilizing frictional heat (it is produced by the friction piece as the simple friction means); the above-mentioned thermochromism writing implement of frictional heat that utilizes can make the people see that interconvertible change color takes place the thermochromism person's handwriting; promptly; from become colorless person's handwriting or become color person's handwriting of coloured person's handwriting, thereby make this thermochromism writing implement can be used as the parts of (for example) study, teaching or toy with another tone from a kind of color person's handwriting.
Also disclose on the rearward end of beam barrel that above-mentioned friction piece is arranged on writing implement portable to satisfy.
Patent documentation 1: the patent disclosure JP-A-2003-206432 of Japanese unexamined
Summary of the invention
The problem to be solved in the present invention
Be provided with friction piece although disclose the above-mentioned rearward end of its beam barrel of thermochromism writing implement of frictional heat of utilizing, this writing implement accommodates refill for ball-point pen in its beam barrel, directly contain ink in this refill for ball-point pen.Therefore, increase owing to constitute the number of components of this writing implement, so need high manufacturing cost, meanwhile, the beam barrel that accommodates pen core in it tends to thickening, becomes big.
In addition, when using a plurality of writing implement manufacturings can form the writing implement set (as the colored pencil assembly) of the different person's handwriting of tone, use above-mentioned writing implement can make the volume of assembly carry than big and inconvenience.
The method of dealing with problems
According to writing implement of the present invention is such writing implement, and it comprises:
Beam barrel is wherein owing to heating turns pale, the ink of colour developing or variable color and follow body (ink follower) and directly be filled in the described beam barrel along with the consumption of ink follows ink that ink advances closely; With
Writing tip, this writing tip directly or by relay part are firmly fixed at an end of described beam barrel,
Wherein, the rubber-like friction piece is set at the rearward end of described beam barrel, perhaps
Be such writing implement, it comprises:
Beam barrel is wherein owing to heating turns pale, the ink of colour developing or variable color and follow body and directly be filled in the described beam barrel along with the consumption of ink follows ink that ink advances closely;
Writing tip, this writing tip are directly or be firmly fixed at an end of described beam barrel by relay part; With
The cap for brush, this cap for brush covers described writing tip,
Wherein, the rubber-like friction piece is set at the rearward end of described beam barrel and/or the end of the cap for brush.
In addition, according to the present invention, in above-mentioned writing implement, following aspect is suitable for.
Described beam barrel has shading character.
Contain microencapsulation pigment (microencapsulated pigment) in the described ink, comprise the reversible thermochromic composition in the described microencapsulation pigment, this reversible thermochromic composition comprises at least: the colour developing organic compound that electronics (i) is provided, (ii) accept the compound of electronics and (iii) be used to control composition (i) and the reaction medium of the color reaction of composition between (ii), and described microencapsulation pigment is heated and takes place from coloured to colourless change color.
Described microencapsulation pigment demonstrates bigger lagging characteristics in its color depth-temperature curve, show the enantiotropy between first form and aspect and second form and aspect, and described microencapsulation pigment has two-phase and keeps temperature range, and this temperature range makes described first form and aspect and described second form and aspect coexist in common temperature range;
Be in the first form and aspect state and in the temperature rise period, when pigment reaches second temperature T
3The time, this pigment begins variable color from described first form and aspect, and this pigment is than second temperature T
3High temperature T
4Become second form and aspect fully in the above temperature range;
Be in the second form and aspect state and in temperature-fall period, when pigment reaches than described second temperature T
3The first low temperature T
2The time, this pigment is since the second form and aspect variable color, and this pigment be not higher than temperature T
1Temperature range in become described first form and aspect fully, wherein said temperature T
1Be lower than described first temperature T
2
Described pigment is in described first temperature T
2With described second temperature T
3Between temperature range in demonstrate lagging characteristics, this lagging characteristics makes the coexistence of described first form and aspect and described second form and aspect,
Described temperature T
1In-30 ℃ to 10 ℃ scope,
Described temperature T
4In 30 ℃ to 80 ℃ scope.
Described friction piece is selected from elastomer and plastic foam.
Described beam barrel firmly fixes by attaching parts each other with friction piece is in the same place.
Described attaching parts also play the effect of beam barrel; And wherein said writing tip is a ball-point pen tip.
Described writing implement is filled with the ink that tone differs from one another respectively.
Effect of the present invention
Compare with the thermochromism writing implement of the routine of utilizing frictional heat, writing implement of the present invention can make with lower cost, and because this writing implement is designed to directly be filled in ink in the beam barrel, therefore it is very thin as pencil, volume is little, thereby has excellent portability.
In addition, although can form the writing implement set of the different person's handwriting of tone is to be made of a plurality of above-mentioned writing implements, it is big that but its volume does not become, therefore the present invention can provide such writing implement set, this writing implement set can carry the different writing implement of a plurality of colors, thereby has satisfied convenience.
Brief Description Of Drawings
Fig. 1 is color depth-temperature profile, and it illustrates the lagging characteristics of employed hot erasing type reversible thermochromic composition among the present invention;
Fig. 2 is color depth-temperature profile, and it illustrates the lagging characteristics of the hot erasing type reversible thermochromic of employed another kind composition among the present invention;
Fig. 3 is color depth-temperature profile, and it illustrates the lagging characteristics of employed hot colour developing type reversible thermochromic composition among the present invention;
Fig. 4 is the profilograph that an example of writing implement of the present invention is shown;
Fig. 5 is the front view of the writing implement of Fig. 3;
Fig. 6 is the profilograph that another example of writing implement of the present invention is shown;
Fig. 7 is the profilograph that another example of writing implement of the present invention is shown;
Fig. 8 is the profilograph that another example of writing implement of the present invention is shown;
Fig. 9 is the profilograph that another example of writing implement of the present invention is shown;
Figure 10 is the profilograph that another example of writing implement of the present invention is shown;
Figure 11 is the profilograph that another example of writing implement of the present invention is shown; And
Figure 12 is the profilograph that another example of writing implement of the present invention is shown;
The note of figure notation:
t
1: complete colour temp
t
2: the beginning colour temp
t
3: beginning colour killing temperature
t
4: complete colour killing temperature
T
1: complete colour killing temperature
T
2: beginning colour killing temperature
T
3: the beginning colour temp
T
4: complete colour temp
Δ H: sluggish width
1: writing implement
2: ink
3: writing tip
4: beam barrel
5: ink is followed body
6: friction piece
7: the cap for brush
8: rubber seal
9: relay part
10: attaching parts
11: anchor clamps
12: the tail plug
13. protuberance
Preferred forms of the present invention
Writing implement of the present invention contains ink, and described ink becomes colorless owing to heating or be coloured, or change color takes place.The effective colouring agent that contains in the ink is a microencapsulation pigment, it obtains by the reversible thermochromic composition is encapsulated in the micro-capsule, wherein said reversible thermochromic composition comprises three kinds of bases at least, that is: (i) provides the colour developing organic compound of electronics, the reaction medium of (ii) accepting the compound of electronics and (iii) determining to take place between these compounds the temperature of color reaction, and described reversible thermochromic composition is owing to heating becomes colorless.
As the reversible thermochromic composition, can use the have less relatively sluggish width composition of (Δ H=1 ℃ to 7 ℃), as the patent disclosure No.JP-B-51-44706, the JP-B-51-44707 that have examined in Japan or described in the JP-B-1-29398 those.
In other words, described composition with predetermined temperature (color transition point) as boundary value generation variable color;
Under the temperature of high temperature one side that is not less than color transition point, described composition is in colourless state;
Under the temperature of low temperature one side that is not higher than color transition point, described composition is in coloured state;
In normal temperature range, described composition is in a kind of particular state in the two states; And
Even apply manifest the required heat of another state or cold and hot in this state be held, but the state (referring to Fig. 1) when not applying described heat or this state also can return to normal temperature range when cold and hot.
Yet, the preferred reversible thermochromic composition with bigger lagging characteristics (Δ H=8 ℃ to 70 ℃) that uses is as at described in patent disclosure No.JP-A-4-17154, JP-A-7-179777, JP-A-7-33997, JP-A-8-39936 or the JP-A-2005-1369 of Japanese unexamined those.
The color depth that is caused by variations in temperature is being changed in the curve of drawing and obtaining, change color takes place in described preferred compositions after the visibly different process of experience, described change color takes place between the moment that temperature one side that is higher than the discoloring temperature scope descends from the moment and the temperature that temperature one side that is lower than the discoloring temperature scope rises in temperature, and in a certain temperature range, said composition can remain colored state or remain colourless state in high temperature range in low temperature range, thereby has memory for color character (referring to Fig. 2).
Hereinafter will the lagging characteristics of the reversible thermochromic composition in color depth-temperature curve be described.
In Fig. 2, color depth is drawn along axis of ordinates, and temperature is drawn along axis of abscissas.The variation of the color depth that causes owing to variations in temperature is moved along the direction of arrow.In this curve map,
A is the temperature t when being illustrated in color and being eliminated fully
4The point of the concentration that (hereinafter being referred to as " colour killing temperature fully ") located;
B is the temperature t when being illustrated in the beginning colour killing
3The point of the concentration that (hereinafter being referred to as " beginning colour killing temperature ") located;
C is the temperature t that is illustrated in when beginning to develop the color
2The point of the concentration that (hereinafter being referred to as " beginning colour temp ") located; With
D is the temperature t that is illustrated in when developing the color fully
1The point of the concentration that (hereinafter being referred to as " colour temp fully ") located.
The temperature range of change color is positioned at t
1And t
4Between, and t
2And t
3Between temperature range (wherein, first form and aspect and second form and aspect exist simultaneously, and the differing greatly of color depth) be essence discoloring temperature scope (two-phase maintenance temperature range).
The length of EF line is the measuring of contrast of expression change color, and is the temperature width (hereinafter being called " sluggish width Delta H ") of the sluggish degree of expression through the HG line of EF line mid point.When Δ H value hour, in normal temperature range, only exist before the change color and the predetermined state in these two states afterwards.On the other hand, bigger Δ H value helps keeping simultaneously before the change color and this two states afterwards.
In particular, by being set as follows parameter, described composition can play the effect that remains on (daily life temperature range) colour developing under the normal condition effectively.These settings are:
Complete colour temp t with reversible thermochromic composition of memory for color character
1, it is in the temperature range that only results from refrigerating chamber or cold area, ,-30 ℃ to 10 ℃, is preferably-30 ℃ to 0 ℃, more preferably-30 ℃ to-10 ℃ that is.
Complete colour killing temperature t
4, it is in the temperature range that frictional heat provided that is produced by friction piece,, 30 ℃ to 90 ℃, is preferably 50 ℃ to 80 ℃, more preferably 60 ℃ to 80 ℃ that is; And
Δ H value is 40 ℃ to 60 ℃.
Preferably, writing implement of the present invention is filled with the ink that contains microencapsulation pigment, described microencapsulation pigment is encapsulated with the reversible thermochromic composition that is under the colored state within it, be wiped free of owing to the finger contact waits by the formed person's handwriting of this writing implement is difficult, and in a single day writing just is wiped free of no longer reproduction.
Therefore, t
1And t
4Temperature set very important for the purpose of the present invention.
Hereinafter will to as each composition (i), (ii) and the object lesson of compound (iii) be described.
The example of composition of the present invention (i) (that is the colour developing organic compound of electronics, is provided) comprising: diphenyl methane phthalide, Phenylindole base phthalide, indyl phthalide, diphenyl methane azepine phthalide, Phenylindole base azepine phthalide, fluorane, styryl quinoline (styrynoquinolines) and diaza rhodamine lactone.
Be the object lesson of these compounds below:
3,3-two (to dimethylaminophenyl)-6-dimethylamino phthalide,
3-(4-diethylamino phenyl)-3-(1-ethyl-2 methyl indole-3-yl) phthalide,
3,3-two (1-normal-butyl-2 methyl indole-3-yl) phthalide,
3,3-two (2-ethyoxyl-4-diethylamino phenyl)-4-azepine phthalide,
3-[2-ethyoxyl-4-(N-ethylaniline base) phenyl]-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalide,
3,6-diphenyl amino fluorane,
3,6-dimethoxy fluorane,
3,6-two n-butoxy fluoranes,
2-methyl-6-(N-ethyl-N-right-tolyl amino) fluorane,
The amino fluorane of 3-chloro-6-cyclohexyl,
The amino fluorane of 2-methyl-6-cyclohexyl,
The amino fluorane of 2-(2-chloroanilino)-6-di-n-butyl,
2-(3-trifluoromethylbenzene amido)-6-diethylamino fluorane
2-(methylphenylamine base)-6-(N-ethyl-N-right-tolyl amino) fluorane,
1,3-dimethyl-6-diethylamino fluorane,
2-chloro-3-methyl-6-diethylamino fluorane,
2-anilino--3-methyl-6-diethylamino fluorane,
The amino fluorane of 2-anilino--3-methyl-6-di-n-butyl,
2-xylidino-3-methyl-6-diethylamino fluorane,
1,2-phenyl-6-diethylamino fluorane,
1,2-phenyl-6-(N-ethyl-N-isobutylamino) fluorane,
1,2-phenyl-6-(N-ethyl-N-isopentyl amino) fluorane,
2-(3-methoxyl group-4-dodecyloxy styryl) quinoline,
Spiral shell [5H-(1) chromene also (2,3-d) pyrimidine-5,1 ' (3 ' H) isomery benzofuran]-3 '-ketone,
2-(diethylamino)-8-(diethylamino)-4-methyl-spiral shell [5H-(1) chromene also (2,3-d) pyrimidine-5,1 ' (3 ' H) isomery benzofuran]-3 '-ketone,
2-(di-n-butyl amino)-8-(di-n-butyl amino)-4-methyl-spiral shell [5H-(1) chromene also (2,3-d) pyrimidine-5,1 ' (3 ' H) isomery benzofuran]-3 '-ketone,
2-(di-n-butyl amino)-8-(diethylamino)-4-methyl-spiral shell [5H-(1) chromene also (2,3-d) pyrimidine-5,1 ' (3 ' H) isomery benzofuran]-3 '-ketone,
2-(di-n-butyl amino)-8-(N-ethyl-N-isopentyl amino)-4-methyl-spiral shell [5H-(1) chromene also (2,3-d) pyrimidine-5,1 ' (3 ' H) isomery benzofuran]-3 '-ketone,
3-(2-methoxyl group-4-dimethylaminophenyl)-3-(1-butyl-2 methyl indole-3-yl)-4,5,6, the 7-Rabcide,
3-(2-ethyoxyl-4-diethylamino phenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4,5,6, the 7-Rabcide and
3-(2-ethyoxyl-4-diethylamino phenyl)-3-(1-phenyl-2 methyl indole-3-yl)-4,5,6, the 7-Rabcide.
Other example comprises: can be used for effectively the yellow colour developing of fluorescence is red pyridine, quinazoline and two quinazoline compound.
Be selected from (for example) as the composition compound of accepting electronics (ii): have active proton compound group, pseudo-acidity compound group (thereby its be not real acid but the effect of playing acid in composition makes composition (i) colour developing) and compound group with electron hole.
Example with compound of active proton comprises: have the compound of phenolic hydroxyl group, as monohydric phenol and polyhydric phenols, these compounds have substituting group, as alkyl, aryl, acyl group, alkoxy carbonyl, carboxyl or its ester group, amide groups or halogen group; Dihydric phenol or trihydric phenol; And phenol formaldehyde condensation resin.They can be above-mentioned slaines with compound of phenolic hydroxyl group.
Be the object lesson of accepting the compound of electronics below.
Its example comprises:
Phenol,
Orthoresol,
Tert-butyl catechol,
Nonyl phenol,
N-octyl phenol,
Dodecyl phenol,
N-octadecane base phenol,
Parachlorophenol,
P bromophenol,
O-phenyl phenol,
The positive butyl ester of P-hydroxybenzoic acid,
The P-hydroxybenzoic acid n-octyl,
Resorcinol,
Gallic acid dodecane ester,
2, two (4-hydroxyphenyl) propane of 2-,
4, the 4-dihydroxy-diphenyl sulfone,
1, two (4-hydroxyphenyl) ethane of 1-,
2, two (4-hydroxyl-3-tolyl) propane of 2-,
Two (4-hydroxyphenyl) thioether,
1-phenyl-1, two (4-hydroxyphenyl) ethane of 1-,
1, two (4-the hydroxyphenyl)-3-methybutanes of 1-,
1, two (4-the hydroxyphenyl)-2-methylpropanes of 1-,
1, two (4-the hydroxyphenyl)-n-hexanes of 1-,
1, two (4-the hydroxyphenyl)-normal heptanes of 1-,
1, two (4-the hydroxyphenyl)-normal octanes of 1-,
1,1-two (4-hydroxyphenyl)-positive nonane,
1, two (4-the hydroxyphenyl)-n-decanes of 1-,
1, two (4-the hydroxyphenyl)-n-dodecanes of 1-,
2, two (4-the hydroxyphenyl)-butane of 2-,
2, two (4-the hydroxyphenyl)-4-methylpentanes of 2-,
2, two (4-the hydroxyphenyl)-HFC-236fas of 2-
2, two (4-the hydroxyphenyl)-normal heptanes of 2-and
2,2-two (4-hydroxyphenyl)-positive nonane.
Although these compounds with phenolic hydroxyl group can show the most effective thermochromism, but composition (ii) can be selected from aromatic carboxylic acid, have the aliphatic carboxylic acid of 2-5 carbon atom, slaine, acid phosphoric acid ester and the slaine thereof and 1 of carboxylic acid, 2, any compound in 3-triazole and the derivative thereof.
To (iii) be described composition below, wherein said composition (iii) is to be used for reversibly making in the temperature range of regulation composition (i) and composition electronics to take place between (ii) providing/reaction medium of acceptable response.Composition example (iii) comprises alcohol, ester, ketone, ether and sour acid amides.
As composition (iii), preferably Δ T value [(fusing point)-(cloud point)] is 5 ℃ or higher but less than 50 ℃, and can form the carboxylic acid ester compound of reversible thermochromic composition, wherein said reversible thermochromic composition (changes the curve that obtains by draw color depth corresponding to variations in temperature at the color depth-temperature curve of said composition, this curve becomes from low temperature under the situation of high temperature in temperature that to become under the situation of low temperature from high temperature with temperature be different) with bigger lagging characteristics generation change color, thereby demonstrate memory for color character.
The example of this compounds comprises:
Have in its molecule substituted aromatic ring carboxylate,
The ester that the carboxylic acid that contains unsubstituted aromatic ring and the fatty alcohol with 10 or more a plurality of carbon atoms form,
Have in its molecule cyclohexyl carboxylate,
Have ester that the aliphatic acid of 6 or more a plurality of carbon atoms and unsubstituted aromatic alcohols or phenol forms,
Have the aliphatic acid of 8 or more a plurality of carbon atoms and ester that branched fatty alcohol forms,
The ester that dicarboxylic acids and aromatic alcohols or branched fatty alcohol form,
Cinnamic acid dibenzyl ester, stearic acid heptyl ester, didecyl adipate, adipic acid two lauryls, adipic acid two myristins, adipic acid double hexadecyl ester, the two stearyl of adipic acid, trilaurin, trimyristin, tristearin, di-myristin and distearing.
The fatty acid ester compound that obtains with having the aliphatic carboxylic acid of even number of carbon atoms by aliphatic monobasic alcohol and be that the fatty acid ester compound of 17-23 also is effective by the total number of carbon atoms that n-amyl alcohol or n-heptanol and the aliphatic carboxylic acid with even number of carbon atoms (10-16 is individual) obtain with 9 or bigger odd number carbon atom.
Its concrete example comprises: acetate n-pentadecane ester, butyric acid n-tridecane ester, butyric acid n-pentadecane ester, caproic acid n-undecane ester, caproic acid n-tridecane ester, caproic acid n-pentadecane ester, sad positive ninth of the ten Heavenly Stems ester, sad n-undecane ester, sad n-tridecane ester, sad n-pentadecane ester, the positive heptyl ester of capric acid, capric acid ester in the positive ninth of the ten Heavenly Stems, capric acid n-undecane ester, capric acid n-tridecane ester, capric acid n-pentadecane ester, the laurate n-pentyl ester, the positive heptyl ester of laurate, laurate ester in the positive ninth of the ten Heavenly Stems, laurate n-undecane ester, laurate n-tridecane ester, laurate n-pentadecane ester, the myristic acid n-pentyl ester, the positive heptyl ester of myristic acid, myristic acid ester in the positive ninth of the ten Heavenly Stems, myristic acid n-undecane ester, myristic acid n-tridecane ester, myristic acid n-pentadecane ester, the palmitic acid n-pentyl ester, the positive heptyl ester of palmitic acid, palmitic acid ester in the positive ninth of the ten Heavenly Stems, palmitic acid n-undecane ester, palmitic acid n-tridecane ester, palmitic acid n-pentadecane ester, stearic acid ester in the positive ninth of the ten Heavenly Stems, stearic acid n-undecane ester, stearic acid n-tridecane ester, stearic acid n-pentadecane ester, arachidic acid ester in the positive ninth of the ten Heavenly Stems, arachidic acid n-undecane ester, arachidic acid n-tridecane ester, arachidic acid n-pentadecane ester behenic acid n-nonyl alkane ester behenic acid n-undecane ester behenic acid n-tridecane ester behenic acid n-pentadecane ester.
As ketone, the total number of carbon atoms be 10 or more aliphatic ketone be effectively, and its example comprises: the 2-decanone, the 3-decanone, the 4-decanone, methyln nonyl ketone, the 3-hendecanone, the 4-hendecanone, the 5-hendecanone, 2-dodecane ketone, 3-dodecane ketone, 4-dodecane ketone, 5-dodecane ketone, methyl n-undecyl ketone, 3-tridecane ketone, 2-tetradecane ketone, the 2-pentadecanone, the 8-pentadecanone, 2-hexadecane ketone, 3-hexadecane ketone, pelargone, the 2-pentadecanone, 2-octadecane ketone, the 2-nonadecanone, the 10-nonadecanone, 2-eicosane ketone, 11-eicosane ketone, 2-heneicosane ketone, 2-docosane ketone, laurone and stearone.
The total number of carbon atoms is that the example of 12 to 24 alkylaryl ketone comprises: n-octadecane base benzophenone, n-heptadecane base benzophenone, the n-hexadecyl benzophenone, n-pentadecane base benzophenone, n-tetradecane base benzophenone, 4-n-dodecane benzoylformaldoxime, n-tridecane base benzophenone, 4-n-undecane benzoylformaldoxime, positive lauryl benzophenone, the positive decyl acetophenone of 4-, n-undecane base benzophenone, 4-n-nonyl acetophenone, positive decyl benzophenone, 4-n-octyl ethyl ketone, the n-nonyl benzophenone, 4-n-heptylphenyl ethyl ketone, the n-octyl benzophenone, 4-positive hexyl phenenyl ethyl ketone, the positive cyclohexyl benzene ethyl ketone of 4-, 4-tert-butyl benzene acetone, the n-heptyl benzophenone, 4-n-amylbenzene ethyl ketone, cyclohexyl-phenyl ketone, benzyl normal-butyl ketone, 4-n-butylbenzene ethyl ketone, the n-hexyl benzophenone, the 4-isobutyl acetophenone, the 1-acetonaphthone, the 2-acetonaphthone, and cyclopenta phenyl ketone.
As ether, the total number of carbon atoms is that 10 or more a plurality of aliphatic ethers are effective.Its example comprises: diamyl ether, two hexyl ethers, two heptyl ethers, dioctyl ether, two the ninth of the ten Heavenly Stems ether, didecyl ether, two undecyl ether, two lauryl ether, double tridecyl ether, two myristyl ether, two pentadecyl ether, double hexadecyl ether, two octadecyl ether, decanediol dimethyl ether, hendecane glycol dimethyl ether, dodecanediol dimethyl ether, tridecane glycol dimethyl ether, decanediol diethyl ether and hendecane two diethylene glycol diethyl ethers.
About composition (iii), the compound that preferably disclosed following formula (2) is represented among the patent disclosure No.JP-A-2006-188660 of the compound of disclosed following formula (1) expression and Japanese unexamined in the patent disclosure No.JP-A-2006-137886 of Japanese unexamined.
[Chemical formula 1]
[wherein, R
1Expression hydrogen atom or methyl, m represents 0 to 2 integer,
X
1And X
2In any one expression-(CH
2)
nOCOR
2Or-(CH
2)
nCOOR
2, and another expression hydrogen atom, n represents 0 to 2 integer, R
2Expression has the alkyl or alkenyl of 4 or more a plurality of carbon atoms,
Y
1And Y
2Represent hydrogen atom separately, have alkyl, methoxyl group or the halogen of 1 to 4 carbon atom, and
R and p represent 1 to 3 integer separately].
[Chemical formula 2]
[wherein, R represents to have the alkyl or alkenyl of 8 or more a plurality of carbon atoms].
In the represented compound of formula (1), R preferably
1Be those compounds of hydrogen atom, this is because it can obtain to have the reversible thermochromic composition of bigger sluggish width.R in the formula (1) more preferably
1Expression hydrogen atom and m represent those compounds of 0.
In formula (2), R represents to have the alkyl or alkenyl of 8 or more a plurality of carbon atoms, preferred expression be alkyl with 10 to 24 carbon atoms, more preferably expression is the alkyl with 12 to 22 carbon atoms.
The object lesson of described compound comprises:
Sad 4-benzyloxy phenethyl ester,
N-nonanoic acid 4-benzyloxy phenethyl ester,
Capric acid 4-benzyloxy phenethyl ester,
Hendecanoic acid 4-benzyloxy phenethyl ester,
Dodecylic acid 4-benzyloxy phenethyl ester,
Tridecanoic acid 4-benzyloxy phenethyl ester,
Tetradecanoic acid 4-benzyloxy phenethyl ester,
Pentadecanoic acid 4-benzyloxy phenethyl ester,
Hexadecanoic acid 4-benzyloxy phenethyl ester,
Heptadecanoic acide 4-benzyloxy phenethyl ester,
Octadecanoid acid 4-benzyloxy phenethyl ester,
Sad 1,1-diphenyl methyl esters,
N-nonanoic acid 1,1-diphenyl methyl esters,
Capric acid 1,1-diphenyl methyl esters,
Hendecanoic acid 1,1-diphenyl methyl esters,
Dodecylic acid 1,1-diphenyl methyl esters,
Tridecanoic acid 1,1-diphenyl methyl esters,
Tetradecanoic acid 1,1-diphenyl methyl esters,
Pentadecanoic acid 1,1-diphenyl methyl esters,
Hexadecanoic acid 1,1-diphenyl methyl esters,
Heptadecanoic acide 1,1-diphenyl methyl esters and
Octadecanoid acid 1,1-diphenyl methyl esters.
In addition, as comprising at least 3 kinds of compositions (promptly, (i) provide the colour developing organic compound of electronics, (ii) accept the compound of electronics and (iii) determining between these two kinds of compounds to take place the reaction medium of the temperature of color reaction) the reversible thermochromic composition, can also use hot colour developing type reversible thermochromic composition (the patent disclosure No.JP-A-2003-253149 of Japanese unexamined), this thermochromism composition uses gallate as the compound (referring to Fig. 3) of accepting electronics.
To specifically describe the color depth-temperature curve among Fig. 3 below.Because the variation of the color depth that variations in temperature causes is moved along the direction of arrow.
Point A is illustrated in the temperature T that color is eliminated fully
1The point of the concentration that (hereinafter will be called " colour killing temperature fully ") located.
Point B is the temperature T when being illustrated in the beginning colour killing
2The point of the concentration that (hereinafter will be called " beginning colour killing temperature ") located.
Point C is the temperature T that is illustrated in when beginning to develop the color
3The point of the concentration that (hereinafter will be called " beginning colour temp ") located.
Point D is the temperature T that is illustrated in when developing the color fully
4The point of the concentration that (hereinafter will be called " colour temp fully ") located.
Do not use the microencapsulation pigment with circular cross section although do not get rid of, the microencapsulation pigment with non-circular cross sections is more effective.
Because microencapsulation pigment is arranged tight and firm fixing, simultaneously, long diameter one side (maximum outside diameter one side) closely contacts with writing surface, so demonstrates the colour rendering of high concentration by writing the person's handwriting that forms.Simultaneously, the distortion of the shape generation micro-elastic of microencapsulation pigment is with lax external force (this external force is owing to using the wiping body (friction piece) such as rubber to come the scratching person's handwriting to produce), thereby prevented the destruction of micro-capsule wall film and can develop the color effectively and do not damage its thermo-color function.
Preferably, the average maximum outside diameter of microencapsulation pigment with non-circular cross sections is in the scope of 0.5 μ m to 5.0 μ m, and the ratio that satisfies reversible thermochromic composition/wall film simultaneously is 7/1 to 1/1 (weight ratio).
Surpass in microencapsulation pigment (comprising the microencapsulation pigment) system of 5.0 μ m at average maximum outside diameter with circular cross section, ink is relatively poor from the outflow of capillary gap, and the microencapsulation pigment that average maximum outside diameter is not more than 0.5 μ m is difficult for showing the colour rendering of high concentration.The average maximum outside diameter of micro-capsule is preferably 1 μ m to 4 μ m, and its average grain diameter [(maximum outside diameter)+(minimum outer diameter of core)/2] is preferably 1 μ m to 3 μ m.
When the ratio of reversible thermochromic composition/wall film exceeded above-mentioned scope, the wall film became thin, thereby caused resistance to pressure or hear resistance to reduce.On the other hand, when the ratio of wall film/reversible thermochromic composition exceeded above-mentioned scope, color depth during colour developing and vividness can reduce inevitably.Therefore, the ratio of reversible thermochromic composition/wall film preferably is in the scope of 6/1 to 1/1 (weight ratio).
By the following method the reversible thermochromic composition is carried out microencapsulation, described method for example is: hard-coating method in interfacial polymerization, interface polycondensation, situ aggregation method, the solution, from the aqueous solution phase separation method, phase separation method, fusion disperse cooling method, gas inner suspension cladding process or spray drying process from organic solvent.Select suitable method according to desired use.Can also give the micro-capsule surface durability by on micro-capsule, forming secondary resin film according to purpose, perhaps before micro-capsule is used for actual use, change its surface nature.
The content of microencapsulation pigment can be 2 weight % to the 50 weight % (being preferably 3 weight % to 40 weight %, more preferably 4 weight % to 30 weight %) of composition for ink total amount.When this measures less than 2 weight %, the color depth deficiency.On the other hand, when this amount surpasses 50 weight %, can make the mobile deterioration of ink and suppress smooth performance of writing.
As ink, it is effective being dispersed in the ink that obtains in the carrier by the pigment with microencapsulation.As described carrier, aqueous based carrier preferably, but also usable oils base carrier.
Its concrete example comprises the shear thinning ink that contains the shear thinning agent.
Add the shear thinning agent and can form good person's handwriting, this is because it can prevent the cohesion and the precipitation of microencapsulation pigment, prevents person's handwriting generation bleeding simultaneously.
In addition, when the writing implement that is filled with ink is ball pen, add the shear thinning agent and can prevent when not using ball pen seepage the gap of ink between ball and nib, ink refluxes when perhaps preventing to place (ball pen is upright) up in the nib portion that makes ball pen.
The example of shear thinning agent comprises:
Xanthans, common vetch orchid (wellan) glue, (it is a kind of heteroglycan to succinoglycan, this heteroglycan serves as to constitute monose and through modified with organic acids with glucose and galactolipin, its mean molecule quantity about 100 to 8,000,000), guar gum, locust bean gum and derivative thereof, hydroxyethylcellulose, the alginic acid Arrcostab, main polymer (the molecular weight 100 that constitutes by alkyl methacrylate, 000 to 150,000), glucomannans, the polysaccharide thickener with gelation function that from marine alga, extracts (as, agar, carrageenan etc.)
Benzylidene sorbitol and benzal xylitol and derivative thereof,
Crosslinked acrylate copolymer,
Inorganic particles,
Polyglyceryl fatty acid ester, polyoxyethylene sorbitan fatty acid ester, cithrol, polyoxyethylene alkyl ether/polyoxypropylene alkyl ether and polyxyethylated phenylate, HLB value be 8～12 non-ionic surface active agent (for example, fatty acid amide)
Dialkyl sulfosuccinates or dialkylene sulfosuccinate,
The mixture of N-alkyl-2-Pyrrolidone and anion surfactant, and
The mixture of polyvinyl alcohol and acrylic resin.
Water can be in ink, added, water-miscible organic solvent can also be added if necessary.
The example of water-miscible organic solvent comprises: ethanol, propyl alcohol, butanols, glycerine, D-sorbite, triethanolamine, diethanol amine, MEA, ethylene glycol, diethylene glycol (DEG), the sulfo-diethylene glycol (DEG), polyethylene glycol, propane diols, butanediol, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, sulfolane, 2-Pyrrolidone, with the N-N-methyl-2-2-pyrrolidone N-.
When by ink being filled to when using in the ball pen, preferably add lubricant, thereby prevent the wearing and tearing of ball bearing, described lubricant for example is: higher fatty acids (as, oleic acid), non-ionic surface active agent with chain alkyl, polyether-modified silicone oil, thiophosphorous acid three esters (for example, thiophosphorous acid three (alkoxy carbonyl methyl) ester or thiophosphorous acid three (alkoxy carbonyl ethyl) ester), the phosphate monoester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, the di-phosphate ester of polyoxyethylene alkyl ether or polyoxyethylene alkylaryl ether, or their slaine, ammonium salt, amine salt, or their alkanolamine.
Except mentioned component, also can add such as resins such as acrylic resin, styrene-maleic acid copolymer, cellulose derivative, PVP, polyvinyl alcohol or dextrin, to give resultant composition viscosity or to the anchorage of paper.
In addition, also can add the pH conditioning agent, for example, inorganic acid salt (as sodium carbonate, sodium phosphate or sodium acetate) or organic basic compound (as water miscible aminated compounds);
Antirust agent, for example, BTA, tolyl-triazole, dicyclohexyl amine nitrite, nitrous acid diisopropylamine or saponin(e;
Anticorrisive agent or mould inhibitor, for example, carbolic acid, 1, the sodium salt of 2-benzisothiazole-3-ketone, Sodium Benzoate, sodium dehydroacetate, potassium sorbate, nipasol or 2,3,5,6-tetrachloro-4-(methyl sulphonyl) pyridine;
Urea; Non-ionic surface active agent; The starch hydrolysate of reproducibility or irreducibility; Oligosaccharide, for example, trehalose, sucrose, cyclodextrin, glucose, dextrin D-sorbite (dextrinsorbitol), sweet mellow wine; NMF, for example sodium pyrophosphate; Defoamer; Dispersant; Be used to improve the fluorine-containing surfactant or the non-ionic surface active agent of ink bleed.
Described ink can contain conventional dyestuff or pigment (non-thermochromism), to demonstrate the metachromatism from a kind of color (1) to another kind of color (2).
Before reality was used, described ink directly was filled in the writing implement, and described writing implement is for example for having the marking pen or the ball pen of mark nib or ball-point pen tip at its writing tip.
In the time of in ink is filled in ball pen, ball pen self has (for example) following structure: the shear thinning ink directly is filled in the beam barrel of ball pen, described beam barrel is connected with ball-point pen tip (its end is attached with ball), and the ink that follows ink along with the consumption of ink closely is followed body (ink refluxes and prevents body) and closely contacted with the end face of ink.
Below ball-point pen tip will be described in further detail.The example of ball-point pen tip comprises:
The nib that in the ball maintaining part, has ball, wherein said ball maintaining part is formed to internal strain by outer surface near its end by make metal tube under pressure;
By metal material being processed the nib that has ball in the ball maintaining part that forms with awl etc.;
The metal or the plastics nib that have the ball-frame carriage that is formed from a resin in nib inside; With
Has owing to the effect of spring the nib of the ball of deflection forwards.
As ball, can use the ball that makes by carbide alloy, stainless steel, ruby, pottery, resin, rubber etc., and the diameter of this ball is about 0.3mm～3.0mm, be preferably about 0.4mm～1.5mm, more preferably about 0.5mm～1.0mm.
Contain the beam barrel of ink as it, can use molding or the formed body made by thermoplastic resins such as polyethylene, polypropylene, PETG or nylon.
The beam barrel that will have light-proofness can prevent as beam barrel because the ink generation deterioration of wherein holding that light causes.
Beam barrel can directly link to each other with writing tip, perhaps can link to each other with writing tip by attaching parts.
Ink is followed body and is filled in the rear end that is contained in the ink in the beam barrel.
Ink is followed body and is comprised nonvolatile liquid or difficult volatile liquid.
Its concrete example comprises: the oligomer of vaseline, bobbin oil, castor oil, olive oil, refined mineral oil, atoleine, polybutene, alpha-olefin, alpha-olefin or co-oligomer, dimethicone, methyl phenyl silicone oil, amino-modified silicone oil, polyether modified silicon oil and fatty acid modified silicone oil etc.Can use wherein a kind of separately or use its two or more combination.
Preferably in above-mentioned fixedness liquid and/or difficult volatile liquid, add gelling agent so that its viscosity increases to proper level.The example of gelling agent comprises: clay class thickener, as bentonite or the imvite of surface through the silica of hydrophobic treatment, the surperficial silicon dioxide microparticle of handling through methylating, alumina silicate, dilatancy mica and process hydrophobic treatment; The fatty acid metal soap is as dolomol, calcium stearate, aluminum stearate and zinc stearate; The tribenzal sorbierite; Fatty acid amide; Acid amides modified polyethylene wax; Rilanit special; The dextrin compounds is as the aliphatic acid dextrin; And cellulose compound.
In addition, solid ink can also be followed body and aforesaid liquid ink follows body and is used in combination.
Described beam barrel portion in its back-end is equipped with the rubber-like friction piece.By using this friction piece, can become color state from a kind of color state, or become colored state from the colored state state that becomes colorless from colourless state with another kind of tone by writing the person's handwriting that obtains.
Be equipped with at writing implement under the situation of the cap for brush, the rubber-like friction piece can be arranged on the rearward end of beam barrel, the rubber-like friction piece can be arranged on the end of the cap for brush, and perhaps the rubber-like friction piece can be arranged on the rearward end of beam barrel and the end of the cap for brush simultaneously.
Friction piece is preferably made by the elastomer (as elastomer or plastic foam) that has elasticity and can produce frictional heat, and this is to rub because it produces when scratching fully.
Can use rubber as friction piece, but it can produce chip when friction, the above-mentioned friction piece of therefore preferred use
Material as friction piece, preferred silicones, SBS resin (s-B-S copolymer), the SEBS resin (styrene-ethylene-butadiene-styrene block copolymer) etc. of using, wherein more preferably SBS resin and SEBS resin, this is because silicones is easy to be attached to owing on the part that rubs after being wiped free of, thereby can prevent to form person's handwriting behind Palingraphia.As friction piece, be 40 or higher those more preferably according to JIS (Japanese Industrial Standards) K6253A, Xiao A hardness.
When friction piece is set at the rearward end of beam barrel or writing implement when being furnished with the cap for brush, the friction piece that is arranged on the place, end of the rearward end of beam barrel and/or the cap for brush can make portable excellent very thin writing implement with lower cost, simultaneously, even when writing implement drops because of carelessness and runs into ground, this friction piece also can shock absorbing and can be prevented ink leakage (ink backflow).
When writing implement directly contains under the situation of ink in its beam barrel, the impulsive force that is produced when dropping is greater than the impulsive force that conventional writing implement (containing barrel in its beam barrel) is applied, and therefore at the place, end of the rearward end of beam barrel and/or the cap for brush rubber-like friction piece being set is the useful structure that is used to improve impact resistance.
Beam barrel and friction piece can directly firmly fix, and perhaps can firmly fix by attaching parts.These attaching parts also play the effect of beam barrel (rear end beam barrel).
Embodiment
Hereinafter will describe embodiment, but the present invention is not limited.In the following embodiments, all " parts " that indicate or " umber " all are meant weight portion or parts by weight.
[embodiment 1 (referring to Fig. 4 and Fig. 5)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, this ink comprises:
12.5 the microencapsulation pigment (T that contains reversible thermochromic composition of part with memory for color character
1:-2 ℃, T
2: 10 ℃, T
3: 35 ℃, T
4: 48 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, this pigment take place from redness to colourless change color), and comprise:
As composition (i), 1.0 parts 1,1 of 2-phenyl-6-(N-ethyl-N-isopentyl amino) fluorane and 2.0 parts, 3-dimethyl-6-diethylamino fluorane,
As composition (ii), 4.0 parts 1,2 of two (4 '-hydroxyphenyl) decane of 1-and 4.0 parts, two (4 '-hydroxyphenyl)-HFC-236fas of 2-, and
As composition (iii), 50.0 parts palmitic acid 4-methyl benzyl ester;
0.33 part succinoglycan (shear thinning agent),
10 parts of urea,
10 parts of glycerine,
0.6 part nonionic penetration enhancers,
0.1 part organic-silicon-modified defoamer,
0.1 part mould inhibitor and
66.37 part water.
(manufacturing of writing implement)
Ink 2 (is cooled to-2 ℃ to show redness in advance with microencapsulation pigment, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its point, and the internal diameter of described beam barrel 4 is that 7mm and external diameter are 10mm.The viscoelastic ink that has that then will be mainly be made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made then.
After the cap for brush 7 that has rubber seal 8 in it places on the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.7mm) that stainless steel is made, simultaneously by spring with ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When this writing implement is chimeric when the cap for brush is arranged, its outward appearance is as pencil.
Form red person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 2 (referring to Fig. 6)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
12.5 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-16 ℃, T
2:-8 ℃, T
3: 48 ℃, T
4: 58 ℃, Δ H:65 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from pink to colourless change color), and comprise:
As composition (i), 2.0 parts 2-(butyl amino)-8-(diphenyl amino)-4-methyl-spiral shell [5H-[1] chromene is [2-3-g] pyrimidine-5,1 (3 ' H)-isobenzofuran also]-3-ketone,
As composition (ii), 5.0 parts 2,4,4 '-(2-methyl propylidene) bis-phenol of two (4 '-hydroxyphenyl) HFC-236fas of 2-and 3.0 parts and
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.33 part succinoglycan (shear thinning agent),
10 parts of urea,
10 parts of glycerine,
0.6 part nonionic penetration enhancers,
0.1 part organic-silicon-modified defoamer,
0.1 part mould inhibitor and
66.37 part water.
(manufacturing of writing implement)
Ink 2 (is cooled to-16 ℃ in advance with microencapsulation pigment, to show pink, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its point, and the internal diameter of described beam barrel 4 is that 6mm and external diameter are 9mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made then.
After the cap for brush 7 that has rubber seal 8 in it places in the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.5mm) that stainless steel is made, simultaneously by spring with ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When this writing implement is removed the cap for brush, its outward appearance is as pencil.
Form pink person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 3 (referring to Fig. 7)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
25.7 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-20 ℃, T
2:-9 ℃, T
3: 40 ℃, T
4: 57 ℃, Δ H:63 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from black to colourless change color), and comprise:
As composition (i), the amino fluorane of 4.5 parts 2-(2-chloroanilino)-6-di-n-butyl,
As composition (ii), 2 of 4.5 parts 4,4 '-(2-methyl propylidene) bis-phenol and 7.5 parts, two (4 '-hydroxyphenyl) HFC-236fas of 2-and
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.2 part succinoglycan (shear thinning agent),
5.5 part urea,
7.5 part glycerine,
0.03 part nonionic penetration enhancers,
0.15 part organic-silicon-modified defoamer,
0.1 part mould inhibitor,
0.5 part lubricant,
0.5 part triethanolamine and
59.82 part water.
(manufacturing of writing implement)
Ink (is cooled to-20 ℃ in advance with microencapsulation pigment, to show black, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its point by relay part 9, and the internal diameter of described beam barrel 4 is that 8mm and external diameter are 11mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made then.
After the cap for brush 7 that has rubber seal 8 in it places in the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 1.0mm) that stainless steel is made, simultaneously by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When this writing implement is removed the cap for brush, its outward appearance is as pencil.
Form black handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 4 (referring to Fig. 8)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
25.7 comprise the microencapsulation pigment (T of reversible thermochromic composition in its of part with memory for color character
1:-14 ℃, T
2:-6 ℃, T
3: 48 ℃, T
4: 60 ℃, Δ H:64 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from blueness to colourless change color), and comprise:
As composition (i), 2.0 parts 3-(the own oxygen base of 4-diethylamino-2-phenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalide,
As composition (ii), 2 of 3.0 parts 4,4 '-(2-methyl propylidene) bis-phenol and 5.0 parts, two (4 '-hydroxy phenyl) HFC-236fas of 2-and
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.2 part succinoglycan (shear thinning agent),
5.5 part urea,
7.5 part glycerine,
0.03 part nonionic penetration enhancers,
0.15 part organic-silicon-modified defoamer,
0.1 part mould inhibitor,
0.5 part lubricant,
0.5 part triethanolamine and
59.82 part water.
(manufacturing of writing implement)
Ink 2 (is cooled to-14 ℃ in advance with microencapsulation pigment, to show blueness, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its point, and the internal diameter of described beam barrel 4 is that 6mm and external diameter are 9mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that SEB S resin is made by attaching parts 10 (rear end beam barrel) then.
After the cap for brush 7 that has rubber seal 8 in it places in the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.7mm) that stainless steel is made, simultaneously by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When being fitted to the cap for brush on the writing implement, its outward appearance is as pencil.
Form blue person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 5 (referring to Fig. 9)]
(preparation of reversible thermochromic microencapsulation pigment)
Preparation reversible thermochromic ink, it comprises:
25.7 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-8 ℃, T
2:-1 ℃, T
3: 52 ℃, T
4: 65 ℃, Δ H:63 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from orange to colourless change color), and comprise:
As composition (i), 2.5 parts 1,3-dimethyl-6-lignocaine fluorane,
As composition (ii), 5.0 parts 2,4,4 '-(2-methyl propylidene) bis-phenol of two (4 '-hydroxyphenyl) HFC-236fas of 2-and 3.0 parts and
As composition (iii), 50.0 parts laurate 4-benzyloxy phenethyl ester,
0.2 part succinoglycan (shear thinning agent),
5.5 part urea,
7.5 part glycerine,
0.03 part nonionic penetration enhancers,
0.15 part organic-silicon-modified defoamer,
0.1 part mould inhibitor,
0.5 part lubricant,
0.5 part triethanolamine and
59.82 part water.
(manufacturing of writing implement)
Ink 2 (is cooled to-8 ℃ in advance with microencapsulation pigment, orange to show, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its point, and the internal diameter of described beam barrel 4 is that 6mm and external diameter are 9mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made by attaching parts 10 (rear end beam barrel) then.
After the cap for brush 7 that has rubber seal 8 in it places in the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.5mm) that stainless steel is made, simultaneously by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When with the cap for brush when writing implement is removed, its outward appearance is as pencil.
Form orange person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 6 (referring to Figure 10)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
12.5 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-16 ℃, T
2:-8 ℃, T
3: 48 ℃, T
4: 58 ℃, Δ H:65 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from pink to colourless variation), and comprise:
As composition (i), 2.0 parts 2-(fourth amino)-8-(diphenyl amino)-4-methylspiro [5H-[1] chromene is [2-3-g] pyrimidine-5,1 (3 ' H)-isobenzofuran also]-3-ketone,
As composition (ii), 5.0 parts 2,4,4 '-(2-methyl propylidene) bis-phenol of two (4 '-hydroxyphenyl) HFC-236fas of 2-and 3.0 parts and
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.33 part succinoglycan (shear thinning agent),
10 parts of urea,
10 parts of glycerine,
0.6 part nonionic penetration enhancers,
0.1 part organic-silicon-modified defoamer,
0.1 part mould inhibitor and
66.37 part water.
(manufacturing of writing implement)
Ink (is cooled to-16 ℃ in advance with microencapsulation pigment, to show pink, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its end by relay part 9, and the internal diameter of described beam barrel 4 is that 4mm and external diameter are 8mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assemblied in the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made by attaching parts 10 then.
After the cap for brush 7 that has rubber seal 8 and be equipped with anchor clamps 11 in it places in the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in by the ball (diameter is 0.6mm) that stainless steel is made in the ball maintaining part and by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When with the cap for brush when writing implement is removed, its outward appearance is as pencil.
Form pink person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 7 (referring to Figure 11)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
25.7 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-20 ℃, T
2:-9 ℃, T
3: 40 ℃, T
4: 57 ℃, Δ H:63 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from black to colourless change color), and comprise:
As composition (i), 4.5 parts 2-(2-chloroanilino)-6-two-n-butyl amine base fluorane;
As composition (ii), 2 of 4.5 parts 4,4 '-(2-methyl propylidene) bis-phenol and 7.5 parts, two (4 '-hydroxyphenyl) HFC-236fas of 2-; With
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.2 part succinoglycan (shear thinning agent),
5.5 part urea,
7.5 part glycerine,
0.03 part nonionic penetration enhancers,
0.15 part organic-silicon-modified defoamer,
0.1 part mould inhibitor,
0.5 part lubricant,
0.5 part triethanolamine and
59.82 part water.
(manufacturing of writing implement)
Ink (is cooled to-20 ℃ in advance with microencapsulation pigment, to show black, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its end by relay part 9, and the internal diameter of described beam barrel 4 is that 5mm and external diameter are 9mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.Then tail plug 11 is assemblied in the rearward end of beam barrel.
The cap for brush 7 (is being had rubber seal 8, is being provided with jut 13 in it, and after the friction piece of making by SEBS 6 with end of being assemblied in the cap for brush) placing on the beam barrel that is obtained, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.8mm) that stainless steel is made, simultaneously by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When with the cap for brush when writing implement is removed, its outward appearance is as pencil.
Form black handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
[embodiment 8 (referring to Figure 12)]
(preparation of reversible thermochromic ink)
Preparation reversible thermochromic ink, it comprises:
25.7 its of part contains the microencapsulation pigment (T of the reversible thermochromic composition with memory for color character
1:-14 ℃, T
2:-6 ℃, T
3: 48 ℃, T
4: 60 ℃, Δ H:64 ℃, average grain diameter: the ratio=2.6/1.0 of 2.5 μ m, reversible thermochromic composition/wall film, pigment take place from blueness to colourless change color), and comprise:
As composition (i), 2.0 parts 3-(the own oxygen base of 4-lignocaine-2-phenyl)-3-(1-ethyl-2 methyl indole-3-yl)-4-azepine phthalide,
As composition (ii), 2 of 3.0 parts 4,4 '-(2-methyl propylidene) bis-phenol and 5.0 parts, two (4 '-hydroxyphenyl) HFC-236fas of 2-and
As composition (iii), 50.0 parts capric acid 4-benzyloxy phenethyl ester,
0.2 part succinoglycan (shear thinning agent),
5.5 part urea,
7.5 part glycerine,
0.03 part nonionic penetration enhancers,
0.15 part organic-silicon-modified defoamer,
0.1 part mould inhibitor,
0.5 part lubricant,
0.5 part triethanolamine and
59.82 part water.
(manufacturing of writing implement)
Ink 2 (is cooled to-14 ℃ in advance with microencapsulation pigment, to show blueness, place it under the room temperature subsequently) be filled in the polypropylene beam barrel 4, described beam barrel 4 has the writing tip 3 (ball-point pen tip) that is securely fixed in its end, and the internal diameter of described beam barrel 4 is that 4mm and external diameter are 9mm.The viscoelastic ink that has that mainly is made of polybutene is followed body 5 and is filled in the beam barrel.To be assembled on the rearward end of beam barrel by the friction piece 6 that the SEBS resin is made then.
The cap for brush 7 (have rubber seal 8 in it and be equipped with another friction piece 6 of being made by the SEBS resin in the end of the cap for brush) is placed obtain beam barrel after, by the centrifugal processing that outgases, to obtain writing implement 1 (ball pen).
By will be set in the ball maintaining part by the ball (diameter is 0.4mm) that stainless steel is made, simultaneously by spring make ball forwards deflection obtain ball-point pen tip, wherein said ball maintaining part forms by utilizing drill bit that metal material is processed.
Thus obtained writing implement is very thin and has excellent portability.When with the cap for brush when writing implement is removed, its outward appearance is as pencil.
Form blue person's handwriting by using this writing implement on paper, to write.
On paper, in the formed person's handwriting, person's handwriting mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.At room temperature keep this state, make and to form person's handwriting again in the part place after wiping.
Wipe person's handwriting with being arranged on friction piece on the cap for brush, and wipe the person's handwriting in big zone with the friction piece that is arranged on the beam barrel than the zonule.
[embodiment 9]
(manufacturing of writing implement set)
The composition for ink for preparing among the embodiment 1-5 is filled in respectively in the writing implement of embodiment 1, with the writing implement set that obtains to make by 5 writing implements.
In this writing implement set, writing implement is very thin and portability that have excellence.When being fitted to the cap for brush in the writing implement, the outward appearance of writing implement is as pencil.
By using these writing implements on paper, to write, form redness, pink, black, blueness and orange picture.
In the picture of on paper, being drawn, picture mistake or unwanted is wiped out with friction piece.So they lose color and become invisible.This state is at room temperature kept, make and to draw picture again in the part place after wiping.
Above-mentioned writing implement set can be the assembly that is formed by a plurality of writing implements, and described writing implement takes place from coloured extremely colourless variation and contains the ink that tone differs from one another.Can be for another mode of selecting for use, it can be by taking place from colourless to coloured variation and contain the formed assembly of writing implement of the ink that tone differs from one another, or by the variation from color (1) to color (2) taking place and containing the formed assembly of writing implement that tone each other is different from the ink of color (1) or color (2).
Although described the present invention in detail or described the present invention, it will be readily apparent to one skilled in the art that and under the situation that does not deviate from the spirit or scope of the present invention, to carry out various variations or modification with reference to specific embodiment.Present patent application is based on the Japanese patent application (No.2006-331292) of Japanese patent application of submitting on October 17th, 2006 (No.2006-282124) and submission on December 8th, 2006, and its content is incorporated herein by reference.
Industrial applicibility
Compare with the conventional thermochromism writing implement that utilizes frictional heat, of the present inventionly write the worker Prodigiosin is enough to be made with lower cost, and writes the worker owing to ink directly is filled to In the beam barrel of tool, so it is very thin and volume is little as pencil, and it has excellent Different portability. In addition, even when consisting of and to form by a plurality of above-mentioned writing implements During the writing implement set of the person's handwriting that tone is different, the volume of this assembly is also constant big, therefore The present invention can provide such writing implement set, and this writing implement set can carry many The writing implement that individual color is different, thus satisfied convenience.
Claims (10)
1. writing implement, this writing implement comprises:
Beam barrel is wherein owing to heating turns pale, the ink of colour developing or variable color and follow body and directly be filled in this beam barrel along with the consumption of ink follows ink that ink advances closely; With
Writing tip, this writing tip directly or by relay part are firmly fixed at an end of described beam barrel,
Wherein, the rubber-like friction piece is set at the rearward end of described beam barrel.
2. writing implement, this writing implement comprises:
Beam barrel is wherein owing to heating turns pale, the ink of colour developing or variable color and follow body and directly be filled in this beam barrel along with the consumption of ink follows ink that ink advances closely;
Writing tip, this writing tip are directly or be firmly fixed at an end of described beam barrel by relay part; With
The cap for brush, this cap for brush covers described writing tip,
Wherein, the rubber-like friction piece is set at the rearward end of described beam barrel and/or the end of the described cap for brush.
3. writing implement according to claim 1 and 2, wherein said beam barrel has light-proofness.
4. according to each described writing implement in the claim 1 to 3, wherein said ink comprises microencapsulation pigment, and this microencapsulation pigment comprises the reversible thermochromic composition within it, and described reversible thermochromic composition comprises at least:
(i) provide the colour developing organic compound of electronics;
(ii) accept electronics compound and
(iii) reaction medium, this reaction medium are used to control described composition (i) and the described composition color reaction between (ii), and this microencapsulation pigment is owing to heating takes place from coloured extremely colourless change color.
5. writing implement according to claim 4, wherein said microencapsulation pigment demonstrates bigger lagging characteristics in its color depth-temperature curve, show the enantiotropy between first form and aspect and second form and aspect, and described microencapsulation pigment has two-phase and keeps temperature range, this temperature range makes described first form and aspect and described second form and aspect coexist in common temperature range
Be in the first form and aspect state and in the temperature rise period, when described pigment reaches second temperature T
3The time, this pigment begins variable color from described first form and aspect, and this pigment is in temperature T
4Become second form and aspect fully, wherein said temperature T in the above temperature range
4Be higher than described second temperature T
3,
Be in the second form and aspect state and in temperature-fall period, be lower than described second temperature T when described pigment reaches
3First temperature T
2The time, this pigment is since the second form and aspect variable color, and this pigment be not higher than temperature T
1Temperature range in become described first form and aspect fully, wherein said temperature T
1Be lower than described first temperature T
2,
Described pigment is in described first temperature T
2With described second temperature T
3Between temperature range in demonstrate lagging characteristics, this lagging characteristics makes described first form and aspect and described second form and aspect coexist simultaneously,
Described temperature T
1In-30 ℃ to 10 ℃ scope, and
Described temperature T
4In 30 ℃ to 80 ℃ scope.
6. according to each described writing implement in the claim 1 to 5, wherein said friction piece is selected from elastomer and plastic foam.
7. according to each described writing implement in the claim 1 to 6, wherein said beam barrel firmly fixes by attaching parts each other with described friction piece is in the same place.
8. writing implement according to claim 7, wherein said attaching parts also play the effect of described beam barrel.
9. according to each described writing implement in the claim 1 to 8, wherein said writing tip is a ball-point pen tip.
10. writing implement set, it comprises each described writing implement in a plurality of claims 1 to 9, wherein said writing implement is filled with the ink that tone differs from one another respectively.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP282124/2006 | 2006-10-17 | ||
| JP2006282124 | 2006-10-17 | ||
| JP331292/2006 | 2006-12-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101528476A true CN101528476A (en) | 2009-09-09 |
Family
ID=41095706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200780038859XA Pending CN101528476A (en) | 2006-10-17 | 2007-10-16 | Writing implement and writing implement set |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101528476A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103788939A (en) * | 2012-10-31 | 2014-05-14 | 上海晨光文具股份有限公司 | Thermochromic composition, thermochromic erasable neutral ink and pen core filled with the same |
| CN104070893A (en) * | 2014-06-26 | 2014-10-01 | 绍兴文理学院 | Rotation type automatic erasure blackboard based on high temperature vanishing pen |
| WO2014166240A1 (en) * | 2013-04-07 | 2014-10-16 | 上海欣渊文化用品有限公司 | Reversible temperature sensitive erasable neutral ink composition and manufacturing method thereof |
| CN104691157A (en) * | 2010-02-03 | 2015-06-10 | 百乐墨水株式会社 | Writing tool |
| US9266379B2 (en) | 2007-02-26 | 2016-02-23 | The Pilot Ink Co., Ltd. | Thermochromic writing instrument |
| CN107849380A (en) * | 2015-05-28 | 2018-03-27 | 株式会社百乐 | Writing implement oil-based ink composition and the writing implement, marker pen and ball pen equipped with it |
| CN109795243A (en) * | 2019-02-02 | 2019-05-24 | 浙江义乌科标制笔有限公司 | A kind of colorful writing implement and its manufacturing method |
| CN111655803A (en) * | 2018-01-29 | 2020-09-11 | 三菱铅笔株式会社 | Water-based ink composition for writing instrument |
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2007
- 2007-10-16 CN CNA200780038859XA patent/CN101528476A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9266379B2 (en) | 2007-02-26 | 2016-02-23 | The Pilot Ink Co., Ltd. | Thermochromic writing instrument |
| CN104691157A (en) * | 2010-02-03 | 2015-06-10 | 百乐墨水株式会社 | Writing tool |
| CN105128559A (en) * | 2010-02-03 | 2015-12-09 | 百乐墨水株式会社 | Pen |
| CN104691157B (en) * | 2010-02-03 | 2016-08-31 | 百乐墨水株式会社 | Pen |
| CN103788939A (en) * | 2012-10-31 | 2014-05-14 | 上海晨光文具股份有限公司 | Thermochromic composition, thermochromic erasable neutral ink and pen core filled with the same |
| WO2014166240A1 (en) * | 2013-04-07 | 2014-10-16 | 上海欣渊文化用品有限公司 | Reversible temperature sensitive erasable neutral ink composition and manufacturing method thereof |
| CN104070893B (en) * | 2014-06-26 | 2016-02-17 | 绍兴文理学院 | A kind of rotary auto-erasing blackboard using high temperature disappearance pen |
| CN104070893A (en) * | 2014-06-26 | 2014-10-01 | 绍兴文理学院 | Rotation type automatic erasure blackboard based on high temperature vanishing pen |
| CN107849380A (en) * | 2015-05-28 | 2018-03-27 | 株式会社百乐 | Writing implement oil-based ink composition and the writing implement, marker pen and ball pen equipped with it |
| CN111655803A (en) * | 2018-01-29 | 2020-09-11 | 三菱铅笔株式会社 | Water-based ink composition for writing instrument |
| CN111655803B (en) * | 2018-01-29 | 2022-12-16 | 三菱铅笔株式会社 | Aqueous ink composition for writing instrument |
| CN109795243A (en) * | 2019-02-02 | 2019-05-24 | 浙江义乌科标制笔有限公司 | A kind of colorful writing implement and its manufacturing method |
| CN109795243B (en) * | 2019-02-02 | 2024-02-27 | 浙江义乌科标制笔有限公司 | Colorful writing tool and manufacturing method thereof |
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